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International audience; The stoichiometric ratio 2:1 mix of 1-phenylpiperazine and oxalic acid dihydrate followed by slow evaporation results in a new material, bis(4-phenylpiperazin-1-ium) oxalate dihydrate, with the general chemical formula (C10H15N2)2(C2O4).2H2O, indicated by PPOXH. The title compound’s asymmetric unit and three-dimensional network have been determined by single crystal X-ray diffraction. Intermolecular O-H…O, N-H…O and C-H…O hydrogen bonding assist in maintaining and stabilization of the crystal structure of this new compound. Hirshfeld surface analysis and two-dimensional fingerprints have been performed to quantify the non-covalent interactions in the PPOXH structure. The vibrational modes of the different characteristic groups of the title chemical were identified using infrared spectrum analysis. The thermal characterization of this product was studied by a coupled TG/DTA analysis. The ultraviolet-visible absorption spectrum has been used to study the optical properties and the energy gap of this compound. DFT calculations were employed to evaluate the composition and properties of PPOXH. The analysis of HOMO-LUMO frontier orbitals analysis allows us to understand the chemical reactivity of this supramolecular compound and to determine the electrophilic and nucleophilic sites responsible for electron transfer. Topological analysis (AIM), reduced density gradient (RDG), molecular electrostatic potential surface (MEPS) and Mulliken population were analyzed to evaluate the types of non-covalent interactions, localization of electrons in space, atomic charges and molecular polarity in depth. © 2023 by the authors.

International audience; This paper deals with the crystal structure of the new material (1,4-phenylenedimethanaminium) bis(perchlorate) monohydrate, (C8H14N2)(ClO4)2·H2O that was prepared in crystalline form by solvent evaporation method at room temperature. Single crystal X-ray diffraction analysis shows that this compound crystallizes in the monoclinic system, with the space group P21/c. The title structure benefits from extensive intermolecular interactions such as C-H… π interactions and hydrogen bonds which are the major forces to make it more stable in the solid-state.The interactions in the solid-state have been also studied using Hirshfeld surface analyses (dnorm, curvedness, and shape index), as well as its 2D fingerprint plots. To reinforce experimental results, DFT calculations have been performed via the B3LYP/LanL2DZ method. HOMO-LUMO energies and the chemical quantum descriptors were taken into account. AIM and RDG analysis has been explored to reveal the steadiness of the molecule. Molecular electrostatic potential inspection has also been submitted in the study.

International audience; Crystals of (H2AMP)2[FeIIIBr4]Br3, where AMP refers to the 2-(Ammoniomethyl)pyridinium ligand, have been successfully synthesized through redox chemistry and analyzed using X-ray crystallography. The new complex crystallizes as red needles in the monoclinic space group, P21/c, with eight formula weights in a unit cell of dimensions: a = 12.358 (13), b = 28.572 (3), c = 13.544 (14) Å and β=92.009(5) °. Analysis of absorption and reflectance data through the visible and near-infrared provide insight into the optical properties of the material. The structural data and the BVS (Bond Valence Sum) calculations are in agreement with the iron (III) oxidation. In this work, the experimental and theoretical study on molecular structure and vibrational spectral analysis of the new product has been reported. Theoretical calculations were performed by using density functional theory (DFT) at the B3LYP/LAN2DZ basis set levels. The electronic parameters such as frontier molecular orbital, electrostatic potential and HOMO-LUMO energy were calculated. Also, NLO were studied with the same level of DFT. The theoretical values show good agreement with experimental values. In addition, (H2AMP)2[FeIIIBr4]Br3 reveals broad absorption across the visible spectrum and an optical bandgap of 1.06 eV. Then the obtained material can be a promising eco-friendly light absorber in solar cell application. Finally, the thermal behavior of this material has been performed by TGA/DTA. In addition, two phase transitions at T1 = 108 °C and T2 = 170 °C were evidenced by DSC measurements.

