DFT calculations, crystal structure, Hirshfeld surface analyses and antibacterial studies of a new tetrachlorocuprate salt: (C6H16N2O)[CuCl4]

Accepted Manuscript DFT calculations, crystal structure, Hirshfeld surface analyses and antibacterial studies of a new tetrachlorocuprate salt: (C6H16N2O)[CuCl4] Chaima Bejaoui, Iness Ameur, Najoua Derbel, Anthony Linden, Sonia Abid PII:

S0022-2860(18)30434-4

DOI:

10.1016/j.molstruc.2018.04.003

Reference:

MOLSTR 25076

To appear in:

Journal of Molecular Structure

Received Date: 16 January 2018 Revised Date:

28 March 2018

Accepted Date: 2 April 2018

Please cite this article as: C. Bejaoui, I. Ameur, N. Derbel, A. Linden, S. Abid, DFT calculations, crystal structure, Hirshfeld surface analyses and antibacterial studies of a new tetrachlorocuprate salt: (C6H16N2O)[CuCl4], Journal of Molecular Structure (2018), doi: 10.1016/j.molstruc.2018.04.003. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT DFT calculations, crystal structure, Hirshfeld surface analyses and antibacterial studies of a new tetrachlorocuprate salt: (C6H16N2O)[CuCl4] Chaima Bejaouia, Iness Ameura, Najoua Derbelb, Anthony Lindenc and Sonia Abida* a

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Laboratoire de Chimie des Matériaux, Université de Carthage, Faculté des Sciences de Bizerte, 7021 Zarzouna, Bizerte, Tunisia, b Laboratoire de Spectroscopie Atomique Moléculaire et Applications (LSAMA), Faculté des Science de Tunis, Université de Tunis El Manar, 2092, Tunis, Tunisie. c Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich, Switzerland.

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ABSTRACT

A novel tetrachlorocuprate salt (C6H16N2O)[CuCl4] was synthesized and its crystal structure determined by single crystal X-ray diffraction analysis. This compound crystallizes in the monoclinic space group Pn with unit cell parameters a=7.71302(11), b=6.33580(8),

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c=13.10453(19)Å, β =104.9526(15)°, V=618.710(15)Å3 and one cation and one anion in the asymmetric unit. Its crystal structure consists of [CuCl4]2- anions surrounded by [C6H16N2O]2+ cations. N−H···Cl, N−H···O and O−H···Cl hydrogen bonding interactions link the entities

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into a three-dimensional framework. Theoretical calculations at the DFT/B3LYP/LanL2DZ level of theory provided good consistency between the calculated and experimental

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vibrational spectra and with the observed geometries of the ions. Compared with reference drugs, the compound exhibited moderate activity against gram-negative bacteria, while it showed modest activity against fungal and the gram-positive strains, except for S. aureus.

keywords: inorganic-organic hybrid material, tetrachlorocuprate, X-ray diffraction, Hirshfeld surface, DFT, antibacterial activity.

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ACCEPTED MANUSCRIPT 1.Introduction During the last decades, inorganic-organic hybrid materials have attracted much attention owing to their special structural features and potential applications derived from

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their optical [1,2], electronic [3,4], and ferroelectric properties [5,6]. Among these compounds, halide-transition metal complexes, such as halocuprates, have drawn growing interest because of their structural flexibility, magnetic properties related to the interionic distances between the [MXn]y- anions (M=metal, X=halogen), and the properties of the

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cations [7,8]. In particular, the Cu(II) ion is an attractive transition metal with a d9 electronic

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system and presents a variety of coordination numbers and geometries, such as octahedral, square planar, tetrahedral and square pyramidal [9]. A variety of amines has been employed previously in the preparation of halocuprates, including aliphatic, aromatic and cyclic amines [10-13]. In particular, protonated N-heterocyclic amines, such as piperazine and its derivatives, have also attracted significant interest amongst crystal engineers, because they are

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able to form hydrogen bonds in multiple directions and are fairly rigid cations [14]. Furthermore, piperazine and its derivatives exhibit a wide range of biological activities

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including antimicrobial, anticancer, antituberculosis, antiviral and antimalarial activity [15]. In this context, we report herein the preparation of a new halogenocuprate complex

