32 卷 10 期 结 构 化 学 （JIEGOU HUAXUE） Vol 32 No 10 2013 10 Chinese J Struct Chem 14651474

Facile Synthesis and Crystal Structures of New

Ammonium Sulfonates (CA-DNBS and TEA-TMBS)①

KHAN Islam Ullaha ARSHAD Muhammad Nadeemb c② ŞAHİN Onurd③ MUBASHAR-Ur-REHMAN Hafiza MUNIR Ayeshaa

HUMAYUN Sabaa ASIRI Abdullah Mb c a (Materials Chemistry Laboratory Department of Chemistry

GC University Lahore 54000 Pakistan) b (Centre of Excellence for Advanced Materials Research (CEAMR)

King Abdulaziz University P O Box 80203 Jeddah 21589 Saudi Arabia) c (Chemistry Department Faculty of Science King Abdulaziz

University P O Box 80203 Jeddah 21589 Saudi Arabia) d (Scientific and Technological Research Application and Research Center Sinop University 57010 Sinop Turkey)

ABSTRACT The title compounds C12H10N3O7SCl (I) and C15H27NO3S (II) crystallize in the monoclinic system space group P21c with a = 73995(1) b = 278489(6) c = 98246(2) Aring β = 131349(1)ordm V = 151982(5) Aring3 Z = 4 F(000) = 768 Rint = 0033 and S = 103 for I and in the orthorhombic system space group Pbca with a = 86227(1) b = 161480(4) c = 238774(6) Aring V = 332467(12) Aring3 Z = 8 F(000) = 1312 Rint = 0024 and S = 104 for II We have devised a convenient procedure for the synthesis of fused organic salts resulting from 11 proton-transfer using an amine and a derivative of benzenesulfonic acid The synthesized salts have a number of applications ranging from their consumption as eco-friendly solvents and catalysts in organic syntheses to being used as efficient precursors for the production of sulfa drugs Structures of compounds 3-chloroanilinium 24-dinitrobenzenesulfonate (CA-DNBS) and triethylaminium 246-trimethylbenzenesulfonate (TEA-TMBS) were determined by single-crystal X-ray diffraction studies and infrared spectroscopy Keywords crystal structure ammonium sulfonates 3-chloroanilinium 24-dinitrobenzenesulfonate triethylaminium 246-trimethylbenzenesulfonate ionic liquids

1 INTRODUCTION

Ionic liquids (ILs) have gained much consideration as they revel in a plethora of applications due to their supple properties which are task-specific because they can be tailored by tuning the structure of the

ionic species involved[1] Some common properties include wide liquid phase range with lower melting points stability in air and moisture insignificant vapor pressure and high degree solubility even in polymeric materials[2] Ionic liquids when used as reaction medium are not merely greener but also

Received 14 March 2013 accepted 12 August 2013 (CCDC 926613 and 926614) ① The authors acknowledge Chemistry Department Centre of Excellence for Advanced Materials Research (CEAMR)

Faculty of Science King Abdulaziz University Jeddah Saudi Arabia for data collection ② Corresponding author E-mail mnachemisthotmailcom and mnarshadkauedusa ③ Corresponding author E-mail onurssinopedutr

KHAN I U et al Facile Synthesis and Crystal Structures of 1466 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

resolve the issues like solvent emission and recycling of catalyst[3] Various organic chemical reactions can be carried out in ionic liquids esterification reac- tion[4-8] aldol condensation[9] Koch carbonylation[10] polymerization[11] hydrogenation regioselective alkylation and Friedal-Crafts reaction[12-15] Diels- Alder reaction[16-17] Mannich reaction[18-19] oxida- tion[20-22] Heck reaction[23] Knoevenagel reac- tion[24-26] Henry reactions[27] heterocyclic synthe- sis[28-31] and some enzyme reactions are to name a few ILs are known since the mid-19th to early 20th century[32-33] and most of the recent studies focused both on their preparation[34] characterization and applications These are applied in organic synthesis as alternative media and as catalysts[35] In analytical chemistry these have their scope as extractants of heavy metal ions[36] and as electrolytes in electro- chemistry[37] Triethylammonium p-toluenesul- fonate [Et3NH]+ [p-CH3C6H4SO3]ndash eg can be used as an ionic liquid in industrial esterification of acetic acid where it is employed as a reaction medium and catalyst both[38] and as a stationary phase in Gas Chromatography (GC) for the determination of benzoic acid in plants like soy[39] Fascinated by such diverse applications we aimed at synthesizing fused organic salts consisting of ions which can serve as ionic liquids Conventional methods known for making ILs involve extended heating followed by repeated washings or extractions of the product with different organic solvents[1 40-42] Recently Rajen- dran et al have reported a relatively facile method for ionic liquid synthesis[43]

A range of therapeutic medications are manufac- tured as salts of benzenesulfonic acid and are called besylates[44] As in this study crystal structures of various derivatives of benzenesulfonate such as ephedrine besylate[45] 2-ethyl-6-methylanilinium 4- methylbenzenesulfonate[46] 2-aminopyrimidin-1- ium 4-methylbenzenesulfonate[47] 4-(cyanomethyl)- anilinium 4-methylbenzenesulfonate monohydrate[48] 1-methyl-2-[(E)-2-(2-thienyl)ethenyl] quinolinium 4-bromobenzenesulfonate[49] and (E)-2-[4-(dime- thylamino) styryl]-1-methylpyridinium 4-methylben-

zene sulfonate monohydrate[50] have been depicted in the literature hence demonstrating their signifi- cance Sulfonate salts derived from primary or secondary amines (analogous to I) when reacted with cyanuric chloride at room temperature afford sulfona- mides (sulfa drugs) in high yields[51] In another reaction the amine derived sulfonate salts can be used to synthesize pentafluorophenyl (PFP) sulfonate esters which act as substantial precursors for the preparation of sulfonamides in good yields without further chromatographic purification[52] These pre- cursors are progressively becoming a striking alterna- tive to sulfonyl chlorides for sulfa drug syntheses on account of their shelf stability convenient handling thermal stability and the ability to react in aqueous reaction medium[53-54] Furthermore aromatic sul- fonyl compounds containing nitro groups (NO2+) can be consumed as chief raw materials in the production of sulfanilamides[55] such as furosemide and sulfadiazine

Herein we speculated the synthesis of 3-chloroani- linium 24-dinitrobenzenesulfonate (CA-DNBS) (I) and triethylaminium 246-trimethylbenzenesulfonate (TEA-TMBS) (II) and further work is in progress to explore these as ionic liquids for various applications The synthesis was processed in such a way that a mixture of 3-chloroaniline and 24-dinitrobenze- nesulfonic acid (equimolar ratios) in distilled water when stirred at room temperature for 10 minutes afforded I in a good yield (Scheme 1) by simple recrystallization In a similar attempt we stirred a mixture of triethyl amine and 2-mesitylenesulfonic acid (in equimolar ratios) in dichloromethane at room temperature and the desired product II was obtained in high yield (Scheme 1) thus rendering the methodologies highly feasible and convenient The synthesized organic salts are roughly categorized as ammonium sulfonates Primary (I) and tertiary (II) organic ammonium salts are analogs of ammonium salts in which one or more hydrogen atoms bonded to the central nitrogen of an ammonium cation (NH4+) have been replaced by organic radicals The subs- tituents can be aryl (as in I) or alkyl (as in II) or the

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1467

nitrogen can act as part of a ring system All organic ammonium cations are weakly acidic while quater- nary ammonium ion is an exception The counter ions (anions) to the substituted ammonium cations in I and

II are sulfonates (RSO2O-) Such anions are conjugate bases of sulfonic acids (RSO2OH) These acids are considerably strong hence they give rise to sulfonates which are weak bases

Substituted group Compound I Compound II R1 3-chloro-ph- C2H5- R2 H C2H5- R3 H C2H5- R4 24-dinitro-ph- 246-trimethyl-ph-

Scheme 1 Synthesis of 3-chloroanilinium 24-dinitrobenzenesulfonate (CA-DNBS) and NN-diethylethanaminium 246-trimethylbenzenesulfonate (TEA-TMBS)

2 EXPERIMENTAL 2 1 Materials and chemicals

All chemicals were obtained from Aldrich chemi- cals and used as received Commercial grade solvents were used after filtration and distillation All melting points were recorded using Branstead

Electrothermal melting point apparatus Both compounds were solid hence the IR spectrum of the complex was recorded on a Perkin-Elmer FTIR 180 spectrophotometer using KBr pellets from 4000 to 400 cm-1 The m p and IR values are given in Tables 1～3

Table 1 Physical Parameters of CA-DNBS and TEA-TMBS

Solubility Sr No Salts Melting point ()

Water Acetone Alcohol Dichloromethane Toluene Benzene

1 CA-DNBS 258～262 S PS S S INS INS 2 TEA-TMBS 98～102 S PS S S INS INS

S = Soluble PS = Partially soluble INS = Insoluble

Table 2 Characteristic Infrared Absorption Frequencies for CA-DNBS (cm-1) Bond

Molecular motion

Observed frequency for CA-DNBS (cm-1)

S=O Stretching 1358 SminusO Stretching 748 Primary aromatic ammonium salt NminusH Stretching 3107 Primary aromatic ammonium salt NminusH Bending 1533 Primary aromatic ammonium salt CminusN Stretching 1219 Aromatic NminusH Stretching 3492 Aromatic CminusH In plane bending 1118 Aromatic CminusH Out of plane bending 637

Table 3 Characteristic Infrared Absorption Frequencies for TEA-TMBS (cm-1)

Bond

Molecular motion

Observed frequency for TEA-TMBS (cm-1)

S=O Stretching 1397 SminusO Stretching 845 Aliphatic NminusH Stretching 3438 Aliphatic NminusH In plane bending 1605 amp 1459

KHAN I U et al Facile Synthesis and Crystal Structures of 1468 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

To be continued Aliphatic NminusH Out of plane bending 795 Tertiary aliphatic ammonium salt NminusH Stretching 2492 amp 2676 Tertiary aliphatic ammonium salt CminusN Stretching 1189 amp 1025 Aromatic CminusH Out of plane bending 683 Aromatic CminusH Stretching 2970 Aromatic CminusH In plane bending 1089

2 2 Methodology

Preparation of organic salt (I) Organic salt (I) was prepared by stirring equimo-

lar quantities of 3-chloro aniline (4 mmol 051 g) and 24-dinitrobenzenesulfonic acid hydrate (4 mmol 106 g) in 10 mL distilled water for 10 minu- tes The reaction mixture was concentrated resulting in precipitation of the product Recrystallization of the product in dichloromethane (DCM) yielded light brown crystals Yield was calculated to be 899

Preparation of organic salt (II) Organic salt (II) was prepared by dissolving equi-

molar quantities of triethyl amine (5 mmol 051 g) and 246-trimethylbenzenesulfonic acid dihydrate (5 mmol 118 g) in 10 mL of dichloromethane The reaction mixture was stirred at room temperature for 2 hours The DCM layer was washed with dilute HCl solution to remove the unreacted TEA and dried over anhydrous MgSO4 Slow evaporation of the solvent resulted in light brownish crystals of the desired product in 946 yield 2 3 Crystal structure determination

Suitable crystals of I and II were selected for data collection which was performed on an Agilent SuperNova CCD diffractometer with mirror mono- chromated Cu-Kα radiation at 296 K The structures were solved by direct methods using SHELXS-97 and refined by full-matrix least-squares methods on F2 using SHELXL-97[56] from within the WINGX[57] suite of software All non-hydrogen atoms were refined with anisotropic parameters Nitrogen H atoms were located in difference maps and refined freely Hydrogen atoms bonded to carbon were placed in the calculated positions (CndashH = 093～097Aring) and treated using a riding model with U = 12 times the U value of the parent atom for CH CH2 and CH3 Molecular diagrams were created using

MERCURY[58] Geometric calculations were perfor- med with PLATON[59]

3 RESULTS AND DISCUSSION

The molecular structure of I C6H3N2O7S-middotC6H7ClN+ has one cation-anion pair in the asymmetric unit (Fig 1) Selected bond lengths and angles are collected in Table 4 The p-NO2 group is nearly coplanar to its carrier ring (O(6)minusN(2)minus C(4)minusC(5) = 69(4)ordm) while the o-NO2 group is twisted by minus558(3)ordm (O(4)minusN(1)minusC(2)minusC(1)) relative to the phenyl ring in order to avoid a short intramo- lecular contact with O(3) Both aromatic rings are in a good approximation plane with the maximum deviations from the least-squares plane calculated by the six ring atoms to be 00119(2) Aring in the anion and 00022(2) Aring in the cation The anion molecule interacts with the protonated N atom through a bifurcated NminusHO hydrogen bond forming R1

2(4) R2

1(4) and R12(7) ring motifs with an adjacent cation

The SminusO bond distances range between 14412(13)～14500(12) Aring and the NminusO bond distances fall in the 1204(3)～ 1219(2) Aring range respectively These bond distances compare well to the literature values[60-63] The OminusNminusO bond angles are 1235(2)ordm and 12552(18)ordm respectively while the OminusSminusO bond angles vary from 11261(8)ordm to 11498(8)ordm respec- tively

Molecules of I are linked into sheets by a com- bination of NminusHO and CminusHO hydrogen bonds and ππ interactions Atom C(6) serves as a hydrogen-bond donor via atom H(6) to atom O(4) at (xminus1 y z) forming a C(6) chain[64] parallel to the [100] direction Atom C(3) in the molecule at (x y z) acts as a hydrogen-bond donor via atom H(3) to atom O(7) at (minusx+1 minusy+1 minusz+1) so forming a

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1469

centrosymmetric R22(10) ring centered at (12 12

12) Propagation of the CminusHO hydrogen bonds thus forms a chain of rings containing R2

2(10)R44(22)

sequences of two edge-fused rings (Fig 2) The combination of NminusHO and CminusHO hydrogen bonds produces R2

1(6) and R32(9) rings (Fig 2)

Compound I also contains two ππ interactions The Cg1 ring (C(1)～C(6)) in the molecule at (x y z)

makes dihedral angles of only 456ordm with the Cg2 ring (C(7)～C(12)) in each of the two molecules at (xminus1 y zminus1) and (x y z) The ring-centroid separations are 3797(1) and 3647(1) Aring and the interplanar spacings are ca 3567 and 3535 Aring respectively The ππ interactions produce a chain running parallel to the [101] direction (Fig 3)

Fig 1 A view of the molecule of I showing the atom-numbering scheme

Fig 2 Crystal structure of I showing the formation of R1

2(4) R21(4) R2

1(6) R2

2(10) R32(9) and R4

4(22) rings (Symmetry code as in Table 5)

KHAN I U et al Facile Synthesis and Crystal Structures of 1470 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 3 Crystal structure of I showing the formation of a chain along [101]

generated by ππ interactions (Symmetry code (vi) xndash1 y zndash1)

Table 4 Selected Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

I

Bond Dist Bond Dist Bond Dist

N(1)minusO(5) 1213(2) N(2)minusO(6) 1208(3) N(1)minusO(4) 1219(2) N(2)minusO(7) 1204(3) O(1)minusS(1) 14483(13) O(2)minusS(1) 14412(13) O(3)minusS(1) 14500(12)

Angle (deg) Angle (deg) Angle (deg)

O(5)minusN(1)minusO(4) 12552(18) O(5)minusN(1)minusC(2) 11743(18) O(4)minusN(1)minusC(2) 11699(17) O(7)minusN(2)minusO(6) 1235(2) O(7)minusN(2)minusC(4) 1185(2) O(6)minusN(2)minusC(4) 1181(2) O(2)minusS(1)minusO(1) 11498(8) O(2)minusS(1)minusO(3) 11261(8) O(1)minusS(1)minusO(3) 11269(8) O(2)minusS(1)minusC(1) 10406(8) O(1)minusS(1)minusC(1) 10535(8) O(3)minusS(1)minusC(1) 10605(8) C(5)minusC(4)minusN(2)minusO(6) 69(4) C(1)minusC(2)minusN(1)minusO(4) -558(3)

II

Bond Dist Bond Dist Bond Dist

S(1)minusO(2) 14373(19) S(1)minusO(3) 1442(2) S(1)minusO(1) 1454(2)

Angle (deg) Angle (deg) Angle (deg)

O(2)minusS(1)minusO(3) 11321(13) O(2)minusS(1)minusO(1) 11343(14) O(3)minusS(1)minusO(1) 10996(13) O(2)minusS(1)minusC(1) 10573(11) O(3)minusS(1)minusC(1) 10870(13) O(1)minusS(1)minusC(1) 10531(12)

The molecular structure of II with atom labeling is

shown in Fig 4 The asymmetric unit of II consists of cation (C6H16N+) and anion (C9H11O3S-) molecules The two C atoms are disordered (occupancy C(11)minus C(12) = 05 C(11A)minusC(12A) = 05) with a proto- nated N atom in the cation molecule The SminusO bond distances range between 14373(19) and 1454(2) Aring while the OminusSminusO bond angles vary from 10996(13) to 11343(14)ordm The benzene ring plane is approxima- tely planar with maximum deviation from the least-squares plane of 00056(16) Aring for atom C(2)

In II intramolecular CminusHO hydrogen bonds define S(6) motifs The intermolecular NminusHO hydrogen bonds produce R1

2(3) rings The com- bination of NminusHO and CminusHO hydrogen bonds produce R4

3(12) chain of rings running parallel to the [100] direction (Fig 5) Atoms C(7) and C(14) in the molecule at (x y z) acts as hydrogen-bond donors to the C(1)～C(6) benzene rings in the molecules at (xminus1 y z) and (x+12 y minusz+12) so forming a zigzag chain running parallel to the [100] direction (Fig 6) Details of these interactions are presented in Table 5

Table 5 Hydrogen Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

DminusHmiddotmiddotmiddotA d(DminusH) d(HmiddotmiddotmiddotA) d(DmiddotmiddotmiddotA) lt(DHA)

I

N(3)minusH(1N)middotmiddotmiddotO(1)i 089(4) 221(4) 3050(2) 157(3) N(3)minusH(1N)middotmiddotmiddotO(2)ii 089(4) 260(3) 3148(2) 121(3)

