Abstract

The uranyl complexes [UO 2(acetamidoxime) 4](NO 3) 2 (1) and [UO 2(benzamidoxime) 4](NO) 3) 2·χS (S = nitromethane or 1,2-dichloroethane, χ < 1) (2) were prepared by the reaction of uranyl nitrate with the corresponding amidoxime in ethanolic solution, and characterized by thermal analysis and infrared spectroscopy. The crystal structures of the acetamidoxime complex and the 1,2-dichloroethane-containing benzamidoxime complex ( 2a) were determined by single crystal X-ray diffraction measurements and refined R 1 = 0.018 and 0.070, respectively. 1 crystallizes in the monoclinic space group I2/c with a = 14.929(3), b = 8.946(2), c = 16.790(4) Å, β = 96.01(2)° and Z = 4, whereas crystals of 2a are triclinic, space group P 1 with a = 9.890(4), b = 14.226(6), c = 15.227(6) Å, α = 75.76(3), β = 87.13(3), γ = 81.22(3)° and Z = 2. In both complexes the linear uranyl group is equatorially surrounded by four oxygen atoms of monodentate amidoxime ligands, the mean bond lengths in 1 and 2a being: UO uranyl = 1.775 and 1.78 Å and UO amidoxime = 2.308 and 2.26 Å, respectively. In accordance with infrared spectroscopic results the nitrate ions are not coordinated to uranium, but interact with the ligand molecules via hydrogen bonds.

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