Li3SbS3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form a mixture of edge and corner-sharing LiS4 tetrahedra. In the second Li site, Li(2) is bonded in a distorted trigonal non-coplanar geometry to one S(3) and two equivalent S(2) atoms. In the third Li site, Li(3) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form a mixture of edge and corner-sharing LiS4 tetrahedra. Sb(1) is bonded in a 3-coordinate geometry to one S(1), one S(2), and one S(3) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted pentagonal planar geometry to two equivalent Li(1), two equivalent Li(3), and one Sb(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Li(3), two equivalent Li(2), and one Sb(1) atom. In the third S site, S(3) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Sb(1) atom to form distorted corner-sharing SLi4Sb trigonal bipyramids.
Li3SbS3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form a mixture of edge and corner-sharing LiS4 tetrahedra. There is one shorter (2.49 Å) and one longer (2.63 Å) Li(1)-S(1) bond length. There is one shorter (2.45 Å) and one longer (2.46 Å) Li(1)-S(3) bond length. In the second Li site, Li(2) is bonded in a distorted trigonal non-coplanar geometry to one S(3) and two equivalent S(2) atoms. The Li(2)-S(3) bond length is 2.43 Å. There is one shorter (2.49 Å) and one longer (2.51 Å) Li(2)-S(2) bond length. In the third Li site, Li(3) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form a mixture of edge and corner-sharing LiS4 tetrahedra. The Li(3)-S(2) bond length is 2.49 Å. The Li(3)-S(3) bond length is 2.53 Å. There is one shorter (2.47 Å) and one longer (2.53 Å) Li(3)-S(1) bond length. Sb(1) is bonded in a 3-coordinate geometry to one S(1), one S(2), and one S(3) atom. The Sb(1)-S(1) bond length is 2.51 Å. The Sb(1)-S(2) bond length is 2.48 Å. The Sb(1)-S(3) bond length is 2.49 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted pentagonal planar geometry to two equivalent Li(1), two equivalent Li(3), and one Sb(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Li(3), two equivalent Li(2), and one Sb(1) atom. In the third S site, S(3) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Sb(1) atom to form distorted corner-sharing SLi4Sb trigonal bipyramids.