Synthesis, crystal structure, thermal analysis and vibrational spectroscopy accomplished with DFT calculation of new hybrid compound [2-CH3C6H4NH3]HSO4.H2O

Accepted Manuscript Synthesis, crystal structure, thermal analysis and vibrational spectroscopy accomplished with DFT calculation of new hybrid compound[2CH3C6H4NH3]HSO4.H2O C. Ben Hassen, M. Boujelbene, S. Marweni, M. Bahri, T. Mhiri PII:

S0022-2860(15)30024-7

DOI:

10.1016/j.molstruc.2015.05.041

Reference:

MOLSTR 21542

To appear in:

Journal of Molecular Structure

Received Date: 12 December 2014 Revised Date:

28 May 2015

Accepted Date: 29 May 2015

Please cite this article as: C. Ben Hassen, M. Boujelbene, S. Marweni, M. Bahri, T. Mhiri, Synthesis, crystal structure, thermal analysis and vibrational spectroscopy accomplished with DFT calculation of new hybrid compound[2-CH3C6H4NH3]HSO4.H2O, Journal of Molecular Structure (2015), doi: 10.1016/ j.molstruc.2015.05.041. 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.

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Synthesis, crystal structure, thermal analysis and vibrational spectroscopy accomplished with DFT calculation of new hybrid compound [2-CH3C6H4NH3]HSO4.H2O

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C. Ben Hassena, M. Boujelbene*a, S. Marwenia, M. Bahrib and T. Mhiria

a- Laboratoire Physico-Chimie de l’Etat Solide, LR11 ES51, Faculté des Sciences de Sfax, Université de Sfax, 3071 Sfax, Tunisia

b- Laboratoire de Spectroscopie Atomique Moléculaire et Applications, Faculté des sciences

* Corresponding author: Mohamed Boujelbene

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de Tunis, Université Tunis-El-Manar II, 1060 le Belvédère, Tunisia

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Laboratoire Physico-Chimie de l’Etat Solide LR11 ES51, Université de Sfax, Faculté des Sciences de Sfax, Route de Soukra Km 3.5, BP 802, Sfax 3071, Tunisia.

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Tel.: (216) 22677645

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ACCEPTED MANUSCRIPT Abstract:

The present paper undertakes the study of a new organic/inorganic hybrid compound [2-CH3C6H4NH3]HSO4.H2O characterized by the X-ray diffraction, TG-DTA, IR and Raman spectroscopy accomplished with DFT calculation. It is crystallized in the monoclinic system

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with the centrosymmetric space group P 21/c, with a= 9.445 (5) Å, b= 10.499 Å, c=10.073 Å, β= 90.627 (5)° and Z= 4.

The atomic arrangement can be described as inorganic layers built by infinite chains, parallel to the (a c) planes between which the organic cations are inserted. In this atomic

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arrangement, hydrogen bonds and π-π interactions between the different species have an important role in the tri-dimensional network cohesion. Besides, the X-ray powder diffraction of the title compound confirms the existence of only one phase at room temperature. The

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thermal decomposition of precursors studied by thermo gravimetric analysis (TGA), the differential thermal analysis (DTA) and the temperature-dependent X-ray diffraction, show crystalline anhydrous compounds upon dehydration. DFT/BHHLYP calculations were performed, using the DZV (d,p) basis set, to determine the harmonic frequencies of the vibrational modes of an optimized cluster structure. The calculated modes were animated

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Raman spectra.

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using the Molden graphical package to give tentative assignments of the observed IR and

Keywords: Hybrid material; X-ray diffraction; Thermal Analysis (TG-DTA); Infrared and Raman spectroscopy; Density Functional Theory (DFT) calculation; 2

ACCEPTED MANUSCRIPT 1. Introduction In recent years, the organic-inorganic hybrid materials have received increasing attention because of their ability to combine the physical and chemical properties of inorganic and organic groups. Concerning the interaction of mono-sulfuric acid with organic molecules having one

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or more lone pairs, leads to the formation of hybrid compounds whose anions have the formula [HSO4]- or [SO4]2-. The anions HSO4- are interconnected by strong hydrogen bonds so as to build infinite networks with various geometries: Isolated groups HSO4 [1, 2], clusters [3], ribbons [4], chains [HSO4]nn- [5] and [HSO4.yH2O]nn- [6] and two-dimensional network

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[7].

Concerning the interaction of 2-methylaniline (o-toluidine) molecules with oxyanions (phosphates, selenites, etc…) having or more accepter hydrogen bonds, leads to the formation

(2-CH3C6H4NH3)(H3O)SO4[10, CH3C6H4NH3)2SeO4 [13].

11],

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of hybrid compounds such as (2-CH3C6H4NH3)NO3 [8], (2-CH3C6H4NH3)H2PO4H3PO4 [9], (2-CH3C6H4NH3)HSO4.H2O

[12]

and

(2-

The present work reports the synthesis, crystal structure, thermal analysis and vibrational study of a new hybrid compound; namely, monohydrate ortho-toluidinium hydrogen sulfate,

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(o-CH3C6H4NH3)HSO4.H2O denoted (OTHS.H2O). In fact, concerning the structural part, it deals with the experimental work which includes the chemical preparation and the structural determination by X-Ray diffraction. With respect to the thermal part, it presents the thermo gravimetric analysis (TGA), differential thermal analysis (DTA) and temperature-dependent

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X-ray diffraction.

Finally regarding vibrational spectroscopies, we present the experimental infrared, and Raman spectra of the title compound and the density functional theory (DFT) calculation

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results. In the light of the theoretical calculations, correlation between IR and Raman spectra and computed results help unambiguous identification of vibrational modes and provide deeper insight into the bonding and structural features of the title compound. 2. Materials and method. 2.1. General About the phase analysis, the X-Ray powder patterns were recorded using a Philips pw 3050 powder diffractometer with Co radiation. Data were collected as a function of temperature with a fixed slit configuration in the range of 5° and 100° 2θ in steps of 0.017.

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ACCEPTED MANUSCRIPT As regards the thermal analysis, it was performed using the ‘multimodule 92 Setaram’ analyzer operating from room temperature up to 650 K in air static with 6.4 mg samples in an open platinum crucibles at an average heating rate of 5 K/min. Fourier’s transformation infrared (FT-IR) measurements were performed at room temperature, on a Perkin-Elmer FT-IR Paragon 1000 PC spectrometer over the 4000 - 400 cmregion, in a KBr pellet. Resolution was set up to 2 cm-1 and 6 scans were performed.