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

To be continued

N(3)minusH(2N)middotmiddotmiddotO(3)ii 083(4) 223(4) 2889(2) 136(3) N(3)minusH(2N)middotmiddotmiddotO(2)iii 083(4) 229(4) 2916(2) 133(3) N(3)minusH(3N)middotmiddotmiddotO(1) 088(4) 201(4) 2858(2) 159(3) N(3)minusH(3N)middotmiddotmiddotO(3)i 088(4) 256(3) 3012(2) 113(3) C(3)minusH(3)middotmiddotmiddotO(7)iv 093 243 3353(3) 173 C(6)minusH(6)middotmiddotmiddotO(4)v 093 260 3273(5) 130 C(12)minusH(12)middotmiddotmiddotO(1)i 093 256 3337(2) 142

II

N(1)minusH(1)middotmiddotmiddotO(1) 083(4) 207(4) 2853(3) 156(4) N(1)minusH(1)middotmiddotmiddotO(3) 083(4) 255(4) 3233(3) 141(3) N(1)minusH(1)middotmiddotmiddotS(1) 083(4) 281(4) 3631(2) 168(3) C(15)minusH(15A)middotmiddotmiddotO(3) 096 193 2760(4) 144 C(13)minusH(13B)middotmiddotmiddotO(2) 096 242 3040(4) 122 C(11)minusH(11B)middotmiddotmiddotO(2)i 097 255 3359(8) 141 C(9)minusH(9A)middotmiddotmiddotO(2)ii 097 258 3308 132(4) C(7)minusH(7B)middotmiddotmiddotCg(1)i 097 258 3373(9) 139 C(14)minusH(14B)middotmiddotmiddotCg(1)iii 096 308 4001(11) 160

Symmetry codes (i) x ndashy+12 z+12 (ii) x+1 y z+1 (iii) x+1 ndashy+12 z+12 (iv) ndashx+1 ndashy+1 ndashz+1 (v) xndash1 y z for I (i) xndash1 y z (ii) xndash12 ndashy+32 ndashz+1 (iii) x+12 y ndashz+12 Cg(1) = C(1)～C(6) for II

Fig 4 A view of the molecule of II showing the atom-numbering scheme

Fig 5 Crystal structure of II showing the formation of R1

2(3) and R43(12) rings

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 6 Crystal structure of II showing the formation of a chain along [100] generated

by CminusHπ interactions (Symmetry code as in Table 5)

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(41) Ying A G Liu L Wua G F Chen G Chen X Z Ye W D Aza-Michael addition of aliphatic or aromatic amines to αβ-unsaturated

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

compounds catalyzed by a DBU-derived ionic liquid under solvent-free conditions Tetrahedron Lett 2009 50 1653minus1657

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(45) Collier E A Davey R J Black S N Roberts R J 17 salts of ephedrine crystal structures and packing analysis Acta Cryst 2006 B62 498minus505

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(47) Tabatabaee M Noozari N 2-Aminopyrimidin-1-ium 4-methylbenzenesulfonate Acta Cryst 2011 E67 o1457

(48) Lin J R 4-(Cyanomethyl)anilinium 4-methylbenzenesulfonate monohydrate Acta Cryst 2010 E66 o1557

(49) Fun H K Kobkeatthawin T Chantrapromma S 1-methyl-2-[(E)-2-(2-thienyl)ethenyl]quinolinium 4-bromobenzenesulfonate Acta Cryst 2010

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Acta Cryst 2010 E66 o1975-o1976

(51) Rad M N S Khalafi-Nezhad A Asrari Z Behrouz S Amini Z Behrouz M One-pot synthesis of sulfonamides from primary and secondary

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(52) Caddick S Wilden J D Bush H D Judd D B synthesis of functionalised sulfonamides via microwave assisted displacement of

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(53) Caddick S Wilden J D Wadman S J Bush H D Judd D B A new route to sulfonamides via intermolecular radical addition to

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(54) Caddick S Wilden J D Judd D B Direct synthesis of sulfonamides and activated sulfonate esters from sulfonic acids J Am Chem Soc 2004

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(58) Mercury version 30 CCDC available online via ccdccamacukproductsmercury

(59) Spek A L PLATON ndash A Multipurpose Crystallographic Tool Utrecht Utrecht University The Netherlands 2005

(60) Suarez S Doctorovich F Baggio R Ammonium 4-methoxybenzenesulfonate Acta Cryst 2012 E68 o2228minuso2229

(61) Beko S L Bats J W Schmidt M U 2-Ammonio-5-chloro-4-methylbenzenesulfonate its 1-methyl-2-pyrrolidone and dimethyl sulfoxide

monosolvates and a corrected structure of 22΄-(14-phenylene)di(45-dihydroimidazolium)bis(4-aminobenzenesulfonate) dehydrate Acta Cryst

2012 C68 o45minuso50

(62) Kennedy A R Morrison C A Briggs N E B Arbuckle W Density and stability differences between enantiopure and racemic salts

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Int Ed Engl 1995 34 1555minus1573

KHAN I U et al Facile Synthesis and Crystal Structures of 1466 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

resolve the issues like solvent emission and recycling of catalyst[3] Various organic chemical reactions can be carried out in ionic liquids esterification reac- tion[4-8] aldol condensation[9] Koch carbonylation[10] polymerization[11] hydrogenation regioselective alkylation and Friedal-Crafts reaction[12-15] Diels- Alder reaction[16-17] Mannich reaction[18-19] oxida- tion[20-22] Heck reaction[23] Knoevenagel reac- tion[24-26] Henry reactions[27] heterocyclic synthe- sis[28-31] and some enzyme reactions are to name a few ILs are known since the mid-19th to early 20th century[32-33] and most of the recent studies focused both on their preparation[34] characterization and applications These are applied in organic synthesis as alternative media and as catalysts[35] In analytical chemistry these have their scope as extractants of heavy metal ions[36] and as electrolytes in electro- chemistry[37] Triethylammonium p-toluenesul- fonate [Et3NH]+ [p-CH3C6H4SO3]ndash eg can be used as an ionic liquid in industrial esterification of acetic acid where it is employed as a reaction medium and catalyst both[38] and as a stationary phase in Gas Chromatography (GC) for the determination of benzoic acid in plants like soy[39] Fascinated by such diverse applications we aimed at synthesizing fused organic salts consisting of ions which can serve as ionic liquids Conventional methods known for making ILs involve extended heating followed by repeated washings or extractions of the product with different organic solvents[1 40-42] Recently Rajen- dran et al have reported a relatively facile method for ionic liquid synthesis[43]

A range of therapeutic medications are manufac- tured as salts of benzenesulfonic acid and are called besylates[44] As in this study crystal structures of various derivatives of benzenesulfonate such as ephedrine besylate[45] 2-ethyl-6-methylanilinium 4- methylbenzenesulfonate[46] 2-aminopyrimidin-1- ium 4-methylbenzenesulfonate[47] 4-(cyanomethyl)- anilinium 4-methylbenzenesulfonate monohydrate[48] 1-methyl-2-[(E)-2-(2-thienyl)ethenyl] quinolinium 4-bromobenzenesulfonate[49] and (E)-2-[4-(dime- thylamino) styryl]-1-methylpyridinium 4-methylben-

zene sulfonate monohydrate[50] have been depicted in the literature hence demonstrating their signifi- cance Sulfonate salts derived from primary or secondary amines (analogous to I) when reacted with cyanuric chloride at room temperature afford sulfona- mides (sulfa drugs) in high yields[51] In another reaction the amine derived sulfonate salts can be used to synthesize pentafluorophenyl (PFP) sulfonate esters which act as substantial precursors for the preparation of sulfonamides in good yields without further chromatographic purification[52] These pre- cursors are progressively becoming a striking alterna- tive to sulfonyl chlorides for sulfa drug syntheses on account of their shelf stability convenient handling thermal stability and the ability to react in aqueous reaction medium[53-54] Furthermore aromatic sul- fonyl compounds containing nitro groups (NO2+) can be consumed as chief raw materials in the production of sulfanilamides[55] such as furosemide and sulfadiazine

Herein we speculated the synthesis of 3-chloroani- linium 24-dinitrobenzenesulfonate (CA-DNBS) (I) and triethylaminium 246-trimethylbenzenesulfonate (TEA-TMBS) (II) and further work is in progress to explore these as ionic liquids for various applications The synthesis was processed in such a way that a mixture of 3-chloroaniline and 24-dinitrobenze- nesulfonic acid (equimolar ratios) in distilled water when stirred at room temperature for 10 minutes afforded I in a good yield (Scheme 1) by simple recrystallization In a similar attempt we stirred a mixture of triethyl amine and 2-mesitylenesulfonic acid (in equimolar ratios) in dichloromethane at room temperature and the desired product II was obtained in high yield (Scheme 1) thus rendering the methodologies highly feasible and convenient The synthesized organic salts are roughly categorized as ammonium sulfonates Primary (I) and tertiary (II) organic ammonium salts are analogs of ammonium salts in which one or more hydrogen atoms bonded to the central nitrogen of an ammonium cation (NH4+) have been replaced by organic radicals The subs- tituents can be aryl (as in I) or alkyl (as in II) or the

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1467

nitrogen can act as part of a ring system All organic ammonium cations are weakly acidic while quater- nary ammonium ion is an exception The counter ions (anions) to the substituted ammonium cations in I and

II are sulfonates (RSO2O-) Such anions are conjugate bases of sulfonic acids (RSO2OH) These acids are considerably strong hence they give rise to sulfonates which are weak bases

Substituted group Compound I Compound II R1 3-chloro-ph- C2H5- R2 H C2H5- R3 H C2H5- R4 24-dinitro-ph- 246-trimethyl-ph-

Scheme 1 Synthesis of 3-chloroanilinium 24-dinitrobenzenesulfonate (CA-DNBS) and NN-diethylethanaminium 246-trimethylbenzenesulfonate (TEA-TMBS)

2 EXPERIMENTAL 2 1 Materials and chemicals

All chemicals were obtained from Aldrich chemi- cals and used as received Commercial grade solvents were used after filtration and distillation All melting points were recorded using Branstead

Electrothermal melting point apparatus Both compounds were solid hence the IR spectrum of the complex was recorded on a Perkin-Elmer FTIR 180 spectrophotometer using KBr pellets from 4000 to 400 cm-1 The m p and IR values are given in Tables 1～3

Table 1 Physical Parameters of CA-DNBS and TEA-TMBS

Solubility Sr No Salts Melting point ()

Water Acetone Alcohol Dichloromethane Toluene Benzene

1 CA-DNBS 258～262 S PS S S INS INS 2 TEA-TMBS 98～102 S PS S S INS INS

S = Soluble PS = Partially soluble INS = Insoluble

Table 2 Characteristic Infrared Absorption Frequencies for CA-DNBS (cm-1) Bond

Molecular motion

Observed frequency for CA-DNBS (cm-1)

S=O Stretching 1358 SminusO Stretching 748 Primary aromatic ammonium salt NminusH Stretching 3107 Primary aromatic ammonium salt NminusH Bending 1533 Primary aromatic ammonium salt CminusN Stretching 1219 Aromatic NminusH Stretching 3492 Aromatic CminusH In plane bending 1118 Aromatic CminusH Out of plane bending 637

Table 3 Characteristic Infrared Absorption Frequencies for TEA-TMBS (cm-1)

Bond

Molecular motion

Observed frequency for TEA-TMBS (cm-1)

S=O Stretching 1397 SminusO Stretching 845 Aliphatic NminusH Stretching 3438 Aliphatic NminusH In plane bending 1605 amp 1459

KHAN I U et al Facile Synthesis and Crystal Structures of 1468 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

To be continued Aliphatic NminusH Out of plane bending 795 Tertiary aliphatic ammonium salt NminusH Stretching 2492 amp 2676 Tertiary aliphatic ammonium salt CminusN Stretching 1189 amp 1025 Aromatic CminusH Out of plane bending 683 Aromatic CminusH Stretching 2970 Aromatic CminusH In plane bending 1089

2 2 Methodology

Preparation of organic salt (I) Organic salt (I) was prepared by stirring equimo-

lar quantities of 3-chloro aniline (4 mmol 051 g) and 24-dinitrobenzenesulfonic acid hydrate (4 mmol 106 g) in 10 mL distilled water for 10 minu- tes The reaction mixture was concentrated resulting in precipitation of the product Recrystallization of the product in dichloromethane (DCM) yielded light brown crystals Yield was calculated to be 899

Preparation of organic salt (II) Organic salt (II) was prepared by dissolving equi-

molar quantities of triethyl amine (5 mmol 051 g) and 246-trimethylbenzenesulfonic acid dihydrate (5 mmol 118 g) in 10 mL of dichloromethane The reaction mixture was stirred at room temperature for 2 hours The DCM layer was washed with dilute HCl solution to remove the unreacted TEA and dried over anhydrous MgSO4 Slow evaporation of the solvent resulted in light brownish crystals of the desired product in 946 yield 2 3 Crystal structure determination

Suitable crystals of I and II were selected for data collection which was performed on an Agilent SuperNova CCD diffractometer with mirror mono- chromated Cu-Kα radiation at 296 K The structures were solved by direct methods using SHELXS-97 and refined by full-matrix least-squares methods on F2 using SHELXL-97[56] from within the WINGX[57] suite of software All non-hydrogen atoms were refined with anisotropic parameters Nitrogen H atoms were located in difference maps and refined freely Hydrogen atoms bonded to carbon were placed in the calculated positions (CndashH = 093～097Aring) and treated using a riding model with U = 12 times the U value of the parent atom for CH CH2 and CH3 Molecular diagrams were created using

MERCURY[58] Geometric calculations were perfor- med with PLATON[59]

3 RESULTS AND DISCUSSION

The molecular structure of I C6H3N2O7S-middotC6H7ClN+ has one cation-anion pair in the asymmetric unit (Fig 1) Selected bond lengths and angles are collected in Table 4 The p-NO2 group is nearly coplanar to its carrier ring (O(6)minusN(2)minus C(4)minusC(5) = 69(4)ordm) while the o-NO2 group is twisted by minus558(3)ordm (O(4)minusN(1)minusC(2)minusC(1)) relative to the phenyl ring in order to avoid a short intramo- lecular contact with O(3) Both aromatic rings are in a good approximation plane with the maximum deviations from the least-squares plane calculated by the six ring atoms to be 00119(2) Aring in the anion and 00022(2) Aring in the cation The anion molecule interacts with the protonated N atom through a bifurcated NminusHO hydrogen bond forming R1

2(4) R2

1(4) and R12(7) ring motifs with an adjacent cation

The SminusO bond distances range between 14412(13)～14500(12) Aring and the NminusO bond distances fall in the 1204(3)～ 1219(2) Aring range respectively These bond distances compare well to the literature values[60-63] The OminusNminusO bond angles are 1235(2)ordm and 12552(18)ordm respectively while the OminusSminusO bond angles vary from 11261(8)ordm to 11498(8)ordm respec- tively

Molecules of I are linked into sheets by a com- bination of NminusHO and CminusHO hydrogen bonds and ππ interactions Atom C(6) serves as a hydrogen-bond donor via atom H(6) to atom O(4) at (xminus1 y z) forming a C(6) chain[64] parallel to the [100] direction Atom C(3) in the molecule at (x y z) acts as a hydrogen-bond donor via atom H(3) to atom O(7) at (minusx+1 minusy+1 minusz+1) so forming a

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1469

centrosymmetric R22(10) ring centered at (12 12

12) Propagation of the CminusHO hydrogen bonds thus forms a chain of rings containing R2

2(10)R44(22)

sequences of two edge-fused rings (Fig 2) The combination of NminusHO and CminusHO hydrogen bonds produces R2

1(6) and R32(9) rings (Fig 2)

Compound I also contains two ππ interactions The Cg1 ring (C(1)～C(6)) in the molecule at (x y z)

makes dihedral angles of only 456ordm with the Cg2 ring (C(7)～C(12)) in each of the two molecules at (xminus1 y zminus1) and (x y z) The ring-centroid separations are 3797(1) and 3647(1) Aring and the interplanar spacings are ca 3567 and 3535 Aring respectively The ππ interactions produce a chain running parallel to the [101] direction (Fig 3)

Fig 1 A view of the molecule of I showing the atom-numbering scheme

Fig 2 Crystal structure of I showing the formation of R1

2(4) R21(4) R2

1(6) R2

2(10) R32(9) and R4

4(22) rings (Symmetry code as in Table 5)

KHAN I U et al Facile Synthesis and Crystal Structures of 1470 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 3 Crystal structure of I showing the formation of a chain along [101]

generated by ππ interactions (Symmetry code (vi) xndash1 y zndash1)

Table 4 Selected Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

I

Bond Dist Bond Dist Bond Dist

N(1)minusO(5) 1213(2) N(2)minusO(6) 1208(3) N(1)minusO(4) 1219(2) N(2)minusO(7) 1204(3) O(1)minusS(1) 14483(13) O(2)minusS(1) 14412(13) O(3)minusS(1) 14500(12)

Angle (deg) Angle (deg) Angle (deg)

O(5)minusN(1)minusO(4) 12552(18) O(5)minusN(1)minusC(2) 11743(18) O(4)minusN(1)minusC(2) 11699(17) O(7)minusN(2)minusO(6) 1235(2) O(7)minusN(2)minusC(4) 1185(2) O(6)minusN(2)minusC(4) 1181(2) O(2)minusS(1)minusO(1) 11498(8) O(2)minusS(1)minusO(3) 11261(8) O(1)minusS(1)minusO(3) 11269(8) O(2)minusS(1)minusC(1) 10406(8) O(1)minusS(1)minusC(1) 10535(8) O(3)minusS(1)minusC(1) 10605(8) C(5)minusC(4)minusN(2)minusO(6) 69(4) C(1)minusC(2)minusN(1)minusO(4) -558(3)

II

Bond Dist Bond Dist Bond Dist

S(1)minusO(2) 14373(19) S(1)minusO(3) 1442(2) S(1)minusO(1) 1454(2)

Angle (deg) Angle (deg) Angle (deg)

O(2)minusS(1)minusO(3) 11321(13) O(2)minusS(1)minusO(1) 11343(14) O(3)minusS(1)minusO(1) 10996(13) O(2)minusS(1)minusC(1) 10573(11) O(3)minusS(1)minusC(1) 10870(13) O(1)minusS(1)minusC(1) 10531(12)

The molecular structure of II with atom labeling is

shown in Fig 4 The asymmetric unit of II consists of cation (C6H16N+) and anion (C9H11O3S-) molecules The two C atoms are disordered (occupancy C(11)minus C(12) = 05 C(11A)minusC(12A) = 05) with a proto- nated N atom in the cation molecule The SminusO bond distances range between 14373(19) and 1454(2) Aring while the OminusSminusO bond angles vary from 10996(13) to 11343(14)ordm The benzene ring plane is approxima- tely planar with maximum deviation from the least-squares plane of 00056(16) Aring for atom C(2)

