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

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.