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The first mononuclear molecular mixed-ligand U(VI) solid containing hydroxide and peroxide ligands, Na 6 [UO 2 (O 2 ) 2 (OH) 2 ](OH) 2 ·14H 2 O (I), was synthesized and structurally characterized using single crystal X-ray diffraction. The crystal structure of I consisted of [UO 2 (O 2 ) 2 (OH) 2 ] 4−  molecular units, with a uranyl(VI) moiety perpendicular to 6 equatorial O atoms belonging to two side-on trans peroxo groups and two terminal trans hydroxo groups. Density functional theory (DFT) calculations determined that the   trans  -conformer of the [UO 2 (O 2 ) 2 (OH) 2 ] 4−  molecular unit found in I was 24 kcal/mol lower in energy than the previously proposed   cis  -conformer. Crystal data: monoclinic, space group  P 2 1 / n  with  a =13.357(4) Å,  b =5.8521(15) Å,  c =15.948(6) Å, β=112.292(4)°, and  Z =2.

radiochimica acta

Synthesis, crystallographic characterization, and conformational prediction of a structurally unique molecular mixed-ligand U(VI) solid, Na 6 [UO 2 (O 2 ) 2 (OH) 2 ](OH) 2 ·14H 2 O