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Title: Syntheses and single-crystal structures of CsTh(MoO{sub 4}){sub 2}Cl and Na{sub 4}Th(WO{sub 4}){sub 4}

Journal Article · · Journal of Solid State Chemistry
 [1];  [1]
  1. Chemical Sciences and Engineering Division, CHM/200 Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439 (United States)

Colorless crystals of CsTh(MoO{sub 4}){sub 2}Cl and Na{sub 4}Th(WO{sub 4}){sub 4} have been synthesized at 993 K by the solid-state reactions of ThO{sub 2}, MoO{sub 3}, CsCl, and ThCl{sub 4} with Na{sub 2}WO{sub 4}. Both compounds have been characterized by the single-crystal X-ray diffraction. The structure of CsTh(MoO{sub 4}){sub 2}Cl is orthorhombic, consisting of two adjacent [Th(MoO{sub 4}){sub 2}] layers separated by an ionic CsCl sublattice. It can be considered as an insertion compound of Th(MoO{sub 4}){sub 2} and reformulated as Th(MoO{sub 4}){sub 2}.CsCl. The Th atom coordinates to seven monodentate MoO{sub 4} tetrahedra and one Cl atom in a highly distorted square antiprism. Na{sub 4}Th(WO{sub 4}){sub 4} adopts a scheelite superlattice structure. The three-dimensional framework of Na{sub 4}Th(WO{sub 4}){sub 4} is constructed from corner-sharing ThO{sub 8} square antiprisms and WO{sub 4} tetrahedra. The space within the channels is filled by six-coordinate Na ions. Crystal data: CsTh(MoO{sub 4}){sub 2}Cl, monoclinic, P2{sub 1}/c, Z=4, a=10.170(1) A, b=10.030(1) A, c=9.649(1) A, {beta}=95.671(2){sup o}, V=979.5(2) A{sup 3}, R(F)=2.65% for I>2{sigma}(I); Na{sub 4}Th(WO{sub 4}){sub 4}, tetragonal, I4{sub 1}/a, Z=4, a=11.437(1) A, c=11.833(2) A, V=1547.7(4) A{sup 3}, R(F)=3.02% for I>2{sigma}(I). -- Graphical abstract: The two-dimensional layered structure of CsTh(MoO{sub 4}){sub 2}Cl viewed down the b axis. Display Omitted Research highlights: {yields} Syntheses of CsTh(MoO{sub 4}){sub 2}Cl and Na{sub 4}Th(WO{sub 4}){sub 4} from chlorides. {yields} Single-crystal structures of CsTh(MoO{sub 4}){sub 2}Cl and Na{sub 4}Th(WO{sub 4}){sub 4}. {yields} CsTh(MoO{sub 4}){sub 2}Cl can be considered as an inclusion compound composed of covalent [Th(MoO{sub 4}){sub 2}] layer and ionic [CsCl] layers. {yields} Na{sub 4}Th(WO{sub 4}){sub 4} adopts a defect scheelite structure.

OSTI ID:
21494207
Journal Information:
Journal of Solid State Chemistry, Vol. 184, Issue 2; Other Information: DOI: 10.1016/j.jssc.2010.12.003; PII: S0022-4596(10)00541-4; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
Country of Publication:
United States
Language:
English