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A new organic–inorganic hybrid centrosymmetric compound, (C4H12NO3)CdCl3·H2O, was synthesized by the slow evaporation method at room temperature and characterized by single X-ray diffraction (SCXRD). The results of the X-ray diffraction study demonstrated that this material crystallizes in the triclinic system with the space group P 1 ¯ and the following unit cell parameters a = 6.822(6) A, b = 8.96(2) A, c = 10.034(3) A, α = 72.901(3)°, β = 71.927(3)°, γ = 89.099(3)° and Z = 2. In the crystal structure, the atomic arrangement is described as an alternation of organic and inorganic layers along the a-axis. The anionic layers are formed by [CdCl5O]− octahedrons, while the cationic layers are made up of [C4H12NO3]+ cations. The crystal packing is governed by N H⋯Cl, N H⋯O, C H⋯Cl, O H⋯Cl and O H⋯O hydrogen bonds, forming a three dimensional supramolecular network. Hirshfeld surfaces and 2D fingerprint plots were determined for visualizing, exploring and quantifying the intermolecular interactions in the crystal lattice of the title compound. Infrared and Raman spectroscopy were reported at room temperature in the frequency domains 400–4000 cm−1 and 50–500 cm−1, respectively. Differential scanning calorimetry (DSC) revealed one exothermic peak located at around T1 = 368 K. Electrical and dielectric properties were investigated as a function of temperature (300–430 K) in the frequency range 40 Hz–110 MHz. The electrical and dielectric studies were performed by means of impedance spectroscopy and dielectric permittivity e ' , e ' ' . Nyquist curves were well fitted to an equivalent circuit formed by parallel combination resistance and capacity fractal of the bulk. The frequency dependence of the alternative current (AC) conductivity was analyzed using the Jonscher law. Overlapping-large polaron tunneling (OLPT) and non-overlapping small polaron tunneling (NSPT) conduction mechanism models successfully explained the behavior of the exponent n.

In this work, a new hybrid material (C5H6N2Cl)2[FeCl4].Cl abbreviated (CAP)2[FeCl4].Cl was prepared using room temperature slow evaporation technique. The X-ray diffraction analysis revealed that the compound is crystallized in the centrosymmetric space group P21/c of the monoclinic system. The crystallographic network consists of an Fe(III) ion located on an inversion center and coordinated by four chlorine, isolated Cl– and two (CAP)+ protonated cations linked by N–H...Cl and C–H...Cl hydrogen bonds to form a zero-dimensional network. Hirshfeld surface analysis was used to analyze intermolecular interactions present in the crystal structure. The vibrational properties were inspected by means of Infra-Red absorption and Raman diffusion spectroscopy techniques. In addition, theoretical calculations based on the DFT/B3LYP/LanL2DZ method and the time-dependent density functional theory (TD–DFT) were performed in order to gain more information and help in the examination of over-all properties of the title compound. Good and interesting experimental findings were presented and good consistency was found with the calculated results. Keywords: Semiconductor material, X-ray diffraction, Hirshfeld surface, Vibrational, Optical, DFT calculations

In this work, we report the synthesis, molecular structure, the vibrational spectral (FT-IR, FT-Raman) analysis and optical properties of the investigated novel non linear optical bis(2, 2, 6, 6– Tetramethylpiperidinium–1–yl) oxidanyl tetrachlorocuprate (II), having a general chemical formula (C9H19NO)2 [CuCl4] abbreviated as (TEMPO-H)2 [CuCl4]. The molecular structure crystallises in the orthorhombic system with the P212121 space group. The crystalline stability is installed by a zero-dimensional network using hydrogen bonds between O H⋯Cl, N H⋯Cl and C H⋯O. In addition, a 3-D Hirshfeld surface analysis was performed to study molecular interactions and connect them with 2-D fingerprint schemes to detect the relative contribution of these interactions to the crystalline structure. Molecular structure, vibrating wave number, non-linear optical characterization (NLO), and Mulliken were calculated with B3LYP/LanL2DZ (DFT the Density Functional Theory) using GAUSSIAN09. The optimized geometry and the vibrational spectra calculated results compared to experimental data, showed a good overall agreement. The UV–Visible absorption and the photoluminescence (PL) spectroscopy of (TEMPO–H)2 [CuCl4] were also presented. The unaided-eye-detectable blue luminescence emission comes from the excitonic transition in the CuCl4 anions. Finally, the electronic property was determined by time-dependent DFT (TD-DFT) approach.

In this work, single crystals of the new hybrid material (C9H8NO)2[FeCl4]·Cl abbreviated (8–HQ)2[FeCl4]·Cl were grown by the solvent evaporation method. The X-ray diffraction (XRD) analysis revealed a triclinic system with space group Pī. The crystal packing is stabilized by hydrogen bonds and π–π interactions. Moreover, Hirshfeld surface analysis was performed to achieve a quantitative insight into the intermolecular interactions. The theoretical analysis of the compound was carried out by (DFT) calculations. The optimized molecular structure and the vibrational spectra are in good consistency with the experimental data. The UV–Visible absorption and the photoluminescence (PL) of (8–HQ)2[FeCl4]·Cl were also presented. The photoluminescence measurements showed a blue emission around 523 nm at room temperature. The lowering in the HOMO and LUMO energy gap explains the eventual charge transfer interactions that take place within the molecules and illustrate its use with a range of applications to semiconducting materials that have been presented in the literature.

