Li5CrS4 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 distorted LiS4 tetrahedra that share  a cornercorner with one Cr(1)S6 octahedra, corners with ten equivalent Li(1)S4 tetrahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with three equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. In the second Li site, Li(2) is bonded in a square co-planar geometry to four equivalent S(1) atoms. Cr(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form CrS6 octahedra that share corners with four equivalent Li(1)S4 tetrahedra, edges with two equivalent Cr(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 Cr(1) atoms to form SLi4Cr2 octahedra that share corners with two equivalent S(2)Li6Cr hexagonal pyramids, corners with four equivalent S(1)Li4Cr2 octahedra, edges with four equivalent S(2)Li6Cr hexagonal pyramids, and edges with four equivalent S(1)Li4Cr2 octahedra. The corner-sharing octahedra are not tilted. In the second S site, S(2) is bonded to six equivalent Li(1) and one Cr(1) atom to form distorted SLi6Cr hexagonal pyramids that share  a cornercorner with one S(2)Li6Cr hexagonal pyramid, corners with two equivalent S(1)Li4Cr2 octahedra, edges with six equivalent S(2)Li6Cr hexagonal pyramids, and edges with four equivalent S(1)Li4Cr2 octahedra. The corner-sharing octahedral tilt angles are 54°.
Li5CrS4 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 distorted LiS4 tetrahedra that share  a cornercorner with one Cr(1)S6 octahedra, corners with ten equivalent Li(1)S4 tetrahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with three equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The Li(1)-S(1) bond length is 2.33 Å. There are two shorter (2.38 Å) and one longer (2.53 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 2.55 Å. Cr(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form CrS6 octahedra that share corners with four equivalent Li(1)S4 tetrahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with eight equivalent Li(1)S4 tetrahedra. Both Cr(1)-S(2) bond lengths are 2.59 Å. All Cr(1)-S(1) bond lengths are 2.49 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 Cr(1) atoms to form SLi4Cr2 octahedra that share corners with two equivalent S(2)Li6Cr hexagonal pyramids, corners with four equivalent S(1)Li4Cr2 octahedra, edges with four equivalent S(2)Li6Cr hexagonal pyramids, and edges with four equivalent S(1)Li4Cr2 octahedra. The corner-sharing octahedra are not tilted. In the second S site, S(2) is bonded to six equivalent Li(1) and one Cr(1) atom to form distorted SLi6Cr hexagonal pyramids that share  a cornercorner with one S(2)Li6Cr hexagonal pyramid, corners with two equivalent S(1)Li4Cr2 octahedra, edges with six equivalent S(2)Li6Cr hexagonal pyramids, and edges with four equivalent S(1)Li4Cr2 octahedra. The corner-sharing octahedral tilt angles are 54°.