Hydrothermal syntheses and structures of three-dimensional oxo-fluorovanadium phosphates: [H2N(C2H4)(2)NH2](0.5)[(VO)(4)V(HPO4)(2)(PO4)(2)F-2(H2O)(4)]center dot 2H(2)O and K-2[(VO)(3)(PO4)(2)F-2(H2O)]center dot H2O

The hydrothermal reactions of FPO3H2 with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F- and PO43-. BY exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)(2)NH2](0.5) [(VO)(4)V(HOP4)(2)(PO4)(2)F-2(H2O)(4)). 2H(2)O(1 . 2H(2)O] and K-2[(VO)(3) (PO4)(2)F-2(H2O)]. H2O (2 . H2O). Both anionic frameworks contain ((VO)-O-IV)-F--phosphate layers, with confacial bioctahedral {((VO)-O-IV)(2)FO6} units as the fundamental motif. In the case of 1, the layers are linked through {(VO6)-O-III} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing (((VO)-O-IV)2 F2O6} units. Crystal data are 1 . 2H(2)O, CH10FN0.5O13P2V2.5, monoclinic C2/m, a = 18.425(4) Angstrom, c = 8.954(2) Angstrom, beta = 93.69(2)degrees, V = 1221.1(4) Angstrom(3), Z = 4, D-calc = 2.423 g cm(-3); 2 . H2O, H4F2K2O13P2V3, triclinic <P(1)over bar>, a = 7.298(1) Angstrom, b = 8.929(2) Angstrom, 10.090(2) Angstrom, alpha = 104.50(2)degrees, beta = 100.39(2)degrees, delta = 92.13(2)degrees, V = 623.8(3) Angstrom(3), Z = 2, D-calc = 2.891 g cm(-3). (C) 1996 Academic Press, Inc.