Cs2Bi2ZnS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(4), and three equivalent S(2) atoms. In the second Cs site, Cs(2) is bonded to one S(1), two equivalent S(3), and three equivalent S(5) atoms to form distorted CsS6 octahedra that share corners with two equivalent Bi(1)S6 octahedra, corners with three equivalent Bi(2)S6 octahedra, corners with three equivalent Zn(1)S4 tetrahedra, edges with two equivalent Bi(2)S6 octahedra, edges with three equivalent Bi(1)S6 octahedra, edges with four equivalent Cs(2)S6 octahedra, and  an edgeedge with one Zn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-60°. Zn(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form ZnS4 tetrahedra that share corners with three equivalent Cs(2)S6 octahedra, corners with two equivalent Zn(1)S4 tetrahedra,  an edgeedge with one Cs(2)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with two equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-27°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(3), one S(4), two equivalent S(2), and two equivalent S(5) atoms to form distorted BiS6 octahedra that share  a cornercorner with one Bi(2)S6 octahedra, corners with two equivalent Cs(2)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, edges with three equivalent Cs(2)S6 octahedra, and edges with two equivalent Zn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 11-34°. In the second Bi site, Bi(2) is bonded to one S(3), one S(5), two equivalent S(1), and two equivalent S(4) atoms to form BiS6 octahedra that share  a cornercorner with one Bi(1)S6 octahedra, corners with three equivalent Cs(2)S6 octahedra, edges with two equivalent Cs(2)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, and edges with two equivalent Zn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-60°. There are five inequivalent S sites. In the first S site, S(4) is bonded to two equivalent Cs(1), one Bi(1), and two equivalent Bi(2) atoms to form SCs2Bi3 square pyramids that share corners with two equivalent S(2)Cs3ZnBi2 octahedra, corners with four equivalent S(1)Cs3ZnBi2 octahedra, edges with two equivalent S(5)Cs3Bi3 octahedra, edges with two equivalent S(1)Cs3ZnBi2 octahedra, edges with three equivalent S(2)Cs3ZnBi2 octahedra, and edges with two equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 5-48°. In the second S site, S(5) is bonded to three equivalent Cs(2), one Bi(2), and two equivalent Bi(1) atoms to form SCs3Bi3 octahedra that share  a cornercorner with one S(1)Cs3ZnBi2 octahedra, corners with two equivalent S(2)Cs3ZnBi2 octahedra,  an edgeedge with one S(2)Cs3ZnBi2 octahedra, edges with two equivalent S(1)Cs3ZnBi2 octahedra, edges with four equivalent S(5)Cs3Bi3 octahedra, and edges with two equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 2-19°. In the third S site, S(1) is bonded to one Cs(2), two equivalent Cs(1), one Zn(1), and two equivalent Bi(2) atoms to form distorted SCs3ZnBi2 octahedra that share  a cornercorner with one S(5)Cs3Bi3 octahedra, corners with four equivalent S(2)Cs3ZnBi2 octahedra, corners with four equivalent S(4)Cs2Bi3 square pyramids, edges with two equivalent S(5)Cs3Bi3 octahedra, edges with two equivalent S(1)Cs3ZnBi2 octahedra, edges with two equivalent S(4)Cs2Bi3 square pyramids, and  a faceface with one S(2)Cs3ZnBi2 octahedra. The corner-sharing octahedral tilt angles range from 19-73°. In the fourth S site, S(2) is bonded to three equivalent Cs(1), one Zn(1), and two equivalent Bi(1) atoms to form distorted SCs3ZnBi2 octahedra that share corners with two equivalent S(5)Cs3Bi3 octahedra, corners with four equivalent S(1)Cs3ZnBi2 octahedra, corners with two equivalent S(4)Cs2Bi3 square pyramids,  an edgeedge with one S(5)Cs3Bi3 octahedra, edges with four equivalent S(2)Cs3ZnBi2 octahedra, edges with three equivalent S(4)Cs2Bi3 square pyramids, and  a faceface with one S(1)Cs3ZnBi2 octahedra. The corner-sharing octahedral tilt angles range from 2-73°. In the fifth S site, S(3) is bonded in a 6-coordinate geometry to two equivalent Cs(2), two equivalent Zn(1), one Bi(1), and one Bi(2) atom.
