Cu6PS5Br crystallizes in the monoclinic Cc space group. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted trigonal planar geometry to one S(2), one S(3), and one S(5) atom. In the second Cu site, Cu(2) is bonded to one S(1), one S(2), one S(5), and one Br(1) atom to form CuS3Br tetrahedra that share corners with two equivalent P(1)S4 tetrahedra, corners with three equivalent Cu(5)S3Br tetrahedra, and corners with three equivalent Cu(6)S3Br tetrahedra. In the third Cu site, Cu(3) is bonded in a distorted trigonal planar geometry to one S(2), one S(4), and one S(5) atom. In the fourth Cu site, Cu(4) is bonded in a distorted trigonal planar geometry to one S(3), one S(4), and one S(5) atom. In the fifth Cu site, Cu(5) is bonded to one S(1), one S(3), one S(5), and one Br(1) atom to form distorted CuS3Br tetrahedra that share corners with two equivalent P(1)S4 tetrahedra, corners with three equivalent Cu(2)S3Br tetrahedra, and corners with three equivalent Cu(6)S3Br tetrahedra. In the sixth Cu site, Cu(6) is bonded to one S(1), one S(4), one S(5), and one Br(1) atom to form distorted CuS3Br tetrahedra that share corners with two equivalent P(1)S4 tetrahedra, corners with three equivalent Cu(2)S3Br tetrahedra, and corners with three equivalent Cu(5)S3Br tetrahedra. P(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form PS4 tetrahedra that share corners with two equivalent Cu(2)S3Br tetrahedra, corners with two equivalent Cu(5)S3Br tetrahedra, and corners with two equivalent Cu(6)S3Br tetrahedra. There are five inequivalent S sites. In the first S site, S(4) is bonded to one Cu(3), one Cu(4), one Cu(6), and one P(1) atom to form SCu3P tetrahedra that share corners with three equivalent S(5)Cu6 octahedra, corners with two equivalent S(1)Cu3P tetrahedra, corners with two equivalent S(2)Cu3P tetrahedra, and corners with two equivalent S(3)Cu3P tetrahedra. The corner-sharing octahedral tilt angles range from 45-69°. In the second S site, S(5) is bonded to one Cu(1), one Cu(2), one Cu(3), one Cu(4), one Cu(5), and one Cu(6) atom to form distorted corner-sharing SCu6 octahedra. In the third S site, S(1) is bonded to one Cu(2), one Cu(5), one Cu(6), and one P(1) atom to form SCu3P tetrahedra that share corners with three equivalent S(5)Cu6 octahedra, corners with two equivalent S(2)Cu3P tetrahedra, corners with two equivalent S(3)Cu3P tetrahedra, and corners with two equivalent S(4)Cu3P tetrahedra. The corner-sharing octahedral tilt angles range from 58-62°. In the fourth S site, S(2) is bonded to one Cu(1), one Cu(2), one Cu(3), and one P(1) atom to form SCu3P tetrahedra that share corners with three equivalent S(5)Cu6 octahedra, corners with two equivalent S(1)Cu3P tetrahedra, corners with two equivalent S(3)Cu3P tetrahedra, and corners with two equivalent S(4)Cu3P tetrahedra. The corner-sharing octahedral tilt angles range from 44-68°. In the fifth S site, S(3) is bonded to one Cu(1), one Cu(4), one Cu(5), and one P(1) atom to form SCu3P tetrahedra that share corners with three equivalent S(5)Cu6 octahedra, corners with two equivalent S(1)Cu3P tetrahedra, corners with two equivalent S(2)Cu3P tetrahedra, and corners with two equivalent S(4)Cu3P tetrahedra. The corner-sharing octahedral tilt angles range from 45-65°. Br(1) is bonded in a trigonal planar geometry to one Cu(2), one Cu(5), and one Cu(6) atom.
