Li3Co4O4F3 is Caswellsilverite-derived structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(2), and four equivalent F(1) atoms to form LiOF5 octahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with five equivalent Li(1)OF5 octahedra, edges with four equivalent Li(2)F6 octahedra, edges with four equivalent Li(1)OF5 octahedra, and edges with four equivalent Co(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second Li site, Li(2) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with two equivalent Co(1)O5F octahedra, corners with four equivalent Li(2)F6 octahedra, edges with four equivalent Li(2)F6 octahedra, and edges with eight equivalent Li(1)OF5 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), four equivalent O(1), and one F(1) atom to form CoO5F octahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Co(2)O6 octahedra, corners with four equivalent Co(1)O5F octahedra, edges with four equivalent Li(1)OF5 octahedra, edges with four equivalent Co(1)O5F octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Co site, Co(2) is bonded to one O(1) and five equivalent O(2) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)OF5 octahedra,  a cornercorner with one Co(1)O5F octahedra, corners with four equivalent Co(2)O6 octahedra, edges with four equivalent Co(1)O5F octahedra, and edges with eight equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Co(2), and four equivalent Co(1) atoms to form OLiCo5 octahedra that share  a cornercorner with one O(2)Co6 octahedra,  a cornercorner with one F(2)Li6 octahedra, corners with four equivalent O(1)LiCo5 octahedra, edges with four equivalent O(2)Co6 octahedra, edges with four equivalent O(1)LiCo5 octahedra, and edges with four equivalent F(1)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Co(1) and five equivalent Co(2) atoms to form OCo6 octahedra that share  a cornercorner with one O(1)LiCo5 octahedra,  a cornercorner with one F(1)Li5Co octahedra, corners with four equivalent O(2)Co6 octahedra, edges with four equivalent O(1)LiCo5 octahedra, and edges with eight equivalent O(2)Co6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), four equivalent Li(1), and one Co(1) atom to form FLi5Co octahedra that share  a cornercorner with one O(2)Co6 octahedra, corners with five equivalent F(1)Li5Co octahedra, edges with four equivalent O(1)LiCo5 octahedra, edges with four equivalent F(1)Li5Co octahedra, and edges with four equivalent F(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second F site, F(2) is bonded to two equivalent Li(1) and four equivalent Li(2) atoms to form FLi6 octahedra that share corners with two equivalent O(1)LiCo5 octahedra, corners with four equivalent F(2)Li6 octahedra, edges with four equivalent F(2)Li6 octahedra, and edges with eight equivalent F(1)Li5Co octahedra. The corner-sharing octahedra are not tilted.
Li3Co4O4F3 is Caswellsilverite-derived structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(2), and four equivalent F(1) atoms to form LiOF5 octahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with five equivalent Li(1)OF5 octahedra, edges with four equivalent Li(2)F6 octahedra, edges with four equivalent Li(1)OF5 octahedra, and edges with four equivalent Co(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-4°. The Li(1)-O(1) bond length is 2.17 Å. The Li(1)-F(2) bond length is 2.05 Å. All Li(1)-F(1) bond lengths are 2.10 Å. In the second Li site, Li(2) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with two equivalent Co(1)O5F octahedra, corners with four equivalent Li(2)F6 octahedra, edges with four equivalent Li(2)F6 octahedra, and edges with eight equivalent Li(1)OF5 octahedra. The corner-sharing octahedra are not tilted. Both Li(2)-F(1) bond lengths are 1.99 Å. All Li(2)-F(2) bond lengths are 2.10 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), four equivalent O(1), and one F(1) atom to form CoO5F octahedra that share  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one Co(2)O6 octahedra, corners with four equivalent Co(1)O5F octahedra, edges with four equivalent Li(1)OF5 octahedra, edges with four equivalent Co(1)O5F octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. The Co(1)-O(2) bond length is 2.15 Å. All Co(1)-O(1) bond lengths are 2.10 Å. The Co(1)-F(1) bond length is 2.22 Å. In the second Co site, Co(2) is bonded to one O(1) and five equivalent O(2) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)OF5 octahedra,  a cornercorner with one Co(1)O5F octahedra, corners with four equivalent Co(2)O6 octahedra, edges with four equivalent Co(1)O5F octahedra, and edges with eight equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Co(2)-O(1) bond length is 2.30 Å. There is one shorter (2.06 Å) and four longer (2.11 Å) Co(2)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Co(2), and four equivalent Co(1) atoms to form OLiCo5 octahedra that share  a cornercorner with one O(2)Co6 octahedra,  a cornercorner with one F(2)Li6 octahedra, corners with four equivalent O(1)LiCo5 octahedra, edges with four equivalent O(2)Co6 octahedra, edges with four equivalent O(1)LiCo5 octahedra, and edges with four equivalent F(1)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Co(1) and five equivalent Co(2) atoms to form OCo6 octahedra that share  a cornercorner with one O(1)LiCo5 octahedra,  a cornercorner with one F(1)Li5Co octahedra, corners with four equivalent O(2)Co6 octahedra, edges with four equivalent O(1)LiCo5 octahedra, and edges with eight equivalent O(2)Co6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), four equivalent Li(1), and one Co(1) atom to form FLi5Co octahedra that share  a cornercorner with one O(2)Co6 octahedra, corners with five equivalent F(1)Li5Co octahedra, edges with four equivalent O(1)LiCo5 octahedra, edges with four equivalent F(1)Li5Co octahedra, and edges with four equivalent F(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second F site, F(2) is bonded to two equivalent Li(1) and four equivalent Li(2) atoms to form FLi6 octahedra that share corners with two equivalent O(1)LiCo5 octahedra, corners with four equivalent F(2)Li6 octahedra, edges with four equivalent F(2)Li6 octahedra, and edges with eight equivalent F(1)Li5Co octahedra. The corner-sharing octahedra are not tilted.