Search

Two new mononuclear complexes, [Cu2Cl1.23(NO3)0.77(Ampy)4(H2O)4](NO3)2·4H2O (I) and [CdI2(Ampy)2] (II) (Ampy = 4-amino-6-methoxypyrimidine) have been synthesized and characterized by single crystal X-ray diffraction studies (CCDC nos. 2023331 (I), 2023331 (II)) at 295 K for (I) and 100 K for (II). The structure of the Cu(II) complex shows that the Cu(II) central atom is five-coordinated with a distorted square pyramidal geometry. In compound (II) the Cd(II) cations are tetracoordinated with a distorted tetrahedral fashion. Intermolecular interactions were investigated by Hirshfeld surfaces. Electronic properties such as HOMO and LUMO energies were derived. [ABSTRACT FROM AUTHOR]

An investigation of the solid-state X-ray structure of the new organic–inorganic compound [C5H14N2]2PbCl6·3H2O shows a layered organization of the (PbCl6)4– anions, with (R2NH2)+ groups and water molecules developed in the [001] plane at x = (2n + 1)/4. The crystal structure is stabilized by N − H···Cl, N − H···O, O − H···Cl, O − H···O, and C − H···Cl hydrogen bonds. The powder X-ray diffraction and X-ray photoelectron spectroscopic (XPS) analyses confirm the phase purity of the crystal sample. The intermolecular contacts are quantified using the Hirshfeld surfaces computational method. The major inter-contacts contributing to the Hirshfeld surfaces are H...Cl, H...H, and O...H. The vibrational modes were identified and assigned by IR and Raman spectroscopies. The optical properties were investigated by UV–visible and photoluminescence spectroscopic studies. The compound was characterized by thermal analysis to determine its thermal behavior with respect to the temperature. Finally, X-ray photoelectron spectroscopy analysis is reported for analyzing the surface chemistry of [C5H14N2]2PbCl6·3H2O. [ABSTRACT FROM AUTHOR]

(C6H18N3)4[CuCl5]2[CuCl4]3·1.42H2O is prepared and characterized by various physicochemical techniques. The single crystal X-ray diffraction structural analysis reveals that the title compound belongs to the orthorhombic system with the space group Cmca. Its unit cell dimensions are: a = 24.286(2) Å, b = 14.3082(14) Å, c = 16.6160(16) Å, Z = 4, V = 5773.8(10) Å3. Its crystal structure is determined and refined down to R = 0.024 and wR(F2) = 0.059. The structure contains three crystallographically independent Cu2+ ions coordinated to chlorine anions in various fashions. Cu1 is five-coordinated in a distorted square pyramidal fashion, while Cu2 and Cu3 are four-coordinated in square planar and distorted tetrahedral fashions, respectively. The entities are interconnected by means of the hydrogen bonding [O(W)-H...Cl, N-H...Cl, C-H...Cl and C-H...O(W)], forming a three-dimensional network. Intermolecular interactions are investigated by Hirshfeld surfaces and the contacts of the eight different chloride atoms are notably compared. The vibrational absorption bands are identified by infrared spectroscopy. The optical study is performed by UV-vis absorption. [ABSTRACT FROM AUTHOR]

The chemical preparation and characterization of a novel coordination compound [CuClO4(C4H6N2O)4H2O]ClO4(C4H6N2O)0.08 is reported. The compound crystallizes in the monoclinic space group P21/c with lattice parameters a = 11.2678(5) Å, b = 12.8102(6) Å, c = 19.7250(8) Å, β = 100.3051(15)°, V = 2801.2(2) Å3. The Cu(II) cation is six-coordinated in an elongated distorted octahedral fashion by four N atoms of four 3-amino-5-methylisoxazole ligands, one water oxygen atom, and one perchlorate oxygen atom. In the atomic arrangement, the coordinated and uncoordinated perchlorate anions are grouped in pairs to form anionic layers parallel to the (a, b) plane. A substantial number of H-bonding interactions leads to the formation of an intricate three-dimensional network. The vibrational absorption bands are identified by infrared spectroscopy and the electrical properties are studied by impedance spectroscopy. The DSC analysis agrees with the electrical conductivity results. Magnetic properties are also determined to characterize the complex. [ABSTRACT FROM AUTHOR]

The synthesis and the structures of two new compounds with the general formula [CHNO]BiX·2HO (X = Br, Cl) are reported. They crystallize in the triclinic system and are isostructural. Crystal structures were solved and refined to R = 0.064, 0.048 and R = 0.15, 0.13 using 3392, 3679 independent reflections for the Cl and Br derivatives, respectively. The atomic arrangement can be described by inorganic chains along the [100] direction. These chains are themselves interconnected by means of N-H···X (X = Cl, Br) originating from the [CHNO] entities, to form three-dimensional network. The organic part consists of one organic cation which orients its two amine groups to the neighboring anions. The inorganic entity is made up of [BiX] dimers composed of two equivalent irregular octahedra sharing one edge. The oxygen atoms of the water molecules (OW) act as donor (O-H···X) and acceptor (N-H···O) of hydrogen bonds. The nature of the distortion of the inorganic polyhedra can be attributed to the stereoactivity of the Bi(III) lone electron pair. Raman and infrared spectra at room temperature were recorded in the 500-100 and 4000-400 cm frequency regions, respectively. This study confirms the presence of the organic cation [CHO] and the bioctahedron [BiX]. The calorimetric study shows that the title compound is stable until 384 K. [ABSTRACT FROM AUTHOR]

The crystal structure of the new inorganic-organic hybrid compound [4-CH3C6H4CH2NH3]3[CdCl4] has been determined by single crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group Pnma with lattice parameters a = 10.721(2), b = 33.986(6), c = 5.326(1) Å, β= 97.222(1)°, V = 1940.8(7) Å3, and Z = 4. The framework of the title compound is built upon layers parallel to (010) made up from corner-sharing CdCl6 octahedra. 4-Methylbenzylammonium cations are situated between the layers and connect them via an N-H… Cl hydrogen bonding network. The Cd atom is located on an inversion centre, and the coordination environment is described as distorted octahedral. Solid state 13C CP-MAS NMR spectroscopy is in agreement with the X-ray structure. DFT calculations allow the attribution of the carbon peaks to the independent crystallographic sites. Thermal analysis and infrared spectroscopy were also used to characterize the complex [ABSTRACT FROM AUTHOR]

The physicochemical properties of a new organic cyclohexaphosphate, [5-Cl-2,4-(OCH3)2C6H2-NH3]6P6O18·4H2O, are discussed on the basis of an X-ray crystal structure investigation. This compound crystallizes in the monoclinic space group C2/c, with cell parameters a = 37.987(7) Å, b = 13.125(4) Å, c = 14.331(5) Å, β = 98.21(3)°, Z = 4, V = 7072(3) Å3. Its crystal structure is determined and refined to a final R = 0.058 for 5223 independent reflections. The atomic arrangement can be described as a layer organization built up by P6O18 ring anions and water molecules. Between these layers, the organic groups are located that form hydrogen bonds with oxygen atoms of P6O18 rings and water molecules. Intermolecular π-π stacking interactions between two neighboring organic cation rings help to establish the crystal packing. Solid 31P MAS-NMR spectroscopy is in agreement with X-ray structure. Ab initio calculations allow the attribution of the three phosphorus signals to the independent crystallographic sites. This compound is also characterized by thermal analysis and IR spectroscopy. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. [ABSTRACT FROM AUTHOR]

