Li6SbS2 crystallizes in the monoclinic P2_1/c space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one Sb(1), one S(2), and two equivalent S(1) atoms. In the second Li site, Li(2) is bonded to one Sb(1), one S(2), and two equivalent S(1) atoms to form a mixture of distorted corner and edge-sharing LiSbS3 tetrahedra. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to two equivalent Sb(1) and one S(2) atom. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to two equivalent Sb(1) and two equivalent S(2) atoms. In the fifth Li site, Li(5) is bonded to one Sb(1), one S(2), and two equivalent S(1) atoms to form a mixture of distorted corner and edge-sharing LiSbS3 tetrahedra. In the sixth Li site, Li(6) is bonded to one Sb(1), one S(2), and two equivalent S(1) atoms to form a mixture of distorted corner and edge-sharing LiSbS3 tetrahedra. Sb(1) is bonded in a 8-coordinate geometry to one Li(1), one Li(2), one Li(5), one Li(6), two equivalent Li(3), and two equivalent Li(4) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a body-centered cubic geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(5), and two equivalent Li(6) atoms. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(5), one Li(6), and two equivalent Li(4) atoms.
Li6SbS2 crystallizes in the monoclinic P2_1/c space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one Sb(1), one S(2), and two equivalent S(1) atoms. The Li(1)-Sb(1) bond length is 3.01 Å. The Li(1)-S(2) bond length is 2.47 Å. Both Li(1)-S(1) bond lengths are 2.54 Å. In the second Li site, Li(2) is bonded to one Sb(1), one S(2), and two equivalent S(1) atoms to form a mixture of distorted corner and edge-sharing LiSbS3 tetrahedra. The Li(2)-Sb(1) bond length is 2.85 Å. The Li(2)-S(2) bond length is 2.39 Å. There is one shorter (2.67 Å) and one longer (2.68 Å) Li(2)-S(1) bond length. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to two equivalent Sb(1) and one S(2) atom. Both Li(3)-Sb(1) bond lengths are 2.66 Å. The Li(3)-S(2) bond length is 2.26 Å. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to two equivalent Sb(1) and two equivalent S(2) atoms. There is one shorter (2.80 Å) and one longer (3.06 Å) Li(4)-Sb(1) bond length. There is one shorter (2.43 Å) and one longer (2.52 Å) Li(4)-S(2) bond length. In the fifth Li site, Li(5) is bonded to one Sb(1), one S(2), and two equivalent S(1) atoms to form a mixture of distorted corner and edge-sharing LiSbS3 tetrahedra. The Li(5)-Sb(1) bond length is 2.87 Å. The Li(5)-S(2) bond length is 2.40 Å. Both Li(5)-S(1) bond lengths are 2.56 Å. In the sixth Li site, Li(6) is bonded to one Sb(1), one S(2), and two equivalent S(1) atoms to form a mixture of distorted corner and edge-sharing LiSbS3 tetrahedra. The Li(6)-Sb(1) bond length is 2.88 Å. The Li(6)-S(2) bond length is 2.41 Å. There is one shorter (2.52 Å) and one longer (2.53 Å) Li(6)-S(1) bond length. Sb(1) is bonded in a 8-coordinate geometry to one Li(1), one Li(2), one Li(5), one Li(6), two equivalent Li(3), and two equivalent Li(4) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a body-centered cubic geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(5), and two equivalent Li(6) atoms. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(5), one Li(6), and two equivalent Li(4) atoms.