International audience; This paper deals with the crystal structure of two new non-centrosymmetric hybrid compounds obtained from an aqueous solution by slow evaporation method and characterized by various techniques mainly single-crystal X-ray diffraction. In the atomic arrangement of 2-methylbenzylammonium chloride (1), the organic cations and the chloride anions are linked to each other via N-H horizontal ellipsis Cl hydrogen bonds; organic cations in zigzag distribution along b-axis in z = 0 and z = 1/2 are also close enough to enable a C-H horizontal ellipsis pi interaction to occur. In 3-methylbenzylammonium chloride (2), the organic cations are linked together by C-H horizontal ellipsis pi interactions and through N-H horizontal ellipsis Cl and C-H horizontal ellipsis Cl hydrogen bonds to form a two-dimensional network. To support experimental results, DFT calculations have been accomplished via the B3LYP method and 6-311++G(d,p) basis set on molecular geometry, vibrational, and electronic properties. The non-covalent interactions were studied quantitatively using the Hirshfeld surfaces (HS) associated with 2D fingerprint plots. The NLO properties have been also investigated by DFT and compared to the urea reference.

International audience; 1,3-Benzenedimethanaminium bis(trioxonitrate), denoted by BD(NO3)(2) was prepared and its structure determined by X-ray crystallography. This compound solidifies into the triclinic system and the P2(1)/c space group with the lattice parameters a = 21.4308 (7) angstrom, b = 5.7255 (2) angstrom, c = 20.4476 (5) angstrom, beta = 108.502 (1) degrees, V = 2379.28 (13) angstrom(3), Z = 8, R = 0.047 and Rw = 0.129. In the crystal, the ions are allied by a huge number of N-H center dot center dot center dot O hydrogen bonds, creating layers parallel to (100). These layers are associated by hydrogen bonding type C-H center dot center dot center dot O, endorsing consequently a 3D arrangement. B3LYP/6-311 ++G**calculations were carried out to analyze the structure and properties of BD(NO3)(2). Intermolecular contacts involved in the selection and packaging of the crystalline structure of BD(NO3)(2) were investigated using fingerprint traces of the Hirshfeld surface. HOMO and LUMO analyses explain the charge transfers within the molecule. Topological analysis, RDG, molecular electrostatic potential (MEP) have been processed to calculate the intermolecular H-bonds interactions in detail. Thermal fusion and decomposition were investigated using TG, DTA and DSC measurements. Ionic conduction (H+) has been intentional in the temperature range 323 to 393 K, indicating semiconductor behavior of the material produced. Complete assignments of bands observed in the FTIR spectrum were reported together with the main force constants. The presence of dimeric species is important to explain why the intense bands predicted for the monomer due to N-H center dot center dot center dot O-N interactions are not observed in the experimental IR spectrum. The biological activity of BD(NO3)(2) was accomplished in silico to investigate their antibacterial activity. (C) 2021 Elsevier B.V. All rights reserved.

International audience; A new organic inorganic hybrid (C8H12N)ClO4 has been synthesized and characterized by spectroscopic (FT-IR,13C NMR and UV-Visible) and single crystal X-ray studies. These properties of 2-methylbenzylammonium perchlorate were also evaluated by DFT method. The title compound crystallized in the monoclinic space group P21/c at room temperature by slow evaporation with the following parameters a = 6.8894 (5) Å, b = 4.9146 (4) Å, c = 29.6565 (18) Å, β = 96.006 °, Z = 4 and V = 998.62(12) Å3. The crystal packing is determined by N–H…O, C–H…O hydrogen bonds and C–H…π interactions. The intermolecular interactions in the crystal structure were quantified and analyzed using Hirshfeld surface analysis. In addition the vibrational assignments, chemical shifts and geometrical parameters (bond lengths, bond angles, torsion angles) of the compound were calculated and found in good agreement with experimental results as well as the 13C NMR spectra are in agreement with the X-ray structure. Furthermore, the optical properties of the synthesized compound were investigated by UV-Vis and luminescence spectroscopy. Molecular electronic potential (MEP) has been calculated by the DFT calculation method. Reduced density gradient (RDG) and atoms in molecules (AIM) studies have also been performed to investigate the nature and strength of hydrogen bonding interactions. Also the HOMO and LUMO analysis have been used to confirm the experimental energy band gap of the compound. Finally, the biological activities of the new compound against four bacteria are also tested showing promising antimicrobial activity.

