LiCo6(OF5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded in a 4-coordinate geometry to one Co(2), one Co(6), one O(1), one F(10), one F(3), and one F(5) atom. 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, and  an edgeedge with one Co(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. In the second Co site, Co(2) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one F(1), one F(10), one F(3), one F(7), and one F(8) atom. 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 distorted edge and corner-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. 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 a mixture of edge and corner-sharing CoO2F4 octahedra. The corner-sharing octahedral tilt angles range from 44-49°. 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 four equivalent Co(3)F6 octahedra, corners with four equivalent Co(1)OF5 octahedra, and  an edgeedge with one Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. In the sixth Co site, Co(6) is bonded in a 6-coordinate geometry to one Li(1), one O(1), one F(10), one F(3), one F(6), and one F(7) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like 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 trigonal planar geometry to 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 trigonal planar geometry to 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 4-coordinate geometry to one Li(1), 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 3-coordinate geometry to one Li(1), one Co(3), and one Co(5) 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 distorted trigonal planar geometry to one Co(2), one Co(4), and one Co(6) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to 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 4-coordinate geometry to one Li(1), 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 in a 4-coordinate geometry to one Co(2), one Co(6), one O(1), one F(10), one F(3), and one F(5) atom. The Li(1)-Co(2) bond length is 2.30 Å. The Li(1)-Co(6) bond length is 2.31 Å. The Li(1)-O(1) bond length is 1.88 Å. The Li(1)-F(10) bond length is 1.91 Å. The Li(1)-F(3) bond length is 1.89 Å. The Li(1)-F(5) bond length is 1.78 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, and  an edgeedge with one Co(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. The Co(1)-O(2) bond length is 1.94 Å. The Co(1)-F(1) bond length is 2.04 Å. The Co(1)-F(2) bond length is 2.09 Å. The Co(1)-F(4) bond length is 2.19 Å. The Co(1)-F(8) bond length is 2.04 Å. The Co(1)-F(9) bond length is 2.09 Å. In the second Co site, Co(2) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one F(1), one F(10), one F(3), one F(7), and one F(8) atom. The Co(2)-O(1) bond length is 2.05 Å. The Co(2)-F(1) bond length is 2.01 Å. The Co(2)-F(10) bond length is 2.32 Å. The Co(2)-F(3) bond length is 2.24 Å. The Co(2)-F(7) bond length is 2.06 Å. The Co(2)-F(8) bond length is 2.01 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 distorted edge and corner-sharing CoF6 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. The Co(3)-F(10) bond length is 2.17 Å. The Co(3)-F(2) bond length is 2.02 Å. The Co(3)-F(3) bond length is 2.26 Å. The Co(3)-F(5) bond length is 2.06 Å. The Co(3)-F(6) bond length is 2.00 Å. The Co(3)-F(9) bond length is 2.03 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 a mixture of edge and corner-sharing CoO2F4 octahedra. The corner-sharing octahedral tilt angles range from 44-49°. The Co(4)-O(1) bond length is 1.95 Å. The Co(4)-O(2) bond length is 1.85 Å. The Co(4)-F(1) bond length is 2.08 Å. The Co(4)-F(4) bond length is 2.09 Å. The Co(4)-F(7) bond length is 2.22 Å. The Co(4)-F(8) bond length is 2.07 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 four equivalent Co(3)F6 octahedra, corners with four equivalent Co(1)OF5 octahedra, and  an edgeedge with one Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. The Co(5)-O(2) bond length is 2.01 Å. The Co(5)-F(2) bond length is 2.08 Å. The Co(5)-F(4) bond length is 2.08 Å. The Co(5)-F(5) bond length is 2.07 Å. The Co(5)-F(6) bond length is 2.27 Å. The Co(5)-F(9) bond length is 2.08 Å. In the sixth Co site, Co(6) is bonded in a 6-coordinate geometry to one Li(1), one O(1), one F(10), one F(3), one F(6), and one F(7) atom. The Co(6)-O(1) bond length is 2.05 Å. The Co(6)-F(10) bond length is 2.15 Å. The Co(6)-F(3) bond length is 2.16 Å. The Co(6)-F(6) bond length is 2.01 Å. The Co(6)-F(7) bond length is 1.96 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like 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 trigonal planar geometry to 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 trigonal planar geometry to 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 4-coordinate geometry to one Li(1), 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 3-coordinate geometry to one Li(1), one Co(3), and one Co(5) 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 distorted trigonal planar geometry to one Co(2), one Co(4), and one Co(6) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to 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 4-coordinate geometry to one Li(1), one Co(2), one Co(3), and one Co(6) atom.