Li2Co4OF8 is Corundum-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(4), one F(6), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Co(1)OF5 octahedra, corners with three equivalent Co(2)OF5 octahedra, corners with three equivalent Co(4)OF5 octahedra, edges with three equivalent Co(3)F6 octahedra, and  a faceface with one Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-64°. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(5), and one F(6) atom to form distorted LiOF5 octahedra that share corners with three equivalent Co(3)F6 octahedra, corners with three equivalent Co(2)OF5 octahedra, corners with three equivalent Co(4)OF5 octahedra, edges with three equivalent Co(1)OF5 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-63°. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(5), and one F(6) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Co(3)F6 octahedra, corners with three equivalent Co(4)OF5 octahedra, edges with three equivalent Li(2)OF5 octahedra, and  a faceface with one Co(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. In the second Co site, Co(2) is bonded to one O(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Co(3)F6 octahedra, edges with three equivalent Co(4)OF5 octahedra, and  a faceface with one Co(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-64°. In the third Co site, Co(3) is bonded to one F(1), one F(3), one F(4), one F(6), one F(7), and one F(8) atom to form CoF6 octahedra that share corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Co(1)OF5 octahedra, corners with three equivalent Co(2)OF5 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Co(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. In the fourth Co site, Co(4) is bonded to one O(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form distorted CoOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Co(1)OF5 octahedra, edges with three equivalent Co(2)OF5 octahedra, and  a faceface with one Co(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-63°. O(1) is bonded to one Li(2), one Co(1), one Co(2), and one Co(4) atom to form distorted OLiCo3 trigonal pyramids that share corners with two equivalent F(3)Li2Co2 trigonal pyramids, corners with two equivalent F(6)Li2Co2 trigonal pyramids, corners with two equivalent F(4)LiCo3 trigonal pyramids,  an edgeedge with one F(1)Li2Co2 trigonal pyramid, and  an edgeedge with one F(7)LiCo3 trigonal pyramid. There are eight inequivalent F sites. In the first F site, F(3) is bonded to one Li(1), one Li(2), one Co(1), and one Co(3) atom to form distorted FLi2Co2 trigonal pyramids that share corners with two equivalent O(1)LiCo3 trigonal pyramids, corners with two equivalent F(1)Li2Co2 trigonal pyramids, corners with two equivalent F(6)Li2Co2 trigonal pyramids, corners with two equivalent F(7)LiCo3 trigonal pyramids,  an edgeedge with one F(1)Li2Co2 trigonal pyramid,  an edgeedge with one F(6)Li2Co2 trigonal pyramid, and  an edgeedge with one F(4)LiCo3 trigonal pyramid. In the second F site, F(4) is bonded to one Li(1), one Co(2), one Co(3), and one Co(4) atom to form distorted FLiCo3 trigonal pyramids that share corners with two equivalent O(1)LiCo3 trigonal pyramids, corners with two equivalent F(1)Li2Co2 trigonal pyramids, corners with two equivalent F(6)Li2Co2 trigonal pyramids, corners with two equivalent F(7)LiCo3 trigonal pyramids,  an edgeedge with one F(3)Li2Co2 trigonal pyramid, and  an edgeedge with one F(7)LiCo3 trigonal pyramid. In the third F site, F(5) is bonded in a 4-coordinate geometry to one Li(2), one Co(1), one Co(2), and one Co(4) atom. In the fourth F site, F(6) is bonded to one Li(1), one Li(2), one Co(1), and one Co(3) atom to form distorted FLi2Co2 trigonal pyramids that share corners with two equivalent O(1)LiCo3 trigonal pyramids, corners with two equivalent F(1)Li2Co2 trigonal pyramids, corners with two equivalent F(3)Li2Co2 trigonal pyramids, corners with two equivalent F(4)LiCo3 trigonal pyramids, corners with two equivalent F(7)LiCo3 trigonal pyramids,  an edgeedge with one F(1)Li2Co2 