LiCoOF2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form distorted LiF6 pentagonal pyramids that share corners with two equivalent Li(2)O2F2 tetrahedra, corners with four equivalent Co(1)O2F3 trigonal bipyramids, edges with two equivalent Li(1)F6 pentagonal pyramids,  an edgeedge with one Li(2)O2F2 tetrahedra, and edges with two equivalent Co(1)O2F3 trigonal bipyramids. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent F(1) atoms to form distorted LiO2F2 tetrahedra that share corners with two equivalent Li(1)F6 pentagonal pyramids, corners with six equivalent Co(1)O2F3 trigonal bipyramids, and  an edgeedge with one Li(1)F6 pentagonal pyramid. Co(1) is bonded to two equivalent O(1), one F(1), and two equivalent F(2) atoms to form CoO2F3 trigonal bipyramids that share corners with two equivalent Li(1)F6 pentagonal pyramids, corners with three equivalent Li(2)O2F2 tetrahedra, corners with four equivalent Co(1)O2F3 trigonal bipyramids, and  an edgeedge with one Li(1)F6 pentagonal pyramid. O(1) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Co(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one Co(1) atom to form a mixture of distorted corner and edge-sharing FLi3Co trigonal pyramids. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Co(1) atoms.
LiCoOF2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form distorted LiF6 pentagonal pyramids that share corners with two equivalent Li(2)O2F2 tetrahedra, corners with four equivalent Co(1)O2F3 trigonal bipyramids, edges with two equivalent Li(1)F6 pentagonal pyramids,  an edgeedge with one Li(2)O2F2 tetrahedra, and edges with two equivalent Co(1)O2F3 trigonal bipyramids. Both Li(1)-F(2) bond lengths are 1.98 Å. There are two shorter (2.16 Å) and two longer (2.21 Å) Li(1)-F(1) bond lengths. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent F(1) atoms to form distorted LiO2F2 tetrahedra that share corners with two equivalent Li(1)F6 pentagonal pyramids, corners with six equivalent Co(1)O2F3 trigonal bipyramids, and  an edgeedge with one Li(1)F6 pentagonal pyramid. Both Li(2)-O(1) bond lengths are 1.96 Å. Both Li(2)-F(1) bond lengths are 1.92 Å. Co(1) is bonded to two equivalent O(1), one F(1), and two equivalent F(2) atoms to form CoO2F3 trigonal bipyramids that share corners with two equivalent Li(1)F6 pentagonal pyramids, corners with three equivalent Li(2)O2F2 tetrahedra, corners with four equivalent Co(1)O2F3 trigonal bipyramids, and  an edgeedge with one Li(1)F6 pentagonal pyramid. There is one shorter (1.76 Å) and one longer (1.90 Å) Co(1)-O(1) bond length. The Co(1)-F(1) bond length is 1.92 Å. There is one shorter (2.02 Å) and one longer (2.15 Å) Co(1)-F(2) bond length. O(1) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Co(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one Co(1) atom to form a mixture of distorted corner and edge-sharing FLi3Co trigonal pyramids. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Co(1) atoms.