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Characterization of New Inorganic- Organic HybridCompounds: (C6H10N2).Cl2 (I), [C6H10N2]2ZnCl4(II): Crystal Structure, Hirsch�eld Surface, IR andNMR spectroscopy Analysis.nejeh hannachi  ( hnejeh@yahoo.fr )

University of Sfaxfaouzi hlel 

University of Sfax

Research Article

Keywords: Crystal structure, Hirshfeld surface, 13C NMR- MAS, vibration absorption

Posted Date: August 18th, 2021

DOI: https://doi.org/10.21203/rs.3.rs-803292/v1

License: This work is licensed under a Creative Commons Attribution 4.0 International License.  Read Full License

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AbstractTwo new organic-inorganic hybrid materials, (C6H10N2).Cl2 (I) and [C6H10N2]2ZnCl4 (II), have beensynthesized by hydrothermal method and characterized by single-crystal X-ray diffraction and XRDpattern investigations. These two compounds are crystallized in the monoclinic system; C2/c spacegroup. In the both structures, the anionic-cationic entities are interconnected by hydrogen bondingcontacts and p-p Interaction forming three-dimensional networks. Intermolecular interactions wereinvestigated by Hirshfeld surfaces and the contacts of the four different chloride atoms in (II) werecompared. The vibrational absorption bands were identi�ed by infrared spectroscopy. These compoundswere also investigated by solid state 13C NMR spectroscopy. 

1. IntroductionOrganic-inorganic metal halides have captivated vigorous concern in the last decades due to bothtechnological features as well as potential applications in several physical properties [1-4]. It was due tothe possible interactions connecting of the organic and inorganic species that show weak interactionsbetween the two phases, such as Van Der-Walls, hydrogen bonding or weak electrostatic interactions [5–7] characteristics with potential phase transition materials and lightness [8–10]. This materials stand for anovel designing of managing the assembling of an extensive variety of structurally well-de�nednanoobjects arranged in a hierarchical order is organized with regard to their structures and functions[13–14].

Nitrogen containing organic species, which may be aliphatic or aromatic amines [15, 16], are goodcandidates for synthesis due to their ability to form covalent or iono-covalent bonds with the metallicanions suchas Cd, Zn, Cu… [17–19]. Hydroxyl and nitrogen containing linkers exhibit a versatilecoordination behavior displaying distinct bonding modes toward metal anions [20, 21]. The hydrogenbonds of hybrid compounds occupy a great interest [22–23].

Especially, research on metal-organic crystals is investigated tremendously with this perspective. Theorganic crystal structure is built on the π-bond co-ordination extended over a large length scale of themolecule, which can be very easily manipulated by substitution of electron donating and electronwithdrawing groups around the aromatic moieties [24].

The organic materials possess excellent nonlinear coe�cient, manipulate and incorporate into differentstructures and are having low mechanical strength and poor thermal behaviors leads to laser damageduring processing. In contrast, the inorganic compounds have good mechanical and thermal propertiesdue to the lack of π-electron delocalization. Hence, there is a possibility to solve this problem to preparethe semi-organic crystals which combine the positive features of inorganic and organic compoundscausing good physical properties [25]

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Zinc is one of the most abundant metals in the human body, and it plays an important and indispensablerole in biological systems [26]. In addition, the basic zinc hybrids have proved physical properties [27–28];etc… Also, the zinc complexes exhibit a wide range of coordination numbers and geometries; tetrahedral[29, 30], trigonal bipyramidal [31], and octahedral [32–35].

In addition, to the study of this compound family, we focus in this work on the synthesis and the crystalstructure of the title compound (C6H10N2).Cl2 (I). This material can be easily incorporate with the d block

transition metal ions such as Cd2+, Zn2+, Hg2+. The electron �lled ‘d’ shells into organic compoundscreates more energy sublevels and enhances the optical non-linearity through a charge-transfermechanism. In this case, the Zn2+ is added to the 1,2-diaminobenzene cations was protonated andcombined sandwiched between anionic layers, formed by isolated tetrachloridozincate forming a new[C6H10N2]2ZnCl4 (II). XRD pattern investigations, single crystal X-ray diffraction, Hirshfeld surface; 13C CP-MAS NMR and vibration absorption for the purpose of con�rming its purity and investigating thestructural properties marked the compounds’ synthesis.

