Li5SbS3I2 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one S(1), two equivalent S(2), and one I(1) atom. In the second Li site, Li(2) is bonded to two equivalent S(2) and two equivalent I(2) atoms to form edge-sharing LiS2I2 tetrahedra. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one S(1), one S(2), one I(2), and two equivalent I(1) atoms. Sb(1) is bonded in a distorted T-shaped geometry to one S(1) and two equivalent S(2) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Li(1), two equivalent Li(3), and one Sb(1) atom to form a mixture of distorted edge and corner-sharing SLi4Sb trigonal bipyramids. In the second S site, S(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Sb(1) atom to form a mixture of distorted edge and corner-sharing SLi4Sb trigonal bipyramids. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 6-coordinate geometry to two equivalent Li(1) and four equivalent Li(3) atoms. In the second I site, I(2) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2) and two equivalent Li(3) atoms.
Li5SbS3I2 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one S(1), two equivalent S(2), and one I(1) atom. The Li(1)-S(1) bond length is 2.44 Å. There is one shorter (2.48 Å) and one longer (2.52 Å) Li(1)-S(2) bond length. The Li(1)-I(1) bond length is 2.80 Å. In the second Li site, Li(2) is bonded to two equivalent S(2) and two equivalent I(2) atoms to form edge-sharing LiS2I2 tetrahedra. Both Li(2)-S(2) bond lengths are 2.45 Å. There is one shorter (2.80 Å) and one longer (2.93 Å) Li(2)-I(2) bond length. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one S(1), one S(2), one I(2), and two equivalent I(1) atoms. The Li(3)-S(1) bond length is 2.48 Å. The Li(3)-S(2) bond length is 2.48 Å. The Li(3)-I(2) bond length is 2.85 Å. There is one shorter (3.15 Å) and one longer (3.35 Å) Li(3)-I(1) bond length. Sb(1) is bonded in a distorted T-shaped geometry to one S(1) and two equivalent S(2) atoms. The Sb(1)-S(1) bond length is 2.49 Å. Both Sb(1)-S(2) bond lengths are 2.47 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Li(1), two equivalent Li(3), and one Sb(1) atom to form a mixture of distorted edge and corner-sharing SLi4Sb trigonal bipyramids. In the second S site, S(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Sb(1) atom to form a mixture of distorted edge and corner-sharing SLi4Sb trigonal bipyramids. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 6-coordinate geometry to two equivalent Li(1) and four equivalent Li(3) atoms. In the second I site, I(2) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2) and two equivalent Li(3) atoms.