Li5FeS4 crystallizes in the orthorhombic Imm2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted LiS4 tetrahedra that share  a cornercorner with one Fe(1)S6 octahedra, corners with five equivalent Li(1)S4 tetrahedra, corners with five equivalent Li(2)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra,  an edgeedge with one Li(1)S4 tetrahedra, and edges with two equivalent Li(2)S4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. In the second Li site, Li(2) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form distorted LiS4 tetrahedra that share  a cornercorner with one Fe(1)S6 octahedra, corners with five equivalent Li(1)S4 tetrahedra, corners with five equivalent Li(2)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra,  an edgeedge with one Li(2)S4 tetrahedra, and edges with two equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. In the third Li site, Li(3) is bonded in a square co-planar geometry to four equivalent S(1) atoms. Fe(1) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form FeS6 octahedra that share corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra, edges with four equivalent Li(1)S4 tetrahedra, and edges with four equivalent Li(2)S4 tetrahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Fe(1) atoms to form a mixture of corner and edge-sharing SLi4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. In the second S site, S(2) is bonded in a 7-coordinate geometry to two equivalent Li(2), four equivalent Li(1), and one Fe(1) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent Li(1), four equivalent Li(2), and one Fe(1) atom.
Li5FeS4 crystallizes in the orthorhombic Imm2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted LiS4 tetrahedra that share  a cornercorner with one Fe(1)S6 octahedra, corners with five equivalent Li(1)S4 tetrahedra, corners with five equivalent Li(2)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra,  an edgeedge with one Li(1)S4 tetrahedra, and edges with two equivalent Li(2)S4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The Li(1)-S(1) bond length is 2.36 Å. The Li(1)-S(3) bond length is 2.49 Å. Both Li(1)-S(2) bond lengths are 2.40 Å. In the second Li site, Li(2) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form distorted LiS4 tetrahedra that share  a cornercorner with one Fe(1)S6 octahedra, corners with five equivalent Li(1)S4 tetrahedra, corners with five equivalent Li(2)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra,  an edgeedge with one Li(2)S4 tetrahedra, and edges with two equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. The Li(2)-S(1) bond length is 2.40 Å. The Li(2)-S(2) bond length is 2.48 Å. Both Li(2)-S(3) bond lengths are 2.38 Å. In the third Li site, Li(3) is bonded in a square co-planar geometry to four equivalent S(1) atoms. All Li(3)-S(1) bond lengths are 2.53 Å. Fe(1) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form FeS6 octahedra that share corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra, edges with four equivalent Li(1)S4 tetrahedra, and edges with four equivalent Li(2)S4 tetrahedra. The Fe(1)-S(2) bond length is 2.77 Å. The Fe(1)-S(3) bond length is 2.64 Å. All Fe(1)-S(1) bond lengths are 2.50 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Fe(1) atoms to form a mixture of corner and edge-sharing SLi4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. In the second S site, S(2) is bonded in a 7-coordinate geometry to two equivalent Li(2), four equivalent Li(1), and one Fe(1) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent Li(1), four equivalent Li(2), and one Fe(1) atom.