Cu7S4 crystallizes in the orthorhombic Pnma space group. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a tetrahedral geometry to one S(1), one S(3), and two equivalent S(2) atoms. In the second Cu site, Cu(2) is bonded in a trigonal planar geometry to one S(1) and two equivalent S(2) atoms. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to one S(1), one S(3), and two equivalent S(2) atoms. In the fourth Cu site, Cu(4) is bonded in a distorted trigonal planar geometry to one S(3) and two equivalent S(2) atoms. In the fifth Cu site, Cu(5) is bonded in a distorted trigonal planar geometry to one S(1), one S(2), and one S(3) atom. There are three inequivalent S sites. In the first S site, S(3) is bonded in a 6-coordinate geometry to one Cu(1), one Cu(3), two equivalent Cu(4), and two equivalent Cu(5) atoms. In the second S site, S(1) is bonded in a 5-coordinate geometry to one Cu(1), one Cu(2), one Cu(3), and two equivalent Cu(5) atoms. In the third S site, S(2) is bonded in a distorted hexagonal planar geometry to one Cu(1), one Cu(2), one Cu(3), one Cu(5), and two equivalent Cu(4) atoms.
Cu7S4 crystallizes in the orthorhombic Pnma space group. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a tetrahedral geometry to one S(1), one S(3), and two equivalent S(2) atoms. The Cu(1)-S(1) bond length is 2.35 Å. The Cu(1)-S(3) bond length is 2.32 Å. Both Cu(1)-S(2) bond lengths are 2.30 Å. In the second Cu site, Cu(2) is bonded in a trigonal planar geometry to one S(1) and two equivalent S(2) atoms. The Cu(2)-S(1) bond length is 2.26 Å. Both Cu(2)-S(2) bond lengths are 2.30 Å. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to one S(1), one S(3), and two equivalent S(2) atoms. The Cu(3)-S(1) bond length is 2.30 Å. The Cu(3)-S(3) bond length is 2.31 Å. Both Cu(3)-S(2) bond lengths are 2.49 Å. In the fourth Cu site, Cu(4) is bonded in a distorted trigonal planar geometry to one S(3) and two equivalent S(2) atoms. The Cu(4)-S(3) bond length is 2.30 Å. There is one shorter (2.26 Å) and one longer (2.35 Å) Cu(4)-S(2) bond length. In the fifth Cu site, Cu(5) is bonded in a distorted trigonal planar geometry to one S(1), one S(2), and one S(3) atom. The Cu(5)-S(1) bond length is 2.23 Å. The Cu(5)-S(2) bond length is 2.27 Å. The Cu(5)-S(3) bond length is 2.33 Å. There are three inequivalent S sites. In the first S site, S(3) is bonded in a 6-coordinate geometry to one Cu(1), one Cu(3), two equivalent Cu(4), and two equivalent Cu(5) atoms. In the second S site, S(1) is bonded in a 5-coordinate geometry to one Cu(1), one Cu(2), one Cu(3), and two equivalent Cu(5) atoms. In the third S site, S(2) is bonded in a distorted hexagonal planar geometry to one Cu(1), one Cu(2), one Cu(3), one Cu(5), and two equivalent Cu(4) atoms.