| In this paper, we take the hydrothermal synthesis of transition metal clusters of V and W as the principle thing, study the synthetic conditions of these compounds, and prepare seven cluster crystals. The structures of seven crystals have been determined by X-ray crystallographic analysis.1.A novel polyoxometalate [Co4(HPO3)2(C12H8N2)8(H2O)2](H3O)[PW9ⅥV3ⅣO40 (VⅣO)2]·H2O(1) has been synthesized under hydrothermal condition. The X-ray crystallography shows that (1) contains a novel bi-capping pseudo-Keggin type heteropolyanion [PW9ⅥV3ⅣO40(VⅣO)2]5- and four nuclei cation [Co4(HPO3)2(C12H8N2)8(H2O)2]4+. The adjacent heteropolyanions are linked by water molecules and the cations [Co4(HPO3)2(C12H8N2)8(H2O)2]4+ through the hydrogen bonds to form a extensive three-dimensional supramolecular assembly. Complex (1) crystallizes in the Monoclinic space group P2(1)/c, with a = 13.321(3)(?), b = 23.351(4)(?), c = 18.877(4)(?),β= 94.858(2)°V = 5850.7(19) (?), Z = 2.2.Three new three dimensional open-frameworks, {[Cu4V13ⅣV5ⅤO42(NO3) (C3H10N2)8]·10H2O}n (2) , {[Cu4V12ⅣV6ⅤO42(SO4)(C3H10N2)8]·10H2O}n (3) and {[Cu4V18O42(HCOO)(H2O)8]·12H2O}n (4) have been hydrothermally synthesized. The structural analysis indicates that Complex (2) and (3) are isomorphic, which are constructed from the cluster anion [V18O42(XOy)]8- (X = N, y = 3 or X = S, y = 4) and the bridging cationμ2-[Cu(C3H10N2)2]2+ with the classical ACO topological structure. Complex (2) crystallizes in the tetragonal space group P4/nnc, with a = b = 15.1128(12) (?), c = 18.670(3) (?), V = 4264.1(9) (?), Z = 2; Complex (3): tetragonal, P4/nnc, a = b = 15.1131(10) (?), c = 18.588(10) (?), V = 4245.5(7) (?), Z = 2. Both complexes keep the same topological framework with channels of dimensions 7.5 (?)×7.5 (?) running along the [001] direction. Complex (4): tetragonal, P4/nnc, a = b = 15.151(4) (?), c = 18.607(10) (?), V = 4271(3) (?), Z = 2.3.A new discrete polyoxovanadate compound of (C6H13N2)4V16O32Cl·2H2O (5) has been hydrothermally synthesized. The structural analysis indicates that complex (5) consists of a discrete {V16O32Cl} anion and a protonized C6H13N2+, which are stably connected by electrostatic interaction to a steady compound. Complex (5): Cubic , F-43m, a = 18.6284(17) (?), V = 6464.4(10) (?), Z = 2.4. A new vanadium phosphate compound Na4P2V5O17·7.67H2O (6) has been hydrothermally synthesized, in which building blocks {V10O26 }are bridged by PO4 tetrahedra leading to a three-dimensional network. PO4 tetrahedra as the bridging is firstly reported in vanadium phosphate. Complex (6): Cubic, C2/m, a = 15.9953(9)(?), V = 4092.4(4) (?), Z = 6.5.A new one-dimensional polyoxovanadate compound of Cu(phen)2V2O6(H2O)·H2O (7) has been hydrothermally synthesized. It represents a one-dimensional chain structure, which is constructed from corner-sharing VO4 tetrahedra, and further linked by [Cu(phen)2]2+groups. Complex (7): Monoclinic, P2(1)/c, a = 16.644(4)(?), b = 14.226(4)(?), c = 10.254(3)(?),β= 97.339(3)°V = 2407.8(11) (?), Z = 4.
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