Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. II. Tubular fragments and cation-cation interactions in the 3D framework structures of Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})], Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})], Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O] Alekseev, Evgeny V., E-mail: e_v_alekseev@mail.r [Institut fuer Geowissenschaften, Universitaet Kiel, D-24118 Kiel (Germany); Nizhny Novgorod State University, 603950 Nizhny Novgorod (Russian Federation)]; Krivovichev, Sergey V [Department of Crystallography, St. Petersburg State University, 199034 St. Petersburg (Russian Federation)]; Institute of Silicate Chemistry, Russian Academy of Sciences, 199034 St. Petersburg (Russian Federation)]; Depmeier, Wulf [Institut fuer Geowissenschaften, Universitaet Kiel, D-24118 Kiel (Germany)] 36 MATERIALS SCIENCE; ARSENATES; CATIONS; LITHIUM IONS; MONOCLINIC LATTICES; MONOCRYSTALS; TETRAGONAL LATTICES; URANYL PHOSPHATES; ACTINIDE COMPOUNDS; ARSENIC COMPOUNDS; CHARGED PARTICLES; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CRYSTALS; IONS; OXYGEN COMPOUNDS; PHOSPHATES; PHOSPHORUS COMPOUNDS; URANIUM COMPOUNDS; URANYL COMPOUNDS ACTINIDE COMPOUNDS; ARSENIC COMPOUNDS; CHARGED PARTICLES; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CRYSTALS; IONS; OXYGEN COMPOUNDS; PHOSPHATES; PHOSPHORUS COMPOUNDS; URANIUM COMPOUNDS; URANYL COMPOUNDS Single crystals of the new compounds Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})] (1), Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] (2), Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] (3) and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O)] (4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1-monoclinic, C2/m, a=26.963(3) A, b=7.063(1) A, c=19.639(1) A, beta=126.890(4){sup o}, V=2991.2(6) A{sup 3}, Z=2, R{sub 1}=0.0357 for 3248 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-triclinic, P1-bar, a=7.1410(8) A, b=13.959(1) A, c=31.925(1) A, alpha=82.850(2){sup o}, beta=88.691(2){sup o}, gamma=79.774(3){sup o}, V=3107.4(4) A{sup 3}, Z=2, R{sub 1}=0.0722 for 9161 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-tetragonal, I4{sub 1}/amd, a=7.160(3) A, c=33.775(9) A, V=1732(1) A{sup 3}, Z=4, R{sub 1}=0.0356 for 318 unique reflections with |F{sub 0}|>=4sigma{sub F}; 4-tetragonal, P4-bar, a=7.2160(5) A, c=14.6540(7) A, V=763.04(8) A{sup 3}, Z=1, R{sub 1}=0.0423 for 1600 unique reflections with |F{sub 0}|>=4sigma{sub F}. Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO{sub 6} and UO{sub 7}) and different types of tetrahedral TO{sub 4} anions (T=P or As): PO{sub 4} and P{sub 4}O{sub 13} in 1, AsO{sub 4} and As{sub 2}O{sub 7} in 2, and single AsO{sub 4} tetrahedra in 3 and 4. In the structures of 1 and 2, UO{sub 7} pentagonal bipyramids share edges to form (UO{sub 5}){sub i}nfinity chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single TO{sub 4} tetrahedra into tubular units with external diameters of 11 A in 1 and 11.5 A in 2, and internal diameters of 4.1 A in 1 and 4.5 A in 2. The channels accommodate Li{sup +} cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4 are based on 3D frameworks composed on layers united by (UO{sub 5}){sub i}nfinity infinite chains. Cation-cation interactions are observed in 2, 3, and 4. In 2, the structure contains a trimeric unit with composition [O=U(1)=O]-U(13)-[O=U(2)=O]. In the structures of 3 and 4, T-shaped dimers are observed. In all the structures, Li{sup +} cations are located in different types of cages and channels and compensate negative charges of anionic 3D frameworks. - Graphical abstract: The crystal structures of Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] separated into tubular units and intertubular complexes. Available from http://dx.doi.org/10.1016/j.jssc.2009.08.003 United States 2009-11-15 English Journal Article Journal Name: Journal of Solid State Chemistry; Journal Volume: 182; Journal Issue: 11; Other Information: DOI: 10.1016/j.jssc.2009.08.003; PII: S0022-4596(09)00380-6; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved. Medium: X; Size: page(s) 2977-2984 https://doi.org/10.1016/j.jssc.2009.08.003 [] 11 182 Journal ID: ISSN 0022-4596; JSSCBI; TRN: US10R1136102829 INIS 2011-12-30 21372375