Rb3Bi5Cu2S10 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(3) atoms. Cu(1) is bonded to one S(1), one S(2), and two equivalent S(5) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Bi(3)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with two equivalent Bi(2)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 distorted BiS6 octahedra that share  a cornercorner with one Bi(2)S6 octahedra, corners with two equivalent Bi(3)S6 octahedra,  an edgeedge with one Bi(3)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 6-42°. In the second Bi site, Bi(2) is bonded to one S(4), one S(5), two equivalent S(1), and two equivalent S(3) atoms to form BiS6 octahedra that share  a cornercorner with one Bi(1)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, edges with two equivalent Bi(3)S6 octahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 42°. In the third Bi site, Bi(3) is bonded to two equivalent S(1) and four equivalent S(4) atoms to form BiS6 octahedra that share corners with four equivalent Bi(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(3)S6 octahedra, and edges with four equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles are 6°. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Rb(1), one Cu(1), one Bi(3), and two equivalent Bi(2) atoms to form distorted SRb2CuBi3 octahedra that share  a cornercorner with one S(1)Rb2CuBi3 octahedra, corners with two equivalent S(2)Rb3CuBi2 octahedra, corners with two equivalent S(3)Rb2Bi3 square pyramids, edges with two equivalent S(1)Rb2CuBi3 octahedra, edges with four equivalent S(4)RbBi5 octahedra,  an edgeedge with one S(3)Rb2Bi3 square pyramid, and  a faceface with one S(2)Rb3CuBi2 octahedra. The corner-sharing octahedral tilt angles range from 0-71°. In the second S site, S(2) is bonded to one Rb(2), two equivalent Rb(1), one Cu(1), and two equivalent Bi(1) atoms to form distorted SRb3CuBi2 octahedra that share  a cornercorner with one S(2)Rb3CuBi2 octahedra, corners with two equivalent S(1)Rb2CuBi3 octahedra, corners with four equivalent S(4)RbBi5 octahedra, corners with two equivalent S(3)Rb2Bi3 square pyramids,  an edgeedge with one S(4)RbBi5 octahedra, edges with two equivalent S(2)Rb3CuBi2 octahedra, edges with two equivalent S(3)Rb2Bi3 square pyramids, and  a faceface with one S(1)Rb2CuBi3 octahedra. The corner-sharing octahedral tilt angles range from 0-71°. In the third S site, S(3) is bonded to two equivalent Rb(2), one Bi(1), and two equivalent Bi(2) atoms to form SRb2Bi3 square pyramids that share corners with two equivalent S(1)Rb2CuBi3 octahedra, corners with two equivalent S(2)Rb3CuBi2 octahedra, corners with two equivalent S(3)Rb2Bi3 square pyramids,  an edgeedge with one S(1)Rb2CuBi3 octahedra, edges with two equivalent S(2)Rb3CuBi2 octahedra, edges with two equivalent S(4)RbBi5 octahedra, and edges with three equivalent S(3)Rb2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 7-73°. In the fourth S site, S(4) is bonded to one Rb(1), one Bi(2), two equivalent Bi(1), and two equivalent Bi(3) atoms to form SRbBi5 octahedra that share corners with two equivalent S(4)RbBi5 octahedra, corners with four equivalent S(2)Rb3CuBi2 octahedra,  an edgeedge with one S(2)Rb3CuBi2 octahedra, edges with three equivalent S(4)RbBi5 octahedra, edges with four equivalent S(1)Rb2CuBi3 octahedra, and edges with two equivalent S(3)Rb2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 0-44°. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to two equivalent Rb(1), two equivalent Cu(1), one Bi(1), and one Bi(2) atom.
