Cu2Pb6Bi8S19 crystallizes in the monoclinic C2/m space group. Cu(1) is bonded to one Pb(1), two equivalent S(4), and two equivalent S(5) atoms to form distorted CuPbS4 tetrahedra that share corners with two equivalent Bi(2)S6 octahedra,  a cornercorner with one S(6)Bi4Pb square pyramid, corners with two equivalent S(8)BiPb4 square pyramids, corners with four equivalent Bi(3)S5 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, and  an edgeedge with one Cu(1)PbS4 tetrahedra. The corner-sharing octahedral tilt angles are 74°. There are three inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one Cu(1), one S(6), two equivalent S(4), and two equivalent S(8) atoms. In the second Pb site, Pb(2) is bonded to one S(3), one S(9), two equivalent S(1), and two equivalent S(8) atoms to form PbS6 octahedra that share  a cornercorner with one Bi(2)S6 octahedra,  a cornercorner with one Bi(4)S6 octahedra, corners with two equivalent Pb(2)S6 octahedra, edges with three equivalent Pb(2)S6 octahedra, and edges with two equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 0-63°. In the third Pb site, Pb(3) is bonded in a distorted rectangular see-saw-like geometry to one S(1), one S(2), and two equivalent S(9) atoms. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(8), two equivalent S(3), and two equivalent S(6) atoms to form BiS5 square pyramids that share corners with four equivalent Bi(2)S6 octahedra,  an edgeedge with one Bi(2)S6 octahedra, edges with two equivalent Pb(2)S6 octahedra, and edges with two equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 6-83°. In the second Bi site, Bi(2) is bonded to one S(3), one S(4), two equivalent S(2), and two equivalent S(6) atoms to form BiS6 octahedra that share  a cornercorner with one Pb(2)S6 octahedra, corners with four equivalent Bi(1)S5 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, edges with two equivalent Bi(2)S6 octahedra, and  an edgeedge with one Bi(1)S5 square pyramid. The corner-sharing octahedral tilt angles are 12°. In the third Bi site, Bi(3) is bonded to one S(7), two equivalent S(10), and two equivalent S(5) atoms to form BiS5 square pyramids that share corners with two equivalent Bi(4)S6 octahedra, corners with four equivalent Cu(1)PbS4 tetrahedra, edges with three equivalent Bi(4)S6 octahedra, and edges with two equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles are 7°. In the fourth Bi site, Bi(4) is bonded to one S(9), two equivalent S(7), and three equivalent S(10) atoms to form BiS6 octahedra that share  a cornercorner with one Pb(2)S6 octahedra, corners with two equivalent Bi(3)S5 square pyramids, edges with four equivalent Bi(4)S6 octahedra, and edges with three equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles are 63°. There are ten inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Pb(3) and four equivalent Pb(2) atoms to form SPb6 octahedra that share corners with four equivalent S(8)BiPb4 square pyramids, edges with two equivalent S(1)Pb6 octahedra, and edges with two equivalent S(8)BiPb4 square pyramids. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Pb(3) and two equivalent Bi(2) atoms. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Pb(2), one Bi(2), and two equivalent Bi(1) atoms. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent Cu(1), two equivalent Pb(1), and one Bi(2) atom. In the fifth S site, S(5) is bonded to two equivalent Cu(1) and two equivalent Bi(3) atoms to form distorted SCu2Bi2 tetrahedra that share corners with two equivalent S(10)Bi5 square pyramids, corners with two equivalent S(5)Cu2Bi2 tetrahedra,  an edgeedge with one S(10)Bi5 square pyramid, and  an edgeedge with one S(5)Cu2Bi2 tetrahedra. In the sixth S site, S(6) is bonded to one Pb(1), two equivalent Bi(1), and two equivalent Bi(2) atoms to form SBi4Pb square pyramids that share  a cornercorner with one Cu(1)PbS4 tetrahedra, edges with two equivalent S(6)Bi4Pb square pyramids, and edges with two equivalent S(8)BiPb4 square pyramids. