Mg2V3FeS8 is Spinel-derived structured and crystallizes in the trigonal R-3m space group. Mg(1) is bonded to one S(1) and three equivalent S(2) atoms to form MgS4 tetrahedra that share corners with three equivalent Fe(1)S6 octahedra and corners with nine equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 57-61°. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form VS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. Fe(1) is bonded to six equivalent S(2) atoms to form FeS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra and edges with six equivalent V(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Mg(1) and three equivalent V(1) atoms to form distorted corner-sharing SMgV3 trigonal pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), two equivalent V(1), and one Fe(1) atom.
Mg2V3FeS8 is Spinel-derived structured and crystallizes in the trigonal R-3m space group. Mg(1) is bonded to one S(1) and three equivalent S(2) atoms to form MgS4 tetrahedra that share corners with three equivalent Fe(1)S6 octahedra and corners with nine equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 57-61°. The Mg(1)-S(1) bond length is 2.42 Å. All Mg(1)-S(2) bond lengths are 2.41 Å. V(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form VS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. Both V(1)-S(1) bond lengths are 2.43 Å. All V(1)-S(2) bond lengths are 2.45 Å. Fe(1) is bonded to six equivalent S(2) atoms to form FeS6 octahedra that share corners with six equivalent Mg(1)S4 tetrahedra and edges with six equivalent V(1)S6 octahedra. All Fe(1)-S(2) bond lengths are 2.33 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Mg(1) and three equivalent V(1) atoms to form distorted corner-sharing SMgV3 trigonal pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), two equivalent V(1), and one Fe(1) atom.