Li4CoO3F crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F tetrahedra. In the second Li site, Li(2) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F tetrahedra. Co(1) is bonded in a trigonal planar geometry to one O(1) and two equivalent O(2) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one Co(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one Co(1) atom to form OLi4Co trigonal bipyramids that share corners with five equivalent O(2)Li4Co trigonal bipyramids, corners with two equivalent F(1)Li4 trigonal pyramids, and  an edgeedge with one F(1)Li4 trigonal pyramid. F(1) is bonded to two equivalent Li(1) and two equivalent Li(2) atoms to form distorted FLi4 trigonal pyramids that share corners with four equivalent O(2)Li4Co trigonal bipyramids and edges with two equivalent O(2)Li4Co trigonal bipyramids.
Li4CoO3F crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F tetrahedra. The Li(1)-O(1) bond length is 1.98 Å. There is one shorter (1.97 Å) and one longer (2.00 Å) Li(1)-O(2) bond length. The Li(1)-F(1) bond length is 1.94 Å. In the second Li site, Li(2) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F tetrahedra. The Li(2)-O(1) bond length is 2.00 Å. There is one shorter (2.00 Å) and one longer (2.03 Å) Li(2)-O(2) bond length. The Li(2)-F(1) bond length is 1.95 Å. Co(1) is bonded in a trigonal planar geometry to one O(1) and two equivalent O(2) atoms. The Co(1)-O(1) bond length is 1.79 Å. Both Co(1)-O(2) bond lengths are 1.80 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one Co(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one Co(1) atom to form OLi4Co trigonal bipyramids that share corners with five equivalent O(2)Li4Co trigonal bipyramids, corners with two equivalent F(1)Li4 trigonal pyramids, and  an edgeedge with one F(1)Li4 trigonal pyramid. F(1) is bonded to two equivalent Li(1) and two equivalent Li(2) atoms to form distorted FLi4 trigonal pyramids that share corners with four equivalent O(2)Li4Co trigonal bipyramids and edges with two equivalent O(2)Li4Co trigonal bipyramids.