LiCo6(OF5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(2), one F(1), one F(4), one F(7), and one F(8) atom to form distorted LiO2F4 octahedra that share corners with two equivalent Co(5)OF5 octahedra, corners with two equivalent Co(6)OF5 octahedra, edges with two equivalent Co(1)OF5 octahedra, edges with two equivalent Co(2)OF5 octahedra, and faces with two equivalent Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 41-49°. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one F(1), one F(2), one F(4), one F(8), and one F(9) atom to form CoOF5 octahedra that share corners with four equivalent Co(4)O2F4 octahedra, corners with four equivalent Co(5)OF5 octahedra,  an edgeedge with one Co(3)F6 octahedra,  an edgeedge with one Co(2)OF5 octahedra, and edges with two equivalent Li(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-62°. In the second Co site, Co(2) is bonded to one O(1), one F(1), one F(10), one F(3), one F(7), and one F(8) atom to form CoOF5 octahedra that share corners with four equivalent Co(4)O2F4 octahedra, corners with four equivalent Co(6)OF5 octahedra,  an edgeedge with one Co(3)F6 octahedra,  an edgeedge with one Co(1)OF5 octahedra, and edges with two equivalent Li(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-62°. In the third Co site, Co(3) is bonded to one F(10), one F(2), one F(3), one F(5), one F(6), and one F(9) atom to form a mixture of corner and edge-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one F(1), one F(4), one F(7), and one F(8) atom to form CoO2F4 octahedra that share corners with four equivalent Co(1)OF5 octahedra, corners with four equivalent Co(2)OF5 octahedra,  an edgeedge with one Co(5)OF5 octahedra,  an edgeedge with one Co(6)OF5 octahedra, and faces with two equivalent Li(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-52°. In the fifth Co site, Co(5) is bonded to one O(2), one F(2), one F(4), one F(5), one F(6), and one F(9) atom to form CoOF5 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with four equivalent Co(3)F6 octahedra, corners with four equivalent Co(1)OF5 octahedra,  an edgeedge with one Co(4)O2F4 octahedra, and  an edgeedge with one Co(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-62°. In the sixth Co site, Co(6) is bonded to one O(1), one F(10), one F(3), one F(5), one F(6), and one F(7) atom to form CoOF5 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with four equivalent Co(3)F6 octahedra, corners with four equivalent Co(2)OF5 octahedra,  an edgeedge with one Co(4)O2F4 octahedra, and  an edgeedge with one Co(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 41-62°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Co(2), one Co(4), and one Co(6) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Co(1), one Co(4), and one Co(5) atom. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like 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 rectangular see-saw-like geometry to one Li(1), 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 rectangular see-saw-like geometry to one Li(1), one Co(2), one Co(4), and one Co(6) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Co(1), one Co(2), and one Co(4) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one Co(5) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(3), and one Co(6) atom.
LiCo6(OF5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(2), one F(1), one F(4), one F(7), and one F(8) atom to form distorted LiO2F4 octahedra that share corners with two equivalent Co(5)OF5 octahedra, corners with two equivalent Co(6)OF5 octahedra, edges with two equivalent Co(1)OF5 octahedra, edges with two equivalent Co(2)OF5 octahedra, and faces with two equivalent Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 41-49°. The Li(1)-O(1) bond length is 2.13 Å. The Li(1)-O(2) bond length is 2.12 Å. The Li(1)-F(1) bond length is 1.88 Å. The Li(1)-F(4) bond length is 2.05 Å. The Li(1)-F(7) bond length is 2.06 Å. The Li(1)-F(8) bond length is 1.87 Å. