Cu2Pb5Bi5S14 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one S(1), one S(13), and two equivalent S(10) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Pb(3)S6 octahedra, corners with two equivalent Pb(4)S6 octahedra, corners with two equivalent Bi(5)S5 square pyramids, corners with two equivalent Cu(1)S4 tetrahedra, and edges with two equivalent Bi(4)S5 square pyramids. The corner-sharing octahedral tilt angles range from 6-81°. In the second Cu site, Cu(2) is bonded to one S(14), one S(2), and two equivalent S(9) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Pb(4)S6 octahedra, corners with two equivalent Pb(3)S6 octahedra, corners with two equivalent Cu(2)S4 tetrahedra, and edges with two equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles range from 12-81°. There are five inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 5-coordinate geometry to one S(5), two equivalent S(10), and two equivalent S(6) atoms. In the second Pb site, Pb(2) is bonded in a 5-coordinate geometry to one S(6), two equivalent S(5), and two equivalent S(9) atoms. In the third Pb site, Pb(3) is bonded to one S(1), one S(7), two equivalent S(12), and two equivalent S(14) atoms to form PbS6 octahedra that share corners with two equivalent Bi(1)S5 square pyramids, corners with two equivalent Bi(2)S5 square pyramids, corners with two equivalent Bi(4)S5 square pyramids,  a cornercorner with one Cu(1)S4 tetrahedra, corners with two equivalent Cu(2)S4 tetrahedra, edges with two equivalent Pb(3)S6 octahedra,  an edgeedge with one Bi(1)S5 square pyramid, and edges with two equivalent Bi(5)S5 square pyramids. In the fourth Pb site, Pb(4) is bonded to one S(2), one S(8), two equivalent S(11), and two equivalent S(13) atoms to form PbS6 octahedra that share corners with two equivalent Bi(1)S5 square pyramids, corners with two equivalent Bi(2)S5 square pyramids, corners with two equivalent Bi(3)S5 square pyramids,  a cornercorner with one Cu(2)S4 tetrahedra, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Pb(4)S6 octahedra, and  an edgeedge with one Bi(2)S5 square pyramid. In the fifth Pb site, Pb(5) is bonded in a 3-coordinate geometry to one S(11) and two equivalent S(4) atoms. There are five inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(3), two equivalent S(12), and two equivalent S(8) atoms to form BiS5 square pyramids that share corners with two equivalent Pb(3)S6 octahedra, corners with two equivalent Pb(4)S6 octahedra,  an edgeedge with one Pb(3)S6 octahedra, edges with two equivalent Bi(1)S5 square pyramids, and edges with two equivalent Bi(5)S5 square pyramids. The corner-sharing octahedral tilt angles range from 19-77°. In the second Bi site, Bi(2) is bonded to one S(4), two equivalent S(11), and two equivalent S(7) atoms to form BiS5 square pyramids that share corners with two equivalent Pb(3)S6 octahedra, corners with two equivalent Pb(4)S6 octahedra,  an edgeedge with one Pb(4)S6 octahedra, and edges with two equivalent Bi(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 10-73°. In the third Bi site, Bi(3) is bonded to one S(9), two equivalent S(2), and two equivalent S(6) atoms to form BiS5 square pyramids that share corners with two equivalent Pb(4)S6 octahedra, edges with two equivalent Bi(3)S5 square pyramids, and edges with two equivalent Cu(2)S4 tetrahedra. The corner-sharing octahedral tilt angles are 80°. In the fourth Bi site, Bi(4) is bonded to one S(10), two equivalent S(1), and two equivalent S(5) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Pb(3)S6 octahedra, corners with two equivalent Bi(5)S5 square pyramids,  an edgeedge with one Bi(5)S5 square pyramid, edges with