2. Experimental Procedure

2.1. Material synthesisThe synthesis of the single crystal of (C6H10N2).Cl2 (I) and [C6H10N2]2ZnCl4 (II) compounds was carriedout at home-built Te�on-lined stainless steel pressure bombs of 90 ml maximum capacity as follow : 1,2-benzen diammonium C6H8N2 (sigma aldrich) was dissolved in a mixture of distilled water (10 mL) andHydrochloric acid (0.5 mL) (sigma aldrich) for a few minutes with agitation successive to ensurecomplete dissolution. Second, such solutions were slowly combined in an autoclave and kept at 95°Cunder auto-genous pressure for 24h. After cooling these solutions for �ve days at room temperature,colourless single crystals C6H4(NH3)2.Cl2 (I) suitable for an X-ray structure.

-1, 2-benzen diammonium C6H8N2 (0.0801 g; 0.622 mmoles) and zinc chloride ZnCl2 (0.5032 g; 1.88mmoles) (sigma aldrich) were dissolved in aqueous solution of HCl (1M; 37%) for a few minutes withagitation successive to ensure complete dissolution of the compound hydrochloric acid (pH ≈ 1.8).Themixture was placed in a Te�on-lined autoclave that was then sealed and heated to 95°C for 24 h. It wasthen allowed to cool to room temperature in a cold water bath. Autoclaves were opened in the air, andproducts were recovered through �ltration. White stick-shaped crystals [C6H10N2]2ZnCl4 (II) with suitabledimensions for crystallographic study were recovered.

Schematically the reaction is shown in the following equation:

2.2. Powder X-ray diffraction and single-crystal datastructure determination

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Phase purity and homogeneity of synthesized of both compounds were determined by x-ray powderdiffraction recorded at room temperature in the angular range 5° < 2θ < 80° (Fig. 1) with a step Δ (2θ) =(0.0170)° using a X’Pert PROMPD diffractometer with CuKα1 radiation (λKα1 = 1.540598 Å).

Suitable crystals selected through an optical examination were mounted a intensity data were obtainedon a D8 VENTURE Bruker AXS diffractometer equipped with a (CMOS) PHOTON 100 detector using MoKα radiation (λ = 0.71073 Å, multilayer monochromator) through the Bruker AXS APEX2 Software Suite[36].

Frame integration and data reduction were carried out with the program SAINT [37]. The programSADABS [38] was then employed for multiscan-type absorption corrections. The crystal structure wassolved in the monoclinic symmetry, space group C2/c;of two compounds, respectively; according to theautomated search for space group available in Wingx [39].

Zinc and chloride atoms were located using the direct methods with the program SIR-2014 [40]. C and Natoms from the amine were found from successive difference Fourier calculations using SHELXL-2014[41]. Their positions were validated from geometrical considerations as well as from the examination ofpossible hydrogen bonds. H atoms were positioned geometrically and allowed to ride on their parentatoms. Structural drawings have been made by Diamond 2 [42] program. Crystallographic data are givenin Table 1.

2.3. Spectroscopy measurements (IR / NMR-MAS)The IR absorption spectrum of the crystallized powders in KBr was recorded on a Perkin- Elmer FT-IR 1000spectrometer in the 400–4000 cm− 1 range. Cross polarization (CP) is to take advantage of the presenceof spins abundant (1H) that we will excite to be able to cause a transfer of energy towards the spinsscarce (13C). This transfer will be much more effective than just irradiation one could practice on thesmall nuclei. The technique cross-polarization (CP) is applied to types of acquisitions. All chemical shifts(d) are given with respect to tetramethylsilane for 13C. According to the IUPAC convention, shieldingcorresponds to negative values. Spectrum simulation was performed by using Bruker WINFIT software[43]. The NMR-MAS experiments were performed at room temperature on a Bruker WB 300. Then, thepowdered sample was packed in a 4 mm diameter rotor and set to rotate at a speed up to 8 kHz with63.669 resonance frequency in a Doty MAS probehead. During the whole acquisition time, the spinningrate of the rotor was locked to the required value using the Bruker pneumatic unit which controls bothbearing and drive inlet nitrogen pressures. The 13C spectrum was collected by a cross-polarization ofproton with 5 ms contact time.