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Furthermore, Raman spectra were measured with a LABRAMHR 800 triple mono-chromator at room temperature under a 50 x LF objective microscope. An He-Ne ion laser operating at about 20mW was used (on the sample) as an excitation source (514.5 nm), with a spectral

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steps of 3 cm-1. 2. 2. Chemical Preparation

The single crystal of [2-CH3C6H4NH3]HSO4.H2O was obtained by slow evaporation of acid with the following reaction:

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aqueous solution containing a 1:1 stoechiometric mixture of Ortho-Toluidine

and sulfuric

H2O 2-CH3C6H4NH2 + H2SO4

[2-CH3C6H4NH3]HSO4.H2O

The resulting solution was allowed to evaporate slowly at room temperature. After several

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days, colorless transparent parallelepiped single crystal of [2-CH3C6H4NH3]HSO4.H2O were obtained.

2. 3. Structure Determination

Single-crystal X-ray diffraction intensity data were obtained on a Bruker APEX-II area

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detector diffractometer using MoKɑ radiation (λ = 0.71073Å). The data were collected at room temperature. Lorentz and polarizing effect corrections were performed before proceeding to the refinement of the structure. Besides, absorption corrections were performed

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using the multi-scan technique and the atomic scattering factors were taken from the International Tables for X-ray Crystallography [14]. The intensities of two standard reflections were periodically recorded to check the stability of the data acquisition. 4313 reflections were measured, 1367 of which had an intensity of I >2σ(I).The structure was successfully developed in the centrosymmetric space group P 21/c. The sulfur atoms were fixed using the direct methods with SHELXS-97 [15] program. The oxygen atoms and the organic moieties were found from successive Fourier calculations using SHELXL-97[16]. The water H atoms were located in a difference map and refined with O-H distance restraints of 0.88(2) Å and H-H restraints of 1.5(2) Å so that the H-O-H angle would fit to the 4

ACCEPTED MANUSCRIPT ideal value of a tetrahedral angle. Next, the hydrogen atoms of the CH, CH3 and NH3 groups were fixed geometrically by the appropriate instructions of the SHELXL-97 program (HFIX 43, HFIX33, and HFIX 137, respectively) [16]. The final cycle of refinement led to the final discrepancy factors R1 = 0.035 and wR2 = 0.95. Moreover, the drawings were made with Diamond [17], and the crystallographic data as

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well as some details of the structure refinement are summarized in Table 1. The final atomic coordinates obtained from the single crystal refinement with Ueq are given in Table 2. Hydrogen bonds and Interatomic distances, bond angles are listed in respectively.

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2.3 Theoretical calculations

Tables 3 and 4,

The molecular geometry optimization and vibrational frequency calculations relative to the title compound were performed using the DFT method implemented in the GAMESS series of

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programs (version 2013) [18] without any symmetry restrictions. According to our previous results [13], the BHHLYP functional was chosen in calculations. In order to take into account the effect of intermolecular interactions on geometrical parameters, vibrational spectroscopy and to describe properly the actual environment for each group (HSO4-, H2O, 2CH3C6H4NH3+) we have considered the cluster built up from one organic cation, three water

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molecule and three HSO42- anion linked by N–H…O and O-H...O hydrogen bonds as described in the crystal structure (Fig. 1).

This cluster represents a relative’s large molecular system (N= 45 atoms), for this reason the standard DZV (d, p) basis set is used. All the geometrical parameters were allowed to relax

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and calculations is considered to be converged a maximum energy gradient less than 10-4. The converged structure with a dipole moment values of 9.413479 Debye is used to calculate the 129

(3* 45 - 6) positive vibrational frequencies. To take into account the anharmonicities

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of the C-H, N-H and O-H stretching modes a frequency scaled factor of 0.92 [19] is used. The experimental Raman spectra consist of well separated peaks that can be subdivided into three main groups presented in (Fig. 2. a), (Fig. 2. b) and (Fig. 2. c). As for the infrared spectrum, it is subdivided into two main groups presented in (Fig. 3. a) and (Fig. 3. b). In fact, in the low frequency range 50-400 cm-1, the Raman bands correspond to the translational and vibrational modes of the organic-inorganic groups and the [HSO4]- external modes. The other bands observed between 400 and 4000 cm-1 in the Raman spectra and those in the IR spectra are assigned to the internal modes of the organic, inorganic and water molecular 3. Results and discussion 3. 1. Description of the structure 5

ACCEPTED MANUSCRIPT A view of the asymmetric unit of the structure is shown in Fig. 4 and contains a monoprotonated 2-methylanilinium cation, a mono-hydrogenosulfate anion and a water molecule. Intra-atomic bond distances and angles in the title compound shows the monoprotonation of the organic entity and confirms the presence of the monohydrogenosulfate (HSO4)- anion. that the

[HSO4]- groups are connected by

O(W)-H(W1)…O(4) and

two

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Fig. 4. displays a projection in the (b, c) plane of the anionic structure. In fact, it shows strong hydrogen bonds

such

as

O(W)-H(W2)…O(3) to form infinite corrugated chains in the b-

direction of composition [HSO4.H2O]nn-. The chains located at (1/2, y, 1/4) and (1/2 ,y, 3/4) are themselves interconnected by means of N-H0A …O4 , N-H0B…O3, N-H0C …O2 and O1-

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H1…OW hydrogen bonds emanating from the NH3 and H2O group so as to build layers formed by HSO4, H2O and NH3 groups. These data show that each anion HSO4- is connected

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to three organic cations and three water molecules. It is the same for organic and water molecules each of which is connected to three HSO4- anions (Fig. 5). Not only are the protonated 2-methylaniline molecules trapped in the inter layers spacing, but also they neutralize the negative charge of the inorganic chains through hydrogen bonds involving the hydrogen atoms of the NH3 groups since

H(N)…O distances vary

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between 2.790(8) and 2.962(4) Å (Fig. 6).

