Li2VCrS4 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form LiS6 octahedra that share corners with six equivalent V(1)S6 octahedra, corners with six equivalent Cr(1)S6 octahedra, edges with six equivalent Li(1)S6 octahedra,  a faceface with one V(1)S6 octahedra, and  a faceface with one Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. V(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form VS6 octahedra that share corners with twelve equivalent Li(1)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and faces with two equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. Cr(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form CrS6 octahedra that share corners with twelve equivalent Li(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with four equivalent V(1)S6 octahedra, and faces with two equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Li(1), two equivalent V(1), and one Cr(1) atom to form distorted SLi3V2Cr pentagonal pyramids that share corners with three equivalent S(1)Li3V2Cr pentagonal pyramids, corners with three equivalent S(2)Li3VCr2 pentagonal pyramids, edges with five equivalent S(1)Li3V2Cr pentagonal pyramids, and edges with seven equivalent S(2)Li3VCr2 pentagonal pyramids. In the second S site, S(2) is bonded to three equivalent Li(1), one V(1), and two equivalent Cr(1) atoms to form distorted SLi3VCr2 pentagonal pyramids that share corners with three equivalent S(1)Li3V2Cr pentagonal pyramids, corners with three equivalent S(2)Li3VCr2 pentagonal pyramids, edges with five equivalent S(2)Li3VCr2 pentagonal pyramids, and edges with seven equivalent S(1)Li3V2Cr pentagonal pyramids.
Li2VCrS4 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form LiS6 octahedra that share corners with six equivalent V(1)S6 octahedra, corners with six equivalent Cr(1)S6 octahedra, edges with six equivalent Li(1)S6 octahedra,  a faceface with one V(1)S6 octahedra, and  a faceface with one Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. There are two shorter (2.60 Å) and one longer (2.62 Å) Li(1)-S(1) bond length. There are two shorter (2.59 Å) and one longer (2.64 Å) Li(1)-S(2) bond length. V(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form VS6 octahedra that share corners with twelve equivalent Li(1)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and faces with two equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. Both V(1)-S(2) bond lengths are 2.45 Å. All V(1)-S(1) bond lengths are 2.43 Å. Cr(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form CrS6 octahedra that share corners with twelve equivalent Li(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with four equivalent V(1)S6 octahedra, and faces with two equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. Both Cr(1)-S(1) bond lengths are 2.43 Å. All Cr(1)-S(2) bond lengths are 2.41 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Li(1), two equivalent V(1), and one Cr(1) atom to form distorted SLi3V2Cr pentagonal pyramids that share corners with three equivalent S(1)Li3V2Cr pentagonal pyramids, corners with three equivalent S(2)Li3VCr2 pentagonal pyramids, edges with five equivalent S(1)Li3V2Cr pentagonal pyramids, and edges with seven equivalent S(2)Li3VCr2 pentagonal pyramids. In the second S site, S(2) is bonded to three equivalent Li(1), one V(1), and two equivalent Cr(1) atoms to form distorted SLi3VCr2 pentagonal pyramids that share corners with three equivalent S(1)Li3V2Cr pentagonal pyramids, corners with three equivalent S(2)Li3VCr2 pentagonal pyramids, edges with five equivalent S(2)Li3VCr2 pentagonal pyramids, and edges with seven equivalent S(1)Li3V2Cr pentagonal pyramids.