Crystal growth, structural characterization, cation-cation interaction classification, and optical properties of uranium(VI) containing oxychlorides, A4U5O16Cl2 (A = K, Rb), Cs5U7O22Cl3, and AUO3Cl (A = Rb, Cs)

Single crystals of five new alkali metal uranium oxychlorides, K4U5O16Cl2, Rb4U5O16Cl2, Cs5U7O22Cl3, RbUO3Cl, and CsUO3Cl, have been grown from molten chloride fluxes and structurally characterized by single crystal X-ray diffraction. All of the materials are monoclinic. The first three crystallize in the space group P2(1)/n and exhibit a 2D layered structure with a novel layer topology, consisting of UO6, UO7, and UO4Cl2 polyhedra and cation-cation interactions (CCIs) within the plane of the uranyl sheet. A general cation-cation classification scheme is presented. RbUO3Cl and CsUO3Cl crystallize in the space group P2(1)/m and exhibit 1D zipper-like chains of UO5Cl2 polyhedra. The lattice parameters of the new oxychlorides are: K4U5O16Cl2, a = 9.9574(4) angstrom, b = 6.9766(3) angstrom, c = 14.3920(6) angstrom, and beta = 105.7690(10)degrees; Rb4U5O16Cl2, a = 10.2164(4) angstrom, b = 7.0160(3) angstrom, c = 14.4930(5) angstrom, and beta = 103.8290(10)degrees; Cs5U7O22Cl3, a = 10.6214(5) angstrom, b = 18.1071(8) angstrom, c = 16.0857(7) angstrom, and beta = 102.9850(10)degrees; RbUO3Cl, a = 7.3602(6) angstrom, b = 4.1127(3) angstrom, c = 8.5556(7) angstrom, and beta = 104.602(2)degrees; CsUO3Cl, a = 7.7768(4) angstrom, b = 4.1245(2) angstrom, c = 8.7701(5) angstrom, and beta = 105.4680(10)degrees. The materials were further characterized by UV-vis reflectance spectroscopy and fluorescence spectroscopy.