CsBiS2 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded in a 7-coordinate geometry to three equivalent S(2) and four equivalent S(1) atoms. Bi(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent S(1) and two equivalent S(2) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to four equivalent Cs(1) and two equivalent Bi(1) atoms to form a mixture of distorted face, corner, and edge-sharing SCs4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 39-40°. In the second S site, S(2) is bonded in a 5-coordinate geometry to three equivalent Cs(1) and two equivalent Bi(1) atoms.
CsBiS2 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded in a 7-coordinate geometry to three equivalent S(2) and four equivalent S(1) atoms. There are a spread of Cs(1)-S(2) bond distances ranging from 3.63-3.88 Å. There are a spread of Cs(1)-S(1) bond distances ranging from 3.57-3.62 Å. Bi(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent S(1) and two equivalent S(2) atoms. There is one shorter (2.56 Å) and one longer (2.76 Å) Bi(1)-S(1) bond length. There is one shorter (2.55 Å) and one longer (2.97 Å) Bi(1)-S(2) bond length. There are two inequivalent S sites. In the first S site, S(1) is bonded to four equivalent Cs(1) and two equivalent Bi(1) atoms to form a mixture of distorted face, corner, and edge-sharing SCs4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 39-40°. In the second S site, S(2) is bonded in a 5-coordinate geometry to three equivalent Cs(1) and two equivalent Bi(1) atoms.