Rh3Bi2S2 crystallizes in the monoclinic C2/m space group. There are three inequivalent Rh sites. In the first Rh site, Rh(1) is bonded in a 2-coordinate geometry to two equivalent Bi(1), two equivalent Bi(2), and two equivalent S(1) atoms. In the second Rh site, Rh(2) is bonded in a 6-coordinate geometry to two equivalent Bi(1), two equivalent Bi(2), and two equivalent S(1) atoms. In the third Rh site, Rh(3) is bonded in a 6-coordinate geometry to two equivalent Bi(1), two equivalent Bi(2), and two equivalent S(1) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to two equivalent Rh(1), two equivalent Rh(2), and two equivalent Rh(3) atoms. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to two equivalent Rh(1), two equivalent Rh(2), and two equivalent Rh(3) atoms. S(1) is bonded in a distorted T-shaped geometry to one Rh(1), one Rh(2), and one Rh(3) atom.
Rh3Bi2S2 crystallizes in the monoclinic C2/m space group. There are three inequivalent Rh sites. In the first Rh site, Rh(1) is bonded in a 2-coordinate geometry to two equivalent Bi(1), two equivalent Bi(2), and two equivalent S(1) atoms. Both Rh(1)-Bi(1) bond lengths are 2.89 Å. Both Rh(1)-Bi(2) bond lengths are 2.99 Å. Both Rh(1)-S(1) bond lengths are 2.29 Å. In the second Rh site, Rh(2) is bonded in a 6-coordinate geometry to two equivalent Bi(1), two equivalent Bi(2), and two equivalent S(1) atoms. Both Rh(2)-Bi(1) bond lengths are 2.98 Å. Both Rh(2)-Bi(2) bond lengths are 2.76 Å. Both Rh(2)-S(1) bond lengths are 2.31 Å. In the third Rh site, Rh(3) is bonded in a 6-coordinate geometry to two equivalent Bi(1), two equivalent Bi(2), and two equivalent S(1) atoms. There is one shorter (2.81 Å) and one longer (3.01 Å) Rh(3)-Bi(1) bond length. There is one shorter (2.71 Å) and one longer (2.91 Å) Rh(3)-Bi(2) bond length. Both Rh(3)-S(1) bond lengths are 2.30 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to two equivalent Rh(1), two equivalent Rh(2), and two equivalent Rh(3) atoms. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to two equivalent Rh(1), two equivalent Rh(2), and two equivalent Rh(3) atoms. S(1) is bonded in a distorted T-shaped geometry to one Rh(1), one Rh(2), and one Rh(3) atom.