In II intramolecular CminusHO hydrogen bonds define S(6) motifs The intermolecular NminusHO hydrogen bonds produce R1

2(3) rings The com- bination of NminusHO and CminusHO hydrogen bonds produce R4

3(12) chain of rings running parallel to the [100] direction (Fig 5) Atoms C(7) and C(14) in the molecule at (x y z) acts as hydrogen-bond donors to the C(1)～C(6) benzene rings in the molecules at (xminus1 y z) and (x+12 y minusz+12) so forming a zigzag chain running parallel to the [100] direction (Fig 6) Details of these interactions are presented in Table 5

Table 5 Hydrogen Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

DminusHmiddotmiddotmiddotA d(DminusH) d(HmiddotmiddotmiddotA) d(DmiddotmiddotmiddotA) lt(DHA)

I

N(3)minusH(1N)middotmiddotmiddotO(1)i 089(4) 221(4) 3050(2) 157(3) N(3)minusH(1N)middotmiddotmiddotO(2)ii 089(4) 260(3) 3148(2) 121(3)

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

To be continued

N(3)minusH(2N)middotmiddotmiddotO(3)ii 083(4) 223(4) 2889(2) 136(3) N(3)minusH(2N)middotmiddotmiddotO(2)iii 083(4) 229(4) 2916(2) 133(3) N(3)minusH(3N)middotmiddotmiddotO(1) 088(4) 201(4) 2858(2) 159(3) N(3)minusH(3N)middotmiddotmiddotO(3)i 088(4) 256(3) 3012(2) 113(3) C(3)minusH(3)middotmiddotmiddotO(7)iv 093 243 3353(3) 173 C(6)minusH(6)middotmiddotmiddotO(4)v 093 260 3273(5) 130 C(12)minusH(12)middotmiddotmiddotO(1)i 093 256 3337(2) 142

II

N(1)minusH(1)middotmiddotmiddotO(1) 083(4) 207(4) 2853(3) 156(4) N(1)minusH(1)middotmiddotmiddotO(3) 083(4) 255(4) 3233(3) 141(3) N(1)minusH(1)middotmiddotmiddotS(1) 083(4) 281(4) 3631(2) 168(3) C(15)minusH(15A)middotmiddotmiddotO(3) 096 193 2760(4) 144 C(13)minusH(13B)middotmiddotmiddotO(2) 096 242 3040(4) 122 C(11)minusH(11B)middotmiddotmiddotO(2)i 097 255 3359(8) 141 C(9)minusH(9A)middotmiddotmiddotO(2)ii 097 258 3308 132(4) C(7)minusH(7B)middotmiddotmiddotCg(1)i 097 258 3373(9) 139 C(14)minusH(14B)middotmiddotmiddotCg(1)iii 096 308 4001(11) 160

Symmetry codes (i) x ndashy+12 z+12 (ii) x+1 y z+1 (iii) x+1 ndashy+12 z+12 (iv) ndashx+1 ndashy+1 ndashz+1 (v) xndash1 y z for I (i) xndash1 y z (ii) xndash12 ndashy+32 ndashz+1 (iii) x+12 y ndashz+12 Cg(1) = C(1)～C(6) for II

Fig 4 A view of the molecule of II showing the atom-numbering scheme

Fig 5 Crystal structure of II showing the formation of R1

2(3) and R43(12) rings

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 6 Crystal structure of II showing the formation of a chain along [100] generated

by CminusHπ interactions (Symmetry code as in Table 5)

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Sheff S Wierzbicki A Davis J H Task-specific ionic liquids for the extraction of metal ions from aqueous solutions Chem Commun 2001

135minus136

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for electrochemistry spectroscopy and synthesis Inorg Chem 1982 21 1263minus1264

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study of structure-activity relationship Journal of Molecular Catalysis A Chem 2008 182minus186

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KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

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(58) Mercury version 30 CCDC available online via ccdccamacukproductsmercury

(59) Spek A L PLATON ndash A Multipurpose Crystallographic Tool Utrecht Utrecht University The Netherlands 2005

(60) Suarez S Doctorovich F Baggio R Ammonium 4-methoxybenzenesulfonate Acta Cryst 2012 E68 o2228minuso2229

(61) Beko S L Bats J W Schmidt M U 2-Ammonio-5-chloro-4-methylbenzenesulfonate its 1-methyl-2-pyrrolidone and dimethyl sulfoxide

monosolvates and a corrected structure of 22΄-(14-phenylene)di(45-dihydroimidazolium)bis(4-aminobenzenesulfonate) dehydrate Acta Cryst

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(63) Fun H K Hemamalini M Shetty D N Narayana B Yathirajan H S 4-(3-carboxy-1-ethyl-6-fluoro-4-oxo-14-dihydro-7-quinolyl)-1-

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Int Ed Engl 1995 34 1555minus1573

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1467

nitrogen can act as part of a ring system All organic ammonium cations are weakly acidic while quater- nary ammonium ion is an exception The counter ions (anions) to the substituted ammonium cations in I and

II are sulfonates (RSO2O-) Such anions are conjugate bases of sulfonic acids (RSO2OH) These acids are considerably strong hence they give rise to sulfonates which are weak bases

Substituted group Compound I Compound II R1 3-chloro-ph- C2H5- R2 H C2H5- R3 H C2H5- R4 24-dinitro-ph- 246-trimethyl-ph-

Scheme 1 Synthesis of 3-chloroanilinium 24-dinitrobenzenesulfonate (CA-DNBS) and NN-diethylethanaminium 246-trimethylbenzenesulfonate (TEA-TMBS)

2 EXPERIMENTAL 2 1 Materials and chemicals

All chemicals were obtained from Aldrich chemi- cals and used as received Commercial grade solvents were used after filtration and distillation All melting points were recorded using Branstead

Electrothermal melting point apparatus Both compounds were solid hence the IR spectrum of the complex was recorded on a Perkin-Elmer FTIR 180 spectrophotometer using KBr pellets from 4000 to 400 cm-1 The m p and IR values are given in Tables 1～3

Table 1 Physical Parameters of CA-DNBS and TEA-TMBS

Solubility Sr No Salts Melting point ()

Water Acetone Alcohol Dichloromethane Toluene Benzene

1 CA-DNBS 258～262 S PS S S INS INS 2 TEA-TMBS 98～102 S PS S S INS INS

S = Soluble PS = Partially soluble INS = Insoluble

Table 2 Characteristic Infrared Absorption Frequencies for CA-DNBS (cm-1) Bond

Molecular motion

Observed frequency for CA-DNBS (cm-1)

S=O Stretching 1358 SminusO Stretching 748 Primary aromatic ammonium salt NminusH Stretching 3107 Primary aromatic ammonium salt NminusH Bending 1533 Primary aromatic ammonium salt CminusN Stretching 1219 Aromatic NminusH Stretching 3492 Aromatic CminusH In plane bending 1118 Aromatic CminusH Out of plane bending 637

Table 3 Characteristic Infrared Absorption Frequencies for TEA-TMBS (cm-1)

Bond

Molecular motion

Observed frequency for TEA-TMBS (cm-1)

S=O Stretching 1397 SminusO Stretching 845 Aliphatic NminusH Stretching 3438 Aliphatic NminusH In plane bending 1605 amp 1459

KHAN I U et al Facile Synthesis and Crystal Structures of 1468 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

To be continued Aliphatic NminusH Out of plane bending 795 Tertiary aliphatic ammonium salt NminusH Stretching 2492 amp 2676 Tertiary aliphatic ammonium salt CminusN Stretching 1189 amp 1025 Aromatic CminusH Out of plane bending 683 Aromatic CminusH Stretching 2970 Aromatic CminusH In plane bending 1089

2 2 Methodology

Preparation of organic salt (I) Organic salt (I) was prepared by stirring equimo-

lar quantities of 3-chloro aniline (4 mmol 051 g) and 24-dinitrobenzenesulfonic acid hydrate (4 mmol 106 g) in 10 mL distilled water for 10 minu- tes The reaction mixture was concentrated resulting in precipitation of the product Recrystallization of the product in dichloromethane (DCM) yielded light brown crystals Yield was calculated to be 899

Preparation of organic salt (II) Organic salt (II) was prepared by dissolving equi-

molar quantities of triethyl amine (5 mmol 051 g) and 246-trimethylbenzenesulfonic acid dihydrate (5 mmol 118 g) in 10 mL of dichloromethane The reaction mixture was stirred at room temperature for 2 hours The DCM layer was washed with dilute HCl solution to remove the unreacted TEA and dried over anhydrous MgSO4 Slow evaporation of the solvent resulted in light brownish crystals of the desired product in 946 yield 2 3 Crystal structure determination

Suitable crystals of I and II were selected for data collection which was performed on an Agilent SuperNova CCD diffractometer with mirror mono- chromated Cu-Kα radiation at 296 K The structures were solved by direct methods using SHELXS-97 and refined by full-matrix least-squares methods on F2 using SHELXL-97[56] from within the WINGX[57] suite of software All non-hydrogen atoms were refined with anisotropic parameters Nitrogen H atoms were located in difference maps and refined freely Hydrogen atoms bonded to carbon were placed in the calculated positions (CndashH = 093～097Aring) and treated using a riding model with U = 12 times the U value of the parent atom for CH CH2 and CH3 Molecular diagrams were created using

MERCURY[58] Geometric calculations were perfor- med with PLATON[59]

3 RESULTS AND DISCUSSION

The molecular structure of I C6H3N2O7S-middotC6H7ClN+ has one cation-anion pair in the asymmetric unit (Fig 1) Selected bond lengths and angles are collected in Table 4 The p-NO2 group is nearly coplanar to its carrier ring (O(6)minusN(2)minus C(4)minusC(5) = 69(4)ordm) while the o-NO2 group is twisted by minus558(3)ordm (O(4)minusN(1)minusC(2)minusC(1)) relative to the phenyl ring in order to avoid a short intramo- lecular contact with O(3) Both aromatic rings are in a good approximation plane with the maximum deviations from the least-squares plane calculated by the six ring atoms to be 00119(2) Aring in the anion and 00022(2) Aring in the cation The anion molecule interacts with the protonated N atom through a bifurcated NminusHO hydrogen bond forming R1

2(4) R2

1(4) and R12(7) ring motifs with an adjacent cation

The SminusO bond distances range between 14412(13)～14500(12) Aring and the NminusO bond distances fall in the 1204(3)～ 1219(2) Aring range respectively These bond distances compare well to the literature values[60-63] The OminusNminusO bond angles are 1235(2)ordm and 12552(18)ordm respectively while the OminusSminusO bond angles vary from 11261(8)ordm to 11498(8)ordm respec- tively

Molecules of I are linked into sheets by a com- bination of NminusHO and CminusHO hydrogen bonds and ππ interactions Atom C(6) serves as a hydrogen-bond donor via atom H(6) to atom O(4) at (xminus1 y z) forming a C(6) chain[64] parallel to the [100] direction Atom C(3) in the molecule at (x y z) acts as a hydrogen-bond donor via atom H(3) to atom O(7) at (minusx+1 minusy+1 minusz+1) so forming a

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1469

centrosymmetric R22(10) ring centered at (12 12

12) Propagation of the CminusHO hydrogen bonds thus forms a chain of rings containing R2

2(10)R44(22)

sequences of two edge-fused rings (Fig 2) The combination of NminusHO and CminusHO hydrogen bonds produces R2

1(6) and R32(9) rings (Fig 2)

Compound I also contains two ππ interactions The Cg1 ring (C(1)～C(6)) in the molecule at (x y z)

makes dihedral angles of only 456ordm with the Cg2 ring (C(7)～C(12)) in each of the two molecules at (xminus1 y zminus1) and (x y z) The ring-centroid separations are 3797(1) and 3647(1) Aring and the interplanar spacings are ca 3567 and 3535 Aring respectively The ππ interactions produce a chain running parallel to the [101] direction (Fig 3)

Fig 1 A view of the molecule of I showing the atom-numbering scheme

Fig 2 Crystal structure of I showing the formation of R1

2(4) R21(4) R2

1(6) R2

2(10) R32(9) and R4

4(22) rings (Symmetry code as in Table 5)

KHAN I U et al Facile Synthesis and Crystal Structures of 1470 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 3 Crystal structure of I showing the formation of a chain along [101]

generated by ππ interactions (Symmetry code (vi) xndash1 y zndash1)

Table 4 Selected Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

I

Bond Dist Bond Dist Bond Dist

N(1)minusO(5) 1213(2) N(2)minusO(6) 1208(3) N(1)minusO(4) 1219(2) N(2)minusO(7) 1204(3) O(1)minusS(1) 14483(13) O(2)minusS(1) 14412(13) O(3)minusS(1) 14500(12)

Angle (deg) Angle (deg) Angle (deg)

O(5)minusN(1)minusO(4) 12552(18) O(5)minusN(1)minusC(2) 11743(18) O(4)minusN(1)minusC(2) 11699(17) O(7)minusN(2)minusO(6) 1235(2) O(7)minusN(2)minusC(4) 1185(2) O(6)minusN(2)minusC(4) 1181(2) O(2)minusS(1)minusO(1) 11498(8) O(2)minusS(1)minusO(3) 11261(8) O(1)minusS(1)minusO(3) 11269(8) O(2)minusS(1)minusC(1) 10406(8) O(1)minusS(1)minusC(1) 10535(8) O(3)minusS(1)minusC(1) 10605(8) C(5)minusC(4)minusN(2)minusO(6) 69(4) C(1)minusC(2)minusN(1)minusO(4) -558(3)

II

Bond Dist Bond Dist Bond Dist

S(1)minusO(2) 14373(19) S(1)minusO(3) 1442(2) S(1)minusO(1) 1454(2)

Angle (deg) Angle (deg) Angle (deg)

O(2)minusS(1)minusO(3) 11321(13) O(2)minusS(1)minusO(1) 11343(14) O(3)minusS(1)minusO(1) 10996(13) O(2)minusS(1)minusC(1) 10573(11) O(3)minusS(1)minusC(1) 10870(13) O(1)minusS(1)minusC(1) 10531(12)

The molecular structure of II with atom labeling is

shown in Fig 4 The asymmetric unit of II consists of cation (C6H16N+) and anion (C9H11O3S-) molecules The two C atoms are disordered (occupancy C(11)minus C(12) = 05 C(11A)minusC(12A) = 05) with a proto- nated N atom in the cation molecule The SminusO bond distances range between 14373(19) and 1454(2) Aring while the OminusSminusO bond angles vary from 10996(13) to 11343(14)ordm The benzene ring plane is approxima- tely planar with maximum deviation from the least-squares plane of 00056(16) Aring for atom C(2)

In II intramolecular CminusHO hydrogen bonds define S(6) motifs The intermolecular NminusHO hydrogen bonds produce R1

2(3) rings The com- bination of NminusHO and CminusHO hydrogen bonds produce R4

3(12) chain of rings running parallel to the [100] direction (Fig 5) Atoms C(7) and C(14) in the molecule at (x y z) acts as hydrogen-bond donors to the C(1)～C(6) benzene rings in the molecules at (xminus1 y z) and (x+12 y minusz+12) so forming a zigzag chain running parallel to the [100] direction (Fig 6) Details of these interactions are presented in Table 5

Table 5 Hydrogen Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

DminusHmiddotmiddotmiddotA d(DminusH) d(HmiddotmiddotmiddotA) d(DmiddotmiddotmiddotA) lt(DHA)

I

N(3)minusH(1N)middotmiddotmiddotO(1)i 089(4) 221(4) 3050(2) 157(3) N(3)minusH(1N)middotmiddotmiddotO(2)ii 089(4) 260(3) 3148(2) 121(3)

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

To be continued

N(3)minusH(2N)middotmiddotmiddotO(3)ii 083(4) 223(4) 2889(2) 136(3) N(3)minusH(2N)middotmiddotmiddotO(2)iii 083(4) 229(4) 2916(2) 133(3) N(3)minusH(3N)middotmiddotmiddotO(1) 088(4) 201(4) 2858(2) 159(3) N(3)minusH(3N)middotmiddotmiddotO(3)i 088(4) 256(3) 3012(2) 113(3) C(3)minusH(3)middotmiddotmiddotO(7)iv 093 243 3353(3) 173 C(6)minusH(6)middotmiddotmiddotO(4)v 093 260 3273(5) 130 C(12)minusH(12)middotmiddotmiddotO(1)i 093 256 3337(2) 142

II

N(1)minusH(1)middotmiddotmiddotO(1) 083(4) 207(4) 2853(3) 156(4) N(1)minusH(1)middotmiddotmiddotO(3) 083(4) 255(4) 3233(3) 141(3) N(1)minusH(1)middotmiddotmiddotS(1) 083(4) 281(4) 3631(2) 168(3) C(15)minusH(15A)middotmiddotmiddotO(3) 096 193 2760(4) 144 C(13)minusH(13B)middotmiddotmiddotO(2) 096 242 3040(4) 122 C(11)minusH(11B)middotmiddotmiddotO(2)i 097 255 3359(8) 141 C(9)minusH(9A)middotmiddotmiddotO(2)ii 097 258 3308 132(4) C(7)minusH(7B)middotmiddotmiddotCg(1)i 097 258 3373(9) 139 C(14)minusH(14B)middotmiddotmiddotCg(1)iii 096 308 4001(11) 160

Symmetry codes (i) x ndashy+12 z+12 (ii) x+1 y z+1 (iii) x+1 ndashy+12 z+12 (iv) ndashx+1 ndashy+1 ndashz+1 (v) xndash1 y z for I (i) xndash1 y z (ii) xndash12 ndashy+32 ndashz+1 (iii) x+12 y ndashz+12 Cg(1) = C(1)～C(6) for II

Fig 4 A view of the molecule of II showing the atom-numbering scheme

Fig 5 Crystal structure of II showing the formation of R1

2(3) and R43(12) rings

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 6 Crystal structure of II showing the formation of a chain along [100] generated

by CminusHπ interactions (Symmetry code as in Table 5)

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(39) Zhang Y Kou D Zhang J Zhang L Li X Study of the triethylammonium p-toluenesulfonate as stationary phase in gc for the determination

of benzoic acid in soy Journal of Instrumental Analysis 2006 25 115minus116

(40) Wanga H Liu Y Li Z Zhang X Zhang S Zhang Y Glycolysis of poly(ethylene terephthalate) catalyzed by ionic liquids Eur Polym J 2009

