A2MnU3O11 (A = K, Rb) and Li3.2Mn1.8U6O22: Three New Alkali-Metal Manganese Uranium(VI) Oxides Related to Natrotantite.

Single crystals of three new alkali-metal manganese uranium oxides, K2MnU3O11, Rb2MnU3O11, and Li3.2Mn1.8U6O22, have been grown from molten chloride fluxes and structurally characterized by single-crystal X-ray diffraction. The first two compounds crystallize in the trigonal space group, R3̅c, in the three-dimensional (3D), natrotantite structure composed of α-U3O8-topological layers connected via MnO6 octahedra. The Li-containing compound crystallizes in the monoclinic space group, Cc, with a related 3D structure, composed of β-U3O8-topological sheets connected via irregular MnO7 polyhedra. All three compounds exhibit typical uranyl, UO2(2+), coordination environments consisting of either UO7 pentagonal bipyramids or UO6 flattened octahedra. The lattice parameters of the new oxides are K2MnU3O11, a = 6.8280(2) Å, c = 36.8354(17) Å; Rb2MnU3O11, a = 6.8407(2) Å, c = 37.5520(17) Å; and Li3.2Mn1.8U6O22, a = 11.8958(8) Å, b = 10.9639(7) Å, c = 13.3269(8) Å, and β = 91.442(4)°. The magnetic susceptibilities of the K and Rb phases are discussed.