Hydrothermal Synthesis and Crystal Structure of a Keggin Polyoxometalate [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O

A Keggin-type tungstosilicate compound [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O 1 （bipy = bipyridine） was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 （C40H40Co2N8O44SiW12） crystallizes in the triclinic system, space group P1 with a = 10.4979（6）, b = 13.3946（7）, c = 13.5756（8）A, α= 70.0769（18）, β = 68.910（3）, γ = 74.186（4）°, V = 1649.84（16）A^3, Mr = 3688.95, Z = 1, Dc = 3.713 mg·m^-3, μ = 21.432 mm^-1, F（000） = 1644, S = 1.058, the final R = 0.0511 and wR =0.1023 for 6523 observed reflections （I 〉 2σ（I））. Compound 1 consists of two coordinated cation fragments [Co^Ⅱ（2,2′-bipy）2（H2O）]^2＋, one normal Keggin polyanion unit [SiW^Ⅵ12O40]^4- and two lattice water molecules. To be noted, each polyanion unit is linked to two cation fragments by its two surface terminal oxygen atoms and two cobalt atoms of two cation fragments forming an organic-inorganic hybrid unit in 1. Furthermore, the compound shows strong photoluminescence property in the solid state at room temperature.

A Potassium Organic-inorganic Hybrid Complex with Channels Hosting Decorated Poly-anion Chains

A potassium organic-inorganic hybrid complex {H2[K（PMo12O40）（CH3CN）3]- （dpdo）2（H2O）}n 1 （dpdo = 4,4＇-bipyridine-N,N＇-dioxide） with special channels for the chain-like assembly of decorated Keggin-type anions was synthesized and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of orthorhombic, space group Cmcm with a = 20.5328（17）, b = 16.8877（14）, c = 16,1454（14） A, V = 5598.4（8） A^3, Z = 4, C26H29N7O45KMo12P, Mr= 2380.91, Dc = 2.825 g/cm^3,μ = 2.813 mm^-1, F（000） = 4528, the final R = 0.0324 and wR = 0.0880 for 2577 observed reflections with I 〉 2σ（I）. Compound 1 exhibits a 3D network structure with large channels hosting decorated poly-anion chains as guests.

Supramolecular Structural Inorganic-organic Hybrid[(4-Bromoanilimiun)([18]crown-6)]3[PMo(12)O(40)]·CH3CN

A novel supramolecular structural inorganic-organic hybrid [（4-bromoanilimiun）（[18]crown-6）]3[PMo（12）O40]·CH3 CN has been synthesized through standard solvent evaporated method. The structure of the title compound was determined through single-crystal X-ray diffraction analysis. It crystallizes in monoclinic system with P21/n space group. The crystal data are a = 18.9529（4）, b = 26.4444（5）, c = 19.0985（4） A, β = 90.132（6）o, V = 9572.1（3） A^3, Z = 4, Dc= 2.203 g·cm^（–1）, μ = 14.956 mm^（–1）, F（000） = 6192, S = 1.098, the final R = 0.0859 and w R（I 〉 2σ（I）） = 0.2100. Supramolecular cations are constructed through strong N–H…O hydrogen bonding interaction between the six oxygen atoms of [18]crown-6 molecule and nitrogen atom of（4-bromoanilimiun） cation. Three kinds of different arranged supramolecular cations exist in the title compound, which are filled into the large space formed by [PMo（12）O40] polyoxoanions. Thermogravimentic differential thermal analysis revealed that hydrogen bonding interaction and intermolecular interaction play an important role in maintaining the stability of the title compound.

Syntheses and Crystal Structures of a Cadmium(Ⅱ) and a Zinc(Ⅱ) Complexes with the Flexible Ligand 1-Acetic Acid-2, 2'-biimidazole

Reactions of NaAcebiim （NaAcebiim = 1-acetic acid-2, 2＇-biimidazote monoso- dium salt） and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd（Acebiim）（NO3）（H20）]n （1） and 0D [Zn（Acebiim）2（H20）2]＇2H20 （2） in acidic aqueous solutions. Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, space group Pi, and 2 is of monoclinic system, space group P2 1/n. In 1, two nitrate groups link two Cd（Ⅱ） ions forming [Cd2（NO3）2（H20）2] as secondary building units that are interconnected by the Acebiim ligand into an infinite ladder. In2, the hydrogen-bonded synthon R22（16） between the N-H moieties and carboxylic acid link [Zn（Acebiim）2（H20）2], generating a 1D-extended ribbon. Moreover, hydrogen bonds and π-π interactions further stabilize the 3D supramolecular architecture.

A Novel Three-dimensional Extended Supramolecular Network Constructed from Octamolybdate Clusters and Morpholine Molecules: Na_2(Hmorph)_2[Mo_8O_(26)]·2H_2O

A novel organic-inorganic hybrid, Na2（Hmorph）2[MosO26]·2H2O （1, Hmorph = morpholine）, has been synthesized by convenient aqueous solution method and structurally characterized by single-crystal X-ray diffraction, IR, UV/Vis spectrum, elemental analysis and thermogravimetric analysis （TGA）. Single-crystal X-ray analysis reveals that the title compound crystallizes in the monoclinic system, space group P21/c with a = 8.0194（4）, b = 16.1398（8）, c = 12.5893（6） A, fl = 92.824（4）°, V = 1627.47（14） A3, Mr = 1439.78, Z = 2, Dc = 2.938 g/cm3, p = 3.116 mm-1, F（000） = 1364, the final R = 0.0250, wR = 0.0628 and S = 1.027 for 3209 observed reflections with I 〉 2σ（/）. In compound 1, the polyanions are stacked through electrostatic interactions, coordination of Na＋ ions and hydrogen bonds to form a novel 3-D extended supramolecular ＂host＂ network with 1-D channels encapsulating organic ＂guests＂.

A New Supramolecular Compound Based on Cd（II）-Schiff-base and Keggin-type [PMo_（12）O_（40）]~3

A new supramolecular compound, {[Cd（L）2]2[PMo12O40NO3]·CH3CN·2H2O}n 1 （L is 1,4-bis（4-imidazolyl）-2,3-diaza-1,3-butadiene）, based on Cd（II）-Schiff-base and Keggin- type [PMo12O40]3- was synthesized via self-assembly and structurally characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a = 12.0128（11）, b = 13.6196（13）, c = 13.9995（13） , α = 103.868（2）, β = 95.225（2）, γ = 101.024（2）°, V = 2160.0（3） 3, Z = 1, C34H39N26O45Cd2Mo12P, Mr = 2938.96, Dc = 2.259 g/cm3, μ = 2.276 mm-1, F（000） = 1400, the final R = 0.0565 and wR = 0.1613 for 4973 observed reflections with I 〉 2σ（I）. The crystal structure can be described by the packing of Keggin anionic and Metal-Schiff-base cationic layers.