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Single crystals of a new organic cyclohexaphosphate (C 8 H 12 N) 4 (Li) 2 (P 6 O 18 )(H 2 O) 6 prepared by an acid/base reaction between cyclohexaphosphoric acid H 6 P 6 O 18 and 2,6-dimethylaniline, have been successfully grown by slow evaporation technique at room temperature. This compound was characterized using X-ray diffraction (XRD) and FT-IR spectroscopy. The results show that the title compound was phased with a triclinic structure and P-1 space group. The crystal structure was solved by using 5203 independent reflections with a final R value of 0.031. The P 6 O 18 ring is centrosymmetrical. Its main geometrical features are those commonly observed in others cyclohexaphosphates. The atomic arrangement of this compound can be described by an organization in a three-dimensional framework, built up from alternated organic and inorganic species. Adjacent P 6 O 18 rings are linked via corner-sharing by LiO 4 tetrahedra, generating anionic [Li 2 (P 6 O 18 )(H 2 O)] 4- layers parallel to (110). Charge balance is achieved by the protonated amine which is trapped in the interlayer space and interacts with the organic framework through strong and medium hydrogen bonding. An extensive network of N H⋯O and O H⋯O hydrogen-bonding interactions link the components into a three-dimensional network and additional stabilization is provided by weak C H⋯O hydrogen bonds. Intermolecular interactions were investigated by Hirshfeld surfaces. The vibrational absorption bands were identified by infrared spectroscopy. The stretching modes of P 6 O 18 ring and band assignments are described. [ABSTRACT FROM AUTHOR]

The new organic–inorganic compound, Tetrakis(2,6-diethylanilinium) decabromodibismuthate(III) hexahydrate, has been synthesized and characterized by single-crystal X-ray diffraction at room temperature. It crystallizes in the monoclinic system (P2 1 /c space group). The structure consists of discrete dinuclear [Bi 2 Br 10 ] 4− anions, [C 10 H 16 N] + cations and water molecules. The organic part consists of two organic cations which orient their two amine groups to the neighboring anions. The inorganic entity is made up by [Bi 2 Br 10 ] 4− dimers composed of two equivalent irregular octahedra sharing one edge. The water molecules are sandwiched between the [Bi 2 Br 10 ] 4− anions and the neighboring [C 10 H 16 N] + cations. The crystal packing is governed by N(O)–H⋯Br and N–H⋯O W hydrogen bonds and π−π interactions to built a three dimensional network. The nature of the inorganic polyhedra distortion, which can be attributed to the stereo-activity of the Bi(III) lone electron pair, has been studied. The infrared and NMR spectra were calculated by Density Functional Theory (DFT) using the B3LYP method with the 6–311++G** basis set. A good consistency was found between the calculated and experimental data. The vibrational absorption bands were identified by infrared spectroscopy. [ABSTRACT FROM AUTHOR]

A new Cu (II) complex with bidentate o-phenanthroline (phen) ligand, ([Cu(phen)](HPO)HPO)(HPO), has been synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy and magnetic data. The crystal structural analysis shows that the title compound contains two phosphate-bridged dimeric units ([Cu(phen)](HPO)HPO), which are crystallographically independent. In these units, each copper atom is five coordinated and the geometry around the Cu(II) can be described as slightly distorted square-based pyramidal, with τ parameter varying between 0.001 and 0.04. The crystal structure is stabilized by O-H...O and C-H...O hydrogen bonds between the dimeric units and the phosphoric acid molecules. In addition, the organic ligands are associated by π-π stacking interactions between neighboring non-nitrogen aromatic rings. The infrared spectrum recorded at room temperature was interpreted on the basis of data published in the literature. The magnetic susceptibilities data show a weak intra-dimer ferromagnetic interaction with J = 31.8 K. [ABSTRACT FROM AUTHOR]

