Rubidium uranyl phosphates and arsenates with polymeric tetrahedral anions: Syntheses and structures of Rb-4[(UO2)(6)(P2O7)(4)(H2O)], Rb-2[(UO2)(3)(P2O7)(P4O12)] and Rb[(UO2)(2)(AS(3)O(10))]

Alekseev, E. V., Krivovichev, S. V. and Depmeier, Wulf (2009) Rubidium uranyl phosphates and arsenates with polymeric tetrahedral anions: Syntheses and structures of Rb-4[(UO2)(6)(P2O7)(4)(H2O)], Rb-2[(UO2)(3)(P2O7)(P4O12)] and Rb[(UO2)(2)(AS(3)O(10))] Journal of Solid State Chemistry, 182 (8). pp. 2074-2080.

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Abstract

The three new framework Rb uranyl phosphates and arsenates with anionic parts based on different type of polymeric anions have been prepared by high-temperature solid-state reactions: Rb-4[(UO2)(6) (P2O7)(4)(H2O)] (1), Rb-2[(UO2)(3)(P2O7)(P4O12)] (2), Rb[(UO2)(2)(As3O10)] (3). The crystal structures of the synthesized compounds have been solved by direct methods: 1-monoclinic P2(1)/c, a = 9.672(1)angstrom, b = 12.951 (1)angstrom, c = 32.231(3)angstrom, beta = 90.116(4)degrees, V = 4037.3(6)angstrom(3), Z = 4, R-1 = 0.0926 for 6351 unique reflections with |F-0| >= 4 sigma(F); 2-monoclinic, P2(1)/c, a = 6.791 (1)angstrom, b = 16.155(3)angstrom, c = 19.856(4)angstrom, beta = 97.48(5)degrees, V = 2159.8(7)angstrom(3), Z = 4. R-1 = 0.0286 for 3617 unique reflections with |F-0| >= 4 sigma(F); 3-orthorhombic, Pbcn, a = 10.558(1)angstrom, b = 11.037(1)angstrom, c = 11.464(1)angstrom, V = 1335.9(2)angstrom(3), Z = 4, R-1 = 0.0489 for 1384 unique reflections with |F-0| 4 sigma(F), The structures of title are compounds based on 3D negatively charged frameworks with chemical compositions [(UO2)(6)(P2O7)(4)(H2O)](4-) in 1, [(UO2)(3)(P2O7)(P4O12)](2-) in 2 and [(UO2)(2)(As3O10)](-) in 3. These negative charges are compensated by rubidium cations which are in the channels of 1 and closed cages in structures of 2 and 3. The channels in 1 are directed along the a direction and have minimum dimensions similar to 5 angstrom x 6 angstrom. This is the first example of porosity generation through solid state synthesis in uranyl compounds. For the first time in uranium chemistry polymeric anionic groups P4O12 and As3O10 were observed in structure of 2 and 3. (C) 2009 Elsevier Inc. All rights reserved.

Document Type: Article
Keywords: uranyl phosphateuranyl arsenate polyphosphate polyarsenates crystal structure solid state reaction polyanions crystal-structures parsonsite framework topology
Research affiliation: OceanRep > The Future Ocean - Cluster of Excellence
Kiel University
Refereed: Yes
ISSN: 0022-4596
Projects: Future Ocean
Date Deposited: 11 Feb 2011 12:13
Last Modified: 27 Jan 2012 05:35
URI: http://eprints.uni-kiel.de/id/eprint/9264

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