Novel Copper(II) Thiodibenzoic Acid Coordination Polymers by in situ Extrusion of Sulfur from...

Journal of Inorganic and General Chemistry

Zeitschrift für anorganische und allgemeine Chemie

www.zaac.wiley-vch.de ARTICLE

DOI: 10.1002/zaac.201500049

Novel Copper(II) Thiodibenzoic Acid Coordination Polymers by in situExtrusion of Sulfur from 2,2�-Dithiodibenzoic Acid and the Unique

Oxidation of Disulfide to Sulfate

Salma B. Moosun,[a] Lisa H. Blair,[b] Simon J. Coles,[b] Sabina J. Laulloo,[a] andMinu G. Bhowon*[a]

Keywords: 2,2�-Dithiodibenzoic acid; Copper; Thiobenzoic acid; Carboxylates; Scission; Oxidation; Sulfate

Abstract. Slow diffusion reaction of 2,2�-dithiodibenzoic acid (dtdb)with CuCl2 in the presence of N-donor ligands results in the formationof different coordination polymers where both S–S and C–S scissionand oxidation of S is observed. X-ray diffraction analysis of[Cu(tdb)(phen)(H2O)]2·2H2O.2DMF] (1), [Cu(tdb)(py)2(H2O)]2 (3),and [Cu(tdb)(bipy)(H2O)]2·0.5H2O (4) (tdb = thiodibenzoic acid,phen = phenanthroline, py = pyridine, bipy = 2,2�-bipyridine) show

1 Introduction

The structural motifs and potential applications of coordina-tion polymers in optical, magnetic, electronic, and porous ma-terials have made the design of metal organic frameworks anactive area in the field of crystal engineering.[1–3] MultidentateN- or O-donor ligands are a fundamental building block forthis approach due to their capacity to bridge between centralmetal atoms to form polymeric and framework structures. Thiswork employs 2,2�-dithiodibenzoic acid, a multifunctional li-gand containing both thio and carboxylic groups. Numerouscomplexes synthesized with this ligand adopt unique structuraltopologies and exhibit interesting properties.[4–10] Conse-quently, the presence of thio and carboxylate groups makesthis ligand flexible and at the same time rigid in coordinationto metal atoms as the phenyl ring can be twisted across the C–S and S–S bond because of the steric effect.[10] Moreover, thetorsional angles between C–S–S–C are generally between 20°to 90°, which can facilitate the formation of helical coordina-tion polymers. In addition to that, the presence of sulfur atomsincreases the dimensionality of the resulting coordination poly-mers due to their ability to contribute to hydrogen bonding orestablish van der Waals interactions.[11–13]

Another striking feature of compounds containing S–S link-ers is the variable transformations of S–S atoms depending

* Dr. M. G. BhowonE-Mail: [email protected]

[a] Department of ChemistryFaculty of ScienceUniversity of MauritiusRéduit, Mauritius

[b] Chemistry, Faculty of Natural & Environmental SciencesUniversity of SouthamptonSouthampton, SO17 1BJ, UK

Z. Anorg. Allg. Chem. 2015, 641, (5), 890–895 © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim890

that the metal ions are coordinated to the carboxylate oxygen atomsof the in situ generated tdb ligand in a monodenate fashion. In[Cu(phen)(SO4)2(H2O)2]n (2) and [Cu(bipy)(SO4)2(H2O)2]n (5), thesulfur is oxidized to sulfate ions prior to coordination with the metal.Complex 1 has a dimeric structure with π–π interactions between thephen ligands, whereas 3 and 4 form 1D polymeric chains.

upon reaction conditions.[14–16] The disulfide atoms can remaineither uncoordinated or take part in weak interactions. As ex-emplified in literature, the S–S bond can also undergo diversi-fied changes such as oxidative or reductive cleavage, extrusionof one sulfur or insertion of one additional atom (S, C, N) andcan adopt mononuclear, hexanuclear, 1D chain, 2D sheet, andnovel 3D frameworks.[17–19] The presence of different co-li-gands such as phenanthroline and bipyridine can influence thestructural features of the complexes formed and can lead to theformation of new products with reduced dimensionality of thenetworks formed.[20] Up to now no reports involve dithiodi-benzoate complexes, where oxidative cleavage of the S–Sbond has been observed under slow diffusion. Hence, in thepresent work, we report the synthesis and structural details ofcopper(II) complexes 1–5, in which oxidative cleavage of theS–S and C–S bond in 1, 3, and 4 and unexpected formation ofsulfate ions in 2 and 5 were observed.