2.4. Hirshfeld surfaces analysisHirshfeld surface analysis is a powerful tool for obtaining additional information on the intermolecularinteraction of molecular crystals. The size and the Hirshfeld surface form allow (allow) qualitative andquantitative investigation and visualization intermolecular close contacts in molecular crystals [44] .The2D �ngerprint of the Hirshfeld surface represents a new method for summarizing the complex

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information contained in a molecular crystalline structure in a single plot single color, which provides a"�ngerprint" of intermolecular interactions in the crystal.

The combination of de and di in the form of a 2D �ngerprint provides a summary of the contactsintermolecular in the crystal and complement the Hirshfeld surfaces [45]. Such parcels provideinformation on intermolecular transport interactions in the immediate environment of each molecule inthe asymmetric unit.

3. Results And Discussions3.1. Structural resolution 

XRD description:

The room temperature powder X-ray patterns of the (I) and (II) compounds are shown in Fig. 1. Theformation of pure phase for the both compounds without secondary phases has been con�rmed. Thepeaks are �ne, indicating that the samples are well crystallized. All the re�ection peaks were indexed inthe monoclinic system with the space group. All the re�ection peaks were indexed in the monoclinicsystem with the space group C2/c. The lattice parameters were re�ned using the least-squares subroutineof a standard computer program. These re�ned lattice parameters of (C6H10N2).Cl2 (I)and [C6H10N2]2ZnCl4 (II) compounds are: a= 7.267(7) Å; b=14.403(1) Å, c=7.941(1) Å, β=94.568(2)°, V=

828.592(2) Å3 ; a= 7.411(7) Å; b= 25.585(1) Å, c=9.342(1) Å, β=94.022(2)° and V=1776.93(2) Å3,respectively. The unit cell parameters are in good agreement with the single crystal X-ray values.

Structure description of  (C6H10N2).Cl2  compound (I) :

The structure of (C6H10N2).Cl2 compound (I) was solved in the monoclinic system, C2/c space group witheach molecule occupying a general position within the unit cell. The unit asymmetric of compound (I)(Fig. 2) consists of two isolated chloride atoms and half of the organic cation [C3H5]+. A projection along

the c-axis of the structure can be described by alternating [C6H10N2]2+ cationic layers and Cl- anioniclayers (Fig.3) through extensive intermolecular N-H...Cl interactions. 

Indeed, the pyridine rings of the original 1,2-benzen diammonium have undergone bi-protonation (H+)during the synthesis process. The organic layer, observed at z/b=1/4, is formed by the cations[C6H10N2]2+, arranged parallel plane in the (a) direction and interconnected via a p-p interaction. 

In the half cation the C-C/C-N bonds are almost equivalent: C2-C3=1.3867(2)Å; C3-C4=1.3929(2)Å and C2-N1=1.4607(2) Å. The C-C-C and C-C-N angles vary within the range from 119.40(1)° and 119.815(1),respectively. The main inter atomic distances and angles in the cation are reported in Table 2. Thesevalues are in agreement with those observed in similar compounds [46-48]. Indeed, the crystal packing is

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assured by three hydrogen bonds (N-H…Cl), N1-H1A···Cl1, N1-H1B···Cl1ii, N1-H1C···Cl1iii (for details andsymmetry code, see Table 5).

Structure description of  [C6H10N2]2ZnCl4 (II) compound (II) :

The crystallographic analysis revealed that the complex [C6H10N2]2ZnCl4 (II) crystallized in the monoclinic

system, space group C2/c, involving the coordination of 1,2-benzen diammonium cation to the Zn2+

anions. It is a three-dimensional (3-D) structure with an asymmetric unit of one [C6H10N2]2+ cation and

one [ZnCl4]2- (Fig. 4). Their following unit cell dimensions are grouped in Table 1.

Projections along the c-axis of the structure present tetrahedral layers, [ZnCl4]2-, sandwiched between two

layers of pyridinium cations [C6H10N2]2+ (Fig.5.a).

