Li2Fe2S3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(2) and three equivalent S(3) atoms to form distorted LiS4 trigonal pyramids that share  a cornercorner with one Li(2)S6 octahedra,  a cornercorner with one Li(3)S6 octahedra, corners with four equivalent Fe(1)S4 tetrahedra, corners with five equivalent Fe(2)S4 tetrahedra, corners with two equivalent Li(1)S4 trigonal pyramids, edges with two equivalent Li(1)S4 trigonal pyramids, and  a faceface with one Li(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 37-46°. In the second Li site, Li(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form LiS6 octahedra that share corners with four equivalent Fe(1)S4 tetrahedra, corners with four equivalent Fe(2)S4 tetrahedra, corners with two equivalent Li(1)S4 trigonal pyramids, edges with three equivalent Li(3)S6 octahedra, edges with two equivalent Fe(1)S4 tetrahedra, edges with two equivalent Fe(2)S4 tetrahedra, and faces with two equivalent Li(1)S4 trigonal pyramids. In the third Li site, Li(3) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form LiS6 octahedra that share corners with two equivalent Fe(1)S4 tetrahedra, corners with four equivalent Fe(2)S4 tetrahedra, corners with two equivalent Li(1)S4 trigonal pyramids, edges with two equivalent Li(3)S6 octahedra, edges with three equivalent Li(2)S6 octahedra, edges with two equivalent Fe(2)S4 tetrahedra, and edges with four equivalent Fe(1)S4 tetrahedra. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form FeS4 tetrahedra that share  a cornercorner with one Li(3)S6 octahedra, corners with two equivalent Li(2)S6 octahedra, corners with two equivalent Fe(1)S4 tetrahedra, corners with three equivalent Fe(2)S4 tetrahedra, corners with four equivalent Li(1)S4 trigonal pyramids,  an edgeedge with one Li(2)S6 octahedra, edges with two equivalent Li(3)S6 octahedra, and  an edgeedge with one Fe(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-54°. In the second Fe site, Fe(2) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form FeS4 tetrahedra that share corners with two equivalent Li(2)S6 octahedra, corners with two equivalent Li(3)S6 octahedra, corners with three equivalent Fe(1)S4 tetrahedra, corners with five equivalent Li(1)S4 trigonal pyramids,  an edgeedge with one Li(2)S6 octahedra,  an edgeedge with one Li(3)S6 octahedra,  an edgeedge with one Fe(1)S4 tetrahedra, and  an edgeedge with one Fe(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-53°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(2), two equivalent Li(3), one Fe(2), and two equivalent Fe(1) atoms to form a mixture of distorted corner and edge-sharing SLi3Fe3 octahedra. The corner-sharing octahedral tilt angles range from 2-70°. In the second S site, S(2) is bonded to one Li(1), one Li(2), one Li(3), one Fe(1), and two equivalent Fe(2) atoms to form a mixture of distorted corner and edge-sharing SLi3Fe3 octahedra. The corner-sharing octahedral tilt angles range from 3-88°. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Li(2), three equivalent Li(1), one Fe(1), and one Fe(2) atom.
Li2Fe2S3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(2) and three equivalent S(3) atoms to form distorted LiS4 trigonal pyramids that share  a cornercorner with one Li(2)S6 octahedra,  a cornercorner with one Li(3)S6 octahedra, corners with four equivalent Fe(1)S4 tetrahedra, corners with five equivalent Fe(2)S4 tetrahedra, corners with two equivalent Li(1)S4 trigonal pyramids, edges with two equivalent Li(1)S4 trigonal pyramids, and  a faceface with one Li(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 37-46°. The Li(1)-S(2) bond length is 2.43 Å. There are a spread of Li(1)-S(3) bond distances ranging from 2.41-2.57 Å. In the second Li site, Li(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form LiS6 octahedra that share corners with four equivalent Fe(1)S4 tetrahedra, corners with four equivalent Fe(2)S4 tetrahedra, corners with two equivalent Li(1)S4 trigonal pyramids, edges with three equivalent Li(3)S6 octahedra, edges with two equivalent Fe(1)S4 tetrahedra, edges with two equivalent Fe(2)S4 tetrahedra, and faces with two equivalent Li(1)S4 trigonal pyramids. Both Li(2)-S(1) bond lengths are 2.67 Å. Both Li(2)-S(2) bond lengths are 2.66 Å. Both Li(2)-S(3) bond lengths are 2.74 Å. In the third Li site, Li(3) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form LiS6 octahedra that share corners with two equivalent Fe(1)S4 tetrahedra, corners with four equivalent Fe(2)S4 tetrahedra, corners with two equivalent Li(1)S4 trigonal pyramids, edges with two equivalent Li(3)S6 octahedra, edges with three equivalent Li(2)S6 octahedra, edges with two equivalent Fe(2)S4 tetrahedra, and edges with four equivalent Fe(1)S4 tetrahedra. Both Li(3)-S(2) bond lengths are 2.63 Å. There are two shorter (2.78 Å) and two longer (2.79 Å) Li(3)-S(1) bond lengths. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form FeS4 tetrahedra that share  a cornercorner with one Li(3)S6 octahedra, corners with two equivalent Li(2)S6 octahedra, corners with two equivalent Fe(1)S4 tetrahedra, corners with three equivalent Fe(2)S4 tetrahedra, corners with four equivalent Li(1)S4 trigonal pyramids,  an edgeedge with one Li(2)S6 octahedra, edges with two equivalent Li(3)S6 octahedra, and  an edgeedge with one Fe(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-54°. The Fe(1)-S(2) bond length is 2.34 Å. The Fe(1)-S(3) bond length is 2.30 Å. There is one shorter (2.35 Å) and one longer (2.37 Å) Fe(1)-S(1) bond length. In the second Fe site, Fe(2) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form FeS4 tetrahedra that share corners with two equivalent Li(2)S6 octahedra, corners with two equivalent Li(3)S6 octahedra, corners with three equivalent Fe(1)S4 tetrahedra, corners with five equivalent Li(1)S4 trigonal pyramids,  an edgeedge with one Li(2)S6 octahedra,  an edgeedge with one Li(3)S6 octahedra,  an edgeedge with one Fe(1)S4 tetrahedra, and  an edgeedge with one Fe(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-53°. The Fe(2)-S(1) bond length is 2.37 Å. The Fe(2)-S(3) bond length is 2.30 Å. There is one shorter (2.34 Å) and one longer (2.37 Å) Fe(2)-S(2) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(2), two equivalent Li(3), one Fe(2), and two equivalent Fe(1) atoms to form a mixture of distorted corner and edge-sharing SLi3Fe3 octahedra. The corner-sharing octahedral tilt angles range from 2-70°. In the second S site, S(2) is bonded to one Li(1), one Li(2), one Li(3), one Fe(1), and two equivalent Fe(2) atoms to form a mixture of distorted corner and edge-sharing SLi3Fe3 octahedra. The corner-sharing octahedral tilt angles range from 3-88°. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Li(2), three equivalent Li(1), one Fe(1), and one Fe(2) atom.