Cu6BiS6 crystallizes in the triclinic P1 space group. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a trigonal planar geometry to one S(2) and two equivalent S(1) atoms. In the second Cu site, Cu(2) is bonded to one S(6) and three equivalent S(5) atoms to form a mixture of distorted edge and corner-sharing CuS4 tetrahedra. In the third Cu site, Cu(3) is bonded to one S(3) and three equivalent S(4) atoms to form CuS4 tetrahedra that share corners with three equivalent Bi(1)S6 octahedra and corners with six equivalent Cu(3)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-58°. In the fourth Cu site, Cu(4) is bonded in a distorted trigonal planar geometry to one S(4) and two equivalent S(5) atoms. In the fifth Cu site, Cu(5) is bonded to one S(5) and three equivalent S(6) atoms to form a mixture of distorted edge and corner-sharing CuS4 tetrahedra. In the sixth Cu site, Cu(6) is bonded in a trigonal planar geometry to one S(6) and two equivalent S(1) atoms. Bi(1) is bonded to three equivalent S(2) and three equivalent S(3) atoms to form BiS6 octahedra that share corners with three equivalent Cu(3)S4 tetrahedra and edges with six equivalent Bi(1)S6 octahedra. There are six inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Cu(1) and two equivalent Cu(6) atoms to form distorted SCu4 tetrahedra that share corners with four equivalent S(1)Cu4 tetrahedra and corners with two equivalent S(6)Cu5 trigonal bipyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Cu(1) and three equivalent Bi(1) atoms. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Cu(3) and three equivalent Bi(1) atoms. In the fourth S site, S(4) is bonded to one Cu(4) and three equivalent Cu(3) atoms to form corner-sharing SCu4 tetrahedra. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to one Cu(5), two equivalent Cu(4), and three equivalent Cu(2) atoms. In the sixth S site, S(6) is bonded to one Cu(2), one Cu(6), and three equivalent Cu(5) atoms to form distorted SCu5 trigonal bipyramids that share corners with two equivalent S(1)Cu4 tetrahedra and corners with six equivalent S(6)Cu5 trigonal bipyramids.
Cu6BiS6 crystallizes in the triclinic P1 space group. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a trigonal planar geometry to one S(2) and two equivalent S(1) atoms. The Cu(1)-S(2) bond length is 2.22 Å. There is one shorter (2.22 Å) and one longer (2.24 Å) Cu(1)-S(1) bond length. In the second Cu site, Cu(2) is bonded to one S(6) and three equivalent S(5) atoms to form a mixture of distorted edge and corner-sharing CuS4 tetrahedra. The Cu(2)-S(6) bond length is 2.33 Å. There are a spread of Cu(2)-S(5) bond distances ranging from 2.28-2.46 Å. In the third Cu site, Cu(3) is bonded to one S(3) and three equivalent S(4) atoms to form CuS4 tetrahedra that share corners with three equivalent Bi(1)S6 octahedra and corners with six equivalent Cu(3)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-58°. The Cu(3)-S(3) bond length is 2.34 Å. There are a spread of Cu(3)-S(4) bond distances ranging from 2.30-2.35 Å. In the fourth Cu site, Cu(4) is bonded in a distorted trigonal planar geometry to one S(4) and two equivalent S(5) atoms. The Cu(4)-S(4) bond length is 2.17 Å. Both Cu(4)-S(5) bond lengths are 2.31 Å. In the fifth Cu site, Cu(5) is bonded to one S(5) and three equivalent S(6) atoms to form a mixture of distorted edge and corner-sharing CuS4 tetrahedra. The Cu(5)-S(5) bond length is 2.50 Å. There are a spread of Cu(5)-S(6) bond distances ranging from 2.30-2.37 Å. In the sixth Cu site, Cu(6) is bonded in a trigonal planar geometry to one S(6) and two equivalent S(1) atoms. The Cu(6)-S(6) bond length is 2.22 Å. There is one shorter (2.19 Å) and one longer (2.20 Å) Cu(6)-S(1) bond length. Bi(1) is bonded to three equivalent S(2) and three equivalent S(3) atoms to form BiS6 octahedra that share corners with three equivalent Cu(3)S4 tetrahedra and edges with six equivalent Bi(1)S6 octahedra. There are a spread of Bi(1)-S(2) bond distances ranging from 2.78-2.84 Å. There are a spread of Bi(1)-S(3) bond distances ranging from 2.75-2.82 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Cu(1) and two equivalent Cu(6) atoms to form distorted SCu4 tetrahedra that share corners with four equivalent S(1)Cu4 tetrahedra and corners with two equivalent S(6)Cu5 trigonal bipyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Cu(1) and three equivalent Bi(1) atoms. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Cu(3) and three equivalent Bi(1) atoms. In the fourth S site, S(4) is bonded to one Cu(4) and three equivalent Cu(3) atoms to form corner-sharing SCu4 tetrahedra. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to one Cu(5), two equivalent Cu(4), and three equivalent Cu(2) atoms. In the sixth S site, S(6) is bonded to one Cu(2), one Cu(6), and three equivalent Cu(5) atoms to form distorted SCu5 trigonal bipyramids that share corners with two equivalent S(1)Cu4 tetrahedra and corners with six equivalent S(6)Cu5 trigonal bipyramids.