In the organic motif, there are π–π interactions between antiparallel cations, with faceto-face distances of 3.714 Å (<3.8 Å) [20], indicating the formation of π−π interactions. Although these interactions are weak, they play a very important role in the crystal structure

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because they connect two organic groups from two successive layers (A-B-A-B….) (Fig. 7). As (O,N)–H · · ·O hydrogen bonds are considered to be strong when the (O,N) · · ·O distance is less than 2.730Å [21], the hydrogen bonds of O–H(T) · · ·O(W) and O–H(W) · ·

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·O(T) type relating the [HSO4]- anions to each other or to the

oxygen atoms of water

molecules, are found to be strong, where “W” and “T” refer to the water molecules and [HSO4]− anions, respectively. However, the N–H…O type is found to be weak (Table 3). It is worth noting that among the four acceptors in the [O-CH3C6H4NH3]HSO4.H2O structure, two atoms [Ow and (O2)] are single acceptors and two atoms [(O3) and (O4)]

are double

acceptors. An examination of the geometrical features of the organic moiety shows that the carbon atoms building the phenyl rings of the title compound have a good co-planarity and they form conjugated planes with average deviations of 0.0051 Å for phenyl (from C1 to C6). The mean value of the C–C bond length is [1.381 Å], which is between a single and a double 6

ACCEPTED MANUSCRIPT bond, complies with that in paraphenolammonium dihydrogenophosphate (1.383 Å) and 2, 3Dimethylanilinium dihydrogenophosphate (1.388 Å) [22, 23]. These values show clearly that in the organic cation, the carbon rings of the phenyl groups are regular. The openings of the angles in the phenyl groups range from 116.4(2)° to 123.2 (2)°. Such angles deviate significantly from the ideal value of 120 ° (Table 4), due to the bi-substituted aromatic group.

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The geometric examination of HSO4 shows two types of S–O distances. The larger one is 1.499 (2) Å, can be attributed to the S–OH distance, while the shorter one varies between 1.461 (2) Å and 1.444 (2) Å. The average values of the S–O distances and O–S–O angles are 1.469 A˚ and 108.64, respectively (Table 4). These geometrical features have also

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been noticed in other crystal structures. Nevertheless, the calculated average values of the distortion indices [24] corresponding to the different angles and distances in the HSO4 tetrahedron [DI(OSO) = 0.02, DI(SO) = 0.0073 and DI(OO) = 0.0059] show a large distortion

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of the OSO angles if compared to S–O and O–O distances. As a result, the SO4 group can be considered as a rigid regular arrangement of oxygen atoms, with the sulfur atom slightly displaced from the gravity center. Therefore, these HSO4- tetrahedra have local C1 symmetry rather than 4 -3m in the ideal.

3. 2. X-ray powder diffraction (XRD) at room temperature

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The lattice parameter and space group of OTHS.H2O were used as a starting model for Rietveld refinement using the FullProf program integrated in WinPLOTR software [25, 26]. With respect to the X-Ray diffraction at room temperature spectrum of the title compound shown in Fig. 8, the observed pattern is in good agreement with the calculated diagram. This

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result confirms the presence of only one phase at room temperature. 3. 2. Thermal decomposition

The two curves corresponding to the DTA and TGA analysis in the open air are given

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in Fig. 9. The first weight loss region (I) occurs over the temperature range of 347-377 K. Approximately 8 % of the mass is lost, which corresponds to one molecule of water per formula unit to form the anhydrous compound OTHS. The first weight loss is accompanied by one endothermic peak in the DTA curve at

361 K. The dehydration of the title compound is accompanied by a change in the initial diffraction pattern. Indeed the TDXD plot represented in Fig. 10 shows a change between the two diffraction lines recorded before and after the mass loss. This difference between this two diffraction line detected at 300K and 400K and the thermal stability detected by the TG-DTA of the title compound in the temperature range

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ACCEPTED MANUSCRIPT between 380- 415K confirm the existence of structural phase transition coupled to the dehydration of the title compound. The second endothermic peak in the DTA curve at 425 K corresponds to the fusion of the title compound. The second weight loss region (II) occurs over the temperature range from 430 to 650 K, where approximately 50 % of the mass is lost [27]. The loss is accompanied by

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several phenomena represented by a series of endothermic peaks in the DTA curve and by three successive weight losses on the TG curve. The sum of these three weight losses (50%) corresponds to the percentage of the organic molecule in the studied compound. This organic molecule has undergone a pyrolysis and a combustion (air) which gives a gaseous release

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(NH3, CO2, CO, H2O. . .), out of which only the liquid of sulfuric acid contaminated by fine particles of black carbon is left. 3. 3. Vibrational study.

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In order to confirm and give more information on the crystal structure results, we have studied the vibrational properties of the studied organic–inorganic compound using the Raman and infrared spectroscopy.

To overcome the difficulties encountered in the assignment of the observed IR and Raman bands [13], the graphical Molden package was used to animate the calculated mode of

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the considered cluster [28].

The experimental Raman and IR frequencies compared to the calculated from DFT method were listed in Table 5 along with a tentative assignment of the observed bands. 3. 3. 1- External modes

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The translation mode of water molecules is observed by one broad band located at 235 -1

cm . The rotation mode of the CH3 group coupled with the translation mode of (HSO4)anion are observed by one shoulder band seen at 155 cm-1. The translation mode of the

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organic group is observed by one shoulder band at 132 cm-1 and one very strong mixed band at 114 cm-1. The torsion modes of the (HSO4)- anion and the water molecules are observed by the very strong mixed band seen at 114 cm-1. The rotation modes of (HSO4)- anion and water molecular are observed by very strong band located at 80 cm-1. The shoulder band located at 56 cm-1 is attributed at the lattice vibration. 3. 3. 2 Internal modes 3. 3. 2. 1- The vibration of HSO4- anion The isolated [SO4]2− tetrahedron with an ideal Td symmetry has four vibrational modes; the non-degenerates ν1, the doubly degenerates ν2, and the triply degenerates ν3 and ν4, observed in 983, 450, 1105, and 611 cm−1, respectively [29]. Compared to the [SO4]2− anion, 8

ACCEPTED MANUSCRIPT the isolated [HSO4]- anion has an extra proton located in one of the oxygen atoms. The symmetry is then reduced from Td to C3v. Under the effect of its interaction with its crystalline environment, the [HSO4]- anion in the studied compound can lose its symmetry and the degeneracy of its vibrational modes is then expected to be moved. This means that the observed splitting of the bands into two or three components around the ideal values of the ν2,

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ν2, ν3, and ν4 modes cited above can be a useful criterion for assigning these modes. The symmetric bending mode ν 2(SO4) is observed in the infrared spectrum by shoulder, very strong and strong bands

found at 448, 438, 420 cm-1, respectively. The

corresponding band in Raman is observed by one very weak band seen at 448 cm-1. The very

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strong band observed in IR at 594 cm-1 and the weak observed in Raman at 600 cm-1 are assigned the asymmetric bending mode ν 4(SO4). The symmetric stretching mode ν 1(SO4) is observed by two very weak bands. The first ones found at 943 cm-1 in IR and the second at

