Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. I. Polymorphism and structure topology: Synthesis and crystal structures of alpha-Li (UO(2))(PO(4)) , alpha-Li (UO(2))(AsO(4)) , beta-Li (UO(2))(AsO(4)) and Li(2) (UO(2))(3)(P(2)O(7))(2)

Alekseev, E. V., Krivovichev, S. V., Malcherek, T. and Depmeier, W. (2008) Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. I. Polymorphism and structure topology: Synthesis and crystal structures of alpha-Li (UO(2))(PO(4)) , alpha-Li (UO(2))(AsO(4)) , beta-Li (UO(2))(AsO(4)) and Li(2) (UO(2))(3)(P(2)O(7))(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[(UO(2))(PO(4))] (1), alpha-Li[(UO(2))(AsO(4))] (2), beta-Li[(UO(2))(AsO(4))] (3) and Li(2)[(UO(2))(3)(P(2)O(7))(2)] (4). The structures of the compounds have been solved by direct methods: 1-triclinic, P (1) over bar, a = 5.0271(1) angstrom, b = 9.8799(2) angstrom, c = 10.8920(2) angstrom, alpha = 108.282(9)degrees, beta = 102.993(8)degrees, gamma = 104.13(1)degrees, V = 470.69(2) angstrom(3), Z = 4, R(1) = 0.0415 for 2786 unique reflections with vertical bar F(0)vertical bar >= 4 sigma(F); 2-triclinic, P (1) over bar, a = 5.129(2) angstrom, b = 10.105(3) angstrom, c = 11.080(3) angstrom, alpha = 107.70(2)degrees, beta = 102.53(3)degrees, gamma = 104.74(3)degrees, V = 501.4(3) angstrom(3), Z = 4, R(1) = 0.055 for 1431 unique reflections with vertical bar F(0)vertical bar >= 4 sigma(F); 3-triclinic, P (1) over bar, a = 5.051 (1) angstrom, b = 5.303(1) angstrom, c = 10.101 (1) angstrom, alpha = 90.31(1)degrees, beta = 97.49(1)degrees, gamma = 105.08(1)degrees, V = 258.80(8) angstrom(3), Z = 2, R(1) = 0.0339 for 2055 unique reflections with vertical bar F(0)vertical bar >= 4 sigma(F); 4-triclinic, P (1) over bar, a 5.312(1) angstrom, b = 6.696(1) angstrom, c = 12.542(1) angstrom, alpha = 94.532(9)degrees, beta = 99.059(8)degrees, 110.189(7)degrees, V = 409.17(10) angstrom(3), Z = 2, R(1) = 0.0565 for 1355 unique reflections with vertical bar F(0)vertical bar >= 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 U(2)O(12) dimers and UO(6) square bipyramids linked by single TO(4) tetrahedra. The structure of 3 consists of 3-D framework of corner-sharing UO(6) bipyramids and AsO(4) tetrahedra. In the structure of 4, the framework is composed of U(2)O(12) dimers, UO(6) bipyramids and P(2)O(7) 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. (C) 2008 Elsevier Inc. All rights reserved.

Document Type: Article
Keywords: Uranyl phosphate Uranyl arsenate Crystal structure Solid-state reactions Polymorphism Structure topology bond-valence parameters uranium parsonsite frameworks polyhedra solids
Research affiliation: Kiel University > Faculty of Mathematics and Natural Sciences > Institute of Geosciences
DOI etc.: 10.1016/j.jssc.2008.07.028
ISSN: 0022-4596
Date Deposited: 12 Jan 2012 05:46
Last Modified: 09 Oct 2012 03:56
URI: http://eprints.uni-kiel.de/id/eprint/15570

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