Fe2VS4 crystallizes in the monoclinic Cm space group. V(1) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(4) atoms to form distorted VS6 octahedra that share corners with six equivalent Fe(1)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with four equivalent Fe(2)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form FeS6 octahedra that share corners with six equivalent V(1)S6 octahedra, corners with six equivalent Fe(2)S6 octahedra, edges with two equivalent Fe(1)S6 octahedra,  a faceface with one V(1)S6 octahedra, and  a faceface with one Fe(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. In the second Fe site, Fe(2) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(3) atoms to form distorted FeS6 octahedra that share corners with six equivalent Fe(1)S6 octahedra, edges with two equivalent Fe(2)S6 octahedra, edges with four equivalent V(1)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent V(1), one Fe(2), and two equivalent Fe(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to one V(1), two equivalent Fe(1), and two equivalent Fe(2) atoms. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one Fe(1), and two equivalent Fe(2) atoms. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent V(1), one Fe(1), and one Fe(2) atom.
Fe2VS4 crystallizes in the monoclinic Cm space group. V(1) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(4) atoms to form distorted VS6 octahedra that share corners with six equivalent Fe(1)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with four equivalent Fe(2)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. The V(1)-S(2) bond length is 2.49 Å. The V(1)-S(3) bond length is 2.25 Å. Both V(1)-S(1) bond lengths are 2.46 Å. Both V(1)-S(4) bond lengths are 2.28 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form FeS6 octahedra that share corners with six equivalent V(1)S6 octahedra, corners with six equivalent Fe(2)S6 octahedra, edges with two equivalent Fe(1)S6 octahedra,  a faceface with one V(1)S6 octahedra, and  a faceface with one Fe(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. The Fe(1)-S(3) bond length is 2.31 Å. The Fe(1)-S(4) bond length is 2.25 Å. Both Fe(1)-S(1) bond lengths are 2.33 Å. Both Fe(1)-S(2) bond lengths are 2.34 Å. In the second Fe site, Fe(2) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(3) atoms to form distorted FeS6 octahedra that share corners with six equivalent Fe(1)S6 octahedra, edges with two equivalent Fe(2)S6 octahedra, edges with four equivalent V(1)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. The Fe(2)-S(1) bond length is 2.39 Å. The Fe(2)-S(4) bond length is 2.23 Å. Both Fe(2)-S(2) bond lengths are 2.44 Å. Both Fe(2)-S(3) bond lengths are 2.22 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent V(1), one Fe(2), and two equivalent Fe(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to one V(1), two equivalent Fe(1), and two equivalent Fe(2) atoms. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one Fe(1), and two equivalent Fe(2) atoms. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent V(1), one Fe(1), and one Fe(2) atom.