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934 cm-1 in Raman. The medium broad band observed at 1123 cm-1 in the infrared spectrum and the three very weak bands observed at 1109, 1102 and 1092 cm-1 in Raman spectrum are assigned the asymmetric stretching mode ν 3(SO4). The δ(S-O-H) mode is observed by one, weak band at 1462 cm-1, one shoulder at 1448 cm-1 in the infrared spectrum and by two very weak bands at 1466 and 1450 cm-1 in Raman spectrum. These values are similar to those observed by Belhouchet and all [30]. The shoulder very weak band observed at 2984 cm-1 in

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the infrared spectrum and the very weak band observed at 2985 cm-1 in the Raman spectrum are assigned the stretching mode of the OT-H group. 3. 3. 2. 2- The vibration of water molecule

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The vibrational analysis of a free water molecule has a C2v symmetry leads to three fundamentals normal modes; the symmetric stretching ʋ1, the asymmetric stretching ʋ3 and

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the in-plane bending mode ʋ2. In the studied compound, both H atoms of the water molecule are involved in two O-H • • •O hydrogen bonds. These hydrogen bonds are also responsible for increasing the deformation modes to higher wave numbers (ʋ2) and lowering the stretching wave numbers (ʋ1and ʋ3).

Indeed, the asymmetric stretching mode is observed by one very weak broad located at

3595 cm-1 in Infrared spectrum, The weak broad band located at 3500 cm-1 in the infrared spectrum and one very weak observed 3490 cm-1 in the Raman are attributed to symmetric stretching mode the H2O groups. The corresponding band of the in-plane bending mode (scissoring) is observed by a shoulder very weak (IR) and a very weak broad (Raman) bands observed at 1740 and 1744 cm-1, respectively. 3. 3. 2. 3- The vibration of organic group 9

ACCEPTED MANUSCRIPT In the studied compound, the 2-methylanilinium group contains 18 atoms. For these numbers of atoms 3*18-6 = 48 internal modes are present. In infrared and Raman spectrums of the title compound, most of the normal vibrational modes of [2-CH3C6H4NH3]+ are observed. Some vibrations of the di-substituted aromatic group are displaced with compared to the 30 benzene derivatives used by Varsanyi and Szoke [31]. These displacements are due

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to the substituent loads the ring with added mass (compared with hydrogen), the lower symmetry permits the ring breathing to interact with other vibrations, thus changing both the frequency and the pattern of atomic displacements and the electrical properties of the substituent are altered [32].These modes are similar to those of benzene as reported in the

methylaniline; p-CH3C6H4NH2 [34],

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case of mono-substituted (C6H5NH3; aniline [33]) and di-substituted benzenes (pm-methylaniline; m-CH3C6H4NH2 [35] and o-

methylaniline; o-CH3C6H4NH2 [36]). Furthermore, the di-substituted benzene ring has various functional groups such as -CH3, -NH3+ , -C-H,

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-C-N-, -C=C-, and -C-C-. These groups are

expected to undergo changes in their intensity and position of infrared spectroscopic according to their environments. The aromatic C-H Vibrations

In our study, the IR and Raman spectra correspond of the di-substituted aromatic

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group shows the presence of C-H stretching vibrations in the region 3090–3000 cm-1 and this is the characteristic region for the identification of the C-H stretching vibrations. Also, the bands are not affected appreciably by the nature of the substituents in this region. The (C-H)ar stretching mode is appears in our calculations at 3051 (mode 2), 3041( mode 20b), 3032

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(mode 7b) and 3021 cm-1 (mode13) [36,37].

Excluding the C-H stretching vibrations, the remaining bending vibrations are expected to have frequencies below 1800 cm−1.

In general, the aromatic C-H in-plane

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deformations (δ(CH)ar) and the out-of-plane C-H vibrations (ɤ(CH)ar) of benzene and its derivatives are usually observed in the

region 1000-1600 and 600-1100 cm-1, respectively

[13, 36, 38-40].

In the present case, the aromatic C-H in-plane bending is observed by several bands

in infrared and Raman spectra

detected between 1602-1209 cm -1. Against to the out-of-

plane bending vibration is observed in the spectral region detected between 1031-742 cm-1 [36]. Carbon–carbon and carbon–nitrogen vibrations The shoulder and very weak bands

as well as medium broad band observed in

infrared spectra at 1428, 1386 and 875 cm-1, respectively, and the weak and very weak bands 10

ACCEPTED MANUSCRIPT observed in Raman spectra at 1406 and 880 cm-1, respectively, should be assigned to the stretching mode of C-CH3 and C-NH3 groups. All these assignments are agreed well with the reported literature values [13]. Under CS symmetry, in the case of 2- methylanilinium, the C=C stretching mode of the benzene molecule in the infrared spectrum is seen at 1710, 1632, 1602 and 1504 cm-1 whereas

similar to that observed by Arjunan and all [39].

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the respective Raman bands are observed at 1652, 1620, and 1600 cm-1. These values are

The in plane bending vibration of aromatic ring δ(CCC) is found in the IR spectrum at 1428, 1386, 1313, 1157, 1048, 875, 763, 632 and 548 cm-1 while the respective Raman 482 cm-1. The ring

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bands are observed at1406, 1330, 1172, 1109, 880, 658, 540, and

breathing mode of the benzene is assigned to the wavenumber observed in the IR spectrum at 875 cm-1 and in the Raman spectrum at 880 cm-1.These values are in good agreement with the

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ring breathing mode at about 800 cm−1 in the substituted benzene [41-45].

Furthermore, the out-of-plane bending type γ(CCC) of aromatic ring are observed in the infrared spectrum at 994, 828, 742, 560, 512 and 503 cm-1. The corresponding bands in the Raman spectrum are observed at 995, 760, 727, 512 and 503 cm-1. The CH3 and NH3 vibrations

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The vibrational analysis of an free (NH3)+/(CH3) groups has a pyramidal structure with a C3v symmetry leads to four fundamentals normal modes: the ʋ1(A1) and ʋ2(A1), the doubly degenerate mode ʋ3 (E) and ʋ4 (E). ʋ1 and ʋ3 involve the symmetric and the asymmetric stretching mode of the N/C–H bonds, whereas ʋ2 and ʋ4 involve mainly H–N/C–H symmetric

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and asymmetric bending modes. Under the effect of its interaction with its crystalline environment, the (NH3)+/(CH3) groups in the studied compound can lose its symmetry and the degeneracy of its vibrational modes is then expected to be moved [33- 34].

