Structure of the hydrated dioxouranium (VI) ion in aqueous solution

An x-ray diffraction and proton NMR study ... Uranyl Carbonate Complexes in Aqueous Solution and Their Ligand NMR Chemical Shifts andO Quadrupolar ...
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Inorg. Chem. 1983, 22, 3986-3989

3986

Contribution from the Department of Inorganic Chemistry, The Royal Institute of Technology, S-100 44 Stockholm, Sweden

Structure of the Hydrated Dioxouranium(V1) Ion in Aqueous Solution. An X-ray Diffraction and 'H NMR Study MARTHA .&BERG, DIEGO FERRI, JULIUS GLASER,* and INGMAR G R E N T H E Received February 28, 1983 X-ray diffraction data on a 1 M aqueous solution of dioxouranium(V1) (uranyl) perchlorate are consistent with the hydrated uran 1 ion having a pentagonal-bipyramidal geometry with the U-O distances 1.702 ( 5 ) .& within the UO?+ ion and 2.421 ( 5 ) between the uranium atom and the water of hydration. This structure is not significantly different from the one found in crystals of UOz(C104)z~7Hz0. From proton magnetic resonance data in water-acetone mixtures a t about -80 OC, the hydration number of the uranyl ion has been determined to be 4.9 (h0.2) in 1 M UOz(C104)zsolution. In more concentrated solutions, with lower HzO/UOZ+ mole ratios, the hydration number decreases. It is shown that these results are not dependent on the acetone concentration. Agreement with previous results is discussed.

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Introduction Very little is known about the hydration of the dioxouranium(V1) (uranyl) ion in solution. X-ray diffraction studies,' ' H N M R measurements,2 and other investigations3 indicate that water molecules in the first hydration shell may be displaced by NO