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(C6H16N2O)[CuCl4], along with its X-ray crystal structure, Hirshfeld surface analysis, vibrational studies, density functional theory (DFT) calculations and antibacterial activity. 2. Experimental and calculations 2.1. Materials and physical measurements The infrared spectrum of the title compound prepared as a KBR disk was recorded using a Nicolet IR 200 FT-IR spectrometer in the range 4000 - 400 cm-1. Powder X-ray diffraction patterns were collected at room temperature in the 2θ range of 10-40° over 2 hours using a

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ACCEPTED MANUSCRIPT BRUKER D8 ADVANCE X-ray diffractometer and graphite monochromated CuKα radiation. 2.2. Synthesis The title compound, (C6H16N2O)[CuCl4], was obtained as follows: a solution of N-(2-

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hydroxyethyl)piperazine (0.13 g, 1 mmol ) in ethanol (10 mL) was added to a solution CuCl2.2H2O (0.170 g, 1 mmol ) in a minimum volume of ethanol. Concentrated hydrochloric acid (1 M, 20 mL) was also added dropwise to pH 1–1.5. The reaction mixture was stored in a

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water bath at 50°C for 1 hour. The resulting solution was kept at room temperature. After two

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weeks of evaporation, orange prismatic monocrystals appeared in the solution. 2.3. X-ray data collection

Single crystal X-ray diffraction data were collected on a Rigaku Oxford Diffraction SuperNova area-detector diffractometer using Mo Kα radiation (λ = 0.71073 Å) from a microfocus X-ray source and an Oxford Instruments Cryojet XL cooler. Intensities were collected

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at 160 K by means of the CrysAlisPro software [16] and were corrected for Lorentz, and polarization effects. An empirical absorption correction using spherical harmonics was

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applied [17]. The structure was solved by direct methods with SHELXS-97 [18]. The molecular model was refined by full-matrix least-squares procedure on F2 with SHELXL-

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2018 [19]. All methylene hydrogen atoms were positioned geometrically and refined using a “riding model” [with Uiso(H) = 1.2Ueq(C)]. The hydroxy and ammonium hydrogen atoms were located from difference Fourier maps and refined isotropically. A summary of the crystallographic data and the structure refinement results is given in Table 1. Crystallographic data for the structure reported in this paper have been deposited in the Cambridge Crystallographic Data Centre as supplementary publication number CCDC-1478572. The data can be obtained free of charge from http://www.ccdc.ac.uk/structures.

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ACCEPTED MANUSCRIPT 2.4. Computational details The starting molecular geometry of (C6H16N2O)[CuCl4] was taken directly from the refined crystal structure model. All calculations were performed using the Gaussian 09 package [20]. The optimization and vibrational frequency calculations of the title compound were carried

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out by using the Becke's three-parameter exchange functional combined with the Lee Yang Parr correlation functional (B3LYP) [21-22]. LanL2DZ was used as the basis set [23-25] as it has been found to yield good results for similar compounds [26-28]. The calculated

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vibrational wavenumbers were compared to the experimental counterparts. Vibrational mode assignments were made by comparison with previous theoretical and experimental results

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from analogous compounds [29-30] and by visual inspection of the modes animated by using the Gauss-View molecular visualization program [31].

The natural bond orbital (NBO) analysis of the title compound was carried out at the B3LYP/LanL2DZ level. The stabilization energies E(2) were computed by using second-

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order perturbation theory for examining the intermolecular interactions among the bonds of the investigated compound. The stabilization energy E(2) connected with electron

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equation [32]:

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delocalization between donor NBO(i) and acceptor NBO(j) was estimated with the following

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൫‫ܨ‬௜௝ ൯ ‫(ܧ‬2) = ‫ݍ‬௜ ε௝ − ε௜

where qi is the donor orbital occupancy, εi, εj are diagonal elements (orbital energies) and Fij is the off-diagonal NBO Fock matrix element. 2.5. Antibacterial activity determination The inhibition efficiencies of the (C6H16N2O)[CuCl4] salt were screened against the bacterial species Escherichia coli ATCC 8739, Salmonella typhimurium ATCC 14028, Staphylococcus aureus ATCC 6538, Enterococcus faecium ATCC 19434, Streptocoque B (Streptococcus

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ACCEPTED MANUSCRIPT agalactiae), and Candida albicans ATCC 10231 by the disc diffusion method [33-35]. The test microorganisms were spread on suitable solid media plates and they were incubated for the whole night at 37°C. After one day, 4-5 loops of pure colonies were turned to a physiological saline solution in a test tube for every bacterial strain and then regulated to the 0.5 McFarland

