RbCr5S8 crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a 10-coordinate geometry to two equivalent S(4), four equivalent S(2), and four equivalent S(3) atoms. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(4), two equivalent S(1), and three equivalent S(2) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. In the second Cr site, Cr(2) is bonded to one S(4), two equivalent S(3), and three equivalent S(1) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. In the third Cr site, Cr(3) is bonded to two equivalent S(3) and four equivalent S(4) atoms to form a mixture of corner and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Cr(1) and three equivalent Cr(2) atoms to form distorted edge-sharing SCr5 trigonal bipyramids. In the second S site, S(2) is bonded in a 3-coordinate geometry to two equivalent Rb(1) and three equivalent Cr(1) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Rb(1), one Cr(3), and two equivalent Cr(2) atoms. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms.
RbCr5S8 crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a 10-coordinate geometry to two equivalent S(4), four equivalent S(2), and four equivalent S(3) atoms. Both Rb(1)-S(4) bond lengths are 3.70 Å. All Rb(1)-S(2) bond lengths are 3.58 Å. All Rb(1)-S(3) bond lengths are 3.39 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(4), two equivalent S(1), and three equivalent S(2) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. The Cr(1)-S(4) bond length is 2.45 Å. Both Cr(1)-S(1) bond lengths are 2.53 Å. All Cr(1)-S(2) bond lengths are 2.36 Å. In the second Cr site, Cr(2) is bonded to one S(4), two equivalent S(3), and three equivalent S(1) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. The Cr(2)-S(4) bond length is 2.38 Å. Both Cr(2)-S(3) bond lengths are 2.35 Å. There is one shorter (2.43 Å) and two longer (2.54 Å) Cr(2)-S(1) bond lengths. In the third Cr site, Cr(3) is bonded to two equivalent S(3) and four equivalent S(4) atoms to form a mixture of corner and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 48°. Both Cr(3)-S(3) bond lengths are 2.41 Å. All Cr(3)-S(4) bond lengths are 2.39 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Cr(1) and three equivalent Cr(2) atoms to form distorted edge-sharing SCr5 trigonal bipyramids. In the second S site, S(2) is bonded in a 3-coordinate geometry to two equivalent Rb(1) and three equivalent Cr(1) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Rb(1), one Cr(3), and two equivalent Cr(2) atoms. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms.