The first vanadium aluminophosphates: Hydrothermal synthesis and structure of Cs[(VO)Al(PO4)2] · H2O, Rb[(VO)Al(PO4)2] · H2O, (NH3CH2CH2NH2)[(VO)Al(PO 4)2], and CH3NH3[(VO)Al(PO4)2]

Linda M. Meyer, Robert C. Haushalter, Jon Zubieta

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Abstract

The first vanadium aluminophosphates, Cs[(VO)Al(PO4)2] · H2O (1), Rb[(VO)Al(PO4)2] · H2O (2), (NH3CH2CH2NH2) [(VO)Al(PO4)2] (3), and CH3NH3[(VO)Al(PO4)2] (4), have been hydrothermally prepared from a vanadium source, AlCl3 · 6H2O, H3PO4, H2O, and a charge compensating organic species. The phosphates are built up from tetrahedrally coordinated aluminum and phosphorous atoms; phosphates (1), (2), and (3) contain octahedrally coordinated vanadium atoms, and phosphate (4) contains a square pyramidal vanadium atom. The frameworks in phosphates (1)-(4) are structurally related and incorporate cations of similar size and charge. In phosphate (3) the 1-aminoethane-2-ammonium cation is bonded through the nitrogen to the vanadium as a monodentate ligand, providing the sixth vertex of the vanadium octahedron, with the other five present as oxygen atoms. In phosphates (1), (2), and (4), the Cs+, Rb+, and methylammonium cations, respectively, replace the charge compensating organic ligand present in phosphate (3). The four phosphates are conceptually constructed of one-dimensional aluminophosphate chains connected into three-dimensional frameworks via vanadium polyhedra that corner share to the phosphate tetrahedra. The Al is oxo bridged only to P5+ with no Al-O-V bonds present. Crystal data for (1): monoclinic, space group P21/n (#14) with a = 8.014(2), b = 8.088(2), c = 14.141(2) Å, β = 105.98(1)°, V = 881.2(4) Å3, Z = 4, Dcalc = 3.262 g · cm-3; for (2): monoclinic, space group P21/n (#14) with a = 7.880(2), b = 8.063(2), c = 14.062(2) Å, β = 105.83(1)°, V = 859.5(3) Å3, Z = 4, Dcalc, = 2.977 g · cm-3; for (3): monoclinic, space group P21/n (#14) with a = 8.172(2), b = 14.232(2), c = 8.873(1) Å, β = 109.88(1)°, V = 970.5(2) Å3, Z = 4, Dcalc = 2.299 g · cm-3; for (4): triclinic, space group P1̄ (#2) with a = 8.151(1), b = 8.784(2), c = 7.842(2), α = 116.22(2)°, β = 95.88(2)°, γ = 69.16(1)°, V = 469.7(2) Å3, Z = 2, Dcalc = 2.191 g · cm-3.

Original languageEnglish (US)
Pages (from-to)200-210
Number of pages11
JournalJournal of Solid State Chemistry
Volume125
Issue number2
DOIs
StatePublished - Sep 5 1996

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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