Complex Topology of Uranyl Polyphosphate Frameworks: Crystal Structures of α‐, β‐K[(UO 2 )(P 3 O 9 )] and K[(UO 2 ) 2 (P 3 O 10 )]

Three new uranyl polyphosphates, α‐K[(UO 2 )(P 3 O 9 )] ( 1 ), β‐K[(UO 2 )(P 3 O 9 )] ( 2 ), and K[(UO 2 ) 2 (P 3 O 10 )] ( 3 ), were prepared by high‐temperature solid‐state reactions. The crystal structures of the compounds have been solved by direct methods: 1 – monoclinic, P 2 1 / m , a = 8.497(1), b = 15.1150(1), c = 14.7890(1) Å, β = 91.911(5)°, V = 1898.3(3) Å 3 , Z = 4, R 1 = 0.0734 for 4181 unique reflections with | F 0 | ≥ 4σ F ; 2 – monoclinic, P 2 1 / n , a = 8.607(1), b = 14.842(2), c = 14.951(1) Å, β = 95.829(5)°, V = 1900.0(4) Å 3 , Z = 4, R 1 = 0.0787 for 3185 unique reflections with | F 0 | ≥ 4σ F ; 3 – Pbcn , a = 10.632(1), b = 10.325(1), c = 11.209(1) Å, V = 1230.5(2) Å 3 , Z = 4, R 1 = 0.0364 for 1338 unique reflections with | F 0 | ≥ 4σ F . In the structures of 1 and 2 , phosphate tetrahedra share corners to form infinite [PO 3 ] − chains, whereas, in the structure of 3 , tetrahedra form linear [P 3 O 10 ] 5− trimers. The structures are based upon 3‐D frameworks of U and P polyhedra linked by sharing common O corners. The infinite [PO 3 ] − chains in the structures of 1 and 2 are parallel to [100] and [–101], respectively. The uranyl polyphosphate frameworks are occupied by host K + cations.