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The new polymorph of Co 2 [PO 4 ]F has been synthesized by a hydrothermal route. Its crystal structure was determined from single-crystal X-ray diffraction data. Co 2 [PO 4 ]F crystallizes with the triplite-type structure, space group  C 2 /c ,  a =12.856(2),  b =6.4369(10),  c =9.6742(16) Å,  β =117.40(1)°,  V =710.7(2) Å 3  and  Z =8. The structure consists of a 3D-framework buildup of condensed PO 4  tetrahedra, and cobalt(II) polyhedra which form chains running along the [101] and [010] directions. The coordination of the cobalt cations and the connectivity between the cobalt polyhedra are not well defined due to the disorder of the fluoride anions which form zigzag chains along [001]. The theoretical ordering of the fluoride anions led to two different structural models, very similar to the triplite  Cc- CoFe[PO 4 ]F and the triploidite  P 2 1 / c -Co 2 [PO 4 ]F, and in which the cobalt atoms are five and six coordinated.

The new disordered triplite polymorph of Co 2 [PO 4 ]F