Hydrothermal chemistry of oligomeric vanadium oxyfluorides

Nine new vanadium oxyfluorides, containing ten different oligomeric vanadium (oxy)fluoride anions have been prepared by solvothermal synthesis in water-ethylene glycol and using organic cations as co-crystallising agents. Crystal structures are reported for each. Amongst the ten structure types, five represent previously unobserved moieties, including one monomeric unit (cis-[VOF4(H2O)]2-), two dimers ([V2O2F6(H2O)2]2- and [V2O2F8]4-) and two tetramers (both isomers of composition [V4O4F14]6-). Structural relationships between the various units are discussed, together with some rationalisation of their occurrence as a function of synthetic variables.