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Bi(3) and two equivalent Bi(4) atoms. In the eighth S site, S(8) is bonded to two equivalent Pb(1), two equivalent Pb(2), and one Bi(1) atom to form distorted SBiPb4 square pyramids that share corners with two equivalent S(1)Pb6 octahedra, corners with two equivalent Cu(1)PbS4 tetrahedra,  an edgeedge with one S(1)Pb6 octahedra, edges with two equivalent S(6)Bi4Pb square pyramids, and edges with two equivalent S(8)BiPb4 square pyramids. The corner-sharing octahedral tilt angles are 9°. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Pb(2), two equivalent Pb(3), and one Bi(4) atom. In the tenth S site, S(10) is bonded to two equivalent Bi(3) and three equivalent Bi(4) atoms to form SBi5 square pyramids that share corners with two equivalent S(5)Cu2Bi2 tetrahedra, edges with four equivalent S(10)Bi5 square pyramids, and  an edgeedge with one S(5)Cu2Bi2 tetrahedra.
Cu2Pb6Bi8S19 crystallizes in the monoclinic C2/m space group. Cu(1) is bonded to one Pb(1), two equivalent S(4), and two equivalent S(5) atoms to form distorted CuPbS4 tetrahedra that share corners with two equivalent Bi(2)S6 octahedra,  a cornercorner with one S(6)Bi4Pb square pyramid, corners with two equivalent S(8)BiPb4 square pyramids, corners with four equivalent Bi(3)S5 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, and  an edgeedge with one Cu(1)PbS4 tetrahedra. The corner-sharing octahedral tilt angles are 74°. The Cu(1)-Pb(1) bond length is 3.11 Å. Both Cu(1)-S(4) bond lengths are 2.42 Å. There is one shorter (2.28 Å) and one longer (2.40 Å) Cu(1)-S(5) bond length. There are three inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one Cu(1), one S(6), two equivalent S(4), and two equivalent S(8) atoms. The Pb(1)-S(6) bond length is 3.00 Å. Both Pb(1)-S(4) bond lengths are 3.03 Å. Both Pb(1)-S(8) bond lengths are 3.05 Å. In the second Pb site, Pb(2) is bonded to one S(3), one S(9), two equivalent S(1), and two equivalent S(8) atoms to form PbS6 octahedra that share  a cornercorner with one Bi(2)S6 octahedra,  a cornercorner with one Bi(4)S6 octahedra, corners with two equivalent Pb(2)S6 octahedra, edges with three equivalent Pb(2)S6 octahedra, and edges with two equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 0-63°. The Pb(2)-S(3) bond length is 3.08 Å. The Pb(2)-S(9) bond length is 2.86 Å. Both Pb(2)-S(1) bond lengths are 2.96 Å. Both Pb(2)-S(8) bond lengths are 3.01 Å. In the third Pb site, Pb(3) is bonded in a distorted rectangular see-saw-like geometry to one S(1), one S(2), and two equivalent S(9) atoms. The Pb(3)-S(1) bond length is 3.07 Å. The Pb(3)-S(2) bond length is 2.93 Å. Both Pb(3)-S(9) bond lengths are 2.79 Å. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(8), two equivalent S(3), and two equivalent S(6) atoms to form BiS5 square pyramids that share corners with four equivalent Bi(2)S6 octahedra,  an edgeedge with one Bi(2)S6 octahedra, edges with two equivalent Pb(2)S6 octahedra, and edges with two equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 6-83°. The Bi(1)-S(8) bond length is 2.61 Å. Both Bi(1)-S(3) bond lengths are 2.80 Å. Both Bi(1)-S(6) bond lengths are 2.91 Å. In the second Bi site, Bi(2) is bonded to one S(3), one S(4), two equivalent S(2), and two equivalent S(6) atoms to