Channels occupancy and distortion in new lithium uranyl phosphates with three-dimensional open-frameworks

Abstract

Three new lithium uranyl phosphates, Li 2(UO 2) 3(PO 4) 2O ( 1), Li(UO 2) 4(PO 4) 3 ( 2) and Li 3(UO 2) 7(PO 4) 5O ( 3) were synthesized and studied. Powders of 1 and 2 were synthesized via solid state reaction, and single crystals of the three compounds were obtained by melting of 1 and 2 powders. The structures of the three compounds have been solved and refined from single crystal X-ray diffraction data. In the three compounds, the uranium atoms occupy square and pentagonal bipyramids. The uranium square bipyramids and phosphate tetrahedra are connected by vertices to form two types of layers with autunite sheet anion-topology ∞ 2 [ ( UO 2 ) ( PO 4 ) 2 ] 4 - and ∞ 2 [ ( UO 2 ) 2 ( PO 4 ) 3 ] 5 - denoted S and D, respectively. The uranyl pentagonal bipyramids share opposite equatorial edges to form ∞ 1 [ UO 5 ] 4 - infinite chains. Mutually perpendicular chains are hung on each side of the sheets to build frameworks with non-crossing perpendicular channels that accommodate the lithium ions. Various stacking sequences of the S and D layers, S–S, D–D and S–D, generate three different frameworks in 1, 2 and 3, respectively. These compounds are similar to the recently reported vanadate analogous. However, the phosphate tetrahedra, smaller than the vanadate ones, gives distortion of the layers and a lowering of the symmetry and/or a change of periodicity. The electrical conductivity of 1 and 2 was measured using impedance spectroscopy method. The rather low conductivity of the lithium cations is explained by the crystal structure and the Li + position within the tunnels. These results corroborate those on the analogous three-dimensional alkaline uranyl vanadates. Crystallographic data: 293 K, BRUKER X8-APEX2 X-ray diffractometer, 4 K CCD detector, Mo Kα, λ=0.71073 Å, full-matrix least-squares refinement on the basis of F. 1, Tetragonal symmetry, space group I4 1/ amd, Z=4 with a=7.1109(2) Å and c=25.0407(8) Å, R=0.034 and w R=0.047 for 38 parameters with 479 independent reflections with I⩾3 σ( I). 2, monoclinic symmetry, space group P2 1/ c, Z=4 and a=9.8829(2) Å, b=9.8909(2) Å, c=17.4871(4) Å and β=106.198(1)°, R=0.021 and w R=0.031 for 249 parameters with 4201 independent reflections with I⩾3 σ( I). 3, Tetragonal symmetry, space group P 4 ¯ 2 1 m with a=9.9305(2) Å and c=14.5741(3) Å, R=0.035 and w R=0.038 for 137 parameters with 4527 independent reflections with i⩾3 σ( I).