CsCr5Te8 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 10-coordinate geometry to two equivalent Te(2), four equivalent Te(3), and four equivalent Te(4) atoms. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one Te(2), two equivalent Te(3), and three equivalent Te(1) atoms to form a mixture of edge, face, and corner-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. In the second Cr site, Cr(2) is bonded to one Te(2), two equivalent Te(1), and three equivalent Te(4) atoms to form a mixture of edge, face, and corner-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. In the third Cr site, Cr(3) is bonded to two equivalent Te(3) and four equivalent Te(2) atoms to form a mixture of edge and corner-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles are 49°. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent Cr(2) and three equivalent Cr(1) atoms to form distorted TeCr5 square pyramids that share corners with four equivalent Te(3)Cs2Cr3 square pyramids,  an edgeedge with one Te(3)Cs2Cr3 square pyramid, and edges with four equivalent Te(1)Cr5 square pyramids. In the second Te site, Te(2) is bonded in a 5-coordinate geometry to one Cs(1), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms. In the third Te site, Te(3) is bonded to two equivalent Cs(1), one Cr(3), and two equivalent Cr(1) atoms to form distorted TeCs2Cr3 square pyramids that share corners with three equivalent Te(3)Cs2Cr3 square pyramids, corners with four equivalent Te(1)Cr5 square pyramids,  an edgeedge with one Te(1)Cr5 square pyramid, and edges with three equivalent Te(3)Cs2Cr3 square pyramids. In the fourth Te site, Te(4) is bonded in a 5-coordinate geometry to two equivalent Cs(1) and three equivalent Cr(2) atoms.
CsCr5Te8 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 10-coordinate geometry to two equivalent Te(2), four equivalent Te(3), and four equivalent Te(4) atoms. Both Cs(1)-Te(2) bond lengths are 4.05 Å. All Cs(1)-Te(3) bond lengths are 3.89 Å. All Cs(1)-Te(4) bond lengths are 4.11 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one Te(2), two equivalent Te(3), and three equivalent Te(1) atoms to form a mixture of edge, face, and corner-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. The Cr(1)-Te(2) bond length is 2.72 Å. Both Cr(1)-Te(3) bond lengths are 2.71 Å. There is one shorter (2.78 Å) and two longer (2.87 Å) Cr(1)-Te(1) bond lengths. In the second Cr site, Cr(2) is bonded to one Te(2), two equivalent Te(1), and three equivalent Te(4) atoms to form a mixture of edge, face, and corner-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. The Cr(2)-Te(2) bond length is 2.81 Å. Both Cr(2)-Te(1) bond lengths are 2.84 Å. There is one shorter (2.71 Å) and two longer (2.73 Å) Cr(2)-Te(4) bond lengths. In the third Cr site, Cr(3) is bonded to two equivalent Te(3) and four equivalent Te(2) atoms to form a mixture of edge and corner-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles are 49°. Both Cr(3)-Te(3) bond lengths are 2.75 Å. All Cr(3)-Te(2) bond lengths are 2.75 Å. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent Cr(2) and three equivalent Cr(1) atoms to form distorted TeCr5 square pyramids that share corners with four equivalent Te(3)Cs2Cr3 square pyramids,  an edgeedge with one Te(3)Cs2Cr3 square pyramid, and edges with four equivalent Te(1)Cr5 square pyramids. In the second Te site, Te(2) is bonded in a 5-coordinate geometry to one Cs(1), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms. In the third Te site, Te(3) is bonded to two equivalent Cs(1), one Cr(3), and two equivalent Cr(1) atoms to form distorted TeCs2Cr3 square pyramids that share corners with three equivalent Te(3)Cs2Cr3 square pyramids, corners with four equivalent Te(1)Cr5 square pyramids,  an edgeedge with one Te(1)Cr5 square pyramid, and edges with three equivalent Te(3)Cs2Cr3 square pyramids. In the fourth Te site, Te(4) is bonded in a 5-coordinate geometry to two equivalent Cs(1) and three equivalent Cr(2) atoms.