LiCo2OF3 is Spinel-derived structured and crystallizes in the monoclinic Pm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one F(9), two equivalent F(1), and two equivalent F(6) atoms to form LiOF5 octahedra that share  a cornercorner with one Co(4)O2F2 tetrahedra,  a cornercorner with one Co(7)OF3 tetrahedra, corners with two equivalent Co(3)F4 tetrahedra, corners with two equivalent Co(6)OF3 tetrahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, and edges with two equivalent Co(2)O3F3 octahedra. In the second Li site, Li(2) is bonded to one F(3), one F(5), two equivalent F(1), and two equivalent F(6) atoms to form LiF6 octahedra that share  a cornercorner with one Co(4)O2F2 tetrahedra,  a cornercorner with one Co(7)OF3 tetrahedra, corners with two equivalent Co(3)F4 tetrahedra, corners with two equivalent Co(6)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with two equivalent Co(2)O3F3 octahedra. In the third Li site, Li(3) is bonded to one F(4), one F(5), one F(6), one F(7), one F(8), and one F(9) atom to form LiF6 octahedra that share  a cornercorner with one Co(6)OF3 tetrahedra,  a cornercorner with one Co(7)OF3 tetrahedra, corners with two equivalent Co(3)F4 tetrahedra, corners with two equivalent Co(4)O2F2 tetrahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Co(5)O2F4 octahedra,  an edgeedge with one Co(1)O3F3 octahedra, and edges with two equivalent Li(3)F6 octahedra. There are seven inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), two equivalent O(3), one F(8), and two equivalent F(7) atoms to form CoO3F3 octahedra that share  a cornercorner with one Co(3)F4 tetrahedra,  a cornercorner with one Co(6)OF3 tetrahedra, corners with two equivalent Co(4)O2F2 tetrahedra, corners with two equivalent Co(7)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Co(5)O2F4 octahedra, and edges with two equivalent Co(2)O3F3 octahedra. In the second Co site, Co(2) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(3) atom to form CoO3F3 octahedra that share  a cornercorner with one Co(3)F4 tetrahedra,  a cornercorner with one Co(4)O2F2 tetrahedra, corners with two equivalent Co(6)OF3 tetrahedra, corners with two equivalent Co(7)OF3 tetrahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Co(5)O2F4 octahedra,  an edgeedge with one Co(1)O3F3 octahedra, and edges with two equivalent Co(2)O3F3 octahedra. In the third Co site, Co(3) is bonded to one F(4), one F(8), and two equivalent F(1) atoms to form CoF4 tetrahedra that share  a cornercorner with one Co(5)O2F4 octahedra,  a cornercorner with one Co(1)O3F3 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Co(2)O3F3 octahedra, and corners with four equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 56-65°. In the fourth Co site, Co(4) is bonded to two equivalent O(3), one F(5), and one F(9) atom to form CoO2F2 tetrahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Li(1)OF5 octahedra, corners with two equivalent Co(5)O2F4 octahedra, corners with two equivalent Co(1)O3F3 octahedra, corners with two equivalent Co(2)O3F3 octahedra, and corners with four equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 54-63°. In the fifth Co site, Co(5) is bonded to two equivalent O(3), one F(2), one F(4), and two equivalent F(7) atoms to form CoO2F4 octahedra that share  a cornercorner with one Co(3)F4 tetrahedra,  a cornercorner with one Co(6)OF3 tetrahedra, corners with two equivalent Co(4)O2F2 tetrahedra, corners with two equivalent Co(7)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Co(1)O3F3 octahedra, and edges with two equivalent Co(2)O3F3 octahedra. In the sixth Co site, Co(6) is bonded to one O(1), one F(2), and two equivalent F(6) atoms to form CoOF3 tetrahedra that share  a cornercorner with one Co(5)O2F4 octahedra,  a cornercorner with one Co(1)O3F3 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(1)OF5 octahedra, and corners with four equivalent Co(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 51-61°. In the seventh Co site, Co(7) is bonded to one O(2), one F(3), and two equivalent F(7) atoms to form CoOF3 tetrahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Li(1)OF5 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Co(5)O2F4 octahedra, corners with two equivalent Co(1)O3F3 octahedra, and corners with four equivalent Co(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 55-63°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Co(1), one Co(6), and two equivalent Co(2) atoms to form OCo4 trigonal pyramids that share corners with two equivalent O(2)LiCo3 tetrahedra,  a cornercorner with one F(8)Li2Co2 trigonal pyramid, and corners with two equivalent F(7)LiCo3 trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Co(7), and two equivalent Co(2) atoms to form distorted OLiCo3 tetrahedra that share corners with two equivalent O(1)Co4 trigonal pyramids and corners with two equivalent F(7)LiCo3 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Co(1), one Co(2), one Co(4), and one Co(5) atom. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Co(2), and one Co(3) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Co(5), one Co(6), and two equivalent Co(2) atoms. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Co(7), and two equivalent Co(2) atoms. In the fourth F site, F(4) is bonded to two equivalent Li(3), one Co(3), and one Co(5) atom to form distorted FLi2Co2 trigonal pyramids that share  a cornercorner with one F(8)Li2Co2 trigonal pyramid,  an edgeedge with one F(8)Li2Co2 trigonal pyramid, and edges with two equivalent F(7)LiCo3 trigonal pyramids. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(3), and one Co(4) 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(6) atom. In the seventh F site, F(7) is bonded to one Li(3), one Co(1), one Co(5), and one Co(7) atom to form distorted FLiCo3 trigonal pyramids that share  a cornercorner with one O(2)LiCo3 tetrahedra,  a cornercorner with one O(1)Co4 trigonal pyramid,  a cornercorner with one F(7)LiCo3 trigonal pyramid,  an edgeedge with one F(4)Li2Co2 trigonal pyramid,  an edgeedge with one F(8)Li2Co2 trigonal pyramid, and  an edgeedge with one F(7)LiCo3 trigonal pyramid. In the eighth F site, F(8) is bonded to two equivalent Li(3), one Co(1), and one Co(3) atom to form distorted FLi2Co2 trigonal pyramids that share  a cornercorner with one O(1)Co4 trigonal pyramid,  a cornercorner with one F(4)Li2Co2 trigonal pyramid,  an edgeedge with one F(4)Li2Co2 trigonal pyramid, and edges with two equivalent F(7)LiCo3 trigonal pyramids. In the ninth F site, F(9) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(3), and one Co(4) atom.
LiCo2OF3 is Spinel-derived structured and crystallizes in the monoclinic Pm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one F(9), two equivalent F(1), and two equivalent F(6) atoms to form LiOF5 octahedra that share  a cornercorner with one Co(4)O2F2 tetrahedra,  a cornercorner with one Co(7)OF3 tetrahedra, corners with two equivalent Co(3)F4 tetrahedra, corners with two equivalent Co(6)OF3 tetrahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, and edges with two equivalent Co(2)O3F3 octahedra. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-F(9) bond length is 2.07 Å. Both Li(1)-F(1) bond lengths are 2.18 Å. Both Li(1)-F(6) bond lengths are 2.07 Å. In the second Li site, Li(2) is bonded to one F(3), one F(5), two equivalent F(1), and two equivalent F(6) atoms to form LiF6 octahedra that share  a cornercorner with one Co(4)O2F2 tetrahedra,  a cornercorner with one Co(7)OF3 tetrahedra, corners with two equivalent Co(3)F4 tetrahedra, corners with two equivalent Co(6)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with two equivalent Co(2)O3F3 octahedra. The Li(2)-F(3) bond length is 2.08 Å. The Li(2)-F(5) bond length is 1.99 Å. Both Li(2)-F(1) bond lengths are 2.11 Å. Both Li(2)-F(6) bond lengths are 2.07 Å. In the third Li site, Li(3) is bonded to one F(4), one F(5), one F(6), one F(7), one F(8), and one F(9) atom to form LiF6 octahedra that share  a cornercorner with one Co(6)OF3 tetrahedra,  a cornercorner with one Co(7)OF3 tetrahedra, corners with two equivalent Co(3)F4 tetrahedra, corners with two equivalent Co(4)O2F2 tetrahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Co(5)O2F4 octahedra,  an edgeedge with one Co(1)O3F3 octahedra, and edges with two equivalent Li(3)F6 octahedra. The Li(3)-F(4) bond length is 2.14 Å. The Li(3)-F(5) bond length is 2.03 Å. The Li(3)-F(6) bond length is 1.97 Å. The Li(3)-F(7) bond length is 2.11 Å. The Li(3)-F(8) bond length is 2.16 Å. The Li(3)-F(9) bond length is 2.04 Å. There are seven inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), two equivalent O(3), one F(8), and two equivalent F(7) atoms to form CoO3F3 octahedra that share  a cornercorner with one Co(3)F4 tetrahedra,  a cornercorner with one Co(6)OF3 tetrahedra, corners with two equivalent Co(4)O2F2 tetrahedra, corners with two equivalent Co(7)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Co(5)O2F4 octahedra, and edges with two equivalent Co(2)O3F3 octahedra. The Co(1)-O(1) bond length is 2.03 Å. Both Co(1)-O(3) bond lengths are 2.04 Å. The Co(1)-F(8) bond length is 2.14 Å. Both Co(1)-F(7) bond lengths are 2.18 Å. In the second Co site, Co(2) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(3) atom to form CoO3F3 octahedra that share  a cornercorner with one Co(3)F4 tetrahedra,  a cornercorner with one Co(4)O2F2 tetrahedra, corners with two equivalent Co(6)OF3 tetrahedra, corners with two equivalent Co(7)OF3 tetrahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Co(5)O2F4 octahedra,  an edgeedge with one Co(1)O3F3 octahedra, and edges with two equivalent Co(2)O3F3 octahedra. The Co(2)-O(1) bond length is 2.01 Å. The Co(2)-O(2) bond length is 1.97 Å. The Co(2)-O(3) bond length is 2.05 Å. The Co(2)-F(1) bond length is 2.18 Å. The Co(2)-F(2) bond