Physicochemical properties of a new organic cation triphosphate, [2,3-(CH3)2C6H3 NH3]4HP3O10.2H2O, are discussed on the basis of X-ray crystal structure investigation. This compound crystallizes in a triclinic unit cell P1 with the parameters: a = 11.963(6) Å, b = 9.858(6) Å, c = 16.205(7) Å, α = 95.50(4)°, β = 95.21(4)°, γ = 89.07(4)°, V = 1894.4(16) Å3, Z = 2, and Dx = 1.365 g.cm- 3. Crystal structure has been solved and refined to R = 0.074 using 3766 independent reflections. In this atomic arrangement, layers built by HP3O104 - groups are developed in (a, b) planes at z = 1/2. Between these layers the 2,3-dimethylphenylammonium entities are located, which form hydrogen bonds with some external atoms of the phosphoric groups. A characterization of this compound by solid-state 13C and 31P MAS NMR, IR spectroscopy and thermal analysis is also reported. [ABSTRACT FROM AUTHOR]

Among the various categories of phosphates, the number of organic cation cyclotriphosphates remains limited. In this work, we report the chemical preparation, crystal structure, thermal analysis, and spectroscopic investigations of a new cyclotriphosphate [C8H11NH3]3P3O9·3H2O. It is characterized by X-ray diffraction, infrared spectroscopy, nuclear magnetic resonance, and thermal analysis. This compound is a triclinic P unit cell with the following parameters: a = 13.949(4), b = 9.867(3), c = 14.180(2) Å, α = 92.22(2), β = 119.27(2), γ = 85.10(10)°, V = 1696.1(8) Å3, and Z = 2. Its structure has been determined and refined to R = 0.041 and Rw = 0.062, using 4527 independent reflections. The atomic arrangement can be described by corrugated thick layers built by [P3O9]3- anions, ammonium groups, and water molecules. The organic entities are located between these layers. H-bonds connecting the different species play an important role in the tridimensionnal network cohesion. This compound is also characterized by infrared spectroscopy, nuclear magnetic resonance, and thermal analysis. [ABSTRACT FROM AUTHOR]

A new crystal of 2-amino-3-methylpyridinium dihydrogenmonophosphate has been prepared and characterized by X-ray crystallography, thermal analysis, and impedance and NMR spectroscopies. This compound crystallizes in the triclinic space group P with a = 7.343(2) Å, b = 7.987(2) Å, c = 8.116(4) Å, α = 77,62(3)°, β = 77,74(3)°, γ = 87,03(2)°, V = 454.3 (3)Å 3 , and Z = 2. The crystal structure was solved and refined to R = 0.030 with 1602 independent reflections. The atomic arrangement can be described as (H 2 PO 4 - ) n polymeric chains anchoring the 2-amino-3-methylpyridinium cations through short hydrogen bonds. All ring atoms of the organic entity are coplanar. The exocyclic N atom is an electron receiving center, which is consistent with features of imino resonance evidenced by bond lengths and angles. Solid state 31 P, 13 C, and 15 N CP-MAS-NMR spectroscopies are in agreement with the X-ray structure. Ab initio calculations allow the attribution of carbons and nitrogen to the independent crystallographic sites. [ABSTRACT FROM AUTHOR]

The synthesis and structures of two new compounds with the general formula N(C 2 H 4 NH 3 ) 3 (H 2 TO 4 )(HTO 4 )·2H 2 O (T = P, As) are reported. They crystallize with triclinic unit cells and are isotropic. We determined the structure of phosphate salt. The following unit cell parameters were found: a = 9.886(4), b = 9.308(2), c = 10.140(3) Å, a = 109.38(2), ß = 108.83(3), ? = 74.40(3)°, V = 819.2(5) Å 3 , and ? cal. = 1.537 g · cm -3 . The crystal structure was solved with a final R = 0.042 for 3748 with I > 3s I). The space group is P-1 and Z = 2. The atomic arrangement can be described as a three-dimensional network of hydrogen bonds made up from H n PO 4 3- n (n = 1, 2) anions and H 2 O molecules between which are trapped the tris(2-ammoniumethyl)amine cations. Solid-state 13 C and 31 P MAS-NMR spectroscopies are in agreement with X-ray structure. Ab initio calculations allow the attribution of the phosphorus signals to the independent crystallographic sites. [ABSTRACT FROM AUTHOR]

[C4N2H12]2HP3O10·H2O, a new hydrate organic cation monohydrogeno-triphosphate, has been synthesized and characterized by X-ray diffraction, IR spectroscopy, mass angle spinning (MAS), NMR, and thermal analysis. The title compound crystallizes in a monoclinic unit cell with a=11.072(5), b=12.324(2), c=13.122(5)Å,β=93.85(5)°, Z=4, V=1787(1)Å3, and a noncentrosymmetric space group P21(no. 4). Crystal structure is determined and refined to R=0.057 using 4262 independent reflections. The atomic arrangement can be described as a typical layers organization. Layers built by HP3O104-anions and water molecules are parallel to the (a, b) planes. Between these layers the piperazinium cations, which form hydrogen bonds with oxygen atoms of the triphosphate anion, are located. [ABSTRACT FROM AUTHOR]

Using acid–base assays and simple slow evaporation method at ambient temperature, we were successful in producing a novel salt with the chemical formula (C5H14N2)[HgCl4]·H2O. According to single-crystal X-ray diffraction data, the crystal packing was regulated by H-bonds and by Coulomb interactions (also called electrostatic interactions) between distinct entities, which formed a 3D network. The 2D fingerprint plots and the Hirshfeld surface were utilized to examine the effect of intermolecular interactions. FTIR spectroscopy, PL spectroscopy, thermal analysis, and electrical conductivity experiments were also carried out, and the antioxidant activity was tested. [ABSTRACT FROM AUTHOR]

Single crystals of bis(3-aminopyridinium)tetrachlorocobaltate(II) were successfully synthesized and structurally characterized using single crystal X-ray diffraction. This study shows that the structure is built on inorganic anionic and organic cationic subnetworks stabilized by Cl...Cl and antiparallel offset face to face π-π stacking interactions, respectively. The cohesion of the overall packing is ensured by N–H...Cl hydrogen bonds leading to a three dimensional network. Structural geometry optimization and gap energy determination were performed thanks to DFT calculation. Thermal decomposition of the title compound powder, at 450 °C in air atmosphere, leads to nanostructured Co3O4 as confirmed by X-ray powder diffraction. The obtained cobalt oxide was used as adsorbent for the removal of hexavalent chromium ions from aqueous solution. The effect of contact time was investigated and showed an unusual behavior consisting of the existence of two equilibrium plateaus at 11 mg.g−1 and 15 mg.g−1 which were attributed to surface heterogeneity, as elucidated by scanning electron microscopy analysis. As a consequence, the kinetic data were analyzed in steps and fitted using non linear pseudo-first order and non linear pseudo-second order models. A comparative study with other adsorbents demonstrated the potential of the synthesized Co3O4 via thermal decomposition of the title compound for hexavalent chromium ions removal. [ABSTRACT FROM AUTHOR]

The new compound based on mercury (II) (C7H10N)2·(HgCl2)2·(Hg2Cl6) 1 was described by numerous approach: X-ray diffraction (powder and single crystal), FT-IR, photoluminescence, UV–Vis, Hirshfeld surface analysis, thermal analysis, electric conductivity and finally a biological study was carried out through the antioxidant activity. Depending on the XRD data, the dimers (Hg2Cl6)2−, the infinite chains (parallel to the c-axis) formed by (HgCl2) and the 2-ethylpyridinium cation are bound together by weak H-bonds and electrostatics interactions forming a 3D network. The purity of 1 was checked by PXRD. The Hirshfeld surface analysis was used to investigate intermolecular interactions present in the compound 1. Infrared spectroscopy has been used to assign the varied functional groups. UV–Vis spectroscopy showed two bands located respectively at 240 nm and 280 nm. The photoluminescence analysis indicates the presence of fluorescence at 235 nm. A phase transition around 345 K has been shown by thermal analysis studies (TG-DSC and TG–DTA). The complex impedance of 1 has been performed in temperature range 295–343 K. Finally, the antioxidant activity study reveals that compound 1 can be used as a free radical scavenging substance. [ABSTRACT FROM AUTHOR]