International audience; This paper deals with the crystal structure of the new non-centrosymmetric organic-inorganic hybrid material, (C6H14N)2[CdCl4]. Single crystal X-ray diffraction analysis shows that this compound crystallizes in the orthorhombic system, with the space group Cmc21 and the following parameters a = 27.257 (2) Å, b = 8.3560 (6) Å, c = 7.8872 (5) Å, V = 1796.4 (2) Å3 and Z = 4. The structure provides a new interesting example of infinite inorganic chains of [CdCl5]n following the c→ crystallographic direction. The monoprotonated cyclohexylammonium cations are linked to the anions via electrostatic, multiple bifurcated N—H…Cl hydrogen bonds and van der Waals interactions. To support experimental results, DFT calculations have been accomplished via the B3LYP method with 6–311++G(d,p) and LANL2DZ basis set on molecular geometry, vibrational and electronic properties. The non-covalent interactions were studied through AIM and RDG analysis and quantitatively using the Hirshfeld surfaces (HS) associated with 2D fingerprint plots. The NLO properties have been also investigated by DFT and compared to the urea reference

International audience; This paper shall address the synthesis and characterization of the novel non-centrosymmetric inorganic-organic hybrid material 3-methylbenzylammonium nitrate with general chemical formula C8H12N(NO3) (3MBAN), this compound has been synthesized via slow evaporation method at room temperature and it is structurally characterized by single-crystal X-ray diffraction, crystallized to the monoclinic system with space group Cc and the following parameters 7.574(3), 29.494(10), 5.1894(15), β = 128.669(11)°, Z = 4, V = 905.1(5) Å3 at 150 K and its crystal structure was determined and refined down to R = 0.057 and wR = 0.140. The monoprotonated 3-methylbenzylammonium cations are linked to the trigonal (NO3−) anions by multiple bifurcated N—H…(O,O) and weak C—H…O hydrogen bonds forming R44(12) and R32(6) motifs. The paper discusses also quantitatively the intermolecular interactions using the Hirshfeld surfaces (HS) associated with 2D fingerprint plots. The optimized molecular structure and the vibrational spectra were calculated by the density functional theory (DFT) method using the B3LYP function. Good consistency is found between the calculated results and the experimental structure; IR spectra confirmed the presence of the principal bands assigned to the internal modes of the organic cation and nitrate anion. Topological approaches such as reduced density gradient (RDG), atoms in molecules (AIM), electron localization function (ELF), endorse the occurrence of intermolecular hydrogen bonds that are responsible for the stabilization of the title compound leading to high nonlinear optical (NLO) activity. The analyses of HOMO and LUMO have been used to explain the charge transfer within the molecule. The thermal analysis of the title compound indicates its melting at 395 K follows a rapid decomposition appearing around 495 K. Finally Optical absorption reveals an important band gap energy indicating stability of the title compound.

