Cs3Ag2Sb3S8 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one S(3), one S(6), two equivalent S(2), two equivalent S(4), and three equivalent S(5) atoms. In the second Cs site, Cs(2) is bonded in a 11-coordinate geometry to two equivalent Ag(1), one S(1), one S(5), three equivalent S(3), and four equivalent S(2) atoms. In the third Cs site, Cs(3) is bonded in a 7-coordinate geometry to two equivalent S(2), two equivalent S(4), and three equivalent S(6) atoms. Ag(1) is bonded in a 4-coordinate geometry to one Cs(2), one S(3), one S(4), and two equivalent S(1) atoms. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 3-coordinate geometry to one S(1) and two equivalent S(2) atoms. In the second Sb site, Sb(2) is bonded in a 3-coordinate geometry to one S(3) and two equivalent S(2) atoms. In the third Sb site, Sb(3) is bonded in a tetrahedral geometry to one S(5), one S(6), and two equivalent S(4) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Cs(2), four equivalent Ag(1), and one Sb(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), one Sb(1), and one Sb(2) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Cs(1), three equivalent Cs(2), two equivalent Ag(1), and one Sb(2) atom. In the fourth S site, S(4) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(3), one Ag(1), and one Sb(3) atom. In the fifth S site, S(5) is bonded to one Cs(2), three equivalent Cs(1), and one Sb(3) atom to form a mixture of distorted corner and edge-sharing SCs4Sb square pyramids. In the sixth S site, S(6) is bonded to one Cs(1), three equivalent Cs(3), and one Sb(3) atom to form a mixture of distorted corner and edge-sharing SCs4Sb square pyramids.
Cs3Ag2Sb3S8 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one S(3), one S(6), two equivalent S(2), two equivalent S(4), and three equivalent S(5) atoms. The Cs(1)-S(3) bond length is 3.65 Å. The Cs(1)-S(6) bond length is 3.64 Å. Both Cs(1)-S(2) bond lengths are 4.15 Å. Both Cs(1)-S(4) bond lengths are 3.93 Å. There are two shorter (3.71 Å) and one longer (3.78 Å) Cs(1)-S(5) bond length. In the second Cs site, Cs(2) is bonded in a 11-coordinate geometry to two equivalent Ag(1), one S(1), one S(5), three equivalent S(3), and four equivalent S(2) atoms. Both Cs(2)-Ag(1) bond lengths are 3.85 Å. The Cs(2)-S(1) bond length is 3.52 Å. The Cs(2)-S(5) bond length is 3.67 Å. There is one shorter (3.84 Å) and two longer (3.90 Å) Cs(2)-S(3) bond lengths. There are two shorter (3.62 Å) and two longer (3.82 Å) Cs(2)-S(2) bond lengths. In the third Cs site, Cs(3) is bonded in a 7-coordinate geometry to two equivalent S(2), two equivalent S(4), and three equivalent S(6) atoms. Both Cs(3)-S(2) bond lengths are 3.91 Å. Both Cs(3)-S(4) bond lengths are 3.72 Å. There is one shorter (3.72 Å) and two longer (3.75 Å) Cs(3)-S(6) bond lengths. Ag(1) is bonded in a 4-coordinate geometry to one Cs(2), one S(3), one S(4), and two equivalent S(1) atoms. The Ag(1)-S(3) bond length is 2.64 Å. The Ag(1)-S(4) bond length is 2.52 Å. There is one shorter (2.63 Å) and one longer (2.85 Å) Ag(1)-S(1) bond length. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 3-coordinate geometry to one S(1) and two equivalent S(2) atoms. The Sb(1)-S(1) bond length is 2.52 Å. Both Sb(1)-S(2) bond lengths are 2.54 Å. In the second Sb site, Sb(2) is bonded in a 3-coordinate geometry to one S(3) and two equivalent S(2) atoms. The Sb(2)-S(3) bond length is 2.42 Å. Both Sb(2)-S(2) bond lengths are 2.53 Å. In the third Sb site, Sb(3) is bonded in a tetrahedral geometry to one S(5), one S(6), and two equivalent S(4) atoms. The Sb(3)-S(5) bond length is 2.36 Å. The Sb(3)-S(6) bond length is 2.35 Å. Both Sb(3)-S(4) bond lengths are 2.38 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Cs(2), four equivalent Ag(1), and one Sb(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), one Sb(1), and one Sb(2) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Cs(1), three equivalent Cs(2), two equivalent Ag(1), and one Sb(2) atom. In the fourth S site, S(4) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(3), one Ag(1), and one Sb(3) atom. In the fifth S site, S(5) is bonded to one Cs(2), three equivalent Cs(1), and one Sb(3) atom to form a mixture of distorted corner and edge-sharing SCs4Sb square pyramids. In the sixth S site, S(6) is bonded to one Cs(1), three equivalent Cs(3), and one Sb(3) atom to form a mixture of distorted corner and edge-sharing SCs4Sb square pyramids.