Li3CoO2F crystallizes in the orthorhombic Pnnm space group. There are three 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 distorted LiO3F trigonal pyramids that share  a cornercorner with one Li(2)O3F tetrahedra, corners with two equivalent Li(1)O3F trigonal pyramids, corners with five equivalent Li(3)O2F2 trigonal pyramids, and edges with two equivalent Li(2)O3F tetrahedra. In the second Li site, Li(2) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent Li(2)O3F tetrahedra,  a cornercorner with one Li(3)O2F2 trigonal pyramid,  a cornercorner with one Li(1)O3F trigonal pyramid, edges with two equivalent Li(3)O2F2 trigonal pyramids, and edges with two equivalent Li(1)O3F trigonal pyramids. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form distorted LiO2F2 trigonal pyramids that share  a cornercorner with one Li(2)O3F tetrahedra, corners with two equivalent Li(3)O2F2 trigonal pyramids, corners with five equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent Li(2)O3F tetrahedra. Co(1) is bonded in a distorted T-shaped geometry to one O(2) and two equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Co(1) atoms to form distorted OLi4Co2 octahedra that share corners with two equivalent O(1)Li4Co2 octahedra,  a cornercorner with one O(2)Li4Co trigonal bipyramid,  an edgeedge with one O(1)Li4Co2 octahedra, and edges with three equivalent O(2)Li4Co trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Co(1) atom to form OLi4Co trigonal bipyramids that share  a cornercorner with one O(1)Li4Co2 octahedra, corners with two equivalent O(2)Li4Co trigonal bipyramids, and edges with three equivalent O(1)Li4Co2 octahedra. The corner-sharing octahedral tilt angles are 18°. F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Li(3) atoms.
Li3CoO2F crystallizes in the orthorhombic Pnnm space group. There are three 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 distorted LiO3F trigonal pyramids that share  a cornercorner with one Li(2)O3F tetrahedra, corners with two equivalent Li(1)O3F trigonal pyramids, corners with five equivalent Li(3)O2F2 trigonal pyramids, and edges with two equivalent Li(2)O3F tetrahedra. The Li(1)-O(1) bond length is 2.21 Å. Both Li(1)-O(2) bond lengths are 1.94 Å. The Li(1)-F(1) bond length is 1.90 Å. In the second Li site, Li(2) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent Li(2)O3F tetrahedra,  a cornercorner with one Li(3)O2F2 trigonal pyramid,  a cornercorner with one Li(1)O3F trigonal pyramid, edges with two equivalent Li(3)O2F2 trigonal pyramids, and edges with two equivalent Li(1)O3F trigonal pyramids. The Li(2)-O(2) bond length is 1.97 Å. Both Li(2)-O(1) bond lengths are 1.97 Å. The Li(2)-F(1) bond length is 1.93 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form distorted LiO2F2 trigonal pyramids that share  a cornercorner with one Li(2)O3F tetrahedra, corners with two equivalent Li(3)O2F2 trigonal pyramids, corners with five equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent Li(2)O3F tetrahedra. The Li(3)-O(1) bond length is 2.22 Å. The Li(3)-O(2) bond length is 1.97 Å. Both Li(3)-F(1) bond lengths are 1.91 Å. Co(1) is bonded in a distorted T-shaped geometry to one O(2) and two equivalent O(1) atoms. The Co(1)-O(2) bond length is 1.82 Å. There is one shorter (1.89 Å) and one longer (2.03 Å) Co(1)-O(1) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Co(1) atoms to form distorted OLi4Co2 octahedra that share corners with two equivalent O(1)Li4Co2 octahedra,  a cornercorner with one O(2)Li4Co trigonal bipyramid,  an edgeedge with one O(1)Li4Co2 octahedra, and edges with three equivalent O(2)Li4Co trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Co(1) atom to form OLi4Co trigonal bipyramids that share  a cornercorner with one O(1)Li4Co2 octahedra, corners with two equivalent O(2)Li4Co trigonal bipyramids, and edges with three equivalent O(1)Li4Co2 octahedra. The corner-sharing octahedral tilt angles are 18°. F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Li(3) atoms.