Hydrothermal Synthesis of Vanadium Oxyfluoride Chains Incorporating Covalently Bound Copper Coordination Complexes

An exploration of the hydrothermal synthesis of vanadium oxyfluorides in the presence of copper−amine coordination complexes has produced six new compounds exhibiting novel one-dimensional structural features. [C2H8N][Cu(C5H5N)4][V2O2F7] incorporates dimeric vanadium(IV) oxyfluoride units (in this case, face-sharing V-centered octahedra) into a compound of this type for the first time; this composition has been prepared in two polymorphs, 1 and 2, which differ in chain configuration and orientation, mediated by H bonding of the uncoordinated dimethylammonium cation. A differing dimeric vanadium(IV) oxyfluoride anion (based on edge-sharing V-centered octahedra) occurs in [C3H5N2]2[Cu(C3H4N2)4][V2O2F8], 4, which incorporates imidazole in two structural roles: as both a ligand and template. [Cu2F2(C10H10N3)2][V2O7], 5, and [Cu(C5H5N)2(C2H8N2)][(VO3)2], 6, both contain V5+ in tetrahedral coordination, in dimers in the former and infinite chains in the latter. In the case of 6, the copper moieties act as “decoration” rather than as linkers to the vanadium oxide sublattice.