Cs2Sb8S13 crystallizes in the triclinic P-1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to one S(1), one S(12), one S(2), one S(3), one S(5), one S(6), and one S(7) atom. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one S(10), one S(11), one S(13), one S(5), one S(6), and one S(9) atom. There are eight inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a distorted T-shaped geometry to one S(5), one S(6), and one S(9) atom. In the second Sb site, Sb(2) is bonded in a 4-coordinate geometry to one S(1), one S(10), one S(4), and one S(8) atom. In the third Sb site, Sb(3) is bonded in a 3-coordinate geometry to one S(2), one S(4), and one S(8) atom. In the fourth Sb site, Sb(4) is bonded in a 3-coordinate geometry to one S(10), one S(2), one S(3), one S(4), and one S(7) atom. In the fifth Sb site, Sb(5) is bonded in a rectangular see-saw-like geometry to one S(11), one S(12), one S(4), and one S(6) atom. In the sixth Sb site, Sb(6) is bonded in a distorted rectangular see-saw-like geometry to one S(1), one S(11), one S(13), and one S(4) atom. In the seventh Sb site, Sb(7) is bonded in a distorted T-shaped geometry to one S(13), one S(5), and one S(9) atom. In the eighth Sb site, Sb(8) is bonded in a distorted rectangular see-saw-like geometry to one S(12), one S(7), and two equivalent S(3) atoms. There are thirteen inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal planar geometry to one Cs(1), one Sb(2), and one Sb(6) atom. In the second S site, S(2) is bonded in a distorted water-like geometry to one Cs(1), one Sb(3), and one Sb(4) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Cs(1), one Sb(4), and two equivalent Sb(8) atoms. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Sb(2), one Sb(3), one Sb(4), one Sb(5), and one Sb(6) atom. In the fifth S site, S(5) is bonded to one Cs(1), one Cs(2), one Sb(1), and one Sb(7) atom to form a mixture of distorted corner and edge-sharing SCs2Sb2 tetrahedra. In the sixth S site, S(6) is bonded to one Cs(1), one Cs(2), one Sb(1), and one Sb(5) atom to form a mixture of distorted corner and edge-sharing SCs2Sb2 tetrahedra. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Cs(1), one Sb(4), and one Sb(8) atom. In the eighth S site, S(8) is bonded in a water-like geometry to one Sb(2) and one Sb(3) atom. In the ninth S site, S(9) is bonded in a distorted water-like geometry to one Cs(2), one Sb(1), and one Sb(7) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Cs(2), one Sb(2), and one Sb(4) atom. In the eleventh S site, S(11) is bonded in a distorted trigonal non-coplanar geometry to one Cs(2), one Sb(5), and one Sb(6) atom. In the twelfth S site, S(12) is bonded in a distorted trigonal planar geometry to one Cs(1), one Sb(5), and one Sb(8) atom. In the thirteenth S site, S(13) is bonded in a 3-coordinate geometry to one Cs(2), one Sb(6), and one Sb(7) atom.
Cs2Sb8S13 crystallizes in the triclinic P-1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to one S(1), one S(12), one S(2), one S(3), one S(5), one S(6), and one S(7) atom. The Cs(1)-S(1) bond length is 3.72 Å. The Cs(1)-S(12) bond length is 3.63 Å. The Cs(1)-S(2) bond length is 3.85 Å. The Cs(1)-S(3) bond length is 3.88 Å. The Cs(1)-S(5) bond length is 3.68 Å. The Cs(1)-S(6) bond length is 3.58 Å. The Cs(1)-S(7) bond length is 3.50 Å. