Li2Fe2S3 is Aluminum carbonitride-like structured and crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Li(1)S4 tetrahedra, corners with three equivalent Li(2)S4 tetrahedra, corners with four equivalent Fe(1)S4 tetrahedra, and  an edgeedge with one Li(2)S4 tetrahedra. In the second Li site, Li(2) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form LiS4 tetrahedra that share corners with three equivalent Li(1)S4 tetrahedra, corners with five equivalent Fe(1)S4 tetrahedra,  an edgeedge with one Li(1)S4 tetrahedra, and  an edgeedge with one Li(2)S4 tetrahedra. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one S(2) and three equivalent S(3) atoms to form distorted FeS4 tetrahedra that share corners with two equivalent Fe(1)S4 tetrahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with five equivalent Li(2)S4 tetrahedra, and edges with two equivalent Fe(1)S4 tetrahedra. In the second Fe site, Fe(2) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(2) atoms. In the third Fe site, Fe(3) is bonded in a 4-coordinate geometry to four equivalent S(1) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), one Fe(2), and two equivalent Fe(3) atoms. In the second S site, S(2) is bonded in a distorted pentagonal planar geometry to one Li(1), two equivalent Li(2), one Fe(1), and one Fe(2) atom. In the third S site, S(3) is bonded to one Li(1), one Li(2), and three equivalent Fe(1) atoms to form a mixture of distorted corner and edge-sharing SLi2Fe3 trigonal bipyramids.
Li2Fe2S3 is Aluminum carbonitride-like structured and crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Li(1)S4 tetrahedra, corners with three equivalent Li(2)S4 tetrahedra, corners with four equivalent Fe(1)S4 tetrahedra, and  an edgeedge with one Li(2)S4 tetrahedra. The Li(1)-S(2) bond length is 2.47 Å. The Li(1)-S(3) bond length is 2.39 Å. There is one shorter (2.42 Å) and one longer (2.46 Å) Li(1)-S(1) bond length. In the second Li site, Li(2) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form LiS4 tetrahedra that share corners with three equivalent Li(1)S4 tetrahedra, corners with five equivalent Fe(1)S4 tetrahedra,  an edgeedge with one Li(1)S4 tetrahedra, and  an edgeedge with one Li(2)S4 tetrahedra. The Li(2)-S(1) bond length is 2.43 Å. The Li(2)-S(3) bond length is 2.49 Å. There is one shorter (2.46 Å) and one longer (2.55 Å) Li(2)-S(2) bond length. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one S(2) and three equivalent S(3) atoms to form distorted FeS4 tetrahedra that share corners with two equivalent Fe(1)S4 tetrahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with five equivalent Li(2)S4 tetrahedra, and edges with two equivalent Fe(1)S4 tetrahedra. The Fe(1)-S(2) bond length is 2.30 Å. There are two shorter (2.36 Å) and one longer (2.39 Å) Fe(1)-S(3) bond length. In the second Fe site, Fe(2) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(2) atoms. Both Fe(2)-S(1) bond lengths are 2.42 Å. Both Fe(2)-S(2) bond lengths are 2.36 Å. In the third Fe site, Fe(3) is bonded in a 4-coordinate geometry to four equivalent S(1) atoms. There are two shorter (2.36 Å) and two longer (2.40 Å) Fe(3)-S(1) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), one Fe(2), and two equivalent Fe(3) atoms. In the second S site, S(2) is bonded in a distorted pentagonal planar geometry to one Li(1), two equivalent Li(2), one Fe(1), and one Fe(2) atom. In the third S site, S(3) is bonded to one Li(1), one Li(2), and three equivalent Fe(1) atoms to form a mixture of distorted corner and edge-sharing SLi2Fe3 trigonal bipyramids.