45 1535minus1544

(41) Ying A G Liu L Wua G F Chen G Chen X Z Ye W D Aza-Michael addition of aliphatic or aromatic amines to αβ-unsaturated

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

compounds catalyzed by a DBU-derived ionic liquid under solvent-free conditions Tetrahedron Lett 2009 50 1653minus1657

(42) Rajender S V Vasudevan V N Solvent-free preparation of ionic liquids using a household microwave oven Pure Appl Chem 2001 73

1309minus1313

(43) Rajendran A Priyadarshini M Synthesis and characterization of a novel ionic liquid (TBA-AMPS) and its applications in Mannich condensation

reactions under solvent free conditions African Journal of Pure and Applied Chemistry 2010 4 183minus187

(44) Jasinski J P Golen J A Praveen A S Yathirajan H S Narayana B 3-chloroanilinium 4-methylbenzenesulfonate Acta Cryst 2011 E67

o2925

(45) Collier E A Davey R J Black S N Roberts R J 17 salts of ephedrine crystal structures and packing analysis Acta Cryst 2006 B62 498minus505

(46) Wu T Q Xia L Hu A X Ye J 2-Ethyl-6-methylanilinium 4-methylbenzenesulfonate Acta Cryst 2009 E65 o368

(47) Tabatabaee M Noozari N 2-Aminopyrimidin-1-ium 4-methylbenzenesulfonate Acta Cryst 2011 E67 o1457

(48) Lin J R 4-(Cyanomethyl)anilinium 4-methylbenzenesulfonate monohydrate Acta Cryst 2010 E66 o1557

(49) Fun H K Kobkeatthawin T Chantrapromma S 1-methyl-2-[(E)-2-(2-thienyl)ethenyl]quinolinium 4-bromobenzenesulfonate Acta Cryst 2010

E66 o1053-o1054

(50) Chantrapromma S Chanawanno K Fun H K (E)-2-[4-(dimethylamino)styryl]-1-methylpyridinium 4-methylbenzenesulfonate monohydrate

Acta Cryst 2010 E66 o1975-o1976

(51) Rad M N S Khalafi-Nezhad A Asrari Z Behrouz S Amini Z Behrouz M One-pot synthesis of sulfonamides from primary and secondary

amine derived sulfonate salts using cyanuric chloride Synthesis 2009 23 3983minus3988

(52) Caddick S Wilden J D Bush H D Judd D B synthesis of functionalised sulfonamides via microwave assisted displacement of

pfp-sulfonates with amines QSAR Comb Sci 2004 23 902minus905

(53) Caddick S Wilden J D Wadman S J Bush H D Judd D B A new route to sulfonamides via intermolecular radical addition to

pentafluorophenyl vinylsulfonate and subsequent aminolysis Org Lett 2002 4 2549minus2551

(54) Caddick S Wilden J D Judd D B Direct synthesis of sulfonamides and activated sulfonate esters from sulfonic acids J Am Chem Soc 2004

126 1024minus1025

(55) Al-Dajani M T M Abdallah H H Mohamed N Quah C K Fun H K Triethylammonium 4-nitrobenzenesulfonate Acta Cryst 2010 E66

o1647

(56) Sheldrick G M A short history of SHELX Acta Cryst 2008 A64 112minus122

(57) Farrugia L J WinGX suite for small-molecule single-crystal crystallography J Apply Cryst 1999 32 837minus838

(58) Mercury version 30 CCDC available online via ccdccamacukproductsmercury

(59) Spek A L PLATON ndash A Multipurpose Crystallographic Tool Utrecht Utrecht University The Netherlands 2005

(60) Suarez S Doctorovich F Baggio R Ammonium 4-methoxybenzenesulfonate Acta Cryst 2012 E68 o2228minuso2229

(61) Beko S L Bats J W Schmidt M U 2-Ammonio-5-chloro-4-methylbenzenesulfonate its 1-methyl-2-pyrrolidone and dimethyl sulfoxide

monosolvates and a corrected structure of 22΄-(14-phenylene)di(45-dihydroimidazolium)bis(4-aminobenzenesulfonate) dehydrate Acta Cryst

2012 C68 o45minuso50

(62) Kennedy A R Morrison C A Briggs N E B Arbuckle W Density and stability differences between enantiopure and racemic salts

Construction and structural analysis of a systematic series of crystalline salt forms of methylephedrine Cryst Growth Des 2011 11

1821minus1834

(63) Fun H K Hemamalini M Shetty D N Narayana B Yathirajan H S 4-(3-carboxy-1-ethyl-6-fluoro-4-oxo-14-dihydro-7-quinolyl)-1-

methylpiperazinium picrate Acta Cryst 2010 E66 o714minuso715

(64) Bernstein J Davis R E Shimoni L Chang N L Patterns in hydrogen bonding functionality and graph set analysis in crystals Angew Chem

Int Ed Engl 1995 34 1555minus1573

KHAN I U et al Facile Synthesis and Crystal Structures of 1468 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

To be continued Aliphatic NminusH Out of plane bending 795 Tertiary aliphatic ammonium salt NminusH Stretching 2492 amp 2676 Tertiary aliphatic ammonium salt CminusN Stretching 1189 amp 1025 Aromatic CminusH Out of plane bending 683 Aromatic CminusH Stretching 2970 Aromatic CminusH In plane bending 1089

2 2 Methodology

Preparation of organic salt (I) Organic salt (I) was prepared by stirring equimo-

lar quantities of 3-chloro aniline (4 mmol 051 g) and 24-dinitrobenzenesulfonic acid hydrate (4 mmol 106 g) in 10 mL distilled water for 10 minu- tes The reaction mixture was concentrated resulting in precipitation of the product Recrystallization of the product in dichloromethane (DCM) yielded light brown crystals Yield was calculated to be 899

Preparation of organic salt (II) Organic salt (II) was prepared by dissolving equi-

molar quantities of triethyl amine (5 mmol 051 g) and 246-trimethylbenzenesulfonic acid dihydrate (5 mmol 118 g) in 10 mL of dichloromethane The reaction mixture was stirred at room temperature for 2 hours The DCM layer was washed with dilute HCl solution to remove the unreacted TEA and dried over anhydrous MgSO4 Slow evaporation of the solvent resulted in light brownish crystals of the desired product in 946 yield 2 3 Crystal structure determination

Suitable crystals of I and II were selected for data collection which was performed on an Agilent SuperNova CCD diffractometer with mirror mono- chromated Cu-Kα radiation at 296 K The structures were solved by direct methods using SHELXS-97 and refined by full-matrix least-squares methods on F2 using SHELXL-97[56] from within the WINGX[57] suite of software All non-hydrogen atoms were refined with anisotropic parameters Nitrogen H atoms were located in difference maps and refined freely Hydrogen atoms bonded to carbon were placed in the calculated positions (CndashH = 093～097Aring) and treated using a riding model with U = 12 times the U value of the parent atom for CH CH2 and CH3 Molecular diagrams were created using

MERCURY[58] Geometric calculations were perfor- med with PLATON[59]

3 RESULTS AND DISCUSSION

The molecular structure of I C6H3N2O7S-middotC6H7ClN+ has one cation-anion pair in the asymmetric unit (Fig 1) Selected bond lengths and angles are collected in Table 4 The p-NO2 group is nearly coplanar to its carrier ring (O(6)minusN(2)minus C(4)minusC(5) = 69(4)ordm) while the o-NO2 group is twisted by minus558(3)ordm (O(4)minusN(1)minusC(2)minusC(1)) relative to the phenyl ring in order to avoid a short intramo- lecular contact with O(3) Both aromatic rings are in a good approximation plane with the maximum deviations from the least-squares plane calculated by the six ring atoms to be 00119(2) Aring in the anion and 00022(2) Aring in the cation The anion molecule interacts with the protonated N atom through a bifurcated NminusHO hydrogen bond forming R1

2(4) R2

1(4) and R12(7) ring motifs with an adjacent cation

The SminusO bond distances range between 14412(13)～14500(12) Aring and the NminusO bond distances fall in the 1204(3)～ 1219(2) Aring range respectively These bond distances compare well to the literature values[60-63] The OminusNminusO bond angles are 1235(2)ordm and 12552(18)ordm respectively while the OminusSminusO bond angles vary from 11261(8)ordm to 11498(8)ordm respec- tively

Molecules of I are linked into sheets by a com- bination of NminusHO and CminusHO hydrogen bonds and ππ interactions Atom C(6) serves as a hydrogen-bond donor via atom H(6) to atom O(4) at (xminus1 y z) forming a C(6) chain[64] parallel to the [100] direction Atom C(3) in the molecule at (x y z) acts as a hydrogen-bond donor via atom H(3) to atom O(7) at (minusx+1 minusy+1 minusz+1) so forming a

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1469

centrosymmetric R22(10) ring centered at (12 12

12) Propagation of the CminusHO hydrogen bonds thus forms a chain of rings containing R2

2(10)R44(22)

sequences of two edge-fused rings (Fig 2) The combination of NminusHO and CminusHO hydrogen bonds produces R2

1(6) and R32(9) rings (Fig 2)

Compound I also contains two ππ interactions The Cg1 ring (C(1)～C(6)) in the molecule at (x y z)

makes dihedral angles of only 456ordm with the Cg2 ring (C(7)～C(12)) in each of the two molecules at (xminus1 y zminus1) and (x y z) The ring-centroid separations are 3797(1) and 3647(1) Aring and the interplanar spacings are ca 3567 and 3535 Aring respectively The ππ interactions produce a chain running parallel to the [101] direction (Fig 3)

Fig 1 A view of the molecule of I showing the atom-numbering scheme

Fig 2 Crystal structure of I showing the formation of R1

2(4) R21(4) R2

1(6) R2

2(10) R32(9) and R4

4(22) rings (Symmetry code as in Table 5)

KHAN I U et al Facile Synthesis and Crystal Structures of 1470 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 3 Crystal structure of I showing the formation of a chain along [101]

generated by ππ interactions (Symmetry code (vi) xndash1 y zndash1)

Table 4 Selected Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

I

Bond Dist Bond Dist Bond Dist

N(1)minusO(5) 1213(2) N(2)minusO(6) 1208(3) N(1)minusO(4) 1219(2) N(2)minusO(7) 1204(3) O(1)minusS(1) 14483(13) O(2)minusS(1) 14412(13) O(3)minusS(1) 14500(12)

Angle (deg) Angle (deg) Angle (deg)

O(5)minusN(1)minusO(4) 12552(18) O(5)minusN(1)minusC(2) 11743(18) O(4)minusN(1)minusC(2) 11699(17) O(7)minusN(2)minusO(6) 1235(2) O(7)minusN(2)minusC(4) 1185(2) O(6)minusN(2)minusC(4) 1181(2) O(2)minusS(1)minusO(1) 11498(8) O(2)minusS(1)minusO(3) 11261(8) O(1)minusS(1)minusO(3) 11269(8) O(2)minusS(1)minusC(1) 10406(8) O(1)minusS(1)minusC(1) 10535(8) O(3)minusS(1)minusC(1) 10605(8) C(5)minusC(4)minusN(2)minusO(6) 69(4) C(1)minusC(2)minusN(1)minusO(4) -558(3)

II

Bond Dist Bond Dist Bond Dist

S(1)minusO(2) 14373(19) S(1)minusO(3) 1442(2) S(1)minusO(1) 1454(2)

Angle (deg) Angle (deg) Angle (deg)

O(2)minusS(1)minusO(3) 11321(13) O(2)minusS(1)minusO(1) 11343(14) O(3)minusS(1)minusO(1) 10996(13) O(2)minusS(1)minusC(1) 10573(11) O(3)minusS(1)minusC(1) 10870(13) O(1)minusS(1)minusC(1) 10531(12)

The molecular structure of II with atom labeling is

shown in Fig 4 The asymmetric unit of II consists of cation (C6H16N+) and anion (C9H11O3S-) molecules The two C atoms are disordered (occupancy C(11)minus C(12) = 05 C(11A)minusC(12A) = 05) with a proto- nated N atom in the cation molecule The SminusO bond distances range between 14373(19) and 1454(2) Aring while the OminusSminusO bond angles vary from 10996(13) to 11343(14)ordm The benzene ring plane is approxima- tely planar with maximum deviation from the least-squares plane of 00056(16) Aring for atom C(2)

In II intramolecular CminusHO hydrogen bonds define S(6) motifs The intermolecular NminusHO hydrogen bonds produce R1

2(3) rings The com- bination of NminusHO and CminusHO hydrogen bonds produce R4

3(12) chain of rings running parallel to the [100] direction (Fig 5) Atoms C(7) and C(14) in the molecule at (x y z) acts as hydrogen-bond donors to the C(1)～C(6) benzene rings in the molecules at (xminus1 y z) and (x+12 y minusz+12) so forming a zigzag chain running parallel to the [100] direction (Fig 6) Details of these interactions are presented in Table 5

Table 5 Hydrogen Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

DminusHmiddotmiddotmiddotA d(DminusH) d(HmiddotmiddotmiddotA) d(DmiddotmiddotmiddotA) lt(DHA)

I

N(3)minusH(1N)middotmiddotmiddotO(1)i 089(4) 221(4) 3050(2) 157(3) N(3)minusH(1N)middotmiddotmiddotO(2)ii 089(4) 260(3) 3148(2) 121(3)

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

To be continued

N(3)minusH(2N)middotmiddotmiddotO(3)ii 083(4) 223(4) 2889(2) 136(3) N(3)minusH(2N)middotmiddotmiddotO(2)iii 083(4) 229(4) 2916(2) 133(3) N(3)minusH(3N)middotmiddotmiddotO(1) 088(4) 201(4) 2858(2) 159(3) N(3)minusH(3N)middotmiddotmiddotO(3)i 088(4) 256(3) 3012(2) 113(3) C(3)minusH(3)middotmiddotmiddotO(7)iv 093 243 3353(3) 173 C(6)minusH(6)middotmiddotmiddotO(4)v 093 260 3273(5) 130 C(12)minusH(12)middotmiddotmiddotO(1)i 093 256 3337(2) 142

II

N(1)minusH(1)middotmiddotmiddotO(1) 083(4) 207(4) 2853(3) 156(4) N(1)minusH(1)middotmiddotmiddotO(3) 083(4) 255(4) 3233(3) 141(3) N(1)minusH(1)middotmiddotmiddotS(1) 083(4) 281(4) 3631(2) 168(3) C(15)minusH(15A)middotmiddotmiddotO(3) 096 193 2760(4) 144 C(13)minusH(13B)middotmiddotmiddotO(2) 096 242 3040(4) 122 C(11)minusH(11B)middotmiddotmiddotO(2)i 097 255 3359(8) 141 C(9)minusH(9A)middotmiddotmiddotO(2)ii 097 258 3308 132(4) C(7)minusH(7B)middotmiddotmiddotCg(1)i 097 258 3373(9) 139 C(14)minusH(14B)middotmiddotmiddotCg(1)iii 096 308 4001(11) 160

Symmetry codes (i) x ndashy+12 z+12 (ii) x+1 y z+1 (iii) x+1 ndashy+12 z+12 (iv) ndashx+1 ndashy+1 ndashz+1 (v) xndash1 y z for I (i) xndash1 y z (ii) xndash12 ndashy+32 ndashz+1 (iii) x+12 y ndashz+12 Cg(1) = C(1)～C(6) for II

Fig 4 A view of the molecule of II showing the atom-numbering scheme

Fig 5 Crystal structure of II showing the formation of R1

2(3) and R43(12) rings

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 6 Crystal structure of II showing the formation of a chain along [100] generated

by CminusHπ interactions (Symmetry code as in Table 5)

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study of structure-activity relationship Journal of Molecular Catalysis A Chem 2008 182minus186

(39) Zhang Y Kou D Zhang J Zhang L Li X Study of the triethylammonium p-toluenesulfonate as stationary phase in gc for the determination

of benzoic acid in soy Journal of Instrumental Analysis 2006 25 115minus116

(40) Wanga H Liu Y Li Z Zhang X Zhang S Zhang Y Glycolysis of poly(ethylene terephthalate) catalyzed by ionic liquids Eur Polym J 2009

45 1535minus1544

(41) Ying A G Liu L Wua G F Chen G Chen X Z Ye W D Aza-Michael addition of aliphatic or aromatic amines to αβ-unsaturated

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

compounds catalyzed by a DBU-derived ionic liquid under solvent-free conditions Tetrahedron Lett 2009 50 1653minus1657

(42) Rajender S V Vasudevan V N Solvent-free preparation of ionic liquids using a household microwave oven Pure Appl Chem 2001 73

1309minus1313

(43) Rajendran A Priyadarshini M Synthesis and characterization of a novel ionic liquid (TBA-AMPS) and its applications in Mannich condensation

reactions under solvent free conditions African Journal of Pure and Applied Chemistry 2010 4 183minus187

(44) Jasinski J P Golen J A Praveen A S Yathirajan H S Narayana B 3-chloroanilinium 4-methylbenzenesulfonate Acta Cryst 2011 E67

o2925

(45) Collier E A Davey R J Black S N Roberts R J 17 salts of ephedrine crystal structures and packing analysis Acta Cryst 2006 B62 498minus505

(46) Wu T Q Xia L Hu A X Ye J 2-Ethyl-6-methylanilinium 4-methylbenzenesulfonate Acta Cryst 2009 E65 o368

(47) Tabatabaee M Noozari N 2-Aminopyrimidin-1-ium 4-methylbenzenesulfonate Acta Cryst 2011 E67 o1457

(48) Lin J R 4-(Cyanomethyl)anilinium 4-methylbenzenesulfonate monohydrate Acta Cryst 2010 E66 o1557

(49) Fun H K Kobkeatthawin T Chantrapromma S 1-methyl-2-[(E)-2-(2-thienyl)ethenyl]quinolinium 4-bromobenzenesulfonate Acta Cryst 2010

E66 o1053-o1054

(50) Chantrapromma S Chanawanno K Fun H K (E)-2-[4-(dimethylamino)styryl]-1-methylpyridinium 4-methylbenzenesulfonate monohydrate

Acta Cryst 2010 E66 o1975-o1976

(51) Rad M N S Khalafi-Nezhad A Asrari Z Behrouz S Amini Z Behrouz M One-pot synthesis of sulfonamides from primary and secondary

amine derived sulfonate salts using cyanuric chloride Synthesis 2009 23 3983minus3988

