Cu2Pb3Bi8Se3S13 crystallizes in the monoclinic Cm space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one Pb(2), one S(3), one S(4), and two equivalent S(1) atoms to form distorted CuPbS4 tetrahedra that share  a cornercorner with one S(5)Bi4Pb square pyramid, corners with two equivalent Bi(7)S5 square pyramids, corners with two equivalent Bi(8)S5 square pyramids, corners with two equivalent Bi(2)Se2S3 square pyramids, corners with two equivalent S(13)BiPb4 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, and  an edgeedge with one Cu(2)PbS4 tetrahedra. In the second Cu site, Cu(2) is bonded to one Pb(3), one S(3), one S(4), and two equivalent S(2) atoms to form distorted CuPbS4 tetrahedra that share corners with two equivalent Pb(3)CuSe2S3 octahedra,  a cornercorner with one S(6)Bi4Pb square pyramid, corners with two equivalent Bi(7)S5 square pyramids, corners with two equivalent Bi(8)S5 square pyramids, corners with two equivalent Bi(1)Se2S3 square pyramids, corners with two equivalent Se(1)BiPb4 square pyramids, corners with two equivalent Cu(2)PbS4 tetrahedra,  an edgeedge with one Pb(3)CuSe2S3 octahedra, and  an edgeedge with one Cu(1)PbS4 tetrahedra. The corner-sharing octahedral tilt angles are 34°. There are three inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to two equivalent Se(1), one S(10), one S(9), and two equivalent S(13) atoms to form PbSe2S4 octahedra that share  a cornercorner with one Bi(5)S6 octahedra,  a cornercorner with one Bi(6)S6 octahedra, corners with two equivalent Pb(3)CuSe2S3 octahedra,  an edgeedge with one Pb(3)CuSe2S3 octahedra, edges with two equivalent Pb(1)Se2S4 octahedra, edges with two equivalent Bi(4)Se2S4 octahedra, and edges with two equivalent Bi(3)SeS5 octahedra. The corner-sharing octahedral tilt angles range from 3-70°. In the second Pb site, Pb(2) is bonded in a 6-coordinate geometry to one Cu(1), one S(5), two equivalent S(1), and two equivalent S(13) atoms. In the third Pb site, Pb(3) is bonded to one Cu(2), two equivalent Se(1), one S(6), and two equivalent S(2) atoms to form distorted PbCuSe2S3 octahedra that share corners with two equivalent Pb(1)Se2S4 octahedra, corners with two equivalent Cu(2)PbS4 tetrahedra,  a cornercorner with one S(3)Cu2Bi2 trigonal pyramid,  a cornercorner with one S(4)Cu2Bi2 trigonal pyramid,  an edgeedge with one Pb(1)Se2S4 octahedra, edges with two equivalent Pb(3)CuSe2S3 octahedra, edges with two equivalent Bi(4)Se2S4 octahedra, edges with two equivalent Bi(1)Se2S3 square pyramids, and  an edgeedge with one Cu(2)PbS4 tetrahedra. The corner-sharing octahedral tilt angles are 3°. There are eight inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent Se(2), one S(2), and two equivalent S(6) atoms to form BiSe2S3 square pyramids that share corners with two equivalent Bi(4)Se2S4 octahedra, corners with two equivalent Bi(3)SeS5 octahedra, corners with two equivalent Cu(2)PbS4 tetrahedra,  an edgeedge with one Bi(4)Se2S4 octahedra, edges with two equivalent Pb(3)CuSe2S3 octahedra, and edges with two equivalent Bi(1)Se2S3 square pyramids. The corner-sharing octahedral tilt angles range from 9-83°. In the second Bi site, Bi(2) is bonded to two equivalent Se(3), one S(1), and two equivalent S(5) atoms to form BiSe2S3 square pyramids that