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It is well known that the (NH3)+/(CH3) groups has stretching (ʋ1 and ʋ3) and bending (ʋ2 and ʋ4) wavenumbers in the region of 3500–2500 and 1800-900 cm-1, respectively.

For the methyl group, the asymmetric stretching mode is observed by one shoulder

very weak band located at 2936 cm-1 in the infrared spectrum while the respective Raman band is observed by one weak band located at 2947 cm-1. The corresponding value in theoretical calculations is seen at 2960 cm-1. The shoulder very weak band infrared located at 2852 cm-1 is assigned to the symmetric stretching mode of CH3 group while the counterparts Raman is obtained by one

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ACCEPTED MANUSCRIPT very weak broad band at 2876 cm-1. This vibrational behavior is observed by us BHHLYP calculations at 2885 cm-1. These values are similar to those observed by Altun and all [35]. The asymmetric deformation of CH3 group is

observed as very weak, medium and

weak bands between 1578 and 1504 cm-1 in the infrared spectrum while in Raman it is absent. In contrast, the symmetric deformation mode (umbrella mode) is observed by one medium

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band located at 1493 cm-1 in the infrared spectrum and one shoulder very weak band located at1481 cm-1 in the Raman spectrum [48].

The very weak band observed in Infrared spectrum at 1048 cm-1 and the shoulder band observed in Raman spectrum at 1056 cm-1

are assigned the rocking mode of CH3

group [22, 48].

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For the NH3+ group, the three hydrogen atoms are hydrogen bonded with three oxygen atoms of the HSO4- anion. These hydrogen atoms placed between two electronegative atoms

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(donor; Nitrogen and acceptor; Oxygen) vibrate differently than a free NH3 group. These hydrogen bonds are also responsible for lowering the stretching wave numbers and shifting the deformation modes to higher wave numbers [49-51]. Hence, the ʋas(NH…O) asymmetric stretching are observed by three bands detected in the region between 2984-2744 , whereas the corresponding bands of the symmetric stretching are absent.

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In the crystal structure, there are three hydrogen bonds of the N-H…O type. According to previous studies, there are one band corresponds to each of the hydrogen bond [13, 52, 53]. Indeed, the shoulder very weak band located at 2936 cm-1 in IR and very weak at 2947 cm-1 in Raman are assigned to the longest hydrogen bond (N-H0B…O3), the very weak band

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observed at 2802 cm-1 in IR is assigned to shorter than the first hydrogen bond (N-H0A…O4) and the weak band located at 2744 cm-1 in IR and very weak broad at 2758 cm-1 are assigned

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to the shorter hydrogen bond (N-H0C…O2). Also, the asymmetric deformation is observed by one shoulder very weak band

located at 1740 cm-1 in infrared spectra while the respective Raman band is observed by one very weak broad at 1740 cm-1. In theoretical calculation, this mode observed by one band located at 1732 cm-1.

The corresponding band due to the symmetric deformation mode (umbrella mode) of NH3 group is observed at 1710 cm-1 in Infrared spectrum and at 1717 cm-1 in the theoretical calculation while in Raman it is absent. The vibrational frequencies observed in the infrared spectrum at 1157 cm-1 and at 1172, and at 1158 cm-1 in the Raman spectrum are attributed to the rocking mode of NH3 group. The corresponding value in theoretical calculations is seen at 1161 cm-1. The rotation mode of the 12

ACCEPTED MANUSCRIPT NH3 group is observed by two shoulder bands seen at 572 and 632 cm-1 in the infrared spectrum. The corresponding band in the Raman spectrum is observed by one very weak band seen at 652 cm-1. 4. Conclusion This paper presents the synthesis, structural determination, thermal analysis and

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vibrational spectroscopy coupled with the theoretical calculations of a new hybrid compound [2-CH3C6H4NH3]HSO4.H2O. This structure was performed at room temperature by single crystal X-ray analysis, showing that this compound is crystallized in a monoclinic system P 21/c. The crystal structure of this compound was found to be built by infinite layers of Between these layers, the

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HSO4.H2O parallel to the bc planes around x = 1/2.

2-methylanilinium cations are located. Both inorganic and organic components perform different interactions (H-bonds and π ... π

interactions) to stabilize the three-dimensional

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network. The existence of a single phase at room temperature is confirmed by X-ray powder diffraction.

The thermal behavior of the title compound was studied by the thermo gravimetric analysis coupled with the differential thermal analysis in the temperature range between 300 and 650 K. it indicated that the studied compound is not stable. Furthermore , the difference

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between the two lines detected at 300 and 400 K and the thermal behavior detected by the TG-DTA of the title compound in the temperature range between 380- 415 K confirm the existence of structural phase transition coupled to the dehydration of the title compound. Besides, the vibrational frequencies of (2CH3-C6H4NH3)HSO4.H2O have been investigated by

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DFT (BHHLYP) method. Moreover, the IR and Raman spectra have been recorded in the range of [400–4000] and [50–4000] cm-1. The vibrational frequency analyses by DFT calculations agree well with the experimental results. Building on the agreement between the

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experimental and calculated results, the assignment of all vibrational modes of the title compound were examined and proposed in this investigation.

Supplementary material

CCDC 934530 contains supplementary crystallographic data for this paper. This data can be obtained free of charge via ttp:// www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Rood, Cambridge CB2 1EZ, UK (Fax: (international): +44 1223/336 033; e-mail: deposit@ ccdc.cam.ac.uk)

References 13

ACCEPTED MANUSCRIPT [1] N. B. Cherif, A. Direm, F. Allouche, L. B. H. Benmenni and K. Soudani, Acta Cryst., E63 (2007) 2054-2056. [2] C.-X. Yin, F.-J. Huo and P. Yang, Acta Cryst., E62 (2006) 2084-2085. [3] F. Giordano, Acta Cryst., B36 (1980) 2458-2460. [4] Z. Elaoud , S. AL-Juaid , T. Mhiri , A. Daoud, J. Alloys Compd., 442 (2007) 306-309.

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[5] Z. Boutobba, A. Direm and N. B. Cherif, Acta Cryst., E66 (2010) 595-597.

[6] M. M. Ilczyszyn, A. J. Barnes, A. Pietraszko and H Ratajaczak, J. Mol. Struct., 354 (1995) 109-118.