2 Experimental Section

2.1 Materials

Dithiosalicylic acid, 2,2�-bipyridine and 1,10-phenanthroline werebought from Sigma Aldrich (Germany, UK). Pyridine was purchasedfrom Fischer Scientific (UK) and copper(II) chloride was obtainedfrom BDH (England). DMF was purchased from Lobachemie andQualichems (India), respectively.

2.2 Physical Measurements

Melting points of the samples were determined with a Stuart ScientificElectronic IA 9100 melting point apparatus and were uncorrected. In-frared spectra were recorded with a Bruker Alpha FTIR spectrometer




in the range of 400–4000 cm–1 on a diamond cell. Carbon, hydrogen,nitrogen, and sulfur contents were obtained with a Eurovector EA 3000elemental analyzer. Magnetic moment was recorded with a SherwoodScientific magnetic susceptibility balance and pH was recorded with aMartini Instruments Mi160 Temperature Bench Meter.

2.3 Synthesis of Copper Complexes

A mixture of dtdb (0.126 g, 0.411 mmol) and 1,10 phen/py/bipy(0.411 mmol) in DMF (5 mL) was carefully layered onto a solution ofCuCl2·2H2O (0.075 g, 0.411 mmol) in water (5 mL). The pH of dtdbwas adjusted to pH 7.2 using 1 m NaOH solution. The resulting mix-ture was kept at room temperature. After 4–9 weeks, 1–5 were ob-tained as crystals, which were suitable for X-ray analysis and separatedmechanically using a hand lens in case of 1 and 2 and 4 and 5.

C58H54Cu2N6O14S2 (1): Yield 15%, μeff = 1.39. Anal. found (calcd):C 55.20 (55.60); H 4.24 (4.32); N 7.12 (6.72); S 5.04 (5.12)%. IR:ν̃ = 1660 (νCO, DMF), 1572 (νCOO), 1363 (νCOO), 847 (phen), 490(νM–O), 431 (νM–N) cm–1.

C12H12CuN2O6S (2): Yield 85%, μeff = 2.51. Anal. found (calcd):C 38.88 (38.60); H 3.11 (3.19); N 7.56 (7.45); S 8.78 (8.51)%. IR:ν̃ = 1581 (νC=N), 1108 (νSO4), 847 (phen), 471 (νM–O), 430 (νM–N) cm–1.

C24H20CuN2O5S (3): Yield, 37%; μeff = 1.11. Anal. found (calcd):C 56.1 (56.3); H 3.90 (3.83); N 5.96 (6.08); S 5.96 (5.61)%. IR:ν̃ = 1632 (νCO), 1604 (νC=N), 1591 (νCOO), 1579 ((νCOO) (νCOO),1369 (νCOO), 690 (py), 466 (νM–O), 434 (νM–N) cm–1.

C48H38Cu2N4O11S2 (4): Yield, 45 %; Anal. found (calcd): C 55.2(55.5); H 4.03 (3.66); N 5.68 (5.39); S 5.75 (6.17)%. IR: ν̃ = 1593(νCOO), 1572 (νCOO), 1380 (νCOO), 649 (bipy), 471 (νM–O), 431(νM–N) cm–1.

C20H24Cu2N4O12S2 (5): Yield: trace; Anal. found (calcd): C 35.55(35.71); H 4.56 (4.76); N 8.44 (8.33); S 10.0 (9.52)%. IR: ν̃ = 1602(νC=N), 1115 (νSO4), 649 (bipy), 472 (νM–O), 431 (νM–N) cm–1.

2.4 X-ray Crystallography

Single-crystal X-ray diffraction data for 1–4 were collected at 100 Kwith a Rigaku AFC12 goniometer equipped with an enhanced sensitiv-ity (HG) Saturn 724+ detector mounted at the window of an FR–E+Superbright Mo-Kα rotating anode generator with optics (HF Varimax100μm focus for 1, 3 and 4 and VHF Varimax 70 μm focus for 2) andequipped with an Oxford Cryosystems Cobra[21] cooling device. Datafor 5 was collected at 200 K with a Bruker Kappa Apex II dif-fractometer with graphite monochromated Mo-Kα radiation (λ =0.71069 Å).