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one F(1), one F(2), one F(4), one F(8), and one F(9) atom to form CoOF5 octahedra that share corners with four equivalent Co(4)O2F4 octahedra, corners with four equivalent Co(5)OF5 octahedra,  an edgeedge with one Co(3)F6 octahedra,  an edgeedge with one Co(2)OF5 octahedra, and edges with two equivalent Li(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-62°. The Co(1)-O(2) bond length is 1.98 Å. The Co(1)-F(1) bond length is 2.11 Å. The Co(1)-F(2) bond length is 2.06 Å. The Co(1)-F(4) bond length is 2.21 Å. The Co(1)-F(8) bond length is 2.09 Å. The Co(1)-F(9) bond length is 2.03 Å. In the second Co site, Co(2) is bonded to one O(1), one F(1), one F(10), one F(3), one F(7), and one F(8) atom to form CoOF5 octahedra that share corners with four equivalent Co(4)O2F4 octahedra, corners with four equivalent Co(6)OF5 octahedra,  an edgeedge with one Co(3)F6 octahedra,  an edgeedge with one Co(1)OF5 octahedra, and edges with two equivalent Li(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-62°. The Co(2)-O(1) bond length is 1.98 Å. The Co(2)-F(1) bond length is 2.08 Å. The Co(2)-F(10) bond length is 2.06 Å. The Co(2)-F(3) bond length is 2.03 Å. The Co(2)-F(7) bond length is 2.21 Å. The Co(2)-F(8) bond length is 2.11 Å. In the third Co site, Co(3) is bonded to one F(10), one F(2), one F(3), one F(5), one F(6), and one F(9) atom to form a mixture of corner and edge-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The Co(3)-F(10) bond length is 2.08 Å. The Co(3)-F(2) bond length is 2.07 Å. The Co(3)-F(3) bond length is 2.08 Å. The Co(3)-F(5) bond length is 2.06 Å. The Co(3)-F(6) bond length is 2.06 Å. The Co(3)-F(9) bond length is 2.07 Å. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one F(1), one F(4), one F(7), and one F(8) atom to form CoO2F4 octahedra that share corners with four equivalent Co(1)OF5 octahedra, corners with four equivalent Co(2)OF5 octahedra,  an edgeedge with one Co(5)OF5 octahedra,  an edgeedge with one Co(6)OF5 octahedra, and faces with two equivalent Li(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-52°. The Co(4)-O(1) bond length is 1.83 Å. The Co(4)-O(2) bond length is 1.83 Å. The Co(4)-F(1) bond length is 2.12 Å. The Co(4)-F(4) bond length is 2.00 Å. The Co(4)-F(7) bond length is 2.00 Å. The Co(4)-F(8) bond length is 2.12 Å. In the fifth Co site, Co(5) is bonded to one O(2), one F(2), one F(4), one F(5), one F(6), and one F(9) atom to form CoOF5 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with four equivalent Co(3)F6 octahedra, corners with four equivalent Co(1)OF5 octahedra,  an edgeedge with one Co(4)O2F4 octahedra, and  an edgeedge with one Co(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-62°. The Co(5)-O(2) bond length is 2.00 Å. The Co(5)-F(2) bond length is 2.11 Å. The Co(5)-F(4) bond length is 2.21 Å. The Co(5)-F(5) bond length is 2.08 Å. The Co(5)-F(6) bond length is 2.10 Å. The Co(5)-F(9) bond length is 2.13 Å. In the sixth Co site, Co(6) is bonded to one O(1), one F(10), one F(3), one F(5), one F(6), and one F(7) atom to form CoOF5 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with four equivalent Co(3)F6 octahedra, corners with four equivalent Co(2)OF5 octahedra,  an edgeedge with one Co(4)O2F4 octahedra, and  an edgeedge with one Co(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 41-62°. The Co(6)-O(1) bond length is 2.00 Å. The Co(6)-F(10) bond length is 2.11 Å. The Co(6)-F(3) bond length is 2.13 Å. The Co(6)-F(5) bond length is 2.10 Å. The Co(6)-F(6) bond length is 2.08 Å. The Co(6)-F(7) bond length is 2.20 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Co(2), one Co(4), and one Co(6) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Co(1), one Co(4), and one Co(5) atom. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like 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 rectangular see-saw-like geometry to one Li(1), 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 rectangular see-saw-like geometry to one Li(1), one Co(2), one Co(4), and one Co(6) atom. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Co(1), one Co(2), and one Co(4) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one Co(5) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Co(2), one Co(3), and one Co(6) atom.