Journal of Molecular Structure 1144 (2017) 25e32 Contents lists available at ScienceDirect Journal of Molecular Structure journal homepage: http://www.elsevier.com/locate/molstruc Synthesis, crystal structure, and spectroscopic characterization supported by DFT calculations of organoarsenic compound * Nasreddine Ennaceur, Ph.D a, b, , Rokaya Henchiri a, b, Boutheina Jalel a, b, Marie Cordier c, Isabelle Ledoux-Rak b, Elimame Elaloui a a Laboratory of Materials, Energy and Environment UR 14/ES 26 University of Gafsa, 2100 Gafsa, Tunisia b Laboratory of Quantum and Molecular Photonics, Institut d'Alembert, Ecole Normale Superieure de Cachan, 94230 Cachan, France c Molecular Chemistry Laboratory, UMR 9168, Ecole Polytechnique, CNRS, 91128 Palaiseau Cedex, France article info abstract Article history: A new semi-organic hydrogen bonding complex salt of 2-ammonium phenylarsonic acid and nitric acid Received 21 March 2017 has been synthesized, thus successfully growing good quality single crystals by means of slow solvent Received in revised form evaporation technique at ambient temperature. The 1H and 13C NMR spectra were recorded to establish 1 May 2017 the molecular structure. The conducted single crystal XRD analysis has shown that the title salt is Accepted 3 May 2017 crystalized in orthorhombic crystal system with centrosymmetric Pbcm space group. The structure Available online 3 May 2017 fi þ À consists of in nite parallel two-dimensional planes built of (C6H6NH3AsO3) organic cation and NO3 inorganic anions connected by hydrogen bonds and p-p interactions giving birth a three-dimensional Keywords: Crystal growth network. The performed TG/DSC thermal analysis has established the thermal stability of the crystal. X-ray diffraction The optimized structural parameters and vibrational frequencies (the experimental and theoretical DFT calculations vibrational frequencies) were assigned and compared by the Density Functional Theory (DFT) using the Optimized geometry Gaussian method (DFT/B3LYP). Good consistency results were found between the calculated and the Delocalized p-electron experimental crystal structure and FT-IR spectra. Infrared spectroscopy © 2017 Elsevier B.V. All rights reserved. Thermal behavior 1. Introduction coccidial intestinal parasites [6e8]. Furthermore, arsanilic acid and its analogs react with several metal ions at different pH values to Aminophenylarsonic acid (ortho and para) was known as a form precipitates, due to the fact that the arsenate group AsO(OH)2 biomedical molecule for example an antihelminth in veterinary acts as a bidentate ligand. This allows the preparation of polymers applications [1]. Besides, some are still used against trypanosomal with good chelating properties [9e13]. Besides, during the last infection despite their toxicity [2] and more commonly as a pre- decade, the search for new efficient nonlinear optical (NLO) ma- viously employed antisyphilitic drug [3], when used as the hy- terials has led to a large investigation for suitable organic, polymers drated sodium salt, under a variety of common names, namely and hybrid compounds [14e17] thanks to their high nonlinear atoxyl. These structures are among only a small number of exam- optical properties compared to inorganic NLO materials. Such in- ples in the crystallographic literature involving this acid in any terest has been driven by a number of potential applications, as form, which include the complexes with some metals like silver, second harmonic generation (SHG), electrooptic modulation, fre- zinc, cadmium, lead and the sodium salt of a hybrid organic- quency mixing and optical parameter oscillation, among others. inorganic polyoxovanadate cluster complex formed with arsani- However, the majority of organic materials crystallized in late anions [4,5]. centrosymmetric space groups and consequently they fail to Moreover, arsanilic acid is an aromatic organoarsenic compound exhibit SHG. To generate SHG from organic structures, different that has been widely used as a feed additive in the poultry and pig techniques have been used to remove the centre of symmetry along farms to improve the growth rate, feed efficiency, and control with the internal charge transfer within conjugated molecules to achieve efficient optical nonlinear effects. The hydrogen-bonding character in organic and inorganic materials can also introduce * Corresponding author. Laboratory of Materials, Energy and Environment UR 14/ noncentrosymmetric crystal structure [18,19]. It is this insufficiency ES 26 University of Gafsa, 2100 Gafsa, Tunisia. found in the literature that encouraged us to make this combined E-mail address: [email protected] (N. Ennaceur). http://dx.doi.org/10.1016/j.molstruc.2017.05.007 0022-2860/© 2017 Elsevier B.V. All rights reserved. 