Li3Co2OF5 crystallizes in the orthorhombic F222 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form LiO2F4 octahedra that share corners with two equivalent Co(1)O2F4 octahedra, corners with four equivalent Li(4)F6 octahedra, edges with two equivalent Co(1)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Co(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Co(3)O2F4 octahedra,  an edgeedge with one Co(2)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Co(1)O2F4 octahedra, and edges with three equivalent Co(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. In the third Li site, Li(3) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Co(2)F6 octahedra, corners with four equivalent Li(2)O2F4 octahedra, edges with two equivalent Co(2)F6 octahedra, edges with two equivalent Co(3)O2F4 octahedra, and edges with four equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth Li site, Li(4) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(4)F6 octahedra, corners with two equivalent Li(1)O2F4 octahedra,  an edgeedge with one Co(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Co(2)F6 octahedra, and edges with two equivalent Co(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form CoO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Co(3)O2F4 octahedra. The corner-sharing octahedra are not tilted. In the second Co site, Co(2) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form CoF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Co(3)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with four equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third Co site, Co(3) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form CoO2F4 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Co(2)F6 octahedra, corners with two equivalent Co(3)O2F4 octahedra,  an edgeedge with one Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Co(1)O2F4 octahedra, and edges with three equivalent Li(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. O(1) is bonded to one Li(1), two equivalent Li(2), one Co(1), and two equivalent Co(3) atoms to form OLi3Co3 octahedra that share corners with two equivalent O(1)Li3Co3 octahedra, corners with four equivalent F(3)Li3Co2 square pyramids, edges with two equivalent O(1)Li3Co3 octahedra, edges with two equivalent F(3)Li3Co2 square pyramids, and edges with eight equivalent F(1)Li3Co2 square pyramids. The corner-sharing octahedra are not tilted. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(4), one Co(1), and one Co(3) atom to form FLi3Co2 square pyramids that share corners with two equivalent F(3)Li3Co2 square pyramids, corners with five equivalent F(1)Li3Co2 square pyramids, edges with four equivalent O(1)Li3Co3 octahedra, edges with two equivalent F(1)Li3Co2 square pyramids, and edges with two equivalent F(3)Li3Co2 square pyramids. In the second F site, F(2) is bonded in a square co-planar geometry to one Li(3), two equivalent Li(4), and one Co(2) atom. In the third F site, F(3) is bonded to one Li(2), one Li(3), one Li(4), one Co(2), and one Co(3) atom to form FLi3Co2 square pyramids that share corners with two equivalent O(1)Li3Co3 octahedra, corners with two equivalent F(1)Li3Co2 square pyramids, corners with three equivalent F(3)Li3Co2 square pyramids,  an edgeedge with one O(1)Li3Co3 octahedra, edges with two equivalent F(1)Li3Co2 square pyramids, and edges with three equivalent F(3)Li3Co2 square pyramids. The corner-sharing octahedral tilt angles range from 2-7°.
Li3Co2OF5 crystallizes in the orthorhombic F222 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form LiO2F4 octahedra that share corners with two equivalent Co(1)O2F4 octahedra, corners with four equivalent Li(4)F6 octahedra, edges with two equivalent Co(1)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Co(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. Both Li(1)-O(1) bond lengths are 2.19 Å. All Li(1)-F(1) bond lengths are 2.09 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Co(3)O2F4 octahedra,  an edgeedge with one Co(2)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Co(1)O2F4 octahedra, and edges with three equivalent Co(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. Both Li(2)-O(1) bond lengths are 2.09 Å. Both Li(2)-F(1) bond lengths are 2.08 Å. Both Li(2)-F(3) bond lengths are 2.18 Å. In the third Li site, Li(3) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Co(2)F6 octahedra, corners with four equivalent Li(2)O2F4 octahedra, edges with two equivalent Co(2)F6 octahedra, edges with two equivalent Co(3)O2F4 octahedra, and edges with four equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. Both Li(3)-F(2) bond lengths are 2.23 Å. All Li(3)-F(3) bond lengths are 2.06 Å. In the fourth Li site, Li(4) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(4)F6 octahedra, corners with two equivalent Li(1)O2F4 octahedra,  an edgeedge with one Co(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Co(2)F6 octahedra, and edges with two equivalent Co(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. Both Li(4)-F(1) bond lengths are 2.25 Å. Both Li(4)-F(2) bond lengths are 1.99 Å. Both Li(4)-F(3) bond lengths are 1.95 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form CoO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Co(3)O2F4 octahedra. The corner-sharing octahedra are not tilted. Both Co(1)-O(1) bond lengths are 2.02 Å. All Co(1)-F(1) bond lengths are 2.11 Å. In the second Co site, Co(2) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form CoF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Co(3)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with four equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. Both Co(2)-F(2) bond lengths are 1.98 Å. All Co(2)-F(3) bond lengths are 2.12 Å. In the third Co site, Co(3) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form CoO2F4 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Co(2)F6 octahedra, corners with two equivalent Co(3)O2F4 octahedra,  an edgeedge with one Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Co(1)O2F4 octahedra, and edges with three equivalent Li(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Both Co(3)-O(1) bond lengths are 2.02 Å. Both Co(3)-F(1) bond lengths are 2.14 Å. Both Co(3)-F(3) bond lengths are 2.20 Å. O(1) is bonded to one Li(1), two equivalent Li(2), one Co(1), and two equivalent Co(3) atoms to form OLi3Co3 octahedra that share corners with two equivalent O(1)Li3Co3 octahedra, corners with four equivalent F(3)Li3Co2 square pyramids, edges with two equivalent O(1)Li3Co3 octahedra, edges with two equivalent F(3)Li3Co2 square pyramids, and edges with eight equivalent F(1)Li3Co2 square pyramids. The corner-sharing octahedra are not tilted. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(4), one Co(1), and one Co(3) atom to form FLi3Co2 square pyramids that share corners with two equivalent F(3)Li3Co2 square pyramids, corners with five equivalent F(1)Li3Co2 square pyramids, edges with four equivalent O(1)Li3Co3 octahedra, edges with two equivalent F(1)Li3Co2 square pyramids, and edges with two equivalent F(3)Li3Co2 square pyramids. In the second F site, F(2) is bonded in a square co-planar geometry to one Li(3), two equivalent Li(4), and one Co(2) atom. In the third F site, F(3) is bonded to one Li(2), one Li(3), one Li(4), one Co(2), and one Co(3) atom to form FLi3Co2 square pyramids that share corners with two equivalent O(1)Li3Co3 octahedra, corners with two equivalent F(1)Li3Co2 square pyramids, corners with three equivalent F(3)Li3Co2 square pyramids,  an edgeedge with one O(1)Li3Co3 octahedra, edges with two equivalent F(1)Li3Co2 square pyramids, and edges with three equivalent F(3)Li3Co2 square pyramids. The corner-sharing octahedral tilt angles range from 2-7°.