Cell determination, data collection, data reduction, cell refinement, andabsorption corrections were carried out using CrystalClear-SM Expert3.1 b27 software.[22] Structures 1, 3 and 4 were solved using Su-perflip[23] whilst structure 2 was solved using Patterson Methodswithin SHELXS.[22] All structures were refined using full-matrix least-squares refinements in the SHELX2013 software.[24] All non-hydrogenatoms were refined with anisotropic displacement parameters. Allhydrogen atoms were added at calculated positions and refined usinga riding model with isotropic displacement parameters based on theequivalent isotropic displacement parameter (Ueq) of the parent atom.Hydrogen atoms of water molecules O1W and O101 in structure 1

Z. Anorg. Allg. Chem. 2015, 890–895 © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim891

were restrained to a standard angle using the DANG restraint to main-tain sensible geometries. Figure 2 and Figure 3 were drawn usingOlex2.[25]

Crystallographic data (excluding structure factors) for the structures inthis paper have been deposited with the Cambridge CrystallographicData Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.Copies of the data can be obtained free of charge on quoting the de-pository numbers CCDC-1020627 (1) and CCDC-1020628 (3)(Fax: +44-1223-336-033; E-Mail: [email protected], http://www.ccdc.cam.ac.uk)

3 Results and Discussions

3.1 General

The synthesis and isolation of copper complexes 1–5 in thepresence of nitrogen donor ligands were carried out using theslow diffusion method under ambient temperature and pressureand the complexes were characterized by elemental analysis,FT-IR spectroscopy, and single-crystal X-ray analysis.

A layered solution of dtdb and phen in DMF on an aqueoussolution of CuCl2 resulted in the dimeric complex 1 (lightgreen), along with the polynuclear complex 2 (dark green).The reaction of bipy with dtdb and CuCl2 resulted in the for-mation of the square pyramidal complex 4 together with thepolynuclear complex 5. Under the same conditions, the use ofpyridine resulted in the dinuclear complex 3.

It is reported in literature that heterocyclic disulfide com-pounds can undergo either insertion or extrusion of sulfur oroxidation of sulfur to sulfonate ion.[19,26–31] Such S–S and C–S cleavage and rearrangement reaction or oxidation generallyproceed under solvothermal conditions[32–34] via oxidativecleavage, radical-assisted cleavage or nucleophilic cleavage,accompanied by a change in oxidation state of the metal insome cases.[35] In a previous study, Zhu et al. reported thereaction of bis[4-pyridin-2-yl)pyrimidinyl] disulfide (ppds)with Cu(NO3)2 under ambient temperature, in which ppds wasturned into its trisulfide 2-ppts and monosulfide 2-pps, prior tocoordination.[19] They also observed that such oxidative cleav-age and rearrangement were not effective with other aromaticdisulfides.[36] In some cases, the disulfide was oxidized to itssulfinate or sulfate ion under mild conditions after prolongedtime through slow evaporation of the coordination compoundsin their solutions used. However, in our research study, weobserved metal mediated desulfurization of dtdb after in situS–S and C–S cleavage and rearrangement generating tdb,which was simultaneously coordinated to the copper ion incomplexes 1, 3, and 4 (Figure 1). The structure of 4 has al-ready been reported by Lui et al.[37] and the authors used adifferent synthetic approach consisting of stirring dtdb, CuCl2,and bipy in the presence of NaN3.

All these reaction were performed under aerobic conditions.In complexes 2 and 5, oxidation of sulfur to sulfate ion wasobserved, where the copper atom is found to be in an octa-hedral geometry surrounded by one phen or bipy unit and twowater molecules in the equatorial plane and two sulfate mo-lecules in the axial position, giving rise to polymers. The X-




Figure 1. Schematic representation of the in situ ligand reaction.

ray structures of complexes 2 or 5 have been reported earlierwhereby the formation of the complexes were achieved withmetal sulfates, either in solvothermal, hydrothermal or conven-tional system.[38–40] However the synthesis reported hereinclearly presents a new route and is a rare example of metalcoordination obtained after extrusion and oxidation of S in thesame reaction system. In the presence of pyridine as co-li-gands, the formation of [Cu(py)2(SO4)2(H2O)2]n was not ob-served. This may be due to the fact that pyridine in the pres-ence of copper sulfate can be oxidized to pyridones, possiblyvia the intramolecular reaction of a base-CuII complex andhence did not form any complex with the copper salt.[41] Thiscurrent study highlights the crucial roles of metal in in situS–S bond changes, where such transition is more probably in-voked alone by metal-coordination effect.

Complexes 1–5 are air stable and maintain their crystallinity.They are also insoluble in common organic solvents and water,confirming their polymeric nature.