Cu6PS5Br crystallizes in the monoclinic Cc space group. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted trigonal planar geometry to one S(2), one S(3), and one S(5) atom. The Cu(1)-S(2) bond length is 2.28 Å. The Cu(1)-S(3) bond length is 2.28 Å. The Cu(1)-S(5) bond length is 2.26 Å. In the second Cu site, Cu(2) is bonded to one S(1), one S(2), one S(5), and one Br(1) atom to form CuS3Br tetrahedra that share corners with two equivalent P(1)S4 tetrahedra, corners with three equivalent Cu(5)S3Br tetrahedra, and corners with three equivalent Cu(6)S3Br tetrahedra. The Cu(2)-S(1) bond length is 2.29 Å. The Cu(2)-S(2) bond length is 2.34 Å. The Cu(2)-S(5) bond length is 2.32 Å. The Cu(2)-Br(1) bond length is 2.61 Å. In the third Cu site, Cu(3) is bonded in a distorted trigonal planar geometry to one S(2), one S(4), and one S(5) atom. The Cu(3)-S(2) bond length is 2.27 Å. The Cu(3)-S(4) bond length is 2.27 Å. The Cu(3)-S(5) bond length is 2.27 Å. In the fourth Cu site, Cu(4) is bonded in a distorted trigonal planar geometry to one S(3), one S(4), and one S(5) atom. The Cu(4)-S(3) bond length is 2.27 Å. The Cu(4)-S(4) bond length is 2.27 Å. The Cu(4)-S(5) bond length is 2.26 Å. In the fifth Cu site, Cu(5) is bonded to one S(1), one S(3), one S(5), and one Br(1) atom to form distorted CuS3Br tetrahedra that share corners with two equivalent P(1)S4 tetrahedra, corners with three equivalent Cu(2)S3Br tetrahedra, and corners with three equivalent Cu(6)S3Br tetrahedra. The Cu(5)-S(1) bond length is 2.28 Å. The Cu(5)-S(3) bond length is 2.32 Å. The Cu(5)-S(5) bond length is 2.30 Å. The Cu(5)-Br(1) bond length is 2.73 Å. In the sixth Cu site, Cu(6) is bonded to one S(1), one S(4), one S(5), and one Br(1) atom to form distorted CuS3Br tetrahedra that share corners with two equivalent P(1)S4 tetrahedra, corners with three equivalent Cu(2)S3Br tetrahedra, and corners with three equivalent Cu(5)S3Br tetrahedra. The Cu(6)-S(1) bond length is 2.30 Å. The Cu(6)-S(4) bond length is 2.36 Å. The Cu(6)-S(5) bond length is 2.32 Å. The Cu(6)-Br(1) bond length is 2.60 Å. P(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form PS4 tetrahedra that share corners with two equivalent Cu(2)S3Br tetrahedra, corners with two equivalent Cu(5)S3Br tetrahedra, and corners with two equivalent Cu(6)S3Br tetrahedra. The P(1)-S(1) bond length is 2.08 Å. The P(1)-S(2) bond length is 2.07 Å. The P(1)-S(3) bond length is 2.08 Å. The P(1)-S(4) bond length is 2.07 Å. There are five inequivalent S sites. In the first S site, S(4) is bonded to one Cu(3), one Cu(4), one Cu(6), and one P(1) atom to form SCu3P tetrahedra that share corners with three equivalent S(5)Cu6 octahedra, corners with two equivalent S(1)Cu3P tetrahedra, corners with two equivalent S(2)Cu3P tetrahedra, and corners with two equivalent S(3)Cu3P tetrahedra. The corner-sharing octahedral tilt angles range from 45-69°. In the second S site, S(5) is bonded to one Cu(1), one Cu(2), one Cu(3), one Cu(4), one Cu(5), and one Cu(6) atom to form distorted corner-sharing SCu6 octahedra. In the third S site, S(1) is bonded to one Cu(2), one Cu(5), one Cu(6), and one P(1) atom to form SCu3P tetrahedra that share corners with three equivalent S(5)Cu6 octahedra, corners with two equivalent S(2)Cu3P tetrahedra, corners with two equivalent S(3)Cu3P tetrahedra, and corners with two equivalent S(4)Cu3P tetrahedra. The corner-sharing octahedral tilt angles range from 58-62°. In the fourth S site, S(2) is bonded to one Cu(1), one Cu(2), one Cu(3), and one P(1) atom to form SCu3P tetrahedra that share corners with three equivalent S(5)Cu6 octahedra, corners with two equivalent S(1)Cu3P tetrahedra, corners with two equivalent S(3)Cu3P tetrahedra, and corners with two equivalent S(4)Cu3P tetrahedra. The corner-sharing octahedral tilt angles range from 44-68°. In the fifth S site, S(3) is bonded to one Cu(1), one Cu(4), one Cu(5), and one P(1) atom to form SCu3P tetrahedra that share corners with three equivalent S(5)Cu6 octahedra, corners with two equivalent S(1)Cu3P tetrahedra, corners with two equivalent S(2)Cu3P tetrahedra, and corners with two equivalent S(4)Cu3P tetrahedra. The corner-sharing octahedral tilt angles range from 45-65°. Br(1) is bonded in a trigonal planar geometry to one Cu(2), one Cu(5), and one Cu(6) atom.