International audience; In the title salt complex (C6H9N2)(2)[CuCl4] symbolized along this work by (2A5PCuCl(4)), the Cu2+ cation is coordinated by four chloride anions and adopts a distorted tetrahedral geometry. This compound has been crystallized in the monoclinic space group C2/c and the following parameters obtained are a = 13.0244(19) angstrom, b = 8.3149(11) angstrom, c = 16.001(2) angstrom, beta = 93.730(6)degrees, Z = 4, V = 1729.2(4) angstrom(3) at 150 K. In the crystal structure, the atomic arrangement consists of isolated tetrahedral entities connected to the organic groups by weak hydrogen bonds N-H horizontal ellipsis Cl and C-H horizontal ellipsis Cl forming a three-dimensional network. The Hirshfeld surface analysis shows on two-dimensional fingerprints maps the great dominance of H horizontal ellipsis Cl and H horizontal ellipsis H contacts in the crystal packaging. The geometrical optimization, electronic, topological and biological properties of 2A5PCuCl(4) were theoretically studied using DFT. The HOMO and LUMO analysis are used to decide the charge transfer within the structure. Natural bond orbital analysis was carried out to study hyperconjugative interactions. Optical transmission measurements investigated by UV-visible and photoluminescence spectroscopy are carried out on a crystalline thin-film of 2A5PCuCl(4) show the detection of two absorption bands centered at 316 and 519 nm coherent with those observed in the perovskites based on CuCl4. Photoluminescence measurements showed two peaks at around 433 and 472 nm. The unaided-eye-detectable blue luminescence emission comes from the excitonic transition in the CuCl4 anions.

International audience; Cyclohexylammonium perchlorate (C6H14N)ClO4 have been achieved from the mixture of perchloric acid with an ethanol solution containing cyclohexylamine by slow evaporation technique. The structure of this compound has been determined by single crystal X-ray diffraction method. This compound crystallizes in monoclinic P21/c space group with the lattice parameters a = 11.1501(19) Å, b = 8.4987(15) Å, c = 9.9517(16) Å, β = 104.166(6) °, Z = 4 and V = 914.4(3) Å3. The FT-IR was used to identify the different vibrational assignments present in the compound. The optical properties were analyzed by UV–Vis spectral analysis. The intermolecular interactions in the crystal structure were examined via topological Atom-in-Molecules (AIM), Natural Bond Orbital (NBO) and Hirshfeld surface (HS) analyses. Reduced density gradient (RDG) was used to study non-covalent interactions. HOMO-LUMO orbital energies were studied by using DFT calculations at B3LYP/6-311++G(d,p) level of theory.

International audience; Bis[4-(dimethylamino)pyridinium]di-mu-chlorido-bis[dichloridomercurate(II)] has been achieved from a mixture of mercury(II) chloride in water with an aqueous HCl solution containing 4-dimethylaminopyridine by the slow evaporation technique. The structure of this compound has been determined by single-crystal X-ray diffraction. This compound crystallizes in the triclinic space group P1 over bar with the following lattice parameters: a = 7.5505(7) angstrom, b = 11.8684(12), c = 13.4777(12) angstrom, alpha = 82.836(3), beta = 76.516(3), gamma = 76.355(3) angstrom, Z = 2 and V = 1138.22(19) angstrom(3). The structure of the compound can be described as organic-inorganic layers stacked along the b and c-axes which are connected by weak N-H center dot center dot center dot Cl and C-H center dot center dot center dot Cl hydrogen bonds forming a three-dimensional network. The IR spectra confirmed the presence of organic cations and the thermal stability of the compound was measured by thermal analysis DSC/TG. Hirshfeld surface analysis and the associated two-dimensional fingerprint plots were used to explore and quantify the intermolecular interactions in the crystal. The geometrical optimization, electronic, topological and biological properties of the compound were theoretically studied using DFT. The HOMO/LUMO analysis was used to determine the charge transfer within the structure. Good consistency was found between the calculated results and the experimental structure and IR spectra. Furthermore, thermodynamic functions for the compound revealed significant evolution with temperature and the potential biological activities were investigated by using molecular docking analysis.

