Li3Fe2S4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form distorted LiS5 square pyramids that share corners with two equivalent Li(1)S5 square pyramids, corners with six equivalent Fe(1)S4 tetrahedra, edges with two equivalent Li(1)S5 square pyramids, edges with two equivalent Fe(1)S4 tetrahedra, and  a faceface with one Li(1)S5 square pyramid. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent S(3) and four equivalent S(2) atoms. Fe(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form FeS4 tetrahedra that share corners with six equivalent Li(1)S5 square pyramids, edges with two equivalent Li(1)S5 square pyramids, and edges with two equivalent Fe(1)S4 tetrahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded to four equivalent Li(1) and two equivalent Fe(1) atoms to form distorted edge-sharing SLi4Fe2 pentagonal pyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent Fe(1) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent Fe(1) atoms.
Li3Fe2S4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form distorted LiS5 square pyramids that share corners with two equivalent Li(1)S5 square pyramids, corners with six equivalent Fe(1)S4 tetrahedra, edges with two equivalent Li(1)S5 square pyramids, edges with two equivalent Fe(1)S4 tetrahedra, and  a faceface with one Li(1)S5 square pyramid. The Li(1)-S(3) bond length is 2.87 Å. There is one shorter (2.55 Å) and one longer (2.61 Å) Li(1)-S(1) bond length. There is one shorter (2.62 Å) and one longer (2.72 Å) Li(1)-S(2) bond length. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent S(3) and four equivalent S(2) atoms. There is one shorter (2.49 Å) and one longer (2.55 Å) Li(2)-S(3) bond length. There are two shorter (2.64 Å) and two longer (2.98 Å) Li(2)-S(2) bond lengths. Fe(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form FeS4 tetrahedra that share corners with six equivalent Li(1)S5 square pyramids, edges with two equivalent Li(1)S5 square pyramids, and edges with two equivalent Fe(1)S4 tetrahedra. The Fe(1)-S(1) bond length is 2.25 Å. The Fe(1)-S(3) bond length is 2.25 Å. There is one shorter (2.26 Å) and one longer (2.28 Å) Fe(1)-S(2) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded to four equivalent Li(1) and two equivalent Fe(1) atoms to form distorted edge-sharing SLi4Fe2 pentagonal pyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent Fe(1) atoms. In the third S site, S(3) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent Fe(1) atoms.