Bis (4-methylbenzylammonium) hydrogen phosphate monohydrate (4MLBAHP) single crystals were grown by reacting 4-methylbenzylamine (4MLBA) and orthophosphoric acid in 2:1 stoichiometric ratio using slow evaporation solution growth method. The structure of the grown crystal is solved and its space group is found to be P 1 ¯ . The (C8H12N+)2 cation, (HPO42−) anion and water molecules present in 4MLBAHP are joined through N–H...O and O–H...O bonds. The vibrations of 4MLBAHP functional groups were identified through FTIR and FT-Raman spectral techniques. The observed P-O, HPO42− vibrations endorses the coordination of HPO42− cation in the crystal structure. The lower cut off wavelength of 4MLBAHP was identified at 245 nm and the optical transmission bandwidth is from 245 to 1100 nm. The molecular structure is also established through NMR spectroscopy. In 1H NMR, the protonation of NH2 to NH3+ causes the deshielding of NH3+ protons and the corresponding signal is observed at 7.839 ppm.The third order nonlinear optical (NLO) susceptibility (χ3) is found to be 1.6949 × 10–6 esu and this large value is attributed to the presence of hydrogen bonds in the molecular structure. [ABSTRACT FROM AUTHOR]

This paper aims to review recent advances on synthesis, crystal structures, thermal, spectroscopic, phase transitions, optical, dielectric, and catalysis properties of hydrate and anhydrous alkylenediammonium halogenometallates materials (Metal: Bi, Sb, Halogen: Cl, Br, I). These hybrid materials present rich structural diversities based on octahedra forming infinite zero dimensional, 1-dimensional chains, 2-dimensional layers, discrete bioctahedra, and discrete tetramer units. The effect, contribution and importance of hydrogen bonding N–H ... X (X: Cl, Br, I) are reviewed in terms of solid state relationship. Particularly, a comparative study is made on hydrate and anyhdrous aliphatic chlorobismuthates with alkylenediammonium +NH3(CH2)nNH3+ based on structural data and V/Z variation with (CH2)n chains (n = 2–8, 12), and variation of BiCl63− Raman frequencies modes versus (CH2)n chains (n = 3–8). Hydrate salts with (n = 3, 12) consist of isolated BiCl63− anions and two water molecules, against others ones with isolated anionic chains [BiCl52−]n or Bi2Cl104− dimers, formed by distorted octahedra BiCl63− sharing corners, vices or edges. The reviewed optical and electronic band gaps suggested interesting compounds with band gaps (1.85–2.4 eV), as suitable materials in optoelectronic properties, photoactive layer in solution-processed photovoltaics, and bio-imaging or photovoltaic applications. It was concluded that iodobismuthate salts have generally the lowest bands gap, compared to that of bromo and chlorobismuthate slats. Catalysis proprieties are reviewed n fast (RhB) degradation under dark conditions for (C4N2H7)4Bi2Cl10, (C5H9N2)BiI4, and {(H-BPA)4·[(BiI6)I13]·2I3}n, and in organic salts synthesis under solvent-free conditions. Herein NH3(CH2)nNH3BiCl5 (n = 5–7) salts were used as highly efficient catalysts, which is a novel tendency in chlorobismuthate researchs in the green chemistry field. [ABSTRACT FROM AUTHOR]

A series of novel quinoxaline based bisspirooxindolo-pyrrolizidines were synthesized through 1,3-dipolar cycloaddition under ultrasonication with shorter reaction time and good yields. The compounds were well characterized by various spectroscopic methods and finally single crystal X-ray diffraction method (4c, 4d). DFT energy calculations confirm the regioselectivity due to enone umpolung effect. The in vitro anti-cancer activity of the synthesized compounds (4a–s) shows that the compounds 4g and 4q exhibited good anti-cancer activity with IC50 values14.51 ± 1.1 and 11.36 ± 0.23 µM against DU-145 prostate cancer cell line; and 16.78 ± 0.95 and 14.28 ± 0.64 µM against Hela cervical cancer cell lines when compared to the standard anti-cancer drug doxorubicin (1.75 ± 0.06 and 1.35 ± 0.09 µM). In silico molecular docking studies indicated that the synthesized compounds may serve as a potential lead for the further development of novel anti-cancer agents. [ABSTRACT FROM AUTHOR]

The 2D hybrid compound bis(2-amino-4-methoxy-6-methylpyrimidinium) bis(μ2-chloro)-tetrachloro-di-copper(II), (C6H10N3O)2Cu2Cl6, is successfully synthesized by slow solvent evaporation at room temperature. Structural properties have been investigated through single-crystal X-ray diffraction and reveal that the structure contains a centrosymmetric hexachlorodicuprate group where each Cu atom is coordinated to four Cl atoms in a slightly distorted square planar geometry. There are short contacts between neighboring [Cu2Cl6]2− dimer units. The crystalline building stability is ensured by N–H⋯Cl and C–H⋯O hydrogen bonding as well as weak C–H···π intermolecular interactions. From the infrared spectroscopy analysis, the functional groups were identified. Simultaneously, the electrical properties and Hirshfeld surface analyses were also elucidated. Furthermore, the molecular docking study of 2D hybrid compound bis(2-amino-4-methoxy-6-methylpyrimidinium) bis(2-chloro)-tetrachloro-di-copper(II) ligand with an HSP90/PDB: 5LRZ was performed by Autodock Vina. Additionally, drug-likeness and ADME properties and evaluations of the newly synthesized molecule were performed in detail. FT-IR was used to explore the modes of vibration of the different functional groups present in the studied compound. [ABSTRACT FROM AUTHOR]

Syntheses and X-ray crystal structures of four 4-(4-methoxyphenyl)piperazin-1-ium (MeOPP) salts, with 2,2,2-trifluoroacetate, C11H17N2O+πC2F3O2- (I), 2,3,4,5,6-pentafluorobenzoate, C11H17N2O+πC7F5O2-πH2O (II), 4-iodobenzoate C11H17N2O+πC7H4IO2-πH2O (III), and 4-methylbenzoate, C11H17N2O+π- C8H7O2-πH2O (IV) anions are presented. The salts form directly from equimolar quantities of N-(4-methoxyphenyl)piperazine and the corresponding organic acid in methanol and crystallize from 1:1 methanol/ethyl acetate. Salt I is anhydrous whereas II, III, and IVare all monohydrates. In all cases, the MeOPP cation conformation is determined by the torsion about the N--C bond between the piperazinium and 4-methoxybenzene rings. Crystal packing in each structure is largely dictated by N--Hπ π πO and (in II, III, and IV) O--Hπ π πO hydrogen bonds, although each also features weak C--Hπ π πO-type hydrogen bonds. Salt II also has π-π-stacking interactions between cation and anion arene rings, and III exhibits Iπ π πI close contacts. [ABSTRACT FROM AUTHOR]