The organic part is formed by a single type of cation [C6H10N2]+ (Fig.5 a and b). The main details ofinteratomic distances and angles are summarized in Table 3. Bond distances and angles in the cationsare normal [49-50], with average of C-C= 1.389(6)Å, C-N= 1.439(5)Å, C-C-C= 119.998(3)° and C-C-N=120.035(2)°. The small angle is of the order of 117.67(2) presents a small variant with that observed inbenzene; this is due to the link N-H…Cl. Protonation double in N in�uences the angles, which indicates�attening of the benzene. A similar behaviour was noticed earlier for quinine and cinchonine [51-52].Furthermore, an in�uence of the proton (H+), attached to the nitrogen atome (N1 or N2), on thesurrounding of this atom may be estimated by a parameter called pyramidality [53]. The C-C distancesequal to 1.383 Å and C-C-C angles equal to 120° [54]. This variation is due to the existence ofintermolecular interactions. The protonation in the N site is well con�rmed by the C-NH3 bond length, infact the distance C1-N2 is equal to 1.413(2) Å, which is signi�cantly longer than in the case of the C-NH2molecule ( CN = 1.335 (3)) [55], the CCN angles range from 119.01 (2)° to 121.45 (2)° .

Geometry and coordination of the anion [ZnCl4]2-: 

The inorganic layer is made up of  [ZnCl4]2- tetrahedral, observed at z/c=1/4 and z/c= 3/4 (Fig. 5 a). Thefour distances between Zn-Cl ranged from 2.2561(4) to 2.2938(4)Å. They are equivalent two to two. SixCl-Zn-Cl angles are varied between 105.155(16)°  and 115.72(3)°.  They are grouped by three, two and awide angle of the order of 115.72(3) (for details see Table 4). These values are in agreement with thoseobserved in similar compounds [56-59].

From the geometric parameters, the [ZnCl4]2- anion has a slightly distorted tetrahedral stereochemistry.The Baur distortion indices [60]  can be calculated using the expressions:

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Where d is the (Zn-Cl) distance, a is the (Cl-Zn-Cl) angle, m is the average value, n1 = 4, and n2 = 6. Thevalues of these indices were 0.00206 and 0.00438, respectively. These Baur's distortion values indicatethat the [ZnCl4]2- tetrahedral; of the Zn metal is less distorted. This slight distortion is correlated todeformations resulting from hydrogen bonding interactions (Table 5). This distortion can be explained bythe stereochemical inactivity of the 5s2 lone pair of Sn (IV) and also by the fact of interaction of [ZnCl4]2-

tetrahedral with neighbors molecules by the means of different hydrogen bonds. A more complete listingof bond distances and angles is given in Table 4.

Hydrogen bonding interactions

The assembly between inorganic and organic entities in the isostructural compounds is provided byhydrogen bonds of the N-H...Cl type. Hence, these interactions have a crucial role in the formation of 3Dsupramolecular structures. The hydrogen bond parameters are given in Tables 5  and 6.

For the compound (I), the N...Cl distances are between 3.093 Ǻ and 3.105 Å and the H ... Cl distances arein the range of 2.266 Ǻ to 2.314 Ǻ. However the NH ... Cl angles vary between 151.34 ° and 168.24 °(Table 5) . 

For the compound (II), the greatest N...Cl distance is 3.712(2) Å and the H ... Cl distances are in the rangeof 2.40(3) Ǻ to 2.93 Ǻ. However the NH... Cl angles vary between 113.4(2)° and 161(2)°. Whereas the N-Hangle ••• N is in the range 123 ° and 153 ° (Table 6). It is deduced that the NH ... N hydrogen bonds aremoderate [61-65].

By comparison between the NH...Cl angles we note that those of the compound (II) are larger. These aredue to the chlorine atoms bound to the Zinc atom, against the chlorine of the �rst compound is free.

Based on values of tables 4 and 5, it can be concluded that the hydrogen bonds are weak [66]. Thecations are connected to each other by π-π stacking interactions. 

3.2  Hirsh�eld surface :

Hirchfeld surfaces, which define the electron density weighing the boundary surfacesbetween molecules in a crystal, are useful for analyzing and displaying intermolecularcontacts [67-68].

