Solvatothermal chemistry of organically-templated vanadium fluorides and oxyfluorides

The solvatothermal reactions of V2O5, the appropriate organoamine and HF in the temperature range 100–180 °C yielded a series of vanadium fluorides and oxyfluorides. The compounds [NH4][H3N(CH2)2NH3][VF6] (1) and [H3N(CH2)2NH3][VF5(H2O)] (2) contain mononuclear V(III) anions, while [H3N(CH2)2NH2(CH2)2NH3]2 [VF5(H2O)]2[VOF4(H2O)] (3) exhibits both V(IV) and V(III) mononuclear anions. Both compound 4, [H3NCH2(C6H4)CH2NH3][VOF4]·H2O (4·H2O) and compound 5, [HN(C2H4)3NH][V2O2F6 (H2O)2] (5) contain binuclear anions constructed from edge-sharing V(IV) octahedra. In contrast, [H3N(CH2)2NH2(CH2)2NH3]2[V4O4F14(H2O)2], (6) exhibits a tetranuclear unit of edge- and corner-sharing V(IV) octahedra. Compound 7, [H3N(CH2)2NH2][VF5], contains chains of corner-sharing {VIVF6} octahedra, while [H2N(C2H4)2NH2]3[V4F17O]·1.5H2O (8·1.5H2O) is two-dimensional with a layer of V(III) and V(IV) octahedra in an edge- and corner-sharing arrangement. In the case of [H3N(CH2)2NH3][V2O6] (9), there was no fluoride incorporation, and the { V 2 O 6 } n 2 n - anion is a one-dimensional chain of corner-sharing V(V) tetrahedra.