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turbidity standards (*108 cells mL-1). Sterile cotton dipped in the bacterial suspension and the agar plates were streaked three times. Each time, the plate was turned at a 60° angle. Finally, the swab was rubbed over the edge of the plate. Sterile filter paper discs Whatman (6 mm in

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diameter) were placed onto inoculated plates. These discs had previously been impregnated with diluted solutions of the (C6H16N2O)[CuCl4] complex in sterile water to give a disc

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loading in the range of 50-250 µg. In the assay, Ampicillin (10µg/disc) was used as positive control for all strains while Nystatin (100µg/disc) was used for Candida albicans. The plates were incubated for 24 h at 37 °C and the results were determined by measuring the diameter of the inhibition zone around each disc. Each of the above tests was performed in duplicate.

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3. Results and discussion 3.1. Crystal structure description

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The experimental powder X-ray diffraction pattern (PXRD) of (C6H16N2O)[CuCl4] is in good agreement with the simulated pattern derived from the model coordinates, indicating the

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purity and homogeneity of the synthesized product (Fig. 1a). Minor differences in the positions, widths, and intensities of some peaks may be due to the different temperatures used for the single crystal (160 K) and powder diffraction measurements (room temperature), and preferred orientation effects with the powder samples [36]. Single-crystal X-ray diffraction analysis of crystals of the title complex showed the asymmetric unit to contain one discrete N(2-hydroxyethyl)piperazine-1,4-diium dication and one discrete tetrachlorocuprate dianion (Fig. 1b). The 6-membered piperazine ring adopts a chair conformation, as is evident from the puckering parameters: Q=0.562 (4) Å, θ=2.7 (4)° and φ= 193 (8)° [37]. The interatomic C−C

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ACCEPTED MANUSCRIPT and C−N distances (Table 2) are comparable with values generally observed in other N-(2hydroxyethyl)piperazine salts [30,38]. The Cu atom is coordinated by four almost equidistant Cl atoms in a geometry which is distorted significantly from tetrahedral towards a seesaw arrangement with a seesaw-typical τ4 value of 0.68; τ4 values range from 1.00 for an ideal

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tetrahedron to 0.0 for a square planar geometry [39]. In the crystal structure, the organic cations are interlinked via N−H···O hydrogen bonds to form extended chains, which run parallel to the [101] direction (Table 3, Fig. 2a) and can be described by a graphset motif of

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C(8) [40]. The anionic species interconnect the organic chains into a 3D famework by means of N−H···Cl and O−H···Cl hydrogen bonds (Fig. 2b). Each cation interacts with four

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different anions and vice-versa. Each chlorine atom of the [CuCl4]2-anion is involved in only one hydrogen-bonding interaction, while one N-atom of the anion is involved in a bifurcated interaction with two different anions, N2−H2A···(Cl2iii, Cl4iv), although the interaction involving Cl4 is very much weaker than the others and has a rather sharp N−H···Cl angle

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(Table 3). These associations generate additional hydrogen-bonded ring motifs such as ܴଷଷ (11) and ܴହହ (23) [40]. The geometry of the ions of the fully optimized theoretical structure of the studied complex (Table 2) is very close to that exhibited by the crystal structure. The

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slight difference between the calculated and experimental distances and angles can be

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explained by the fact that the experimental values occur in the solid state, while the theoretical values correspond to the isolated ions in a vacuum. 3.2. Hirshfeld surface analysis The intermolecular interactions of the tetrachlorocuprate salt can be visualized using Hirshfeld surface analysis [41]. The 3D Hirshfeld surface mapped over a dnorm range of -0.650 to 1.247Å is illustrated in Fig.3. Fig.4 presents the 2D fingerprint maps which are unique for each entity in the asymmetric unit of a given crystal. The H···Cl and H···H intermolecular contacts are the most abundant in the crystal packing (65.5% and 23.3% respectively) [42].

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ACCEPTED MANUSCRIPT They have the most significant contribution to the total Hirshfeld surfaces. The Cl···H/H···Cl contacts, which are attributed to N−H···Cl and O−H···Cl hydrogen-bonding interactions, appear as two sharp symmetric spikes in the 2D fingerprint maps with a prominent long spike at de+di= 2.2 Å. The O···H/H···O contacts, that are attributed to H···O (de>di) and O···H

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(di>de) from N−H···O intercationic contacts, appear as two sharp symmetric spikes in the 2D fingerprint maps and account for 5.5% of the area of the Hirshfeld surface.

