Li5BiS4 crystallizes in the orthorhombic Immm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1) and three equivalent S(2) atoms to form LiS4 tetrahedra that share  a cornercorner with one Bi(1)S6 octahedra, corners with ten equivalent Li(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with three equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. In the second Li site, Li(2) is bonded in a square co-planar geometry to four equivalent S(1) atoms. Bi(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form BiS6 octahedra that share corners with four equivalent Li(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with eight equivalent Li(1)S4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing SLi4Bi2 octahedra. The corner-sharing octahedra are not tilted. In the second S site, S(2) is bonded in a 7-coordinate geometry to six equivalent Li(1) and one Bi(1) atom.
Li5BiS4 crystallizes in the orthorhombic Immm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1) and three equivalent S(2) atoms to form LiS4 tetrahedra that share  a cornercorner with one Bi(1)S6 octahedra, corners with ten equivalent Li(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with three equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. The Li(1)-S(1) bond length is 2.48 Å. There are two shorter (2.51 Å) and one longer (2.57 Å) Li(1)-S(2) bond length. In the second Li site, Li(2) is bonded in a square co-planar geometry to four equivalent S(1) atoms. All Li(2)-S(1) bond lengths are 2.56 Å. Bi(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form BiS6 octahedra that share corners with four equivalent Li(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with eight equivalent Li(1)S4 tetrahedra. Both Bi(1)-S(2) bond lengths are 2.89 Å. All Bi(1)-S(1) bond lengths are 2.80 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing SLi4Bi2 octahedra. The corner-sharing octahedra are not tilted. In the second S site, S(2) is bonded in a 7-coordinate geometry to six equivalent Li(1) and one Bi(1) atom.