share corners with two equivalent Bi(4)Se2S4 octahedra, corners with two equivalent Bi(3)SeS5 octahedra, corners with two equivalent Cu(1)PbS4 tetrahedra,  an edgeedge with one Bi(3)SeS5 octahedra, and edges with two equivalent Bi(2)Se2S3 square pyramids. The corner-sharing octahedral tilt angles range from 8-82°. In the third Bi site, Bi(3) is bonded to one Se(2), one S(13), two equivalent S(5), and two equivalent S(9) atoms to form BiSeS5 octahedra that share corners with two equivalent Bi(6)S6 octahedra, corners with two equivalent Bi(1)Se2S3 square pyramids, corners with two equivalent Bi(2)Se2S3 square pyramids, edges with two equivalent Pb(1)Se2S4 octahedra, edges with two equivalent Bi(3)SeS5 octahedra, and  an edgeedge with one Bi(2)Se2S3 square pyramid. The corner-sharing octahedral tilt angles are 56°. In the fourth Bi site, Bi(4) is bonded to one Se(1), one Se(3), two equivalent S(10), and two equivalent S(6) atoms to form BiSe2S4 octahedra that share corners with two equivalent Bi(5)S6 octahedra, corners with two equivalent Bi(1)Se2S3 square pyramids, corners with two equivalent Bi(2)Se2S3 square pyramids, edges with two equivalent Pb(3)CuSe2S3 octahedra, edges with two equivalent Pb(1)Se2S4 octahedra, edges with two equivalent Bi(4)Se2S4 octahedra, and  an edgeedge with one Bi(1)Se2S3 square pyramid. The corner-sharing octahedral tilt angles are 55°. In the fifth Bi site, Bi(5) is bonded to one S(10), one S(11), two equivalent S(12), and two equivalent S(7) atoms to form BiS6 octahedra that share  a cornercorner with one Pb(1)Se2S4 octahedra, corners with two equivalent Bi(4)Se2S4 octahedra, corners with two equivalent Bi(8)S5 square pyramids, edges with two equivalent Bi(5)S6 octahedra, edges with two equivalent Bi(6)S6 octahedra,  an edgeedge with one Bi(8)S5 square pyramid, and edges with two equivalent Bi(7)S5 square pyramids. The corner-sharing octahedral tilt angles range from 55-70°. In the sixth Bi site, Bi(6) is bonded to one S(12), one S(9), two equivalent S(11), and two equivalent S(8) atoms to form BiS6 octahedra that share  a cornercorner with one Pb(1)Se2S4 octahedra, corners with two equivalent Bi(3)SeS5 octahedra, corners with two equivalent Bi(7)S5 square pyramids, edges with two equivalent Bi(5)S6 octahedra, edges with two equivalent Bi(6)S6 octahedra,  an edgeedge with one Bi(7)S5 square pyramid, and edges with two equivalent Bi(8)S5 square pyramids. The corner-sharing octahedral tilt angles range from 56-66°. In the seventh Bi site, Bi(7) is bonded to one S(7), two equivalent S(11), and two equivalent S(3) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Bi(6)S6 octahedra, corners with two equivalent Cu(1)PbS4 tetrahedra, corners with two equivalent Cu(2)PbS4 tetrahedra,  an edgeedge with one Bi(6)S6 octahedra, edges with two equivalent Bi(5)S6 octahedra, and edges with two equivalent Bi(7)S5 square pyramids. The corner-sharing octahedral tilt angles are 7°. In the eighth Bi site, Bi(8) is bonded to one S(8), two equivalent S(12), and two equivalent S(4) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Bi(5)S6 octahedra, corners with two equivalent Cu(1)PbS4 tetrahedra, corners with two equivalent Cu(2)PbS4 tetrahedra,  an edgeedge with one Bi(5)S6 octahedra, edges with two equivalent Bi(6)S6 octahedra, and edges with two equivalent Bi(8)S5 square pyramids. The corner-sharing octahedral tilt angles are 8°. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Pb(1), two equivalent Pb(3), and one Bi(4) atom to form SeBiPb4 square pyramids that share corners with two equivalent S(13)BiPb4 square pyramids, corners with two equivalent Cu(2)PbS4 tetrahedra, corners with two equivalent S(9)Bi3Pb trigonal pyramids,  an edgeedge with one S(13)BiPb4 square pyramid, edges with two equivalent Se(1)BiPb4 square pyramids, edges with two equivalent S(6)Bi4Pb square pyramids, and edges with two equivalent S(10)Bi3Pb trigonal pyramids. In the second Se site, Se(2) is bonded in a 3-coordinate geometry to one Bi(3) and two equivalent Bi(1) atoms. In the third Se site, Se(3) is bonded in a 3-coordinate geometry to one Bi(4) and two equivalent Bi(2) atoms. There are thirteen inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cu(1), two equivalent Pb(2), and one Bi(2) atom. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cu(2), two equivalent Pb(3), and one Bi(1) atom. In the third S site, S(3) is bonded to one Cu(1), one Cu(2), and two equivalent Bi(7) atoms to form distorted SCu2Bi2 trigonal pyramids that share  a cornercorner with one Pb(3)CuSe2S3 octahedra, corners with two equivalent S(11)Bi5 square pyramids, corners with two equivalent S(3)Cu2Bi2 trigonal pyramids,  an edgeedge with one S(11)Bi5 square pyramid, and  an edgeedge with one S(4)Cu2Bi2 trigonal pyramid. The corner-sharing octahedral tilt angles are 2°. In the fourth S site, S(4) is bonded to one Cu(1), one Cu(2), and two equivalent Bi(8) atoms to form distorted SCu2Bi2 trigonal pyramids that share  a cornercorner with one Pb(3)CuSe2S3 octahedra, corners with two equivalent S(12)Bi5 square pyramids, corners with two equivalent S(4)Cu2Bi2 trigonal pyramids,  an edgeedge with one S(12)Bi5 square pyramid, and  an edgeedge with one S(3)Cu2Bi2 trigonal pyramid. The corner-sharing octahedral tilt angles are 103°. In the fifth S site, S(5) is bonded to one Pb(2), two equivalent Bi(2), and two equivalent Bi(3) atoms to form SBi4Pb square pyramids that share  a cornercorner with one Cu(1)PbS4 tetrahedra, corners with two equivalent S(9)Bi3Pb trigonal pyramids, edges with two equivalent S(5)Bi4Pb square pyramids, edges with two equivalent S(13)BiPb4 square pyramids, and  an edgeedge with one S(9)Bi3Pb trigonal pyramid. In the sixth S site, S(6) is bonded to one Pb(3), two equivalent Bi(1), and two equivalent Bi(4) atoms to form SBi4Pb square pyramids that share  a cornercorner with one Cu(2)PbS4 tetrahedra, corners with two equivalent S(10)Bi3Pb trigonal pyramids, edges with two equivalent Se(1)BiPb4 square pyramids, edges with two equivalent S(6)Bi4Pb square pyramids, and  an edgeedge with one S(10)Bi3Pb trigonal pyramid. