CsAgSb4S7 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 2-coordinate geometry to two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to two equivalent S(3), two equivalent S(5), and two equivalent S(6) atoms. Ag(1) is bonded in a 4-coordinate geometry to one S(2), one S(7), and two equivalent S(4) atoms. There are four inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 3-coordinate geometry to one S(1), one S(2), and one S(4) atom. In the second Sb site, Sb(2) is bonded in a distorted rectangular see-saw-like geometry to one S(2), one S(3), one S(5), and one S(7) atom. In the third Sb site, Sb(3) is bonded in a distorted rectangular see-saw-like geometry to one S(2), one S(3), and two equivalent S(6) atoms. In the fourth Sb site, Sb(4) is bonded in a 4-coordinate geometry to one S(1), one S(5), one S(6), and one S(7) atom. There are seven inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one Cs(1), one Sb(1), and one Sb(4) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Cs(1), one Ag(1), one Sb(1), one Sb(2), and one Sb(3) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Cs(2), one Sb(2), and one Sb(3) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to two equivalent Ag(1) and one Sb(1) atom. In the fifth S site, S(5) is bonded in a 4-coordinate geometry to one Cs(1), one Cs(2), one Sb(2), and one Sb(4) atom. In the sixth S site, S(6) is bonded in a 4-coordinate geometry to one Cs(2), one Sb(4), and two equivalent Sb(3) atoms. In the seventh S site, S(7) is bonded in a 3-coordinate geometry to one Ag(1), one Sb(2), and one Sb(4) atom.
CsAgSb4S7 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 2-coordinate geometry to two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. Both Cs(1)-S(1) bond lengths are 3.50 Å. Both Cs(1)-S(2) bond lengths are 3.90 Å. Both Cs(1)-S(5) bond lengths are 3.94 Å. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to two equivalent S(3), two equivalent S(5), and two equivalent S(6) atoms. Both Cs(2)-S(3) bond lengths are 3.81 Å. Both Cs(2)-S(5) bond lengths are 3.92 Å. Both Cs(2)-S(6) bond lengths are 3.78 Å. Ag(1) is bonded in a 4-coordinate geometry to one S(2), one S(7), and two equivalent S(4) atoms. The Ag(1)-S(2) bond length is 2.99 Å. The Ag(1)-S(7) bond length is 2.70 Å. There is one shorter (2.52 Å) and one longer (2.55 Å) Ag(1)-S(4) bond length. There are four inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 3-coordinate geometry to one S(1), one S(2), and one S(4) atom. The Sb(1)-S(1) bond length is 2.56 Å. The Sb(1)-S(2) bond length is 2.52 Å. The Sb(1)-S(4) bond length is 2.45 Å. In the second Sb site, Sb(2) is bonded in a distorted rectangular see-saw-like geometry to one S(2), one S(3), one S(5), and one S(7) atom. The Sb(2)-S(2) bond length is 2.95 Å. The Sb(2)-S(3) bond length is 2.53 Å. The Sb(2)-S(5) bond length is 2.65 Å. The Sb(2)-S(7) bond length is 2.46 Å. In the third Sb site, Sb(3) is bonded in a distorted rectangular see-saw-like geometry to one S(2), one S(3), and two equivalent S(6) atoms. The Sb(3)-S(2) bond length is 2.60 Å. The Sb(3)-S(3) bond length is 2.49 Å. There is one shorter (2.51 Å) and one longer (3.05 Å) Sb(3)-S(6) bond length. In the fourth Sb site, Sb(4) is bonded in a 4-coordinate geometry to one S(1), one S(5), one S(6), and one S(7) atom. The Sb(4)-S(1) bond length is 2.48 Å. The Sb(4)-S(5) bond length is 2.45 Å. The Sb(4)-S(6) bond length is 2.64 Å. The Sb(4)-S(7) bond length is 2.96 Å. There are seven inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one Cs(1), one Sb(1), and one Sb(4) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Cs(1), one Ag(1), one Sb(1), one Sb(2), and one Sb(3) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Cs(2), one Sb(2), and one Sb(3) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to two equivalent Ag(1) and one Sb(1) atom. In the fifth S site, S(5) is bonded in a 4-coordinate geometry to one Cs(1), one Cs(2), one Sb(2), and one Sb(4) atom. In the sixth S site, S(6) is bonded in a 4-coordinate geometry to one Cs(2), one Sb(4), and two equivalent Sb(3) atoms. In the seventh S site, S(7) is bonded in a 3-coordinate geometry to one Ag(1), one Sb(2), and one Sb(4) atom.