Li5SbS crystallizes in the orthorhombic P2_12_12_1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one Sb(1) and three equivalent S(1) atoms. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to two equivalent Sb(1) and one S(1) atom. In the third Li site, Li(3) is bonded to one Sb(1) and three equivalent S(1) atoms to form distorted corner-sharing LiSbS3 tetrahedra. In the fourth Li site, Li(4) is bonded in a distorted trigonal non-coplanar geometry to four equivalent Sb(1) atoms. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to three equivalent Sb(1) and one S(1) atom. Sb(1) is bonded in a 11-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), three equivalent Li(5), and four equivalent Li(4) atoms. S(1) is bonded in a body-centered cubic geometry to one Li(2), one Li(5), three equivalent Li(1), and three equivalent Li(3) atoms.
Li5SbS crystallizes in the orthorhombic P2_12_12_1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one Sb(1) and three equivalent S(1) atoms. The Li(1)-Sb(1) bond length is 2.98 Å. There are a spread of Li(1)-S(1) bond distances ranging from 2.43-2.64 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to two equivalent Sb(1) and one S(1) atom. Both Li(2)-Sb(1) bond lengths are 2.72 Å. The Li(2)-S(1) bond length is 2.35 Å. In the third Li site, Li(3) is bonded to one Sb(1) and three equivalent S(1) atoms to form distorted corner-sharing LiSbS3 tetrahedra. The Li(3)-Sb(1) bond length is 2.81 Å. There are a spread of Li(3)-S(1) bond distances ranging from 2.48-2.68 Å. In the fourth Li site, Li(4) is bonded in a distorted trigonal non-coplanar geometry to four equivalent Sb(1) atoms. There are a spread of Li(4)-Sb(1) bond distances ranging from 2.84-3.24 Å. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to three equivalent Sb(1) and one S(1) atom. There are two shorter (2.82 Å) and one longer (3.02 Å) Li(5)-Sb(1) bond length. The Li(5)-S(1) bond length is 2.53 Å. Sb(1) is bonded in a 11-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), three equivalent Li(5), and four equivalent Li(4) atoms. S(1) is bonded in a body-centered cubic geometry to one Li(2), one Li(5), three equivalent Li(1), and three equivalent Li(3) atoms.