(52) Caddick S Wilden J D Bush H D Judd D B synthesis of functionalised sulfonamides via microwave assisted displacement of

pfp-sulfonates with amines QSAR Comb Sci 2004 23 902minus905

(53) Caddick S Wilden J D Wadman S J Bush H D Judd D B A new route to sulfonamides via intermolecular radical addition to

pentafluorophenyl vinylsulfonate and subsequent aminolysis Org Lett 2002 4 2549minus2551

(54) Caddick S Wilden J D Judd D B Direct synthesis of sulfonamides and activated sulfonate esters from sulfonic acids J Am Chem Soc 2004

126 1024minus1025

(55) Al-Dajani M T M Abdallah H H Mohamed N Quah C K Fun H K Triethylammonium 4-nitrobenzenesulfonate Acta Cryst 2010 E66

o1647

(56) Sheldrick G M A short history of SHELX Acta Cryst 2008 A64 112minus122

(57) Farrugia L J WinGX suite for small-molecule single-crystal crystallography J Apply Cryst 1999 32 837minus838

(58) Mercury version 30 CCDC available online via ccdccamacukproductsmercury

(59) Spek A L PLATON ndash A Multipurpose Crystallographic Tool Utrecht Utrecht University The Netherlands 2005

(60) Suarez S Doctorovich F Baggio R Ammonium 4-methoxybenzenesulfonate Acta Cryst 2012 E68 o2228minuso2229

(61) Beko S L Bats J W Schmidt M U 2-Ammonio-5-chloro-4-methylbenzenesulfonate its 1-methyl-2-pyrrolidone and dimethyl sulfoxide

monosolvates and a corrected structure of 22΄-(14-phenylene)di(45-dihydroimidazolium)bis(4-aminobenzenesulfonate) dehydrate Acta Cryst

2012 C68 o45minuso50

(62) Kennedy A R Morrison C A Briggs N E B Arbuckle W Density and stability differences between enantiopure and racemic salts

Construction and structural analysis of a systematic series of crystalline salt forms of methylephedrine Cryst Growth Des 2011 11

1821minus1834

(63) Fun H K Hemamalini M Shetty D N Narayana B Yathirajan H S 4-(3-carboxy-1-ethyl-6-fluoro-4-oxo-14-dihydro-7-quinolyl)-1-

methylpiperazinium picrate Acta Cryst 2010 E66 o714minuso715

(64) Bernstein J Davis R E Shimoni L Chang N L Patterns in hydrogen bonding functionality and graph set analysis in crystals Angew Chem

Int Ed Engl 1995 34 1555minus1573

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1469

centrosymmetric R22(10) ring centered at (12 12

12) Propagation of the CminusHO hydrogen bonds thus forms a chain of rings containing R2

2(10)R44(22)

sequences of two edge-fused rings (Fig 2) The combination of NminusHO and CminusHO hydrogen bonds produces R2

1(6) and R32(9) rings (Fig 2)

Compound I also contains two ππ interactions The Cg1 ring (C(1)～C(6)) in the molecule at (x y z)

makes dihedral angles of only 456ordm with the Cg2 ring (C(7)～C(12)) in each of the two molecules at (xminus1 y zminus1) and (x y z) The ring-centroid separations are 3797(1) and 3647(1) Aring and the interplanar spacings are ca 3567 and 3535 Aring respectively The ππ interactions produce a chain running parallel to the [101] direction (Fig 3)

Fig 1 A view of the molecule of I showing the atom-numbering scheme

Fig 2 Crystal structure of I showing the formation of R1

2(4) R21(4) R2

1(6) R2

2(10) R32(9) and R4

4(22) rings (Symmetry code as in Table 5)

KHAN I U et al Facile Synthesis and Crystal Structures of 1470 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 3 Crystal structure of I showing the formation of a chain along [101]

generated by ππ interactions (Symmetry code (vi) xndash1 y zndash1)

Table 4 Selected Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

I

Bond Dist Bond Dist Bond Dist

N(1)minusO(5) 1213(2) N(2)minusO(6) 1208(3) N(1)minusO(4) 1219(2) N(2)minusO(7) 1204(3) O(1)minusS(1) 14483(13) O(2)minusS(1) 14412(13) O(3)minusS(1) 14500(12)

Angle (deg) Angle (deg) Angle (deg)

O(5)minusN(1)minusO(4) 12552(18) O(5)minusN(1)minusC(2) 11743(18) O(4)minusN(1)minusC(2) 11699(17) O(7)minusN(2)minusO(6) 1235(2) O(7)minusN(2)minusC(4) 1185(2) O(6)minusN(2)minusC(4) 1181(2) O(2)minusS(1)minusO(1) 11498(8) O(2)minusS(1)minusO(3) 11261(8) O(1)minusS(1)minusO(3) 11269(8) O(2)minusS(1)minusC(1) 10406(8) O(1)minusS(1)minusC(1) 10535(8) O(3)minusS(1)minusC(1) 10605(8) C(5)minusC(4)minusN(2)minusO(6) 69(4) C(1)minusC(2)minusN(1)minusO(4) -558(3)

II

Bond Dist Bond Dist Bond Dist

S(1)minusO(2) 14373(19) S(1)minusO(3) 1442(2) S(1)minusO(1) 1454(2)

Angle (deg) Angle (deg) Angle (deg)

O(2)minusS(1)minusO(3) 11321(13) O(2)minusS(1)minusO(1) 11343(14) O(3)minusS(1)minusO(1) 10996(13) O(2)minusS(1)minusC(1) 10573(11) O(3)minusS(1)minusC(1) 10870(13) O(1)minusS(1)minusC(1) 10531(12)

The molecular structure of II with atom labeling is

shown in Fig 4 The asymmetric unit of II consists of cation (C6H16N+) and anion (C9H11O3S-) molecules The two C atoms are disordered (occupancy C(11)minus C(12) = 05 C(11A)minusC(12A) = 05) with a proto- nated N atom in the cation molecule The SminusO bond distances range between 14373(19) and 1454(2) Aring while the OminusSminusO bond angles vary from 10996(13) to 11343(14)ordm The benzene ring plane is approxima- tely planar with maximum deviation from the least-squares plane of 00056(16) Aring for atom C(2)

In II intramolecular CminusHO hydrogen bonds define S(6) motifs The intermolecular NminusHO hydrogen bonds produce R1

2(3) rings The com- bination of NminusHO and CminusHO hydrogen bonds produce R4

3(12) chain of rings running parallel to the [100] direction (Fig 5) Atoms C(7) and C(14) in the molecule at (x y z) acts as hydrogen-bond donors to the C(1)～C(6) benzene rings in the molecules at (xminus1 y z) and (x+12 y minusz+12) so forming a zigzag chain running parallel to the [100] direction (Fig 6) Details of these interactions are presented in Table 5

Table 5 Hydrogen Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

DminusHmiddotmiddotmiddotA d(DminusH) d(HmiddotmiddotmiddotA) d(DmiddotmiddotmiddotA) lt(DHA)

I

N(3)minusH(1N)middotmiddotmiddotO(1)i 089(4) 221(4) 3050(2) 157(3) N(3)minusH(1N)middotmiddotmiddotO(2)ii 089(4) 260(3) 3148(2) 121(3)

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

To be continued

N(3)minusH(2N)middotmiddotmiddotO(3)ii 083(4) 223(4) 2889(2) 136(3) N(3)minusH(2N)middotmiddotmiddotO(2)iii 083(4) 229(4) 2916(2) 133(3) N(3)minusH(3N)middotmiddotmiddotO(1) 088(4) 201(4) 2858(2) 159(3) N(3)minusH(3N)middotmiddotmiddotO(3)i 088(4) 256(3) 3012(2) 113(3) C(3)minusH(3)middotmiddotmiddotO(7)iv 093 243 3353(3) 173 C(6)minusH(6)middotmiddotmiddotO(4)v 093 260 3273(5) 130 C(12)minusH(12)middotmiddotmiddotO(1)i 093 256 3337(2) 142

II

N(1)minusH(1)middotmiddotmiddotO(1) 083(4) 207(4) 2853(3) 156(4) N(1)minusH(1)middotmiddotmiddotO(3) 083(4) 255(4) 3233(3) 141(3) N(1)minusH(1)middotmiddotmiddotS(1) 083(4) 281(4) 3631(2) 168(3) C(15)minusH(15A)middotmiddotmiddotO(3) 096 193 2760(4) 144 C(13)minusH(13B)middotmiddotmiddotO(2) 096 242 3040(4) 122 C(11)minusH(11B)middotmiddotmiddotO(2)i 097 255 3359(8) 141 C(9)minusH(9A)middotmiddotmiddotO(2)ii 097 258 3308 132(4) C(7)minusH(7B)middotmiddotmiddotCg(1)i 097 258 3373(9) 139 C(14)minusH(14B)middotmiddotmiddotCg(1)iii 096 308 4001(11) 160

Symmetry codes (i) x ndashy+12 z+12 (ii) x+1 y z+1 (iii) x+1 ndashy+12 z+12 (iv) ndashx+1 ndashy+1 ndashz+1 (v) xndash1 y z for I (i) xndash1 y z (ii) xndash12 ndashy+32 ndashz+1 (iii) x+12 y ndashz+12 Cg(1) = C(1)～C(6) for II

Fig 4 A view of the molecule of II showing the atom-numbering scheme

Fig 5 Crystal structure of II showing the formation of R1

2(3) and R43(12) rings

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 6 Crystal structure of II showing the formation of a chain along [100] generated

by CminusHπ interactions (Symmetry code as in Table 5)

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(61) Beko S L Bats J W Schmidt M U 2-Ammonio-5-chloro-4-methylbenzenesulfonate its 1-methyl-2-pyrrolidone and dimethyl sulfoxide

monosolvates and a corrected structure of 22΄-(14-phenylene)di(45-dihydroimidazolium)bis(4-aminobenzenesulfonate) dehydrate Acta Cryst

2012 C68 o45minuso50

(62) Kennedy A R Morrison C A Briggs N E B Arbuckle W Density and stability differences between enantiopure and racemic salts

Construction and structural analysis of a systematic series of crystalline salt forms of methylephedrine Cryst Growth Des 2011 11

1821minus1834

(63) Fun H K Hemamalini M Shetty D N Narayana B Yathirajan H S 4-(3-carboxy-1-ethyl-6-fluoro-4-oxo-14-dihydro-7-quinolyl)-1-

methylpiperazinium picrate Acta Cryst 2010 E66 o714minuso715

(64) Bernstein J Davis R E Shimoni L Chang N L Patterns in hydrogen bonding functionality and graph set analysis in crystals Angew Chem

Int Ed Engl 1995 34 1555minus1573

KHAN I U et al Facile Synthesis and Crystal Structures of 1470 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 3 Crystal structure of I showing the formation of a chain along [101]

generated by ππ interactions (Symmetry code (vi) xndash1 y zndash1)

Table 4 Selected Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

I

Bond Dist Bond Dist Bond Dist

N(1)minusO(5) 1213(2) N(2)minusO(6) 1208(3) N(1)minusO(4) 1219(2) N(2)minusO(7) 1204(3) O(1)minusS(1) 14483(13) O(2)minusS(1) 14412(13) O(3)minusS(1) 14500(12)

Angle (deg) Angle (deg) Angle (deg)

O(5)minusN(1)minusO(4) 12552(18) O(5)minusN(1)minusC(2) 11743(18) O(4)minusN(1)minusC(2) 11699(17) O(7)minusN(2)minusO(6) 1235(2) O(7)minusN(2)minusC(4) 1185(2) O(6)minusN(2)minusC(4) 1181(2) O(2)minusS(1)minusO(1) 11498(8) O(2)minusS(1)minusO(3) 11261(8) O(1)minusS(1)minusO(3) 11269(8) O(2)minusS(1)minusC(1) 10406(8) O(1)minusS(1)minusC(1) 10535(8) O(3)minusS(1)minusC(1) 10605(8) C(5)minusC(4)minusN(2)minusO(6) 69(4) C(1)minusC(2)minusN(1)minusO(4) -558(3)

II

Bond Dist Bond Dist Bond Dist

S(1)minusO(2) 14373(19) S(1)minusO(3) 1442(2) S(1)minusO(1) 1454(2)

Angle (deg) Angle (deg) Angle (deg)

O(2)minusS(1)minusO(3) 11321(13) O(2)minusS(1)minusO(1) 11343(14) O(3)minusS(1)minusO(1) 10996(13) O(2)minusS(1)minusC(1) 10573(11) O(3)minusS(1)minusC(1) 10870(13) O(1)minusS(1)minusC(1) 10531(12)

The molecular structure of II with atom labeling is

shown in Fig 4 The asymmetric unit of II consists of cation (C6H16N+) and anion (C9H11O3S-) molecules The two C atoms are disordered (occupancy C(11)minus C(12) = 05 C(11A)minusC(12A) = 05) with a proto- nated N atom in the cation molecule The SminusO bond distances range between 14373(19) and 1454(2) Aring while the OminusSminusO bond angles vary from 10996(13) to 11343(14)ordm The benzene ring plane is approxima- tely planar with maximum deviation from the least-squares plane of 00056(16) Aring for atom C(2)

In II intramolecular CminusHO hydrogen bonds define S(6) motifs The intermolecular NminusHO hydrogen bonds produce R1

2(3) rings The com- bination of NminusHO and CminusHO hydrogen bonds produce R4

3(12) chain of rings running parallel to the [100] direction (Fig 5) Atoms C(7) and C(14) in the molecule at (x y z) acts as hydrogen-bond donors to the C(1)～C(6) benzene rings in the molecules at (xminus1 y z) and (x+12 y minusz+12) so forming a zigzag chain running parallel to the [100] direction (Fig 6) Details of these interactions are presented in Table 5

Table 5 Hydrogen Bond Lengths (Aring) and Bond Angles (deg) for Compounds (I) and (II)

DminusHmiddotmiddotmiddotA d(DminusH) d(HmiddotmiddotmiddotA) d(DmiddotmiddotmiddotA) lt(DHA)

I

N(3)minusH(1N)middotmiddotmiddotO(1)i 089(4) 221(4) 3050(2) 157(3) N(3)minusH(1N)middotmiddotmiddotO(2)ii 089(4) 260(3) 3148(2) 121(3)

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

To be continued

N(3)minusH(2N)middotmiddotmiddotO(3)ii 083(4) 223(4) 2889(2) 136(3) N(3)minusH(2N)middotmiddotmiddotO(2)iii 083(4) 229(4) 2916(2) 133(3) N(3)minusH(3N)middotmiddotmiddotO(1) 088(4) 201(4) 2858(2) 159(3) N(3)minusH(3N)middotmiddotmiddotO(3)i 088(4) 256(3) 3012(2) 113(3) C(3)minusH(3)middotmiddotmiddotO(7)iv 093 243 3353(3) 173 C(6)minusH(6)middotmiddotmiddotO(4)v 093 260 3273(5) 130 C(12)minusH(12)middotmiddotmiddotO(1)i 093 256 3337(2) 142

II

N(1)minusH(1)middotmiddotmiddotO(1) 083(4) 207(4) 2853(3) 156(4) N(1)minusH(1)middotmiddotmiddotO(3) 083(4) 255(4) 3233(3) 141(3) N(1)minusH(1)middotmiddotmiddotS(1) 083(4) 281(4) 3631(2) 168(3) C(15)minusH(15A)middotmiddotmiddotO(3) 096 193 2760(4) 144 C(13)minusH(13B)middotmiddotmiddotO(2) 096 242 3040(4) 122 C(11)minusH(11B)middotmiddotmiddotO(2)i 097 255 3359(8) 141 C(9)minusH(9A)middotmiddotmiddotO(2)ii 097 258 3308 132(4) C(7)minusH(7B)middotmiddotmiddotCg(1)i 097 258 3373(9) 139 C(14)minusH(14B)middotmiddotmiddotCg(1)iii 096 308 4001(11) 160

Symmetry codes (i) x ndashy+12 z+12 (ii) x+1 y z+1 (iii) x+1 ndashy+12 z+12 (iv) ndashx+1 ndashy+1 ndashz+1 (v) xndash1 y z for I (i) xndash1 y z (ii) xndash12 ndashy+32 ndashz+1 (iii) x+12 y ndashz+12 Cg(1) = C(1)～C(6) for II

Fig 4 A view of the molecule of II showing the atom-numbering scheme

Fig 5 Crystal structure of II showing the formation of R1

2(3) and R43(12) rings

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 6 Crystal structure of II showing the formation of a chain along [100] generated

by CminusHπ interactions (Symmetry code as in Table 5)

REFERENCES (1) Hajipoura A R Rafieeb F Basic ionic liquids A short review J Iran Chem Soc 2009 6 647minus678

(2) Yavari I Kowsari E Ionic liquids as novel and recyclable reaction media for N-alkylation of amino-910-anthraquinones by trialkyl phosphites

Tetrahedron Lett 2007 48 3753minus3756

(3) Gong K Wang H L Fang D Liu Z L Basic ionic liquid as catalyst for the rapid and green synthesis of substituted 2-amino-2-chromenes in

aqueous media Catal Commun 2008 9 650minus653

(4) Fraga-Dubreuil J Bourahla K Rahmouni M Bazureau J P Hamelin J Catalysed esterifications in room temperature ionic liquids with acidic

counteranion as recyclable reaction media Catal Commun 2002 3 185minus190

(5) Joseph T Sahoo S Halligudi S B Broumlnsted acidic ionic liquids a green efficient and reusable catalyst system and reaction medium for Fischer

esterification J Mol Catal A Chem 2005 234 107minus110

(6) Xing H Wang T Zhou Z Dai Y Novel Broslashnsted-acidic ionic liquids for esterifications Ind Eng Chem Res 2005 44 4147minus4150

(7) Zhu H P Yang F Tang J He M Y Broslashnsted acidic ionic liquid 1-methylimidazolium tetrafluoroborate a green catalyst and recyclable medium

for esterification Green Chem 2003 5 38minus39

(8) Fang D Zhou X Ye Z Liu Z Broslashnsted acidic ionic liquids and their use as dual solvent-catalysts for fischer esterifications Ind Eng Chem

Res 2006 45 7982minus7984

(9) Zhu A Jiang T Wang D Han B Liu L Huang J Zhang J Sun D Direct aldol reactions catalyzed by 1133-tetramethylguanidine lactate

without solvent Green Chem 2005 7 514minus517

(10) Qiao K Yokoyama C Koch carbonylation of tertiary alcohols in the presence of acidic ionic liquids Catal Commun 2006 7 450minus453

