Crystal Structure of Uranyl Carboxylates

摘要

Uranyl-organic complexation in geologic fluids can have a profound impact upon uranium solubility and transport. Studies of uranyl organometallic crystal structures provide a basis for understanding complexation of the uranyl ion in solution. The crystal structures of several novel uranyl oxalates, synthesized under mild hydrothermal conditions, have been determined. These structures demonstrate new features little seen or not previously known in this chemical system, in particular polymerization into infinite sheets and direct linkage of uranyl polyhedra. Further work on the chemistry of this and other systems of hexavalent uranium and low molecular weight carboxylic acids, especially formic acid, is likely to turn up new insights. Although a hierarchical scheme exists for classifying inorganic uranyl compounds, no similar work has been done for organic compounds. Such a hierarchy would have practical benefits, in particular making structural information more accessible and understandable to workers studying related problems such as the environmental transport of hexavalent uranium as dissolved organic complexes. We offer a simple scheme that classifies uranyl oxalate structures by analyzing the long-range structural features and the coordination environments of uranyl ions, which leads to a structural symbol that can be used to easily identify uranyl oxalates with common structural features. This system is equally applicable to other carboxylate complexes with the uranyl ion, and could be extended to apply to any organic complex of the uranyl ion.