CsCr5S8 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 10-coordinate geometry to two equivalent S(1), 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 two equivalent S(2) and four equivalent S(1) atoms to form a mixture of edge and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 48°. 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 edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. 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 edge, face, and corner-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 distorted rectangular see-saw-like geometry to one Cs(1), one Cr(2), one Cr(3), and two equivalent Cr(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one Cr(1), and two equivalent Cr(2) atoms. In the third S site, S(3) is bonded in a 3-coordinate geometry to two equivalent Cs(1) and three equivalent Cr(3) atoms. In the fourth S site, S(4) is bonded to two equivalent Cr(3) and three equivalent Cr(2) atoms to form distorted edge-sharing SCr5 trigonal bipyramids.
CsCr5S8 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 10-coordinate geometry to two equivalent S(1), four equivalent S(2), and four equivalent S(3) atoms. Both Cs(1)-S(1) bond lengths are 3.71 Å. All Cs(1)-S(2) bond lengths are 3.47 Å. All Cs(1)-S(3) bond lengths are 3.62 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 edge and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 48°. Both Cr(1)-S(2) bond lengths are 2.41 Å. All Cr(1)-S(1) bond lengths are 2.41 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 edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. The Cr(2)-S(1) bond length is 2.38 Å. Both Cr(2)-S(2) bond lengths are 2.35 Å. There is one shorter (2.44 Å) and two longer (2.54 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 edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. The Cr(3)-S(1) bond length is 2.48 Å. Both Cr(3)-S(4) bond lengths are 2.53 Å. All Cr(3)-S(3) bond lengths are 2.36 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Cs(1), one Cr(2), one Cr(3), and two equivalent Cr(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one Cr(1), and two equivalent Cr(2) atoms. In the third S site, S(3) is bonded in a 3-coordinate geometry to two equivalent Cs(1) and three equivalent Cr(3) atoms. In the fourth S site, S(4) is bonded to two equivalent Cr(3) and three equivalent Cr(2) atoms to form distorted edge-sharing SCr5 trigonal bipyramids.