two equivalent Bi(4)S5 square pyramids, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 82°. In the fifth Bi site, Bi(5) is bonded to one S(12), two equivalent S(1), and two equivalent S(3) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Bi(4)S5 square pyramids, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Pb(3)S6 octahedra,  an edgeedge with one Bi(4)S5 square pyramid, edges with two equivalent Bi(1)S5 square pyramids, and edges with two equivalent Bi(5)S5 square pyramids. There are fourteen inequivalent S sites. In the first S site, S(1) is bonded to one Cu(1), one Pb(3), two equivalent Bi(4), and two equivalent Bi(5) atoms to form distorted SCuBi4Pb octahedra that share corners with two equivalent S(5)Bi2Pb3 square pyramids, edges with two equivalent S(1)CuBi4Pb octahedra,  an edgeedge with one S(5)Bi2Pb3 square pyramid, and edges with two equivalent S(12)Bi3Pb2 square pyramids. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Cu(2), one Pb(4), and two equivalent Bi(3) atoms. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Bi(1) and two equivalent Bi(5) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to two equivalent Pb(5) and one Bi(2) atom. In the fifth S site, S(5) is bonded to one Pb(1), two equivalent Pb(2), and two equivalent Bi(4) atoms to form distorted SBi2Pb3 square pyramids that share corners with two equivalent S(1)CuBi4Pb octahedra,  an edgeedge with one S(1)CuBi4Pb octahedra, edges with two equivalent S(5)Bi2Pb3 square pyramids, and edges with two equivalent S(6)Bi2Pb3 square pyramids. The corner-sharing octahedral tilt angles are 18°. In the sixth S site, S(6) is bonded to one Pb(2), two equivalent Pb(1), and two equivalent Bi(3) atoms to form distorted edge-sharing SBi2Pb3 square pyramids. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Pb(3) and two equivalent Bi(2) atoms. In the eighth S site, S(8) is bonded in a 3-coordinate geometry to one Pb(4) and two equivalent Bi(1) atoms. In the ninth S site, S(9) is bonded in a 5-coordinate geometry to two equivalent Cu(2), two equivalent Pb(2), and one Bi(3) atom. In the tenth S site, S(10) is bonded in a 5-coordinate geometry to two equivalent Cu(1), two equivalent Pb(1), and one Bi(4) atom. In the eleventh S site, S(11) is bonded to one Pb(5), two equivalent Pb(4), and two equivalent Bi(2) atoms to form distorted edge-sharing SBi2Pb3 square pyramids. In the twelfth S site, S(12) is bonded to two equivalent Pb(3), one Bi(5), and two equivalent Bi(1) atoms to form distorted SBi3Pb2 square pyramids that share edges with two equivalent S(1)CuBi4Pb octahedra and edges with two equivalent S(12)Bi3Pb2 square pyramids. In the thirteenth S site, S(13) is bonded in a distorted single-bond geometry to one Cu(1) and two equivalent Pb(4) atoms. In the fourteenth S site, S(14) is bonded in a 3-coordinate geometry to one Cu(2) and two equivalent Pb(3) atoms.
Cu2Pb5Bi5S14 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one S(1), one S(13), and two equivalent S(10) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Pb(3)S6 octahedra, corners with two equivalent Pb(4)S6 octahedra, corners with two equivalent Bi(5)S5 square pyramids, corners with two equivalent Cu(1)S4 tetrahedra, and edges with two equivalent Bi(4)S5 square pyramids. The corner-sharing octahedral tilt angles range from 6-81°. The Cu(1)-S(1) bond length is 2.47 Å. The Cu(1)-S(13) bond length is 2.26 Å. Both Cu(1)-S(10) bond lengths are 2.33 Å. In the second Cu site, Cu(2) is bonded to one S(14), one S(2), and two equivalent S(9) atoms to form distorted CuS4 tetrahedra that share  a cornercorner with one Pb(4)S6 octahedra, corners with two equivalent Pb(3)S6 