Co2(PO4)F crystallizes in the monoclinic C2/c space group. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form distorted CoO4F2 octahedra that share corners with four equivalent P(1)O4 tetrahedra, corners with two equivalent Co(2)O4F trigonal bipyramids, edges with two equivalent Co(1)O4F2 octahedra, and  an edgeedge with one Co(2)O4F trigonal bipyramid. In the second Co site, Co(2) is bonded to one O(1), one O(3), two equivalent O(4), and one F(1) atom to form distorted CoO4F trigonal bipyramids that share corners with two equivalent Co(1)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra,  an edgeedge with one Co(1)O4F2 octahedra, and  an edgeedge with one Co(2)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-71°. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with four equivalent Co(1)O4F2 octahedra and corners with four equivalent Co(2)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 47-59°. There are four inequivalent O sites. In the first O site, O(3) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one P(1) atom. In the second O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Co(2) and one P(1) atom. In the third O site, O(1) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Co(1) and one P(1) atom. F(1) is bonded in a 3-coordinate geometry to one Co(2) and two equivalent Co(1) atoms.
Co2(PO4)F crystallizes in the monoclinic C2/c space group. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form distorted CoO4F2 octahedra that share corners with four equivalent P(1)O4 tetrahedra, corners with two equivalent Co(2)O4F trigonal bipyramids, edges with two equivalent Co(1)O4F2 octahedra, and  an edgeedge with one Co(2)O4F trigonal bipyramid. The Co(1)-O(1) bond length is 2.07 Å. The Co(1)-O(3) bond length is 2.08 Å. There is one shorter (2.11 Å) and one longer (2.12 Å) Co(1)-O(2) bond length. There is one shorter (2.07 Å) and one longer (2.37 Å) Co(1)-F(1) bond length. In the second Co site, Co(2) is bonded to one O(1), one O(3), two equivalent O(4), and one F(1) atom to form distorted CoO4F trigonal bipyramids that share corners with two equivalent Co(1)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra,  an edgeedge with one Co(1)O4F2 octahedra, and  an edgeedge with one Co(2)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-71°. The Co(2)-O(1) bond length is 2.09 Å. The Co(2)-O(3) bond length is 2.13 Å. There is one shorter (2.05 Å) and one longer (2.10 Å) Co(2)-O(4) bond length. The Co(2)-F(1) bond length is 2.03 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with four equivalent Co(1)O4F2 octahedra and corners with four equivalent Co(2)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 47-59°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.56 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one P(1) atom. In the second O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Co(2) and one P(1) atom. In the third O site, O(1) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Co(1) and one P(1) atom. F(1) is bonded in a 3-coordinate geometry to one Co(2) and two equivalent Co(1) atoms.