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 UO2(2+) with zinc under hydrothermal conditions at 570 °C and 150 MPa. Its structure consists of extended sheets of edge-sharing U(VI) pentagonal bipyramids and U(V) square bipyramids. The overall anion topology is the same as that of the uranyl mineral sayrite, but the squares are populated by U(V)(OH)2(3+) 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.