Cs2Bi2ZnS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(4), and three equivalent S(2) atoms. Both Cs(1)-S(1) bond lengths are 3.53 Å. Both Cs(1)-S(4) bond lengths are 3.52 Å. There is one shorter (3.51 Å) and two longer (3.57 Å) Cs(1)-S(2) bond lengths. In the second Cs site, Cs(2) is bonded to one S(1), two equivalent S(3), and three equivalent S(5) atoms to form distorted CsS6 octahedra that share corners with two equivalent Bi(1)S6 octahedra, corners with three equivalent Bi(2)S6 octahedra, corners with three equivalent Zn(1)S4 tetrahedra, edges with two equivalent Bi(2)S6 octahedra, edges with three equivalent Bi(1)S6 octahedra, edges with four equivalent Cs(2)S6 octahedra, and  an edgeedge with one Zn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-60°. The Cs(2)-S(1) bond length is 3.46 Å. Both Cs(2)-S(3) bond lengths are 3.55 Å. There are two shorter (3.59 Å) and one longer (3.65 Å) Cs(2)-S(5) bond length. Zn(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form ZnS4 tetrahedra that share corners with three equivalent Cs(2)S6 octahedra, corners with two equivalent Zn(1)S4 tetrahedra,  an edgeedge with one Cs(2)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with two equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-27°. The Zn(1)-S(1) bond length is 2.37 Å. The Zn(1)-S(2) bond length is 2.34 Å. Both Zn(1)-S(3) bond lengths are 2.42 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(3), one S(4), two equivalent S(2), and two equivalent S(5) atoms to form distorted BiS6 octahedra that share  a cornercorner with one Bi(2)S6 octahedra, corners with two equivalent Cs(2)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, edges with three equivalent Cs(2)S6 octahedra, and edges with two equivalent Zn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 11-34°. The Bi(1)-S(3) bond length is 3.20 Å. The Bi(1)-S(4) bond length is 2.64 Å. Both Bi(1)-S(2) bond lengths are 2.80 Å. Both Bi(1)-S(5) bond lengths are 2.90 Å. In the second Bi site, Bi(2) is bonded to one S(3), one S(5), two equivalent S(1), and two equivalent S(4) atoms to form BiS6 octahedra that share  a cornercorner with one Bi(1)S6 octahedra, corners with three equivalent Cs(2)S6 octahedra, edges with two equivalent Cs(2)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, and edges with two equivalent Zn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-60°. The Bi(2)-S(3) bond length is 2.94 Å. The Bi(2)-S(5) bond length is 2.76 Å. Both Bi(2)-S(1) bond lengths are 2.82 Å. Both Bi(2)-S(4) bond lengths are 2.85 Å. There are five inequivalent S sites. In the first S site, S(4) is bonded to two equivalent Cs(1), one Bi(1), and two equivalent Bi(2) atoms to form SCs2Bi3 square pyramids that share corners with two equivalent S(2)Cs3ZnBi2 octahedra, corners with four equivalent S(1)Cs3ZnBi2 octahedra, edges with two equivalent S(5)Cs3Bi3 octahedra, edges with two equivalent S(1)Cs3ZnBi2 octahedra, edges with three equivalent S(2)Cs3ZnBi2 octahedra, and edges with two equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 5-48°. In the second S site, S(5) is bonded to three equivalent Cs(2), one Bi(2), and two equivalent Bi(1) atoms to form SCs3Bi3 octahedra that share  a cornercorner with one S(1)Cs3ZnBi2 octahedra, corners with two equivalent S(2)Cs3ZnBi2 octahedra,  an edgeedge with one S(2)Cs3ZnBi2 octahedra, edges with two equivalent S(1)Cs3ZnBi2 octahedra, edges with four equivalent S(5)Cs3Bi3 octahedra, and edges with two equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 2-19°. In the third S site, S(1) is bonded to one Cs(2), two equivalent Cs(1), one Zn(1), and two equivalent Bi(2) atoms to form distorted SCs3ZnBi2 octahedra that share  a cornercorner with one S(5)Cs3Bi3 octahedra, corners with four equivalent S(2)Cs3ZnBi2 octahedra, corners with four equivalent S(4)Cs2Bi3 square pyramids, edges with two equivalent S(5)Cs3Bi3 octahedra, edges with two equivalent S(1)Cs3ZnBi2 octahedra, edges with two equivalent S(4)Cs2Bi3 square pyramids, and  a faceface with one S(2)Cs3ZnBi2 octahedra. The corner-sharing octahedral tilt angles range from 19-73°. In the fourth S site, S(2) is bonded to three equivalent Cs(1), one Zn(1), and two equivalent Bi(1) atoms to form distorted SCs3ZnBi2 octahedra that share corners with two equivalent S(5)Cs3Bi3 octahedra, corners with four equivalent S(1)Cs3ZnBi2 octahedra, corners with two equivalent S(4)Cs2Bi3 square pyramids,  an edgeedge with one S(5)Cs3Bi3 octahedra, edges with four equivalent S(2)Cs3ZnBi2 octahedra, edges with three equivalent S(4)Cs2Bi3 square pyramids, and  a faceface with one S(1)Cs3ZnBi2 octahedra. The corner-sharing octahedral tilt angles range from 2-73°. In the fifth S site, S(3) is bonded in a 6-coordinate geometry to two equivalent Cs(2), two equivalent Zn(1), one Bi(1), and one Bi(2) atom.