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The first indiumsilicate oxysulfide Ba2In2Si3O10S ( 1) was obtained by an alkali polychalcogenide flux method through a high-temperature solid-state reaction. It crystallizes in the non-centrosymmetric space group Pca21 (No. 29), with a = 23.060(6), b = 5.2954(6), c = 8.779(2) Å, and Z = 4. Its three-dimensional (3D) framework is constructed from one-dimensional (1D) infinite ∞1[In2O7S2/2] double octahedral chains bridged by corner-sharing Si tetrahedral trimers [Si3O10]8-, yielding a 3D framework with the channels filled with Ba2+ cations along the b direction. It is unprecedented in that the two distorted indium octahedra in 1 face-share to form a [In2O7S2] dimer in indium oxides and oxide chalcogenides. [ABSTRACT FROM AUTHOR]

Two new inorganic supramolecular compounds, (Hg11P4)(GaCl4)4 (1) and (Hg3AsS)(GaCl4) (2), have been prepared by the solid-state reactions. Their structures are characterized by mercury-containing cationic hosts and discrete (GaCl4)− guests, which is a derivative of a very strong Lewis acid. The three-dimensional cationic framework of 1, (Hg11P4)4+, is marvellously extended by Hg22+ and Hg32+ groups as well as Hg2+ ions to form two large tunnels with different sizes each embedded with two columns of (GaCl4)− anions. Compound 2 features a layered structure with (GaCl4)− tetrahedra being intercalated between two-dimensional (Hg3AsS)+ layers and it is the first mercury pnictidechalcohalide. It is found that the weak electrostatic forces between hosts and guests play a key role in the stabilization of the whole structures of 1 and 2, which is strikingly different from almost all the reported metal pnictidehalide and chalcohalide supramolecular compounds. Optical dielectric constants calculations show that both 1 and 2 possess strong dielectric anisotropy. [ABSTRACT FROM AUTHOR]

Abstract: High-quality single crystals of RbInS2, CsInS2 were isolated from the halide flux as a major phase of the repeated fusion of CaS and In2S3 followed by slow cooling. RbInS2 and CsInS2 are practically isostructural with KInS2. RbInS2: C2/c, a =11.071(6)Å, b =11.068(1)Å, c =15.610(7)Å, β =100.36(3)°, V =1882(2)Å3, Z =16, d x =3.74g/cm3, R =6.38%, R w =6.42%. CsInS2: C2/c, a =11.197(3)Å, b =11.158(3)Å, c =16.358(4)Å, β =99.92(2)°, V =2013(2)Å3, Z =16, d x =4.12g/cm3, R =5.60%, R w =6.20%. The AInS2 (A=Rb, Cs) structure is characterized by double layers of vertex-sharing [In4S10] units that each consists of four [InS4] polyhedra. The charge-balancing alkali-metal cations are stuffed into the channels created by the packing of these anionic [In4S10] blocks. The optical reflectance measurements show a band gap of 3.3eV for RbInS2 and 3.4eV for CsInS2, suggesting that both are semiconductors. [Copyright &y& Elsevier]

Two new inorganic supramolecular compounds, (Hg11P4)(GaCl4)4 (1) and (Hg3AsS)(GaCl4) (2), have been prepared by the solid-state reactions. Their structures are characterized by mercury-containing cationic hosts and discrete (GaCl4)− guests, which is a derivative of a very strong Lewis acid. The three-dimensional cationic framework of 1, (Hg11P4)4+, is marvellously extended by Hg22+ and Hg32+ groups as well as Hg2+ ions to form two large tunnels with different sizes each embedded with two columns of (GaCl4)− anions. Compound 2 features a layered structure with (GaCl4)− tetrahedra being intercalated between two-dimensional (Hg3AsS)+ layers and it is the first mercury pnictidechalcohalide. It is found that the weak electrostatic forces between hosts and guests play a key role in the stabilization of the whole structures of 1 and 2, which is strikingly different from almost all the reported metal pnictidehalide and chalcohalide supramolecular compounds. Optical dielectric constants calculations show that both 1 and 2 possess strong dielectric anisotropy. [ABSTRACT FROM AUTHOR]

Hydrothermal reactions of N,N-bis(phosphonomethyl)aminoacetic acid (HO2CCH2N(CH2PO3H2)2) with metal(II) salts afforded two new metal carboxylate-phosphonates, namely, Pb2[O2CCH2N(CH2PO3)(CH2PO3H)]·H2O (1) and {NH3CH2CH2NH3}{Ni[O2CCH2N(CH2PO3H)2](H2O)2}2 (2). Among two unique lead(II) ions in the asymmetric unit of complex 1, one is five coordinated by five phosphonate oxygen atoms from 5 ligands, whereas the other one is five-coordinated by a tridentate chelating ligand (1 N and 2 phosphonate O atoms) and two phosphonate oxygen atoms from two other ligands. The carboxylate group of the ligand remains non-coordinated. The bridging of above two types of lead(II) ions through phosphonate groups resulted in a 〈002〉 double layer with the carboxylate group of the ligand as a pendant group. These double layers are further interlinked via hydrogen bonds between the carboxylate groups into a 3D network. The nickel(II) ion in complex 2 is octahedrally coordinated by a tetradentate chelating ligand (two phosphonate oxygen atoms, one nitrogen and one carboxylate oxygen atoms) and two aqua ligands. These {Ni[O2CCH2N(CH2PO3H)2][H2O]2}− anions are further interlinked via hydrogen bonds between non-coordinated phosphonate oxygen atoms to form a 〈800〉 hydrogen bonded 2D layer. The 2H-protonated ethylenediamine cations are intercalated between two layers, forming hydrogen bonds with the non-coordinated carboxylate oxygen atoms. Results of magnetic measurements for complex 2 indicate that there is weak Curie–Weiss behavior with θ=−4.4 K indicating predominant antiferromagnetic interaction between the Ni(II) ions. Indication for magnetic low-dimension magnetism could not be detected. [Copyright &y& Elsevier]