Abstract: | VIV oxyfluorides are of interest as frustrated magnets. The successful synthesis of two‐dimensionally connected vanadium(IV) oxyfluoride structures generally requires the use of ionic liquids as solvents. During solvothermal synthesis experiments aimed at producing two‐ and three‐dimensional vanadium(IV) selenites with triangular lattices, the title compound, diaquatetra‐μ‐fluorido‐dioxidodivanadium(IV) monohydrate, V2O2F4(H2O)2·H2O, was discovered and features a new infinite V4+‐containing two‐dimensional layer comprised of fluorine‐bridged corner‐ and edge‐sharing VOF4(H2O) octahedral building units. The synthesis was carried out under solvothermal conditions. The V4+ centre exhibits a typical off‐centring, with a short V=O bond and an elongated trans‐V—F bond. Hydrogen‐bonded water molecules occur between the layers. The structure is related to previously reported vanadium oxyfluoride structures, in particular, the same layer topology is seen in VOF3. |