Li7Sb2S crystallizes in the monoclinic P2_1/c space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 1-coordinate geometry to one Sb(2), two equivalent Sb(1), and one S(1) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one Sb(1), two equivalent Sb(2), and one S(1) atom. In the third Li site, Li(3) is bonded to one Sb(1), two equivalent Sb(2), and one S(1) atom to form a mixture of distorted corner and edge-sharing LiSb3S tetrahedra. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one Sb(1), one Sb(2), and one S(1) atom. In the fifth Li site, Li(5) is bonded to one Sb(2), two equivalent Sb(1), and one S(1) atom to form a mixture of distorted corner and edge-sharing LiSb3S tetrahedra. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one Sb(2), two equivalent Sb(1), and one S(1) atom. In the seventh Li site, Li(7) is bonded in a 1-coordinate geometry to one Sb(1), two equivalent Sb(2), and one S(1) atom. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 10-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(7), two equivalent Li(1), two equivalent Li(5), and two equivalent Li(6) atoms. In the second Sb site, Sb(2) is bonded in a 10-coordinate geometry to one Li(1), one Li(4), one Li(5), one Li(6), two equivalent Li(2), two equivalent Li(3), and two equivalent Li(7) atoms. S(1) is bonded in a distorted pentagonal bipyramidal geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Li(7) atom.
Li7Sb2S crystallizes in the monoclinic P2_1/c space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 1-coordinate geometry to one Sb(2), two equivalent Sb(1), and one S(1) atom. The Li(1)-Sb(2) bond length is 2.92 Å. There is one shorter (2.99 Å) and one longer (3.31 Å) Li(1)-Sb(1) bond length. The Li(1)-S(1) bond length is 2.41 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one Sb(1), two equivalent Sb(2), and one S(1) atom. The Li(2)-Sb(1) bond length is 2.86 Å. There is one shorter (2.82 Å) and one longer (2.96 Å) Li(2)-Sb(2) bond length. The Li(2)-S(1) bond length is 2.44 Å. In the third Li site, Li(3) is bonded to one Sb(1), two equivalent Sb(2), and one S(1) atom to form a mixture of distorted corner and edge-sharing LiSb3S tetrahedra. The Li(3)-Sb(1) bond length is 2.88 Å. There is one shorter (2.88 Å) and one longer (2.92 Å) Li(3)-Sb(2) bond length. The Li(3)-S(1) bond length is 2.46 Å. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one Sb(1), one Sb(2), and one S(1) atom. The Li(4)-Sb(1) bond length is 2.80 Å. The Li(4)-Sb(2) bond length is 2.80 Å. The Li(4)-S(1) bond length is 2.44 Å. In the fifth Li site, Li(5) is bonded to one Sb(2), two equivalent Sb(1), and one S(1) atom to form a mixture of distorted corner and edge-sharing LiSb3S tetrahedra. The Li(5)-Sb(2) bond length is 2.89 Å. There is one shorter (2.81 Å) and one longer (2.83 Å) Li(5)-Sb(1) bond length. The Li(5)-S(1) bond length is 2.43 Å. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one Sb(2), two equivalent Sb(1), and one S(1) atom. The Li(6)-Sb(2) bond length is 2.81 Å. There is one shorter (2.81 Å) and one longer (2.88 Å) Li(6)-Sb(1) bond length. The Li(6)-S(1) bond length is 2.42 Å. In the seventh Li site, Li(7) is bonded in a 1-coordinate geometry to one Sb(1), two equivalent Sb(2), and one S(1) atom. The Li(7)-Sb(1) bond length is 2.87 Å. There is one shorter (3.00 Å) and one longer (3.26 Å) Li(7)-Sb(2) bond length. The Li(7)-S(1) bond length is 2.40 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 10-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(7), two equivalent Li(1), two equivalent Li(5), and two equivalent Li(6) atoms. In the second Sb site, Sb(2) is bonded in a 10-coordinate geometry to one Li(1), one Li(4), one Li(5), one Li(6), two equivalent Li(2), two equivalent Li(3), and two equivalent Li(7) atoms. S(1) is bonded in a distorted pentagonal bipyramidal geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Li(7) atom.