Hydrothermal syntheses and structures of vanadium oxyfluorides templated by organic and metal organic cations

The hydrothermal reactions of V2O5, HF and an organodiphosphonic acid, in the presence of appropriate templating organoammonium or metal–organic complex cations provided three new oxyfluorovanadate compounds. The V(IV) species [H3N(CH2)2NH2(CH2)2NH2(CH2)2NH3][V3O3F2(H2O){O3PCH2PO3}2]·2H2O (1·2H2O) exhibits a three-dimensional anionic framework constructed from {VO(O3PCH2PO3)}n2n− chains and {VF2O4} octahedra. The molecular structure of [N(CH2CH2NH3)3]2[NH4][V3O2F6(O3PCH2PO3)2]·2H2O (2·2H2O) is characterized by the presence of unique {V3O2F6(O3PCH2PO3)2}7− clusters. The bimetallic phase [{Cu(ophen)}VOF{HO3P(CH2)5PO3}] (3) is one-dimensional with {Cu2V2O2F2(HO3PR)2(O3PR)2} cluster building blocks.