RbCr3S5 is Orthorhombic Perovskite-like structured and crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a 8-coordinate geometry to one S(3), two equivalent S(4), two equivalent S(5), and three equivalent S(1) atoms. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the second Cr site, Cr(2) is bonded to one S(3), two equivalent S(2), and three equivalent S(5) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. In the third Cr site, Cr(3) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form a mixture of corner and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 48°. In the fourth Cr site, Cr(4) is bonded to two equivalent S(2) and four equivalent S(4) atoms to form a mixture of corner and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to three equivalent Rb(1), one Cr(3), and two equivalent Cr(1) atoms. In the second S site, S(2) is bonded to one Cr(4), two equivalent Cr(1), and two equivalent Cr(2) atoms to form distorted SCr5 trigonal bipyramids that share corners with two equivalent S(4)Rb2Cr3 square pyramids,  a cornercorner with one S(2)Cr5 trigonal bipyramid, edges with two equivalent S(4)Rb2Cr3 square pyramids, and edges with two equivalent S(2)Cr5 trigonal bipyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Rb(1), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms. In the fourth S site, S(4) is bonded to two equivalent Rb(1), one Cr(1), and two equivalent Cr(4) atoms to form distorted SRb2Cr3 square pyramids that share corners with two equivalent S(4)Rb2Cr3 square pyramids, corners with two equivalent S(2)Cr5 trigonal bipyramids, edges with three equivalent S(4)Rb2Cr3 square pyramids, and edges with two equivalent S(2)Cr5 trigonal bipyramids. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to two equivalent Rb(1) and three equivalent Cr(2) atoms.
RbCr3S5 is Orthorhombic Perovskite-like structured and crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a 8-coordinate geometry to one S(3), two equivalent S(4), two equivalent S(5), and three equivalent S(1) atoms. The Rb(1)-S(3) bond length is 3.44 Å. Both Rb(1)-S(4) bond lengths are 3.28 Å. Both Rb(1)-S(5) bond lengths are 3.28 Å. There are two shorter (3.45 Å) and one longer (3.70 Å) Rb(1)-S(1) bond length. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 47°. The Cr(1)-S(3) bond length is 2.42 Å. The Cr(1)-S(4) bond length is 2.37 Å. Both Cr(1)-S(1) bond lengths are 2.38 Å. Both Cr(1)-S(2) bond lengths are 2.54 Å. In the second Cr site, Cr(2) is bonded to one S(3), two equivalent S(2), and three equivalent S(5) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. The Cr(2)-S(3) bond length is 2.45 Å. Both Cr(2)-S(2) bond lengths are 2.51 Å. There is one shorter (2.35 Å) and two longer (2.37 Å) Cr(2)-S(5) bond lengths. In the third Cr site, Cr(3) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form a mixture of corner and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 48°. Both Cr(3)-S(1) bond lengths are 2.48 Å. All Cr(3)-S(3) bond lengths are 2.39 Å. In the fourth Cr site, Cr(4) is bonded to two equivalent S(2) and four equivalent S(4) atoms to form a mixture of corner and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 50°. Both Cr(4)-S(2) bond lengths are 2.45 Å. All Cr(4)-S(4) bond lengths are 2.42 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to three equivalent Rb(1), one Cr(3), and two equivalent Cr(1) atoms. In the second S site, S(2) is bonded to one Cr(4), two equivalent Cr(1), and two equivalent Cr(2) atoms to form distorted SCr5 trigonal bipyramids that share corners with two equivalent S(4)Rb2Cr3 square pyramids,  a cornercorner with one S(2)Cr5 trigonal bipyramid, edges with two equivalent S(4)Rb2Cr3 square pyramids, and edges with two equivalent S(2)Cr5 trigonal bipyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Rb(1), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms. In the fourth S site, S(4) is bonded to two equivalent Rb(1), one Cr(1), and two equivalent Cr(4) atoms to form distorted SRb2Cr3 square pyramids that share corners with two equivalent S(4)Rb2Cr3 square pyramids, corners with two equivalent S(2)Cr5 trigonal bipyramids, edges with three equivalent S(4)Rb2Cr3 square pyramids, and edges with two equivalent S(2)Cr5 trigonal bipyramids. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to two equivalent Rb(1) and three equivalent Cr(2) atoms.