(11) Ogoshi T Onodera T Yamagishi T Nakamoto Y Green polymerization of phenol in ionic liquids Macromolecules 2008 41 8533-8536

(12) Cui S Lu B Cai Q Cai X Li X Xiao X Hou L Han Y Highly selective synthesis of diphenylmethane with acidic ionic liquids Ind

Eng Chem Res 2006 45 1571-1574

(13) Gui J Ban H Cong X Zhang X Hu Z Sun Z Selective alkylation of phenol with tert-butyl alcohol catalyzed by Broumlnsted acidic imidazolium

salts J Mol Catal A Chem 2005 225 27minus31

(14) Wasserscheid P Sesing M Korth W Hydrogensulfate and tetrakis(hydrogensulfato)borate ionic liquids synthesis and catalytic application in

highly Broslashnsted-acidic systems for Friedel-Crafts alkylation Green Chem 2002 4 134minus138

(15) Lin J H Zhang C P Zhu Z Q Chen Q Y Xiao J C A novel pyrrolidinium ionic liquid with 1122-tetrafluoro-2-(1122-tetrafluoroethoxy)

ethanesulfonate anion as a recyclable reaction medium and efficient catalyst for Friedel-Crafts alkylations of indoles with nitroalkenes J Fluorine

Chem 2009 130 394minus398

(16) Janus E Maciejewsk I G Skib M Pernak J Diels-Alder reaction in protic ionic liquids Tetrahedron Lett 2006 47 4079minus4083

(17) Fischer T Sethi A Welton T Woolf J Diels-Alder reactions in room-temperature ionic liquids Tetrahedron Lett 1999 40 793minus796

(18) Sahoo S Joseph T Halligudi S B Mannich reaction in Broumlnsted acidic ionic liquid a facile synthesis of β-amino carbonyl compounds J Mol

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

Catal A Chem 2006 244179minus182

(19) Zhao G Jiang T Gao H Han B Huang J Sun D Mannich reaction using acidic ionic liquids as catalysts and solvents Green Chem 2004 6

75minus77

(20) Chaskar A C Bhandari S R Patil A B Sharma O P Mayeker S Solvent-free oxidation of alcohols with potassium persulphate in the

presence of broumlnsted acidic ionic liquids Synth Commun 2009 39 366minus370

(21) Hajipour A R Rafiee F Ruoho A E Facile and selective oxidation of benzylic alcohols to their corresponding carbonyl compounds with

sodium nitrate in the presence of Broslashnsted acidic ionic liquids Synlett 2007 7 1118minus1120

(22) Hajipour A R Rafiee F Ruoho A E Oxidation of benzylic alcohols to their corresponding carbonyl compounds using KIO4 in ionic liquid by

microwave irradiation Synth Commun 2006 36 2563minus2568

(23) Li S Lin Y Xie H Zhang S Xu J broslashnsted guanidine acid-base ionic liquids novel reaction media for the palladium-catalyzed heck

reaction Org Lett 2006 8 391minus394

(24) Zhang J Jiang T Han B Zhu A Xiumin M Knoevenagel condensation catalyzed by 1133-tetramethylguanidium lactate Synth Commun

2006 36 3305minus3317

(25) Hu Y Chen J Le Z G Zheng Q G Organic reactions in ionic liquids ionic liquids ethylammonium nitrate promoted knoevenagel

condensation of aromatic aldehydes with active methylene compounds Synth Commun 2005 35 739minus744

(26) Harjani J R Nara S J Salunkhe M M Lewis acidic ionic liquids for the synthesis of electrophilic alkenes via the Knoevenagel condensation

Tetrahedron Lett 2002 43 1127minus1130

(27) Jiang T Gao H Han B Zhao G Chang Y Wu W Gao L Yang G Ionic liquid catalyzed Henry reactions Tetrahedron Lett 2004 45

2699minus2701

(28) Siddiqui S A Narkhede U C Palimkar S S Daniel T Lahoti R J Srinivasan K V Room temperature ionic liquid promoted improved and

rapid synthesis of 245-triaryl imidazoles from aryl aldehydes and 12-diketones or α-hydroxyketone Tetrahedron 2005 61 3539minus3546

(29) Bao Q Qiao K Tomida D Yokoyama C Preparation of 5-hydroymethylfurfural by dehydration of fructose in the presence of acidic ionic liquid

Catal Commun 2008 9 1383minus1388

(30) Potewar T M Siddiqui S A Lahoti R J Srinivasan K V Efficient and rapid synthesis of 1-substituted-1H-1234-tetrazoles in the acidic ionic

liquid 1-n-butylimidazolium tetrafluoroborate Tetra Lett 2007 48 1721minus1724

(31) Wang Y Y Li W Dai L Y Broslashnsted acidic ionic liquids as efficient reaction medium for cyclodehydration of diethylene glycol Chin J

Chem 2008 26 1390minus1394

(32) Kim K Lang C M Kohl P A Properties of asymmetric benzyl-substituted ammonium ionic liquids and their electrochemical properties J

Electrochem Soc 2005 152 E56minusE60

(33) Sun J Forsyth M Macfarlene D R Room-temperature molten salts based on the quaternary ammonium ion J Phys Chem B 1998 102

8858minus8864

(34) Macfarlane D R Golding J Forsyth S Forsyth M Deacon G B Low viscosity ionic liquids based on organic salts of the dicyanamide anion

Chem Commun 2001 1430minus1431

(35) Zhao D B Wu M Kou Y Min E Z Ionic liquids applications in catalysis Catalysis Today 2002 74 157minus189

(36) Visser A E Swatloski R P Rogers R D Green Chem 2000 2 1 Visser A E Swatloski R P Reichert W M Rogers R D Mayton R

Sheff S Wierzbicki A Davis J H Task-specific ionic liquids for the extraction of metal ions from aqueous solutions Chem Commun 2001

135minus136

(37) Wilkes J S Levinsky J A Wilson R A Hussey C L Dialkylimidazolium chloroaluminate melts a new class of room-temperature ionic liquids

for electrochemistry spectroscopy and synthesis Inorg Chem 1982 21 1263minus1264

(38) Pralhad A G Gigi G Jagannath D Broslashnsted acidic ionic liquids derived from alkylamines as catalysts and mediums for Fischer esterification

study of structure-activity relationship Journal of Molecular Catalysis A Chem 2008 182minus186

(39) Zhang Y Kou D Zhang J Zhang L Li X Study of the triethylammonium p-toluenesulfonate as stationary phase in gc for the determination

of benzoic acid in soy Journal of Instrumental Analysis 2006 25 115minus116

(40) Wanga H Liu Y Li Z Zhang X Zhang S Zhang Y Glycolysis of poly(ethylene terephthalate) catalyzed by ionic liquids Eur Polym J 2009

45 1535minus1544

(41) Ying A G Liu L Wua G F Chen G Chen X Z Ye W D Aza-Michael addition of aliphatic or aromatic amines to αβ-unsaturated

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

compounds catalyzed by a DBU-derived ionic liquid under solvent-free conditions Tetrahedron Lett 2009 50 1653minus1657

(42) Rajender S V Vasudevan V N Solvent-free preparation of ionic liquids using a household microwave oven Pure Appl Chem 2001 73

1309minus1313

(43) Rajendran A Priyadarshini M Synthesis and characterization of a novel ionic liquid (TBA-AMPS) and its applications in Mannich condensation

reactions under solvent free conditions African Journal of Pure and Applied Chemistry 2010 4 183minus187

(44) Jasinski J P Golen J A Praveen A S Yathirajan H S Narayana B 3-chloroanilinium 4-methylbenzenesulfonate Acta Cryst 2011 E67

o2925

(45) Collier E A Davey R J Black S N Roberts R J 17 salts of ephedrine crystal structures and packing analysis Acta Cryst 2006 B62 498minus505

(46) Wu T Q Xia L Hu A X Ye J 2-Ethyl-6-methylanilinium 4-methylbenzenesulfonate Acta Cryst 2009 E65 o368

(47) Tabatabaee M Noozari N 2-Aminopyrimidin-1-ium 4-methylbenzenesulfonate Acta Cryst 2011 E67 o1457

(48) Lin J R 4-(Cyanomethyl)anilinium 4-methylbenzenesulfonate monohydrate Acta Cryst 2010 E66 o1557

(49) Fun H K Kobkeatthawin T Chantrapromma S 1-methyl-2-[(E)-2-(2-thienyl)ethenyl]quinolinium 4-bromobenzenesulfonate Acta Cryst 2010

E66 o1053-o1054

(50) Chantrapromma S Chanawanno K Fun H K (E)-2-[4-(dimethylamino)styryl]-1-methylpyridinium 4-methylbenzenesulfonate monohydrate

Acta Cryst 2010 E66 o1975-o1976

(51) Rad M N S Khalafi-Nezhad A Asrari Z Behrouz S Amini Z Behrouz M One-pot synthesis of sulfonamides from primary and secondary

amine derived sulfonate salts using cyanuric chloride Synthesis 2009 23 3983minus3988

(52) Caddick S Wilden J D Bush H D Judd D B synthesis of functionalised sulfonamides via microwave assisted displacement of

pfp-sulfonates with amines QSAR Comb Sci 2004 23 902minus905

(53) Caddick S Wilden J D Wadman S J Bush H D Judd D B A new route to sulfonamides via intermolecular radical addition to

pentafluorophenyl vinylsulfonate and subsequent aminolysis Org Lett 2002 4 2549minus2551

(54) Caddick S Wilden J D Judd D B Direct synthesis of sulfonamides and activated sulfonate esters from sulfonic acids J Am Chem Soc 2004

126 1024minus1025

(55) Al-Dajani M T M Abdallah H H Mohamed N Quah C K Fun H K Triethylammonium 4-nitrobenzenesulfonate Acta Cryst 2010 E66

o1647

(56) Sheldrick G M A short history of SHELX Acta Cryst 2008 A64 112minus122

(57) Farrugia L J WinGX suite for small-molecule single-crystal crystallography J Apply Cryst 1999 32 837minus838

(58) Mercury version 30 CCDC available online via ccdccamacukproductsmercury

(59) Spek A L PLATON ndash A Multipurpose Crystallographic Tool Utrecht Utrecht University The Netherlands 2005

(60) Suarez S Doctorovich F Baggio R Ammonium 4-methoxybenzenesulfonate Acta Cryst 2012 E68 o2228minuso2229

(61) Beko S L Bats J W Schmidt M U 2-Ammonio-5-chloro-4-methylbenzenesulfonate its 1-methyl-2-pyrrolidone and dimethyl sulfoxide

monosolvates and a corrected structure of 22΄-(14-phenylene)di(45-dihydroimidazolium)bis(4-aminobenzenesulfonate) dehydrate Acta Cryst

2012 C68 o45minuso50

(62) Kennedy A R Morrison C A Briggs N E B Arbuckle W Density and stability differences between enantiopure and racemic salts

Construction and structural analysis of a systematic series of crystalline salt forms of methylephedrine Cryst Growth Des 2011 11

1821minus1834

(63) Fun H K Hemamalini M Shetty D N Narayana B Yathirajan H S 4-(3-carboxy-1-ethyl-6-fluoro-4-oxo-14-dihydro-7-quinolyl)-1-

methylpiperazinium picrate Acta Cryst 2010 E66 o714minuso715

(64) Bernstein J Davis R E Shimoni L Chang N L Patterns in hydrogen bonding functionality and graph set analysis in crystals Angew Chem

Int Ed Engl 1995 34 1555minus1573

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

To be continued

N(3)minusH(2N)middotmiddotmiddotO(3)ii 083(4) 223(4) 2889(2) 136(3) N(3)minusH(2N)middotmiddotmiddotO(2)iii 083(4) 229(4) 2916(2) 133(3) N(3)minusH(3N)middotmiddotmiddotO(1) 088(4) 201(4) 2858(2) 159(3) N(3)minusH(3N)middotmiddotmiddotO(3)i 088(4) 256(3) 3012(2) 113(3) C(3)minusH(3)middotmiddotmiddotO(7)iv 093 243 3353(3) 173 C(6)minusH(6)middotmiddotmiddotO(4)v 093 260 3273(5) 130 C(12)minusH(12)middotmiddotmiddotO(1)i 093 256 3337(2) 142

II

N(1)minusH(1)middotmiddotmiddotO(1) 083(4) 207(4) 2853(3) 156(4) N(1)minusH(1)middotmiddotmiddotO(3) 083(4) 255(4) 3233(3) 141(3) N(1)minusH(1)middotmiddotmiddotS(1) 083(4) 281(4) 3631(2) 168(3) C(15)minusH(15A)middotmiddotmiddotO(3) 096 193 2760(4) 144 C(13)minusH(13B)middotmiddotmiddotO(2) 096 242 3040(4) 122 C(11)minusH(11B)middotmiddotmiddotO(2)i 097 255 3359(8) 141 C(9)minusH(9A)middotmiddotmiddotO(2)ii 097 258 3308 132(4) C(7)minusH(7B)middotmiddotmiddotCg(1)i 097 258 3373(9) 139 C(14)minusH(14B)middotmiddotmiddotCg(1)iii 096 308 4001(11) 160

Symmetry codes (i) x ndashy+12 z+12 (ii) x+1 y z+1 (iii) x+1 ndashy+12 z+12 (iv) ndashx+1 ndashy+1 ndashz+1 (v) xndash1 y z for I (i) xndash1 y z (ii) xndash12 ndashy+32 ndashz+1 (iii) x+12 y ndashz+12 Cg(1) = C(1)～C(6) for II

Fig 4 A view of the molecule of II showing the atom-numbering scheme

Fig 5 Crystal structure of II showing the formation of R1

2(3) and R43(12) rings

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 6 Crystal structure of II showing the formation of a chain along [100] generated

by CminusHπ interactions (Symmetry code as in Table 5)

REFERENCES (1) Hajipoura A R Rafieeb F Basic ionic liquids A short review J Iran Chem Soc 2009 6 647minus678

(2) Yavari I Kowsari E Ionic liquids as novel and recyclable reaction media for N-alkylation of amino-910-anthraquinones by trialkyl phosphites

Tetrahedron Lett 2007 48 3753minus3756

(3) Gong K Wang H L Fang D Liu Z L Basic ionic liquid as catalyst for the rapid and green synthesis of substituted 2-amino-2-chromenes in

aqueous media Catal Commun 2008 9 650minus653

(4) Fraga-Dubreuil J Bourahla K Rahmouni M Bazureau J P Hamelin J Catalysed esterifications in room temperature ionic liquids with acidic

counteranion as recyclable reaction media Catal Commun 2002 3 185minus190

(5) Joseph T Sahoo S Halligudi S B Broumlnsted acidic ionic liquids a green efficient and reusable catalyst system and reaction medium for Fischer

esterification J Mol Catal A Chem 2005 234 107minus110

(6) Xing H Wang T Zhou Z Dai Y Novel Broslashnsted-acidic ionic liquids for esterifications Ind Eng Chem Res 2005 44 4147minus4150

(7) Zhu H P Yang F Tang J He M Y Broslashnsted acidic ionic liquid 1-methylimidazolium tetrafluoroborate a green catalyst and recyclable medium

for esterification Green Chem 2003 5 38minus39

(8) Fang D Zhou X Ye Z Liu Z Broslashnsted acidic ionic liquids and their use as dual solvent-catalysts for fischer esterifications Ind Eng Chem

Res 2006 45 7982minus7984

(9) Zhu A Jiang T Wang D Han B Liu L Huang J Zhang J Sun D Direct aldol reactions catalyzed by 1133-tetramethylguanidine lactate

without solvent Green Chem 2005 7 514minus517

(10) Qiao K Yokoyama C Koch carbonylation of tertiary alcohols in the presence of acidic ionic liquids Catal Commun 2006 7 450minus453

(11) Ogoshi T Onodera T Yamagishi T Nakamoto Y Green polymerization of phenol in ionic liquids Macromolecules 2008 41 8533-8536

(12) Cui S Lu B Cai Q Cai X Li X Xiao X Hou L Han Y Highly selective synthesis of diphenylmethane with acidic ionic liquids Ind

Eng Chem Res 2006 45 1571-1574

(13) Gui J Ban H Cong X Zhang X Hu Z Sun Z Selective alkylation of phenol with tert-butyl alcohol catalyzed by Broumlnsted acidic imidazolium

salts J Mol Catal A Chem 2005 225 27minus31

(14) Wasserscheid P Sesing M Korth W Hydrogensulfate and tetrakis(hydrogensulfato)borate ionic liquids synthesis and catalytic application in

highly Broslashnsted-acidic systems for Friedel-Crafts alkylation Green Chem 2002 4 134minus138

(15) Lin J H Zhang C P Zhu Z Q Chen Q Y Xiao J C A novel pyrrolidinium ionic liquid with 1122-tetrafluoro-2-(1122-tetrafluoroethoxy)

ethanesulfonate anion as a recyclable reaction medium and efficient catalyst for Friedel-Crafts alkylations of indoles with nitroalkenes J Fluorine

Chem 2009 130 394minus398

(16) Janus E Maciejewsk I G Skib M Pernak J Diels-Alder reaction in protic ionic liquids Tetrahedron Lett 2006 47 4079minus4083

(17) Fischer T Sethi A Welton T Woolf J Diels-Alder reactions in room-temperature ionic liquids Tetrahedron Lett 1999 40 793minus796

(18) Sahoo S Joseph T Halligudi S B Mannich reaction in Broumlnsted acidic ionic liquid a facile synthesis of β-amino carbonyl compounds J Mol

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

Catal A Chem 2006 244179minus182

(19) Zhao G Jiang T Gao H Han B Huang J Sun D Mannich reaction using acidic ionic liquids as catalysts and solvents Green Chem 2004 6

75minus77

(20) Chaskar A C Bhandari S R Patil A B Sharma O P Mayeker S Solvent-free oxidation of alcohols with potassium persulphate in the

presence of broumlnsted acidic ionic liquids Synth Commun 2009 39 366minus370

(21) Hajipour A R Rafiee F Ruoho A E Facile and selective oxidation of benzylic alcohols to their corresponding carbonyl compounds with

sodium nitrate in the presence of Broslashnsted acidic ionic liquids Synlett 2007 7 1118minus1120

