Cs3Bi5Cu2S10 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to two equivalent S(1) and four equivalent S(4) atoms. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. Cu(1) is bonded to one S(1), one S(2), and two equivalent S(5) atoms to form CuS4 tetrahedra that share  a cornercorner with one Bi(3)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, and edges with two equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles are 13°. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(3), one S(5), two equivalent S(2), and two equivalent S(4) atoms to form BiS6 octahedra that share edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(3)S6 octahedra, and edges with two equivalent Cu(1)S4 tetrahedra. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(1), and two equivalent S(3) atoms. In the third Bi site, Bi(3) is bonded to two equivalent S(2) and four equivalent S(3) atoms to form BiS6 octahedra that share corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(3)S6 octahedra, and edges with four equivalent Bi(1)S6 octahedra. There are five inequivalent S sites. In the first S site, S(1) is bonded to one Cs(1), two equivalent Cs(2), one Cu(1), and two equivalent Bi(2) atoms to form distorted SCs3CuBi2 octahedra that share  a cornercorner with one S(1)Cs3CuBi2 octahedra, corners with two equivalent S(2)Cs2CuBi3 octahedra, corners with four equivalent S(3)CsBi5 octahedra, corners with two equivalent S(4)Cs2Bi3 square pyramids,  an edgeedge with one S(3)CsBi5 octahedra, edges with two equivalent S(1)Cs3CuBi2 octahedra, edges with two equivalent S(4)Cs2Bi3 square pyramids, and  a faceface with one S(2)Cs2CuBi3 octahedra. The corner-sharing octahedral tilt angles range from 0-74°. In the second S site, S(2) is bonded to two equivalent Cs(2), one Cu(1), one Bi(3), and two equivalent Bi(1) atoms to form distorted SCs2CuBi3 octahedra that share  a cornercorner with one S(2)Cs2CuBi3 octahedra, corners with two equivalent S(1)Cs3CuBi2 octahedra, corners with two equivalent S(4)Cs2Bi3 square pyramids, edges with two equivalent S(2)Cs2CuBi3 octahedra, edges with four equivalent S(3)CsBi5 octahedra,  an edgeedge with one S(4)Cs2Bi3 square pyramid, and  a faceface with one S(1)Cs3CuBi2 octahedra. The corner-sharing octahedral tilt angles range from 0-74°. In the third S site, S(3) is bonded to one Cs(2), one Bi(1), two equivalent Bi(2), and two equivalent Bi(3) atoms to form SCsBi5 octahedra that share corners with two equivalent S(3)CsBi5 octahedra, corners with four equivalent S(1)Cs3CuBi2 octahedra,  an edgeedge with one S(1)Cs3CuBi2 octahedra, edges with three equivalent S(3)CsBi5 octahedra, edges with four equivalent S(2)Cs2CuBi3 octahedra, and edges with two equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 0-46°. In the fourth S site, S(4) is bonded to two equivalent Cs(1), one Bi(2), and two equivalent Bi(1) atoms to form SCs2Bi3 square pyramids that share corners with two equivalent S(2)Cs2CuBi3 octahedra, corners with two equivalent S(1)Cs3CuBi2 octahedra, corners with two equivalent S(4)Cs2Bi3 square pyramids,  an edgeedge with one S(2)Cs2CuBi3 octahedra, edges with two equivalent S(1)Cs3CuBi2 octahedra, edges with two equivalent S(3)CsBi5 octahedra, and edges with three equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 6-69°. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to two equivalent Cs(2), two equivalent Cu(1), and one Bi(1) atom.
