LiCo6(OF5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one F(10), one F(5), one F(6), and one F(9) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one Co(1)OF5 octahedra,  a cornercorner with one Co(2)OF5 octahedra, corners with two equivalent Co(3)F6 octahedra, and  an edgeedge with one Co(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 3-59°. 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  a cornercorner with one Li(1)F4 tetrahedra, corners with three equivalent Co(4)O2F3 trigonal bipyramids,  an edgeedge with one Co(3)F6 octahedra, and  an edgeedge with one Co(2)OF5 octahedra. 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  a cornercorner with one Li(1)F4 tetrahedra, corners with three equivalent Co(4)O2F3 trigonal bipyramids,  an edgeedge with one Co(3)F6 octahedra, and  an edgeedge with one Co(1)OF5 octahedra. 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 CoF6 octahedra that share corners with two equivalent Li(1)F4 tetrahedra,  an edgeedge with one Co(1)OF5 octahedra,  an edgeedge with one Co(2)OF5 octahedra, and  an edgeedge with one Li(1)F4 tetrahedra. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one F(4), one F(7), and one F(8) atom to form distorted corner-sharing CoO2F3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 44-51°. 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(5), and one F(6) atom. In the sixth Co site, Co(6) is bonded in a 5-coordinate geometry to one O(1), one F(3), one F(5), 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 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 water-like geometry to one Co(1) and one Co(2) 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 4-coordinate geometry to one Li(1), one Co(3), one Co(5), and one Co(6) atom. In the sixth F site, F(6) is bonded in a distorted trigonal pyramidal geometry to one Li(1), 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 distorted T-shaped geometry to one Co(1), one Co(2), and one Co(4) atom. In the ninth F site, F(9) is bonded in a T-shaped geometry to one Li(1), one Co(1), and one Co(3) atom. In the tenth F site, F(10) is bonded in a T-shaped geometry to one Li(1), one Co(2), and one Co(3) atom.
LiCo6(OF5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one F(10), one F(5), one F(6), and one F(9) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one Co(1)OF5 octahedra,  a cornercorner with one Co(2)OF5 octahedra, corners with two equivalent Co(3)F6 octahedra, and  an edgeedge with one Co(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 3-59°. The Li(1)-F(10) bond length is 1.85 Å. The Li(1)-F(5) bond length is 1.91 Å. The Li(1)-F(6) bond length is 1.95 Å. The Li(1)-F(9) bond length is 1.85 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  a cornercorner with one Li(1)F4 tetrahedra, corners with three equivalent Co(4)O2F3 trigonal bipyramids,  an edgeedge with one Co(3)F6 octahedra, and  an edgeedge with one Co(2)OF5 octahedra. The Co(1)-O(2) bond length is 1.97 Å. The Co(1)-F(1) bond length is 1.98 Å. The Co(1)-F(2) bond length is 2.23 Å. The Co(1)-F(4) bond length is 2.09 Å. The Co(1)-F(8) bond length is 2.13 Å. The Co(1)-F(9) bond length is 2.11 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  a cornercorner with one Li(1)F4 tetrahedra, corners with three equivalent Co(4)O2F3 trigonal bipyramids,  an edgeedge with one Co(3)F6 octahedra, and  an edgeedge with one Co(1)OF5 octahedra. The Co(2)-O(1) bond length is 1.97 Å. The Co(2)-F(1) bond length is 1.99 Å. The Co(2)-F(10) bond length is 2.09 Å. The Co(2)-F(3) bond length is 2.26 Å. The Co(2)-F(7) bond length is 2.10 Å. The Co(2)-F(8) bond length is 2.12 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 CoF6 octahedra that share corners with two equivalent Li(1)F4 tetrahedra,  an edgeedge with one Co(1)OF5 octahedra,  an edgeedge with one Co(2)OF5 octahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The Co(3)-F(10) bond length is 2.03 Å. The Co(3)-F(2) bond length is 2.00 Å. The Co(3)-F(3) bond length is 2.00 Å. The Co(3)-F(5) bond length is 2.09 Å. The Co(3)-F(6) bond length is 2.14 Å. The Co(3)-F(9) bond length is 2.04 Å. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one F(4), one F(7), and one F(8) atom to form distorted corner-sharing CoO2F3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 44-51°. The Co(4)-O(1) bond length is 1.83 Å. The Co(4)-O(2) bond length is 1.82 Å. The Co(4)-F(4) bond length is 2.21 Å. The Co(4)-F(7) bond length is 2.15 Å. The Co(4)-F(8) bond length is 2.01 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(5), and one F(6) atom. The Co(5)-O(2) bond length is 1.91 Å. The Co(5)-F(2) bond length is 1.98 Å. The Co(5)-F(4) bond length is 2.01 Å. The Co(5)-F(5) bond length is 2.22 Å. The Co(5)-F(6) bond length is 2.19 Å. In the sixth Co site, Co(6) is bonded in a 5-coordinate geometry to one O(1), one F(3), one F(5), one F(6), and one F(7) atom. The Co(6)-O(1) bond length is 1.93 Å. The Co(6)-F(3) bond length is 1.97 Å. The Co(6)-F(5) bond length is 2.27 Å. The Co(6)-F(6) bond length is 2.16 Å. The Co(6)-F(7) bond length is 2.00 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 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 water-like geometry to one Co(1) and one Co(2) 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 4-coordinate geometry to one Li(1), one Co(3), one Co(5), and one Co(6) atom. In the sixth F site, F(6) is bonded in a distorted trigonal pyramidal geometry to one Li(1), 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 distorted T-shaped geometry to one Co(1), one Co(2), and one Co(4) atom. In the ninth F site, F(9) is bonded in a T-shaped geometry to one Li(1), one Co(1), and one Co(3) atom. In the tenth F site, F(10) is bonded in a T-shaped geometry to one Li(1), one Co(2), and one Co(3) atom.