RbCr5Te8 crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a 10-coordinate geometry to two equivalent Te(1), four equivalent Te(2), and four equivalent Te(3) atoms. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent Te(2) and four equivalent Te(1) atoms to form a mixture of edge and corner-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the second Cr site, Cr(2) is bonded to one Te(1), two equivalent Te(2), 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 one Te(1), two equivalent Te(4), and three equivalent Te(3) atoms to form a mixture of edge, face, and corner-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Cr(2), one Cr(3), and two equivalent Cr(1) atoms. In the second Te site, Te(2) is bonded to two equivalent Rb(1), one Cr(1), and two equivalent Cr(2) atoms to form distorted TeRb2Cr3 square pyramids that share corners with three equivalent Te(2)Rb2Cr3 square pyramids, corners with four equivalent Te(4)Cr5 trigonal bipyramids, edges with three equivalent Te(2)Rb2Cr3 square pyramids, and  an edgeedge with one Te(4)Cr5 trigonal bipyramid. In the third Te site, Te(3) is bonded in a 5-coordinate geometry to two equivalent Rb(1) and three equivalent Cr(3) atoms. In the fourth Te site, Te(4) is bonded to two equivalent Cr(3) and three equivalent Cr(2) atoms to form distorted TeCr5 trigonal bipyramids that share corners with four equivalent Te(2)Rb2Cr3 square pyramids,  an edgeedge with one Te(2)Rb2Cr3 square pyramid, and edges with four equivalent Te(4)Cr5 trigonal bipyramids.
RbCr5Te8 crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a 10-coordinate geometry to two equivalent Te(1), four equivalent Te(2), and four equivalent Te(3) atoms. Both Rb(1)-Te(1) bond lengths are 4.02 Å. All Rb(1)-Te(2) bond lengths are 3.82 Å. All Rb(1)-Te(3) bond lengths are 4.08 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent Te(2) and four equivalent Te(1) atoms to form a mixture of edge and corner-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles are 49°. Both Cr(1)-Te(2) bond lengths are 2.75 Å. All Cr(1)-Te(1) bond lengths are 2.74 Å. In the second Cr site, Cr(2) is bonded to one Te(1), two equivalent Te(2), 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(1) bond length is 2.73 Å. Both Cr(2)-Te(2) bond lengths are 2.71 Å. There is one shorter (2.77 Å) and two longer (2.86 Å) Cr(2)-Te(4) bond lengths. In the third Cr site, Cr(3) is bonded to one Te(1), two equivalent Te(4), and three equivalent Te(3) 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(3)-Te(1) bond length is 2.79 Å. Both Cr(3)-Te(4) bond lengths are 2.84 Å. There is one shorter (2.71 Å) and two longer (2.73 Å) Cr(3)-Te(3) bond lengths. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Cr(2), one Cr(3), and two equivalent Cr(1) atoms. In the second Te site, Te(2) is bonded to two equivalent Rb(1), one Cr(1), and two equivalent Cr(2) atoms to form distorted TeRb2Cr3 square pyramids that share corners with three equivalent Te(2)Rb2Cr3 square pyramids, corners with four equivalent Te(4)Cr5 trigonal bipyramids, edges with three equivalent Te(2)Rb2Cr3 square pyramids, and  an edgeedge with one Te(4)Cr5 trigonal bipyramid. In the third Te site, Te(3) is bonded in a 5-coordinate geometry to two equivalent Rb(1) and three equivalent Cr(3) atoms. In the fourth Te site, Te(4) is bonded to two equivalent Cr(3) and three equivalent Cr(2) atoms to form distorted TeCr5 trigonal bipyramids that share corners with four equivalent Te(2)Rb2Cr3 square pyramids,  an edgeedge with one Te(2)Rb2Cr3 square pyramid, and edges with four equivalent Te(4)Cr5 trigonal bipyramids.