LiCo2OF3 is Spinel-derived structured and crystallizes in the monoclinic P2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one F(1), one F(4), one F(5), and one F(6) atom to form LiO2F4 octahedra that share corners with three equivalent Co(3)OF3 tetrahedra, corners with three equivalent Co(5)OF3 tetrahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Co(2)O2F4 octahedra,  an edgeedge with one Co(1)O4F2 octahedra, and edges with two equivalent Co(4)OF5 octahedra. In the second Li site, Li(2) is bonded to two equivalent F(3), two equivalent F(5), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with two equivalent Co(5)OF3 tetrahedra, corners with four equivalent Co(3)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and edges with two equivalent Co(4)OF5 octahedra. In the third Li site, Li(3) is bonded to two equivalent F(3), two equivalent F(4), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with two equivalent Co(5)OF3 tetrahedra, corners with four equivalent Co(3)OF3 tetrahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and edges with two equivalent Co(4)OF5 octahedra. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(2) atoms to form distorted CoO4F2 octahedra that share corners with two equivalent Co(3)OF3 tetrahedra, corners with four equivalent Co(5)OF3 tetrahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Co(2)O2F4 octahedra, and edges with two equivalent Co(4)OF5 octahedra. In the second Co site, Co(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form CoO2F4 octahedra that share corners with two equivalent Co(3)OF3 tetrahedra, corners with four equivalent Co(5)OF3 tetrahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Co(1)O4F2 octahedra, and edges with two equivalent Co(4)OF5 octahedra. In the third Co site, Co(3) is bonded to one O(2), one F(1), one F(3), and one F(6) atom to form CoOF3 tetrahedra that share  a cornercorner with one Co(2)O2F4 octahedra,  a cornercorner with one Co(1)O4F2 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with three equivalent Li(1)O2F4 octahedra, and corners with three equivalent Co(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-65°. In the fourth Co site, Co(4) is bonded to one O(2), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form CoOF5 octahedra that share corners with three equivalent Co(3)OF3 tetrahedra, corners with three equivalent Co(5)OF3 tetrahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Co(2)O2F4 octahedra,  an edgeedge with one Co(1)O4F2 octahedra, and edges with two equivalent Li(1)O2F4 octahedra. In the fifth Co site, Co(5) is bonded to one O(1), one F(2), one F(4), and one F(5) atom to form CoOF3 tetrahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Li(3)F6 octahedra, corners with two equivalent Co(2)O2F4 octahedra, corners with two equivalent Co(1)O4F2 octahedra, corners with three equivalent Li(1)O2F4 octahedra, and corners with three equivalent Co(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 49-65°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Co(1), one Co(2), and one Co(5) atom to form a mixture of distorted corner and edge-sharing OLiCo3 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Co(1), one Co(3), and one Co(4) atom to form a mixture of distorted corner and edge-sharing OLiCo3 trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(2), one Co(3), and one Co(4) atom. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Co(1), one Co(2), one Co(4), and one Co(5) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(3), and one Co(4) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Co(4), and one Co(5) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Co(4), and one Co(5) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Co(3) atom.