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Bi(7) and two equivalent Bi(5) atoms. In the eighth S site, S(8) is bonded in a trigonal non-coplanar geometry to one Bi(8) and two equivalent Bi(6) atoms. In the ninth S site, S(9) is bonded to one Pb(1), one Bi(6), and two equivalent Bi(3) atoms to form distorted SBi3Pb trigonal pyramids that share  a cornercorner with one S(12)Bi5 square pyramid, corners with two equivalent Se(1)BiPb4 square pyramids, corners with two equivalent S(5)Bi4Pb square pyramids, corners with two equivalent S(11)Bi5 square pyramids,  a cornercorner with one S(10)Bi3Pb trigonal pyramid, corners with two equivalent S(9)Bi3Pb trigonal pyramids,  an edgeedge with one S(5)Bi4Pb square pyramid, and edges with two equivalent S(13)BiPb4 square pyramids. In the tenth S site, S(10) is bonded to one Pb(1), one Bi(5), and two equivalent Bi(4) atoms to form distorted SBi3Pb trigonal pyramids that share  a cornercorner with one S(11)Bi5 square pyramid, corners with two equivalent S(6)Bi4Pb square pyramids, corners with two equivalent S(12)Bi5 square pyramids, corners with two equivalent S(13)BiPb4 square pyramids,  a cornercorner with one S(9)Bi3Pb trigonal pyramid, corners with two equivalent S(10)Bi3Pb trigonal pyramids,  an edgeedge with one S(6)Bi4Pb square pyramid, and edges with two equivalent Se(1)BiPb4 square pyramids. In the eleventh S site, S(11) is bonded to one Bi(5), two equivalent Bi(6), and two equivalent Bi(7) atoms to form SBi5 square pyramids that share  a cornercorner with one S(10)Bi3Pb trigonal pyramid, corners with two equivalent S(9)Bi3Pb trigonal pyramids, corners with two equivalent S(3)Cu2Bi2 trigonal pyramids, edges with two equivalent S(11)Bi5 square pyramids, edges with two equivalent S(12)Bi5 square pyramids, and  an edgeedge with one S(3)Cu2Bi2 trigonal pyramid. In the twelfth S site, S(12) is bonded to one Bi(6), two equivalent Bi(5), and two equivalent Bi(8) atoms to form SBi5 square pyramids that share  a cornercorner with one S(9)Bi3Pb trigonal pyramid, corners with two equivalent S(10)Bi3Pb trigonal pyramids, corners with two equivalent S(4)Cu2Bi2 trigonal pyramids, edges with two equivalent S(11)Bi5 square pyramids, edges with two equivalent S(12)Bi5 square pyramids, and  an edgeedge with one S(4)Cu2Bi2 trigonal pyramid. In the thirteenth S site, S(13) is bonded to two equivalent Pb(1), two equivalent Pb(2), and one Bi(3) atom to form SBiPb4 square pyramids that share corners with two equivalent Se(1)BiPb4 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, corners with two equivalent S(10)Bi3Pb trigonal pyramids,  an edgeedge with one Se(1)BiPb4 square pyramid, edges with two equivalent S(5)Bi4Pb square pyramids, edges with two equivalent S(13)BiPb4 square pyramids, and edges with two equivalent S(9)Bi3Pb trigonal pyramids.
Cu2Pb3Bi8Se3S13 crystallizes in the monoclinic Cm space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one Pb(2), one S(3), one S(4), and two equivalent S(1) atoms to form distorted CuPbS4 tetrahedra that share  a cornercorner with one S(5)Bi4Pb square pyramid, corners with two equivalent Bi(7)S5 square pyramids, corners with two equivalent Bi(8)S5 square pyramids, corners with two equivalent Bi(2)Se2S3 square pyramids, corners with two equivalent S(13)BiPb4 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, and  an edgeedge with one Cu(2)PbS4 tetrahedra. The Cu(1)-Pb(2) bond length is 3.19 Å. The Cu(1)-S(3) bond length is 2.40 Å. The Cu(1)-S(4) bond length is 2.29 Å. Both Cu(1)-S(1) bond lengths are 2.43 Å. In the second Cu site, Cu(2) is bonded to one Pb(3), one S(3), one S(4), and two equivalent S(2) atoms to form distorted CuPbS4 tetrahedra that share corners with two equivalent Pb(3)CuSe2S3 octahedra,  