Li5Co2O2F5 is Caswellsilverite-derived structured and crystallizes in the tetragonal I4/mmm space group. There are four 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 Li(3)F6 octahedra,  a cornercorner with one Co(1)O5F octahedra, corners with four 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 0-1°. In the second Li site, Li(2) is bonded to one F(1), one F(3), and four equivalent F(2) atoms to form LiF6 octahedra that share  a cornercorner with one Co(1)O5F octahedra, corners with five equivalent Li(2)F6 octahedra, edges with four equivalent Li(2)F6 octahedra, edges with four equivalent Li(3)F6 octahedra, and edges with four equivalent Li(1)OF5 octahedra. The corner-sharing octahedra are not tilted. In the third Li site, Li(3) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with four equivalent Li(3)F6 octahedra, edges with four equivalent Li(3)F6 octahedra, and edges with eight equivalent Li(2)F6 octahedra. The corner-sharing octahedra are not tilted. In the fourth Li site, Li(3) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with four equivalent Li(3)F6 octahedra, edges with four equivalent Li(3)F6 octahedra, and edges with eight equivalent Li(2)F6 octahedra. The corner-sharing octahedra are not tilted. Co(1) is bonded to five 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 Li(1)OF5 octahedra, corners with four equivalent Co(1)O5F octahedra, edges with four equivalent Li(1)OF5 octahedra, and edges with eight equivalent Co(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-13°. O(1) is bonded to one Li(1) and five equivalent Co(1) atoms to form OLiCo5 octahedra that share  a cornercorner with one F(1)Li5Co octahedra,  a cornercorner with one F(2)Li6 octahedra, corners with four equivalent O(1)LiCo5 octahedra, edges with four equivalent F(1)Li5Co octahedra, and edges with eight equivalent O(1)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. There are four 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(1)LiCo5 octahedra,  a cornercorner with one F(3)Li6 octahedra, corners with four 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 0-1°. In the second F site, F(2) is bonded to one Li(1), one Li(3), and four equivalent Li(2) atoms to form FLi6 octahedra that share  a cornercorner with one O(1)LiCo5 octahedra, corners with five equivalent F(2)Li6 octahedra, edges with four equivalent F(1)Li5Co octahedra, edges with four equivalent F(2)Li6 octahedra, and edges with four equivalent F(3)Li6 octahedra. The corner-sharing octahedra are not tilted. In the third F site, F(3) is bonded to two equivalent Li(2) and four equivalent Li(3) atoms to form FLi6 octahedra that share corners with two equivalent F(1)Li5Co octahedra, corners with four equivalent F(3)Li6 octahedra, edges with four equivalent F(3)Li6 octahedra, and edges with eight equivalent F(2)Li6 octahedra. The corner-sharing octahedra are not tilted. In the fourth F site, F(3) is bonded to two equivalent Li(2) and four equivalent Li(3) atoms to form FLi6 octahedra that share corners with two equivalent F(1)Li5Co octahedra, corners with four equivalent F(3)Li6 octahedra, edges with four equivalent F(3)Li6 octahedra, and edges with eight equivalent F(2)Li6 octahedra. The corner-sharing octahedra are not tilted.
Li5Co2O2F5 is Caswellsilverite-derived structured and crystallizes in the tetragonal I4/mmm space group. There are four 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 Li(3)F6 octahedra,  a cornercorner with one Co(1)O5F octahedra, corners with four 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 0-1°. The Li(1)-O(1) bond length is 2.07 Å. The Li(1)-F(2) bond length is 2.02 Å. All Li(1)-F(1) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to one F(1), one F(3), and four equivalent F(2) atoms to form LiF6 octahedra that share  a cornercorner with one Co(1)O5F octahedra, corners with five equivalent Li(2)F6 octahedra, edges with four equivalent Li(2)F6 octahedra, edges with four equivalent Li(3)F6 octahedra, and edges with four equivalent Li(1)OF5 octahedra. The corner-sharing octahedra are not tilted. The Li(2)-F(1) bond length is 2.02 Å. The Li(2)-F(3) bond length is 1.99 Å. All Li(2)-F(2) bond lengths are 2.08 Å. In the third Li site, Li(3) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with four equivalent Li(3)F6 octahedra, edges with four equivalent Li(3)F6 octahedra, and edges with eight equivalent Li(2)F6 octahedra. The corner-sharing octahedra are not tilted. Both Li(3)-F(2) bond lengths are 2.00 Å. All Li(3)-F(3) bond lengths are 2.08 Å. In the fourth Li site, Li(3) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with four equivalent Li(3)F6 octahedra, edges with four equivalent Li(3)F6 octahedra, and edges with eight equivalent Li(2)F6 octahedra. The corner-sharing octahedra are not tilted. Both Li(3)-F(2) bond lengths are 2.00 Å. All Li(3)-F(3) bond lengths are 2.08 Å. Co(1) is bonded to five 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 Li(1)OF5 octahedra, corners with four equivalent Co(1)O5F octahedra, edges with four equivalent Li(1)OF5 octahedra, and edges with eight equivalent Co(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-13°. There is one shorter (2.06 Å) and four longer (2.10 Å) Co(1)-O(1) bond lengths. The Co(1)-F(1) bond length is 2.32 Å. O(1) is bonded to one Li(1) and five equivalent Co(1) atoms to form OLiCo5 octahedra that share  a cornercorner with one F(1)Li5Co octahedra,  a cornercorner with one F(2)Li6 octahedra, corners with four equivalent O(1)LiCo5 octahedra, edges with four equivalent F(1)Li5Co octahedra, and edges with eight equivalent O(1)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. There are four 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(1)LiCo5 octahedra,  a cornercorner with one F(3)Li6 octahedra, corners with four 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 0-1°. In the second F site, F(2) is bonded to one Li(1), one Li(3), and four equivalent Li(2) atoms to form FLi6 octahedra that share  a cornercorner with one O(1)LiCo5 octahedra, corners with five equivalent F(2)Li6 octahedra, edges with four equivalent F(1)Li5Co octahedra, edges with four equivalent F(2)Li6 octahedra, and edges with four equivalent F(3)Li6 octahedra. The corner-sharing octahedra are not tilted. In the third F site, F(3) is bonded to two equivalent Li(2) and four equivalent Li(3) atoms to form FLi6 octahedra that share corners with two equivalent F(1)Li5Co octahedra, corners with four equivalent F(3)Li6 octahedra, edges with four equivalent F(3)Li6 octahedra, and edges with eight equivalent F(2)Li6 octahedra. The corner-sharing octahedra are not tilted. Both F(3)-Li(2) bond lengths are 1.99 Å. In the fourth F site, F(3) is bonded to two equivalent Li(2) and four equivalent Li(3) atoms to form FLi6 octahedra that share corners with two equivalent F(1)Li5Co octahedra, corners with four equivalent F(3)Li6 octahedra, edges with four equivalent F(3)Li6 octahedra, and edges with eight equivalent F(2)Li6 octahedra. The corner-sharing octahedra are not tilted.