Li2VFeS4 is Caswellsilverite-derived structured and crystallizes in the trigonal P-3m1 space group. Li(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted LiS6 octahedra that share corners with six equivalent V(1)S6 octahedra, corners with six equivalent Fe(1)S6 octahedra, edges with six equivalent Li(1)S6 octahedra,  a faceface with one V(1)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. V(1) is bonded to six equivalent S(2) atoms to form VS6 octahedra that share corners with twelve equivalent Li(1)S6 octahedra, edges with six equivalent V(1)S6 octahedra, and faces with two equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles are 46°. Fe(1) is bonded to six equivalent S(1) atoms to form FeS6 octahedra that share corners with twelve equivalent Li(1)S6 octahedra, edges with six equivalent Fe(1)S6 octahedra, and faces with two equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to three equivalent Li(1) and three equivalent Fe(1) atoms. In the second S site, S(2) is bonded to three equivalent Li(1) and three equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing SLi3V3 pentagonal pyramids.
Li2VFeS4 is Caswellsilverite-derived structured and crystallizes in the trigonal P-3m1 space group. Li(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted LiS6 octahedra that share corners with six equivalent V(1)S6 octahedra, corners with six equivalent Fe(1)S6 octahedra, edges with six equivalent Li(1)S6 octahedra,  a faceface with one V(1)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. All Li(1)-S(1) bond lengths are 2.59 Å. All Li(1)-S(2) bond lengths are 2.59 Å. V(1) is bonded to six equivalent S(2) atoms to form VS6 octahedra that share corners with twelve equivalent Li(1)S6 octahedra, edges with six equivalent V(1)S6 octahedra, and faces with two equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles are 46°. All V(1)-S(2) bond lengths are 2.40 Å. Fe(1) is bonded to six equivalent S(1) atoms to form FeS6 octahedra that share corners with twelve equivalent Li(1)S6 octahedra, edges with six equivalent Fe(1)S6 octahedra, and faces with two equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles are 48°. All Fe(1)-S(1) bond lengths are 2.29 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to three equivalent Li(1) and three equivalent Fe(1) atoms. In the second S site, S(2) is bonded to three equivalent Li(1) and three equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing SLi3V3 pentagonal pyramids.