Syntheses, Structures, and Ion-Exchange Properties of the Three-Dimensional Framework Uranyl Gallium Phosphates, Cs4[(UO2)2(GaOH)2(PO4)4]·H2O and Cs[UO2Ga(PO4)2]

摘要: The reaction of UO(2)(NO(3))(2).6H(2)O with Cs(2)CO(3) or CsCl, H(3)PO(4), and Ga(2)O(3) under mild hydrothermal conditions results in the formation Cs(4)[(UO(2))(2)(GaOH)(2)(PO(4))(4)].H(2)O (UGaP-1) Cs[UO(2)Ga(PO(4))(2)] (UGaP-2). structure UGaP-1 was solved from a twinned crystal revealing three-dimensional framework consisting one-dimensional (1)(infinity)[Ga(OH)(PO(4))(2)](4-) chains composed corner-sharing GaO(6) octahedra bridging PO(4) tetrahedra that extend along c axis. phosphate anions bind UO(2)(2+) cations to form UO(7) pentagonal bipyramids. moieties edge-share create dimers link gallium substructure into (3)(infinity)[(UO(2))(2)(GaOH)(2)(PO(4))(4)](4-) anionic lattice has intersecting channels running down b axes. Cs(+) water molecules occupy these channels. UGaP-2 is also contains (1)(infinity)[Ga(PO(4))(2)](3-) These are formed fused eight-membered rings GaO(4) tetrahedra. turn linked together (3)(infinity)[UO(2)Ga(PO(4))(2)](1-) by edge-sharing as occurs UGaP-1. There run axes through framework. contain cations. Ion-exchange studies indicate can be exchanged for Ca(2+) Ba(2+). Crystallographic data: UGaP-1, monoclinic, space group P2(1)/c, = 18.872(1), 9.5105(7), 14.007(1) A, beta 109.65(3)(o) , Z 4 (T 295 K); UGaP-2, triclinic, P, 7.7765(6), 8.5043(7), 8.9115(7) alpha 66.642(1)(o), 70.563(1)(o), gamma 84.003(2)(o), 2 193 K).