THE FIRST VANADIUM ALUMINOPHOSPHATES - HYDROTHERMAL SYNTHESIS AND STRUCTURE OF CS[(VO)AL(PO4)(2)]CENTER-DOT-H2O, RB[(VO)AL(PO4)(2)]CENTER-DOT-H2O, (NH3CH2CH2NH2)[(VO)AL(PO4)(2)], AND CH3NH3[(VO)AL(PO4)(2)]

摘要

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 . 6H(2)O, 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 P2(1) (#14) with a = 8.014(2), b = 8.088(2), c = 14.141(2) Angstrom, beta = 105.98(1)degrees, V = 881.2(4) Angstrom(3), Z = 4, D-calc = 3.262 g . cm(-3); for (2): monoclinic, space group P2(1) (#14) with a = 7.880(2), b = 8.063(2), c = 14.062(2) Angstrom, beta = 105.83(1)degrees, V = 859.5(3) Angstrom(3), Z = 4, D-calc = 2.977 g . cm(-3); far (3): monoclinic, space group P2(1) (#14) with a = 8.172(2), b = 14.232(2), c = 8.873(1) Angstrom, beta = 109.88(1)degrees, V = 970.5sd( 2) Angstrom(3), Z = 4, D-calc = 2.299 g . cm(-3); for (4): triclinic, space group (#2) with a = 8.151(1), b = 8.784(2), c = 7.842(2), alpha = 116.22(2)degrees, beta = 95.88(2)degrees, gamma = 69.16(1)degrees, V = 469.7(2) Angstrom(3), Z = 2, D-calc = 2.191 g . cm(-3). (C) 1996 Academic Press, Inc. [References: 19]