Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. I. Polymorphism and structure topology: Synthesis and crystal structures of [alpha]-Li[(UO2)(PO4)], [alpha]-Li[(UO2)(AsO4)], [beta]-Li[(UO2)(AsO4)] and Li2[(UO2)3(P2O7)2]

Alekseev, Evgeny V., Krivovichev, Sergey V., Malcherek, Thomas and Depmeier, Wulf (2008) Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. I. Polymorphism and structure topology: Synthesis and crystal structures of [alpha]-Li[(UO2)(PO4)], [alpha]-Li[(UO2)(AsO4)], [beta]-Li[(UO2)(AsO4)] and Li2[(UO2)3(P2O7)2] Journal of Solid State Chemistry, 181 (11). pp. 3010-3015. DOI 10.1016/j.jssc.2008.07.028.

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Abstract

Four new Li uranyl phosphates and arsenates have been prepared by high-temperature solid-state reactions: [alpha]-Li[(UO2)(PO4)] (1), [alpha]-Li[(UO2)(AsO4)] (2), [beta]-Li[(UO2)(AsO4)] (3) and Li2[(UO2)3(P2O7)2] (4). The structures of the compounds have been solved by direct methods: 1--triclinic, , a=5.0271(1) Å, b=9.8799(2) Å, c=10.8920(2) Å, [alpha]=108.282(9)°, [beta]=102.993(8)°, [gamma]=104.13(1)°, V=470.69(2) Å3, Z=4, R1=0.0415 for 2786 unique reflections with F0[greater-or-equal, slanted]4[sigma]F; 2--triclinic, , a=5.129(2) Å, b=10.105(3) Å, c=11.080(3) Å, [alpha]=107.70(2)°, [beta]=102.53(3)°, [gamma]=104.74(3)°, V=501.4(3) Å3, Z=4, R1=0.055 for 1431 unique reflections with F0[greater-or-equal, slanted]4[sigma]F; 3--triclinic, , a=5.051(1) Å, b=5.303(1) Å, c=10.101(1) Å, [alpha]=90.31(1)°, [beta]=97.49(1)°, [gamma]=105.08(1)°, V=258.80(8) Å3, Z=2, R1=0.0339 for 2055 unique reflections with F0[greater-or-equal, slanted]4[sigma]F; 4--triclinic, , a=5.312(1) Å, b=6.696(1) Å, c=12.542(1) Å, [alpha]=94.532(9)°, [beta]=99.059(8)°, [gamma]=110.189(7)°, V=409.17(10) Å3, Z=2, R1=0.0565 for 1355 unique reflections with F0[greater-or-equal, slanted]4[sigma]F. The structures of all four compounds are based upon 3-D frameworks of U and T polyhedra (T=P, As). Phases 1 and 2 are isostructural and consist of U2O12 dimers and UO6 square bipyramids linked by single TO4 tetrahedra. The structure of 3 consists of 3-D framework of corner-sharing UO6 bipyramids and AsO4 tetrahedra. In the structure of 4, the framework is composed of U2O12 dimers, UO6 bipyramids and P2O7 dimers. In all the compounds, Li+ cations reside in framework cavities. The topologies of the 3-D frameworks can be described as derivatives of the PtS (cooperite) network.

Document Type: Article
Keywords: Uranyl phosphate Uranyl arsenate Crystal structure Solid-state reactions Polymorphism Structure topology
Research affiliation: Kiel University
DOI etc.: 10.1016/j.jssc.2008.07.028
ISSN: 0022-4596
Date Deposited: 02 Feb 2012 08:50
Last Modified: 08 Oct 2012 10:14
URI: http://eprints.uni-kiel.de/id/eprint/15827

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