Ti2VTe4 crystallizes in the monoclinic Cm space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one Te(1), one Te(2), two equivalent Te(3), and two equivalent Te(4) atoms to form TiTe6 octahedra that share corners with six equivalent Ti(2)Te6 octahedra, corners with six equivalent V(1)Te6 octahedra, edges with two equivalent Ti(1)Te6 octahedra,  a faceface with one Ti(2)Te6 octahedra, and  a faceface with one V(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-58°. In the second Ti site, Ti(2) is bonded to one Te(1), one Te(3), two equivalent Te(2), and two equivalent Te(4) atoms to form distorted TiTe6 octahedra that share corners with six equivalent Ti(1)Te6 octahedra, edges with two equivalent Ti(2)Te6 octahedra, edges with four equivalent V(1)Te6 octahedra, and  a faceface with one Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. V(1) is bonded to one Te(2), one Te(4), two equivalent Te(1), and two equivalent Te(3) atoms to form distorted VTe6 octahedra that share corners with six equivalent Ti(1)Te6 octahedra, edges with two equivalent V(1)Te6 octahedra, edges with four equivalent Ti(2)Te6 octahedra, and  a faceface with one Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-56°. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded in a 4-coordinate geometry to one Ti(1), one Ti(2), and two equivalent V(1) atoms. In the second Te site, Te(2) is bonded in a distorted rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one V(1) atom. In the third Te site, Te(3) is bonded in a 5-coordinate geometry to one Ti(2), two equivalent Ti(1), and two equivalent V(1) atoms. In the fourth Te site, Te(4) is bonded in a 5-coordinate geometry to two equivalent Ti(1), two equivalent Ti(2), and one V(1) atom.
Ti2VTe4 crystallizes in the monoclinic Cm space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one Te(1), one Te(2), two equivalent Te(3), and two equivalent Te(4) atoms to form TiTe6 octahedra that share corners with six equivalent Ti(2)Te6 octahedra, corners with six equivalent V(1)Te6 octahedra, edges with two equivalent Ti(1)Te6 octahedra,  a faceface with one Ti(2)Te6 octahedra, and  a faceface with one V(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-58°. The Ti(1)-Te(1) bond length is 2.77 Å. The Ti(1)-Te(2) bond length is 2.77 Å. Both Ti(1)-Te(3) bond lengths are 2.85 Å. Both Ti(1)-Te(4) bond lengths are 2.83 Å. In the second Ti site, Ti(2) is bonded to one Te(1), one Te(3), two equivalent Te(2), and two equivalent Te(4) atoms to form distorted TiTe6 octahedra that share corners with six equivalent Ti(1)Te6 octahedra, edges with two equivalent Ti(2)Te6 octahedra, edges with four equivalent V(1)Te6 octahedra, and  a faceface with one Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. The Ti(2)-Te(1) bond length is 2.72 Å. The Ti(2)-Te(3) bond length is 2.98 Å. Both Ti(2)-Te(2) bond lengths are 2.76 Å. Both Ti(2)-Te(4) bond lengths are 2.86 Å. V(1) is bonded to one Te(2), one Te(4), two equivalent Te(1), and two equivalent Te(3) atoms to form distorted VTe6 octahedra that share corners with six equivalent Ti(1)Te6 octahedra, edges with two equivalent V(1)Te6 octahedra, edges with four equivalent Ti(2)Te6 octahedra, and  a faceface with one Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-56°. The V(1)-Te(2) bond length is 2.71 Å. The V(1)-Te(4) bond length is 2.94 Å. Both V(1)-Te(1) bond lengths are 2.73 Å. Both V(1)-Te(3) bond lengths are 2.83 Å. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded in a 4-coordinate geometry to one Ti(1), one Ti(2), and two equivalent V(1) atoms. In the second Te site, Te(2) is bonded in a distorted rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one V(1) atom. In the third Te site, Te(3) is bonded in a 5-coordinate geometry to one Ti(2), two equivalent Ti(1), and two equivalent V(1) atoms. In the fourth Te site, Te(4) is bonded in a 5-coordinate geometry to two equivalent Ti(1), two equivalent Ti(2), and one V(1) atom.