Li34(Sb3S2)3 crystallizes in the tetragonal I4/m space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 2-coordinate geometry to two equivalent Sb(1) and two equivalent S(1) atoms. In the second Li site, Li(2) is bonded in a 2-coordinate geometry to two equivalent Sb(1), one S(1), and one S(2) atom. In the third Li site, Li(3) is bonded to one Sb(2), two equivalent Sb(1), and one S(1) atom to form distorted LiSb3S tetrahedra that share corners with two equivalent Li(5)Sb2S2 tetrahedra, corners with two equivalent Li(6)Sb4 tetrahedra, corners with four equivalent Li(3)Sb3S tetrahedra, corners with four equivalent Li(4)Sb3S tetrahedra,  an edgeedge with one Li(5)Sb2S2 tetrahedra,  an edgeedge with one Li(4)Sb3S tetrahedra, and edges with three equivalent Li(3)Sb3S tetrahedra. In the fourth Li site, Li(4) is bonded to three equivalent Sb(1) and one S(2) atom to form distorted LiSb3S tetrahedra that share  a cornercorner with one Li(6)Sb4 tetrahedra, corners with three equivalent Li(5)Sb2S2 tetrahedra, corners with three equivalent Li(4)Sb3S tetrahedra, corners with four equivalent Li(3)Sb3S tetrahedra,  an edgeedge with one Li(3)Sb3S tetrahedra,  an edgeedge with one Li(6)Sb4 tetrahedra, and edges with three equivalent Li(4)Sb3S tetrahedra. In the fifth Li site, Li(5) is bonded to two equivalent Sb(1) and two equivalent S(1) atoms to form distorted LiSb2S2 tetrahedra that share corners with four equivalent Li(3)Sb3S tetrahedra, corners with six equivalent Li(4)Sb3S tetrahedra,  an edgeedge with one Li(5)Sb2S2 tetrahedra,  an edgeedge with one Li(6)Sb4 tetrahedra, and edges with two equivalent Li(3)Sb3S tetrahedra. In the sixth Li site, Li(6) is bonded to four equivalent Sb(1) atoms to form LiSb4 tetrahedra that share corners with four equivalent Li(4)Sb3S tetrahedra, corners with eight equivalent Li(3)Sb3S tetrahedra, edges with two equivalent Li(5)Sb2S2 tetrahedra, and edges with four equivalent Li(4)Sb3S tetrahedra. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 10-coordinate geometry to one Li(1), one Li(5), one Li(6), two equivalent Li(2), two equivalent Li(3), and three equivalent Li(4) atoms. In the second Sb site, Sb(2) is bonded in a body-centered cubic geometry to eight equivalent Li(3) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 8-coordinate geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), and two equivalent Li(5) atoms. In the second S site, S(2) is bonded in a 8-coordinate geometry to four equivalent Li(2) and four equivalent Li(4) atoms.
Li34(Sb3S2)3 crystallizes in the tetragonal I4/m space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 2-coordinate geometry to two equivalent Sb(1) and two equivalent S(1) atoms. Both Li(1)-Sb(1) bond lengths are 3.10 Å. There is one shorter (2.40 Å) and one longer (2.54 Å) Li(1)-S(1) bond length. In the second Li site, Li(2) is bonded in a 2-coordinate geometry to two equivalent Sb(1), one S(1), and one S(2) atom. Both Li(2)-Sb(1) bond lengths are 3.05 Å. The Li(2)-S(1) bond length is 2.56 Å. The Li(2)-S(2) bond length is 2.53 Å. In the third Li site, Li(3) is bonded to one Sb(2), two equivalent Sb(1), and one S(1) atom to form distorted LiSb3S tetrahedra that share corners with two equivalent Li(5)Sb2S2 tetrahedra, corners with two equivalent Li(6)Sb4 tetrahedra, corners with four equivalent Li(3)Sb3S tetrahedra, corners with four equivalent Li(4)Sb3S tetrahedra,  an edgeedge with one Li(5)Sb2S2 tetrahedra,  an edgeedge with one Li(4)Sb3S tetrahedra, and edges with three equivalent Li(3)Sb3S tetrahedra. The Li(3)-Sb(2) bond length is 2.73 Å. There is one shorter (2.78 Å) and one longer (2.80 Å) Li(3)-Sb(1) bond length. The Li(3)-S(1) bond length is 2.47 Å. In the fourth Li site, Li(4) is bonded to three equivalent Sb(1) and one S(2) atom to form distorted LiSb3S tetrahedra that share  a cornercorner with one Li(6)Sb4 tetrahedra, corners with three equivalent Li(5)Sb2S2 tetrahedra, corners with three equivalent Li(4)Sb3S tetrahedra, corners with four equivalent Li(3)Sb3S tetrahedra,  an edgeedge with one Li(3)Sb3S tetrahedra,  an edgeedge with one Li(6)Sb4 tetrahedra, and edges with three equivalent Li(4)Sb3S tetrahedra. There are a spread of Li(4)-Sb(1) bond distances ranging from 2.78-2.86 Å. The Li(4)-S(2) bond length is 2.51 Å. In the fifth Li site, Li(5) is bonded to two equivalent Sb(1) and two equivalent S(1) atoms to form distorted LiSb2S2 tetrahedra that share corners with four equivalent Li(3)Sb3S tetrahedra, corners with six equivalent Li(4)Sb3S tetrahedra,  an edgeedge with one Li(5)Sb2S2 tetrahedra,  an edgeedge with one Li(6)Sb4 tetrahedra, and edges with two equivalent Li(3)Sb3S tetrahedra. Both Li(5)-Sb(1) bond lengths are 2.76 Å. Both Li(5)-S(1) bond lengths are 2.51 Å. In the sixth Li site, Li(6) is bonded to four equivalent Sb(1) atoms to form LiSb4 tetrahedra that share corners with four equivalent Li(4)Sb3S tetrahedra, corners with eight equivalent Li(3)Sb3S tetrahedra, edges with two equivalent Li(5)Sb2S2 tetrahedra, and edges with four equivalent Li(4)Sb3S tetrahedra. All Li(6)-Sb(1) bond lengths are 2.87 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 10-coordinate geometry to one Li(1), one Li(5), one Li(6), two equivalent Li(2), two equivalent Li(3), and three equivalent Li(4) atoms. In the second Sb site, Sb(2) is bonded in a body-centered cubic geometry to eight equivalent Li(3) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 8-coordinate geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), and two equivalent Li(5) atoms. In the second S site, S(2) is bonded in a 8-coordinate geometry to four equivalent Li(2) and four equivalent Li(4) atoms.