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Synthesis and Structural Characterization of 0D Vanadium Borophosphate [Co(en)3]2[V3P3BO19][H2PO4]·4H2O and 1D Vanadium Oxides [Co(en)3][V3O9]·H2O and [Co(dien)2][V3O9]·H2O Templated by Cobalt Complexes:  Cooperative Organization of the Complexes and the Inorganic Networks

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posted on 2003-12-16, 00:00 authored by Yu Wang, Jihong Yu, Qinhe Pan, Yu Du, Yongchun Zou, Ruren Xu
A 0D vanadium borophosphate [Co(en)3]2[V3P3BO19][H2PO4]·4H2O (1) and two 1D vanadium oxides [Co(en)3][V3O9]·H2O (2) and [Co(dien)2][V3O9]·H2O (3) have been synthesized hydrothermally from the reaction mixture of V2O5−H3PO4−H3BO3−CoCl2−R−H2O at 110 °C (R:  en or dien). The complex cations Co(en)33+ and Co(dien)23+ are cooperatively organized in the reaction medium to play a structure-directing role in the formation of the inorganic clusters and chains. The structures are determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The structure of 1 contains isolated [V3P3BO19]5- cluster anions, H2PO4- anions, racemic Co(en)33+ cations, and H2O molecules, which form a complex H-bond network. 2 and 3 both contain chains of corner-sharing VO4 tetrahedra running along the 21 screw axis. The complex cations located in the interchain region interact with the chains through H-bonds. 2 is crystallized in an enantiomorphic space group and only one enantiomer of Co(en)33+ is involved in the structure. Crystal data:  1, monoclinic, C2/c, a = 32.8492(14) Å, b = 11.9601(3) Å, c = 22.6001(7) Å, β = 108.9630(8)°, Z = 8; 2, orthorhombic, P212121, a = 8.1587(16) Å, b = 12.675(3) Å, c = 18.046(4) Å, Z = 4; 3, monoclinic, P21/c, a = 16.1663(10) Å, b = 8.7028(3) Å, c = 13.9773(5) Å, β = 103.1340(18)°, Z = 4.

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