Li6CoCl8 crystallizes in the cubic Fm-3m space group. Li(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form LiCl6 octahedra that share corners with six equivalent Li(1)Cl6 octahedra, edges with two equivalent Co(1)Cl6 octahedra, and edges with eight equivalent Li(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. Co(1) is bonded to six equivalent Cl(2) atoms to form CoCl6 octahedra that share edges with twelve equivalent Li(1)Cl6 octahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to six equivalent Li(1) atoms to form ClLi6 octahedra that share corners with six equivalent Cl(1)Li6 octahedra and edges with twelve equivalent Cl(2)Li4Co square pyramids. The corner-sharing octahedra are not tilted. In the second Cl site, Cl(2) is bonded to four equivalent Li(1) and one Co(1) atom to form ClLi4Co square pyramids that share corners with nine equivalent Cl(2)Li4Co square pyramids, edges with four equivalent Cl(1)Li6 octahedra, and edges with four equivalent Cl(2)Li4Co square pyramids.
Li6CoCl8 crystallizes in the cubic Fm-3m space group. Li(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form LiCl6 octahedra that share corners with six equivalent Li(1)Cl6 octahedra, edges with two equivalent Co(1)Cl6 octahedra, and edges with eight equivalent Li(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. Both Li(1)-Cl(1) bond lengths are 2.57 Å. All Li(1)-Cl(2) bond lengths are 2.58 Å. Co(1) is bonded to six equivalent Cl(2) atoms to form CoCl6 octahedra that share edges with twelve equivalent Li(1)Cl6 octahedra. All Co(1)-Cl(2) bond lengths are 2.44 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to six equivalent Li(1) atoms to form ClLi6 octahedra that share corners with six equivalent Cl(1)Li6 octahedra and edges with twelve equivalent Cl(2)Li4Co square pyramids. The corner-sharing octahedra are not tilted. In the second Cl site, Cl(2) is bonded to four equivalent Li(1) and one Co(1) atom to form ClLi4Co square pyramids that share corners with nine equivalent Cl(2)Li4Co square pyramids, edges with four equivalent Cl(1)Li6 octahedra, and edges with four equivalent Cl(2)Li4Co square pyramids.