Cu9S5 crystallizes in the triclinic P1 space group. There are nine inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 3-coordinate geometry to one S(1), one S(2), one S(3), and one S(5) atom. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(5) atom. In the third Cu site, Cu(3) is bonded in a distorted tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. In the fourth Cu site, Cu(4) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(5) atom. In the fifth Cu site, Cu(5) is bonded in a distorted trigonal planar geometry to one S(2), one S(3), one S(4), and one S(5) atom. In the sixth Cu site, Cu(6) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(5) atom. In the seventh Cu site, Cu(7) is bonded in a 3-coordinate geometry to one S(1), one S(3), one S(4), and one S(5) atom. In the eighth Cu site, Cu(8) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(5) atom. In the ninth Cu site, Cu(9) is bonded in a distorted trigonal planar geometry to one S(1), one S(2), one S(4), and one S(5) atom. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 8-coordinate geometry to one Cu(1), one Cu(2), one Cu(3), one Cu(4), one Cu(6), one Cu(7), one Cu(8), and one Cu(9) atom. In the second S site, S(2) is bonded in a 8-coordinate geometry to one Cu(1), one Cu(2), one Cu(3), one Cu(4), one Cu(5), one Cu(6), one Cu(8), and one Cu(9) atom. In the third S site, S(3) is bonded in a 8-coordinate geometry to one Cu(1), one Cu(2), one Cu(3), one Cu(4), one Cu(5), one Cu(6), one Cu(7), and one Cu(8) atom. In the fourth S site, S(4) is bonded in a 8-coordinate geometry to one Cu(2), one Cu(3), one Cu(4), one Cu(5), one Cu(6), one Cu(7), one Cu(8), and one Cu(9) atom. In the fifth S site, S(5) is bonded in a distorted hexagonal bipyramidal geometry to one Cu(1), one Cu(2), one Cu(4), one Cu(5), one Cu(6), one Cu(7), one Cu(8), and one Cu(9) atom.
Cu9S5 crystallizes in the triclinic P1 space group. There are nine inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 3-coordinate geometry to one S(1), one S(2), one S(3), and one S(5) atom. The Cu(1)-S(1) bond length is 2.33 Å. The Cu(1)-S(2) bond length is 2.30 Å. The Cu(1)-S(3) bond length is 2.77 Å. The Cu(1)-S(5) bond length is 2.34 Å. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(5) atom. The Cu(2)-S(1) bond length is 2.69 Å. The Cu(2)-S(2) bond length is 2.91 Å. The Cu(2)-S(3) bond length is 2.51 Å. The Cu(2)-S(4) bond length is 2.38 Å. The Cu(2)-S(5) bond length is 2.50 Å. In the third Cu site, Cu(3) is bonded in a distorted tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. The Cu(3)-S(1) bond length is 2.38 Å. The Cu(3)-S(2) bond length is 2.38 Å. The Cu(3)-S(3) bond length is 2.38 Å. The Cu(3)-S(4) bond length is 2.37 Å. In the fourth Cu site, Cu(4) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(5) atom. The Cu(4)-S(1) bond length is 2.51 Å. The Cu(4)-S(2) bond length is 2.69 Å. The Cu(4)-S(3) bond length is 2.46 Å. The Cu(4)-S(4) bond length is 2.90 Å. The Cu(4)-S(5) bond length is 2.49 Å. In the fifth Cu site, Cu(5) is bonded in a distorted trigonal planar geometry to one S(2), one S(3), one S(4), and one S(5) atom. The Cu(5)-S(2) bond length is 2.85 Å. The Cu(5)-S(3) bond length is 2.28 Å. The Cu(5)-S(4) bond length is 2.31 Å. The Cu(5)-S(5) bond length is 2.36 Å. In the sixth Cu site, Cu(6) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(5) atom. The Cu(6)-S(1) bond length is 2.92 Å. The Cu(6)-S(2) bond length is 2.38 Å. The Cu(6)-S(3) bond length is 2.69 Å. The Cu(6)-S(4) bond length is 2.61 Å. The Cu(6)-S(5) bond length is 2.42 Å. In the seventh Cu site, Cu(7) is bonded in a 3-coordinate geometry to one S(1), one S(3), one S(4), and one S(5) atom. The Cu(7)-S(1) bond length is 2.29 Å. The Cu(7)-S(3) bond length is 2.34 Å. The Cu(7)-S(4) bond length is 2.75 Å. The Cu(7)-S(5) bond length is 2.38 Å. In the eighth Cu site, Cu(8) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(5) atom. The Cu(8)-S(1) bond length is 2.41 Å. The Cu(8)-S(2) bond length is 2.51 Å. The Cu(8)-S(3) bond length is 2.94 Å. The Cu(8)-S(4) bond length is 2.74 Å. The Cu(8)-S(5) bond length is 2.49 Å. In the ninth Cu site, Cu(9) is bonded in a distorted trigonal planar geometry to one S(1), one S(2), one S(4), and one S(5) atom. The Cu(9)-S(1) bond length is 2.86 Å. The Cu(9)-S(2) bond length is 2.31 Å. The Cu(9)-S(4) bond length is 2.30 Å. The Cu(9)-S(5) bond length is 2.34 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 8-coordinate geometry to one Cu(1), one Cu(2), one Cu(3), one Cu(4), one Cu(6), one Cu(7), one Cu(8), and one Cu(9) atom. In the second S site, S(2) is bonded in a 8-coordinate geometry to one Cu(1), one Cu(2), one Cu(3), one Cu(4), one Cu(5), one Cu(6), one Cu(8), and one Cu(9) atom. In the third S site, S(3) is bonded in a 8-coordinate geometry to one Cu(1), one Cu(2), one Cu(3), one Cu(4), one Cu(5), one Cu(6), one Cu(7), and one Cu(8) atom. In the fourth S site, S(4) is bonded in a 8-coordinate geometry to one Cu(2), one Cu(3), one Cu(4), one Cu(5), one Cu(6), one Cu(7), one Cu(8), and one Cu(9) atom. In the fifth S site, S(5) is bonded in a distorted hexagonal bipyramidal geometry to one Cu(1), one Cu(2), one Cu(4), one Cu(5), one Cu(6), one Cu(7), one Cu(8), and one Cu(9) atom.