International audience; The novel complex, (2-amino-5-picolinium) tetrachlorocobaltate(II), (2A5PCoCl4) have been synthesized and crystallized to the monoclinic system with space group P21/c and the lattice parameters obtained are a = 8.0734 (6) Å, b = 14.6297 (11) Å, c = 15.6913 (11) Å, β = 103.034 (4) °, V = 1805.6 (2) Å3 and Z = 4. His atomic arrangement can be described as an alternation of inorganic and organic layers, [CoCl4]2- tetrahedral anions and 2-amino-5-picolinium cations are connected by bifurcated and no-bifurcated N–H⋯Cl and C–H⋯Cl hydrogen bonds. The intermolecular interactions in the crystal structure were quantified by using the three-dimensional Hirshfeld surfaces and two-dimensional fingerprint plots and interactions were analyzed by topological AIM, RDG and NBO approaches. Infrared spectrum confirms the existence of functional groups and used to gain more information of the elaborated material. The DTA/TG analyses were accomplished to inspect the thermal stability of 2A5PCoCl4.

The crystal structure of a novel compound (C8H14N2)2[CdCl6] denoted (MXDCdCl6) is discussed based on single crystal X-ray diffraction. This compound crystallizes in the triclinic system, with the space group P 1 ¯ and the lattice parameters obtained are a = 7.5482(8)A, b = 8.495(1)A, c = 10.4656(12) A, α = 101.649(3)°, β = 100.006(3)°, γ = 112.971(3)°, V = 580.92(11) A3 and Z = 1. The compound is built up from inorganic layers formed by CdCl64− anions and ammonium groups. The organic entities are located between these layers, and are linked to the anions through N–H⋯Cl and C–H⋯Cl hydrogen bonds generating a three-dimensional network, which stabilizes the crystal packing. The surface mapped over the dnorm support the X-ray structural analysis and highlights the hydrogen bonds as the main intermolecular contacts. An infrared spectrum was registered to reveal the vibrational modes of the various characteristic groups of the title compound. Optical property asserts a noteworthy band gap energy stating the stability of the resulting structure. The non-covalent interactions were studied through AIM and RDG analysis. Subsequently, DFT and TD-DFT calculations were carried out to study the molecular structure, vibrational and electronic properties of the investigated molecule. In silico investigation was performed via molecular docking analysis to explore the anticipated antibacterial activity possessed in the title compound.

Synthesis, crystalline architecture, vibrational spectroscopy, thermal analysis, electrical behavior and detailed theoretical DFT studies has been reported for the new inorganic-organic hybrid material phenylethylammonium trioxonitrate with general chemical formula (C6H5(CH2)(2)NH3)NO3 (PEAN). The determination of crystal structures plays a significant to understanding weak, intra and intermolecular, interactions that great influence crystal packing. PEAN has been crystallized to the monoclinic system with space group P2(1)/c and the network parameters obtained are a = 5.9497(8) angstrom, b = 20. 494(3) angstrom, c = 8.4528(11) angstrom, beta = 113. 812(8)degrees, V = 942.9(2) angstrom(3) and Z = 4. The atomic arrangement of the PEAN compound can be described by 3D framework. The organic cations are linked to the nitrate anions by means of an assortment of N-H center dot center dot center dot O hydrogen bonding trapped in layers at y = 1/4 and 3/4. These layers are interrelated via C-H center dot center dot center dot pi interactions involving organic cations, an infinite chain are consequently created along the c-axis. Hirshfeld surfaces and 2D fingerprint plots estimate the weak intermolecular interactions accountable for the generation of crystal packing. The structural propriety and vibrational spectral analyze of PEAN have been investigated by using DFT calculations at B3LYP/6-311++G(d,p) level of theory. Intermolecular interactions were studied by NBO and AIM analyses. Thermal analysis (TG-DTA and DSC) and dielectric conductivity was also investigated. These measurements were realized to discuss the observed phase transition mechanism in the vicinity of 340 K. (C) 2019 Elsevier B.V. All rights reserved.