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3.3.Vibrational spectra study

The simulated IR spectra of (C6H16N2O)[CuCl4] performed with the B3LYP/LanL2DZ basis

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set and the experimental IR spectra are presented in Fig. 5. The experimental vibrational wavenumbers were correlated with the calculated vibrational wavenumbers and the correlation graph is shown in Fig. 6. The calculated correlation coefficient (R2) is 0.9999 for the studied compound. The calculated and experimental vibrational frequencies as well as the

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proposed assignments are collected in Table 4. The IR spectrum of the complex is not merely the sum of the spectra of the components (see Supplementary Figure S1), and the differences can be attributed to the electrostatic and hydrogen-bonding interactions between the ions.

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[CuCl4]2- anion vibrational modes

The bands in the 311-233 cm-1 range are attributed to Cu−Cl stretching modes. The

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vibrational modes observed between 211 and 166 cm-1 are assigned to the Cu−Cl bending modes. The CuCl4 bending vibrations appear at 118 and 103 cm-1. N-(2-hydroxyethyl)piperazine-1,4-diium cation vibrational modes The symmetric and asymmetric stretching modes of NH2 are observed at 3022 and 2913 cm-1. The corresponding calculated values are 3005 and 2913 cm-1. The bands assigned to the O−H and N−H stretching modes are found experimentally at 3300 and 2838 cm-1 (calculated at 3305 and 2824 cm-1). The band located at 1636 cm-1 in the IR spectrum is assigned to the O−H in-plane deformation. The vibrational modes located between 1587 and 1219 cm-1 are 7

ACCEPTED MANUSCRIPT attributed to the NH2 and CH2 bending modes. The bands in the 1160-1006 cm-1 range are associated with the C−H, C−N and C−O stretching modes. Theoretically, these modes are observed between 1125 and 1006 cm-1. The bands observed at 877 and 514 cm-1 are assigned to CCN and CCO bending, which are theoretically predicted at 871 and 519 cm-1.

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3.4.NBO analysis

The NBO analysis of the studied structure presents an efficient method for calculating the stabilization energies E(2) due to electron delocalization processes. Table 5 presents the

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stabilization energies E(2), which indicate the electron delocalization from the donor NBO to acceptor [43,44]. The results indicate that the total stabilization energies of n(Cl3i)

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→σ*(N1−H1), n(Cl2ii) →σ*(N2−H1A) and n(Cl1) →σ*(O1−H11) interactions are, respectively, 14.64, 12.55 and 10.69 kcal/mol. These important interactions prove the existence of intermolecular N−H···Cl and O−H···Cl hydrogen-bonding interactions in the compound. Consequently, it is apparent that the N−H···Cl and O−H···Cl intermolecular

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interactions significantly influence crystal packing in this system. 3.5. Thermodynamic properties

Based on the vibrational analysis and statistical thermodynamics, the standard thermodynamic

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଴ ଴ ଴ functions: heat capacity (‫ܥ‬௣,௠ ), enthalpy (‫ܪ‬௠ ) and entropy (ܵ௠ ), listed in Table 6, were

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obtained at the B3LYP/LanL2DZ level. From the table, these thermodynamic functions increase with temperature from 50 to 600 K, because the intensities of the molecular vibrations increase with temperature. The correlation equations between thermodynamic properties and temperature T are as follows: ଴ ‫ܪ‬௠ = -2,58341+ 0,07224T + 7,96114T2 x 10-4 ; (R2=0,99988) ଴ ‫ܥ‬௣,௠ = 48,39318+ 0,31818T-2,2596T2 x 10-4 ; (R2= 0,98627)

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ACCEPTED MANUSCRIPT ଴ ܵ௠ = 96,97318+ 0,78837 T- 5,35958 T2 x 10-4 ; (R2= 0,99637)

3.6. Antibacterial activity The elaborated copper complex was screened for antibacterial and antifungal activity against

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three gram-positive bacteria (E. coli, S. typhimurium, S.aureus), two gram-positive bacteria (E. faecium and S. agalactiae) and against fungi (Candida albicans). The susceptibility of the bacteria and fungi strains toward the copper complex was screened by measuring the diameter of the growth inhibition zone. The results reported in Table 7, indicate that the synthesized

