LiCo6(OF5)2 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one F(7), and two equivalent F(1) atoms. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form distorted CoOF5 octahedra that share corners with four equivalent Co(5)OF5 octahedra,  an edgeedge with one Co(3)F6 octahedra, and  an edgeedge with one Co(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-68°. In the second Co site, Co(2) is bonded to one O(1), one F(7), two equivalent F(1), and two equivalent F(3) atoms to form distorted CoOF5 octahedra that share corners with four equivalent Co(6)OF5 octahedra,  an edgeedge with one Co(3)F6 octahedra, and  an edgeedge with one Co(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 31-64°. In the third Co site, Co(3) is bonded to one F(5), one F(6), two equivalent F(2), and two equivalent F(3) atoms to form a mixture of corner and edge-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. In the fourth Co site, Co(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(4), and two equivalent F(1) atoms. In the fifth Co site, Co(5) is bonded to one O(2), one F(4), one F(5), one F(6), and two equivalent F(2) atoms to form CoOF5 octahedra that share corners with four equivalent Co(3)F6 octahedra, corners with four equivalent Co(1)OF5 octahedra, and  an edgeedge with one Co(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-68°. In the sixth Co site, Co(6) is bonded to one O(1), one F(5), one F(6), one F(7), and two equivalent F(3) atoms to form CoOF5 octahedra that share corners with four equivalent Co(3)F6 octahedra, corners with four equivalent Co(2)OF5 octahedra, and  an edgeedge with one Co(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 31-64°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Co(2), one Co(4), and one Co(6) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(1), one Co(4), and one Co(5) atom. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one Co(1), one Co(2), and one Co(4) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one Co(5) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(3), and one Co(6) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Co(1), one Co(4), and one Co(5) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Co(3), one Co(5), and one Co(6) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Co(3), one Co(5), and one Co(6) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Li(1), one Co(2), and one Co(6) atom.
LiCo6(OF5)2 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one F(7), and two equivalent F(1) atoms. The Li(1)-O(2) bond length is 1.89 Å. The Li(1)-F(7) bond length is 1.73 Å. Both Li(1)-F(1) bond lengths are 1.89 Å. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form distorted CoOF5 octahedra that share corners with four equivalent Co(5)OF5 octahedra,  an edgeedge with one Co(3)F6 octahedra, and  an edgeedge with one Co(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-68°. The Co(1)-O(2) bond length is 2.06 Å. The Co(1)-F(4) bond length is 2.09 Å. Both Co(1)-F(1) bond lengths are 2.16 Å. Both Co(1)-F(2) bond lengths are 2.02 Å. In the second Co site, Co(2) is bonded to one O(1), one F(7), two equivalent F(1), and two equivalent F(3) atoms to form distorted CoOF5 octahedra that share corners with four equivalent Co(6)OF5 octahedra,  an edgeedge with one Co(3)F6 octahedra, and  an edgeedge with one Co(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 31-64°. The Co(2)-O(1) bond length is 1.94 Å. The Co(2)-F(7) bond length is 2.06 Å. Both Co(2)-F(1) bond lengths are 2.30 Å. Both Co(2)-F(3) bond lengths are 2.04 Å. In the third Co site, Co(3) is bonded to one F(5), one F(6), two equivalent F(2), and two equivalent F(3) atoms to form a mixture of corner and edge-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. The Co(3)-F(5) bond length is 2.09 Å. The Co(3)-F(6) bond length is 2.07 Å. Both Co(3)-F(2) bond lengths are 2.08 Å. Both Co(3)-F(3) bond lengths are 2.07 Å. In the fourth Co site, Co(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(4), and two equivalent F(1) atoms. The Co(4)-O(1) bond length is 1.80 Å. The Co(4)-O(2) bond length is 1.87 Å. The Co(4)-F(4) bond length is 1.96 Å. Both Co(4)-F(1) bond lengths are 2.19 Å. In the fifth Co site, Co(5) is bonded to one O(2), one F(4), one F(5), one F(6), and two equivalent F(2) atoms to form CoOF5 octahedra that share corners with four equivalent Co(3)F6 octahedra, corners with four equivalent Co(1)OF5 octahedra, and  an edgeedge with one Co(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-68°. The Co(5)-O(2) bond length is 2.08 Å. The Co(5)-F(4) bond length is 2.13 Å. The Co(5)-F(5) bond length is 2.13 Å. The Co(5)-F(6) bond length is 2.08 Å. Both Co(5)-F(2) bond lengths are 2.07 Å. In the sixth Co site, Co(6) is bonded to one O(1), one F(5), one F(6), one F(7), and two equivalent F(3) atoms to form CoOF5 octahedra that share corners with four equivalent Co(3)F6 octahedra, corners with four equivalent Co(2)OF5 octahedra, and  an edgeedge with one Co(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 31-64°. The Co(6)-O(1) bond length is 2.12 Å. The Co(6)-F(5) bond length is 2.08 Å. The Co(6)-F(6) bond length is 2.16 Å. The Co(6)-F(7) bond length is 2.04 Å. Both Co(6)-F(3) bond lengths are 2.07 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Co(2), one Co(4), and one Co(6) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(1), one Co(4), and one Co(5) atom. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one Co(1), one Co(2), and one Co(4) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one Co(5) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(3), and one Co(6) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Co(1), one Co(4), and one Co(5) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Co(3), one Co(5), and one Co(6) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Co(3), one Co(5), and one Co(6) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Li(1), one Co(2), and one Co(6) atom.