octahedra, corners with two equivalent Cu(2)S4 tetrahedra, and edges with two equivalent Bi(3)S5 square pyramids. The corner-sharing octahedral tilt angles range from 12-81°. The Cu(2)-S(14) bond length is 2.26 Å. The Cu(2)-S(2) bond length is 2.49 Å. Both Cu(2)-S(9) bond lengths are 2.34 Å. There are five inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 5-coordinate geometry to one S(5), two equivalent S(10), and two equivalent S(6) atoms. The Pb(1)-S(5) bond length is 2.91 Å. Both Pb(1)-S(10) bond lengths are 3.07 Å. Both Pb(1)-S(6) bond lengths are 3.01 Å. In the second Pb site, Pb(2) is bonded in a 5-coordinate geometry to one S(6), two equivalent S(5), and two equivalent S(9) atoms. The Pb(2)-S(6) bond length is 2.96 Å. Both Pb(2)-S(5) bond lengths are 3.12 Å. Both Pb(2)-S(9) bond lengths are 3.04 Å. In the third Pb site, Pb(3) is bonded to one S(1), one S(7), two equivalent S(12), and two equivalent S(14) atoms to form PbS6 octahedra that share corners with two equivalent Bi(1)S5 square pyramids, corners with two equivalent Bi(2)S5 square pyramids, corners with two equivalent Bi(4)S5 square pyramids,  a cornercorner with one Cu(1)S4 tetrahedra, corners with two equivalent Cu(2)S4 tetrahedra, edges with two equivalent Pb(3)S6 octahedra,  an edgeedge with one Bi(1)S5 square pyramid, and edges with two equivalent Bi(5)S5 square pyramids. The Pb(3)-S(1) bond length is 2.95 Å. The Pb(3)-S(7) bond length is 3.03 Å. Both Pb(3)-S(12) bond lengths are 3.08 Å. Both Pb(3)-S(14) bond lengths are 2.82 Å. In the fourth Pb site, Pb(4) is bonded to one S(2), one S(8), two equivalent S(11), and two equivalent S(13) atoms to form PbS6 octahedra that share corners with two equivalent Bi(1)S5 square pyramids, corners with two equivalent Bi(2)S5 square pyramids, corners with two equivalent Bi(3)S5 square pyramids,  a cornercorner with one Cu(2)S4 tetrahedra, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Pb(4)S6 octahedra, and  an edgeedge with one Bi(2)S5 square pyramid. The Pb(4)-S(2) bond length is 2.91 Å. The Pb(4)-S(8) bond length is 3.11 Å. Both Pb(4)-S(11) bond lengths are 3.02 Å. Both Pb(4)-S(13) bond lengths are 2.87 Å. In the fifth Pb site, Pb(5) is bonded in a 3-coordinate geometry to one S(11) and two equivalent S(4) atoms. The Pb(5)-S(11) bond length is 2.94 Å. Both Pb(5)-S(4) bond lengths are 2.84 Å. There are five inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(3), two equivalent S(12), and two equivalent S(8) atoms to form BiS5 square pyramids that share corners with two equivalent Pb(3)S6 octahedra, corners with two equivalent Pb(4)S6 octahedra,  an edgeedge with one Pb(3)S6 octahedra, edges with two equivalent Bi(1)S5 square pyramids, and edges with two equivalent Bi(5)S5 square pyramids. The corner-sharing octahedral tilt angles range from 19-77°. The Bi(1)-S(3) bond length is 2.68 Å. Both Bi(1)-S(12) bond lengths are 2.92 Å. Both Bi(1)-S(8) bond lengths are 2.73 Å. In the second Bi site, Bi(2) is bonded to one S(4), two equivalent S(11), and two equivalent S(7) atoms to form BiS5 square pyramids that share corners with two equivalent Pb(3)S6 octahedra, corners with two equivalent Pb(4)S6 octahedra,  an edgeedge with one Pb(4)S6 octahedra, and edges with two equivalent Bi(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 10-73°. The Bi(2)-S(4) bond length is 2.59 Å. Both Bi(2)-S(11) bond lengths are 2.89 Å. Both Bi(2)-S(7) bond lengths are 2.76 Å. In the third Bi site, Bi(3) is bonded to one S(9), two equivalent S(2), and two equivalent S(6) atoms to form BiS5 square pyramids that share corners with two equivalent Pb(4)S6 octahedra, edges with two equivalent Bi(3)S5 square pyramids, and