Highlights: What are the main findings? A complete series of structures differing from H-DIP to I-DIP. Rationalizing the Cl-DIP structure (Z' = 3) with two distinct conformations. The great wall of bromines at the 2D sheet interfaces in Br-DIP. What is the implication of the main finding? Comparison of organic halogenated materials Br-DIP and the inorganic PbBr2, CuBr2. The unusual synthon formed by the tightly bound hydrate in I-DIP•½(H2O). Simple Summary: Crystal and modelled structures of five N1,N3-di(5-X-pyridin-2-yl)isophthalamides (X = H, F to I) as (X-DIP) are reported. The roles that their molecular conformations and interactions play in solid-state aggregation are assessed. Cl-DIP (Z' = 3) exhibits both syn/anti and anti/anti molecular conformations in 2:1 ratio. The hydrogen bonding hierarchy and sheet formation in Br-DIP induces the formation of a bromine-rich environment manifesting as a 'wall of bromine atoms' at the sheet interfaces. The hydrate in I-DIP•½(H2O) forms a rare synthon. The synthesis and spectroscopic characterisation of six bis(5-X-pyridine-2-yl)isophthalamides (X = H, F, Br, Cl, I, NO2) are reported, together with five crystal structure analyses (for X = H, F to I). The isophthalamides span a range of conformations as syn/anti (H-DIP; I-DIP), anti/anti- (F-DIP; Br-DIP) and with both present in ratio 2:1 in Cl-DIP. The essentially isostructural F-DIP and Br-DIP molecules (using strong amide...amide interactions) aggregate into 2D molecular sheets that align with either F/H or Br atoms at the sheet surfaces (interfaces), respectively. Sheets are linked by weak C-H⋯F contacts in F-DIP and by Br⋯Br halogen bonding interactions as a 'wall of bromines' at the Br atom rich interfaces in Br-DIP. Cl-DIP is an unusual crystal structure incorporating both syn/anti and anti/anti molecular conformations in the asymmetric unit (Z' = 3). The I-DIP•½(H2O) hemihydrate structure has a water molecule residing on a twofold axis between two I-DIPs and has hydrogen and N⋯I (Nc = 0.88) halogen bonding. The hydrate is central to an unusual synthon and involved in six hydrogen bonding interactions/contacts. Contact enrichment analysis on the Hirshfeld surface demonstrates that F-DIP, Cl-DIP and Br-DIP have especially over-represented halogen···halogen interactions. With the F-DIP, Cl-DIP and Br-DIP molecules having an elongated skeleton, the formation of layers of halogen atoms in planes perpendicular to the long unit cell axis occurs in the crystal packings. All six DIPs were analysed by ab initio calculations and conformational analysis; comparisons are made between their minimized structures and the five crystal structures. In addition, physicochemical properties are compared and assessed. [ABSTRACT FROM AUTHOR]

A new organic–inorganic material, dimethylaminium hexabromobismuthate (C2H8N)3BiBr6 was elaborated by the slow evaporation technique at room temperature. This compound is synthesized and characterized by X-ray diffraction, Raman spectroscopy scattering, Hirshfeld surface analysis, 13C NMR spectroscopy, photoluminescence and by UV–Vis spectroscopy. The crystal lattice is formed by discrete [BiBr6]3− anions surrounded by dimethylaminium cations. Besides, the title compound crystallizes in the space group R 3 ¯ of trigonal system. The unit cell parameters are a = 29.3387(9) Å, b = 29.3387(9) Å and c = 8.4642(3) Å. The Raman and infrared spectra recorded at room temperature were interpreted by analogy with homologous materials. The cohesion of the structure is ensured by a huge network of N–H...Br hydrogen bonds and van der Waals interaction (C–H....Cl). The UV–Vis measurements, performed from 200 to 2400 nm, show a direct and wide optical bandgap evaluated at (2.840 ± 0.005), (2.482 ± 0.004) and (2.805 ± 0.006) eV by different methods. The Urbach energy presents a low value estimated at (182 ± 3) meV confirming the high quality of our compound. In addition, the evolution of the extinction coefficient (ke) and the refractive index n with the wavelength λ were determined. Furthermore, we have demonstrated that n obeys to Cauchy relation. Other optical parameters such as the skin depth and the optical conductivity were calculated, and all obtained results were discussed. We have demonstrated, in addition, that the energy losses are mainly in the bulk rather than the surface of the studied material. Based on the Wemple–Di-Domenico model, the dispersion parameters E0 and Ed relative to the (C2H8N)3BiBr6 sample were calculated. These encouraging results such as the obtained high and direct optical bandgap value prompt us to propose this compound as a basic material for optoelectronic devices. [ABSTRACT FROM AUTHOR]

Herein, we report the preparation of methyl 6-methyl-4-(4-nitrophenyl)-2-oxo-1,2-dihydropyrimidine-5-carboxylate 2, obtained by the regioselective oxidative dehydrogenation of the dihydropyrimidine derivative 1 in the presence of cerium ammonium nitrate. The structure of compound 2 was investigated by single-crystal X-ray diffraction (SC-XRD), which allowed the determination of its tautomeric form. Moreover, the presence of non-covalent interactions and their impact on the crystal structure were analyzed. To better characterize the intermolecular contacts, the Hirshfeld surface and enrichment ratio analyses were performed. Furthermore, the antimycotic activity of compounds 1 and 2 was investigated against Candida albicans, Aspergillus flavus, and Aspergillus niger, and their efficacy was compared to that of fluconazole. Computational investigations on the putative target of the compounds provided insights to explain the better activity of 2 with respect to its synthetic precursor. [ABSTRACT FROM AUTHOR]

The synthesis and crystal structures of the molecular salts of 4-(4-nitrophenyl) piperazine with trifluoroacetate, namely, 4-(4-nitrophenyl)piperazin-1-ium trifluoroacetate, C10H14N3O2+·C2F3O2- (I), and with trichloroacetate, namely, 4-(4-nitrophenyl)piperazin-1-ium trichloroacetate, C10H14N3O2+·C2Cl3O2-, (II), are reported and compared. A partial positional disorder of the anions was found. In both structures, the piperazine rings adopt a chair conformation, whereas the positions of the nitrophenyl group on the piperazine ring differ from bisectional in (I) to equatorial in (II). In both structures, the supramolecular assemblies are mono-periodic on the basis of the chain-of-rings motifs supported by aromatic π-π interactions. Hirshfeld surface analysis was used to explore the intermolecular close contacts in both crystals. The most dominant contacts of the Hirshfeld surface of the cation-anion pairs of the asymmetric units are O...H/H...O, and those with a contribution of halogen atoms: F...H/H...F in (I) and Cl...H/H...Cl in (II), respectively. [ABSTRACT FROM AUTHOR]

The title compound, C6H15N2O+·C6H2N3O7-·H2O, was synthesized via slow evaporation of an aqueous solution of picric acid with the substituted morpholine base and crystallized with one cation (C6H15N2O)+, one anion (C6H2N3O7)- and a water molecule in the asymmetric unit. The morpholine ring in the cation adopts a chair conformation. The structure is stabilized by C--H...O, O--H...O, O--H...N and N--H...O hydrogen-bonding interactions and π-π stacking. The intermolecular interactions of the synthesized compound were quantified by Hirshfeld surface analysis. [ABSTRACT FROM AUTHOR]

The reaction of homopiperazine, C5N2H12, with BiBr3 in strong hydrobromic acid affords a new organic-inorganic hybrid (C5N2H14)2[BiBr6]Br·H2O. It crystallizes in the orthorhombic space group, Pbca, with unit cell dimensions of a = 15.0775 (2), b = 15.7569 (2), and c = 20.7881 (4) Å, and eight formula units per unit cell. The crystal structure features slightly distorted octahedral BiBr63− and monoatomic Br− anions in the inorganic substructure and C5N2H142+ dications and adjacent water molecules in the organic substructure. Various weak interactions that include (N)H···Br, (N)H···O, and (O)H···Br hydrogen bonds ensure the assembling of the structural moieties into a 3D supramolecular structure. (C5N2H14)2[BiBr6]Br·H2O shows two emission bands in the photoluminescence spectrum, a rather narrow deep-blue PL at 432 nm, and a broadband red PL centered at 650 nm. Their nature and relations to the crystal structure are discussed in this paper. [ABSTRACT FROM AUTHOR]

