[Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3], crystal structure and comparison with uranium minerals with U3O8-type sheets

The new U(VI) compound, [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3], was synthesized by mild hydrothermal reaction of uranyl and nickel nitrates. The crystal-structure was solved in the P-1 space group, a=8.627(2), b=10.566(2), c=12.091(4) Å and α=110.59(1), β=102.96(2), γ=105.50(1)°, R=0.0539 and wR=0.0464 from 3441 unique observed reflections and 151 parameters. The structure of the title compound is built from sheets of uranium polyhedra closely related to that in β-U3O8. Within the sheets [(UO2)(OH)O4] pentagonal bipyramids share equatorial edges to form chains, which are cross-linked by [(UO2)O4] and [UO4(H2O)(OH)] square bipyramids and through hydroxyl groups shared between [(UO2)(OH)O4] pentagonal bipyramids. The sheets are pillared by sharing the apical oxygen atoms of the [(UO2)(OH)O4] pentagonal bipyramids with the oxygen atoms of [NiO2(H2O)4] octahedral units. That builds a three-dimensional framework with water molecules pointing towards the channels. On heating [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3] decomposes into NiU3O10.