edges with two equivalent Cu(2)S4 tetrahedra. The corner-sharing octahedral tilt angles are 80°. The Bi(3)-S(9) bond length is 2.64 Å. Both Bi(3)-S(2) bond lengths are 2.83 Å. Both Bi(3)-S(6) bond lengths are 2.85 Å. In the fourth Bi site, Bi(4) is bonded to one S(10), two equivalent S(1), and two equivalent S(5) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Pb(3)S6 octahedra, corners with two equivalent Bi(5)S5 square pyramids,  an edgeedge with one Bi(5)S5 square pyramid, edges with two equivalent Bi(4)S5 square pyramids, and edges with two equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 82°. The Bi(4)-S(10) bond length is 2.63 Å. Both Bi(4)-S(1) bond lengths are 2.92 Å. Both Bi(4)-S(5) bond lengths are 2.79 Å. In the fifth Bi site, Bi(5) is bonded to one S(12), two equivalent S(1), and two equivalent S(3) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Bi(4)S5 square pyramids, corners with two equivalent Cu(1)S4 tetrahedra, edges with two equivalent Pb(3)S6 octahedra,  an edgeedge with one Bi(4)S5 square pyramid, edges with two equivalent Bi(1)S5 square pyramids, and edges with two equivalent Bi(5)S5 square pyramids. The Bi(5)-S(12) bond length is 2.69 Å. Both Bi(5)-S(1) bond lengths are 3.08 Å. Both Bi(5)-S(3) bond lengths are 2.78 Å. There are fourteen inequivalent S sites. In the first S site, S(1) is bonded to one Cu(1), one Pb(3), two equivalent Bi(4), and two equivalent Bi(5) atoms to form distorted SCuBi4Pb octahedra that share corners with two equivalent S(5)Bi2Pb3 square pyramids, edges with two equivalent S(1)CuBi4Pb octahedra,  an edgeedge with one S(5)Bi2Pb3 square pyramid, and edges with two equivalent S(12)Bi3Pb2 square pyramids. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Cu(2), one Pb(4), and two equivalent Bi(3) atoms. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Bi(1) and two equivalent Bi(5) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to two equivalent Pb(5) and one Bi(2) atom. In the fifth S site, S(5) is bonded to one Pb(1), two equivalent Pb(2), and two equivalent Bi(4) atoms to form distorted SBi2Pb3 square pyramids that share corners with two equivalent S(1)CuBi4Pb octahedra,  an edgeedge with one S(1)CuBi4Pb octahedra, edges with two equivalent S(5)Bi2Pb3 square pyramids, and edges with two equivalent S(6)Bi2Pb3 square pyramids. The corner-sharing octahedral tilt angles are 18°. In the sixth S site, S(6) is bonded to one Pb(2), two equivalent Pb(1), and two equivalent Bi(3) atoms to form distorted edge-sharing SBi2Pb3 square pyramids. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Pb(3) and two equivalent Bi(2) atoms. In the eighth S site, S(8) is bonded in a 3-coordinate geometry to one Pb(4) and two equivalent Bi(1) atoms. In the ninth S site, S(9) is bonded in a 5-coordinate geometry to two equivalent Cu(2), two equivalent Pb(2), and one Bi(3) atom. In the tenth S site, S(10) is bonded in a 5-coordinate geometry to two equivalent Cu(1), two equivalent Pb(1), and one Bi(4) atom. In the eleventh S site, S(11) is bonded to one Pb(5), two equivalent Pb(4), and two equivalent Bi(2) atoms to form distorted edge-sharing SBi2Pb3 square pyramids. In the twelfth S site, S(12) is bonded to two equivalent Pb(3), one Bi(5), and two equivalent Bi(1) atoms to form distorted SBi3Pb2 square pyramids that share edges with two equivalent S(1)CuBi4Pb octahedra and edges with two equivalent S(12)Bi3Pb2 square pyramids. In the thirteenth S site, S(13) is bonded in a distorted single-bond geometry to one Cu(1) and two equivalent Pb(4) atoms. In the fourteenth S site, S(14) is bonded in a 3-coordinate geometry to one Cu(2) and two equivalent Pb(3) atoms.