CsCu5S3 crystallizes in the orthorhombic Pmma space group. Cs(1) is bonded in a 11-coordinate geometry to two equivalent Cu(1), one S(2), and eight equivalent S(1) atoms. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a bent 150 degrees geometry to two equivalent Cs(1) and two equivalent S(1) atoms. In the second Cu site, Cu(2) is bonded in a distorted trigonal non-coplanar geometry to one S(1) and two equivalent S(2) atoms. In the third Cu site, Cu(3) is bonded in a distorted trigonal planar geometry to one S(2) and two equivalent S(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to four equivalent Cs(1), one Cu(1), one Cu(2), and two equivalent Cu(3) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Cs(1), two equivalent Cu(3), and four equivalent Cu(2) atoms.
CsCu5S3 crystallizes in the orthorhombic Pmma space group. Cs(1) is bonded in a 11-coordinate geometry to two equivalent Cu(1), one S(2), and eight equivalent S(1) atoms. Both Cs(1)-Cu(1) bond lengths are 3.67 Å. The Cs(1)-S(2) bond length is 3.59 Å. There are four shorter (3.62 Å) and four longer (3.84 Å) Cs(1)-S(1) bond lengths. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a bent 150 degrees geometry to two equivalent Cs(1) and two equivalent S(1) atoms. Both Cu(1)-S(1) bond lengths are 2.21 Å. In the second Cu site, Cu(2) is bonded in a distorted trigonal non-coplanar geometry to one S(1) and two equivalent S(2) atoms. The Cu(2)-S(1) bond length is 2.28 Å. Both Cu(2)-S(2) bond lengths are 2.38 Å. In the third Cu site, Cu(3) is bonded in a distorted trigonal planar geometry to one S(2) and two equivalent S(1) atoms. The Cu(3)-S(2) bond length is 2.33 Å. Both Cu(3)-S(1) bond lengths are 2.38 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to four equivalent Cs(1), one Cu(1), one Cu(2), and two equivalent Cu(3) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Cs(1), two equivalent Cu(3), and four equivalent Cu(2) atoms.