a cornercorner with one S(6)Bi4Pb square pyramid, corners with two equivalent Bi(7)S5 square pyramids, corners with two equivalent Bi(8)S5 square pyramids, corners with two equivalent Bi(1)Se2S3 square pyramids, corners with two equivalent Se(1)BiPb4 square pyramids, corners with two equivalent Cu(2)PbS4 tetrahedra,  an edgeedge with one Pb(3)CuSe2S3 octahedra, and  an edgeedge with one Cu(1)PbS4 tetrahedra. The corner-sharing octahedral tilt angles are 34°. The Cu(2)-Pb(3) bond length is 3.16 Å. The Cu(2)-S(3) bond length is 2.29 Å. The Cu(2)-S(4) bond length is 2.41 Å. Both Cu(2)-S(2) bond lengths are 2.43 Å. There are three inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to two equivalent Se(1), one S(10), one S(9), and two equivalent S(13) atoms to form PbSe2S4 octahedra that share  a cornercorner with one Bi(5)S6 octahedra,  a cornercorner with one Bi(6)S6 octahedra, corners with two equivalent Pb(3)CuSe2S3 octahedra,  an edgeedge with one Pb(3)CuSe2S3 octahedra, edges with two equivalent Pb(1)Se2S4 octahedra, edges with two equivalent Bi(4)Se2S4 octahedra, and edges with two equivalent Bi(3)SeS5 octahedra. The corner-sharing octahedral tilt angles range from 3-70°. Both Pb(1)-Se(1) bond lengths are 3.04 Å. The Pb(1)-S(10) bond length is 3.02 Å. The Pb(1)-S(9) bond length is 2.98 Å. Both Pb(1)-S(13) bond lengths are 2.95 Å. In the second Pb site, Pb(2) is bonded in a 6-coordinate geometry to one Cu(1), one S(5), two equivalent S(1), and two equivalent S(13) atoms. The Pb(2)-S(5) bond length is 2.86 Å. Both Pb(2)-S(1) bond lengths are 3.10 Å. Both Pb(2)-S(13) bond lengths are 2.96 Å. In the third Pb site, Pb(3) is bonded to one Cu(2), two equivalent Se(1), one S(6), and two equivalent S(2) atoms to form distorted PbCuSe2S3 octahedra that share corners with two equivalent Pb(1)Se2S4 octahedra, corners with two equivalent Cu(2)PbS4 tetrahedra,  a cornercorner with one S(3)Cu2Bi2 trigonal pyramid,  a cornercorner with one S(4)Cu2Bi2 trigonal pyramid,  an edgeedge with one Pb(1)Se2S4 octahedra, edges with two equivalent Pb(3)CuSe2S3 octahedra, edges with two equivalent Bi(4)Se2S4 octahedra, edges with two equivalent Bi(1)Se2S3 square pyramids, and  an edgeedge with one Cu(2)PbS4 tetrahedra. The corner-sharing octahedral tilt angles are 3°. Both Pb(3)-Se(1) bond lengths are 3.06 Å. The Pb(3)-S(6) bond length is 2.85 Å. Both Pb(3)-S(2) bond lengths are 3.10 Å. There are eight inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent Se(2), one S(2), and two equivalent S(6) atoms to form BiSe2S3 square pyramids that share corners with two equivalent Bi(4)Se2S4 octahedra, corners with two equivalent Bi(3)SeS5 octahedra, corners with two equivalent Cu(2)PbS4 tetrahedra,  an edgeedge with one Bi(4)Se2S4 octahedra, edges with two equivalent Pb(3)CuSe2S3 octahedra, and edges with two equivalent Bi(1)Se2S3 square pyramids. The corner-sharing octahedral tilt angles range from 9-83°. Both Bi(1)-Se(2) bond lengths are 2.84 Å. The Bi(1)-S(2) bond length is 2.62 Å. Both Bi(1)-S(6) bond lengths are 2.99 Å. In the second Bi site, Bi(2) is bonded to two equivalent Se(3), one S(1), and two equivalent S(5) atoms to form BiSe2S3 square pyramids that share corners with two equivalent Bi(4)Se2S4 octahedra, corners with two equivalent Bi(3)SeS5 