form BiS6 octahedra that share  a cornercorner with one Pb(2)S6 octahedra, corners with four equivalent Bi(1)S5 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, edges with two equivalent Bi(2)S6 octahedra, and  an edgeedge with one Bi(1)S5 square pyramid. The corner-sharing octahedral tilt angles are 12°. The Bi(2)-S(3) bond length is 3.10 Å. The Bi(2)-S(4) bond length is 2.66 Å. Both Bi(2)-S(2) bond lengths are 2.69 Å. Both Bi(2)-S(6) bond lengths are 3.06 Å. In the third Bi site, Bi(3) is bonded to one S(7), two equivalent S(10), and two equivalent S(5) atoms to form BiS5 square pyramids that share corners with two equivalent Bi(4)S6 octahedra, corners with four equivalent Cu(1)PbS4 tetrahedra, edges with three equivalent Bi(4)S6 octahedra, and edges with two equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles are 7°. The Bi(3)-S(7) bond length is 2.63 Å. Both Bi(3)-S(10) bond lengths are 3.12 Å. Both Bi(3)-S(5) bond lengths are 2.71 Å. In the fourth Bi site, Bi(4) is bonded to one S(9), two equivalent S(7), and three equivalent S(10) atoms to form BiS6 octahedra that share  a cornercorner with one Pb(2)S6 octahedra, corners with two equivalent Bi(3)S5 square pyramids, edges with four equivalent Bi(4)S6 octahedra, and edges with three equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles are 63°. The Bi(4)-S(9) bond length is 2.83 Å. Both Bi(4)-S(7) bond lengths are 2.87 Å. There is one shorter (2.78 Å) and two longer (2.85 Å) Bi(4)-S(10) bond lengths. There are ten inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Pb(3) and four equivalent Pb(2) atoms to form SPb6 octahedra that share corners with four equivalent S(8)BiPb4 square pyramids, edges with two equivalent S(1)Pb6 octahedra, and edges with two equivalent S(8)BiPb4 square pyramids. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Pb(3) and two equivalent Bi(2) atoms. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Pb(2), one Bi(2), and two equivalent Bi(1) atoms. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent Cu(1), two equivalent Pb(1), and one Bi(2) atom. In the fifth S site, S(5) is bonded to two equivalent Cu(1) and two equivalent Bi(3) atoms to form distorted SCu2Bi2 tetrahedra that share corners with two equivalent S(10)Bi5 square pyramids, corners with two equivalent S(5)Cu2Bi2 tetrahedra,  an edgeedge with one S(10)Bi5 square pyramid, and  an edgeedge with one S(5)Cu2Bi2 tetrahedra. In the sixth S site, S(6) is bonded to one Pb(1), two equivalent Bi(1), and two equivalent Bi(2) atoms to form SBi4Pb square pyramids that share  a cornercorner with one Cu(1)PbS4 tetrahedra, edges with two equivalent S(6)Bi4Pb square pyramids, and edges with two equivalent S(8)BiPb4 square pyramids. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Bi(3) and two equivalent Bi(4) atoms. In the eighth S site, S(8) is bonded to two equivalent Pb(1), two equivalent Pb(2), and one Bi(1) atom to form distorted SBiPb4 square pyramids that share corners with two equivalent S(1)Pb6 octahedra, corners with two equivalent Cu(1)PbS4 tetrahedra,  an edgeedge with one S(1)Pb6 octahedra, edges with two equivalent S(6)Bi4Pb square pyramids, and edges with two equivalent S(8)BiPb4 square pyramids. The corner-sharing octahedral tilt angles are 9°. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Pb(2), two equivalent Pb(3), and one Bi(4) atom. In the tenth S site, S(10) is bonded to two equivalent Bi(3) and three equivalent Bi(4) atoms to form SBi5 square pyramids that share corners with two equivalent S(5)Cu2Bi2 tetrahedra, edges with four equivalent S(10)Bi5 square pyramids, and  an edgeedge with one S(5)Cu2Bi2 tetrahedra.