Structural Complexity of Barium Uranyl Arsenates: Synthesis, Structure, and Topology of Ba(4) (UO(2))(2)(As(2)O(7))(3) , Ba(3) (UO(2))(2)(AsO(4))(2)(As(2)O(7)) , and Ba(5)Ca (UO(2))(8)(AsO(4))(4)O(8)

Alekseev, E. V., Krivovichev, S. V. and Depmeier, W. (2011) Structural Complexity of Barium Uranyl Arsenates: Synthesis, Structure, and Topology of Ba(4) (UO(2))(2)(As(2)O(7))(3) , Ba(3) (UO(2))(2)(AsO(4))(2)(As(2)O(7)) , and Ba(5)Ca (UO(2))(8)(AsO(4))(4)O(8) Crystal Growth & Design, 11 (7). pp. 3295-3300. DOI 10.1021/cg200592s.

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Abstract

Three new barium uranyl arsenates, Ba(4)[(UO(2))(2)(As(2)O(7))(3)] (1), Ba(3)[(UO(2))(2)(AsO(4))(2)(As(2)O(7))] (2), and Ba(5)Ca[(UO(2))(8)(AsO(4))(4)O(8)] (3), with mono-, pyro-, and mixed arsenate oxoanions have been prepared by high-temperature solid-state reactions. The crystal structures have been solved by direct methods and refined using the least-squares method: 1 - orthorhombic, Pbc2(1), 5.6010(6), b = 13.344(1), c = 31.751(2) angstrom, V = 2373.1(3) angstrom(3), Z = 4, R(1) = 0.044; 2 - monoclinic, C2/c, a = 19.246(2), b = 9.536(1), c = 9.619(1) angstrom, beta = 95.585(6)degrees, V = 1757.0(3) angstrom(3), Z = 4, R(1) = 0.049; 3 - monoclinic, P2(1)/c, a = 12.073(1), b = 12.838(1), c = 13.472(1) angstrom, beta = 116.969(3)degrees, V = 1861.0(3) angstrom(3), Z = 2 R(1) = 0.0584. The compounds demonstrate unprecedented structural topologies (one-dimensional chains in 1, three-dimensional framework in 2, two-dimensional layers in 3), which, however, can be related to previously known structures by topological analysis. The novelty of the compounds obtained can be attributed in part to the synthesis method, which implies the absence of water in the system at the reaction temperature. In turn, the higher ionic strength of divalent cations defines enhanced structural complexity and the deviation of the observed structural topologies from those known for similar systems with monovalent cations.

Document Type: Article
Keywords: cation-cation interactions crystal-structures fullerene topologies autunite group nuclear-waste cage clusters uranium phosphates nanotubules chemistry
Research affiliation: Kiel University
DOI etc.: 10.1021/cg200592s
ISSN: 1528-7483
Date Deposited: 15 Dec 2011 05:14
Last Modified: 08 Oct 2012 09:26
URI: http://eprints.uni-kiel.de/id/eprint/15605

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