Eleven (4-phenyl)piperazinium salts containing organic anions have been prepared and structurally characterized, namely, 4-phenylpiperazin-1-ium f4l-uorobenzoate monohydrate, C10H15N2+-C7H4FO2-H2O, 1; 4-phenylpiperazin-1-ium 4-bromobenzoate monohydrate, C10H15N2+-C7H4NO2-H2O, 3; 4-phenylpiperazin-1-ium 4-iodobenzoate, C10H15N2+-C7H4IO2_, 4; 4-phenylpiperazin-1-ium 4-nitrobenzoate, C10H15N2+-C7H4NO4_, 5; 4-phenylpiperazin-1-ium 3,5-dinitrosalicylate, C10H15N2+-C7H3N2O7_, 6; 4-phenylpiperazin-1-ium 3d,i5n-itrobenzoate, C10H15N2+-C7H3N2O6_, 7; 4-phenylpiperazin-1-ium picrate, C10H15N2+-C6H2N3O7_, 8; 4-phenylpiperazin-1-ium benzoate monohydrate, C10H15N2+-C7H5O2_-H2O, 9; 4-phenylpiperazin-1-ium p-toluenesulfonate, C10H15N2+-C7H7O3S_, 10; 4-phenylpiperazin-1-ium tartarate monohydrate, C10H15N2+-C4H5O6~-H2O, 11; and 4-phenylpiperazin-1-ium fumarate, C10H15N2+-C4H3O4_, 12. Compounds 1 and 3-12 are all 1:1 salts with the acid proton transferred to the phenylpiperaizine basic N atom (the secondary amine) with the exception of 3 where there is disorder in the proton position with it being 68% attached to the base and 32% attached to the acid. Of the structures with similar stoichiometries only 3 and 9 are isomorphous. The 4-phenyl substituent in all cases occupies an equatorial position except for 12 where it is in an axial position. The crystal chosen for structure 7 was refined as a nonmerohedral twin. There is disorder in 5, 6, 10 and 11. For both 5 and 6, a nitro group is disordered and was modeled with two equivalent orientations with occupancies of 0.62 (3)/0.38 (3) and 0.690 (11)/0.310 (11), respectively. For 6,10 and 11, this disorder is associated with the phenyl ring of the phenylpiperazinium cation with occupancies of 0.687 (10)/0.313 (10), 0.51 (7)/0.49 (7) and 0.611 (13)/389 (13), respectively. For all salts, the packing is dominated by the N--H--O hydrogen bonds formed by the cation and anion. In addition, several structures contain C--H--Ä (1, 3, 4, 8, 9,10, and 12) and aromatic ä-ä stacking interactions (6 and 8) and one structure (5) contains a -NO2"-x interaction. For all structures, the Hirshfeld surface fingerprint plots show the expected prominent spikes as a result of the N--H--O and O--H--O hydrogen bonds. [ABSTRACT FROM AUTHOR]

A novel organic–inorganic hybrid compound, named (1-phenylpiperazinium) trihydrogen triphosphate, with the formula (C10H15N2)2H3P3O10 has been obtained by low speed of evaporation of a mixture of an alcoholic solution of 1-phenylpiperazine and triphosphoric acid H5P3O10 at room temperature after using the ion exchange chemical procedure. To carry out a detailed crystallographic structure analysis, single-crystal X-ray diffraction has been reported. In the molecular arrangement, the different entities are held together through N–H...O, O–H...O, and C-H...O hydrogen bonds, building up a three-dimensional packing. Powder X-ray diffraction analysis is acquired to confirm the purity of the product. The nature and the proportion of intermolecular interactions were investigated by Hirshfeld surface analysis. In order to support the experimental results, a density functional theory (DFT) calculation was performed, using the Becke-3-parameter-Lee–Yang–Parr (B3LYP) function with LANL2DZ basis set, and the data indicate much agreement between the experimental and the theoretical results. Thus, the physicochemical properties were studied employing a variety of techniques (FTIR, NMR, UV–visible, and photoluminescence). To get an insight of the possible employment of the present material in biology, cell viability assays were performed. [ABSTRACT FROM AUTHOR]

2-(3-Hydroxypropyl)-1H-benzimidazole, C10H12N2O, which has potential biological activity, can be used as a ligand for complexation with metals. This compound is an electron donor, due to the lone pair of the nitrogen atom in the imidazole ring. This nitrogen atom also acts as a proton acceptor. In the crystalline phase, the nitrate salt, namely, 2-(3-hydroxypropyl)-1H-benzimidazol-3-ium nitrate, C10H13N2O+·NO3-, has been studied. The protonation of the 2-(3-hydroxypropyl)benzimidazole unit results in significant delocalization of the electron density within the imidazole ring. The salt formation leads to variations in the intermolecular interactions, which were studied by analysis of the Hirshfeld surfaces and two-dimensional fingerprint plots. [ABSTRACT FROM AUTHOR]

The synthesis and crystal structure of a new noncentosymmetric compound with the general formula: [C48H51N8O8S4](HPO4)H2PO4 are reported. The structure, determined by single-crystal X-ray diffraction at 150 K can be described as organic layers [C48H51N8O8S4]3+ parallel to the (a and c) plane between which the inorganic groups consisting of H2PO4 − and HPO4 2− entities are inserted as inorganic layers. In this atomic arrangement, H-bonds and Vander-Waals interactions between the different species play an important role in the tridimensional network cohesion. Solid-state 13C and 31P MAS NMR spectroscopies are in agreement with the X-ray structure. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. [ABSTRACT FROM PUBLISHER]

C19H16CuN6O5, triclinic, P 1 ‾ (no. 2), a = 9.0143(3) Å, b = 9.2122(3) Å, c = 11.8205(4) Å, α = 82.900(3)°, β = 74.593(3)°, γ = 83.612(3), V = 935.90(5) Å3, Z = 2, Rgt(F) = 0.0284, wRref(F2) = 0.0684, T = 293 K. [ABSTRACT FROM AUTHOR]

In this paper, a new organic salt bis(2-ethyl-6-methylanilinium)tetrachloromercurate (II)) has been synthesized, characterized, and studied theoretically using DFT. The synthesized compound was found to crystallize in the monoclinic system with space group P21/c with the following unit cell parameters a = 23.1696(2), b = 25.7951 (6), c = 7.5980 (4) Å, β = 96.5790 (11)°, and Z = 8. Its atomic arrangement can be described asmutually alternating organic and inorganic entities in the (ab) plane. The cohesion is achieved through N-H...Cl hydrogen bonds and π...π stacking interacting neighboring aromatic cations. The PXRD was carried out. The intermolecular interactions in the crystal packing were investigated using Hirshfeld surface analysis. Its associated 2D fingerprint plots revealed their contribution quantitatively. High-resolution images of the surface were obtained by the SEM technique, and the EDX spectrum assured the existence of all nonhydrogen atoms. The infrared spectrum was used to gain more information about vibrational modes. Analysis of thermal differential and gravimetric (TGA/DTA) shows two-phase transitions observed at 362 and 394 K. AC conductivity measurements were performed to confirm these two-phase transitions. [ABSTRACT FROM AUTHOR]

