LiCo6(OF5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one F(2), one F(4), one F(5), and one F(9) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one Co(4)O2F4 octahedra,  a cornercorner with one Co(6)OF5 octahedra,  a faceface with one Co(3)F6 octahedra, and  a faceface with one Co(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 21-29°. 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 distorted CoOF5 octahedra that share corners with four equivalent Co(4)O2F4 octahedra,  an edgeedge with one Co(3)F6 octahedra,  an edgeedge with one Co(2)OF5 octahedra, and  a faceface with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 47-56°. 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, and  an edgeedge with one Co(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-56°. 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 distorted CoF6 octahedra that share corners with four equivalent Co(6)OF5 octahedra,  an edgeedge with one Co(1)OF5 octahedra,  an edgeedge with one Co(2)OF5 octahedra, and  a faceface with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 46-55°. 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 distorted CoO2F4 octahedra that share corners with four equivalent Co(1)OF5 octahedra, corners with four equivalent Co(2)OF5 octahedra,  a cornercorner with one Li(1)F4 trigonal pyramid, and  an edgeedge with one Co(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-56°. In the fifth Co site, Co(5) is bonded in a 5-coordinate geometry to one O(2), one F(2), one F(4), one F(6), and one F(9) atom. 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 four equivalent Co(3)F6 octahedra, corners with four equivalent Co(2)OF5 octahedra,  a cornercorner with one Li(1)F4 trigonal pyramid, and  an edgeedge with one Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-56°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted 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 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 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 4-coordinate geometry to one Li(1), 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 4-coordinate 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 3-coordinate geometry to one Li(1), one Co(3), 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 distorted T-shaped geometry to one Co(2), one Co(4), and one Co(6) atom. In the eighth F site, F(8) is bonded in a 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 4-coordinate geometry to one Li(1), 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 F(2), one F(4), one F(5), and one F(9) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one Co(4)O2F4 octahedra,  a cornercorner with one Co(6)OF5 octahedra,  a faceface with one Co(3)F6 octahedra, and  a faceface with one Co(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 21-29°. The Li(1)-F(2) bond length is 2.00 Å. The Li(1)-F(4) bond length is 1.78 Å. The Li(1)-F(5) bond length is 1.79 Å. The Li(1)-F(9) bond length is 1.93 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 distorted CoOF5 octahedra that share corners with four equivalent Co(4)O2F4 octahedra,  an edgeedge with one Co(3)F6 octahedra,  an edgeedge with one Co(2)OF5 octahedra, and  a faceface with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 47-56°. The Co(1)-O(2) bond length is 1.93 Å. The Co(1)-F(1) bond length is 2.02 Å. The Co(1)-F(2) bond length is 2.31 Å. The Co(1)-F(4) bond length is 2.17 Å. The Co(1)-F(8) bond length is 2.02 Å. The Co(1)-F(9) bond length is 2.35 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, and  an edgeedge with one Co(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-56°. The Co(2)-O(1) bond length is 2.00 Å. The Co(2)-F(1) bond length is 2.05 Å. The Co(2)-F(10) bond length is 2.10 Å. The Co(2)-F(3) bond length is 2.10 Å. The Co(2)-F(7) bond length is 2.13 Å. The Co(2)-F(8) bond length is 2.05 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 distorted CoF6 octahedra that share corners with four equivalent Co(6)OF5 octahedra,  an edgeedge with one Co(1)OF5 octahedra,  an edgeedge with one Co(2)OF5 octahedra, and  a faceface with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 46-55°. The Co(3)-F(10) bond length is 2.02 Å. The Co(3)-F(2) bond length is 2.23 Å. The Co(3)-F(3) bond length is 2.02 Å. The Co(3)-F(5) bond length is 2.04 Å. The Co(3)-F(6) bond length is 2.00 Å. The Co(3)-F(9) bond length is 2.23 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 distorted CoO2F4 octahedra that share corners with four equivalent Co(1)OF5 octahedra, corners with four equivalent Co(2)OF5 octahedra,  a cornercorner with one Li(1)F4 trigonal pyramid, and  an edgeedge with one Co(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-56°. The Co(4)-O(1) bond length is 1.80 Å. The Co(4)-O(2) bond length is 1.90 Å. The Co(4)-F(1) bond length is 2.05 Å. The Co(4)-F(4) bond length is 2.45 Å. The Co(4)-F(7) bond length is 2.10 Å. The Co(4)-F(8) bond length is 2.05 Å. In the fifth Co site, Co(5) is bonded in a 5-coordinate geometry to one O(2), one F(2), one F(4), one F(6), and one F(9) atom. The Co(5)-O(2) bond length is 1.86 Å. The Co(5)-F(2) bond length is 2.15 Å. The Co(5)-F(4) bond length is 2.33 Å. The Co(5)-F(6) bond length is 2.01 Å. The Co(5)-F(9) bond length is 2.14 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 four equivalent Co(3)F6 octahedra, corners with four equivalent Co(2)OF5 octahedra,  a cornercorner with one Li(1)F4 trigonal pyramid, and  an edgeedge with one Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-56°. The Co(6)-O(1) bond length is 2.04 Å. The Co(6)-F(10) bond length is 2.04 Å. The Co(6)-F(3) bond length is 2.04 Å. The Co(6)-F(5) bond length is 2.06 Å. The Co(6)-F(6) bond length is 2.34 Å. The Co(6)-F(7) bond length is 2.08 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted 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 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 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 4-coordinate geometry to one Li(1), 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 4-coordinate 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 3-coordinate geometry to one Li(1), one Co(3), 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 distorted T-shaped geometry to one Co(2), one Co(4), and one Co(6) atom. In the eighth F site, F(8) is bonded in a 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 4-coordinate geometry to one Li(1), 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.