Li2Fe3S4 is Spinel-like structured and crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one S(2) and three equivalent S(1) atoms to form distorted LiS4 trigonal pyramids that share corners with six equivalent Fe(1)S4 tetrahedra, corners with two equivalent Li(1)S4 trigonal pyramids, and edges with two equivalent Li(1)S4 trigonal pyramids. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one S(1) and three equivalent S(2) atoms to form FeS4 tetrahedra that share corners with four equivalent Fe(1)S4 tetrahedra, corners with six equivalent Li(1)S4 trigonal pyramids, and  an edgeedge with one Fe(1)S4 tetrahedra. In the second Fe site, Fe(2) is bonded in a 4-coordinate geometry to four equivalent S(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Li(1), one Fe(1), and two equivalent Fe(2) atoms to form distorted SLi3Fe3 octahedra that share corners with five equivalent S(1)Li3Fe3 octahedra, corners with six equivalent S(2)LiFe3 tetrahedra, edges with two equivalent S(1)Li3Fe3 octahedra, and  a faceface with one S(1)Li3Fe3 octahedra. The corner-sharing octahedral tilt angles range from 42-80°. In the second S site, S(2) is bonded to one Li(1) and three equivalent Fe(1) atoms to form distorted SLiFe3 tetrahedra that share corners with six equivalent S(1)Li3Fe3 octahedra, corners with four equivalent S(2)LiFe3 tetrahedra, and  an edgeedge with one S(2)LiFe3 tetrahedra. The corner-sharing octahedral tilt angles range from 60-74°.
Li2Fe3S4 is Spinel-like structured and crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one S(2) and three equivalent S(1) atoms to form distorted LiS4 trigonal pyramids that share corners with six equivalent Fe(1)S4 tetrahedra, corners with two equivalent Li(1)S4 trigonal pyramids, and edges with two equivalent Li(1)S4 trigonal pyramids. The Li(1)-S(2) bond length is 2.41 Å. There are a spread of Li(1)-S(1) bond distances ranging from 2.50-2.55 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one S(1) and three equivalent S(2) atoms to form FeS4 tetrahedra that share corners with four equivalent Fe(1)S4 tetrahedra, corners with six equivalent Li(1)S4 trigonal pyramids, and  an edgeedge with one Fe(1)S4 tetrahedra. The Fe(1)-S(1) bond length is 2.33 Å. There are a spread of Fe(1)-S(2) bond distances ranging from 2.30-2.32 Å. In the second Fe site, Fe(2) is bonded in a 4-coordinate geometry to four equivalent S(1) atoms. There are two shorter (2.38 Å) and two longer (2.42 Å) Fe(2)-S(1) bond lengths. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Li(1), one Fe(1), and two equivalent Fe(2) atoms to form distorted SLi3Fe3 octahedra that share corners with five equivalent S(1)Li3Fe3 octahedra, corners with six equivalent S(2)LiFe3 tetrahedra, edges with two equivalent S(1)Li3Fe3 octahedra, and  a faceface with one S(1)Li3Fe3 octahedra. The corner-sharing octahedral tilt angles range from 42-80°. In the second S site, S(2) is bonded to one Li(1) and three equivalent Fe(1) atoms to form distorted SLiFe3 tetrahedra that share corners with six equivalent S(1)Li3Fe3 octahedra, corners with four equivalent S(2)LiFe3 tetrahedra, and  an edgeedge with one S(2)LiFe3 tetrahedra. The corner-sharing octahedral tilt angles range from 60-74°.