The Hirshfeld surfaces of the both compounds are showed in Fig. 6. and Fig.7. Hirchfeld molecularsurface calculations were performed using the Crystal program Explorer [69-70], CIF �les have beenregistered in this program. Hirchfeld surfaces are calculated using the following equation:

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Some parameters can be plotted on Hirshfeld surface: 

-de is the distance from the Hirshfeld surface to the nearest nucleus outside the surface, 

-di is the corresponding distance to the nearest nucleus inside the surface, 

- and dnorm is a normalized contact distance and is the sum of these two (di and de) normalized by thevan der Waals radii quantities.

The dnorm value is negative or positive when the intermolecular contacts are shorter or longer than theVan Der Waals (VDW) rays, respectively. The Hirshfeld surface uses a red - blue - white color scheme: thered regions represent the closest contacts and a negative reference value; the blue regions representlonger contacts and a positive dnorm value; and the white regions represent a contact distance exactlyequal to the VDW separation with a dnorm value of zero [71].

D �ngerprints of the Hirshfeld surface of the study structure to highlight atoms involved in close contact[72-73].

Fig. 8 illustrates the 2D �ngerprint of all the contacts contributing to the Hirshfeld surface ofC6H4(NH2)2.HCl (I) compound. The graph in Fig.9 illustrates the 2D Fingerprint of all the contactscontributing to the Hirshfeld surface of [C6H10N2]2ZnCl4 (II) compound, associated with the hydrogenatoms.

These graphs represents the H-Cl / Cl-H contacts between the hydrogen atoms located inside theHirshfeld surface and the externally located in chlorine atoms and vice versa. The H-Cl / Cl-H contactshave the largest contribution to the total Hirshfeld surface (41.9%).

Thus the intermolecular interactions H ••• ClCl • •• H and H ••• H were the most abundant in thecrystallization. It is obvious that the van der Waals forces exert an important in�uence on the stabilizationof settlement in the crystalline structure. While other interconnects contribute

less to Hirshfeld surfaces: H-C / C-H (7.6%)(Fig. 8 c) .However, the contacts Cl-Cl (Fig.8 f), C-Cl / C-Cl (Fig.8 f) and N-H / H-N (Fig.8 g) have contributions of very small percentages of interactions (0.6%), (0.1%)and (0.2%), respectively.

In order to give some insight into the nature of forces stabilizing the discussed structures, theintermolecular interactions were analyzed with the help of Hirshfeld surface. The 3D Hirshfeld surfaceand 2D �ngerprint histogram of the title molecule of for the [C6H10N2]2ZnCl4 (II) were given in Figure 9.This state indicates presence of the C-H…Cl type intermolecular hydrogen bond interactions in crystalstructure. The C-H…Zn type intermolecular hydrogen bond distances in crystal. Similarly, as seen fromcrystallographic analysis, the contact distances between Cl are obtained between and hydrogen atomshave considerable small values and the Cl-H/H-Cl interactions contribute to Hirshfeld surface with 34.2%

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value. The major contributions to Hirshfeld surface are H-H with 32.2% and C-H/H-C with 7.3%. The�ngerprint of [C6H10N2]2ZnCl4 (II) compound, suggest that the H···H and C···H contacts dominate thecrystal interactions. However, these interactions present higher interatomic distance. Interactions withless interatomic distance (stronger interactions) are observed in �ngerprint plots as pointy regions. TheH···H contacts are present in higher percentages on the surface probably due to the close packing,resulting in the greater proximity between the molecules in the crystal arrangements. Contacts for C···Hpresents contributions with close values in the crystalline forms, smaller in polymorph II. The wingsrepresent contacts C–H ··π, present in all cases. 

3.3 IR and NMR Spectroscopy studies.  

The IR spectrum of crystal compound of (C6H10N2).Cl2 (I) and [C6H10N2]2ZnCl4 (II) is shown in Figure 10and 11 at room temperature respectively ; to give more information on the crystal structure. A band at3400 cm-1, attributed to asymmetric, stretching vibration νas (NH3), and a less intense band at 3370 cm-1

relative to the symmetrical elongation vibration νs (NH3). The modes of vibration (C-H) of the benzene

nucleus appear at 3220 cm-1 and 2800 cm-1.