trigonal pyramid, and  an edgeedge with one F(3)Li2Co2 trigonal pyramid. In the fifth F site, F(7) is bonded to one Li(1), one Co(2), one Co(3), and one Co(4) atom to form distorted FLiCo3 trigonal pyramids that share corners with two equivalent F(3)Li2Co2 trigonal pyramids, corners with two equivalent F(6)Li2Co2 trigonal pyramids, corners with two equivalent F(4)LiCo3 trigonal pyramids,  an edgeedge with one O(1)LiCo3 trigonal pyramid,  an edgeedge with one F(1)Li2Co2 trigonal pyramid, and  an edgeedge with one F(4)LiCo3 trigonal pyramid. In the sixth F site, F(8) is bonded in a distorted see-saw-like geometry to one Li(1), one Co(2), one Co(3), and one Co(4) atom. In the seventh F site, F(1) is bonded to one Li(1), one Li(2), one Co(1), and one Co(3) atom to form distorted FLi2Co2 trigonal pyramids that share corners with two equivalent F(3)Li2Co2 trigonal pyramids, corners with two equivalent F(6)Li2Co2 trigonal pyramids, corners with two equivalent F(4)LiCo3 trigonal pyramids,  an edgeedge with one O(1)LiCo3 trigonal pyramid,  an edgeedge with one F(3)Li2Co2 trigonal pyramid,  an edgeedge with one F(6)Li2Co2 trigonal pyramid, and  an edgeedge with one F(7)LiCo3 trigonal pyramid. In the eighth F site, F(2) is bonded in a 4-coordinate geometry to one Li(2), one Co(1), one Co(2), and one Co(4) atom.
Li2Co4OF8 is Corundum-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(4), one F(6), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Co(1)OF5 octahedra, corners with three equivalent Co(2)OF5 octahedra, corners with three equivalent Co(4)OF5 octahedra, edges with three equivalent Co(3)F6 octahedra, and  a faceface with one Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-64°. The Li(1)-F(1) bond length is 2.10 Å. The Li(1)-F(3) bond length is 2.14 Å. The Li(1)-F(4) bond length is 2.09 Å. The Li(1)-F(6) bond length is 2.10 Å. The Li(1)-F(7) bond length is 2.02 Å. The Li(1)-F(8) bond length is 2.07 Å. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(5), and one F(6) atom to form distorted LiOF5 octahedra that share corners with three equivalent Co(3)F6 octahedra, corners with three equivalent Co(2)OF5 octahedra, corners with three equivalent Co(4)OF5 octahedra, edges with three equivalent Co(1)OF5 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-63°. The Li(2)-O(1) bond length is 1.98 Å. The Li(2)-F(1) bond length is 2.16 Å. The Li(2)-F(2) bond length is 1.98 Å. The Li(2)-F(3) bond length is 2.29 Å. The Li(2)-F(5) bond length is 2.02 Å. The Li(2)-F(6) bond length is 2.28 Å. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(5), and one F(6) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Co(3)F6 octahedra, corners with three equivalent Co(4)OF5 octahedra, edges with three equivalent Li(2)OF5 octahedra, and  a faceface with one Co(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. The Co(1)-O(1) bond length is 1.98 Å. The Co(1)-F(1) bond length is 2.05 Å. The Co(1)-F(2) bond length is 2.26 Å. The Co(1)-F(3) bond length is 2.06 Å. The Co(1)-F(5) bond length is 2.16 Å. The Co(1)-F(6) bond length is 2.07 Å. In the second Co site, Co(2) is bonded to one O(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Co(3)F6 octahedra, edges with three equivalent Co(4)OF5 octahedra, and  a faceface with one Co(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-64°. The Co(2)-O(1) bond length is 1.97 Å. The Co(2)-F(2) bond length is 2.16 Å. The Co(2)-F(4) bond length is 2.07 Å. The Co(2)-F(5) bond length is 2.27 Å. The Co(2)-F(7) bond length is 2.09 Å. The Co(2)-F(8) bond length is 2.08 Å. In the third Co site, Co(3) is bonded to one F(1), one F(3), one F(4), one F(6), one F(7), and one F(8) atom to form CoF6 octahedra that share corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Co(1)OF5 octahedra, corners with three equivalent Co(2)OF5 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one Co(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 44-62°. The Co(3)-F(1) bond length is 2.02 Å. The Co(3)-F(3) bond length is 2.03 Å. The Co(3)-F(4) bond length is 2.16 Å. The