LiCoPO4F crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(2), two equivalent O(4), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent Co(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Co(1)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-60°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent F(1) atoms to form CoO4F2 octahedra that share corners with two equivalent Co(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. In the second Co site, Co(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(1) atoms to form CoO4F2 octahedra that share corners with two equivalent Co(1)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. 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 two equivalent Co(1)O4F2 octahedra, corners with two equivalent Co(2)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 31-56°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Co(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one Co(1), and one P(1) atom. F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one Co(2) atom.
LiCoPO4F crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(2), two equivalent O(4), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent Co(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Co(1)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-60°. The Li(1)-O(1) bond length is 2.06 Å. The Li(1)-O(2) bond length is 2.22 Å. There is one shorter (2.12 Å) and one longer (2.17 Å) Li(1)-O(4) bond length. The Li(1)-F(1) bond length is 1.92 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent F(1) atoms to form CoO4F2 octahedra that share corners with two equivalent Co(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. Both Co(1)-O(2) bond lengths are 1.89 Å. Both Co(1)-O(4) bond lengths are 2.07 Å. Both Co(1)-F(1) bond lengths are 2.01 Å. In the second Co site, Co(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(1) atoms to form CoO4F2 octahedra that share corners with two equivalent Co(1)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. Both Co(2)-O(1) bond lengths are 2.00 Å. Both Co(2)-O(3) bond lengths are 1.94 Å. Both Co(2)-F(1) bond lengths are 2.01 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 two equivalent Co(1)O4F2 octahedra, corners with two equivalent Co(2)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 31-56°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.56 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Co(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one Co(1), and one P(1) atom. F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(1), and one Co(2) atom.