Crystal Chemistry and Structural Complexity of Uranium(IV) Sulfates: Synthesis of U3H2(SO4)7(H2O)5·3H2O and U3(UO2)0.2(SO4)6(OH)0.4·2.3H2O with Framework Structures by the Photochemical Reduction of Uranyl.

Two uranium(IV) sulfate framework compounds were crystallized at room temperature from aqueous solutions containing uranyl ions by photochemical reduction in the presence of 2-propanol. U3H2(SO4)7(H2O)5·3H2O (1) crystallizes in space group P65 with a = 9.3052(17) Å, c = 53.515(10) Å, V = 4012.9(13) Å3, and Z = 6, and U3(UO2)0.2(SO4)6(OH)0.4·2.3H2O (2) is tetragonal, with space group P42/nmc, a = 25.624(3) Å, c = 8.9435(10) Å, V = 5872.2(11) Å3, and Z = 8. The structures of 1 and 2 are the most complex among uranium(IV) sulfates.