FeV2S4 crystallizes in the monoclinic C2/m space group. V(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted VS6 octahedra that share corners with six equivalent Fe(1)S6 octahedra, edges with six equivalent V(1)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. Fe(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form FeS6 octahedra that share corners with twelve equivalent V(1)S6 octahedra, edges with two equivalent Fe(1)S6 octahedra, and faces with two equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. There are two inequivalent S sites. In the first S site, S(2) is bonded in a 5-coordinate geometry to three equivalent V(1) and two equivalent Fe(1) atoms. In the second S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent V(1) and one Fe(1) atom.
FeV2S4 crystallizes in the monoclinic C2/m space group. V(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted VS6 octahedra that share corners with six equivalent Fe(1)S6 octahedra, edges with six equivalent V(1)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. There is one shorter (2.29 Å) and two longer (2.30 Å) V(1)-S(1) bond lengths. There are two shorter (2.47 Å) and one longer (2.52 Å) V(1)-S(2) bond length. Fe(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form FeS6 octahedra that share corners with twelve equivalent V(1)S6 octahedra, edges with two equivalent Fe(1)S6 octahedra, and faces with two equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. Both Fe(1)-S(1) bond lengths are 2.30 Å. All Fe(1)-S(2) bond lengths are 2.35 Å. There are two inequivalent S sites. In the first S site, S(2) is bonded in a 5-coordinate geometry to three equivalent V(1) and two equivalent Fe(1) atoms. In the second S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent V(1) and one Fe(1) atom.