Li2CdCl4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Cl(1) and two equivalent Cl(2) atoms to form LiCl4 tetrahedra that share corners with six equivalent Li(2)Cl6 octahedra and corners with six equivalent Cd(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 52-62°. 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 six equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Li(2)Cl6 octahedra, and edges with four equivalent Cd(1)Cl6 octahedra. Cd(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form CdCl6 octahedra that share corners with six equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Cd(1)Cl6 octahedra, and edges with four equivalent Li(2)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 one Li(1), two equivalent Li(2), and one Cd(1) atom. In the second Cl site, Cl(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Cd(1) atoms.
Li2CdCl4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Cl(1) and two equivalent Cl(2) atoms to form LiCl4 tetrahedra that share corners with six equivalent Li(2)Cl6 octahedra and corners with six equivalent Cd(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 52-62°. Both Li(1)-Cl(1) bond lengths are 2.38 Å. Both Li(1)-Cl(2) bond lengths are 2.41 Å. 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 six equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Li(2)Cl6 octahedra, and edges with four equivalent Cd(1)Cl6 octahedra. Both Li(2)-Cl(2) bond lengths are 2.57 Å. All Li(2)-Cl(1) bond lengths are 2.58 Å. Cd(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form CdCl6 octahedra that share corners with six equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Cd(1)Cl6 octahedra, and edges with four equivalent Li(2)Cl6 octahedra. Both Cd(1)-Cl(1) bond lengths are 2.59 Å. All Cd(1)-Cl(2) bond lengths are 2.66 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Cd(1) atom. In the second Cl site, Cl(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Cd(1) atoms.