Li2CoCl4 crystallizes in the tetragonal P4_122 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form LiCl6 octahedra that share corners with two equivalent Li(2)Cl6 octahedra, corners with four equivalent Co(1)Cl6 octahedra, edges with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Co(1)Cl6 octahedra, and edges with four equivalent Li(2)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. In the second Li site, Li(2) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form LiCl6 octahedra that share corners with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Li(2)Cl6 octahedra, edges with four equivalent Li(1)Cl6 octahedra, and edges with four equivalent Co(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 5°. Co(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form CoCl6 octahedra that share corners with four equivalent Li(1)Cl6 octahedra, edges with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Co(1)Cl6 octahedra, and edges with four equivalent Li(2)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Co(1) atom to form a mixture of corner and edge-sharing ClLi4Co square pyramids. In the second Cl site, Cl(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Co(1) atoms.
Li2CoCl4 crystallizes in the tetragonal P4_122 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form LiCl6 octahedra that share corners with two equivalent Li(2)Cl6 octahedra, corners with four equivalent Co(1)Cl6 octahedra, edges with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Co(1)Cl6 octahedra, and edges with four equivalent Li(2)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. Both Li(1)-Cl(2) bond lengths are 2.00 Å. There are two shorter (1.99 Å) and two longer (2.00 Å) Li(1)-Cl(1) bond lengths. In the second Li site, Li(2) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form LiCl6 octahedra that share corners with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Li(2)Cl6 octahedra, edges with four equivalent Li(1)Cl6 octahedra, and edges with four equivalent Co(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Li(2)-Cl(2) bond lengths are 2.10 Å. There are two shorter (1.97 Å) and two longer (2.10 Å) Li(2)-Cl(1) bond lengths. Co(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form CoCl6 octahedra that share corners with four equivalent Li(1)Cl6 octahedra, edges with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Co(1)Cl6 octahedra, and edges with four equivalent Li(2)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. Both Co(1)-Cl(1) bond lengths are 2.08 Å. There are two shorter (2.08 Å) and two longer (2.13 Å) Co(1)-Cl(2) bond lengths. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Co(1) atom to form a mixture of corner and edge-sharing ClLi4Co square pyramids. In the second Cl site, Cl(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Co(1) atoms.