Bis(2-amino-4-methylpyrimidinium) hexachlorodicuprate(II), (C5H8N3)2[Cu2Cl6], contains a centrosymmetric hexachlorodicuprate group where each Cu atom is coordinated to two bridging Cl atoms in a slightly distorted square planar geometry. There are short contacts between neighboring [Cu2Cl6]2− dimer units. In the crystal, cations and anions are connected by N–H···Cl and C–H···Cl hydrogen bonds into layers parallel to ( 10 2 ¯ ). Hirshfeld surface analyses and fingerprint plots are used for decoding intermolecular interactions in the crystal network and contribution of component units for the construction of the 3D architecture. The vibrational absorption bands were identified by infrared spectroscopy. [ABSTRACT FROM AUTHOR]

A new 0D organic--inorganic hybrid material bis[1-(prop-2-en-1-yl)-1Himidazol- 3-ium] hexachloridostannate(IV), (C6H9N2)2[SnCl6], has been prepared and characterized by single-crystal X-ray diffraction, Hirshfeld surface analysis and UV--visible spectroscopy. The structure consists of isolated [SnCl6]2 octahedral anions separated by layers of organic 1-(prop-2-en-1-yl)- 1H-imidazol-3-ium cations. The 1-(prop-2-en-1-yl) fragment in the organic cation exhibits disorder over two sets of atomic sites having occupancies of 0.512 (9) and 0.488 (9). The crystal packing of the title compound is established by intermolecular N/C--H Cl hydrogen bond and п-п stacking interactions. Hirshfeld surface analysis employing three-dimensional molecular surface contours and two-dimensional fingerprint plots has been used to analyse the intermolecular interactions present in the structure. The optical properties of the crystal were studied using UV--visible absorption spectroscopy, showing one intense band at 208 nm, which is attributed to п-п transitions in the cations. [ABSTRACT FROM AUTHOR]

In the title molecular salt, (C5H7N2)2[SnCl6], the cation is protonated at the pyridine N atom and the complete dianion is generated by a crystallographic centre of symmetry. In the crystal, N—HCl hydrogen bonds link the components into a three-dimensional network built up from the stacking of alternate cationic and anionic layers. The nature of the intermolecular interactions has been analysed in terms of the Hirshfeld surfaces of the cations and the anions. The thermal behaviour and the Raman spectrum of the title compound are reported. [ABSTRACT FROM AUTHOR]

In the title molecular salt, 1,3-dimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purin-9- ium aquatrichloridozincate(II), (C7H9N4O2)[ZnCl3(H2O)], the fused ring system of the cation is close to planar, with the largest deviation from the mean plane being 0.037 (3) A ° . In the complex anion, the ZnII cation is coordinated by three chloride ions and one oxygen atom from the water ligand in a distorted tetrahedral geometry. In the crystal, inversion dimers between pairs of cations linked by pairwise N--H…O hydrogen bonds generate R2 2(10) rings. The anions are linked into dimers by pairs of O--H…Cl hydrogen bonds and the respective dimers are linked by O--H…O and N--H…Cl hydrogen bonds. Together, these generate a three-dimensional supramolecular network. Hirshfeld surfaces were generated to gain further insight into the packing. [ABSTRACT FROM AUTHOR]

The new organic–inorganic hybrid material (C6H7N2S)2[SbCl4]Cl was synthesized by slow evaporation method and characterized by single-crystal X-ray diffraction, infrared absorption, Hirshfeld surface analysis, optical absorption and photoluminescence measurements. The Centro symmetric compound crystallizes in the triclinic system of space group P 1 ¯ with two formula units cell (Z = 2).The crystal structure is composed of a discrete [SbCl4]− anion and two isolated chloride Cl− anions which carried the same negative charge to balance the total charge of this compound surrounded by the 4 pyridiniumethioamide cations. Organic and inorganic parts which are linked by means of hydrogen bonding contacts N–H···Cl with N···Cl length are varied in the range of 3.221–3.456 Å to form a Zero-dimensional network. The infrared study performed at room temperature charge in the 4000–400 cm−1 frequency regions confirms the existence of the organic cation [C6H7N2S]+ and that of the [SbCl4]− anion. The Photoluminescence spectrum exhibits a broad and strong band of luminescence located at 1.95 eV (635 nm), which can be even observed with the naked eye at room temperature and is due to exaction emission. The various intermolecular interactions of the two independent cations and six chloride atoms were examined via Hirshfeld surface analysis. [ABSTRACT FROM AUTHOR]

Charge-assisted hydrogen bonding plays a significant role in the crystal structures of solvates of ionic com­pounds, especially when the cation or cations are primary ammonium salts. We report the crystal structures of four ammonium salts of molybdenum halide cluster solvates where we observe significant hydrogen bonding between the solvent molecules and cations. The crystal structures of bis(anilinium) octa-μ3-chlorido-hexa­chlorido-octa­hedro-hexa­molybdate N,N-di­­methyl­formamide tetra­solvate, (C6H8N)2[Mo6Cl8Cl6]·4C3H7NO, (I), p-phenyl­enedi­ammonium octa-μ3-chlorido-hexa­chlorido-octa­hedro-hexa­mol­yb­date N,N-di­methyl­formamide hexa­solvate, (C6H10N2)[Mo6Cl8Cl6]·6C3H7NO, (II), N,N′-(1,4-phenyl­ene)bis­(propan-2-iminium) octa-μ3-chlorido-hexa­chlo­rido-octa­hedro-hexa­molybdate acetone tris­olvate, (C12H18N2)[Mo6Cl8Cl6]·3C3H6O, (III), and 1,1′-dimethyl-4,4′-bipyridinium octa-μ3-chlo­rido-hexa­chlorido-octa­hedro-hexa­molybdate N,N-di­methyl­formamide tetra­solvate, (C12H14N2)[Mo6Cl8Cl6]·4C3H7NO, (IV), are reported and described. In (I), the anilinium cations and N,N-di­methyl­formamide (DMF) solvent mol­ecules form a cyclic R4²(8) hydrogen-bonded motif centered on a crystallographic inversion center with an additional DMF mol­ecule forming a D(2) inter­action. The p-phenyl­enedi­ammonium cation in (II) forms three D(2) inter­actions between the three N—H bonds and three independent N,N-di­methyl­formamide mol­ecules. The dication in (III) is a protonated Schiff base solvated by acetone mol­ecules. Compound (IV) contains a methyl viologen dication with N,N-di­methyl­formamide mol­ecules forming close contacts with both aromatic and methyl H atoms. [ABSTRACT FROM AUTHOR]

The reaction of 2-methylthio-5-amino-1,3,4-thiadiazole (Me-SNTD; C3H5N3S2) with copper(II) acetate monohydrate [Cu(OAc)2·H2O; C4H8CuO5] resulted in the formation of the title binuclear compound, [Cu2(C2H3O2)4(C3H5N3S2)2] or [Cu2(OAc)4(Me-SNTD)2]. The structure has triclinic (P 1) symmetry with a crystallographic inversion centre located at the midpoint of the line connecting the Cu atoms in the dimer. These two Cu atoms of the dimer [Cu···Cu = 2.6727(6)Å] are held together by four carboxylate groups. Each Cu atom is further coordinated to the N atom of an Me-SNTD molecule and exhibits a Jahn-Teller-distorted octahedral geometry. The dimers are connected into infinite chains by hydrogen bonds between the NH (Me-SNTD) and the carboxylate groups of neighbouring molecules, generating an R²2(12) ring motif. The molecules are further linked by C--H···π interactions between the thiadiazole rings and the methyl groups of the acetate units. [ABSTRACT FROM AUTHOR]

