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The new disordered triplite polymorph of Co2[PO4]F

Abstract The new polymorph of Co2[PO4]F has been synthesized by a hydrothermal route. Its crystal structure was determined from single-crystal X-ray diffraction data. Co2[PO4]F crystallizes with the triplite-type structure, space group C2/c, a=12.856(2), b=6.4369(10), c=9.6742(16) Å, β=117.40(1)°, V=710.7(2) Å3 and Z=8. The structure consists of a 3D-framework buildup of condensed PO4 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[PO4]F and the triploidite P21/c-Co2[PO4]F, and in which the cobalt atoms are five and six coordinated.