Li8SbS6 crystallizes in the trigonal R-3 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 LiS4 tetrahedra that share corners with two equivalent Sb(1)S6 octahedra, corners with four equivalent Li(2)S6 octahedra, corners with six equivalent Li(1)S4 tetrahedra,  an edgeedge with one Sb(1)S6 octahedra, edges with two equivalent Li(2)S6 octahedra, and edges with three equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-58°. In the second Li site, Li(2) is bonded to six equivalent S(1) atoms to form distorted LiS6 octahedra that share corners with twelve equivalent Li(1)S4 tetrahedra, edges with three equivalent Li(2)S6 octahedra, edges with three equivalent Sb(1)S6 octahedra, and edges with six equivalent Li(1)S4 tetrahedra. Sb(1) is bonded to six equivalent S(1) atoms to form SbS6 octahedra that share corners with twelve equivalent Li(1)S4 tetrahedra, edges with six equivalent Li(2)S6 octahedra, and edges with six equivalent Li(1)S4 tetrahedra. S(1) is bonded in a 7-coordinate geometry to two equivalent Li(2), four equivalent Li(1), and one Sb(1) atom.
Li8SbS6 crystallizes in the trigonal R-3 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 LiS4 tetrahedra that share corners with two equivalent Sb(1)S6 octahedra, corners with four equivalent Li(2)S6 octahedra, corners with six equivalent Li(1)S4 tetrahedra,  an edgeedge with one Sb(1)S6 octahedra, edges with two equivalent Li(2)S6 octahedra, and edges with three equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-58°. There are a spread of Li(1)-S(1) bond distances ranging from 2.41-2.50 Å. In the second Li site, Li(2) is bonded to six equivalent S(1) atoms to form distorted LiS6 octahedra that share corners with twelve equivalent Li(1)S4 tetrahedra, edges with three equivalent Li(2)S6 octahedra, edges with three equivalent Sb(1)S6 octahedra, and edges with six equivalent Li(1)S4 tetrahedra. There are three shorter (2.63 Å) and three longer (2.98 Å) Li(2)-S(1) bond lengths. Sb(1) is bonded to six equivalent S(1) atoms to form SbS6 octahedra that share corners with twelve equivalent Li(1)S4 tetrahedra, edges with six equivalent Li(2)S6 octahedra, and edges with six equivalent Li(1)S4 tetrahedra. All Sb(1)-S(1) bond lengths are 2.66 Å. S(1) is bonded in a 7-coordinate geometry to two equivalent Li(2), four equivalent Li(1), and one Sb(1) atom.