(22) Hajipour A R Rafiee F Ruoho A E Oxidation of benzylic alcohols to their corresponding carbonyl compounds using KIO4 in ionic liquid by

microwave irradiation Synth Commun 2006 36 2563minus2568

(23) Li S Lin Y Xie H Zhang S Xu J broslashnsted guanidine acid-base ionic liquids novel reaction media for the palladium-catalyzed heck

reaction Org Lett 2006 8 391minus394

(24) Zhang J Jiang T Han B Zhu A Xiumin M Knoevenagel condensation catalyzed by 1133-tetramethylguanidium lactate Synth Commun

2006 36 3305minus3317

(25) Hu Y Chen J Le Z G Zheng Q G Organic reactions in ionic liquids ionic liquids ethylammonium nitrate promoted knoevenagel

condensation of aromatic aldehydes with active methylene compounds Synth Commun 2005 35 739minus744

(26) Harjani J R Nara S J Salunkhe M M Lewis acidic ionic liquids for the synthesis of electrophilic alkenes via the Knoevenagel condensation

Tetrahedron Lett 2002 43 1127minus1130

(27) Jiang T Gao H Han B Zhao G Chang Y Wu W Gao L Yang G Ionic liquid catalyzed Henry reactions Tetrahedron Lett 2004 45

2699minus2701

(28) Siddiqui S A Narkhede U C Palimkar S S Daniel T Lahoti R J Srinivasan K V Room temperature ionic liquid promoted improved and

rapid synthesis of 245-triaryl imidazoles from aryl aldehydes and 12-diketones or α-hydroxyketone Tetrahedron 2005 61 3539minus3546

(29) Bao Q Qiao K Tomida D Yokoyama C Preparation of 5-hydroymethylfurfural by dehydration of fructose in the presence of acidic ionic liquid

Catal Commun 2008 9 1383minus1388

(30) Potewar T M Siddiqui S A Lahoti R J Srinivasan K V Efficient and rapid synthesis of 1-substituted-1H-1234-tetrazoles in the acidic ionic

liquid 1-n-butylimidazolium tetrafluoroborate Tetra Lett 2007 48 1721minus1724

(31) Wang Y Y Li W Dai L Y Broslashnsted acidic ionic liquids as efficient reaction medium for cyclodehydration of diethylene glycol Chin J

Chem 2008 26 1390minus1394

(32) Kim K Lang C M Kohl P A Properties of asymmetric benzyl-substituted ammonium ionic liquids and their electrochemical properties J

Electrochem Soc 2005 152 E56minusE60

(33) Sun J Forsyth M Macfarlene D R Room-temperature molten salts based on the quaternary ammonium ion J Phys Chem B 1998 102

8858minus8864

(34) Macfarlane D R Golding J Forsyth S Forsyth M Deacon G B Low viscosity ionic liquids based on organic salts of the dicyanamide anion

Chem Commun 2001 1430minus1431

(35) Zhao D B Wu M Kou Y Min E Z Ionic liquids applications in catalysis Catalysis Today 2002 74 157minus189

(36) Visser A E Swatloski R P Rogers R D Green Chem 2000 2 1 Visser A E Swatloski R P Reichert W M Rogers R D Mayton R

Sheff S Wierzbicki A Davis J H Task-specific ionic liquids for the extraction of metal ions from aqueous solutions Chem Commun 2001

135minus136

(37) Wilkes J S Levinsky J A Wilson R A Hussey C L Dialkylimidazolium chloroaluminate melts a new class of room-temperature ionic liquids

for electrochemistry spectroscopy and synthesis Inorg Chem 1982 21 1263minus1264

(38) Pralhad A G Gigi G Jagannath D Broslashnsted acidic ionic liquids derived from alkylamines as catalysts and mediums for Fischer esterification

study of structure-activity relationship Journal of Molecular Catalysis A Chem 2008 182minus186

(39) Zhang Y Kou D Zhang J Zhang L Li X Study of the triethylammonium p-toluenesulfonate as stationary phase in gc for the determination

of benzoic acid in soy Journal of Instrumental Analysis 2006 25 115minus116

(40) Wanga H Liu Y Li Z Zhang X Zhang S Zhang Y Glycolysis of poly(ethylene terephthalate) catalyzed by ionic liquids Eur Polym J 2009

45 1535minus1544

(41) Ying A G Liu L Wua G F Chen G Chen X Z Ye W D Aza-Michael addition of aliphatic or aromatic amines to αβ-unsaturated

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

compounds catalyzed by a DBU-derived ionic liquid under solvent-free conditions Tetrahedron Lett 2009 50 1653minus1657

(42) Rajender S V Vasudevan V N Solvent-free preparation of ionic liquids using a household microwave oven Pure Appl Chem 2001 73

1309minus1313

(43) Rajendran A Priyadarshini M Synthesis and characterization of a novel ionic liquid (TBA-AMPS) and its applications in Mannich condensation

reactions under solvent free conditions African Journal of Pure and Applied Chemistry 2010 4 183minus187

(44) Jasinski J P Golen J A Praveen A S Yathirajan H S Narayana B 3-chloroanilinium 4-methylbenzenesulfonate Acta Cryst 2011 E67

o2925

(45) Collier E A Davey R J Black S N Roberts R J 17 salts of ephedrine crystal structures and packing analysis Acta Cryst 2006 B62 498minus505

(46) Wu T Q Xia L Hu A X Ye J 2-Ethyl-6-methylanilinium 4-methylbenzenesulfonate Acta Cryst 2009 E65 o368

(47) Tabatabaee M Noozari N 2-Aminopyrimidin-1-ium 4-methylbenzenesulfonate Acta Cryst 2011 E67 o1457

(48) Lin J R 4-(Cyanomethyl)anilinium 4-methylbenzenesulfonate monohydrate Acta Cryst 2010 E66 o1557

(49) Fun H K Kobkeatthawin T Chantrapromma S 1-methyl-2-[(E)-2-(2-thienyl)ethenyl]quinolinium 4-bromobenzenesulfonate Acta Cryst 2010

E66 o1053-o1054

(50) Chantrapromma S Chanawanno K Fun H K (E)-2-[4-(dimethylamino)styryl]-1-methylpyridinium 4-methylbenzenesulfonate monohydrate

Acta Cryst 2010 E66 o1975-o1976

(51) Rad M N S Khalafi-Nezhad A Asrari Z Behrouz S Amini Z Behrouz M One-pot synthesis of sulfonamides from primary and secondary

amine derived sulfonate salts using cyanuric chloride Synthesis 2009 23 3983minus3988

(52) Caddick S Wilden J D Bush H D Judd D B synthesis of functionalised sulfonamides via microwave assisted displacement of

pfp-sulfonates with amines QSAR Comb Sci 2004 23 902minus905

(53) Caddick S Wilden J D Wadman S J Bush H D Judd D B A new route to sulfonamides via intermolecular radical addition to

pentafluorophenyl vinylsulfonate and subsequent aminolysis Org Lett 2002 4 2549minus2551

(54) Caddick S Wilden J D Judd D B Direct synthesis of sulfonamides and activated sulfonate esters from sulfonic acids J Am Chem Soc 2004

126 1024minus1025

(55) Al-Dajani M T M Abdallah H H Mohamed N Quah C K Fun H K Triethylammonium 4-nitrobenzenesulfonate Acta Cryst 2010 E66

o1647

(56) Sheldrick G M A short history of SHELX Acta Cryst 2008 A64 112minus122

(57) Farrugia L J WinGX suite for small-molecule single-crystal crystallography J Apply Cryst 1999 32 837minus838

(58) Mercury version 30 CCDC available online via ccdccamacukproductsmercury

(59) Spek A L PLATON ndash A Multipurpose Crystallographic Tool Utrecht Utrecht University The Netherlands 2005

(60) Suarez S Doctorovich F Baggio R Ammonium 4-methoxybenzenesulfonate Acta Cryst 2012 E68 o2228minuso2229

(61) Beko S L Bats J W Schmidt M U 2-Ammonio-5-chloro-4-methylbenzenesulfonate its 1-methyl-2-pyrrolidone and dimethyl sulfoxide

monosolvates and a corrected structure of 22΄-(14-phenylene)di(45-dihydroimidazolium)bis(4-aminobenzenesulfonate) dehydrate Acta Cryst

2012 C68 o45minuso50

(62) Kennedy A R Morrison C A Briggs N E B Arbuckle W Density and stability differences between enantiopure and racemic salts

Construction and structural analysis of a systematic series of crystalline salt forms of methylephedrine Cryst Growth Des 2011 11

1821minus1834

(63) Fun H K Hemamalini M Shetty D N Narayana B Yathirajan H S 4-(3-carboxy-1-ethyl-6-fluoro-4-oxo-14-dihydro-7-quinolyl)-1-

methylpiperazinium picrate Acta Cryst 2010 E66 o714minuso715

(64) Bernstein J Davis R E Shimoni L Chang N L Patterns in hydrogen bonding functionality and graph set analysis in crystals Angew Chem

Int Ed Engl 1995 34 1555minus1573

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

Fig 6 Crystal structure of II showing the formation of a chain along [100] generated

by CminusHπ interactions (Symmetry code as in Table 5)

REFERENCES (1) Hajipoura A R Rafieeb F Basic ionic liquids A short review J Iran Chem Soc 2009 6 647minus678

(2) Yavari I Kowsari E Ionic liquids as novel and recyclable reaction media for N-alkylation of amino-910-anthraquinones by trialkyl phosphites

Tetrahedron Lett 2007 48 3753minus3756

(3) Gong K Wang H L Fang D Liu Z L Basic ionic liquid as catalyst for the rapid and green synthesis of substituted 2-amino-2-chromenes in

aqueous media Catal Commun 2008 9 650minus653

(4) Fraga-Dubreuil J Bourahla K Rahmouni M Bazureau J P Hamelin J Catalysed esterifications in room temperature ionic liquids with acidic

counteranion as recyclable reaction media Catal Commun 2002 3 185minus190

(5) Joseph T Sahoo S Halligudi S B Broumlnsted acidic ionic liquids a green efficient and reusable catalyst system and reaction medium for Fischer

esterification J Mol Catal A Chem 2005 234 107minus110

(6) Xing H Wang T Zhou Z Dai Y Novel Broslashnsted-acidic ionic liquids for esterifications Ind Eng Chem Res 2005 44 4147minus4150

(7) Zhu H P Yang F Tang J He M Y Broslashnsted acidic ionic liquid 1-methylimidazolium tetrafluoroborate a green catalyst and recyclable medium

for esterification Green Chem 2003 5 38minus39

(8) Fang D Zhou X Ye Z Liu Z Broslashnsted acidic ionic liquids and their use as dual solvent-catalysts for fischer esterifications Ind Eng Chem

Res 2006 45 7982minus7984

(9) Zhu A Jiang T Wang D Han B Liu L Huang J Zhang J Sun D Direct aldol reactions catalyzed by 1133-tetramethylguanidine lactate

without solvent Green Chem 2005 7 514minus517

(10) Qiao K Yokoyama C Koch carbonylation of tertiary alcohols in the presence of acidic ionic liquids Catal Commun 2006 7 450minus453

(11) Ogoshi T Onodera T Yamagishi T Nakamoto Y Green polymerization of phenol in ionic liquids Macromolecules 2008 41 8533-8536

(12) Cui S Lu B Cai Q Cai X Li X Xiao X Hou L Han Y Highly selective synthesis of diphenylmethane with acidic ionic liquids Ind

Eng Chem Res 2006 45 1571-1574

(13) Gui J Ban H Cong X Zhang X Hu Z Sun Z Selective alkylation of phenol with tert-butyl alcohol catalyzed by Broumlnsted acidic imidazolium

salts J Mol Catal A Chem 2005 225 27minus31

(14) Wasserscheid P Sesing M Korth W Hydrogensulfate and tetrakis(hydrogensulfato)borate ionic liquids synthesis and catalytic application in

highly Broslashnsted-acidic systems for Friedel-Crafts alkylation Green Chem 2002 4 134minus138

(15) Lin J H Zhang C P Zhu Z Q Chen Q Y Xiao J C A novel pyrrolidinium ionic liquid with 1122-tetrafluoro-2-(1122-tetrafluoroethoxy)

ethanesulfonate anion as a recyclable reaction medium and efficient catalyst for Friedel-Crafts alkylations of indoles with nitroalkenes J Fluorine

Chem 2009 130 394minus398

(16) Janus E Maciejewsk I G Skib M Pernak J Diels-Alder reaction in protic ionic liquids Tetrahedron Lett 2006 47 4079minus4083

(17) Fischer T Sethi A Welton T Woolf J Diels-Alder reactions in room-temperature ionic liquids Tetrahedron Lett 1999 40 793minus796

(18) Sahoo S Joseph T Halligudi S B Mannich reaction in Broumlnsted acidic ionic liquid a facile synthesis of β-amino carbonyl compounds J Mol

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

Catal A Chem 2006 244179minus182

(19) Zhao G Jiang T Gao H Han B Huang J Sun D Mannich reaction using acidic ionic liquids as catalysts and solvents Green Chem 2004 6

75minus77

(20) Chaskar A C Bhandari S R Patil A B Sharma O P Mayeker S Solvent-free oxidation of alcohols with potassium persulphate in the

presence of broumlnsted acidic ionic liquids Synth Commun 2009 39 366minus370

(21) Hajipour A R Rafiee F Ruoho A E Facile and selective oxidation of benzylic alcohols to their corresponding carbonyl compounds with

sodium nitrate in the presence of Broslashnsted acidic ionic liquids Synlett 2007 7 1118minus1120

(22) Hajipour A R Rafiee F Ruoho A E Oxidation of benzylic alcohols to their corresponding carbonyl compounds using KIO4 in ionic liquid by

microwave irradiation Synth Commun 2006 36 2563minus2568

(23) Li S Lin Y Xie H Zhang S Xu J broslashnsted guanidine acid-base ionic liquids novel reaction media for the palladium-catalyzed heck

reaction Org Lett 2006 8 391minus394

(24) Zhang J Jiang T Han B Zhu A Xiumin M Knoevenagel condensation catalyzed by 1133-tetramethylguanidium lactate Synth Commun

2006 36 3305minus3317

(25) Hu Y Chen J Le Z G Zheng Q G Organic reactions in ionic liquids ionic liquids ethylammonium nitrate promoted knoevenagel

condensation of aromatic aldehydes with active methylene compounds Synth Commun 2005 35 739minus744

(26) Harjani J R Nara S J Salunkhe M M Lewis acidic ionic liquids for the synthesis of electrophilic alkenes via the Knoevenagel condensation

Tetrahedron Lett 2002 43 1127minus1130

(27) Jiang T Gao H Han B Zhao G Chang Y Wu W Gao L Yang G Ionic liquid catalyzed Henry reactions Tetrahedron Lett 2004 45

2699minus2701

(28) Siddiqui S A Narkhede U C Palimkar S S Daniel T Lahoti R J Srinivasan K V Room temperature ionic liquid promoted improved and

rapid synthesis of 245-triaryl imidazoles from aryl aldehydes and 12-diketones or α-hydroxyketone Tetrahedron 2005 61 3539minus3546

(29) Bao Q Qiao K Tomida D Yokoyama C Preparation of 5-hydroymethylfurfural by dehydration of fructose in the presence of acidic ionic liquid

Catal Commun 2008 9 1383minus1388

(30) Potewar T M Siddiqui S A Lahoti R J Srinivasan K V Efficient and rapid synthesis of 1-substituted-1H-1234-tetrazoles in the acidic ionic

liquid 1-n-butylimidazolium tetrafluoroborate Tetra Lett 2007 48 1721minus1724

(31) Wang Y Y Li W Dai L Y Broslashnsted acidic ionic liquids as efficient reaction medium for cyclodehydration of diethylene glycol Chin J

Chem 2008 26 1390minus1394

(32) Kim K Lang C M Kohl P A Properties of asymmetric benzyl-substituted ammonium ionic liquids and their electrochemical properties J

Electrochem Soc 2005 152 E56minusE60

(33) Sun J Forsyth M Macfarlene D R Room-temperature molten salts based on the quaternary ammonium ion J Phys Chem B 1998 102

8858minus8864

(34) Macfarlane D R Golding J Forsyth S Forsyth M Deacon G B Low viscosity ionic liquids based on organic salts of the dicyanamide anion

Chem Commun 2001 1430minus1431

(35) Zhao D B Wu M Kou Y Min E Z Ionic liquids applications in catalysis Catalysis Today 2002 74 157minus189

(36) Visser A E Swatloski R P Rogers R D Green Chem 2000 2 1 Visser A E Swatloski R P Reichert W M Rogers R D Mayton R

Sheff S Wierzbicki A Davis J H Task-specific ionic liquids for the extraction of metal ions from aqueous solutions Chem Commun 2001

135minus136

(37) Wilkes J S Levinsky J A Wilson R A Hussey C L Dialkylimidazolium chloroaluminate melts a new class of room-temperature ionic liquids

for electrochemistry spectroscopy and synthesis Inorg Chem 1982 21 1263minus1264

(38) Pralhad A G Gigi G Jagannath D Broslashnsted acidic ionic liquids derived from alkylamines as catalysts and mediums for Fischer esterification

study of structure-activity relationship Journal of Molecular Catalysis A Chem 2008 182minus186

(39) Zhang Y Kou D Zhang J Zhang L Li X Study of the triethylammonium p-toluenesulfonate as stationary phase in gc for the determination

of benzoic acid in soy Journal of Instrumental Analysis 2006 25 115minus116

(40) Wanga H Liu Y Li Z Zhang X Zhang S Zhang Y Glycolysis of poly(ethylene terephthalate) catalyzed by ionic liquids Eur Polym J 2009

45 1535minus1544

(41) Ying A G Liu L Wua G F Chen G Chen X Z Ye W D Aza-Michael addition of aliphatic or aromatic amines to αβ-unsaturated

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

compounds catalyzed by a DBU-derived ionic liquid under solvent-free conditions Tetrahedron Lett 2009 50 1653minus1657

(42) Rajender S V Vasudevan V N Solvent-free preparation of ionic liquids using a household microwave oven Pure Appl Chem 2001 73

1309minus1313

(43) Rajendran A Priyadarshini M Synthesis and characterization of a novel ionic liquid (TBA-AMPS) and its applications in Mannich condensation

reactions under solvent free conditions African Journal of Pure and Applied Chemistry 2010 4 183minus187