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compound exhibited varying degrees of inhibitory effect on the growth of different tested

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strains. Compared to reference drugs, the tested compound exhibited moderate activity against the gram-negative bacteria, while it showed modest activity against the fungal and the grampositive strains, except for S. aureus. 4. Conclusion

The present work investigates the synthesis and subsequent characterization of a new

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compound (C6H16N2O)[CuCl4]. Single crystal X-ray diffraction showed the presence of onedimensional N−H···O hydrogen-bonded chains linking the organic cations. This chain

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interconnects the anionic species into a three-dimensional framework by means of N−H···Cl and O−H···Cl hydrogen bonds. Reproduction of the molecular geometry and FT-IR

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vibrational spectra of the title compound, as well as an NBO analysis were carried out by using the density functional method (B3LYP) with the Lanl2DZ basis set. The calculated results show that the optimized geometry can well reproduce the crystal structure, and the theoretical vibrational wavenumbers values are in agreement with experimental values. The ଴ ଴ ଴ correlations between the thermodynamic properties ‫ܪ‬௠ , ‫ܥ‬௣,௠ , ܵ௠ and temperature were

obtained. The NBO analysis indicated that the N−H···Cl and N−H···Cl intermolecular interactions significantly influence crystal packing in this system.

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ACCEPTED MANUSCRIPT Acknowledgments This work has been supported by the Ministry of Scientific Research and Development of Tunisia.

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[41]S. K. Wolff, D. J. Grimwood, J. J. McKinnon, D. Jayatilaka, M. A. Spackamn, Crystal Explorer, University of Western Australia (2012). [42]C. F. Matta, J. Hernandez-Trujillo, T. H. Tang, R. F. W. Bader, Hydrogen-Hydrogen Bonding: A Stabilizing Interaction in Molecules and Crystals, Chem. Eur. J. 9 (2003) 1940-1951.

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ACCEPTED MANUSCRIPT [43]Sebastian, N. Sundaraganesan, The spectroscopic (FT-IR, FT-IR gas phase, FT-Raman and UV) and NBO analysis of 4-Hydroxypiperidine by density functional method, Spectrochim. Acta A, 75 (2010) 941-952. [44]J. Hubert, I. Kostova, C. Ravikumar, M. Amalanathan, S. C. Pinzaru, Theoretical and

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vibrational spectral investigation of sodium salt of acenocoumarol, J. Raman

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Spectrosc.40 (2009) 1033-1038.

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Fig.1. (a) Simulated and experimental powder X-ray diffraction patterns of (C6H16N2O)[CuCl4]. (b)Asymmetric unit of (C6H16N2O)[CuCl4]with the atom numbering scheme and displacement ellipsoids at 50 % probability.

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Fig.2. (a) View of the 1D cationic chain running along the [101] direction formed by the N– H···O interactions. (b) Projection of the crystal structure of (C6H16N2O)[CuCl4] in the (ac) plane showing the N–H···O, N–H···Cl and O–H···Cl hydrogen bonds.

Fig.3. Hirshfeld surface mapped over dnorm of (C6H16N2O)[CuCl4].

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different contacts.

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Fig.4. Two-dimensional fingerprint plots for (C6H16N2O)[CuCl4] showing contributions from

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Fig.5. (a) Simulated and (b) experimental IR spectrum of (C6H16N2O)[CuCl4].

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Fig.6. Correlation graph between the experimental and calculated wavenumbers (cm-1)

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7.71302(11) 6.33580(8) 13.10453(19) 104.9526(15) 618.710(15) 2 1.812 2.600 342 0.15 x 0.16 x 0.24 −11, 11 −9, 9 −19, 18 2.79 ≤ θ≤ 32.47 18521 4130 / 4078 0.025 Full-matrix least-squares on F2 4130 /2 / 144 1.044 0.030 0.072 w=1/ σ2(Fo2) + (0.034P)2 + 0.8434P] where P = (Fo2 + 2Fc2)/3 1.47, -0.57 0.001(4)

