Li8BiS6 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 Bi(1)S6 octahedra, corners with six equivalent Li(1)S4 tetrahedra,  an edgeedge with one Bi(1)S6 octahedra, and edges with three equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-56°. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to six equivalent S(1) atoms. Bi(1) is bonded to six equivalent S(1) atoms to form BiS6 octahedra that share corners with twelve equivalent Li(1)S4 tetrahedra 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 Bi(1) atom.
Li8BiS6 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 Bi(1)S6 octahedra, corners with six equivalent Li(1)S4 tetrahedra,  an edgeedge with one Bi(1)S6 octahedra, and edges with three equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-56°. There are a spread of Li(1)-S(1) bond distances ranging from 2.41-2.49 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to six equivalent S(1) atoms. There are three shorter (2.64 Å) and three longer (3.04 Å) Li(2)-S(1) bond lengths. Bi(1) is bonded to six equivalent S(1) atoms to form BiS6 octahedra that share corners with twelve equivalent Li(1)S4 tetrahedra and edges with six equivalent Li(1)S4 tetrahedra. All Bi(1)-S(1) bond lengths are 2.76 Å. S(1) is bonded in a 7-coordinate geometry to two equivalent Li(2), four equivalent Li(1), and one Bi(1) atom.