Li3SbS4 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(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted LiS5 trigonal bipyramids that share corners with three equivalent Sb(1)S4 tetrahedra, corners with seven equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one Sb(1)S4 tetrahedra, and  an edgeedge with one Li(1)S5 trigonal bipyramid. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to two equivalent S(1) and two equivalent S(2) atoms. Sb(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form SbS4 tetrahedra that share corners with six equivalent Li(1)S5 trigonal bipyramids and edges with two equivalent Li(1)S5 trigonal bipyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one Sb(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Sb(1) atom. In the third S site, S(3) is bonded to four equivalent Li(1) and one Sb(1) atom to form edge-sharing SLi4Sb trigonal bipyramids.
Li3SbS4 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(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted LiS5 trigonal bipyramids that share corners with three equivalent Sb(1)S4 tetrahedra, corners with seven equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one Sb(1)S4 tetrahedra, and  an edgeedge with one Li(1)S5 trigonal bipyramid. The Li(1)-S(1) bond length is 2.91 Å. There is one shorter (2.55 Å) and one longer (2.69 Å) Li(1)-S(2) bond length. There is one shorter (2.59 Å) and one longer (2.63 Å) Li(1)-S(3) bond length. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to two equivalent S(1) and two equivalent S(2) atoms. There is one shorter (2.53 Å) and one longer (2.59 Å) Li(2)-S(1) bond length. Both Li(2)-S(2) bond lengths are 2.57 Å. Sb(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form SbS4 tetrahedra that share corners with six equivalent Li(1)S5 trigonal bipyramids and edges with two equivalent Li(1)S5 trigonal bipyramids. The Sb(1)-S(1) bond length is 2.37 Å. The Sb(1)-S(3) bond length is 2.38 Å. Both Sb(1)-S(2) bond lengths are 2.37 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one Sb(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Sb(1) atom. In the third S site, S(3) is bonded to four equivalent Li(1) and one Sb(1) atom to form edge-sharing SLi4Sb trigonal bipyramids.