Cs3Bi5Cu2S10 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to two equivalent S(1) and four equivalent S(4) atoms. Both Cs(1)-S(1) bond lengths are 3.46 Å. All Cs(1)-S(4) bond lengths are 3.44 Å. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. The Cs(2)-S(3) bond length is 3.80 Å. Both Cs(2)-S(1) bond lengths are 3.65 Å. Both Cs(2)-S(2) bond lengths are 3.48 Å. Both Cs(2)-S(5) bond lengths are 3.52 Å. Cu(1) is bonded to one S(1), one S(2), and two equivalent S(5) atoms to form CuS4 tetrahedra that share  a cornercorner with one Bi(3)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, and edges with two equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles are 13°. The Cu(1)-S(1) bond length is 2.34 Å. The Cu(1)-S(2) bond length is 2.69 Å. Both Cu(1)-S(5) bond lengths are 2.36 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(3), one S(5), two equivalent S(2), and two equivalent S(4) atoms to form BiS6 octahedra that share edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(3)S6 octahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The Bi(1)-S(3) bond length is 3.08 Å. The Bi(1)-S(5) bond length is 2.68 Å. Both Bi(1)-S(2) bond lengths are 2.81 Å. Both Bi(1)-S(4) bond lengths are 2.88 Å. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(1), and two equivalent S(3) atoms. The Bi(2)-S(4) bond length is 2.65 Å. Both Bi(2)-S(1) bond lengths are 2.74 Å. Both Bi(2)-S(3) bond lengths are 3.10 Å. In the third Bi site, Bi(3) is bonded to two equivalent S(2) and four equivalent S(3) atoms to form BiS6 octahedra that share corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(3)S6 octahedra, and edges with four equivalent Bi(1)S6 octahedra. Both Bi(3)-S(2) bond lengths are 2.85 Å. All Bi(3)-S(3) bond lengths are 2.90 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded to one Cs(1), two equivalent Cs(2), one Cu(1), and two equivalent Bi(2) atoms to form distorted SCs3CuBi2 octahedra that share  a cornercorner with one S(1)Cs3CuBi2 octahedra, corners with two equivalent S(2)Cs2CuBi3 octahedra, corners with four equivalent S(3)CsBi5 octahedra, corners with two equivalent S(4)Cs2Bi3 square pyramids,  an edgeedge with one S(3)CsBi5 octahedra, edges with two equivalent S(1)Cs3CuBi2 octahedra, edges with two equivalent S(4)Cs2Bi3 square pyramids, and  a faceface with one S(2)Cs2CuBi3 octahedra. The corner-sharing octahedral tilt angles range from 0-74°. In the second S site, S(2) is bonded to two equivalent Cs(2), one Cu(1), one Bi(3), and two equivalent Bi(1) atoms to form distorted SCs2CuBi3 octahedra that share  a cornercorner with one S(2)Cs2CuBi3 octahedra, corners with two equivalent S(1)Cs3CuBi2 octahedra, corners with two equivalent S(4)Cs2Bi3 square pyramids, edges with two equivalent S(2)Cs2CuBi3 octahedra, edges with four equivalent S(3)CsBi5 octahedra,  an edgeedge with one S(4)Cs2Bi3 square pyramid, and  a faceface with one S(1)Cs3CuBi2 octahedra. The corner-sharing octahedral tilt angles range from 0-74°. In the third S site, S(3) is bonded to one Cs(2), one Bi(1), two equivalent Bi(2), and two equivalent Bi(3) atoms to form SCsBi5 octahedra that share corners with two equivalent S(3)CsBi5 octahedra, corners with four equivalent S(1)Cs3CuBi2 octahedra,  an edgeedge with one S(1)Cs3CuBi2 octahedra, edges with three equivalent S(3)CsBi5 octahedra, edges with four equivalent S(2)Cs2CuBi3 octahedra, and edges with two equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 0-46°. In the fourth S site, S(4) is bonded to two equivalent Cs(1), one Bi(2), and two equivalent Bi(1) atoms to form SCs2Bi3 square pyramids that share corners with two equivalent S(2)Cs2CuBi3 octahedra, corners with two equivalent S(1)Cs3CuBi2 octahedra, corners with two equivalent S(4)Cs2Bi3 square pyramids,  an edgeedge with one S(2)Cs2CuBi3 octahedra, edges with two equivalent S(1)Cs3CuBi2 octahedra, edges with two equivalent S(3)CsBi5 octahedra, and edges with three equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 6-69°. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to two equivalent Cs(2), two equivalent Cu(1), and one Bi(1) atom.