CsSbS6 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded in a 11-coordinate geometry to one S(1), one S(2), two equivalent S(3), two equivalent S(5), two equivalent S(6), and three equivalent S(4) atoms. Sb(1) is bonded in a distorted see-saw-like geometry to one S(1), one S(4), and two equivalent S(3) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Cs(1), one Sb(1), and one S(2) atom. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one Cs(1), one S(1), and one S(6) atom. In the third S site, S(3) is bonded to two equivalent Cs(1) and two equivalent Sb(1) atoms to form distorted SCs2Sb2 trigonal pyramids that share corners with five equivalent S(4)Cs3SbS trigonal bipyramids, corners with two equivalent S(3)Cs2Sb2 trigonal pyramids, corners with four equivalent S(6)Cs2S2 trigonal pyramids,  an edgeedge with one S(3)Cs2Sb2 trigonal pyramid, and  a faceface with one S(4)Cs3SbS trigonal bipyramid. In the fourth S site, S(4) is bonded to three equivalent Cs(1), one Sb(1), and one S(5) atom to form distorted SCs3SbS trigonal bipyramids that share corners with two equivalent S(4)Cs3SbS trigonal bipyramids,  a cornercorner with one S(6)Cs2S2 trigonal pyramid, corners with five equivalent S(3)Cs2Sb2 trigonal pyramids, edges with two equivalent S(4)Cs3SbS trigonal bipyramids, edges with three equivalent S(6)Cs2S2 trigonal pyramids, and  a faceface with one S(3)Cs2Sb2 trigonal pyramid. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one S(4), and one S(6) atom. In the sixth S site, S(6) is bonded to two equivalent Cs(1), one S(2), and one S(5) atom to form distorted SCs2S2 trigonal pyramids that share  a cornercorner with one S(4)Cs3SbS trigonal bipyramid, corners with four equivalent S(3)Cs2Sb2 trigonal pyramids, edges with three equivalent S(4)Cs3SbS trigonal bipyramids, and  an edgeedge with one S(6)Cs2S2 trigonal pyramid.
CsSbS6 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded in a 11-coordinate geometry to one S(1), one S(2), two equivalent S(3), two equivalent S(5), two equivalent S(6), and three equivalent S(4) atoms. The Cs(1)-S(1) bond length is 3.69 Å. The Cs(1)-S(2) bond length is 3.82 Å. There is one shorter (3.61 Å) and one longer (3.68 Å) Cs(1)-S(3) bond length. There is one shorter (3.71 Å) and one longer (4.21 Å) Cs(1)-S(5) bond length. There is one shorter (4.02 Å) and one longer (4.04 Å) Cs(1)-S(6) bond length. There are a spread of Cs(1)-S(4) bond distances ranging from 3.70-3.83 Å. Sb(1) is bonded in a distorted see-saw-like geometry to one S(1), one S(4), and two equivalent S(3) atoms. The Sb(1)-S(1) bond length is 2.54 Å. The Sb(1)-S(4) bond length is 2.74 Å. There is one shorter (2.40 Å) and one longer (2.66 Å) Sb(1)-S(3) bond length. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Cs(1), one Sb(1), and one S(2) atom. The S(1)-S(2) bond length is 2.05 Å. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one Cs(1), one S(1), and one S(6) atom. The S(2)-S(6) bond length is 2.07 Å. In the third S site, S(3) is bonded to two equivalent Cs(1) and two equivalent Sb(1) atoms to form distorted SCs2Sb2 trigonal pyramids that share corners with five equivalent S(4)Cs3SbS trigonal bipyramids, corners with two equivalent S(3)Cs2Sb2 trigonal pyramids, corners with four equivalent S(6)Cs2S2 trigonal pyramids,  an edgeedge with one S(3)Cs2Sb2 trigonal pyramid, and  a faceface with one S(4)Cs3SbS trigonal bipyramid. In the fourth S site, S(4) is bonded to three equivalent Cs(1), one Sb(1), and one S(5) atom to form distorted SCs3SbS trigonal bipyramids that share corners with two equivalent S(4)Cs3SbS trigonal bipyramids,  a cornercorner with one S(6)Cs2S2 trigonal pyramid, corners with five equivalent S(3)Cs2Sb2 trigonal pyramids, edges with two equivalent S(4)Cs3SbS trigonal bipyramids, edges with three equivalent S(6)Cs2S2 trigonal pyramids, and  a faceface with one S(3)Cs2Sb2 trigonal pyramid. The S(4)-S(5) bond length is 2.04 Å. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one S(4), and one S(6) atom. The S(5)-S(6) bond length is 2.06 Å. In the sixth S site, S(6) is bonded to two equivalent Cs(1), one S(2), and one S(5) atom to form distorted SCs2S2 trigonal pyramids that share  a cornercorner with one S(4)Cs3SbS trigonal bipyramid, corners with four equivalent S(3)Cs2Sb2 trigonal pyramids, edges with three equivalent S(4)Cs3SbS trigonal bipyramids, and  an edgeedge with one S(6)Cs2S2 trigonal pyramid.