Rb3(Cu4S3)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to two equivalent S(2), two equivalent S(3), and three equivalent S(1) atoms. In the second Rb site, Rb(2) is bonded in a distorted body-centered cubic geometry to four equivalent S(2) and four equivalent S(3) atoms. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted trigonal planar geometry to one S(1) and two equivalent S(3) atoms. In the second Cu site, Cu(2) is bonded in a distorted trigonal planar geometry to one S(3) and two equivalent S(1) atoms. In the third Cu site, Cu(3) is bonded in a distorted bent 120 degrees geometry to one S(2), one S(3), and two equivalent S(1) atoms. In the fourth Cu site, Cu(4) is bonded to one S(1) and three equivalent S(2) atoms to form a mixture of corner and edge-sharing CuS4 tetrahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 9-coordinate geometry to three equivalent Rb(1), one Cu(1), one Cu(4), two equivalent Cu(2), and two equivalent Cu(3) atoms. In the second S site, S(2) is bonded in a 8-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), one Cu(3), and three equivalent Cu(4) atoms. In the third S site, S(3) is bonded in a 8-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), one Cu(2), one Cu(3), and two equivalent Cu(1) atoms.
Rb3(Cu4S3)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to two equivalent S(2), two equivalent S(3), and three equivalent S(1) atoms. Both Rb(1)-S(2) bond lengths are 3.30 Å. Both Rb(1)-S(3) bond lengths are 3.35 Å. There are two shorter (3.33 Å) and one longer (3.83 Å) Rb(1)-S(1) bond length. In the second Rb site, Rb(2) is bonded in a distorted body-centered cubic geometry to four equivalent S(2) and four equivalent S(3) atoms. All Rb(2)-S(2) bond lengths are 3.46 Å. All Rb(2)-S(3) bond lengths are 3.43 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted trigonal planar geometry to one S(1) and two equivalent S(3) atoms. The Cu(1)-S(1) bond length is 2.35 Å. Both Cu(1)-S(3) bond lengths are 2.33 Å. In the second Cu site, Cu(2) is bonded in a distorted trigonal planar geometry to one S(3) and two equivalent S(1) atoms. The Cu(2)-S(3) bond length is 2.25 Å. Both Cu(2)-S(1) bond lengths are 2.34 Å. In the third Cu site, Cu(3) is bonded in a distorted bent 120 degrees geometry to one S(2), one S(3), and two equivalent S(1) atoms. The Cu(3)-S(2) bond length is 2.20 Å. The Cu(3)-S(3) bond length is 2.29 Å. Both Cu(3)-S(1) bond lengths are 2.72 Å. In the fourth Cu site, Cu(4) is bonded to one S(1) and three equivalent S(2) atoms to form a mixture of corner and edge-sharing CuS4 tetrahedra. The Cu(4)-S(1) bond length is 2.44 Å. All Cu(4)-S(2) bond lengths are 2.37 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 9-coordinate geometry to three equivalent Rb(1), one Cu(1), one Cu(4), two equivalent Cu(2), and two equivalent Cu(3) atoms. In the second S site, S(2) is bonded in a 8-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), one Cu(3), and three equivalent Cu(4) atoms. In the third S site, S(3) is bonded in a 8-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), one Cu(2), one Cu(3), and two equivalent Cu(1) atoms.