Li6CrS4 crystallizes in the tetragonal P4_2/nmc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent S(1) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Cr(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with eight equivalent Li(1)S4 tetrahedra,  an edgeedge with one Cr(1)S4 tetrahedra, edges with two equivalent Li(1)S4 tetrahedra, and edges with two equivalent Li(2)S4 tetrahedra. In the second Li site, Li(2) is bonded to four equivalent S(1) atoms to form LiS4 tetrahedra that share corners with four equivalent Cr(1)S4 tetrahedra, corners with eight equivalent Li(1)S4 tetrahedra, edges with two equivalent Li(2)S4 tetrahedra, and edges with four equivalent Li(1)S4 tetrahedra. Cr(1) is bonded to four equivalent S(1) atoms to form distorted CrS4 tetrahedra that share corners with eight equivalent Li(1)S4 tetrahedra, corners with eight equivalent Li(2)S4 tetrahedra, and edges with four equivalent Li(1)S4 tetrahedra. S(1) is bonded to two equivalent Li(2), four equivalent Li(1), and one Cr(1) atom to form a mixture of distorted corner and edge-sharing SLi6Cr pentagonal bipyramids.
Li6CrS4 crystallizes in the tetragonal P4_2/nmc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent S(1) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Cr(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with eight equivalent Li(1)S4 tetrahedra,  an edgeedge with one Cr(1)S4 tetrahedra, edges with two equivalent Li(1)S4 tetrahedra, and edges with two equivalent Li(2)S4 tetrahedra. There are two shorter (2.50 Å) and two longer (2.53 Å) Li(1)-S(1) bond lengths. In the second Li site, Li(2) is bonded to four equivalent S(1) atoms to form LiS4 tetrahedra that share corners with four equivalent Cr(1)S4 tetrahedra, corners with eight equivalent Li(1)S4 tetrahedra, edges with two equivalent Li(2)S4 tetrahedra, and edges with four equivalent Li(1)S4 tetrahedra. There are two shorter (2.41 Å) and two longer (2.42 Å) Li(2)-S(1) bond lengths. Cr(1) is bonded to four equivalent S(1) atoms to form distorted CrS4 tetrahedra that share corners with eight equivalent Li(1)S4 tetrahedra, corners with eight equivalent Li(2)S4 tetrahedra, and edges with four equivalent Li(1)S4 tetrahedra. All Cr(1)-S(1) bond lengths are 2.40 Å. S(1) is bonded to two equivalent Li(2), four equivalent Li(1), and one Cr(1) atom to form a mixture of distorted corner and edge-sharing SLi6Cr pentagonal bipyramids.