A novel series of materials composed of arrays of vanadium oxide container molecules, [V18O42(X)] (X = H2O, Cl-, Br-): synthesis and characterization of [M2(H2N(CH2)2NH2)5][(M(H2N(CH2)2NH2)2]2V18O42(X)]. 9H2O (M = Zn, Cd).

The synthesis and characterization of the novel systems [Zn(2)(H(2)N(CH(2))(2)NH(2))(5)][(Zn(H(2)N(CH(2))(2)NH(2))(2))(2)V(18)O(42)(H(2)O)].9H(2)O (1), [Cd(2)(H(2)N(CH(2))(2)NH(2))(5)][(Cd(H(2)N(CH(2))(2)NH(2))(2))(2)V(18)O(42)(Br)].9H(2)O (2), and [Zn(2)(H(2)N(CH(2))(2)NH(2))(5)][(Zn(H(2)N(CH(2))(2)NH(2))(2))(2)V(18)O(42)(Cl)].9H(2)O (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 [V(18)O(42)(X)] (X = H(2)O, Br-, Cl-) interlinked by the transition metal complex moieties [M(H(2)N(CH(2))(2)NH(2))(2)] (M = Zn, Cd). These compounds contain an unprecedented complex cation, [M(2)(H(2)N(CH(2))(2)NH(2))(5)](4+). Crystal data for 1: C(9)H(46)N(9)O(26)V(9)Zn(2), monoclinic space group P2(1)/m (No. 11), a = 12.3723(7) A, b = 20.9837(11) A, c = 15.8379(8) A, beta = 97.3320(10) degrees, Z = 4.