title: Aqueous reactions of U(VI) at high chloride concentrations: syntheses and structures of new uranyl chloride polymers.
abstract: The reactions of UO(3) with acidic aqueous chloride solutions resulted in the formation of two new polymeric U(VI) compounds. Single crystals of Cs(2)[(UO(2))(3)Cl(2)(IO(3))(OH)O(2)].2H(2)O (1) were formed under hydrothermal conditions with HIO(3) and CsCl, and Li(H(2)O)(2)[(UO(2))(2)Cl(3)(O)(H(2)O)] (2) was obtained from acidic LiCl solutions under ambient temperature and pressure. Both compounds contain pentagonal bipyramidal coordination of the uranyl dication, UO(2)(2+). The structure of 1 consists of infinite [(UO(2))(3)Cl(2)(IO(3))(mu(3)-OH)(mu(3)-O)(2)](2-) ribbons that run down the b axis that are formed from edge-sharing pentagonal bipyramidal [UO(6)Cl] and [UO(5)Cl(2)] units. The Cs(+) cations separate the chains from one another and form long ionic contacts with terminal oxygen atoms from iodate ligands, uranyl oxygen atoms, water molecules, and chloride anions. In 2, edge-sharing [UO(3)Cl(4)] and [UO(5)Cl(2)] units build up tetranuclear [(UO(2))(4)(mu-Cl)(6)(mu(3)-O)(2)(H(2)O)(2)](2-) anions that are bridged by chloride to form one-dimensional chains. These chains are connected in a complex network of hydrogen bonds and interactions of uranyl oxygen atoms with Li(+) cations. Crystal data: 1, orthorhombic, space group Pnma, a = 8.2762(4) A, b = 12.4809(6) A, c = 17.1297(8) A, Z = 4; 2, triclinic, space group P1, a = 8.110(1) A, b = 8.621(1) A, c = 8.740(1) A, Z = 2.
authors.affiliation: Department of Chemistry, Auburn University, Auburn, Alabama 36849, USA.
authors.forename: Amanda C
authors.initials: AC
authors.lastname: Bean
authors.forename: Youwen
authors.initials: Y
authors.lastname: Xu
authors.forename: Janet A
authors.initials: JA
authors.lastname: Danis
authors.forename: Thomas E
authors.initials: TE
authors.lastname: Albrecht-Schmitt
authors.forename: Brian L
authors.initials: BL
authors.lastname: Scott
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Runde