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  • Title: New molybdenum(VI) phosphates: synthesis, characterization, and calculations of centrosymmetric RbMoO2PO4 and noncentrosymmetric Rb4Mo5P2O22.
    Author: Wang Y, Pan S, Su X, Yang Z, Dong L, Zhang M.
    Journal: Inorg Chem; 2013 Feb 04; 52(3):1488-95. PubMed ID: 23320926.
    Abstract:
    Two new molybdenum(VI) phosphates, RbMoO(2)PO(4) and Rb(4)Mo(5)P(2)O(22), have been synthesized by standard solid-state reactions, and their structures were determined by single-crystal X-ray diffraction. The former is centrosymmetric, whereas the latter is noncentrosymmetric and chiral. Their crystal structures both consist of corner- and edge-shared MoO(6) octahedra, PO(4) tetrahedra, and RbO(n) (n = 8 or 10) polyhedra and exhibit three- and one-dimensional structures, respectively. Powder second-harmonic generation (SHG) measurements revealed an SHG efficiency of approximately 1.4 × KH(2)PO(4) (KDP) for Rb(4)Mo(5)P(2)O(22). Thermal analysis, infrared and UV-vis-NIR diffuse reflectance spectroscopy, and electronic band structure calculations were also performed on the reported materials. Crystal data are the following: RbMoO(2)PO(4), orthorhombic, space group Fddd (No. 70), a = 11.012(5) Å, b = 12.403(5) Å, c = 15.839(7) Å, V = 2163.3(16) Å(3), and Z = 16; Rb(4)Mo(5)P(2)O(22), orthorhombic, space group C222(1) (No. 20), a = 6.5300(5) Å, b = 19.7834(18) Å, c = 17.3451(15) Å, V = 2240.7(3) Å(3), and Z = 4.
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