octahedra, corners with two equivalent Cu(1)PbS4 tetrahedra,  an edgeedge with one Bi(3)SeS5 octahedra, and edges with two equivalent Bi(2)Se2S3 square pyramids. The corner-sharing octahedral tilt angles range from 8-82°. Both Bi(2)-Se(3) bond lengths are 2.85 Å. The Bi(2)-S(1) bond length is 2.62 Å. Both Bi(2)-S(5) bond lengths are 2.98 Å. In the third Bi site, Bi(3) is bonded to one Se(2), one S(13), two equivalent S(5), and two equivalent S(9) atoms to form BiSeS5 octahedra that share corners with two equivalent Bi(6)S6 octahedra, corners with two equivalent Bi(1)Se2S3 square pyramids, corners with two equivalent Bi(2)Se2S3 square pyramids, edges with two equivalent Pb(1)Se2S4 octahedra, edges with two equivalent Bi(3)SeS5 octahedra, and  an edgeedge with one Bi(2)Se2S3 square pyramid. The corner-sharing octahedral tilt angles are 56°. The Bi(3)-Se(2) bond length is 3.02 Å. The Bi(3)-S(13) bond length is 2.77 Å. Both Bi(3)-S(5) bond lengths are 3.03 Å. Both Bi(3)-S(9) bond lengths are 2.73 Å. In the fourth Bi site, Bi(4) is bonded to one Se(1), one Se(3), two equivalent S(10), and two equivalent S(6) atoms to form BiSe2S4 octahedra that share corners with two equivalent Bi(5)S6 octahedra, corners with two equivalent Bi(1)Se2S3 square pyramids, corners with two equivalent Bi(2)Se2S3 square pyramids, edges with two equivalent Pb(3)CuSe2S3 octahedra, edges with two equivalent Pb(1)Se2S4 octahedra, edges with two equivalent Bi(4)Se2S4 octahedra, and  an edgeedge with one Bi(1)Se2S3 square pyramid. The corner-sharing octahedral tilt angles are 55°. The Bi(4)-Se(1) bond length is 2.90 Å. The Bi(4)-Se(3) bond length is 3.03 Å. Both Bi(4)-S(10) bond lengths are 2.72 Å. Both Bi(4)-S(6) bond lengths are 3.04 Å. In the fifth Bi site, Bi(5) is bonded to one S(10), one S(11), two equivalent S(12), and two equivalent S(7) atoms to form BiS6 octahedra that share  a cornercorner with one Pb(1)Se2S4 octahedra, corners with two equivalent Bi(4)Se2S4 octahedra, corners with two equivalent Bi(8)S5 square pyramids, edges with two equivalent Bi(5)S6 octahedra, edges with two equivalent Bi(6)S6 octahedra,  an edgeedge with one Bi(8)S5 square pyramid, and edges with two equivalent Bi(7)S5 square pyramids. The corner-sharing octahedral tilt angles range from 55-70°. The Bi(5)-S(10) bond length is 3.04 Å. The Bi(5)-S(11) bond length is 2.69 Å. Both Bi(5)-S(12) bond lengths are 2.92 Å. Both Bi(5)-S(7) bond lengths are 2.83 Å. In the sixth Bi site, Bi(6) is bonded to one S(12), one S(9), two equivalent S(11), and two equivalent S(8) atoms to form BiS6 octahedra that share  a cornercorner with one Pb(1)Se2S4 octahedra, corners with two equivalent Bi(3)SeS5 octahedra, corners with two equivalent Bi(7)S5 square pyramids, edges with two equivalent Bi(5)S6 octahedra, edges with two equivalent Bi(6)S6 octahedra,  an edgeedge with one Bi(7)S5 square pyramid, and edges with two equivalent Bi(8)S5 square pyramids. The corner-sharing octahedral tilt angles range from 56-66°. The Bi(6)-S(12) bond length is 2.69 Å. The Bi(6)-S(9) bond length is 3.07 Å. Both Bi(6)-S(11) bond lengths are 2.93 Å. Both Bi(6)-S(8) bond lengths are 2.82 Å. In the seventh Bi site, Bi(7) is bonded to one S(7), two equivalent S(11), and two equivalent S(3) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Bi(6)S6 