LiCo5O3F5 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(3), one F(3), two equivalent F(1), and two equivalent F(2) atoms to form LiOF5 octahedra that share corners with three equivalent Co(4)O2F2 tetrahedra, corners with three equivalent Co(2)OF3 tetrahedra, edges with two equivalent Co(3)O2F4 octahedra, and edges with four equivalent Co(1)O3F3 octahedra. There are four inequivalent Co sites. In the first Co site, Co(1) 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 corners with three equivalent Co(4)O2F2 tetrahedra, corners with three equivalent Co(2)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Co(3)O2F4 octahedra, and edges with two equivalent Co(1)O3F3 octahedra. In the second Co site, Co(2) is bonded to one O(2), one F(3), and two equivalent F(2) atoms to form CoOF3 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Co(3)O2F4 octahedra, and corners with six equivalent Co(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. In the third Co site, Co(3) is bonded to one O(1), one O(2), two equivalent F(1), and two equivalent F(2) atoms to form CoO2F4 octahedra that share corners with three equivalent Co(4)O2F2 tetrahedra, corners with three equivalent Co(2)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with four equivalent Co(1)O3F3 octahedra. In the fourth Co site, Co(4) is bonded to one O(1), one O(3), and two equivalent F(1) atoms to form CoO2F2 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Co(3)O2F4 octahedra, and corners with six equivalent Co(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 49-64°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Co(3), one Co(4), and two equivalent Co(1) atoms to form distorted OCo4 tetrahedra that share corners with three equivalent O(2)Co4 tetrahedra,  a cornercorner with one O(3)LiCo3 trigonal pyramid, and  an edgeedge with one O(3)LiCo3 trigonal pyramid. In the second O site, O(2) is bonded to one Co(2), one Co(3), and two equivalent Co(1) atoms to form OCo4 tetrahedra that share corners with three equivalent O(1)Co4 tetrahedra and corners with two equivalent O(3)LiCo3 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), one Co(4), and two equivalent Co(1) atoms to form a mixture of distorted edge and corner-sharing OLiCo3 trigonal pyramids. There are three 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(1), one Co(3), and one Co(4) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(1), one Co(2), and one Co(3) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(2), and two equivalent Co(1) atoms.
LiCo5O3F5 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(3), one F(3), two equivalent F(1), and two equivalent F(2) atoms to form LiOF5 octahedra that share corners with three equivalent Co(4)O2F2 tetrahedra, corners with three equivalent Co(2)OF3 tetrahedra, edges with two equivalent Co(3)O2F4 octahedra, and edges with four equivalent Co(1)O3F3 octahedra. The Li(1)-O(3) bond length is 1.99 Å. The Li(1)-F(3) bond length is 2.19 Å. Both Li(1)-F(1) bond lengths are 2.06 Å. Both Li(1)-F(2) bond lengths are 2.07 Å. There are four inequivalent Co sites. In the first Co site, Co(1) 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 corners with three equivalent Co(4)O2F2 tetrahedra, corners with three equivalent Co(2)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Co(3)O2F4 octahedra, and edges with two equivalent Co(1)O3F3 octahedra. The Co(1)-O(1) bond length is 2.03 Å. The Co(1)-O(2) bond length is 2.02 Å. The Co(1)-O(3) bond length is 2.00 Å. The Co(1)-F(1) bond length is 2.27 Å. The Co(1)-F(2) bond length is 2.20 Å. The Co(1)-F(3) bond length is 2.24 Å. In the second Co site, Co(2) is bonded to one O(2), one F(3), and two equivalent F(2) atoms to form CoOF3 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Co(3)O2F4 octahedra, and corners with six equivalent Co(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 53-64°. The Co(2)-O(2) bond length is 1.91 Å. The Co(2)-F(3) bond length is 2.02 Å. Both Co(2)-F(2) bond lengths are 2.02 Å. In the third Co site, Co(3) is bonded to one O(1), one O(2), two equivalent F(1), and two equivalent F(2) atoms to form CoO2F4 octahedra that share corners with three equivalent Co(4)O2F2 tetrahedra, corners with three equivalent Co(2)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with four equivalent Co(1)O3F3 octahedra. The Co(3)-O(1) bond length is 1.98 Å. The Co(3)-O(2) bond length is 2.00 Å. Both Co(3)-F(1) bond lengths are 2.16 Å. Both Co(3)-F(2) bond lengths are 2.19 Å. In the fourth Co site, Co(4) is bonded to one O(1), one O(3), and two equivalent F(1) atoms to form CoO2F2 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Co(3)O2F4 octahedra, and corners with six equivalent Co(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 49-64°. The Co(4)-O(1) bond length is 1.96 Å. The Co(4)-O(3) bond length is 1.90 Å. Both Co(4)-F(1) bond lengths are 2.06 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Co(3), one Co(4), and two equivalent Co(1) atoms to form distorted OCo4 tetrahedra that share corners with three equivalent O(2)Co4 tetrahedra,  a cornercorner with one O(3)LiCo3 trigonal pyramid, and  an edgeedge with one O(3)LiCo3 trigonal pyramid. In the second O site, O(2) is bonded to one Co(2), one Co(3), and two equivalent Co(1) atoms to form OCo4 tetrahedra that share corners with three equivalent O(1)Co4 tetrahedra and corners with two equivalent O(3)LiCo3 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), one Co(4), and two equivalent Co(1) atoms to form a mixture of distorted edge and corner-sharing OLiCo3 trigonal pyramids. There are three 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(1), one Co(3), and one Co(4) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(1), one Co(2), and one Co(3) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(2), and two equivalent Co(1) atoms.