CuPbBi3S6 crystallizes in the orthorhombic Pmc2_1 space group. Cu(1) is bonded to one S(3), one S(5), and two equivalent S(2) atoms to form CuS4 tetrahedra that share corners with two equivalent Bi(2)S6 pentagonal pyramids, corners with three equivalent Bi(3)S5 square pyramids, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(2)S6 pentagonal pyramids, and  an edgeedge with one Bi(3)S5 square pyramid. Pb(1) is bonded in a 3-coordinate geometry to one S(4) and two equivalent S(1) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one S(1), one S(5), two equivalent S(4), and two equivalent S(6) atoms. In the second Bi site, Bi(2) is bonded to one S(2), one S(6), two equivalent S(3), and two equivalent S(5) atoms to form distorted BiS6 pentagonal pyramids that share corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(2)S6 pentagonal pyramids, edges with two equivalent Bi(3)S5 square pyramids, and edges with two equivalent Cu(1)S4 tetrahedra. In the third Bi site, Bi(3) is bonded to one S(3), two equivalent S(2), and two equivalent S(4) atoms to form distorted BiS5 square pyramids that share corners with three equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(2)S6 pentagonal pyramids, edges with two equivalent Bi(3)S5 square pyramids, and  an edgeedge with one Cu(1)S4 tetrahedra. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Pb(1) and one Bi(1) atom. In the second S site, S(2) is bonded to two equivalent Cu(1), one Bi(2), and two equivalent Bi(3) atoms to form distorted SCu2Bi3 square pyramids that share corners with two equivalent S(4)Bi4Pb square pyramids,  an edgeedge with one S(4)Bi4Pb square pyramid, and edges with two equivalent S(2)Cu2Bi3 square pyramids. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Cu(1), one Bi(3), and two equivalent Bi(2) atoms. In the fourth S site, S(4) is bonded to one Pb(1), two equivalent Bi(1), and two equivalent Bi(3) atoms to form distorted SBi4Pb square pyramids that share corners with two equivalent S(2)Cu2Bi3 square pyramids,  an edgeedge with one S(2)Cu2Bi3 square pyramid, and edges with two equivalent S(4)Bi4Pb square pyramids. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Cu(1), one Bi(1), and two equivalent Bi(2) atoms. In the sixth S site, S(6) is bonded in a trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(1) atoms.
CuPbBi3S6 crystallizes in the orthorhombic Pmc2_1 space group. Cu(1) is bonded to one S(3), one S(5), and two equivalent S(2) atoms to form CuS4 tetrahedra that share corners with two equivalent Bi(2)S6 pentagonal pyramids, corners with three equivalent Bi(3)S5 square pyramids, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(2)S6 pentagonal pyramids, and  an edgeedge with one Bi(3)S5 square pyramid. The Cu(1)-S(3) bond length is 2.40 Å. The Cu(1)-S(5) bond length is 2.34 Å. Both Cu(1)-S(2) bond lengths are 2.35 Å. Pb(1) is bonded in a 3-coordinate geometry to one S(4) and two equivalent S(1) atoms. The Pb(1)-S(4) bond length is 2.87 Å. Both Pb(1)-S(1) bond lengths are 2.80 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one S(1), one S(5), two equivalent S(4), and two equivalent S(6) atoms. The Bi(1)-S(1) bond length is 2.61 Å. The Bi(1)-S(5) bond length is 3.23 Å. Both Bi(1)-S(4) bond lengths are 3.18 Å. Both Bi(1)-S(6) bond lengths are 2.70 Å. In the second Bi site, Bi(2) is bonded to one S(2), one S(6), two equivalent S(3), and two equivalent S(5) atoms to form distorted BiS6 pentagonal pyramids that share corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(2)S6 pentagonal pyramids, edges with two equivalent Bi(3)S5 square pyramids, and edges with two equivalent Cu(1)S4 tetrahedra. The Bi(2)-S(2) bond length is 2.80 Å. The Bi(2)-S(6) bond length is 3.00 Å. Both Bi(2)-S(3) bond lengths are 2.95 Å. Both Bi(2)-S(5) bond lengths are 2.75 Å. In the third Bi site, Bi(3) is bonded to one S(3), two equivalent S(2), and two equivalent S(4) atoms to form distorted BiS5 square pyramids that share corners with three equivalent Cu(1)S4 tetrahedra, edges with two equivalent Bi(2)S6 pentagonal pyramids, edges with two equivalent Bi(3)S5 square pyramids, and  an edgeedge with one Cu(1)S4 tetrahedra. The Bi(3)-S(3) bond length is 2.69 Å. Both Bi(3)-S(2) bond lengths are 3.02 Å. Both Bi(3)-S(4) bond lengths are 2.78 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Pb(1) and one Bi(1) atom. In the second S site, S(2) is bonded to two equivalent Cu(1), one Bi(2), and two equivalent Bi(3) atoms to form distorted SCu2Bi3 square pyramids that share corners with two equivalent S(4)Bi4Pb square pyramids,  an edgeedge with one S(4)Bi4Pb square pyramid, and edges with two equivalent S(2)Cu2Bi3 square pyramids. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Cu(1), one Bi(3), and two equivalent Bi(2) atoms. In the fourth S site, S(4) is bonded to one Pb(1), two equivalent Bi(1), and two equivalent Bi(3) atoms to form distorted SBi4Pb square pyramids that share corners with two equivalent S(2)Cu2Bi3 square pyramids,  an edgeedge with one S(2)Cu2Bi3 square pyramid, and edges with two equivalent S(4)Bi4Pb square pyramids. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Cu(1), one Bi(1), and two equivalent Bi(2) atoms. In the sixth S site, S(6) is bonded in a trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(1) atoms.