International audience; The p-xylylenediaminium bis(nitrate) compound have been synthesized and then, it was characterized by using Fourier Transform infrared (FT-IR) in the solid phase and, by using the Ultraviolet–Visible (UV–Visible) and Hydrogen and Carbon Nuclear Magnetic Resonance (1H- and 13C-NMR) spectra in aqueous solution and in dimethylsulfoxide solvent. In this work, two monodentate and bidentate coordination modes were considered for the nitrate ligands in both media in order to study the structural and vibrational properties of that salt. Hence, the natural bond orbital (NBO), atoms in molecules (AIM), Merz-Kollman (MK) charges, molecular electrostatic potentials (MEP) and frontier orbitals studies were performed for p-xylylenediaminium bis(nitrate) and their cation and anion species taking into account for the salt those two coordination modes for the nitrate ligands. The intermolecular interactions of this salt were also evaluated by Hirshfeld surface analysis. The B3LYP calculations performed by using the hybrid method and the 6-311G* and 6-311++G** basis sets generate monodentate and bidentate structures with Ci and C2 symmetries, respectively. The force fields and the force constants values for these two structures were also computed and their complete vibrational assignments were performed by using those both levels of theory. The strong band at 1536 cm−1, the bands between 2754 and 2547 cm−1 and the bands between 1779 and 1704 cm−1 support clearly the presence of the dimeric species while the IR bands at 1986/1856 cm−1 could justify the presence of the bidentate species in the solid phase.

The potentials, spectroscopic properties and electric dipole moments of SrH+ are computed for 63 molecular states dissociating up to Sr2+ + H− using an ab initio approach. The ab initio formalism is based on large basis sets, nonempirical atomic pseudopotential for strontium core, correlation treatment for core valence through the effective core polarization potentials and for valence through full valence configuration interaction. Our theoretical molecular constants match published values very well and a large amount of new results is produced. Unusual potential shapes are found in 1Σ+ states often caused by avoided crossing series between them and imprinted by the ionic state Sr2+H−. The high potential energy curves suggest, it is possible to form H− or at least to neutralize H+ in collisions with strontium. © 2014 Wiley Periodicals, Inc.

The solvation of the Na(+) ion in helium clusters has been studied theoretically using optimization methods. A many-body empirical potential was developed to account for Na(+)-He and polarization interactions, and the most stable structures of Na(+)He(n) clusters were determined using the basin-hopping method. Vibrational delocalization was accounted for using zero-point energy corrections at the harmonic or anharmonic levels, the latter being evaluated from quantum Monte Carlo simulations for spinless particles. From the static perspective, many-body effects are found to play a minor role, and the structures obtained reflect homogeneous covering up to n = 10, followed by polyicosahedral packing above this size, the cluster obtained at n = 12 appearing particularly stable. The cationic impurity binds the closest helium atoms sufficiently to negate vibrational delocalization at small sizes. However, this snowball effect is obliterated earlier than shell completion, the nuclear wavefunctions of (4)He(n)Na(+) with n = 5-7, and n > 10 already exhibiting multiple inherent structures. The decrease in the snowball size due to many-body effects is consistent with recent mass spectrometry measurements.

The potential energy curves, vibrational energy levels, spectroscopic constants, and dipole moment curves for the ground and excited states of BaXe and its ion Ba(+)Xe molecules are calculated with an ab initio method using pseudopotential techniques and core polarization potentials. The molecules are treated as two (BaXe) or one (Ba(+)Xe) active electrons systems taking benefit of the zero pseudopotential approach for Xe. The vibrational levels and their energy spacing have been also determined for Σ(+), Π, and Δ states. The permanent and transition dipole moment curves are investigated for the (1,3)Σ(+) states of the BaXe neutral molecule and (2)Σ(+) states of the Ba(+)Xe ion. The analysis of these numerous results shows interesting behavior in potential energy curves imprinted by the strong repulsive interactions between electron and Xe and also indicates an intense transition dipole moment for both Ba(+)Xe and BaXe.