Reaction of uranyl nitrate with carboxylic diacids under hydrothermal conditions. Crystal structure of complexes with l(+)-tartaric and oxalic acids

Abstract

l(+)-tartaric acid reacts with uranyl nitrate in the presence of KOH, under mild hydrothermal conditions, to give the complex [UO 2(C 4H 4O 6)(H 2O)] ( 1), the first uranyl tartrate to be crystallographically characterized. Each tartrate ligand bridges three uranyl ions, one of them in chelating fashion through proximal carboxylate and hydroxyl groups. The resulting assemblage is two-dimensional, with the uranyl pentagonal bipyramidal coordination polyhedra separated from one another. Prolonged heating of an uranyl tartrate solution resulted in oxidative cleavage of the acid and formation of the oxalate complex [(UO 2) 2(C 2O 4) 2(OH)Na(H 2O) 2] ( 2). The bis-bidentate oxalate and bridging hydroxide groups ensure the formation of sheets with corner-sharing uranyl pentagonal bipyramidal coordination polyhedra, in which six-membered metallacycles encompass the sodium ions. These sheets are assembled into a three-dimensional framework through further oxo-bonding of the sodium ions.