CuPbBi3S6 crystallizes in the orthorhombic Pmc2_1 space group. Cu(1) is bonded to one Pb(1), one S(4), one S(5), and two equivalent S(3) atoms to form CuPbS4 tetrahedra that share  a cornercorner with one Bi(1)S6 octahedra,  a cornercorner with one S(5)CuBi4Pb octahedra, corners with two equivalent Bi(2)S6 octahedra, corners with two equivalent Bi(3)S5 square pyramids, corners with two equivalent S(2)Bi3Pb2 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, and edges with two equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 14-98°. Pb(1) is bonded in a 8-coordinate geometry to one Cu(1), one S(5), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(4), one S(6), two equivalent S(1), and two equivalent S(2) atoms to form distorted BiS6 octahedra that share  a cornercorner with one Cu(1)PbS4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, and edges with two equivalent Bi(3)S5 square pyramids. In the second Bi site, Bi(2) is bonded to one S(1), one S(3), two equivalent S(4), and two equivalent S(5) atoms to form distorted BiS6 octahedra that share corners with two equivalent Bi(3)S5 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra,  an edgeedge with one Bi(3)S5 square pyramid, and edges with two equivalent Cu(1)PbS4 tetrahedra. In the third Bi site, Bi(3) is bonded to one S(2), two equivalent S(5), and two equivalent S(6) atoms to form BiS5 square pyramids that share corners with two equivalent Bi(2)S6 octahedra, corners with two equivalent Cu(1)PbS4 tetrahedra,  an edgeedge with one Bi(2)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with two equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles are 10°. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Pb(1), one Bi(2), and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded to two equivalent Pb(1), one Bi(3), and two equivalent Bi(1) atoms to form distorted SBi3Pb2 square pyramids that share corners with two equivalent Cu(1)PbS4 tetrahedra, edges with two equivalent S(5)CuBi4Pb octahedra, and edges with two equivalent S(2)Bi3Pb2 square pyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Cu(1), two equivalent Pb(1), and one Bi(2) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Cu(1), one Bi(1), and two equivalent Bi(2) atoms. In the fifth S site, S(5) is bonded to one Cu(1), one Pb(1), two equivalent Bi(2), and two equivalent Bi(3) atoms to form distorted SCuBi4Pb octahedra that share  a cornercorner with one Cu(1)PbS4 tetrahedra, edges with two equivalent S(5)CuBi4Pb octahedra, and edges with two equivalent S(2)Bi3Pb2 square pyramids. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Bi(1) and two equivalent Bi(3) atoms.
CuPbBi3S6 crystallizes in the orthorhombic Pmc2_1 space group. Cu(1) is bonded to one Pb(1), one S(4), one S(5), and two equivalent S(3) atoms to form CuPbS4 tetrahedra that share  a cornercorner with one Bi(1)S6 octahedra,  a cornercorner with one S(5)CuBi4Pb octahedra, corners with two equivalent Bi(2)S6 octahedra, corners with two equivalent Bi(3)S5 square pyramids, corners with two equivalent S(2)Bi3Pb2 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, and edges with two equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 14-98°. The Cu(1)-Pb(1) bond length is 3.38 Å. The Cu(1)-S(4) bond length is 2.43 Å. The Cu(1)-S(5) bond length is 2.32 Å. Both Cu(1)-S(3) bond lengths are 2.35 Å. Pb(1) is bonded in a 8-coordinate geometry to one Cu(1), one S(5), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The Pb(1)-S(5) bond length is 3.00 Å. Both Pb(1)-S(1) bond lengths are 3.21 Å. Both Pb(1)-S(2) bond lengths are 3.01 Å. Both Pb(1)-S(3) bond lengths are 3.01 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(4), one S(6), two equivalent S(1), and two equivalent S(2) atoms to form distorted BiS6 octahedra that share  a cornercorner with one Cu(1)PbS4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, and edges with two equivalent Bi(3)S5 square pyramids. The Bi(1)-S(4) bond length is 3.07 Å. The Bi(1)-S(6) bond length is 2.74 Å. Both Bi(1)-S(1) bond lengths are 2.72 Å. Both Bi(1)-S(2) bond lengths are 2.99 Å. In the second Bi site, Bi(2) is bonded to one S(1), one S(3), two equivalent S(4), and two equivalent S(5) atoms to form distorted BiS6 octahedra that share corners with two equivalent Bi(3)S5 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra,  an edgeedge with one Bi(3)S5 square pyramid, and edges with two equivalent Cu(1)PbS4 tetrahedra. The Bi(2)-S(1) bond length is 3.06 Å. The Bi(2)-S(3) bond length is 2.70 Å. Both Bi(2)-S(4) bond lengths are 2.75 Å. Both Bi(2)-S(5) bond lengths are 3.01 Å. In the third Bi site, Bi(3) is bonded to one S(2), two equivalent S(5), and two equivalent S(6) atoms to form BiS5 square pyramids that share corners with two equivalent Bi(2)S6 octahedra, corners with two equivalent Cu(1)PbS4 tetrahedra,  an edgeedge with one Bi(2)S6 octahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with two equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles are 10°. The Bi(3)-S(2) bond length is 2.63 Å. Both Bi(3)-S(5) bond lengths are 2.99 Å. Both Bi(3)-S(6) bond lengths are 2.77 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Pb(1), one Bi(2), and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded to two equivalent Pb(1), one Bi(3), and two equivalent Bi(1) atoms to form distorted SBi3Pb2 square pyramids that share corners with two equivalent Cu(1)PbS4 tetrahedra, edges with two equivalent S(5)CuBi4Pb octahedra, and edges with two equivalent S(2)Bi3Pb2 square pyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Cu(1), two equivalent Pb(1), and one Bi(2) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Cu(1), one Bi(1), and two equivalent Bi(2) atoms. In the fifth S site, S(5) is bonded to one Cu(1), one Pb(1), two equivalent Bi(2), and two equivalent Bi(3) atoms to form distorted SCuBi4Pb octahedra that share  a cornercorner with one Cu(1)PbS4 tetrahedra, edges with two equivalent S(5)CuBi4Pb octahedra, and edges with two equivalent S(2)Bi3Pb2 square pyramids. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Bi(1) and two equivalent Bi(3) atoms.