The hydrothermal reactions of vanadium oxide and molybdenum oxide starting materials with divalent first-row transition metal cations in the presence of nitrogen donor chelating ligands yield the heterometallic hexanuclear clusters [{Zn(bipy)(2)}(2)V4O12] (2), [{Zn(phen)(2)}(2)V4O12]. H2O (3 . H2O), and [{Ni(bipy)(2)}(2)Mo4O14] (4) A similar reaction in the presence of excess 2,2’-bipyridine yields [Zn(bipy)(3)](2)[V4O12]. 11H(2)O (1 . 11H(2)O), a species with an isolated {V4O12}(4-) cluster. The structure of 2 consists of a {V4O12}(4-) ring covalently attached to each of two {Zn(bipy)(2)}(2+) moieties through the terminal oxo groups of alternate vanadium sites. In contrast, the structure of 3 exhibits a {V4O12}(4-) ring linked through oxo groups of adjacent vanadium sites to two (Zn(phen)(2))(2+) moieties. The structure of 4 is constructed from two {Mo2P7}(2-) units linked through two {Ni(bipy)(2)}(2+) groups to form a cyclic 12-membered {Mo4Ni2O6} core. Crystal data : [Zn(bipy)(3)](2)[V4O12]. 11H(2)O (1 . 11H(2)O), a = 21.910(4) Angstrom, b = 14.044(2) Angstrom, c = 23.815(4) Angstrom, beta = 106.15(1)degrees, monoclinic, C2/c, Z = 4; [{Zn(bipy)(2)](2)V4O12] (2), a = 12.017(2) Angstrom, c = 15.120(2) Angstrom, tetragonal P4(2)/n, Z = 2. [{Zn(o-phen)(2)}(2)V4O12]. H2O (3 . H2O), a = 18.182(2) Angstrom, b = 11.3668(9) Angstrom, c = 23.455(2) Angstrom, beta = 97.815(7)degrees, monoclinic P2(1)/c, Z = 4; [{Ni(bipy)(2){2Mo4O14] (4), a = 12.323(2) Angstrom, c = 14.897(4) Angstrom, tetragonal P4(2)2(1)2, Z = 2.