[7] T. Sahbani, W. Smirani, Salem S. Al-Deyab and M. Rzaigui, , J. Mater. Res. Bull,. 47

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[8] N. B. Cherif, H. Boussekine, Z. Boutobba and A. Kateb. Acta cryst., E63 (2007) 3287-

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3289.

[9] H. Khemiri, S. Akriche and M. Rzaigui, Acta cryst., E65 (2009) 1152-1154. [10] K. M. Anderson, A. E. Goeta, J. E. Martin, S. A. Mason, G. J. McIntyre, B. C. R. Sansam, C. Wilkinson, J. W. Steed, J. Cryst. Growth Des.,11 (2011) 4904-4919. [11] C. Ben Hassen, M. Boujelbene, M. Khitouni, J. J. Suñol, T. Mhiri, Mediterr. J. Chem.., 2(6) (2014), 701-707.

(2014) 602–608.

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[12] A. I. Gubin, G. D. Khakimzhanova, N. N. Nurakhemetov, R. S. Erkasov, M. Z. Buranbaev, J. Soviet physics. Crystallography, 35 (1990) 925-927. [13] C. Ben hassen, M. Boujelbene, M. Bahri, N. Zouari and T. Mhiri, J. Mol. Struct., 1074

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[14] International Tables for X-ray Crystallography, vol. C, Kluwer, Dordrecht, 1992. [15] G.M. Sheldrick, SHELXS-97, Programs for Crystal Solution, University of

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Gottingen, Germany, 1997.

[16] G.M. Sheldrick, SHELXL-97, Programs for Crystal Structure Refinement, University of Gottingen, Germany, 1997. [17] K. Brandenburg, Diamond Version 2.0 Impact GbR. Bonn, Germany, 1998. [18] M.W. Schmidt, K.K. Baldridge, J.A. Boatz, S.T. Elbert, M.S. Gorden, J.H. Jensen, S. Koseki, N. Matsunaga, K.A. Nguyen, S.J. Su, T.L. Windus, M. Dupuis, J.A. Montgomery, J. Comp. Chem. 14 (1993) 1347- 1363. [19] A. K. Pathak, T. Mukherjee and D. K. Maity, J. Chem. Phys. Chem 11 (2010) 220-228. [20] C. Janiak, J. Chem. Soc. Dalton. Trans.,(2000) 3885-3896. [21] I.D. Brown, Acta Crystallogr., A32 (1976) 24-31. [22] E. H. Soumhi, A. Driss and T. Jouini, J. Mater. Res. Bull.,29 (1994) 767-775. 14

ACCEPTED MANUSCRIPT [23] K. Kaabi, C. Ben Nasr and M. Rzaigui, J. Phys. Chem. Solids, 65 (2004) 1759-1764. [24] W. Baur, Acta Crystallogr., B30 (1974) 1195-1215. [25] J. Rodriguez-Carvajal, Programme FULLPROF, version 2.6.1., 2005. [26] T. Roisnel, J. Rodriguez-Carvajal, Programme WinPLOTR, Mater

Sci Forum,118

(2001) 378-381.

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[27] G. Singh, I. P. Singh Kapoor, J. Singh, Thermochim. Acta 335 (1999) 11-17. [28] J. A. Boatz, M. S. Gordon, J. Phys. Chem. 93 (1989) 1819-1826.

[29] Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Wiley-Interscience, 1986.

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[30]M. Belhouchet, M. Bahri, J. M. Savariault and T. Mhiri, J. Spectrochim. Acta, Part A., 61 (2005) 387-393.

[31] G. Varsanyi, S. Szoke, Vibratinal Spectra of Benzene Derivatives, Academic Press, New

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York, 1969.

[32] F.A. Miller, J. Raman Spectrosc. 19 (1988) 219-221.

[33] E. Akalin and S. Akyuz, J. Mol Struct. 482 (1999) 175–181.

[34] W. B. Tzeng and K. Narayanan , J. Mol Struct 446 (1998) 93-102. [35] A. Altun, K. Golcuk, M. Kumru , J. Mol Struct (Theochem) 625 (2003) 17–24.

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[36] W.B. Tzeng, K. Narayanan, J .L. Lin and C. C. Tung, J. Spectrochim. Acta, Part A., 55 (1999) 153–162

[37] A. Altun, K. Golcuk and M. Kumru , J. Mol Struct (Theochem) 637 (2003) 155–169 [38] Y. Koysal and H. Tanak, J. Spectrochim. Acta, Part A., 93 (2012) 106–115.

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[39] V. Arjunan, N. Puviarasan and S. Mohan, J. Spectrochim. Acta, Part A., 64 (2006) 233– 239

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[40] H. Tanak, K. Pawlus, M. K. Marchewka and A. Pietraszko, J. Spectrochim. Acta, Part A., 118 (2014) 82–93

[41] V. Arjunan, P. Ravindran, K. Subhalakshmi and S. Mohan, J. Spectrochim. Acta, Part A., 74 (2009) 607–616.

[42] V. Arjunan, T. Rani, C. V. Mythili and S. Mohan, European Journal of Chemistry 2 (1) (2011) 70‐76 [43] N. Puviarasan, V. Arjunan and S. Mohan, Turk. J. Chem. 26 (2002) 323. [44]. S. Periandy and S. Mohan, Proc. Nat. Acad. Sci. India, 68A, III, 1998. [45]. S. Periandy and S. Mohan, Asian J. Chem. 84, 707, 1996. [46] J. R. Ferraro, G. Sill and U. Fink, Appl. Spectrosc. 34 (1980) 525-533.

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ACCEPTED MANUSCRIPT [47] M. Kurt, M. Yurdakul and S. Yurdakul, J. Mol. Struct. (Theochem.) 711 (2004) 2532. [48] E. Lizarraga, E. Romano, A. Raschi, P. Leyton, C. Paipa, C. A. N. Catalán and S. A. Brandán, J. Mol Struct., 1048 (2013) 331–338 [49] V. Krishnakumar and R. John Xavier, J. Spectrochim. Acta, Part A., 61 (2005) 253–

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260. [50] J. Bernstein, R.E. Davis, L. Shimoni and N. L. Chang, Angew. Chem. Int. Ed. Engl. 34 (1995) 1555–1573.

[51] R. Anitha, S. Athimoolam, M. Gunasekaran and K. Anitha, J. Mol struct., 1076 (2014)

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115–125

[52] M. K. Marchewka, M. Drozd and A. Pietraszko, J. Mat. Sci. Eng., B100 (2003) 225-233

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[53] M. K. Marchewka and A. Pietraszko, J. Phys. Chem., 66 (2005) 1039–1048.

