Ti2VTe4 crystallizes in the monoclinic C2/m space group. Ti(1) is bonded to three equivalent Te(1) and three equivalent Te(2) atoms to form distorted TiTe6 octahedra that share corners with six equivalent V(1)Te6 octahedra, edges with six equivalent Ti(1)Te6 octahedra, and  a faceface with one V(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 51-54°. V(1) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form VTe6 octahedra that share corners with twelve equivalent Ti(1)Te6 octahedra, edges with two equivalent V(1)Te6 octahedra, and faces with two equivalent Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 51-54°. There are two inequivalent Te sites. In the first Te site, Te(2) is bonded in a 5-coordinate geometry to three equivalent Ti(1) and two equivalent V(1) atoms. In the second Te site, Te(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ti(1) and one V(1) atom.
Ti2VTe4 crystallizes in the monoclinic C2/m space group. Ti(1) is bonded to three equivalent Te(1) and three equivalent Te(2) atoms to form distorted TiTe6 octahedra that share corners with six equivalent V(1)Te6 octahedra, edges with six equivalent Ti(1)Te6 octahedra, and  a faceface with one V(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 51-54°. There is one shorter (2.73 Å) and two longer (2.77 Å) Ti(1)-Te(1) bond lengths. There are two shorter (2.87 Å) and one longer (2.99 Å) Ti(1)-Te(2) bond length. V(1) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form VTe6 octahedra that share corners with twelve equivalent Ti(1)Te6 octahedra, edges with two equivalent V(1)Te6 octahedra, and faces with two equivalent Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 51-54°. Both V(1)-Te(1) bond lengths are 2.78 Å. All V(1)-Te(2) bond lengths are 2.84 Å. There are two inequivalent Te sites. In the first Te site, Te(2) is bonded in a 5-coordinate geometry to three equivalent Ti(1) and two equivalent V(1) atoms. In the second Te site, Te(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ti(1) and one V(1) atom.