Structural Variability of the Vanadium-Organodiphosphonate System: Hydrothermal Syntheses and Structural Characterizations of One-Dimensional, Two-Dimensional, and Three-Dimensional Phases

The hydrothermal chemistry of the CsVO(3)/methylenediphosphonate system was investigated. Variations in reaction temperatures, heating times, and stoichiometries of reactants resulted in the isolation of mononuclear, one-, two-, and three-dimensional species: Cs[VO(HO(3)PCH(2)PO(3)H)(2)(H(2)O)] (1), Cs[VO(HO(3)PCH(2)PO(3))] (2), Cs[(VO)(2)V (O(3)PCH(2)PO(3))(2)(H(2)O)(2)] (3), and [V(HO(3)PCH(2)PO(3))(H(2)O)] (4), respectively. The structure of the anion of 1 consists of isolated V(IV) octahedra. Phase 2 adopts a chain structure constructed from corner-sharing V(IV) octahedra, forming infinite {-V=OV=O-} linkages. The layer structure of 3 contains trinuclear units of corner-sharing {VO(6)} octahedra with the central V site in the III oxidation state and V(IV) centers at the extremities of the cluster. The diphosphonate ligands serve to link neighboring trinuclear motifs into a layer structure three octahedra in depth. The Cs(+) cations occupy cavities within the layers, rather than the more common interlamellar positions. The structure of 4 consists of isolated {V(III)O(6)} octahedra linked by diphosphonate groups into a three-dimensional framework. Crystal data: for 1, CH(6)O(7)P(2)V(0.5)Cs, monoclinic C2, a = 10.991(2) ?, b = 10.161(2) ?, c = 7.445(1) ?, beta = 92.97(3) degrees, Z = 4; for 2, CH(3)O(7)P(2)VCs, monoclinic C2, a = 10.212(2) ?, b = 10.556(2) ?, c = 14.699(3) ?, beta = 94.57(2) degrees, Z = 8; for 3, C(2)H(8)O(16)P(4)V(3)Cs, monoclinic C2/m, a = 9.724(2) ?, b = 8.136(2) ?, c = 10.268(2) ?, beta = 103.75(3) degrees, Z = 2; for 4, CH(5)O(7)P(2)V, monoclinic P2(1)()/n, a = 5.341(1) ?, b = 11.516(2) ?, c = 10.558(2) ?, beta = 99.89(1) degrees, Z = 4.