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A new caesium aluminophosphate, Cs 3 Al 2 P 3 O 12 , has been synthesized by spontaneous crystallization from the melt and structurally characterized. The compound crystallizes in the orthorhombic space group  Pnma , with  a =9.7675(2) Å,  b =17.7537(3) Å,  c =8.1063(2) Å,  V =1405.71(2) Å 3 , and  Z =4. Its crystal structure is based on an open interrupted framework built by alternating AlO 4  and PO 4  tetrahedra with Cs ions occupying the channels. The Cs 3 Al 2 P 3 O 12  framework topology resembles the previously known 4.8.12-net, which has been reported in the [C 4 N 3 H 16 ][Al 2 P 3 O 12 ] phase prepared by solvothermal synthesis in the presence of diethylenetriamine (DETA). The crystal chemical relationships between the K, Rb, Cs, Tl, [NH 4 ] and [C 4 N 3 H 16 ]-members of the  A  3 Al 2 P 3 O 12  family of compounds are discussed.

A “missing” caesium member in the family of A 3 Al 2 P 3 O 12 aluminophosphates