length is 2.30 Å. The Co(2)-F(3) bond length is 2.22 Å. In the third Co site, Co(3) is bonded to one F(4), one F(8), and two equivalent F(1) atoms to form CoF4 tetrahedra that share  a cornercorner with one Co(5)O2F4 octahedra,  a cornercorner with one Co(1)O3F3 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Co(2)O3F3 octahedra, and corners with four equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 56-65°. The Co(3)-F(4) bond length is 1.97 Å. The Co(3)-F(8) bond length is 1.97 Å. Both Co(3)-F(1) bond lengths are 1.95 Å. In the fourth Co site, Co(4) is bonded to two equivalent O(3), one F(5), and one F(9) atom to form CoO2F2 tetrahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Li(1)OF5 octahedra, corners with two equivalent Co(5)O2F4 octahedra, corners with two equivalent Co(1)O3F3 octahedra, corners with two equivalent Co(2)O3F3 octahedra, and corners with four equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 54-63°. Both Co(4)-O(3) bond lengths are 1.95 Å. The Co(4)-F(5) bond length is 2.02 Å. The Co(4)-F(9) bond length is 2.03 Å. In the fifth Co site, Co(5) is bonded to two equivalent O(3), one F(2), one F(4), and two equivalent F(7) atoms to form CoO2F4 octahedra that share  a cornercorner with one Co(3)F4 tetrahedra,  a cornercorner with one Co(6)OF3 tetrahedra, corners with two equivalent Co(4)O2F2 tetrahedra, corners with two equivalent Co(7)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Co(1)O3F3 octahedra, and edges with two equivalent Co(2)O3F3 octahedra. Both Co(5)-O(3) bond lengths are 1.97 Å. The Co(5)-F(2) bond length is 2.23 Å. The Co(5)-F(4) bond length is 2.11 Å. Both Co(5)-F(7) bond lengths are 2.17 Å. In the sixth Co site, Co(6) is bonded to one O(1), one F(2), and two equivalent F(6) atoms to form CoOF3 tetrahedra that share  a cornercorner with one Co(5)O2F4 octahedra,  a cornercorner with one Co(1)O3F3 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(1)OF5 octahedra, and corners with four equivalent Co(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 51-61°. The Co(6)-O(1) bond length is 1.90 Å. The Co(6)-F(2) bond length is 2.03 Å. Both Co(6)-F(6) bond lengths are 1.98 Å. In the seventh Co site, Co(7) is bonded to one O(2), one F(3), and two equivalent F(7) atoms to form CoOF3 tetrahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Li(1)OF5 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Co(5)O2F4 octahedra, corners with two equivalent Co(1)O3F3 octahedra, and corners with four equivalent Co(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 55-63°. The Co(7)-O(2) bond length is 1.87 Å. The Co(7)-F(3) bond length is 2.02 Å. Both Co(7)-F(7) bond lengths are 2.05 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Co(1), one Co(6), and two equivalent Co(2) atoms to form OCo4 trigonal pyramids that share corners with two equivalent O(2)LiCo3 tetrahedra,  a cornercorner with one F(8)Li2Co2 trigonal pyramid, and corners with two equivalent F(7)LiCo3 trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Co(7), and two equivalent Co(2) atoms to form distorted OLiCo3 tetrahedra that share corners with two equivalent O(1)Co4 trigonal pyramids and corners with two equivalent F(7)LiCo3 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Co(1), one Co(2), one Co(4), and one Co(5) atom. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Co(2), and one Co(3) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Co(5), one Co(6), and two equivalent Co(2) atoms. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Co(7), and two equivalent Co(2) atoms. In the fourth F site, F(4) is bonded to two equivalent Li(3), one Co(3), and one Co(5) atom to form distorted FLi2Co2 trigonal pyramids that share  a cornercorner with one F(8)Li2Co2 trigonal pyramid,  an edgeedge with one F(8)Li2Co2 trigonal pyramid, and edges with two equivalent F(7)LiCo3 trigonal pyramids. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(3), and one Co(4) 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(6) atom. In the seventh F site, F(7) is bonded to one Li(3), one Co(1), one Co(5), and one Co(7) atom to form distorted FLiCo3 trigonal pyramids that share  a cornercorner with one O(2)LiCo3 tetrahedra,  a cornercorner with one O(1)Co4 trigonal pyramid,  a cornercorner with one F(7)LiCo3 trigonal pyramid,  an edgeedge with one F(4)Li2Co2 trigonal pyramid,  an edgeedge with one F(8)Li2Co2 trigonal pyramid, and  an edgeedge with one F(7)LiCo3 trigonal pyramid. In the eighth F site, F(8) is bonded to two equivalent Li(3), one Co(1), and one Co(3) atom to form distorted FLi2Co2 trigonal pyramids that share  a cornercorner with one O(1)Co4 trigonal pyramid,  a cornercorner with one F(4)Li2Co2 trigonal pyramid,  an edgeedge with one F(4)Li2Co2 trigonal pyramid, and edges with two equivalent F(7)LiCo3 trigonal pyramids. In the ninth F site, F(9) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(3), and one Co(4) atom.