(44) Jasinski J P Golen J A Praveen A S Yathirajan H S Narayana B 3-chloroanilinium 4-methylbenzenesulfonate Acta Cryst 2011 E67

o2925

(45) Collier E A Davey R J Black S N Roberts R J 17 salts of ephedrine crystal structures and packing analysis Acta Cryst 2006 B62 498minus505

(46) Wu T Q Xia L Hu A X Ye J 2-Ethyl-6-methylanilinium 4-methylbenzenesulfonate Acta Cryst 2009 E65 o368

(47) Tabatabaee M Noozari N 2-Aminopyrimidin-1-ium 4-methylbenzenesulfonate Acta Cryst 2011 E67 o1457

(48) Lin J R 4-(Cyanomethyl)anilinium 4-methylbenzenesulfonate monohydrate Acta Cryst 2010 E66 o1557

(49) Fun H K Kobkeatthawin T Chantrapromma S 1-methyl-2-[(E)-2-(2-thienyl)ethenyl]quinolinium 4-bromobenzenesulfonate Acta Cryst 2010

E66 o1053-o1054

(50) Chantrapromma S Chanawanno K Fun H K (E)-2-[4-(dimethylamino)styryl]-1-methylpyridinium 4-methylbenzenesulfonate monohydrate

Acta Cryst 2010 E66 o1975-o1976

(51) Rad M N S Khalafi-Nezhad A Asrari Z Behrouz S Amini Z Behrouz M One-pot synthesis of sulfonamides from primary and secondary

amine derived sulfonate salts using cyanuric chloride Synthesis 2009 23 3983minus3988

(52) Caddick S Wilden J D Bush H D Judd D B synthesis of functionalised sulfonamides via microwave assisted displacement of

pfp-sulfonates with amines QSAR Comb Sci 2004 23 902minus905

(53) Caddick S Wilden J D Wadman S J Bush H D Judd D B A new route to sulfonamides via intermolecular radical addition to

pentafluorophenyl vinylsulfonate and subsequent aminolysis Org Lett 2002 4 2549minus2551

(54) Caddick S Wilden J D Judd D B Direct synthesis of sulfonamides and activated sulfonate esters from sulfonic acids J Am Chem Soc 2004

126 1024minus1025

(55) Al-Dajani M T M Abdallah H H Mohamed N Quah C K Fun H K Triethylammonium 4-nitrobenzenesulfonate Acta Cryst 2010 E66

o1647

(56) Sheldrick G M A short history of SHELX Acta Cryst 2008 A64 112minus122

(57) Farrugia L J WinGX suite for small-molecule single-crystal crystallography J Apply Cryst 1999 32 837minus838

(58) Mercury version 30 CCDC available online via ccdccamacukproductsmercury

(59) Spek A L PLATON ndash A Multipurpose Crystallographic Tool Utrecht Utrecht University The Netherlands 2005

(60) Suarez S Doctorovich F Baggio R Ammonium 4-methoxybenzenesulfonate Acta Cryst 2012 E68 o2228minuso2229

(61) Beko S L Bats J W Schmidt M U 2-Ammonio-5-chloro-4-methylbenzenesulfonate its 1-methyl-2-pyrrolidone and dimethyl sulfoxide

monosolvates and a corrected structure of 22΄-(14-phenylene)di(45-dihydroimidazolium)bis(4-aminobenzenesulfonate) dehydrate Acta Cryst

2012 C68 o45minuso50

(62) Kennedy A R Morrison C A Briggs N E B Arbuckle W Density and stability differences between enantiopure and racemic salts

Construction and structural analysis of a systematic series of crystalline salt forms of methylephedrine Cryst Growth Des 2011 11

1821minus1834

(63) Fun H K Hemamalini M Shetty D N Narayana B Yathirajan H S 4-(3-carboxy-1-ethyl-6-fluoro-4-oxo-14-dihydro-7-quinolyl)-1-

methylpiperazinium picrate Acta Cryst 2010 E66 o714minuso715

(64) Bernstein J Davis R E Shimoni L Chang N L Patterns in hydrogen bonding functionality and graph set analysis in crystals Angew Chem

Int Ed Engl 1995 34 1555minus1573

2013 Vol 32 结 构 化 学（JIEGOU HUAXUE）Chinese J Struct Chem 1473

Catal A Chem 2006 244179minus182

(19) Zhao G Jiang T Gao H Han B Huang J Sun D Mannich reaction using acidic ionic liquids as catalysts and solvents Green Chem 2004 6

75minus77

(20) Chaskar A C Bhandari S R Patil A B Sharma O P Mayeker S Solvent-free oxidation of alcohols with potassium persulphate in the

presence of broumlnsted acidic ionic liquids Synth Commun 2009 39 366minus370

(21) Hajipour A R Rafiee F Ruoho A E Facile and selective oxidation of benzylic alcohols to their corresponding carbonyl compounds with

sodium nitrate in the presence of Broslashnsted acidic ionic liquids Synlett 2007 7 1118minus1120

(22) Hajipour A R Rafiee F Ruoho A E Oxidation of benzylic alcohols to their corresponding carbonyl compounds using KIO4 in ionic liquid by

microwave irradiation Synth Commun 2006 36 2563minus2568

(23) Li S Lin Y Xie H Zhang S Xu J broslashnsted guanidine acid-base ionic liquids novel reaction media for the palladium-catalyzed heck

reaction Org Lett 2006 8 391minus394

(24) Zhang J Jiang T Han B Zhu A Xiumin M Knoevenagel condensation catalyzed by 1133-tetramethylguanidium lactate Synth Commun

2006 36 3305minus3317

(25) Hu Y Chen J Le Z G Zheng Q G Organic reactions in ionic liquids ionic liquids ethylammonium nitrate promoted knoevenagel

condensation of aromatic aldehydes with active methylene compounds Synth Commun 2005 35 739minus744

(26) Harjani J R Nara S J Salunkhe M M Lewis acidic ionic liquids for the synthesis of electrophilic alkenes via the Knoevenagel condensation

Tetrahedron Lett 2002 43 1127minus1130

(27) Jiang T Gao H Han B Zhao G Chang Y Wu W Gao L Yang G Ionic liquid catalyzed Henry reactions Tetrahedron Lett 2004 45

2699minus2701

(28) Siddiqui S A Narkhede U C Palimkar S S Daniel T Lahoti R J Srinivasan K V Room temperature ionic liquid promoted improved and

rapid synthesis of 245-triaryl imidazoles from aryl aldehydes and 12-diketones or α-hydroxyketone Tetrahedron 2005 61 3539minus3546

(29) Bao Q Qiao K Tomida D Yokoyama C Preparation of 5-hydroymethylfurfural by dehydration of fructose in the presence of acidic ionic liquid

Catal Commun 2008 9 1383minus1388

(30) Potewar T M Siddiqui S A Lahoti R J Srinivasan K V Efficient and rapid synthesis of 1-substituted-1H-1234-tetrazoles in the acidic ionic

liquid 1-n-butylimidazolium tetrafluoroborate Tetra Lett 2007 48 1721minus1724

(31) Wang Y Y Li W Dai L Y Broslashnsted acidic ionic liquids as efficient reaction medium for cyclodehydration of diethylene glycol Chin J

Chem 2008 26 1390minus1394

(32) Kim K Lang C M Kohl P A Properties of asymmetric benzyl-substituted ammonium ionic liquids and their electrochemical properties J

Electrochem Soc 2005 152 E56minusE60

(33) Sun J Forsyth M Macfarlene D R Room-temperature molten salts based on the quaternary ammonium ion J Phys Chem B 1998 102

8858minus8864

(34) Macfarlane D R Golding J Forsyth S Forsyth M Deacon G B Low viscosity ionic liquids based on organic salts of the dicyanamide anion

Chem Commun 2001 1430minus1431

(35) Zhao D B Wu M Kou Y Min E Z Ionic liquids applications in catalysis Catalysis Today 2002 74 157minus189

(36) Visser A E Swatloski R P Rogers R D Green Chem 2000 2 1 Visser A E Swatloski R P Reichert W M Rogers R D Mayton R

Sheff S Wierzbicki A Davis J H Task-specific ionic liquids for the extraction of metal ions from aqueous solutions Chem Commun 2001

135minus136

(37) Wilkes J S Levinsky J A Wilson R A Hussey C L Dialkylimidazolium chloroaluminate melts a new class of room-temperature ionic liquids

for electrochemistry spectroscopy and synthesis Inorg Chem 1982 21 1263minus1264

(38) Pralhad A G Gigi G Jagannath D Broslashnsted acidic ionic liquids derived from alkylamines as catalysts and mediums for Fischer esterification

study of structure-activity relationship Journal of Molecular Catalysis A Chem 2008 182minus186

(39) Zhang Y Kou D Zhang J Zhang L Li X Study of the triethylammonium p-toluenesulfonate as stationary phase in gc for the determination

of benzoic acid in soy Journal of Instrumental Analysis 2006 25 115minus116

(40) Wanga H Liu Y Li Z Zhang X Zhang S Zhang Y Glycolysis of poly(ethylene terephthalate) catalyzed by ionic liquids Eur Polym J 2009

45 1535minus1544

(41) Ying A G Liu L Wua G F Chen G Chen X Z Ye W D Aza-Michael addition of aliphatic or aromatic amines to αβ-unsaturated

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

compounds catalyzed by a DBU-derived ionic liquid under solvent-free conditions Tetrahedron Lett 2009 50 1653minus1657

(42) Rajender S V Vasudevan V N Solvent-free preparation of ionic liquids using a household microwave oven Pure Appl Chem 2001 73

1309minus1313

(43) Rajendran A Priyadarshini M Synthesis and characterization of a novel ionic liquid (TBA-AMPS) and its applications in Mannich condensation

reactions under solvent free conditions African Journal of Pure and Applied Chemistry 2010 4 183minus187

(44) Jasinski J P Golen J A Praveen A S Yathirajan H S Narayana B 3-chloroanilinium 4-methylbenzenesulfonate Acta Cryst 2011 E67

o2925

(45) Collier E A Davey R J Black S N Roberts R J 17 salts of ephedrine crystal structures and packing analysis Acta Cryst 2006 B62 498minus505

(46) Wu T Q Xia L Hu A X Ye J 2-Ethyl-6-methylanilinium 4-methylbenzenesulfonate Acta Cryst 2009 E65 o368

(47) Tabatabaee M Noozari N 2-Aminopyrimidin-1-ium 4-methylbenzenesulfonate Acta Cryst 2011 E67 o1457

(48) Lin J R 4-(Cyanomethyl)anilinium 4-methylbenzenesulfonate monohydrate Acta Cryst 2010 E66 o1557

(49) Fun H K Kobkeatthawin T Chantrapromma S 1-methyl-2-[(E)-2-(2-thienyl)ethenyl]quinolinium 4-bromobenzenesulfonate Acta Cryst 2010

E66 o1053-o1054

(50) Chantrapromma S Chanawanno K Fun H K (E)-2-[4-(dimethylamino)styryl]-1-methylpyridinium 4-methylbenzenesulfonate monohydrate

Acta Cryst 2010 E66 o1975-o1976

(51) Rad M N S Khalafi-Nezhad A Asrari Z Behrouz S Amini Z Behrouz M One-pot synthesis of sulfonamides from primary and secondary

amine derived sulfonate salts using cyanuric chloride Synthesis 2009 23 3983minus3988

(52) Caddick S Wilden J D Bush H D Judd D B synthesis of functionalised sulfonamides via microwave assisted displacement of

pfp-sulfonates with amines QSAR Comb Sci 2004 23 902minus905

(53) Caddick S Wilden J D Wadman S J Bush H D Judd D B A new route to sulfonamides via intermolecular radical addition to

pentafluorophenyl vinylsulfonate and subsequent aminolysis Org Lett 2002 4 2549minus2551

(54) Caddick S Wilden J D Judd D B Direct synthesis of sulfonamides and activated sulfonate esters from sulfonic acids J Am Chem Soc 2004

126 1024minus1025

(55) Al-Dajani M T M Abdallah H H Mohamed N Quah C K Fun H K Triethylammonium 4-nitrobenzenesulfonate Acta Cryst 2010 E66

o1647

(56) Sheldrick G M A short history of SHELX Acta Cryst 2008 A64 112minus122

(57) Farrugia L J WinGX suite for small-molecule single-crystal crystallography J Apply Cryst 1999 32 837minus838

(58) Mercury version 30 CCDC available online via ccdccamacukproductsmercury

(59) Spek A L PLATON ndash A Multipurpose Crystallographic Tool Utrecht Utrecht University The Netherlands 2005

(60) Suarez S Doctorovich F Baggio R Ammonium 4-methoxybenzenesulfonate Acta Cryst 2012 E68 o2228minuso2229

(61) Beko S L Bats J W Schmidt M U 2-Ammonio-5-chloro-4-methylbenzenesulfonate its 1-methyl-2-pyrrolidone and dimethyl sulfoxide

monosolvates and a corrected structure of 22΄-(14-phenylene)di(45-dihydroimidazolium)bis(4-aminobenzenesulfonate) dehydrate Acta Cryst

2012 C68 o45minuso50

(62) Kennedy A R Morrison C A Briggs N E B Arbuckle W Density and stability differences between enantiopure and racemic salts

Construction and structural analysis of a systematic series of crystalline salt forms of methylephedrine Cryst Growth Des 2011 11

1821minus1834

(63) Fun H K Hemamalini M Shetty D N Narayana B Yathirajan H S 4-(3-carboxy-1-ethyl-6-fluoro-4-oxo-14-dihydro-7-quinolyl)-1-

methylpiperazinium picrate Acta Cryst 2010 E66 o714minuso715

(64) Bernstein J Davis R E Shimoni L Chang N L Patterns in hydrogen bonding functionality and graph set analysis in crystals Angew Chem

Int Ed Engl 1995 34 1555minus1573

KHAN I U et al Facile Synthesis and Crystal Structures of 1474 New Ammonium Sulfonates (CA-DNBS and TEA-TMBS) No 10

compounds catalyzed by a DBU-derived ionic liquid under solvent-free conditions Tetrahedron Lett 2009 50 1653minus1657

(42) Rajender S V Vasudevan V N Solvent-free preparation of ionic liquids using a household microwave oven Pure Appl Chem 2001 73

1309minus1313

(43) Rajendran A Priyadarshini M Synthesis and characterization of a novel ionic liquid (TBA-AMPS) and its applications in Mannich condensation

reactions under solvent free conditions African Journal of Pure and Applied Chemistry 2010 4 183minus187

(44) Jasinski J P Golen J A Praveen A S Yathirajan H S Narayana B 3-chloroanilinium 4-methylbenzenesulfonate Acta Cryst 2011 E67

o2925

(45) Collier E A Davey R J Black S N Roberts R J 17 salts of ephedrine crystal structures and packing analysis Acta Cryst 2006 B62 498minus505

(46) Wu T Q Xia L Hu A X Ye J 2-Ethyl-6-methylanilinium 4-methylbenzenesulfonate Acta Cryst 2009 E65 o368

(47) Tabatabaee M Noozari N 2-Aminopyrimidin-1-ium 4-methylbenzenesulfonate Acta Cryst 2011 E67 o1457

(48) Lin J R 4-(Cyanomethyl)anilinium 4-methylbenzenesulfonate monohydrate Acta Cryst 2010 E66 o1557

(49) Fun H K Kobkeatthawin T Chantrapromma S 1-methyl-2-[(E)-2-(2-thienyl)ethenyl]quinolinium 4-bromobenzenesulfonate Acta Cryst 2010

E66 o1053-o1054

(50) Chantrapromma S Chanawanno K Fun H K (E)-2-[4-(dimethylamino)styryl]-1-methylpyridinium 4-methylbenzenesulfonate monohydrate

Acta Cryst 2010 E66 o1975-o1976

(51) Rad M N S Khalafi-Nezhad A Asrari Z Behrouz S Amini Z Behrouz M One-pot synthesis of sulfonamides from primary and secondary

amine derived sulfonate salts using cyanuric chloride Synthesis 2009 23 3983minus3988

(52) Caddick S Wilden J D Bush H D Judd D B synthesis of functionalised sulfonamides via microwave assisted displacement of

pfp-sulfonates with amines QSAR Comb Sci 2004 23 902minus905

(53) Caddick S Wilden J D Wadman S J Bush H D Judd D B A new route to sulfonamides via intermolecular radical addition to

pentafluorophenyl vinylsulfonate and subsequent aminolysis Org Lett 2002 4 2549minus2551

(54) Caddick S Wilden J D Judd D B Direct synthesis of sulfonamides and activated sulfonate esters from sulfonic acids J Am Chem Soc 2004

126 1024minus1025

(55) Al-Dajani M T M Abdallah H H Mohamed N Quah C K Fun H K Triethylammonium 4-nitrobenzenesulfonate Acta Cryst 2010 E66

o1647

(56) Sheldrick G M A short history of SHELX Acta Cryst 2008 A64 112minus122

(57) Farrugia L J WinGX suite for small-molecule single-crystal crystallography J Apply Cryst 1999 32 837minus838

(58) Mercury version 30 CCDC available online via ccdccamacukproductsmercury

(59) Spek A L PLATON ndash A Multipurpose Crystallographic Tool Utrecht Utrecht University The Netherlands 2005

(60) Suarez S Doctorovich F Baggio R Ammonium 4-methoxybenzenesulfonate Acta Cryst 2012 E68 o2228minuso2229

(61) Beko S L Bats J W Schmidt M U 2-Ammonio-5-chloro-4-methylbenzenesulfonate its 1-methyl-2-pyrrolidone and dimethyl sulfoxide

monosolvates and a corrected structure of 22΄-(14-phenylene)di(45-dihydroimidazolium)bis(4-aminobenzenesulfonate) dehydrate Acta Cryst

2012 C68 o45minuso50

(62) Kennedy A R Morrison C A Briggs N E B Arbuckle W Density and stability differences between enantiopure and racemic salts

Construction and structural analysis of a systematic series of crystalline salt forms of methylephedrine Cryst Growth Des 2011 11

1821minus1834

(63) Fun H K Hemamalini M Shetty D N Narayana B Yathirajan H S 4-(3-carboxy-1-ethyl-6-fluoro-4-oxo-14-dihydro-7-quinolyl)-1-

methylpiperazinium picrate Acta Cryst 2010 E66 o714minuso715

(64) Bernstein J Davis R E Shimoni L Chang N L Patterns in hydrogen bonding functionality and graph set analysis in crystals Angew Chem

Int Ed Engl 1995 34 1555minus1573