LiCo3(OF3)2 is Hydrophilite-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with four equivalent Co(3)O2F4 octahedra, corners with four equivalent Co(4)O2F4 octahedra, and edges with two equivalent Co(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. In the second Li site, Li(2) is bonded to two equivalent F(2), two equivalent F(4), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with four equivalent Co(1)O2F4 octahedra, corners with four equivalent Co(2)O2F4 octahedra, and edges with two equivalent Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(2), two equivalent F(2), and two equivalent F(4) atoms to form CoO2F4 octahedra that share corners with four equivalent Li(2)F6 octahedra, corners with four equivalent Co(4)O2F4 octahedra, and edges with two equivalent Co(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. In the second Co site, Co(2) is bonded to one O(1), one O(2), one F(1), one F(4), one F(5), and one F(6) atom to form CoO2F4 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Co(3)O2F4 octahedra, corners with four equivalent Co(4)O2F4 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Co(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. In the third Co site, Co(3) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form CoO2F4 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Co(2)O2F4 octahedra, and edges with two equivalent Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one F(2), one F(3), one F(5), and one F(6) atom to form CoO2F4 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Co(1)O2F4 octahedra, corners with four equivalent Co(2)O2F4 octahedra,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Co(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. 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(3), and one Co(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one Co(4) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(2), and one Co(3) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2), one Co(1), and one Co(4) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(3), and one Co(4) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(1), and one Co(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(2), and one Co(4) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Li(2), one Co(2), and one Co(4) atom.
LiCo3(OF3)2 is Hydrophilite-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with four equivalent Co(3)O2F4 octahedra, corners with four equivalent Co(4)O2F4 octahedra, and edges with two equivalent Co(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. Both Li(1)-F(1) bond lengths are 2.04 Å. Both Li(1)-F(3) bond lengths are 1.97 Å. Both Li(1)-F(5) bond lengths are 2.11 Å. In the second Li site, Li(2) is bonded to two equivalent F(2), two equivalent F(4), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with four equivalent Co(1)O2F4 octahedra, corners with four equivalent Co(2)O2F4 octahedra, and edges with two equivalent Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. Both Li(2)-F(2) bond lengths are 1.99 Å. Both Li(2)-F(4) bond lengths are 1.94 Å. Both Li(2)-F(6) bond lengths are 2.17 Å. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(2), two equivalent F(2), and two equivalent F(4) atoms to form CoO2F4 octahedra that share corners with four equivalent Li(2)F6 octahedra, corners with four equivalent Co(4)O2F4 octahedra, and edges with two equivalent Co(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. Both Co(1)-O(2) bond lengths are 1.92 Å. Both Co(1)-F(2) bond lengths are 1.99 Å. Both Co(1)-F(4) bond lengths are 2.00 Å. In the second Co site, Co(2) is bonded to one O(1), one O(2), one F(1), one F(4), one F(5), and one F(6) atom to form CoO2F4 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Co(3)O2F4 octahedra, corners with four equivalent Co(4)O2F4 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Co(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The Co(2)-O(1) bond length is 1.79 Å. The Co(2)-O(2) bond length is 2.04 Å. The Co(2)-F(1) bond length is 2.04 Å. The Co(2)-F(4) bond length is 1.98 Å. The Co(2)-F(5) bond length is 2.05 Å. The Co(2)-F(6) bond length is 1.99 Å. In the third Co site, Co(3) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form CoO2F4 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Co(2)O2F4 octahedra, and edges with two equivalent Co(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. Both Co(3)-O(1) bond lengths are 1.99 Å. Both Co(3)-F(1) bond lengths are 1.92 Å. Both Co(3)-F(3) bond lengths are 1.97 Å. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one F(2), one F(3), one F(5), and one F(6) atom to form CoO2F4 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Co(1)O2F4 octahedra, corners with four equivalent Co(2)O2F4 octahedra,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Co(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The Co(4)-O(1) bond length is 2.00 Å. The Co(4)-O(2) bond length is 1.80 Å. The Co(4)-F(2) bond length is 1.99 Å. The Co(4)-F(3) bond length is 2.01 Å. The Co(4)-F(5) bond length is 2.00 Å. The Co(4)-F(6) bond length is 2.05 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(3), and one Co(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one Co(4) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(2), and one Co(3) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2), one Co(1), and one Co(4) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(3), and one Co(4) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Co(1), and one Co(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Co(2), and one Co(4) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Li(2), one Co(2), and one Co(4) atom.