A Novel Series of Materials Composed of Arrays of Vanadium Oxide Container Molecules, {V<sub>18</sub>O<sub>42</sub>(X)} (X = H<sub>2</sub>O, Cl<sup>-</sup>, Br<sup>-</sup>): Synthesis and Characterization of [M<sub>2</sub>(H<sub>2</sub>N(CH<sub>2</sub>)<sub>2</sub>NH<sub>2</sub>)<sub>5</sub>][{M(H<sub>2</sub>N(CH<sub>2</sub>)<sub>2</sub>NH<sub>2</sub>)<sub>2</sub>}<sub>2</sub>V<sub>18</sub>O<sub>42</sub>(X)]· 9H<sub>2</sub>O (M = Zn, Cd)
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The synthesis and characterization of the novel systems [Zn2(H2N(CH2)2NH2)5][{Zn(H2N(CH2)2NH2)2}2V18O42(H2O)]·9H2O (1), [Cd2(H2N(CH2)2NH2)5][{Cd(H2N(CH2)2NH2)2}2V18O42(Br)]·9H2O (2), and [Zn2(H2N(CH2)2NH2)5][{Zn(H2N(CH2)2NH2)2}2V18O42(Cl)]·9H2O (3) have been described. These materials represent a new class of solids that have been prepared by combining conventional coordination compounds with spherical polyoxovanadate clusters. The isomorphous structures of these hybrid solids consist of two-dimensional arrays of container cluster molecules {V18O42(X)} (X = H2O, Br-, Cl-) interlinked by the transition metal complex moieties {M(H2N(CH2)2NH2)2} (M = Zn, Cd). These compounds contain an unprecedented complex cation, [M2(H2N(CH2)2NH2)5]4+. Crystal data for 1: C9H46N9O26V9Zn2, monoclinic space group P21/m (No. 11), a = 12.3723(7) Å, b = 20.9837(11) Å, c = 15.8379(8) Å, β = 97.3320(10)°, Z = 4.
