FeV2Te4 crystallizes in the monoclinic Cm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one Fe(1), one Te(1), one Te(2), two equivalent Te(3), and two equivalent Te(4) atoms to form distorted VFeTe6 octahedra that share corners with six equivalent V(2)Te6 octahedra, edges with two equivalent V(1)FeTe6 octahedra, and  a faceface with one V(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. In the second V site, V(2) 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 V(1)FeTe6 octahedra, edges with two equivalent V(2)Te6 octahedra, and  a faceface with one V(1)FeTe6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. Fe(1) is bonded in a 7-coordinate geometry to one V(1), one Te(1), one Te(3), two equivalent Te(2), and two equivalent Te(4) atoms. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one V(1), two equivalent V(2), and one Fe(1) atom. In the second Te site, Te(2) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(2), and two equivalent Fe(1) atoms. In the third Te site, Te(3) is bonded in a 5-coordinate geometry to two equivalent V(1), two equivalent V(2), and one Fe(1) atom. In the fourth Te site, Te(4) is bonded in a 5-coordinate geometry to one V(2), two equivalent V(1), and two equivalent Fe(1) atoms.
FeV2Te4 crystallizes in the monoclinic Cm space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one Fe(1), one Te(1), one Te(2), two equivalent Te(3), and two equivalent Te(4) atoms to form distorted VFeTe6 octahedra that share corners with six equivalent V(2)Te6 octahedra, edges with two equivalent V(1)FeTe6 octahedra, and  a faceface with one V(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. The V(1)-Fe(1) bond length is 2.93 Å. The V(1)-Te(1) bond length is 2.69 Å. The V(1)-Te(2) bond length is 2.76 Å. Both V(1)-Te(3) bond lengths are 2.78 Å. Both V(1)-Te(4) bond lengths are 2.73 Å. In the second V site, V(2) 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 V(1)FeTe6 octahedra, edges with two equivalent V(2)Te6 octahedra, and  a faceface with one V(1)FeTe6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. The V(2)-Te(2) bond length is 2.72 Å. The V(2)-Te(4) bond length is 2.78 Å. Both V(2)-Te(1) bond lengths are 2.69 Å. Both V(2)-Te(3) bond lengths are 2.79 Å. Fe(1) is bonded in a 7-coordinate geometry to one V(1), one Te(1), one Te(3), two equivalent Te(2), and two equivalent Te(4) atoms. The Fe(1)-Te(1) bond length is 2.63 Å. The Fe(1)-Te(3) bond length is 2.76 Å. Both Fe(1)-Te(2) bond lengths are 2.65 Å. Both Fe(1)-Te(4) bond lengths are 2.76 Å. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one V(1), two equivalent V(2), and one Fe(1) atom. In the second Te site, Te(2) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(2), and two equivalent Fe(1) atoms. In the third Te site, Te(3) is bonded in a 5-coordinate geometry to two equivalent V(1), two equivalent V(2), and one Fe(1) atom. In the fourth Te site, Te(4) is bonded in a 5-coordinate geometry to one V(2), two equivalent V(1), and two equivalent Fe(1) atoms.