LiCo2OF3 is Spinel-derived structured and crystallizes in the monoclinic P2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one F(1), one F(4), one F(5), and one F(6) atom to form LiO2F4 octahedra that share corners with three equivalent Co(3)OF3 tetrahedra, corners with three equivalent Co(5)OF3 tetrahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Co(2)O2F4 octahedra,  an edgeedge with one Co(1)O4F2 octahedra, and edges with two equivalent Co(4)OF5 octahedra. The Li(1)-O(1) bond length is 2.04 Å. The Li(1)-O(2) bond length is 2.07 Å. The Li(1)-F(1) bond length is 2.18 Å. The Li(1)-F(4) bond length is 2.08 Å. The Li(1)-F(5) bond length is 2.22 Å. The Li(1)-F(6) bond length is 2.11 Å. In the second Li site, Li(2) is bonded to two equivalent F(3), two equivalent F(5), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with two equivalent Co(5)OF3 tetrahedra, corners with four equivalent Co(3)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and edges with two equivalent Co(4)OF5 octahedra. Both Li(2)-F(3) bond lengths are 2.17 Å. Both Li(2)-F(5) bond lengths are 2.02 Å. Both Li(2)-F(6) bond lengths are 2.05 Å. In the third Li site, Li(3) is bonded to two equivalent F(3), two equivalent F(4), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with two equivalent Co(5)OF3 tetrahedra, corners with four equivalent Co(3)OF3 tetrahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and edges with two equivalent Co(4)OF5 octahedra. Both Li(3)-F(3) bond lengths are 2.16 Å. Both Li(3)-F(4) bond lengths are 2.02 Å. Both Li(3)-F(6) bond lengths are 2.03 Å. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(2) atoms to form distorted CoO4F2 octahedra that share corners with two equivalent Co(3)OF3 tetrahedra, corners with four equivalent Co(5)OF3 tetrahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Co(2)O2F4 octahedra, and edges with two equivalent Co(4)OF5 octahedra. Both Co(1)-O(1) bond lengths are 2.00 Å. Both Co(1)-O(2) bond lengths are 2.03 Å. Both Co(1)-F(2) bond lengths are 2.42 Å. In the second Co site, Co(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form CoO2F4 octahedra that share corners with two equivalent Co(3)OF3 tetrahedra, corners with four equivalent Co(5)OF3 tetrahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Co(1)O4F2 octahedra, and edges with two equivalent Co(4)OF5 octahedra. Both Co(2)-O(1) bond lengths are 1.94 Å. Both Co(2)-F(1) bond lengths are 2.18 Å. Both Co(2)-F(2) bond lengths are 2.19 Å. In the third Co site, Co(3) is bonded to one O(2), one F(1), one F(3), and one F(6) atom to form CoOF3 tetrahedra that share  a cornercorner with one Co(2)O2F4 octahedra,  a cornercorner with one Co(1)O4F2 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with three equivalent Li(1)O2F4 octahedra, and corners with three equivalent Co(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 50-65°. The Co(3)-O(2) bond length is 1.88 Å. The Co(3)-F(1) bond length is 2.03 Å. The Co(3)-F(3) bond length is 2.02 Å. The Co(3)-F(6) bond length is 1.99 Å. In the fourth Co site, Co(4) is bonded to one O(2), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form CoOF5 octahedra that share corners with three equivalent Co(3)OF3 tetrahedra, corners with three equivalent Co(5)OF3 tetrahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Co(2)O2F4 octahedra,  an edgeedge with one Co(1)O4F2 octahedra, and edges with two equivalent Li(1)O2F4 octahedra. The Co(4)-O(2) bond length is 1.93 Å. The Co(4)-F(1) bond length is 2.15 Å. The Co(4)-F(2) bond length is 2.14 Å. The Co(4)-F(3) bond length is 2.08 Å. The Co(4)-F(4) bond length is 2.12 Å. The Co(4)-F(5) bond length is 2.10 Å. In the fifth Co site, Co(5) is bonded to one O(1), one F(2), one F(4), and one F(5) atom to form CoOF3 tetrahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Li(3)F6 octahedra, corners with two equivalent Co(2)O2F4 octahedra, corners with two equivalent Co(1)O4F2 octahedra, corners with three equivalent Li(1)O2F4 octahedra, and corners with three equivalent Co(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 49-65°. The Co(5)-O(1) bond length is 1.87 Å. The Co(5)-F(2) bond length is 2.05 Å. The Co(5)-F(4) bond length is 2.02 Å. The Co(5)-F(5) bond length is 2.03 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Co(1), one Co(2), and one Co(5) atom to form a mixture of distorted corner and edge-sharing OLiCo3 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Co(1), one Co(3), and one Co(4) atom to form a mixture of distorted corner and edge-sharing OLiCo3 trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(2), one Co(3), and one Co(4) atom. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Co(1), one Co(2), one Co(4), and one Co(5) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(3), and one Co(4) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Co(4), and one Co(5) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Co(4), and one Co(5) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Co(3) atom.