3.2 Infrared Spectroscopy

IR spectra of carboxylates are known to be helpful in de-termining their coordination modes with metals. The com-plexes showed double strong asymmetric frequency bands at1593–1572 cm–1, while the symmetric stretching bands ap-peared at 1380–1369 cm–1 for 1, 3, and 4 respectively.[42] Thepresence of characteristics band at 1632 cm–1 is due to theuncoordinated carboxylate in 3. The Δν [ν(OCO)asym –ν(OCO)sym] in 1, 3, and 4 is greater than 200 cm–1, indicatingmonodentate coordination for the carboxylate oxygens to themetal.[43] The IR spectrum of 1 exhibits a strong absorption at1660 cm–1 due to the trapped DMF molecule. Peaks at 3445–3364 cm–1 are attributed to the vibrational frequencies of watermolecules in the complexes.[44] The peak at 1108–1115 cm–1

can be assigned to the vibration of SO42– in 2 and 5.[45] The

new peaks at 490–466 and 430–434 cm–1 were due to M–Oand M–N vibrational frequencies.[46]


3.3 Structural Studies

The single-crystal X-ray structures were determined forC58H54Cu2N6O14S2 (1), C12H12CuN2O6S (2), C24H20CuN2O5S(3), C48H38Cu2N4O11S2 (4), and C12H12CuN2O6S (5). Crystal-lographic data and structural refinement parameters of 1 and 3are given in Table 1. Selected bond lengths and bond anglesof the complexes are given in Table 2.

Table 1. X-ray crystallography summary for structures 1 and 3.

1 3

Empirical formula C58H54Cu2N6O14S2 C24H20CuN2O5S1

Formula weight 1250.27 512.02Temperature /K 100(2) K 100(2) KWavelength /Å 0.71075 0.71075Crystal system triclinic monoclinicSpace group P1̄ P21/nUnit cell dimensionsa /Å 10.8790(8) 11.2119(8)b /Å 11.5638(8) 9.7392(7)c /Å 13.0647(10) 20.4526(14)α /° 115.991(5) 90β /° 97.565(5) 95.9160(10)γ /° 108.744(4) 90Volume /Å3 1325.38(18) 2221.4(3)Z 1 4ρcalc /mg·mm–3 1.566 1.531Absorption coefficient /mm–1 0.958 1.117F(000) 646 1052Crystal plate, green block, blueCrystal size /mm3 0.200�0.070�0.030 0.150�0.080�0.060θ range for data collection /° 3.121–27.485 3.015–27.481Reflections collected 17992 29415Independent reflections 6034 [0.0334] 5105 [0.0373]Completeness to θ max 99.7% 99.8%Max and min transmission 1.000 and 0.778 1.000 and 0.796Data/restraints/parameters 6034 / 2 / 384 5105 / 0 / 306Goodness-of-fit on F2 1.052 1.079Final R indexes [I � 2σ (I)] R1 = 0.0307, R1 = 0.0265,

wR2 = 0.0813 wR2 = 0.0718Final R indexes [all data] R1 = 0.0361, R1 = 0.0291,

wR2 = 0.0837 wR2 = 0.0732Largest diff. peak/hole /e Å–3 0.506/–0.376 0.386 and –0.286




Table 2. Selected bond lengths /Å and angles /° for 1 and 3.

1 3

Cu bond lengthsCu–N(C) N21–Cu1 2.008(2) 2.017(1)

N22–Cu1 2.040(2) –N31–Cu1 – 2.023(1)

Cu–O(C) O1–Cu1 2.201(1) 1.961(1)O4–Cu1 1.996(1) 1.966(1)

Cu–O(H2O) O1W–Cu1 1.966(1) 2.310(1)

Bond anglesC–S–C C7–S1–C8 102.33(8) 101.22(7)

Torsion anglesC–C–S–C C2–C7–S1–C8 171.53(14) –174.29(12)C–S–C–C C7–S1–C8–C13 105.94(17) –96.26(13)

Angle between planesRing 1 – Ring 2 N�N–tdb A 73.33(8) 77.98(8)

N�N–tdbA (2nd 22.97(8)pyridine)

Ring 1 – Ring 3 N�N–tdbB 38.96(8) 69.88(8)N�N–tdbB (2nd 26.23(8)pyridine)

Ring 2 – Ring 3 tdb A – tdbB 79.08(10) 85.72(7)

3.3.1 [Cu(tdb)(phen)(H2O)]2·2H2O.2DMF] (1)

The X-ray analysis shows that the copper atom in 1 adoptsa square pyramidal arrangement, bonding to two oxygen atomsfrom two different tdb ligands in an asymmetric and mono-dentate fashion, with Cu–O bond lengths being 1.966 and

Figure 2. (a) The X-ray crystal structure of [Cu(tdb)(phen)(H2O)]2·2H2O·2DMF] (1). Thermal ellipsoids are drawn at 50% probability level.All hydrogen atoms are omitted for clarity. (b) Molecular structure of 1 viewed along c axis in its dimer form, solvent included (DMF andwater).