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ACCEPTED MANUSCRIPT Table 1:Crystal data and experimental parameters used for the intensity data collection strategy and final results of the structure determination. Table 2: Atomic coordinates and equivalent isotropic displacement parameters for (2CH3C6H4NH3)HSO4.H2O. Table 3: Hydrogen-bond geometry (Å).

arrangement. Table 5: Experimental and calculated frequencies (cm-1) of the

(2-

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CH3C6H4NH3)HSO4.H2O compound.

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Table 4: Main distances (Å) and angles (°) for (2-CH3C6H4NH3)HSO4.H2O atomic

1

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293(2) K

Empirical Formula

C7H14NO5S

Formula Weight (g.mol-1)

223.24

Crystal system

Monoclinic

Space group

P 21/c

a

9.445 (5) Å

b

10.499 (5) Å

c

10.073 (5) Å

α

90°

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Temperature

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Table 1.

Β

90.627 (5)°

γ

90°

Z

4

998.8 (9) Å3

V

1.485 Mg m−3

ρcal F(000)

152

0.32 mm−1

Index ranges

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µ (Mo Kα)

-11≤ h ≤ 10.-11 ≤ k ≤12.-11 ≤ l ≤ 5 4313

Independent reflexions

1654

reflections with I> 2σ(I)

1367

Rint

0.023

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Reflexionscollected

Refinedparameters 2

140

2

R[F > 2σ(F )]

0.035

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2

wR(F )

0.095

Goodness of fit

1.11

θmin

2.2°

θmax

25°

2

ACCEPTED MANUSCRIPT Table 2.

Y

Z

Uiso*/Ueq

S

0.48880 (6)

0.35945 (6)

0.73511 (6)

0.0285 (2)

O1

0.3946 (2)

0.44685 (18)

0.65640 (19)

0.0462 (5)

O2

0.49911 (18)

0.23821 (16)

0.66830 (17)

O3

0.62499 (18)

0.42373 (19)

0.75148 (18)

O4

0.42314 (18)

0.34495 (16)

0.86620 (16)

OW

0.33392 (18)

0.38606 (17)

0.42848 (17)

N

0.68891 (18)

0.07736 (18)

0.54003 (19)

0.0290 (4)

H0A

0.6666

−0.0002

0.5688

0.044

H0B

0.6811

0.0798

0.4519

0.044

H0C

0.6304

0.1342

0.5753

0.044

C1

0.8356 (2)

0.1075 (2)

0.5799 (2)

0.0267 (5)

C2

0.8926 (2)

0.2223 (2)

0.5401 (2)

0.0338 (6)

C3

1.0321 (3)

0.2461 (3)

0.5793 (3)

0.0485 (7)

H3

1.0750

0.3219

0.5539

0.058*

C4

1.1077 (3)

0.1600 (3)

0.6548 (3)

0.0535 (8)

H4

1.2006

0.1783

0.6799

0.064

C5

1.0472 (3)

0.0471 (3)

0.6933 (3)

0.0462 (7)

H5

1.0986

−0.0106

0.7446

0.055

C6

0.9091 (2)

0.0200 (2)

0.6552 (2)

0.0339 (6)

H6

0.8668

−0.0562

0.6802

0.041

0.0398 (5) 0.0493 (5) 0.0389 (4) 0.0385 (4)

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X

C7

0.8105 (3)

0.3152 (3)

0.4556 (3)

0.0512 (7)

H7A

0.8680

0.3887

0.4385

0.077

H7B

0.7265

0.3408

0.5014

0.077

H7C

0.7846

0.2755

0.3730

0.077

HW1

0.360 (3)

0.3080 (9)

0.409 (2)

0.071 (11)

HW2

0.353 (3)

0.4457 (14)

0.3699 (17)

0.080 (12)

H1

0.369 (4)

0.424 (3)

0.5823 (15)

0.117 (17)

[ Uéq=1/3∑i∑j Uij ai* aj* ai aj]

3

ACCEPTED MANUSCRIPT Table 3.

H…O(Ǻ)

(O/N)…H(Ǻ)

(O/N)-H...O(°)

OW-HW1…O4i

0.88(2)

1.771(2)

2.646(6)

172.88(3)

OW-HW2…O3ii

0.88(2)

1.862(3)

2.727(7)

167.44(3)

O1-H1…OW

0.821(2)

1.626(5)

2.445(5)

176.07(3)

N-H0A…O4iii

0.890(2)

1.950(5)

2.826(7)

167.47(3)

N-H0B…O3i

0.890(2)

2.082(7)

2.962(4)

169.66(3)

N-H0C…O2

0.890(2)

1.906(3)

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(O/N)-H(Ǻ)

2.790(8)

172.03(3)

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Note: symmetry code ; (i) : x, -y+1/2, x-1/2 ; ( ii): –x +1, -y+1, -z+1 ; (iii) : –x +1, y -1/2 , -z+3/2

Table 4. 4

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Bond lengths (Å)

Angles (°)

1.499(2)

O1-S-O2

106.63(11)

S-O2

1.444(2)

O1-S-O3

107.08(12)

S-O3

1.461(2)

O1-S-O4

106.52(11)

S-O4

1.473(2)

O2-S-O3

113.34(11)

O2-S-O3 O3-S-O4

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S-O1

110.97(10) 109.00(11)

C1-C2

1.381(3)

C1-C2-C3

116.4(2)

C2-C3

1.394(4)

C2-C3-C4

C3-C4

1.377(4)

C3-C4-C5

C4-C5

1.373(4)

C4-C5-C6

119.5(3)

C5-C6

1.386(3)

C5-C6-C1

118.9(3)

C6-C1

1.375(4)

C2-C7

1.504(2)

C1-N

1.473(3)

121.4(3)

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120.5(2)

Table 5. 5

C6-C1-C2

123.2(2)

C1-C2-C7

122(2)

C3-C2-C7

121.6(2)

C6-C1-N

118.3(2)

C2-C1-N

118.5(2)

ACCEPTED MANUSCRIPT Experimental IR Raman 3595 vw, br 3500 w, br 3490 vw 3090 w 3074 vw 3071 w 3032 sh, vw 3031 vw 3000 vw 3002 vw

