CsBiAg2S3 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded in a 5-coordinate geometry to one S(2), two equivalent S(1), and two equivalent S(3) atoms. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a distorted linear geometry to two equivalent S(1) atoms. In the second Ag site, Ag(2) is bonded in a distorted rectangular see-saw-like geometry to one S(1), one S(3), and two equivalent S(2) atoms. Bi(1) is bonded to three equivalent S(2) and three equivalent S(3) atoms to form edge-sharing BiS6 octahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one Ag(2), and two equivalent Ag(1) atoms. In the second S site, S(2) is bonded to one Cs(1), two equivalent Ag(2), and three equivalent Bi(1) atoms to form SCsAg2Bi3 octahedra that share  a cornercorner with one S(3)Cs2AgBi3 octahedra, corners with two equivalent S(2)CsAg2Bi3 octahedra, edges with three equivalent S(2)CsAg2Bi3 octahedra, and edges with six equivalent S(3)Cs2AgBi3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the third S site, S(3) is bonded to two equivalent Cs(1), one Ag(2), and three equivalent Bi(1) atoms to form SCs2AgBi3 octahedra that share  a cornercorner with one S(2)CsAg2Bi3 octahedra, corners with two equivalent S(3)Cs2AgBi3 octahedra, edges with three equivalent S(3)Cs2AgBi3 octahedra, and edges with six equivalent S(2)CsAg2Bi3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°.
CsBiAg2S3 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded in a 5-coordinate geometry to one S(2), two equivalent S(1), and two equivalent S(3) atoms. The Cs(1)-S(2) bond length is 3.63 Å. There is one shorter (3.65 Å) and one longer (3.84 Å) Cs(1)-S(1) bond length. There is one shorter (3.62 Å) and one longer (3.65 Å) Cs(1)-S(3) bond length. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a distorted linear geometry to two equivalent S(1) atoms. There is one shorter (2.40 Å) and one longer (2.41 Å) Ag(1)-S(1) bond length. In the second Ag site, Ag(2) is bonded in a distorted rectangular see-saw-like geometry to one S(1), one S(3), and two equivalent S(2) atoms. The Ag(2)-S(1) bond length is 2.50 Å. The Ag(2)-S(3) bond length is 2.93 Å. There is one shorter (2.59 Å) and one longer (2.79 Å) Ag(2)-S(2) bond length. Bi(1) is bonded to three equivalent S(2) and three equivalent S(3) atoms to form edge-sharing BiS6 octahedra. There are a spread of Bi(1)-S(2) bond distances ranging from 2.72-3.05 Å. There are a spread of Bi(1)-S(3) bond distances ranging from 2.77-2.92 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one Ag(2), and two equivalent Ag(1) atoms. In the second S site, S(2) is bonded to one Cs(1), two equivalent Ag(2), and three equivalent Bi(1) atoms to form SCsAg2Bi3 octahedra that share  a cornercorner with one S(3)Cs2AgBi3 octahedra, corners with two equivalent S(2)CsAg2Bi3 octahedra, edges with three equivalent S(2)CsAg2Bi3 octahedra, and edges with six equivalent S(3)Cs2AgBi3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the third S site, S(3) is bonded to two equivalent Cs(1), one Ag(2), and three equivalent Bi(1) atoms to form SCs2AgBi3 octahedra that share  a cornercorner with one S(2)CsAg2Bi3 octahedra, corners with two equivalent S(3)Cs2AgBi3 octahedra, edges with three equivalent S(3)Cs2AgBi3 octahedra, and edges with six equivalent S(2)CsAg2Bi3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°.