Rb3Bi5Cu2S10 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(5) atoms. The Rb(1)-S(4) bond length is 3.76 Å. Both Rb(1)-S(1) bond lengths are 3.37 Å. Both Rb(1)-S(2) bond lengths are 3.55 Å. Both Rb(1)-S(5) bond lengths are 3.38 Å. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to two equivalent S(2) and four equivalent S(3) atoms. Both Rb(2)-S(2) bond lengths are 3.30 Å. All Rb(2)-S(3) bond lengths are 3.30 Å. Cu(1) is bonded to one S(1), one S(2), and two equivalent S(5) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Bi(3)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with two equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles are 13°. The Cu(1)-S(1) bond length is 2.68 Å. The Cu(1)-S(2) bond length is 2.34 Å. Both Cu(1)-S(5) bond lengths are 2.35 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 distorted BiS6 octahedra that share  a cornercorner with one Bi(2)S6 octahedra, corners with two equivalent Bi(3)S6 octahedra,  an edgeedge with one Bi(3)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 6-42°. The Bi(1)-S(3) bond length is 2.68 Å. The Bi(1)-S(5) bond length is 3.13 Å. Both Bi(1)-S(2) bond lengths are 2.73 Å. Both Bi(1)-S(4) bond lengths are 3.08 Å. In the second Bi site, Bi(2) is bonded to one S(4), one S(5), two equivalent S(1), and two equivalent S(3) atoms to form BiS6 octahedra that share  a cornercorner with one Bi(1)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, edges with two equivalent Bi(3)S6 octahedra, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 42°. The Bi(2)-S(4) bond length is 3.03 Å. The Bi(2)-S(5) bond length is 2.70 Å. Both Bi(2)-S(1) bond lengths are 2.81 Å. Both Bi(2)-S(3) bond lengths are 2.87 Å. In the third Bi site, Bi(3) is bonded to two equivalent S(1) and four equivalent S(4) atoms to form BiS6 octahedra that share corners with four equivalent Bi(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(3)S6 octahedra, and edges with four equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles are 6°. Both Bi(3)-S(1) bond lengths are 2.84 Å. All Bi(3)-S(4) bond lengths are 2.87 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Rb(1), one Cu(1), one Bi(3), and two equivalent Bi(2) atoms to form distorted SRb2CuBi3 octahedra that share  a cornercorner with one S(1)Rb2CuBi3 octahedra, corners with two equivalent S(2)Rb3CuBi2 octahedra, corners with two equivalent S(3)Rb2Bi3 square pyramids, edges with two equivalent S(1)Rb2CuBi3 octahedra, edges with four equivalent S(4)RbBi5 octahedra,  an edgeedge with one S(3)Rb2Bi3 square pyramid, and  a faceface with one S(2)Rb3CuBi2 octahedra. The corner-sharing octahedral tilt angles range from 0-71°. In the second S site, S(2) is bonded to one Rb(2), two equivalent Rb(1), one Cu(1), and two equivalent Bi(1) atoms to form distorted SRb3CuBi2 octahedra that share  a cornercorner with one S(2)Rb3CuBi2 octahedra, corners with two equivalent S(1)Rb2CuBi3 octahedra, corners with four equivalent S(4)RbBi5 octahedra, corners with two equivalent S(3)Rb2Bi3 square pyramids,  an edgeedge with one S(4)RbBi5 octahedra, edges with two equivalent S(2)Rb3CuBi2 octahedra, edges with two equivalent S(3)Rb2Bi3 square pyramids, and  a faceface with one S(1)Rb2CuBi3 octahedra. The corner-sharing octahedral tilt angles range from 0-71°. In the third S site, S(3) is bonded to two equivalent Rb(2), one Bi(1), and two equivalent Bi(2) atoms to form SRb2Bi3 square pyramids that share corners with two equivalent S(1)Rb2CuBi3 octahedra, corners with two equivalent S(2)Rb3CuBi2 octahedra, corners with two equivalent S(3)Rb2Bi3 square pyramids,  an edgeedge with one S(1)Rb2CuBi3 octahedra, edges with two equivalent S(2)Rb3CuBi2 octahedra, edges with two equivalent S(4)RbBi5 octahedra, and edges with three equivalent S(3)Rb2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 7-73°. In the fourth S site, S(4) is bonded to one Rb(1), one Bi(2), two equivalent Bi(1), and two equivalent Bi(3) atoms to form SRbBi5 octahedra that share corners with two equivalent S(4)RbBi5 octahedra, corners with four equivalent S(2)Rb3CuBi2 octahedra,  an edgeedge with one S(2)Rb3CuBi2 octahedra, edges with three equivalent S(4)RbBi5 octahedra, edges with four equivalent S(1)Rb2CuBi3 octahedra, and edges with two equivalent S(3)Rb2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 0-44°. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to two equivalent Rb(1), two equivalent Cu(1), one Bi(1), and one Bi(2) atom.