Syntheses and single-crystal structures of CsTh(MoO 4) 2Cl and Na 4Th(WO 4) 4

• Published in: Journal of solid state chemistry Vol. 184; no. 2; pp. 337 - 342
• Main Authors: Bang Jin, Geng, Soderholm, L.
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 2011
• Subjects: Insertion compound; Molybdate; Single-crystal structure; Thorium; Tungstate; Molybdate; Insertion compound; Single-crystal structure; Tungstate; Thorium
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2010.12.003

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