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Unit cell parameters a (Å) b (Å) c (Å) β (º) Volume (Å3) Z Calculated density (Mg/m3) µ (mm−1) F000 Crystal size (mm) hmin, hmax kmin, kmax lmin, lmax Theta range for data collection (º) Measured reflections Independent / [I >2σ(I)reflections] Rint Refinement method Data / restraints / parameters Goodness-of-fit on F2 R(F) [I >2σ(I)reflections] wR(F2)(all data) Weighting scheme

Orange, prism C6H16Cl4CuN2O 337.55 160 0.71073 MoKα Monoclinic Pn

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Color, habit Chemical formula Formula weight (g.mol-1) Temperature (K) Wavelength (Å) Crystal system Space group

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∆ρmax, ∆ρmin (e/Å3) Absolute structure parameter

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Table 1. Crystal data and structure refinement parameters for (C6H16N2O)[CuCl4].

ACCEPTED MANUSCRIPT Table 2. Experimental and calculated inter-atomic parameters (Å, °) of (C6H16N2O)[CuCl4].

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2.2709(9) 2.2442(9) 2.2465(10) 1.429(5) 1.496(6) 1.489(6) 1.520(5) 1.496(5) 1.469(5) 1.548(7) 1.470(6) 1.475(6) 136.89(4) 98.29(4) 99.55(4) 100.24(4) 99.35(3) 127.44(4) 109.6(3) 110.6(3) 107.4 (3) 113.6 (3) 109.7 (3) 112.0(3) 112.9(3)

B3LYP 2.327 2.325 2.460 2.443 1.455 1.523 1.523 1.535 1.510 1.510 1.532 1.534 1.534 128.39 102.39 97.96 99.92 100.75 128.65 111.53 110.82 110.82 112.92 110.86 110.65 114.28

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X-ray 2.2212(9)

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Parameters Cu1—Cl1 Cu1—Cl2 Cu1—Cl3 Cu1—Cl4 O1—C6 N1—C1 N1—C4 N1—C5 N2—C2 N2—C3 C1—C2 C3—C4 C5—C6 Cl1—Cu1—Cl3 Cl1—Cu1—Cl4 Cl3—Cu1—Cl4 Cl1—Cu1—Cl2 Cl3—Cu1—Cl2 Cl4—Cu1—Cl2 C3—N2—C2 C4—N1—C1 C4—N1—C5 C1—N1—C5 N2—C2—C1 N1—C1—C2 C6—C5—N1

ACCEPTED MANUSCRIPT Table 3. Hydrogen-bond geometry (Å, °) of (C6H16N2O)[CuCl4].

D−H

H⋅⋅⋅A

D⋅⋅⋅A

D−H⋅⋅⋅A

N1−H1⋅⋅⋅Cl3i

0.92(6)

2.33(6)

3.240(4)

171(5)

N2−H2A⋅⋅⋅Olii

0.99(6)

1.80(6)

2.752(4)

162(6)

N2−H2B⋅⋅⋅Cl2iii

0.88(6)

2.44(6)

3.162(3)

N2−H2B⋅⋅Cl4iv

0.88(6)

2.74(6)

3.254(3)

O1−H11⋅⋅⋅Cl1

0.86(6)

2.22(6)

3.084(3)

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D−H⋅⋅⋅A

140(5) 119(5)

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Symmetry codes: (i) -1+x, y, z; (ii) -1/2+x,-y, -1/2+z; (iii) -3/2+x, 1-y,-1/2+z; (iv) -3/2+x,-y,-1/2+z.

ACCEPTED MANUSCRIPT Table 4. Observed and scaled calculated (B3LYP/Lanl2DZ) wavenumbers (cm-1) for (C6H16N2O)[CuCl4] and proposed assignments. Calculated wavenumbers (cm_1) IR 3305 3005

2913 2838 1636 1578

2913 2824 1711 1561

1461

1468

1428

1417

1349

1347

1319 1260 1219 1160 1073 1035 1006 877 852 773 580 514 480 447

1325 1268 1213 1125 1084 1049 1006 871 855 787 594 519 475 453

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296 285 247 233 211 199 166 118 103

ν (OH) νas (NH2) νs (NH2) ν (NH ) δ(OH) scissoring (NH2) ω(NH2) ω(CH2)+ τ (NH2) ω(CH2) τ(CH2) τ (CH2) τ (CH2) + ρ (NH2)

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417 311

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Assignement

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Observed wavenumbers (cm_1) IR 3300 3022