 The band at 1497 cm-1 is attributed to C = C elongation vibration and the two vibration bands (C-C) arelocated between 1500 cm-1 and 1526 cm-1. Two bands: one at 1253 cm-1 relative to asymmetric valencevibration νas (C-N) and the other less intense at 1189 cm-1 correspond to symmetric valence vibration νs(C-N). The more intense band at 778 cm-1 attributed the off-plane aromatic (CH) bond, while the twomoderately intense bands in the 479-515 cm-1 frequency range corresponds respectively to δ (CCN) andtorsion outside the plan of the group NH3. We conclude that infrared spectroscopy con�rms the presence

of the [C6H4 (NH2)]2+ cationic part of our compound (C6H10N2).Cl2 (I) [74-78].

The IR spectrum has several bands that can be assigned as follows:

-The bands observed at high frequency between 3550 and 3800 cm-1 in IR is related to symmetrical andasymmetric stretching of an amine group (NH2). In addition, the groups observed in 3100, 3300 cm-1 in IRare attributed to symmetric and asymmetric NH stretching.

 a wide band containing two signals, one around 2800 cm-1 and the other at 2550 cm-1, correspond to theelongation vibrations of (= C-H).

-The bung, which is located at 1620 cm-1 is probably due to the shear vibration of δ (NH2) which is

combined with (N-H) + of the symmetrical plane (sway) appearing at 1500 cm-1.

-The band observed at 1498 cm-1 is attributed to (C = C) elongation vibration. Stretching vibrations (C-C)were observed at 1250 cm-1. A stretching, vibration (C-N) appeared at 1200 cm-1. The symmetrical off-plane vibration (C-H) (C-H wagging oop) created a band at 750 cm-1.

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- The band observed at 738 cm-1 is attributed to (C - C) torsional vibration. Finally, the intense peak thatappeared at 450 cm-1 is due to the band (C-N) in the plane of �exion.

 -The bands observed at 450 cm-1 correspond to (C-C-C) in the plane.

 In conclusion, the infrared study only con�rms the presence of the organic group [C6H9N2]2+.

The experimental spectrum (in blue) and the spectrum obtained by smoothing, using the β-DMFITsoftware (in red) are shown in Fig. 12.

The isotropic band of 13C CP-MAS-NMR spectrum of the crystalline powder sample rotating at the magicangle with frequency 8 kHz illustrated in Fig. 11. Spinning the sample at different frequencies allows usto identify the isotropic band. The spectrum is composed of three isotropic bands P1, P2 and P3.Simulation of the isotropic bands permits to identify twelve peaks using Gaussian-Lorentzian functionsby means of a Dm�t program [43] (Table 7).The deconvolution of three signal shows con�rm that thenitrogen-bonded atoms (heteroatom) with a higher electronegativity undergo the phenomenon ofshielding consequently these carbon atoms move towards the high chemical shifts in ppm, correspond tothe P1 band (to 268.83 at 135.74 ppm). The least shielded peaks observed towards the low ppm; P2 band(130.97 at 117.28 ppm) correspond to the ring carbon atoms not bound to the most unshielded carbonnitrogen atoms; P3 band (108.82-87.75 ppm) (Table 7). The chemical shift values were commonlyobserved in similar compounds  [79-80].

This study shows that the compound consists of organic groups that have non-equivalent carbons. Thisresult will be con�rmed by the study of single-crystal X-rays.

4. ConclusionIn conclusion, the study of newly-prepared hybrids (C6H10N2).Cl2 (I) and [C6H10N2]2ZnCl4 (II) compounds.This studies has revealed that new both compounds were found to crystallize in the same crystallinesystem and the same space group; monoclinic C2/c. Whose their structural arrangements can bedescribed as an alternation of organic–inorganic layers, are performed via N-H…Cl hydrogen bonding andπ-π stacking interactions. Hirshfeld surface analysis reveals the percentage of intermolecular contacts ofthe both compounds. Furthermore, the infrared study con�rms the presence of the organic group[C6H9N2]2+. Moreover, Solid state NMR spectra showed three isotropic bands P1, P2 and P3, correspondto the non-equivalent carbon atoms. Thus con�rming the solid state structure determined by X-raydiffraction. 