The chemical preparation, characterization by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy of the new Fe(III) complex (C5H7.50N3O)2[FeCl4] are reported. The Fe(III) cation is four-coordinated, in tetrahedral fashion, by four chlorine atoms. The [FeCl4]− tetrahedra are located parallel to the (a, b) plane at z = ¼ (2n + 1) between layers of organic cations (C5H7.50N3O)2+. The FeCl4 moieties are inserted between these planes by establishing N–H...Cl and C–H...Cl hydrogen bonds generated by amino and methyl groups as donors and Cl− anions as acceptors to form a three-dimensional network. The organic groups are linked together by N–H...N hydrogen bonds to form chains extending along the [110] direction. These chains are arranged in planes parallel to (a, b) at z = ½n. Intermolecular contacts on the Hirshfeld surface were investigated statistically. The most favored and stabilizing contacts are the strong (N–H...Cl−, N–H...N) hydrogen bonds as well as the weaker ones C–H...Cl−. The vibrational absorption bands were identified by infrared spectroscopy. Electronic properties such as HOMO and LUMO energies were also derived. [ABSTRACT FROM AUTHOR]

Abstract: Three binuclear Cu(II) and Ni(II) perchlorate complexes with the potentially bidentate ligand 2-amino-6-methylpyrimidin-4(1H)-one (AMPO) [Cu(AMPO)4][Cu(H2O)5](ClO4)4·6H2O (1), [Cu2(AMPO)4(H2O)3](ClO4)4·½H2O (2) and[Ni(AMPO)4][Ni(H2O)6](ClO4)4·5H2O (3), have been prepared and were characterized by single crystal X-ray diffraction, IR spectroscopy and elemental analysis. Structural and IR data indicate that the ligand is present in its tautomeric form protonated at nitrogen in position one and metal coordinated at position three. The basic coordination pattern of the AMPO coordinated metal cations in all three complexes is square planar by four pyrimidyl nitrogen atoms of four different AMPO ligands. The coordination sphere is augmented by weak M⋯O interactions between the metal centers and AMPO keto oxygen atoms. Bond valence calculations indicate the M⋯O interactions to be most pronounced for nickel compound (3), and least for copper complex (2). The structural and geometrical differences between compounds (1) and (3) on the one hand and compound (2) on the other can to a large part be traced back to the lack of available water in the crystallization solvent in (2) which starves the cation not coordinated to AMPO nitrogen atoms of water molecules to saturate its coordination sphere, thus forcing two of the AMPO ligands in (2) to act as a bridging ligands, while the other AMPO ligands in the three structures are mostly monodentate with the coordination mode of the AMPO ligand being completed by weak secondary chelating M⋯O interactions. [Copyright &y& Elsevier]

(C 6 H 7 FN) 4 (Li) 2 (P 6 O 18 ) (H 2 O) 6 (I) , a new organic cyclohexaphosphate, has been synthesized and grown at room temperature by an acid/base reaction between H 6 P 6 O 18 and 2-fluoroaniline as an organic template. The crystal structure of (I) was solved by single crystal X-ray diffraction analysis and it was found that the material belongs to triclinic system with space group P-1 and refined R -factor of 0.0520. Adjacent P 6 O 18 rings are connected via corner-sharing by LiO 4 tetrahedra, generating anionic [Li 2 P 6 O 18 ·H 2 O] 4- layers parallel to the ( a , b ) plane. The 2-fluoro-anilinium cations are inserted in the interlayer space and interact with the inorganic framework through N H⋯O and O H⋯O hydrogen-bonding interactions. Additional stabilization is provided by strong N H⋯F and weak C H⋯O hydrogen bonds. Hirshfeld surface analysis reveals the nature of intermolecular contacts of the title compound and their enrichment ratio reveals if they are over-represented. The crystal packing is a combination of strong electrostatic attractive interactions and of weaker hydrophobic contacts. The title compound was further characterized by FT-IR and NMR spectroscopies. Crystal symmetry is confirmed by 31 P magic angle spinning NMR and the vibrational absorption bands were identified by infrared spectroscopy. Electrical conductivity was studied using impedance spectroscopy and results showed that the conductivity at 150 °C was equal to 4.93 × 10 −4  S cm −1 . It is therefore concluded that (C 6 H 7 FN) 4 (Li) 2 (P 6 O 18 ) (H 2 O) 6 can be further used in lithium batteries. [ABSTRACT FROM AUTHOR]