τ(CH2)+ τ (NH2)

ν(CN) + ν(CC) ν(CN) ν(OC) ν(CC) δ (CCN) Ring def out plane Ring def out plane Ring def in plane

δ (CCO) Ring def in plane Ring def in plane Ring def in plane ν (Cu-Cl)+ Ring def out plane ν (Cu-Cl) ν (Cu-Cl)

Ring def out plane ν (Cu-Cl) δ (Cu-Cl)+ring def out plane δ (Cu-Cl)+Ring def out plane δ (Cu-Cl)+Ring def out plane δs (CuCl4)+Ring def out plane δas (CuCl4)+Ring def out plane

ν: stretching; δ :bending in plane, τ: twisting, ω: wagging, ρ: rocking

ACCEPTED MANUSCRIPT Table 5. Calculated stabilization energies by 2nd order perturbation analysis of the Fock matrix in the NBO basis, using the DFT/B3LYP/LanL2DZ method.

LP (3)Cl3i LP (1)Cl3i LP (4)Cl3i LP (3)Cl2ii LP (1)Cl2ii LP (3)Cl1 LP (4)Cl1 LP (1)Cl1

BD*(1)N1-H1 BD*(1)N1-H1 BD*(1)N1-H1 BD*(1)N2-H1A BD*(1)N2-H1A BD*(1)O1-H11 BD*(1)O1-H11 BD*(1)O1-H11

E(2) kcal/mol 13.18 0.66 0.80 11.99 0.56 9.94 0.19 0.56

E(j)-E(i) a.u. 0.68 0.79 0.65 0.64 0.84 0.72 0.77 0.87

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F(i,j) a.u. 0.120 0.030 0.029 0.111 0.028 0.107 0.016 0.028

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Acceptor NBO (j)

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ACCEPTED MANUSCRIPT Table 6. Thermodynamic properties at different temperatures at the B3LYP/Lanl2DZ level.

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ࡿ૙࢓ (cal.mol-1 .K-1) 125.79 173.34 209.61 238.85 263.50 285.08 304.49 322.29 338.80 354.26 368.81 382.58

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࡯૙࢖,࢓ (cal.mol-1 .K-1) 55.87 81.89 96.73 106.53 114.63 122.28 129.72 136.87 143.61 149.85 155.60 160.86

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ࡴ૙࢓ (kcal.mol-1) 1.72 5.22 9.72 14.81 20.34 26.27 32.57 39.23 46.25 53.59 61.23 69.14

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T (K) 50 100 150 200 250 300 350 400 450 500 550 600

ACCEPTED MANUSCRIPT Table 7. Antibacterial activities at different concentrations of the (C6H16N2O)[CuCl4] complex.

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Disc charge (µg) 250 200 Escherichia coli ATCC 8739 G(-) 150 100 50 250 200 Salmonella typhimurium ATCC 14028 G(-) 150 100 50 250 200 Staphylococus aureus ATCC 6538 G(+) 150 100 50 250 200 Enterococcusfeacium ATCC 19434 G(+) 150 100 50 250 200 Streptocoque B (Streptococcus agalactiae) 150 G(+) 100 50 250 200 Candida albicans ATCC 10231 150 100 50 - : Resist, Solvent: sterile water, Drug: Ampicillin / Nystatin

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Name of bacterial strains

Zones of growth inhibition surrounding the disc (mm) Solvent Drug complex 11.17±0.7 10.17±0.2 9.33±0.5 11.75±0.3 7.83±0.2 10.50±0.5 9.83±0.2 9.17±0.2 13.75±1.0 7.17±0.2 35.5±0.7 11.75±1.0 10.25±0.0 9.00±0.3 37.5±0.7 7.50±0.7 11.67±1.1 10.50±0.5 9.83±0.7 31±1.4 8.00±0.5 7.25±0.3 11.00±0.0 10.00±0.0 8.83±0.2 34.5±0.7 7.67±0.5 -

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Highlights

Synthesis and X-ray crystal structure determination of a novel tetrachlorocuprate salt IR spectrum and NBO analysis are reported.

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଴ ଴ ଴ The correlations between the thermodynamic properties ‫ܪ‬௠ , ‫ܥ‬௣,௠ , ܵ௠ and temperature were

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obtained.

Intermolecular interactions in the crystal packing have been studied using Hirshfeld surface

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analyses.