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one S(10), one S(11), one S(13), one S(5), one S(6), and one S(9) atom. The Cs(2)-S(10) bond length is 3.94 Å. The Cs(2)-S(11) bond length is 3.57 Å. The Cs(2)-S(13) bond length is 3.60 Å. The Cs(2)-S(5) bond length is 3.59 Å. The Cs(2)-S(6) bond length is 3.59 Å. The Cs(2)-S(9) bond length is 4.03 Å. There are eight inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a distorted T-shaped geometry to one S(5), one S(6), and one S(9) atom. The Sb(1)-S(5) bond length is 2.50 Å. The Sb(1)-S(6) bond length is 2.43 Å. The Sb(1)-S(9) bond length is 2.48 Å. In the second Sb site, Sb(2) is bonded in a 4-coordinate geometry to one S(1), one S(10), one S(4), and one S(8) atom. The Sb(2)-S(1) bond length is 2.51 Å. The Sb(2)-S(10) bond length is 2.51 Å. The Sb(2)-S(4) bond length is 3.11 Å. The Sb(2)-S(8) bond length is 2.48 Å. In the third Sb site, Sb(3) is bonded in a 3-coordinate geometry to one S(2), one S(4), and one S(8) atom. The Sb(3)-S(2) bond length is 2.50 Å. The Sb(3)-S(4) bond length is 2.41 Å. The Sb(3)-S(8) bond length is 2.51 Å. In the fourth Sb site, Sb(4) is bonded in a 3-coordinate geometry to one S(10), one S(2), one S(3), one S(4), and one S(7) atom. The Sb(4)-S(10) bond length is 2.56 Å. The Sb(4)-S(2) bond length is 2.49 Å. The Sb(4)-S(3) bond length is 3.10 Å. The Sb(4)-S(4) bond length is 3.16 Å. The Sb(4)-S(7) bond length is 2.48 Å. In the fifth Sb site, Sb(5) is bonded in a rectangular see-saw-like geometry to one S(11), one S(12), one S(4), and one S(6) atom. The Sb(5)-S(11) bond length is 2.51 Å. The Sb(5)-S(12) bond length is 2.44 Å. The Sb(5)-S(4) bond length is 2.94 Å. The Sb(5)-S(6) bond length is 2.60 Å. In the sixth Sb site, Sb(6) is bonded in a distorted rectangular see-saw-like geometry to one S(1), one S(11), one S(13), and one S(4) atom. The Sb(6)-S(1) bond length is 2.45 Å. The Sb(6)-S(11) bond length is 2.46 Å. The Sb(6)-S(13) bond length is 2.55 Å. The Sb(6)-S(4) bond length is 3.08 Å. In the seventh Sb site, Sb(7) is bonded in a distorted T-shaped geometry to one S(13), one S(5), and one S(9) atom. The Sb(7)-S(13) bond length is 2.46 Å. The Sb(7)-S(5) bond length is 2.49 Å. The Sb(7)-S(9) bond length is 2.47 Å. In the eighth Sb site, Sb(8) is bonded in a distorted rectangular see-saw-like geometry to one S(12), one S(7), and two equivalent S(3) atoms. The Sb(8)-S(12) bond length is 2.73 Å. The Sb(8)-S(7) bond length is 2.56 Å. There is one shorter (2.42 Å) and one longer (2.77 Å) Sb(8)-S(3) bond length. There are thirteen inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal planar geometry to one Cs(1), one Sb(2), and one Sb(6) atom. In the second S site, S(2) is bonded in a distorted water-like geometry to one Cs(1), one Sb(3), and one Sb(4) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Cs(1), one Sb(4), and two equivalent Sb(8) atoms. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Sb(2), one Sb(3), one Sb(4), one Sb(5), and one Sb(6) atom. In the fifth S site, S(5) is bonded to one Cs(1), one Cs(2), one Sb(1), and one Sb(7) atom to form a mixture of distorted corner and edge-sharing SCs2Sb2 tetrahedra. In the sixth S site, S(6) is bonded to one Cs(1), one Cs(2), one Sb(1), and one Sb(5) atom to form a mixture of distorted corner and edge-sharing SCs2Sb2 tetrahedra. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Cs(1), one Sb(4), and one Sb(8) atom. In the eighth S site, S(8) is bonded in a water-like geometry to one Sb(2) and one Sb(3) atom. In the ninth S site, S(9) is bonded in a distorted water-like geometry to one Cs(2), one Sb(1), and one Sb(7) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Cs(2), one Sb(2), and one Sb(4) atom. In the eleventh S site, S(11) is bonded in a distorted trigonal non-coplanar geometry to one Cs(2), one Sb(5), and one Sb(6) atom. In the twelfth S site, S(12) is bonded in a distorted trigonal planar geometry to one Cs(1), one Sb(5), and one Sb(8) atom. In the thirteenth S site, S(13) is bonded in a 3-coordinate geometry to one Cs(2), one Sb(6), and one Sb(7) atom.