Abstract The new organic-inorganic compound, (C 9 H 14 N) 2 [SnCl 6 ], has been synthesized and characterized by single-crystal X-ray diffraction at room temperature. Structural analysis indicates that this compound crystallizes in the monoclinic system with C2/m space group. The N H⋯Cl hydrogen bonds between (C 9 H 14 N)+ cations and [SnCl 6 ]2- dianions contribute to the cohesion and the stability of the atomic arrangement. Hirshfeld surface analysis was used to investigate intermolecular interactions, as well 2D finger plots were conducted to reveal the contribution of these interactions in the crystal structure quantitatively. Furthermore, the room temperature Infrared (IR) spectrum of the title compound was analyzed on the basis of data found in the literature. The optical properties of the crystal were studied using optical absorption UV–visible and photoluminescence (PL) spectroscopy, which were investigated at room temperature exhibited one band at 237 nm and a photoluminescence emission at 407 nm. Experimental room-temperature X-ray studies were supported by theoretical methods using the DFT/B3LYP methods with the LanL2DZ basis set. The X-ray powder is in agreement with the X-ray structure. To determine molecular electrical transport properties we studied the energy difference between Occupied, HOMO, and Lowest Unoccupied, LUMO orbitals. Moreover, this compound was characterized by thermal analysis between 300 and 750 K and shows that the compound remains stable up to the temperature 383 K. Finally, X-ray photoelectron spectroscopy (XPS) analysis is reported to determine the degree of oxidation of tin in this compound and analyze the surface chemistry of (C 9 H 14 N) 2 [SnCl 6 ]. Graphical abstract Image 1 Highlights • The crystal structure is built by alternating organic and inorganic entities. • The optical properties were studied by UV–visible, photoluminescence and XPS study. • This compound was characterized by thermal analysis between 300 and 750 K. [ABSTRACT FROM AUTHOR]

Abstract A novel hybrid material, [C 10 H 22 N 2 ] 3 ·PbCl 5 ·3Cl·3H 2 O, has been synthesized and its structure was determined by single-crystal X-ray diffraction. In the atomic arrangement, the different entities are held together through N H⋯Cl, O H⋯Cl and O H⋯O hydrogen bonds to form a three-dimensional network. Intermolecular interactions were investigated by Hirshfeld surfaces. The powder XRD data confirms the phase purity of the crystalline sample. The resulting IR spectrum calculated by the DFT/B3LYP/LanL2DZ method, is similar to the experimental spectrum allowing a good correlation between the experimental and theoretical wavenumbers. The optical properties in the UV–visible region have been explored by the UV–visible absorption. The photoluminescence (PL) spectroscopy, which was investigated at room temperature, exhibited one emission at 426 nm. Thermal analysis discloses a phase transition at 435 K and the decomposition of the sample starts from 554 K. Graphical abstract Image 1 Highlights • The entities [C 10 H 22 N 2 ]2+ and [PbCl 5 ]3- ions are interconnected by means of hydrogen bonding contacts, forming a three-dimensional network. • The vibrational frequencies were also predicted from the calculated intensities by DFT method. • The optical properties were studied by UV–visible absorption and photoluminescence study. • This compound was characterized by thermal analysis between 300 and 750 K. [ABSTRACT FROM AUTHOR]

In the title compound, C18H12O3S2, synthesized by the Claisen-Schmidt condensation method, the essentially planar chalcone unit adopts an s-cis configuration with respect to the carbonyl group within the ethyl­enic bridge. In the crystal, weak C--H...π inter­actions connect the mol­ecules into zigzag chains along the b-axis direction. The mol­ecular structure was optimized geometrically using Density Functional Theory (DFT) calculations at the B3LYP/6-311 G++(d,p) basis set level and compared with the experimental values. Mol­ecular orbital calculations providing electron-density plots of HOMO and LUMO mol­ecular orbitals and mol­ecular electrostatic potentials (MEP) were also computed both with the DFT/B3LYP/6-311 G++(d,p) basis set. The experimental energy gap is 3.18 eV, whereas the theoretical HOMO-LUMO energy gap value is 2.73 eV. Hirshfeld surface analysis was used to further investigate the weak inter­actions present. [ABSTRACT FROM AUTHOR]

Abstract In this study, a new organic-inorganic hybrid metal compound (C 5 H 14 N 2) 2 [SnCl 6 ] 2 ·5H 2 O was crystallized at room temperature in the orthorhombic system (space group P2 1 2 1 2 1) where the structure is determined by single crystal X-ray diffraction analysis. The examination of the structure shows the cohesion and stability of the atomic arrangement result from the establishment of N—H⋯Cl, O(W)—H(W)⋯Cl, N—H⋯O(W) and O(W)—H(W)⋯O(W) hydrogen bonds between 1-methylpiperazine-1,4-diium (C 5 H 14 N 2)2+cations, isolated (SnCl 6)2– anions and water molecules to form organic and inorganic layers parallel to the (a, c) plane and alternate along the b-axis. Hirshfeld surface analysis was used to investigate intermolecular interactions, as well 2D fingerprint plots were conducted to reveal the contribution of these interactions in the crystal structure quantitatively. The solid phase FTIR and FT-Raman spectra of this compound have been recorded in the regions 400–4000 and 100–500 cm−1, respectively. The vibrational frequencies were also predicted from the calculated intensities by DFT method and were compared with the experimental frequencies, which yield good agreement between observed and calculated frequencies. Besides, the optical proprieties were investigated by UV-visible and photoluminescence spectroscopy studies in the region 200–700 nm and the electronic properties HOMO and LUMO energies were measured by TD-DFT approach. Moreover, this compound was characterized by thermal analysis between 300 and 500 K which revealing two phase transitions. Finally, X-ray photoelectron spectroscopy (XPS) analysis is reported to determine the degree of oxidation of tin in this compound and analyzing the surface chemistry of (C 5 H 14 N 2) 2 [SnCl 6 ] 2 ·5H 2 O. Graphical abstract Image 1 The different characterization techniques of (C 5 H 14 N 2) 2 [SnCl 6 ] 2 ·5H 2 O. Highlights • The crystal structure exhibits organic and inorganic layers parallel to the (a, c) plane and alternate along the b-axis. • The 3D Hirshfield surfaces and the associated 2D fingerprint plots were investigated for intermolecular interactions. • The vibrational frequencies were also predicted from the calculated intensities by DFT method and were compared with the experimental frequencies. • The optical properties were studied by UV–visible absorption, photoluminescence spectroscopy studies and XPS technique. • This compound was characterized by thermal analysis between 300 and 500. [ABSTRACT FROM AUTHOR]

The synthesis and the structure of (C 10 H 15 N 2 ) 4 (Li) 2 (P 6 O 18 )(H 2 O) 6 are described. This compound crystallizes in the triclinic system, with the centric space group P-1 and the following unit cell parameters: a  = 9.7762(6), b  = 10.2502(8), c  = 15.2173(11) Å, α  = 92.588(4), β  = 98.855(4), γ  = 115.724(4)°, Z  = 2 and V  = 1346.62(17) Å 3 . The crystal structure has been solved and refined to R  = 0.0452 and Rw  = 0.1121. [Li 2 (P 6 O 18 )(H 2 O)] 4- entities are associated by strong O H⋯O hydrogen bonds to form inorganic layers lying in the (a, b) plane. These layers are interconnected with the organic entities via N H⋯O and C H⋯O hydrogen bonds. In this atomic arrangement, H bonds between the different species play an important role in the three-dimensional network. The contacts enrichment ratios derived from the Hirshfeld surface analysis show that the crystal packing is stabilized by ionic bridges Li + … O, strong N/O H⋯O hydrogen bonds but also hydrophobic interactions between the two independant 1-phenylpiperazine-1,4-dium ligands. The Molecular Electrostatic Potential (MEP) maps and the HOMO and LUMO energy gaps of the new compound were computed. The title compound was further characterized by FT-IR and NMR spectroscopies. The crystal symmetry was confirmed by 31 P and 7 Li MAS NMR and the vibrational absorption bands were identified by infrared spectroscopy. The new compound was also characterized by thermal analysis to determine the thermal behavior. [ABSTRACT FROM AUTHOR]