The present paper work investigates a new complex bis (4-amino-2-chloropyridinium) dichlorocuprate(II) with the formula [Cu(C5H5ClN2)2Cl2] abbreviated as [Cu(CAP)2Cl2]. The sample was characterized by X-ray diffraction, Hirshfeld surface analysis, thermal analysis, FT-IR, FT-Raman and CP/MAS-NMR spectroscopy and optical properties. It was crystallized in the monoclinic system with space group P21/n. The crystal structure was stabilized by the presence of N–H⋯Cl hydrogen bond, forming a three-dimensional network. The Hirshfeld surfaces and the 2D fingerprint plots were analysed in the intermolecular interactions within the crystal network. Solid state CP/MAS-NMR spectra showed five isotropic resonances, 13C confirming the existence of five non-equivalent carbon atoms of the asymmetric unit determined by X-ray diffraction. The density functional theory using B3LYP/LanL2DZ basis sets, showed an excellent overall agreement between the calculated values and the experimental data. The energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital was determined by a time-dependent DFT approach.

A novel inorganic-organic hybrid material of bis (5,7-dichloro-8-hydroxyquinolium) tetrachlorozincate (II) dihydrate was crystallized and characterized by IR, Raman, 13C NMR spectroscopy, scanning electron microscopy (SEM) and thermal analyses (TG/DTG/SDTA). The solid-state structures were determined by single crystal X-ray diffraction. The compound was found to crystallizes in the non-centrosymmetric orthorhombic system, space group P212121 with the following cell parameters a = 10.4872(3) Å, b = 13.4464 (5) Å, c = 18.0305 (7) Å, V = 2542.57(15) Ǻ3 and Z = 4, to ensure that our samples are single-phase, the purity of our products was verified by X-Ray Powder Diffraction Analysis, while the composition of our phase was verified by semi-quantitative analysis EDXS. Thermal analysis showed that the complexes decompose in three steps: the structural water was firstly progressively lost, then the neutral ligand of 5,7-dichloro-8-hydroxyquinolium and lastly the second ligand with 4 mol of chlorine in the form of hydrochloric acid. The final phase solid product at 713 °C is zinc oxide. The theoretical calculations were conducted using B3LYP/LanL2DZ basis sets using GAUSSIAN09, for studying the structural parameters, vibrational and non-linear optical characterization (NLO) of the investigated compound. The analyses of the optical spectra indicate that this compound has a direct band gap energy equal to (2.72 eV) due to direct transition. This energy is much larger than 0.02 eV. The photoluminescence properties (PL) of the compound were investigated in the solid-state at room temperature., Financial support from Faculty of Science in University of Sfax, Tunisia, Spanish Ministerio de Economía y Competitividad (MINECO-13-MAT2013-40950-R, MAT2016-78155-C2-1-R and FPI grant BES-2011-046948 to MSM.A.), Gobierno del Principado de Asturias (GRUPIN14-060) and FEDER funding are acknowledged.

Single crystals of a new organic-inorganic material (C6H10(NH3)2) CdCl4·H2O, were grown through a slow evaporation at room temperature and were characterized using X-ray diffraction, FT–IR, FT–Raman, UV–Vis and impedance spectroscopy analyses. This compound crystallizes in the monoclinic system (P21/c space group). The [CdCl4]2- anions form an infinite sheet of octahedrons and diprotonated (C6H10(NH3)2)2+ cations that are arranged in an opposite way. The crystal pattern is stabilized by 2D network via non-covalent N–H⋯Cl, N–H⋯O and O–H⋯Cl interactions. The density functional theory DFT was applied to investigate molecular structure and vibrational modes. The calculations were performed by using B3LYP functional method combined with LanL2DZ basis set. The optimized structure and the vibrational spectra are in good agreement with the experimental measurements. The topological atom-in-molecules (AIM) and the Hirshfeld Surface (HS) analyses were carried out to investigate quantitatively the intermolecular contacts in crystal packing in a visual manner. The optical properties were investigated by optical absorption explains the eventual charge transfer interactions that take place within the molecules. Finally the electrical and the dielectric properties of this compound were investigated by means of impedance spectroscopy measurements over a wide range of frequencies and temperatures, 209 Hz–5 MHz and 300–393 K, respectively. Nyquist plots reveal a non-Debye type relaxation process and confirmed that the complex impedance curves of the title compound obeyed the Cole–Cole formalism. Furthermore, The AC conductivity behavior of the compound has been analyzed by the Jonscher's universal power law.