A hydrothermal reaction of zinc acetate with molybdenum trioxide, vanadium pentoxide, phosphorus pentoxide and 2,2?-bpy (2,2?-bipyridine) led to the title compound [Zn(2,2?- bpy)2(H2O)]2[HPMo12O40(VO)2] 1. Single-crystal X-ray diffraction revealed that 1 (C40H36- N8O44PV2Zn2Mo12) crystallizes in the triclinic system, space group P1 with a = 11.881(2), b = 12.468(2), c = 12.622(2) ?, α = 71.333(8), β = 74.485(4), γ = 86.896(5)o, V = 1705.8(4) ?3, Mr = 2747.64, Z = 1, Dc = 2.675 g/cm3, μ = 3.201 mm-1, F(000) = 1309, S = 1.070, the final R = 0.0697 and wR = 0.1905 for 5368 observed reflections with I > 2σ(I). Compound 1 is built on a mixed-metal bicapped [HPMo12V2O42] subunit covalently bonded to two [Zn(2,2?-bpy)2(H2O)]2+ clusters via terminal oxygen atoms of the capping V atoms. Each Zn atom is six-coordinated by four nitrogen atoms from two 2,2?-bpy ligands, one terminal oxygen atom from coordinated water mole- cule and another one from the capped {VO} unit.
A Keggin-type tungstohosphate compound [Cu^l（2,2＇-bipy）2]3[PW^Ⅵ12O40] 1 （bipy = bipyddine） was prepared by the hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 （C60H48Cu3N12O40PW12） crystallizes in the monoclinic system, space group P21/c with a = 16.9837（10）, b = 17.9732（13） c = 27.8701（13）A°, β = 96.1039（10）°, V = 8459.2（9） A°^3, Mr = 4004.89, Z = 4, Dc = 3.145 g/cm^3, μ = 17.089 mm^-1, F（000） = 7208, S = 1.005, the final R = 0.0469 and wR = 0.0827 for 10807 observed reflections （I 〉 2σ（I））. Compound 1 consists of one discrete normal Keggin polyanion [PW^Ⅵ 12O40]^3- and three isolated coordinated cations [Cu^1（2,2＇-bipy）2]^＋. Significantly, there exist three crystallographically independent asymmetric reduced copper （I） centers in 1. Furthermore, the compound shows strong photoluminescence property in solid state at room temperature.
A new molybdenum phosphate [Zn（Mo^v6P4O31H10）2（C4H144N3）2].2C4H13N3.8H2O 1 （C4H13N3 = diethylenetriamine） has been synthesized under hydrothermal condition. Single-crystal X-ray diffraction reveals that compound 1 crystallizes in the monoclinic, space group P21/n, a = 13.1679（3）, b = 22.1240（6）, c = 13.6146（3） A, β= 103.4847（7）°, V = 3856.95（16） A^3, C16H90N12O70P8ZnMo12, Mr = 3035.41, Z = 2, Dc = 2.614 g/cm^3, μ = 2.483 mm^-1, F（000） = 2968, S = 1.014, the final R = 0.0196 and wR = 0.0506 for 7486 observed reflections （1 〉 2σ（I））. Compound 1 consists of two identical rings of six edge-sharing MoOt, octahedra interconnected by one ZnO6 octahedron, whereas the PO4 tetrahedra which share their apices with the MoO6, octahedra are only located on one side of each Mo6, ring. The 2-charge of polyanion [Zn（Mo^v6P4O31H10）2]^2- unit is compensated in the crystal by two mono-protonated diethylenetriamines （C4H14N3）^＋. By hydrogen bonding interactions the polyanion of compound 1 is interconnected to form pseudo threedimensional molybdophosphate. Other characterizations by elemental analyses, IR spectrum and fluorescent spectrum are also described.