octahedra, corners with two equivalent Cu(1)PbS4 tetrahedra, corners with two equivalent Cu(2)PbS4 tetrahedra,  an edgeedge with one Bi(6)S6 octahedra, edges with two equivalent Bi(5)S6 octahedra, and edges with two equivalent Bi(7)S5 square pyramids. The corner-sharing octahedral tilt angles are 7°. The Bi(7)-S(7) bond length is 2.64 Å. Both Bi(7)-S(11) bond lengths are 3.16 Å. Both Bi(7)-S(3) bond lengths are 2.72 Å. In the eighth Bi site, Bi(8) is bonded to one S(8), two equivalent S(12), and two equivalent S(4) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Bi(5)S6 octahedra, corners with two equivalent Cu(1)PbS4 tetrahedra, corners with two equivalent Cu(2)PbS4 tetrahedra,  an edgeedge with one Bi(5)S6 octahedra, edges with two equivalent Bi(6)S6 octahedra, and edges with two equivalent Bi(8)S5 square pyramids. The corner-sharing octahedral tilt angles are 8°. The Bi(8)-S(8) bond length is 2.64 Å. Both Bi(8)-S(12) bond lengths are 3.16 Å. Both Bi(8)-S(4) bond lengths are 2.72 Å. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Pb(1), two equivalent Pb(3), and one Bi(4) atom to form SeBiPb4 square pyramids that share corners with two equivalent S(13)BiPb4 square pyramids, corners with two equivalent Cu(2)PbS4 tetrahedra, corners with two equivalent S(9)Bi3Pb trigonal pyramids,  an edgeedge with one S(13)BiPb4 square pyramid, edges with two equivalent Se(1)BiPb4 square pyramids, edges with two equivalent S(6)Bi4Pb square pyramids, and edges with two equivalent S(10)Bi3Pb trigonal pyramids. In the second Se site, Se(2) is bonded in a 3-coordinate geometry to one Bi(3) and two equivalent Bi(1) atoms. In the third Se site, Se(3) is bonded in a 3-coordinate geometry to one Bi(4) and two equivalent Bi(2) atoms. There are thirteen inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cu(1), two equivalent Pb(2), and one Bi(2) atom. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cu(2), two equivalent Pb(3), and one Bi(1) atom. In the third S site, S(3) is bonded to one Cu(1), one Cu(2), and two equivalent Bi(7) atoms to form distorted SCu2Bi2 trigonal pyramids that share  a cornercorner with one Pb(3)CuSe2S3 octahedra, corners with two equivalent S(11)Bi5 square pyramids, corners with two equivalent S(3)Cu2Bi2 trigonal pyramids,  an edgeedge with one S(11)Bi5 square pyramid, and  an edgeedge with one S(4)Cu2Bi2 trigonal pyramid. The corner-sharing octahedral tilt angles are 2°. In the fourth S site, S(4) is bonded to one Cu(1), one Cu(2), and two equivalent Bi(8) atoms to form distorted SCu2Bi2 trigonal pyramids that share  a cornercorner with one Pb(3)CuSe2S3 octahedra, corners with two equivalent S(12)Bi5 square pyramids, corners with two equivalent S(4)Cu2Bi2 trigonal pyramids,  an edgeedge with one S(12)Bi5 square pyramid, and  an edgeedge with one S(3)Cu2Bi2 trigonal pyramid. The corner-sharing octahedral tilt angles are 103°. In the fifth S site, S(5) is bonded to one Pb(2), two equivalent Bi(2), and two equivalent Bi(3) atoms to form SBi4Pb square pyramids that share  a cornercorner with one Cu(1)PbS4 tetrahedra, corners with two equivalent S(9)Bi3Pb trigonal pyramids, edges with two equivalent S(5)Bi4Pb square pyramids, edges with two equivalent S(13)BiPb4 square pyramids, and  an edgeedge with one S(9)Bi3Pb trigonal pyramid. In the sixth S site, S(6) is bonded to one Pb(3), two equivalent Bi(1), and two equivalent Bi(4) atoms to form SBi4Pb square pyramids that share  a cornercorner with one Cu(2)PbS4 tetrahedra, corners with two equivalent S(10)Bi3Pb trigonal pyramids, edges with two equivalent Se(1)BiPb4 square pyramids, edges with two equivalent S(6)Bi4Pb square pyramids, and  an edgeedge with one S(10)Bi3Pb trigonal pyramid. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Bi(7) and two equivalent Bi(5) atoms. In the eighth S site, S(8) is bonded in a trigonal non-coplanar geometry to one Bi(8) and two equivalent Bi(6) atoms. In the ninth S site, S(9) is bonded to one Pb(1), one Bi(6), and two equivalent Bi(3) atoms to form distorted SBi3Pb trigonal pyramids that share  a cornercorner with one S(12)Bi5 square pyramid, corners with two equivalent Se(1)BiPb4 square pyramids, corners with two equivalent S(5)Bi4Pb square pyramids, corners with two equivalent S(11)Bi5 square pyramids,  a cornercorner with one S(10)Bi3Pb trigonal pyramid, corners with two equivalent S(9)Bi3Pb trigonal pyramids,  an edgeedge with one S(5)Bi4Pb square pyramid, and edges with two equivalent S(13)BiPb4 square pyramids. In the tenth S site, S(10) is bonded to one Pb(1), one Bi(5), and two equivalent Bi(4) atoms to form distorted SBi3Pb trigonal pyramids that share  a cornercorner with one S(11)Bi5 square pyramid, corners with two equivalent S(6)Bi4Pb square pyramids, corners with two equivalent S(12)Bi5 square pyramids, corners with two equivalent S(13)BiPb4 square pyramids,  a cornercorner with one S(9)Bi3Pb trigonal pyramid, corners with two equivalent S(10)Bi3Pb trigonal pyramids,  an edgeedge with one S(6)Bi4Pb square pyramid, and edges with two equivalent Se(1)BiPb4 square pyramids. In the eleventh S site, S(11) is bonded to one Bi(5), two equivalent Bi(6), and two equivalent Bi(7) atoms to form SBi5 square pyramids that share  a cornercorner with one S(10)Bi3Pb trigonal pyramid, corners with two equivalent S(9)Bi3Pb trigonal pyramids, corners with two equivalent S(3)Cu2Bi2 trigonal pyramids, edges with two equivalent S(11)Bi5 square pyramids, edges with two equivalent S(12)Bi5 square pyramids, and  an edgeedge with one S(3)Cu2Bi2 trigonal pyramid. In the twelfth S site, S(12) is bonded to one Bi(6), two equivalent Bi(5), and two equivalent Bi(8) atoms to form SBi5 square pyramids that share  a cornercorner with one S(9)Bi3Pb trigonal pyramid, corners with two equivalent S(10)Bi3Pb trigonal pyramids, corners with two equivalent S(4)Cu2Bi2 trigonal pyramids, edges with two equivalent S(11)Bi5 square pyramids, edges with two equivalent S(12)Bi5 square pyramids, and  an edgeedge with one S(4)Cu2Bi2 trigonal pyramid. In the thirteenth S site, S(13) is bonded to two equivalent Pb(1), two equivalent Pb(2), and one Bi(3) atom to form SBiPb4 square pyramids that share corners with two equivalent Se(1)BiPb4 square pyramids, corners with two equivalent Cu(1)PbS4 tetrahedra, corners with two equivalent S(10)Bi3Pb trigonal pyramids,  an edgeedge with one Se(1)BiPb4 square pyramid, edges with two equivalent S(5)Bi4Pb square pyramids, edges with two equivalent S(13)BiPb4 square pyramids, and edges with two equivalent S(9)Bi3Pb trigonal pyramids.