2.200(2) Å (Figure 2). The Cu atom is further bonded to twonitrogen atoms of phen and one water molecule. The bondlengths of Cu–O and Cu–N [2.009–2.040(2) Å] are in the nor-mal range and similar to those found in other copper com-plexes.[47–52] The bond length of C–S is 1.789(2) Å, corre-sponding to a single bond and is within the average C–S bondlength [1.781(1) Å] reported for related structures.[53] Cop-per(II) ion is known to be Jahn teller active and hence adopts[4 + 2] coordination environment, with two long axial bondsand four shorter equatorial ones. The arrangement of 1 couldbe considered to be the same but with one equatorial sitevacant, therefore making it square pyramidal. N21(phen),N22(phen), O4(tdb), and O1W(coordinated water) occupy theequatorial sites, whilst O1 (tda) occupies the axial position.The bond angles accordingly deviate appreciably from 90° andvary from 95.17(5) to 103.15(5)° for the O–Cu–O andN–Cu–O angles. In addition, the N21–Cu–N22 bond angle is81.56(6)° and deviates from a perfect right angle. In complex1 the coordinated water is ca. 180° to the N containing ligand,with the Cu–O(H2O) bond length being 1.966(1) Å. The Cu–Cu distance is 6.613 Å, which is longer than the van der Waalsradii sum for copper atoms (2.8 Å) and clearly shows that thereis no interaction between the copper atoms.[54] In structure 1,discrete dimers pack in such a way that the phenanthrolinegroups are π–π stacked with respect to each other. Presence oftrapped solvent molecules is also observed in the crystal latticeand they participate in hydrogen bonding to the oxygen atoms,which are not bound to the central CuII atoms.




Figure 3. (a) The X-ray crystal structure of [Cu(tdb)(py)2(H2O)]2 (3). Thermal ellipsoids are drawn at 50% probability level. All hydrogenatoms are omitted for clarity. (b) The X-ray crystal structure of [Cu(tdb)(py)2(H2O)]2 (3) displaying the polymeric chain.

3.3.2 [Cu(tdb)(py)2(H2O)]2 (3)

Complex 3 crystallizes in a monoclinic system with spacegroup P21/n. The CuII ion in 3 is coordinated to two py, twooxygen atoms from two different tdb ligands, and one watermolecule in the axial position and the coordination environ-ment around the metal can be described as a distorted squarepyramidal arrangement. The bond lengths of Cu–O, Cu–N, andC–S are 1.962–2.310(1), 2.017–2.023(1), and 1.785(2) Å. TheCu–Cu distance of 7.709 Å is longer than the sum of the vander Waals radii (2.8 Å) as well as that in complex 1, showingthat there is also no interaction between the copper atoms incomplex 3. In complex 3, the water molecule is coordinated atca. 90° to the pyridine, with the Cu–O(H2O) bond length beinglonger than in complex 1 (2.310 Å). The two central copperatoms in 3 bond through O1 and O4 of two tdb ligands, form-ing 1D polymeric chains, which run along the crystallographicb axis (Figure 3).

3.3.3 [Cu(tdb)(bipy)(H2O)]2·0.5H2O (4)

The crystal structure of 4 has already been reported by Luiet al.[38] The copper atoms, tdb and bipy ligands combine to-gether via the oxygen atoms to form polymeric chains alongthe c axis. Water molecules reside in the channels between thepolymeric chains along both the crystallographic a axis andthe crystallographic b axis.

4 Conclusions

This work shows the unusual and simultaneous S–S andC–S scission in dithiodibenzoic acid under slow diffusion con-ditions mediated by copper chloride leading to the formationof 1D coordination polymers. In the case of phen and bipy, inaddition to extrusion of sulfur atom, the oxidation of sulfur tosulfate ion was observed. Future effort will be needed to clarifythe detailed mechanism involved in these in situ reactions.


Acknowledgements

One of the authors is thankful to Tertiary Education Commission ofMauritius for financial grant. We thank Dr. Eric Hosten from NelsonMandela Metropolitan University (South Africa) for the X-ray struc-ture of compound 5.

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Received: January 29, 2015Published Online: March 6, 2015

Novel Copper(II) Thiodibenzoic Acid Coordination Polymers by in situ Extrusion of Sulfur from...

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