RbCr5S8 crystallizes in the monoclinic Cm space group. Rb(1) is bonded in a 10-coordinate geometry to one S(7), one S(8), two equivalent S(3), two equivalent S(4), two equivalent S(5), and two equivalent S(6) atoms. There are five inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(3), one S(7), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. In the second Cr site, Cr(2) is bonded to one S(4), one S(8), two equivalent S(1), and two equivalent S(3) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. In the third Cr site, Cr(3) is bonded to one S(1), one S(7), two equivalent S(2), and two equivalent S(6) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. In the fourth Cr site, Cr(4) is bonded to one S(2), one S(8), two equivalent S(1), and two equivalent S(5) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the fifth Cr site, Cr(5) is bonded to one S(5), one S(6), two equivalent S(7), and two equivalent S(8) atoms to form a mixture of edge and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. There are eight inequivalent S sites. In the first S site, S(1) is bonded to one Cr(3), two equivalent Cr(2), and two equivalent Cr(4) atoms to form distorted edge-sharing SCr5 trigonal bipyramids. In the second S site, S(2) is bonded to one Cr(4), two equivalent Cr(1), and two equivalent Cr(3) atoms to form distorted edge-sharing SCr5 trigonal bipyramids. In the third S site, S(3) is bonded in a 3-coordinate geometry to two equivalent Rb(1), one Cr(1), and two equivalent Cr(2) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to two equivalent Rb(1), one Cr(2), and two equivalent Cr(1) atoms. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to two equivalent Rb(1), one Cr(5), and two equivalent Cr(4) atoms. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to two equivalent Rb(1), one Cr(5), and two equivalent Cr(3) atoms. In the seventh S site, S(7) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Cr(1), one Cr(3), and two equivalent Cr(5) atoms. In the eighth S site, S(8) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Cr(2), one Cr(4), and two equivalent Cr(5) atoms.
RbCr5S8 crystallizes in the monoclinic Cm space group. Rb(1) is bonded in a 10-coordinate geometry to one S(7), one S(8), two equivalent S(3), two equivalent S(4), two equivalent S(5), and two equivalent S(6) atoms. The Rb(1)-S(7) bond length is 3.63 Å. The Rb(1)-S(8) bond length is 3.54 Å. Both Rb(1)-S(3) bond lengths are 3.55 Å. Both Rb(1)-S(4) bond lengths are 3.51 Å. Both Rb(1)-S(5) bond lengths are 3.39 Å. Both Rb(1)-S(6) bond lengths are 3.41 Å. There are five inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(3), one S(7), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The Cr(1)-S(3) bond length is 2.35 Å. The Cr(1)-S(7) bond length is 2.47 Å. Both Cr(1)-S(2) bond lengths are 2.54 Å. Both Cr(1)-S(4) bond lengths are 2.35 Å. In the second Cr site, Cr(2) is bonded to one S(4), one S(8), two equivalent S(1), and two equivalent S(3) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The Cr(2)-S(4) bond length is 2.37 Å. The Cr(2)-S(8) bond length is 2.42 Å. Both Cr(2)-S(1) bond lengths are 2.46 Å. Both Cr(2)-S(3) bond lengths are 2.37 Å. In the third Cr site, Cr(3) is bonded to one S(1), one S(7), two equivalent S(2), and two equivalent S(6) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. The Cr(3)-S(1) bond length is 2.41 Å. The Cr(3)-S(7) bond length is 2.37 Å. Both Cr(3)-S(2) bond lengths are 2.51 Å. Both Cr(3)-S(6) bond lengths are 2.33 Å. In the fourth Cr site, Cr(4) is bonded to one S(2), one S(8), two equivalent S(1), and two equivalent S(5) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. The Cr(4)-S(2) bond length is 2.49 Å. The Cr(4)-S(8) bond length is 2.31 Å. Both Cr(4)-S(1) bond lengths are 2.49 Å. Both Cr(4)-S(5) bond lengths are 2.34 Å. In the fifth Cr site, Cr(5) is bonded to one S(5), one S(6), two equivalent S(7), and two equivalent S(8) atoms to form a mixture of edge and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. The Cr(5)-S(5) bond length is 2.36 Å. The Cr(5)-S(6) bond length is 2.44 Å. Both Cr(5)-S(7) bond lengths are 2.40 Å. Both Cr(5)-S(8) bond lengths are 2.37 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded to one Cr(3), two equivalent Cr(2), and two equivalent Cr(4) atoms to form distorted edge-sharing SCr5 trigonal bipyramids. In the second S site, S(2) is bonded to one Cr(4), two equivalent Cr(1), and two equivalent Cr(3) atoms to form distorted edge-sharing SCr5 trigonal bipyramids. In the third S site, S(3) is bonded in a 3-coordinate geometry to two equivalent Rb(1), one Cr(1), and two equivalent Cr(2) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to two equivalent Rb(1), one Cr(2), and two equivalent Cr(1) atoms. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to two equivalent Rb(1), one Cr(5), and two equivalent Cr(4) atoms. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to two equivalent Rb(1), one Cr(5), and two equivalent Cr(3) atoms. In the seventh S site, S(7) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Cr(1), one Cr(3), and two equivalent Cr(5) atoms. In the eighth S site, S(8) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Cr(2), one Cr(4), and two equivalent Cr(5) atoms.