Co(3)-F(6) bond length is 2.00 Å. The Co(3)-F(7) bond length is 2.11 Å. The Co(3)-F(8) bond length is 2.13 Å. In the fourth Co site, Co(4) is bonded to one O(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form distorted CoOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)OF5 octahedra, corners with three equivalent Co(1)OF5 octahedra, edges with three equivalent Co(2)OF5 octahedra, and  a faceface with one Co(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-63°. The Co(4)-O(1) bond length is 1.92 Å. The Co(4)-F(2) bond length is 2.04 Å. The Co(4)-F(4) bond length is 2.27 Å. The Co(4)-F(5) bond length is 2.03 Å. The Co(4)-F(7) bond length is 2.22 Å. The Co(4)-F(8) bond length is 2.26 Å. O(1) is bonded to one Li(2), one Co(1), one Co(2), and one Co(4) atom to form distorted OLiCo3 trigonal pyramids that share corners with two equivalent F(3)Li2Co2 trigonal pyramids, corners with two equivalent F(6)Li2Co2 trigonal pyramids, corners with two equivalent F(4)LiCo3 trigonal pyramids,  an edgeedge with one F(1)Li2Co2 trigonal pyramid, and  an edgeedge with one F(7)LiCo3 trigonal pyramid. There are eight inequivalent F sites. In the first F site, F(3) is bonded to one Li(1), one Li(2), one Co(1), and one Co(3) atom to form distorted FLi2Co2 trigonal pyramids that share corners with two equivalent O(1)LiCo3 trigonal pyramids, corners with two equivalent F(1)Li2Co2 trigonal pyramids, corners with two equivalent F(6)Li2Co2 trigonal pyramids, corners with two equivalent F(7)LiCo3 trigonal pyramids,  an edgeedge with one F(1)Li2Co2 trigonal pyramid,  an edgeedge with one F(6)Li2Co2 trigonal pyramid, and  an edgeedge with one F(4)LiCo3 trigonal pyramid. In the second F site, F(4) is bonded to one Li(1), one Co(2), one Co(3), and one Co(4) atom to form distorted FLiCo3 trigonal pyramids that share corners with two equivalent O(1)LiCo3 trigonal pyramids, corners with two equivalent F(1)Li2Co2 trigonal pyramids, corners with two equivalent F(6)Li2Co2 trigonal pyramids, corners with two equivalent F(7)LiCo3 trigonal pyramids,  an edgeedge with one F(3)Li2Co2 trigonal pyramid, and  an edgeedge with one F(7)LiCo3 trigonal pyramid. In the third F site, F(5) is bonded in a 4-coordinate geometry to one Li(2), one Co(1), one Co(2), and one Co(4) atom. In the fourth F site, F(6) is bonded to one Li(1), one Li(2), one Co(1), and one Co(3) atom to form distorted FLi2Co2 trigonal pyramids that share corners with two equivalent O(1)LiCo3 trigonal pyramids, corners with two equivalent F(1)Li2Co2 trigonal pyramids, corners with two equivalent F(3)Li2Co2 trigonal pyramids, corners with two equivalent F(4)LiCo3 trigonal pyramids, corners with two equivalent F(7)LiCo3 trigonal pyramids,  an edgeedge with one F(1)Li2Co2 trigonal pyramid, and  an edgeedge with one F(3)Li2Co2 trigonal pyramid. In the fifth F site, F(7) is bonded to one Li(1), one Co(2), one Co(3), and one Co(4) atom to form distorted FLiCo3 trigonal pyramids that share corners with two equivalent F(3)Li2Co2 trigonal pyramids, corners with two equivalent F(6)Li2Co2 trigonal pyramids, corners with two equivalent F(4)LiCo3 trigonal pyramids,  an edgeedge with one O(1)LiCo3 trigonal pyramid,  an edgeedge with one F(1)Li2Co2 trigonal pyramid, and  an edgeedge with one F(4)LiCo3 trigonal pyramid. In the sixth F site, F(8) is bonded in a distorted see-saw-like geometry to one Li(1), one Co(2), one Co(3), and one Co(4) atom. In the seventh F site, F(1) is bonded to one Li(1), one Li(2), one Co(1), and one Co(3) atom to form distorted FLi2Co2 trigonal pyramids that share corners with two equivalent F(3)Li2Co2 trigonal pyramids, corners with two equivalent F(6)Li2Co2 trigonal pyramids, corners with two equivalent F(4)LiCo3 trigonal pyramids,  an edgeedge with one O(1)LiCo3 trigonal pyramid,  an edgeedge with one F(3)Li2Co2 trigonal pyramid,  an edgeedge with one F(6)Li2Co2 trigonal pyramid, and  an edgeedge with one F(7)LiCo3 trigonal pyramid. In the eighth F site, F(2) is bonded in a 4-coordinate geometry to one Li(2), one Co(1), one Co(2), and one Co(4) atom.