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Phase formation in the mixed sulfate-selenate aqueous system of uranyl nitrate and cesium nitrate has been investigated. Two types of crystalline compounds have been obtained and characterized using a number of experimental (single crystal XRD, FTIR, SEM) and theoretical (information-based complexity calculations, topological analysis) techniques. No miscibility gaps have been observed for Cs 2 [(UO 2 ) 2 ( T O 4 ) 3 ] ( T = S, Se), which crystallizes in tetragonal system, P -42 1 m , a =9.616(1)–9.856(2), c =8.105(1)–8.159(1) Å, V =749.6(2)–792.5(3) Å 3 . Nine phases with variable amount of S and Se have been structurally characterized. The structures of the Cs 2 [(UO 2 ) 2 ( T O 4 ) 3 ] ( T = S, Se) compounds are based upon the [(UO 2 ) 2 ( T O 4 ) 3 ] 2- layers of corner-sharing uranyl pentagonal bipyramids and T O 4 tetrahedra. The layers contain two types of tetrahedral sites: T 1 (3-connected, i.e. having three O atoms shared by adjacent uranyl polyhedra) and T 2 (4-connected). The Se-for-S substitution in tetrahedral sites is highly selective with smaller S 6+ cation showing a strong preference for the more tightly bonded T 2 site. Crystallization in the pure Se system starts with the formation of Cs 2 [(UO 2 )(SeO 4 ) 2 (H 2 O)](H 2 O) crystals, its subsequent dissolution and formation of Cs 2 [(UO 2 ) 2 (SeO 4 ) 3 ]. The information-based structural complexity calculations for these two phases support the rule that more topologically complex structures form at the latest stages of crystallization. [ABSTRACT FROM AUTHOR]

Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C 2 H 8 N] 2 [(UO 2 )(SeO 4 ) 2 (H 2 O)] ( I ), [C 2 H 8 N] 2 [(UO 2 ) 2 (SeO 4 ) 3 (H 2 O)] ( II ), [C 4 H 15 N 3 ][H 3 O] 0.5 [(UO 2 ) 2 (SeO 4 ) 2.93 (SeO 3 ) 0.07 (H 2 O)](NO 3 ) 0.5 ( III ), [C 2 H 8 N] 3 [H 5 O 2 ][(UO 2 ) 2 (SeO 4 ) 3 (H 2 O) 2 ] 2 (H 2 O) 5 ( IV ), [C 2 H 8 N] 2 [H 3 O][(UO 2 ) 3 (SeO 4 ) 4 (HSeO 3 )(H 2 O)](H 2 SeO 3 ) 0.2 ( V ), [C 4 H 12 N] 3 [H 3 O][(UO 2 ) 3 (SeO 4 ) 5 (H 2 O)] ( VI ), and [C 2 H 8 N] 3 (C 2 H 7 N)[(UO 2 ) 3 (SeO 4 ) 4 (HSeO 3 )(H 2 O)] ( VII ) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite–selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U–O br –Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers. [ABSTRACT FROM AUTHOR]