Polyoxoanion Coordination Chemistry: Synthesis and Characterization of the Heterometallic, Hexanuclear Clusters [{Zn(bipy)(2)}(2)V(4)O(12)], [{Zn(phen)(2)}(2)V(4)O(12)].H(2)O, and [{Ni(bipy)(2)}(2)Mo(4)O(14)].
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)V(4)O(12)] (2), [{Zn(phen)(2)}(2)V(4)O(12)].H(2)O (3.H(2)O), and [{Ni(bipy)(2)}(2)Mo(4)O(14)] (4). A similar reaction in the presence of excess 2,2'-bipyridine yields [Zn(bipy)(3)](2)[V(4)O(12)].11H(2)O (1.11H(2)O), a species with an isolated {V(4)O(12)}(4)(-) cluster. The structure of 2 consists of a {V(4)O(12)}(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 {V(4)O(12)}(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 {Mo(2)O(7)}(2)(-) units linked through two {Ni(bipy)(2)}(2+) groups to form a cyclic 12-membered {Mo(4)Ni(2)O(6)} core. Crystal data: [Zn(bipy)(3)](2)[V(4)O(12)].11H(2)O (1.11H(2)O), a = 21.910(4) Å, b = 14.044(2) Å, c = 23.815(4) Å, beta = 106.15(1) degrees, monoclinic, C2/c, Z = 4; [{Zn(bipy)(2)}(2)V(4)O(12)] (2), a = 12.017(2) Å, c = 15.120(2) Å, tetragonal P4(2)/n, Z = 2. [{Zn(o-phen)(2)}(2)V(4)O(12)].H(2)O (3.H(2)O), a = 18.182(2) Å, b = 11.3668(9) Å, c = 23.455(2) Å, beta = 97.815(7) degrees, monoclinic P2(1)/c, Z = 4; [{Ni(bipy)(2){(2)Mo(4)O(14)] (4), a = 12.323(2) Å, c = 14.897(4) Å, tetragonal P4(2)2(1)2, Z = 2.
Zhang
Yiping
Y
NEC Research Institute, 4 Independence Way, Princeton, New Jersey 08540, and Department of Chemistry, Syracuse University, Syracuse, New York 13244.
Zapf
Pamela J.
PJ
Meyer
Linda M.
LM
Haushalter
Robert C.
RC
Zubieta
Jon
J