Bonavia Grant, Haushalter Robert C., O'Connor C. J., Zubieta Jon
Department of Chemistry, Syracuse University, Syracuse, New York 13244-4100, Department of Chemistry, University of New Orleans, New Orleans, Louisiana 70148, and NEC Research Institute, 4 Independence Way, Princeton, New Jersey 08540.
Inorg Chem. 1996 Sep 11;35(19):5603-5612. doi: 10.1021/ic960224b.
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) Å, b = 10.161(2) Å, c = 7.445(1) Å, beta = 92.97(3) degrees, Z = 4; for 2, CH(3)O(7)P(2)VCs, monoclinic C2, a = 10.212(2) Å, b = 10.556(2) Å, c = 14.699(3) Å, 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) Å, b = 8.136(2) Å, c = 10.268(2) Å, beta = 103.75(3) degrees, Z = 2; for 4, CH(5)O(7)P(2)V, monoclinic P2(1)()/n, a = 5.341(1) Å, b = 11.516(2) Å, c = 10.558(2) Å, beta = 99.89(1) degrees, Z = 4.
研究了CsVO(3)/亚甲基二膦酸盐体系的水热化学。反应温度、加热时间和反应物化学计量比的变化导致分离出单核、一维、二维和三维物种：分别为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)和[V(HO(3)PCH(2)PO(3))(H(2)O)] (4)。1的阴离子结构由孤立的V(IV)八面体组成。2相采用由角共享V(IV)八面体构成的链状结构，形成无限的{-V=OV=O-}键。3的层状结构包含角共享{VO(6)}八面体的三核单元，中心V位点处于III氧化态，V(IV)中心位于簇的末端。二膦酸盐配体用于将相邻的三核基序连接成一个深度为三个八面体的层状结构。Cs(+)阳离子占据层内的空穴，而不是更常见的层间位置。4的结构由通过二膦酸盐基团连接成三维框架的孤立{V(III)O(6)}八面体组成。晶体数据：对于1，CH(6)O(7)P(2)V(0.5)Cs，单斜晶系C2，a = 10.991(2) Å，b = 10.161(2) Å，c = 7.445(1) Å，β = 92.97(3)°，Z = 4；对于2，CH(3)O(7)P(2)VCs，单斜晶系C2，a = 10.212(2) Å，b = 10.556(2) Å，c = 14.699(3) Å，β = 94.57(2)°，Z = 8；对于3，C(2)H(8)O(16)P(4)V(3)Cs，单斜晶系C2/m，a = 9.724(2) Å，b = 8.136(2) Å，c = 10.268(2) Å，β = 103.75(3)°，Z = 2；对于4，CH(5)O(7)P(2)V，单斜晶系P2(1)()/n，a = 5.341(1) Å，b = 11.516(2) Å，c = 10.558(2) Å，β = 99.89(1)°，Z = 4。
