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Two uranyl tungstates, (UO 2 )(W 2 O 7 )(H 2 O) 3  ( 1 ) and (UO 2 ) 3 (W 2 O 8 )F 2 (H 2 O) 3  ( 2 ), were synthesized under hydrothermal conditions at 220°C and were structurally, chemically, and spectroscopically characterized.  1  Crystallizes in space group  Pbcm ,  a  = 6.673(5) Å,  b  = 12.601(11) Å,  c  = 11.552 Å;  2  is in  C 2/ m ,  a  = 13.648(1) Å,  b  = 16.852(1) Å,  c  = 9.832(1) Å,  β  = 125.980(1)°. In  1  the U(VI) cations are present as (UO 2 ) 2+  uranyl ions that are coordinated by five oxygen atoms to give pentagonal bipyramids. These share two edges with two tungstate octahedra and single vertices with four additional octahedra, resulting in a sheet with the iriginite-type anion topology. Only water molecules are located in the interlayer. The structural units of  2  consist of (UO 2 ) 2+  uranyl oxy-fluoride pentagonal bipyramids present as either [UO 2 F 2 O 3 ] –6  or [UO 2 FO 4 ] –5  , and strongly distorted tungstate octahedra. The linkage of uranyl pentagonal bipyramids and tungstate octahedra gives a unique sheet anion topology consisting of pentagons, squares and triangles. In  2 , the uranyl tungstates sheets are connected into a novel electro-neutral three-dimensional framework through dimers of uranyl pentagonal bipyramids. These dimers connecting the sheets share an edge defined by F anions.  2  is the first example of a uranyl tungstate oxy-fluoride, and  1  and  2  are rare examples of uranyl compounds containing electro-neutral structural units.

Hydrothermal syntheses and characterization of uranyl tungstates with electro-neutral structural units