DeclarationsAcknowledgments : This work was supported by the Ministry of Higher Education and Scienti�c Researchin Tunisia, Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) and National Center for

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Research in Materials Science (CNRSM), laboratory for the valorization of useful materials (LVMU),  Borjcedria in Tunisia.

Supplementary material 

CCDC 1916484 (C6H10N2).Cl2 (I) and CCDC 1881531 [C6H10N2]2ZnCl4 (II) contains the supplementarycrystallographic data for this paper. The data can be obtained free of charge at http://www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data Center, 12 Union Road, CambridgeCB2 1EZ, UK; fax: 44 1223 336 033; E-mail: deposit@ccda.cam.ac.uk.

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TablesTable 1: Summary of crystal data and structure re�nement

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Complex 

Empirical formula

(C6H10N2).Cl2 (I) [C6H10N2]2ZnCl4 (II)

Formula weight (g.mol-1) 181.06 425.47

Crystal system/ Space group Monoclinic, C2/c Monoclinic, C2/c

Temperature (K) 150 150

Unit cell dimensions 

a (Å)

b (Å) 

c (Å)

 

7.284(9) 

14.498 (2) 

7.945 (1)

 

7.443(3)

 25.598 (1)

 9.354 (1)

β (°) 94.676 (5) 94.017(2)

V (Å3)/ Z 836.4 (2)/ 4 1777.86 (14)/ 4

Radiation Mo Kα Mo Kα

µ (mm−1) 0.703 1.980

h, k, l ranges -7≤h≤9

 -18≤k≤18

-10≤l≤10

-9≤h≤9

 -33≤k≤29

-12≤l≤12

Crystal size  (mm) 0.58 × 0.51 × 0.35 0.51× 0.54 × 0.58

Re�ections     collected /unique /  

observed re�ections  [I > 2σ(I)]

3745 / 967 / 

 

930

7007 / 2003 / 

1893

Rint 0.0345 0.0259

(sin θ/λ)max (Å−1) 0.649 0.649

Structure re�nement with SHELXL-97 SHELXL-97

Goodness of �t 1.333 1.064

Final R and Rw 0.345/0.0983 0.0259/0.0665

Re�nement F2 full matrix F2 full matrix

Re�ned parameters 56 67

Δρmax, Δρmin (e Å−3) 0.8 ; −0.694 0.743 ; −0.69

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w=1/[\s^2^(Fo^2^)+(0.0544P)

^2^+0.3015P] 

where P=(Fo^2^+2Fc^2^)/3

w=1/[\s^2^(Fo^2^)+(0.0309P)^2^+3.1449P] 

where P=(Fo^2^+2Fc^2^)/3

Table 2 : Principal interatomic distances (Å) and angles (°) of organic groups of (C6H10N2).Cl2 (I).

   

                           Distances (Å)             Angles(°)                           

Cation  N1—C2 1.460(2) C3—C2—N1 118.66(1)

  C2—C3 1.386(2) C3—C2—N1 120.97(1)

  C3—C4 1.392(2) C2—C3—C4 119.40(2)

Table 3 : Principal interatomic distances (Å) and angles (°) of organic groups of [C6H10N2]2ZnCl4 (II).

   

                           Distances (Å)             Angles(°)                           

Cation  N1—C2 1.466(2) C3—C2—N1 119.01(2)

  N2—C1 1.413(2) C1—C2—N1 119.03(2)

  C2—C3 1.390(3) C2—C1—N2 121.45(2)

  C2—C1 1.393(2) C6—C1—N2 120.65(2)

  C3—C4 1.382(2) C3—C2—C1 121.91(2)

  C4—C5 1.391(3 C4—C3—C2 119.65(2)

  C5—C6 1.386(3) C3—C4—C5 119.27(2)

  C6—C1 1.396(3) C6—C5—C4 120.82(2)

  C5—C6—C1 120.67(2)

  C2—C1—C6 117.67(2)

