A New Oxoanion:  [IO4]3- Containing I(V) with a Stereochemically Active Lone-Pair in the Silver Uranyl Iodate Tetraoxoiodate(V), Ag4(UO2)4(IO3)2(IO4)2O2

The hydrothermal reaction of elemental Ag, or water-soluble silver sources, with UO3 and I2O5 at 200 °C for 5 days yields Ag4(UO2)4(IO3)2(IO4)2O2 in the form of orange fibrous needles. Single-crystal X-ray diffraction studies on this compound reveal a highly complex network structure consisting of three interconnected low-dimensional substructures. The first of these substructures are ribbons of UO8 hexagonal bipyramids that edge-share to form one-dimensional chains. These units further edge-share with pentagonal bipyramidal UO7 units to create ribbons. The edges of the ribbons are partially terminated by tetraoxoiodate(V), [IO4]3-, anions. The uranium oxide ribbons are joined by bridging iodate ligands to yield two-dimensional undulating sheets. These sheets help to form, and are linked together by, one-dimensional chains of edge-sharing AgO7 capped octahedral units and ribbons formed by corner-sharing capped trigonal planar AgO4 polyhedra, AgO6 capped square pyramids, and AgO6 octahedra. The [IO4]3- anions in Ag4(UO2)4(IO3)2(IO4)2O2 are tetraoxoiodate(V), not metaperiodate, and contain I(V) with a stereochemically active lone-pair. Bond valence sum calculations are consistent with this formulation. Differential scanning calorimetry measurements show distinctly different thermal behavior of Ag4(UO2)4(IO3)2(IO4)2O2 versus other uranyl iodate compounds with endotherms at 479 and 494 °C. Density functional theory (DFT) calculations demonstrate that the approximate C 2 v geometry of the [IO4]3- anion can be attributed to a second-order Jahn−Teller distortion. DFT optimized geometry for the [IO4]3- anion is in good agreement with those measured from single-crystal X-ray diffraction studies on Ag4(UO2)4(IO3)2(IO4)2O2.