2876 vw,br 2758 vw, br

1740 sh, vw

1744 vw,br

1710 w 1632 m 1602 vw

1074 vw 1048 vw 1031 vw 994 vw 943 vw -

1652 sh, vw 1620 w 1600 sh, vw 1481 sh,vw 1466 vw 1450 vw 1406 w 1330 vw 1312 vw 1251 w 1223 vw 1209 vw 1172 vw 1158 sh, vw 1109 vw 1102 vw 1092 vw 1065 w 1056 sh 1013 vw 995 m 934 vw -

875 m, br 828 w , br 760 VS 742 sh 702 w

880 vw 760 m 727 vw -

2885 2812 2785 1749 1732 1717 1637 1600

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1578 vw 1532 m 1504 w 1493 m 1462 w 1448 sh 1428 sh 1386 vw 1313 vw 1238 sh, vw 1157 m, br 1123 m, br -

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2852 vw 2802 vw 2744 w

2990 2960 2946

1566 1551 1532 1485 1472 1446 1397 1385 1320 1233 1227 1215 1214 1161 1109 1105 1098 1092 1056 1038 1003 940 928 898

δasy (H2O) δasy (NH3) + ʋ(C=C) δsy (NH3) (umbrella) ʋ(C=C)

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2947 w

ʋas(H2O) ʋas(H2O) ʋ(CH)ar ʋ(CH)ar ʋ(CH)ar ʋ(CH)ar ʋ(OH…O) ʋasy(CH3) ʋ(N-H…O)i ʋsy(CH3) ʋ(N-H…O)j ʋ(N-H…O)k

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2936 sh, vw

3543 3490 3051 3041 3032 3021

ʋ(C=C) + ʋ(C=C) + δ(CH)ar

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2985 vw

Asignment

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2984 sh, vw

Calculated

δasy (CH3) δasy (CH3) δasy (CH3)+ ʋ(C=C) + δ(CH)ar δsy (CH3) (umbrella) δ(O-H) δ(O-H) δ(CCC) + δ(CH)ar+ ʋ(C-N) + ʋ(C-Cm) δ(CCC) + δ(CH)ar+ ʋ(C-N) + ʋ(C-Cm) δ(CCC) + δ(CH)ar δ(CH)ar δ(CH)ar δ(CH)ar δ(CH)ar ρ(NH3) + δ(CCC)

ʋ3(SO4)+ δ(CCC) ʋ3(SO4) ʋ3(SO4) ʋ3(SO4) ρ(CH3) + δ(CCC) ɤ(CH)ar

ɤ(CH)ar+ɤ(CCC)ar ʋ1(SO4) ʋ1(SO4) ʋ1(SO4) δ(CCC)ar + δ(CH)ar+ ʋ(C-N) + ʋ(C-Cm) ɤ(CH)ar + ɤ(CCC)ar ɤ(CH)ar+ɤ(CCC)ar

873 794 757 -

6

ACCEPTED MANUSCRIPT 632 619 592

572 sh 560 sh 548 sh 512 m 503 m 475 vw

540 w 512 vw 503 vw 482 vw

586 560 544 475 473 467

448 sh 438 VS 420 S

448 vw 235 br 155 sh 132 sh 114 VS 80 VS 56 sh

441 420 240 157 128 104 80 58

rot (NH3 ) + δ(CCC) ʋ4(SO4) ʋ4(SO4) rot (NH3 ) ɤ(CCC)ar δ(CCC)ar ɤ(CCC)ar ɤ(CCC)ar δ(CCC)ar ʋ2(SO4)

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658 vw 600 w -

Trans (H2O) rot(CH3)+ Trans (HSO4) Trans (org) Trans (org) + tor (HSO4) , tor (H2O) rot (HSO4) , rot (H2O) Lattice vibration

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632 sh 594 S -

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s, strong; w, weak; v, very; sh, shoulder; br, broad; m, medium; ʋ, stretching,δ, in plane bending; γ, out of plane bending;ρ, rocking mode ; ar; aromatic ring, met; methyl group, org; organic group, Trans , translation mode, rot; rotation mode, tor, torsion mode

7

ACCEPTED MANUSCRIPT Figure 1. Optimized structure of the organic and inorganic groups coordinated (H-bonds are

Figure 2. a.

Exprimental Raman

spectra in the

50–400 cm-1 of

(2-

400–1800 cm-1 of

(2-

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represented by dashed lines).

2600–3800 cm-1 of

(2-

400–1800 cm-1 of

(2-

2600–3800 cm-1 of

(2-

range

CH3C6H4NH3)HSO4.H2O at room temperature. Figure 2. b. Exprimental Raman

spectra in the

range

CH3C6H4NH3)HSO4.H2O at room temperature. Figure 2. c. Exprimental Raman

spectra in the

range

CH3C6H4NH3)HSO4.H2O at room temperature. Figure 3. a. Exprimental IR

spectra in the

range

Figure 3. b.

Exprimental IR

spectra in the

CH3C6H4NH3)HSO4.H2O at room temperature.

range

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Figure 4. Asymmetric unit of the title structure

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CH3C6H4NH3)HSO4.H2O at room temperature.

Figure 5. H-Bonds between inorganic-inorganic and organic-inorganic entities in the crystal structure of (2-CH3C6H4NH3)HSO4.H2O in projection along the a-axis. Figure 6. The atomic arrangement of (2-CH3C6H4NH3)HSO4.H2O in projection along the baxis.

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Figure 7. Offset-face-to-face interactions motifs (π - π stacking, broken lines) in the cationcation layer.

Figure 8. The final Rietveld refinement plot of the (2-CH3C6H4NH3)HSO4.H2O. Points

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correspond to the experimental values and the continuous lines; the calculated pattern and vertical bars indicate the positions of Bragg peaks. The bottom trace depicts the difference

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between the experimental and the calculated intensity values. Figure 9. The differential thermal analysis (DTA) and the thermogravimetry (TG) of (2CH3C6H4NH3)HSO4.H2O.

Figure 10. X-ray powder diffraction in function of temperature of the title compound.

.

1

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Figure 1.

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Figure 2. a.

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Figure 2. b.

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Figure 2. c.

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Figure 3. a.

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Figure 3. b.

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Figure 4.

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Figure 5.

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Figure 6.

10

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Figure 7.

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Figure 8.

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Figure 9.

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Figure 10.

14

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Highlights

- (2-CH3C6H4NH3)HSO4.H2O. is a new two dimensional hybrid compound. Vibrational properties were studied by infrared spectroscopy and by DFT calculation.

-

Thermal decomposition was studied by TG- DTA and X-ray powder diffraction in

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-

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function of temperature.