Li2CoCl4 crystallizes in the orthorhombic Cmmm 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 four equivalent Li(1)Cl6 octahedra, and edges with four equivalent Co(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 7°. Co(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form CoCl6 octahedra that share edges with two equivalent Co(1)Cl6 octahedra and edges with eight equivalent Li(1)Cl6 octahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Co(1) atoms. In the second Cl site, Cl(2) is bonded to four equivalent Li(1) and one Co(1) atom to form a mixture of edge and corner-sharing ClLi4Co square pyramids.
Li2CoCl4 crystallizes in the orthorhombic Cmmm 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 four equivalent Li(1)Cl6 octahedra, and edges with four equivalent Co(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 7°. Both Li(1)-Cl(1) bond lengths are 2.46 Å. All Li(1)-Cl(2) bond lengths are 2.55 Å. Co(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form CoCl6 octahedra that share edges with two equivalent Co(1)Cl6 octahedra and edges with eight equivalent Li(1)Cl6 octahedra. Both Co(1)-Cl(2) bond lengths are 2.30 Å. All Co(1)-Cl(1) bond lengths are 2.44 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Co(1) atoms. In the second Cl site, Cl(2) is bonded to four equivalent Li(1) and one Co(1) atom to form a mixture of edge and corner-sharing ClLi4Co square pyramids.