Li2ZnI4 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 I(1), two equivalent I(2), and two equivalent I(3) atoms to form LiI6 octahedra that share corners with four equivalent Li(2)I6 octahedra, corners with two equivalent Zn(1)I4 tetrahedra, edges with two equivalent Li(1)I6 octahedra, edges with two equivalent Li(2)I6 octahedra, and edges with two equivalent Zn(1)I4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-54°. In the second Li site, Li(2) is bonded to one I(1), one I(2), and four equivalent I(3) atoms to form LiI6 octahedra that share corners with four equivalent Li(1)I6 octahedra, corners with four equivalent Li(2)I6 octahedra, corners with four equivalent Zn(1)I4 tetrahedra, edges with two equivalent Li(1)I6 octahedra, and  an edgeedge with one Zn(1)I4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-54°. Zn(1) is bonded to one I(1), one I(2), and two equivalent I(3) atoms to form ZnI4 tetrahedra that share corners with two equivalent Li(1)I6 octahedra, corners with four equivalent Li(2)I6 octahedra,  an edgeedge with one Li(2)I6 octahedra, and edges with two equivalent Li(1)I6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°. There are three inequivalent I sites. In the first I site, I(1) is bonded to one Li(2), two equivalent Li(1), and one Zn(1) atom to form distorted corner-sharing ILi3Zn trigonal pyramids. In the second I site, I(2) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Zn(1) atom. In the third I site, I(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Zn(1) atom.
Li2ZnI4 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 I(1), two equivalent I(2), and two equivalent I(3) atoms to form LiI6 octahedra that share corners with four equivalent Li(2)I6 octahedra, corners with two equivalent Zn(1)I4 tetrahedra, edges with two equivalent Li(1)I6 octahedra, edges with two equivalent Li(2)I6 octahedra, and edges with two equivalent Zn(1)I4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-54°. Both Li(1)-I(1) bond lengths are 3.01 Å. Both Li(1)-I(2) bond lengths are 3.01 Å. Both Li(1)-I(3) bond lengths are 3.05 Å. In the second Li site, Li(2) is bonded to one I(1), one I(2), and four equivalent I(3) atoms to form LiI6 octahedra that share corners with four equivalent Li(1)I6 octahedra, corners with four equivalent Li(2)I6 octahedra, corners with four equivalent Zn(1)I4 tetrahedra, edges with two equivalent Li(1)I6 octahedra, and  an edgeedge with one Zn(1)I4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-54°. The Li(2)-I(1) bond length is 3.09 Å. The Li(2)-I(2) bond length is 2.98 Å. There are two shorter (3.06 Å) and two longer (3.09 Å) Li(2)-I(3) bond lengths. Zn(1) is bonded to one I(1), one I(2), and two equivalent I(3) atoms to form ZnI4 tetrahedra that share corners with two equivalent Li(1)I6 octahedra, corners with four equivalent Li(2)I6 octahedra,  an edgeedge with one Li(2)I6 octahedra, and edges with two equivalent Li(1)I6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°. The Zn(1)-I(1) bond length is 2.61 Å. The Zn(1)-I(2) bond length is 2.66 Å. Both Zn(1)-I(3) bond lengths are 2.66 Å. There are three inequivalent I sites. In the first I site, I(1) is bonded to one Li(2), two equivalent Li(1), and one Zn(1) atom to form distorted corner-sharing ILi3Zn trigonal pyramids. In the second I site, I(2) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Zn(1) atom. In the third I site, I(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Zn(1) atom.