The chemical preparation and characterization of a novel coordination compound [CuClO4(C4H6N2O)4H2O]ClO4(C4H6N2O)0.08 is reported. The compound crystallizes in the monoclinic space group P21/c with lattice parameters a = 11.2678(5) Å, b = 12.8102(6) Å, c = 19.7250(8) Å, β = 100.3051(15)°, V = 2801.2(2) Å3. The Cu(II) cation is six-coordinated in an elongated distorted octahedral fashion by four N atoms of four 3-amino-5-methylisoxazole ligands, one water oxygen atom, and one perchlorate oxygen atom. In the atomic arrangement, the coordinated and uncoordinated perchlorate anions are grouped in pairs to form anionic layers parallel to the (a, b) plane. A substantial number of H-bonding interactions leads to the formation of an intricate three-dimensional network. The vibrational absorption bands are identified by infrared spectroscopy and the electrical properties are studied by impedance spectroscopy. The DSC analysis agrees with the electrical conductivity results. Magnetic properties are also determined to characterize the complex. [ABSTRACT FROM AUTHOR]

C10H16Cl4MnN2, monoclinic, P21 (no. 4), a = 7.28276(7) Å, b = 13.22972(12) Å, c = 8.01007(7) Å, β = 97.5018(9)°, V = 765.155(12) Å3, Z = 2, Rgt(F) = 0.0165, wRref(F2) = 0.0392, T = 123(2) K. [ABSTRACT FROM AUTHOR]

Crystal structures of 4-chloro-N-(4-chlorobenzoyl)-N-(2-pyridyl)benzamide (I) Clpod, 3-chloro-N-(3-chlorobenzoyl)-N-(2-pyridyl)benzamide (II) Clmod and 2-chloro-N-(2-chlorobenzoyl)-N-(2-pyridyl)benzamide (III) Clood together with three methylated analogues, Mpod, Mmod and Mood, are presented herein. The Clxod acyclic imides are produced from reacting the 4-/3-/2-chlorobenzoyl chlorides (Clx) with 2-aminopyridine (o), respectively, together with their benzamide analogues Clxo; the Mxod/Mxo triad are produced similarly and in good yield. The five Clxod, Mpod and Mmod structures adopt the open transoid conformations as expected, but Mood crystallises with cisoid oriented benzoyl groups, and this conformation was unexpected, though not unknown. Halogen bonding contacts and weak hydrogen bonding C-H···N/O/π contacts are noted in the structures lacking strong hydrogen bonding donor atoms/groups but possessing a variety of strong and weaker acceptor atoms/groups. For Clxod, contact studies show that both hydrogen and carbon account for a high percentage of elements (70-75%) on the molecular surface and being the most abundant have C···H forming 26-30% of the contacts. Contact enrichment ratios are an indicator of the likelihood of chemical species to form intermolecular interactions with themselves and other species. The C-H···N and C-H···O are the most enriched (with EHN > 2.15), indicating that these weak hydrogen bonds are the driving force in the Clxod crystal packing formation. For Mxod, the C···H contact type at 40-52% is the most abundant contact type and C-H···O and C-H···N weak hydrogen bonds dominate with enrichment values in the 1.48-1.78 range. In Mxod, N/O···N/O contacts are effectively absent, except for Mpod (0.2%, N···N contacts) and both H···H and C···C non-polar contacts are moderately impoverished while the C···H interactions are slightly enriched (E = 1.1-1.21). [ABSTRACT FROM AUTHOR]

Two new organic-inorganic hybrid materials, 4-methoxybenzylammonium nitrate, (C 8 H 12 NO)·[NO 3 ] (I) , and 2-(1-piperazinyl)pyrimidinium bis(perchlorate), (C 8 H 14 N 4 )·[ClO 4 ] 2 (II) , have been synthesized by an acid/base reaction at room temperature, their structures were determined by single crystal X-ray diffraction. Compound (I) crystallizes in the orthorhombic system and Pnma space group with a  = 15.7908 (7), b  = 6.8032 (3), c  = 8.7091 (4) Å, V  = 935.60 (7) Å 3 with Z  = 4. Full-matrix least-squares refinement converged at R  = 0.038 and w R ( F 2 ) = 0.115. Compound (II) belongs to the monoclinic system, space group P 2 1 / c with the following parameters: a  = 10.798(2), b  = 7.330(1), c  = 21.186(2) Å, β  = 120.641 (4)°, V  = 1442.7 (3) Å 3 and Z  = 4. The structure was refined to R  = 0.044, w R ( F 2 ) = 0.132. In the structures of ( I ) and ( II ), the anionic and cationic entities are interconnected by hydrogen bonding contacts forming three-dimensional networks. Intermolecular interactions were investigated by Hirshfeld surfaces and the contacts of the four different chloride atoms in (II) were compared. The Molecular Electrostatic Potential (MEP) maps and the HOMO and LUMO energy gaps of both compounds were computed. The vibrational absorption bands were identified by infrared spectroscopy. These compounds were also investigated by solid-state 13 C, 35 Cl and 15 N NMR spectroscopy. DFT calculations allowed the attribution of the IR and NMR bands. [ABSTRACT FROM AUTHOR]

The reaction of perchloric acid with 1-(2-aminoethyl)piperazine or 5,6-dimethyl-benzimidazole results in the formation of 1-(2-amonioethyl)piperazine-1,4-dium triperchlorate hydrate (C 6 H 18 N 3 )·(ClO 4 ) 3 ·H 2 O (I) or 5,6-dimethyl-benzylimidazolium perchlorate (C 9 H 11 N 2 )·ClO 4 (II) . Both compounds were fully structurally characterized including single crystal X-ray diffraction analysis. Compound (I) crystallizes in the centrosymmetric triclinic space group P 1 ¯ with the lattice parameters a = 7.455 (2), b = 10.462 (2), c = 10.824 (2) Å, α = 80.832 (2), β = 88.243 (2), γ = 88.160 (2) °, Z = 2 and V = 832.77 (3) Å 3 . Compound (II) has been found to belong to the P 2 1 /c space group of the monoclinic system, with a  = 7.590 (3), b  = 9.266 (3), c  = 16.503 (6) Å, β = 107.38 (2) °, V = 1107.69 (7) Å 3 and Z = 4. The structures of (I) and (II) consist of slightly distorted [ClO 4 ] - tetrahedra anions and 1-(2-amonioethyl)piperazine-1,4-dium trication (I) or 5,6-dimethyl-benzylimidazolium cations (II) and additionally a lattice water in (I) . The crystal structures of ( I) and ( II) exhibit complex three-dimensional networks of H-bonds connecting all their components. In the atomic arrangement of (I) , the ClO 4 − anions form corrugated chains, while in (II) the atomic arrangement exhibits wide pseudo-hexagonal channels of ClO 4 tetrahedra including the organic entities. The lattice water serves as a link between pairs of cations and pairs of anions via several O H⋯O and N-H⋯O interactions in compound (I) . The vibrational absorption bands were identified by infrared spectroscopy. These compounds were also investigated by solid-state 13 C, 35 Cl and 15 N NMR spectroscopy. DFT calculations allowed the attribution of the IR and NMR bands. Intermolecular interactions were investigated by Hirshfeld surfaces. Electronic properties such as HOMO and LUMO energies were derived. [ABSTRACT FROM AUTHOR]