Li2ZnCl4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form LiCl6 octahedra that share corners with four equivalent Li(2)Cl6 octahedra, corners with two equivalent Zn(1)Cl4 tetrahedra, edges with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Li(2)Cl6 octahedra, and edges with two equivalent Zn(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-54°. In the second Li site, Li(2) is bonded to one Cl(2), one Cl(3), and four equivalent Cl(1) atoms to form LiCl6 octahedra that share corners with four equivalent Li(1)Cl6 octahedra, corners with four equivalent Li(2)Cl6 octahedra, corners with four equivalent Zn(1)Cl4 tetrahedra, edges with two equivalent Li(1)Cl6 octahedra, and  an edgeedge with one Zn(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-54°. Zn(1) is bonded to one Cl(2), one Cl(3), and two equivalent Cl(1) atoms to form ZnCl4 tetrahedra that share corners with two equivalent Li(1)Cl6 octahedra, corners with four equivalent Li(2)Cl6 octahedra,  an edgeedge with one Li(2)Cl6 octahedra, and edges with two equivalent Li(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 59-63°. There are three 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 Zn(1) atom. In the second Cl site, Cl(2) is bonded to one Li(2), two equivalent Li(1), and one Zn(1) atom to form distorted corner-sharing ClLi3Zn trigonal pyramids. In the third Cl site, Cl(3) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Zn(1) atom.
Li2ZnCl4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form LiCl6 octahedra that share corners with four equivalent Li(2)Cl6 octahedra, corners with two equivalent Zn(1)Cl4 tetrahedra, edges with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Li(2)Cl6 octahedra, and edges with two equivalent Zn(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-54°. Both Li(1)-Cl(1) bond lengths are 2.60 Å. Both Li(1)-Cl(2) bond lengths are 2.52 Å. Both Li(1)-Cl(3) bond lengths are 2.57 Å. In the second Li site, Li(2) is bonded to one Cl(2), one Cl(3), and four equivalent Cl(1) atoms to form LiCl6 octahedra that share corners with four equivalent Li(1)Cl6 octahedra, corners with four equivalent Li(2)Cl6 octahedra, corners with four equivalent Zn(1)Cl4 tetrahedra, edges with two equivalent Li(1)Cl6 octahedra, and  an edgeedge with one Zn(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-54°. The Li(2)-Cl(2) bond length is 2.60 Å. The Li(2)-Cl(3) bond length is 2.50 Å. There are two shorter (2.54 Å) and two longer (2.70 Å) Li(2)-Cl(1) bond lengths. Zn(1) is bonded to one Cl(2), one Cl(3), and two equivalent Cl(1) atoms to form ZnCl4 tetrahedra that share corners with two equivalent Li(1)Cl6 octahedra, corners with four equivalent Li(2)Cl6 octahedra,  an edgeedge with one Li(2)Cl6 octahedra, and edges with two equivalent Li(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 59-63°. The Zn(1)-Cl(2) bond length is 2.23 Å. The Zn(1)-Cl(3) bond length is 2.29 Å. Both Zn(1)-Cl(1) bond lengths are 2.28 Å. There are three 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 Zn(1) atom. In the second Cl site, Cl(2) is bonded to one Li(2), two equivalent Li(1), and one Zn(1) atom to form distorted corner-sharing ClLi3Zn trigonal pyramids. In the third Cl site, Cl(3) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Zn(1) atom.