Cs2Sn3(SbS5)2 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded in a 9-coordinate geometry to one S(2), two equivalent S(1), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form edge-sharing SnS6 octahedra. In the second Sn site, Sn(2) is bonded to one S(2), one S(3), one S(4), and two equivalent S(5) atoms to form distorted SnS5 trigonal bipyramids that share  an edgeedge with one Sn(1)S6 octahedra and  an edgeedge with one Sn(2)S5 trigonal bipyramid. Sb(1) is bonded in a distorted T-shaped geometry to one S(1), one S(2), and one S(4) atom. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Cs(1), one Sn(1), and one Sb(1) atom to form distorted corner-sharing SCs2SnSb trigonal pyramids. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Cs(1), one Sn(1), one Sn(2), and one Sb(1) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to two equivalent Cs(1), one Sn(1), and one Sn(2) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cs(1), one Sn(2), and one Sb(1) atom. In the fifth S site, S(5) is bonded in a 4-coordinate geometry to two equivalent Cs(1) and two equivalent Sn(2) atoms.
Cs2Sn3(SbS5)2 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded in a 9-coordinate geometry to one S(2), two equivalent S(1), two equivalent S(3), two equivalent S(4), and two equivalent S(5) atoms. The Cs(1)-S(2) bond length is 3.88 Å. There is one shorter (3.47 Å) and one longer (3.57 Å) Cs(1)-S(1) bond length. There is one shorter (3.65 Å) and one longer (3.87 Å) Cs(1)-S(3) bond length. There is one shorter (3.81 Å) and one longer (3.84 Å) Cs(1)-S(4) bond length. There is one shorter (3.70 Å) and one longer (3.98 Å) Cs(1)-S(5) bond length. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form edge-sharing SnS6 octahedra. Both Sn(1)-S(1) bond lengths are 2.57 Å. Both Sn(1)-S(2) bond lengths are 2.64 Å. Both Sn(1)-S(3) bond lengths are 2.61 Å. In the second Sn site, Sn(2) is bonded to one S(2), one S(3), one S(4), and two equivalent S(5) atoms to form distorted SnS5 trigonal bipyramids that share  an edgeedge with one Sn(1)S6 octahedra and  an edgeedge with one Sn(2)S5 trigonal bipyramid. The Sn(2)-S(2) bond length is 3.00 Å. The Sn(2)-S(3) bond length is 2.42 Å. The Sn(2)-S(4) bond length is 2.43 Å. There is one shorter (2.46 Å) and one longer (2.53 Å) Sn(2)-S(5) bond length. Sb(1) is bonded in a distorted T-shaped geometry to one S(1), one S(2), and one S(4) atom. The Sb(1)-S(1) bond length is 2.46 Å. The Sb(1)-S(2) bond length is 2.49 Å. The Sb(1)-S(4) bond length is 2.54 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Cs(1), one Sn(1), and one Sb(1) atom to form distorted corner-sharing SCs2SnSb trigonal pyramids. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Cs(1), one Sn(1), one Sn(2), and one Sb(1) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to two equivalent Cs(1), one Sn(1), and one Sn(2) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cs(1), one Sn(2), and one Sb(1) atom. In the fifth S site, S(5) is bonded in a 4-coordinate geometry to two equivalent Cs(1) and two equivalent Sn(2) atoms.