Ti4CrTe8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one Te(1), one Te(2), and four equivalent Te(3) atoms to form TiTe6 octahedra that share corners with two equivalent Cr(1)Te6 octahedra, edges with two equivalent Ti(1)Te6 octahedra, edges with four equivalent Ti(2)Te6 octahedra, and  a faceface with one Cr(1)Te6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the second Ti site, Ti(2) is bonded to two equivalent Te(1), two equivalent Te(2), and two equivalent Te(3) atoms to form TiTe6 octahedra that share corners with four equivalent Cr(1)Te6 octahedra, edges with two equivalent Ti(2)Te6 octahedra, and edges with four equivalent Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. Cr(1) is bonded to two equivalent Te(1) and four equivalent Te(3) atoms to form CrTe6 octahedra that share corners with four equivalent Ti(1)Te6 octahedra, corners with eight equivalent Ti(2)Te6 octahedra, and faces with two equivalent Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Cr(1) atom. In the second Te site, Te(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms. In the third Te site, Te(3) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(1), and one Cr(1) atom.
Ti4CrTe8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one Te(1), one Te(2), and four equivalent Te(3) atoms to form TiTe6 octahedra that share corners with two equivalent Cr(1)Te6 octahedra, edges with two equivalent Ti(1)Te6 octahedra, edges with four equivalent Ti(2)Te6 octahedra, and  a faceface with one Cr(1)Te6 octahedra. The corner-sharing octahedral tilt angles are 49°. The Ti(1)-Te(1) bond length is 2.81 Å. The Ti(1)-Te(2) bond length is 2.79 Å. There are two shorter (2.79 Å) and two longer (2.82 Å) Ti(1)-Te(3) bond lengths. In the second Ti site, Ti(2) is bonded to two equivalent Te(1), two equivalent Te(2), and two equivalent Te(3) atoms to form TiTe6 octahedra that share corners with four equivalent Cr(1)Te6 octahedra, edges with two equivalent Ti(2)Te6 octahedra, and edges with four equivalent Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. Both Ti(2)-Te(1) bond lengths are 2.83 Å. Both Ti(2)-Te(2) bond lengths are 2.75 Å. Both Ti(2)-Te(3) bond lengths are 2.79 Å. Cr(1) is bonded to two equivalent Te(1) and four equivalent Te(3) atoms to form CrTe6 octahedra that share corners with four equivalent Ti(1)Te6 octahedra, corners with eight equivalent Ti(2)Te6 octahedra, and faces with two equivalent Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. Both Cr(1)-Te(1) bond lengths are 2.77 Å. All Cr(1)-Te(3) bond lengths are 2.77 Å. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Cr(1) atom. In the second Te site, Te(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms. In the third Te site, Te(3) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(1), and one Cr(1) atom.