Mixed-Valence Uranium(V,VI) and Uranyl Oxyhydroxides Synthesized under High-Temperature, High-Pressure Hydrothermal Conditions: Na5[U5O16(OH)2] and Na5[U5O17(OH)]

An unusaul mixed-valence uranium­(V,VI) oxyhydroxide, Na5[U5O16(OH)2], was synthesized via reduction of UO22+ with zinc under hydrothermal conditions at 570 °C and 150 MPa. Its structure consists of extended sheets of edge-sharing UVI pentagonal bipyramids and UV square bipyramids. The overall anion topology is the same as that of the uranyl mineral sayrite, but the squares are populated by UV(OH)23+ ions. The valence state of uranium was confirmed by X-ray photoelectron spectroscopy. A hydrothermal reaction without zinc under the same reaction conditions yielded a uranyl oxyhydroxide, Na5[U5O17(OH)], with a new sheet structure. The sheet anion topology, which is closely related to that of the mixed-valence compound, contains chains of edge-sharing pentagons as well as dimers of corner-sharing squares.