Hydrothermal synthesis and structural characterization of reduced vanadium phosphates, α-Rb[VIII(HPO4)2], β-Rb[VIII(HPO4)2] and NH4[VIII(HPO4)2], octahedral-tetrahedral framework solids

Robert C. Haushalter, Zhanwen Wang, Mark E. Thompson, Jon A Zubieta

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Abstract

The vanadium(III) phosphates α-Rb[V(HPO4)2] (1), β-Rb[V(HPO4)2] (2) and NH4[V(HPO4)2] (3) were prepared by hydrothermal reactions of V2O5, vanadium metal, H3PO4, water and an appropriate cation source. The three-dimensional framework of 1 is constructed from the corner-sharing of {VO6} octahedra and {HPO4} tetrahedra which fuse to generate structural motifs based on {V22-HPO4)3} and {Vμ2-HPO4)2} units. The resultant network is characterized by the presence of channels defined by the corner-sharing of four {VO6} octahedra and four {HPO4} tetrahedra and occupied by Rb+ cations. In contrast, the structural motif of 2 is the {V22-HPO4)2} unit exclusively, which produces a framework containing channels defined by the corner-sharing of six {VO6} octahedra and six {HPO4} tetrahedra. Compound 3 is isostructural with 2. Crystal data: Rb1.5V1.5P3O12H3 (1), P1, a = 8.831(1), b = 9.450(2), c = 7.188(2) Å, α = 109.55(2), β = 110.26(1), γ = 65.34(1)°, V = 498.5(2)Å, Z = 2, Dcalc = 3.261 g cm-3, structure solution and refinement based on 1047 reflections converged at R = 0.068; RbVP2O8H2 (2), P21 c, a=5.21(1), b =8.789(8), c=14.330(5) A ̊, β=94.39(4)°, V=654(1) A ̊3, Z = 4, Dcalc=3.315 g cm-3, 668 reflections, R = 0.083; VP2O8NH6 (3), P21 c, a=5.201(2), b=8.738(2), c=14.389(3) A ̊, β=94.83(1)°, V=652.0(3) A ̊3, Dcalc=2.627 g cm-3, 1561 reflections, R = 0.052.

Original languageEnglish (US)
Pages (from-to)83-89
Number of pages7
JournalInorganica Chimica Acta
Volume232
Issue number1-2
DOIs
StatePublished - 1995
Externally publishedYes

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Keywords

  • Crystal structures
  • Phosphate complexes
  • Vanadium complexes

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

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