Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)₂}₂V₄O₁₂] ·5H₂O and [Ni(phen)₃]₂[V₄O₁₂] ·17.5H₂O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen₂)₂V₄O₁₂] ·5H₂O (1) and [Ni(phen)₃]₂[V₄O₁₂] ·17.5H₂O (2). Crystal data: C₄₈H₅₂Cd₂N₈ O₂₂V₄ (1), triclinic. P1̄, a = 10.3366(10), b = 11.320(3), c = 13.268(3) Å, α = 103.888(17)°, β = 92.256(15)°, γ = 107.444(14)°, Z = 1; C₇₂H₁₃₁N₁₂Ni₂ O_29.5V₄ (2), triclinic. P1̄, a = 12.305(3), b = 13.172(6), c = 15.133(4), α = 79.05(3)°, β = 76.09(2)°, γ = 74.66(3)°, Z = 1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59° < 0 < 26.02° and 2.01° < θ < 25.01° using the ω-scan technique, respectively. The structure of 1 consists of a [V₄O₁₂]^4- cluster covalently attached to two {Cd(phen)₂}²⁺ fragments, in which the [V₄O₁₂]^4- cluster adopts a chair-like configuration. In the structure of 2, the [V₄O₁₂]^4- cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the [V₄O₁₂]^4- unit and crystallization water molecules.