Table 4 : Principal interatomic distances (Å) and angles (°) of inorganic groups of [ZnCl4]2- 

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                           Distances (Å)             Angles(°)                           

Cation  Zn1—Cl2 2.256(4) Cl2—Zn1— Cl 2 115.72(3)

  Zn1—Cl2 2.256(4) Cl2—Zn1— Cl 1 105.15(2)

  Zn1—Cl1 2.293(4) Cl2—Zn1— Cl 1 110.27(2)

  Zn1—Cl1 2.293(4) Cl2—Zn1— Cl 1 110.27(2)

  Cl2—Zn1— Cl 1 105.15(2)

  Cl2—Zn1— Cl 1 110.31(2)

Table 5: Hydrogen Bonds in the Structure (I) (Å and °).

D-H d(D-H) d(H···A) <DHA d(D···A)

N1-H1A···Cl1 0.88(3) 2.294 166.22 3.104(6)

N1-H1B···Cl1ii 0.88(3) 2.266 168.24 3.104(6)

N1-H1C···Cl1iii 0.89(3) 2.314 151.34 3.092(5)

Codes de Symétrie : (ii) −x+3/2, -y+1/2, −z+1 ; (ii) −x+1, y, −z+1/2 

Table 6 : Hydrogen Bonds in the Structure (II) (Å and °).

D—H···A D—H H···A D···A D—H···A

N1—H1A···N2ii 0.84 (3) 2.20 (3) 2.970 (2) 153 (2)

N1—H1A···Cl1iii 0.84 (3) 2.83 (2) 3.2563 (2) 113.4 (2)

N1—H1B···Cl1iv 0.92 (3) 2.40 (3) 3.2854 (2) 161 (2)

N1—H1C···Cl2 0.89 (3) 2.44 (3) 3.2589 (17) 154 (2)

N1—H1C···Cl2iv 0.89 (3) 2.88 (2) 3.3485 (18) 115.0 (2)

C6—H6···Cl2ii 0.95 2.93 3.712 (2) 140.1

N2—H2A···Cl1v 0.91 2.63 3.4089 (17) 143.8

N2—H2B···N1ii 0.91 2.38 2.970 (2) 123

N2—H2B···N2ii 0.91 2.62 3.427 (3) 147.8

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Table 7 : 13C cross-polarization NMR MAS of the synthesized compound at 8 kHz.

Figures

Page 22/32

Figure 1

X-ray Powder diffraction pattern of: (a) (C6H10N2).Cl2 (I) and (b) [C6H10N2]2ZnCl4 (II) at roomtemperature.

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Figure 2

Unit asymmetric of (C6H10N2).Cl2 (I) structure.

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Figure 3

A projection, along the c axis, of the layers in the structure of (C6H10N2).Cl2 (I).

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Figure 4

unit asymmetric of [C6H10N2]2ZnCl4 (II) structure.

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Figure 5

(a and b): Packing diagram of [C6H10N2]2 ZnCl4 (II) viewed parallel to the a-axis (a). All atoms areshown as spheres of arbitrary size. Dashed lines represent N-H…Cl contacts from hydrogen bonds (b).

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Figure 6

Hirshfeld surface analysis of (C6H10N2).Cl2 (I), dnorm (a) di (b) de (c).

Figure 7

Hirshfeld surface analysis of [C6H10N2]2ZnCl4 (II), dnorm , di and de.

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Figure 8

Fingerprint of all the contacts contributing to the Hirshfeld surface of (C6H10N2).Cl2 (I) compound: (a) H-H contacts, (b) HCl/HCl, (c) H-C/C-H, (d) all intermolecular contacts, (f) Cl-Cl, (g) C-Cl/Cl-C and (h) N-H/H-N.

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Figure 9

Fingerprint of all the contacts contributing to the Hirshfeld surface of [C6H10N2]2ZnCl4 (II) compound.

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Figure 10

Infrared spectrum of (C6H10N2).Cl2 (I).

Page 31/32

Figure 11

Infrared spectrum of [C6H10N2]2ZnCl4 (II).

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Figure 12

Deconvolution of isotropic band of 13C spectrum of [C6H10N2]2ZnCl4 (II).