26 N. Ennaceur et al. / Journal of Molecular Structure 1144 (2017) 25e32 theoretical and experimental study, as it is a powerful tool for the employing a Perkin Elmer FT-IR spectrometer in the range À confirmation of the expected crystal obtaining and the description 4000e400 cm 1. The TGA and DSC studies were carried out on a of crystalline materials (nitrate 2-aminophenylarsonate mono- PERKIN ELMER DIAMOND instrument with a heating rate of 10 C/ hydrate abbreviated NAPM). The spectroscopic analysis can also min in the temperature range from 20 to 600 C in nitrogen at- provide more precise information about the strong relation be- mosphere. The UVevis spectrum of the molecule was also recorded tween molecular structure and charge transfer. The present by the UVeVis spectrophotometer in the wavelength region research work deals with the single X-ray diffraction (XRD) study, 200e800 nm using deionized water as a solvent. the detailed vibrational spectral studies assisted by density func- tional theory (DFT) calculations, nuclear magnetic resonance 3. Results and discussion spectral studies, ultravioletevisible (UVeVis) spectroscopic studies and thermal analysis TGeDSC of the NAPM. 3.1. EDAX analysis 2. Experimental procedure The percentage composition of the elements present in NAPM was confirmed by using JEOL JSM-6380LA analytical scanning 2.1. Materials synthesis, crystal growth electron microscope (SEM) system. Fig. 2 shows the resulting spectrum over a certain area. The typical peaks in the spectrum The starting material of 2-aminophenylarsonic acid and nitric proved the presence of various elements in the grown crystal. acid was taken in 1:1 stoichiometric ratio to synthesize nitrate 2- aminophenylarsonate monohydrate. The calculated amount of the 3.2. Single crystal X - ray diffraction study 2-aminophenylarsonic acid was first dissolved in deionized water. The nitric acid was then slowly added to the solution by stirring. The single crystal of NAPM compound was mounted on a Kapton The prepared solution was allowed to dry at room temperature and loop using a Paratone N oil. An APEX II CCD BRUKER detector and a the salt was obtained by slow evaporation technique. The purity of graphite Mo-Ka monochromator was used to obtain the data. One 3 the synthesized salt was successfully improved by recrystallization. single crystal of the size of 0.26 Â 0.20 Â 0.080 mm was used for After 20 days of growth, a transparent single crystal of dimension the present study. All measurements were carried out at 150 K, a 10 Â 9 Â 4 mm was obtained by the slow evaporation technique. refinement method was used for solving the structure, whose The photograph of the as-grown crystal of NAPM is shown in Fig. 1. resolution was accomplished using the SHELXT-2014 [20] program, The crystal had good compositional stability and showed no and the refinement was done with the SHELXL-2014 program [21]. degradation when stored in the open air for several months. NAPM The solution structure and refinement were achieved with was synthesized according to the following chemical reaction. the PLATON software. During the refinement steps, all atoms except hydrogens were refined anisotropically. The position of the H O C H NH AsO þ HNO 2!ðC H AsNO ÞðNO Þ$H O hydrogen was determined using residual electronic densities, 6 6 2 3 3 6 9 3 3 2 which are calculated by a Fourier difference. The single crystal diffraction studies were carried out to find the crystal structure and the cell parameters of the grown material. The single crystal XRD 2.2. Characterization study has proven that the crystal belongs to orthorombic system, and the space group has been found as Pbcm with the lattice pa- To confirm the molecular structure of NAPM crystal, the per- rameters: a ¼ 11.6562(3) Å, b ¼ 12.1577(3) Å, c ¼ 7.4854(2) Å and 3 centage composition of the elements present in NAPM was V ¼ 1060.78(5) Å . The crystal data and the structure refinement for confirmed by using JEOL JSM-6380LA analytical scanning electron NAPM material is given in Table 1. Isotropic or equivalent isotropic microscope (SEM) system. The NMR study was recorded employing displacement parameters and fractional atomic coordinates are a Bruker 400 MHz spectrometer in deuterated solvent. The crystal summarized in Table 2. For further details of the structure deter- structure was determined from the single-crystal X-ray diffraction mination, they are available from the Cambridge crystallographic data obtained with an APEX CCD area-detector diffractometer. FT-IR data centre CCDC 1476254. spectrum was recorded using potassium bromide pellet method 3.2.1. Description of the structure The structural determination of NAPM compound has estab- lished the structural model in which the asymmetric unit (Fig. 3) þ consists of a protonated organic cation (C6H6NH3AsO3) , one À inorganic anions NO3 and H2O molecule. These entities are linked by hydrogen bonds and p-p interactions involving a crystal struc- ture in a three-dimensional network. Fig. 4 shows the projection of the crystal structure of NAPM in the (a, b) plane. Anionic group constituted by nitrate developed in wires along the [100] direction þ alternately with the cationic group (C6H6NH3AsO3) and water molecule H2O. The latter are inserted between the organic (cationic) and mineral (anionic) groups. These positions provide stability and cohesion to the structure. 3.2.2.