CsCr5S8 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 4-coordinate geometry to two equivalent S(2) and two equivalent S(3) atoms. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form a mixture of 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(1), two equivalent S(2), and three equivalent S(4) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. In the third Cr site, Cr(3) is bonded to one S(1), two equivalent S(4), and three equivalent S(3) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Cr(2), one Cr(3), and two equivalent Cr(1) atoms. In the second S site, S(2) is bonded to one Cs(1), one Cr(1), and two equivalent Cr(2) atoms to form distorted SCsCr3 trigonal pyramids that share corners with two equivalent S(3)CsCr3 tetrahedra, corners with four equivalent S(4)Cr5 trigonal bipyramids, corners with four equivalent S(2)CsCr3 trigonal pyramids, and  an edgeedge with one S(4)Cr5 trigonal bipyramid. In the third S site, S(3) is bonded to one Cs(1) and three equivalent Cr(3) atoms to form distorted SCsCr3 tetrahedra that share corners with three equivalent S(3)CsCr3 tetrahedra, corners with four equivalent S(4)Cr5 trigonal bipyramids, corners with two equivalent S(2)CsCr3 trigonal pyramids, edges with two equivalent S(3)CsCr3 tetrahedra, and  an edgeedge with one S(4)Cr5 trigonal bipyramid. In the fourth S site, S(4) is bonded to two equivalent Cr(3) and three equivalent Cr(2) atoms to form distorted SCr5 trigonal bipyramids that share corners with four equivalent S(3)CsCr3 tetrahedra, corners with four equivalent S(2)CsCr3 trigonal pyramids,  an edgeedge with one S(3)CsCr3 tetrahedra, edges with four equivalent S(4)Cr5 trigonal bipyramids, and  an edgeedge with one S(2)CsCr3 trigonal pyramid.
CsCr5S8 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 4-coordinate geometry to two equivalent S(2) and two equivalent S(3) atoms. Both Cs(1)-S(2) bond lengths are 3.22 Å. Both Cs(1)-S(3) bond lengths are 3.29 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form a mixture of corner and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 47°. Both Cr(1)-S(2) bond lengths are 2.39 Å. All Cr(1)-S(1) bond lengths are 2.45 Å. In the second Cr site, Cr(2) is bonded to one S(1), two equivalent S(2), and three equivalent S(4) atoms to form a mixture of face, corner, and edge-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. The Cr(2)-S(1) bond length is 2.40 Å. Both Cr(2)-S(2) bond lengths are 2.33 Å. There is one shorter (2.46 Å) and two longer (2.53 Å) Cr(2)-S(4) bond lengths. In the third Cr site, Cr(3) is bonded to one S(1), two equivalent S(4), and three equivalent S(3) 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(3)-S(1) bond length is 2.57 Å. Both Cr(3)-S(4) bond lengths are 2.53 Å. There are two shorter (2.35 Å) and one longer (2.36 Å) Cr(3)-S(3) bond length. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Cr(2), one Cr(3), and two equivalent Cr(1) atoms. In the second S site, S(2) is bonded to one Cs(1), one Cr(1), and two equivalent Cr(2) atoms to form distorted SCsCr3 trigonal pyramids that share corners with two equivalent S(3)CsCr3 tetrahedra, corners with four equivalent S(4)Cr5 trigonal bipyramids, corners with four equivalent S(2)CsCr3 trigonal pyramids, and  an edgeedge with one S(4)Cr5 trigonal bipyramid. In the third S site, S(3) is bonded to one Cs(1) and three equivalent Cr(3) atoms to form distorted SCsCr3 tetrahedra that share corners with three equivalent S(3)CsCr3 tetrahedra, corners with four equivalent S(4)Cr5 trigonal bipyramids, corners with two equivalent S(2)CsCr3 trigonal pyramids, edges with two equivalent S(3)CsCr3 tetrahedra, and  an edgeedge with one S(4)Cr5 trigonal bipyramid. In the fourth S site, S(4) is bonded to two equivalent Cr(3) and three equivalent Cr(2) atoms to form distorted SCr5 trigonal bipyramids that share corners with four equivalent S(3)CsCr3 tetrahedra, corners with four equivalent S(2)CsCr3 trigonal pyramids,  an edgeedge with one S(3)CsCr3 tetrahedra, edges with four equivalent S(4)Cr5 trigonal bipyramids, and  an edgeedge with one S(2)CsCr3 trigonal pyramid.