Li4VS4 is Aluminum carbonitride-like structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted LiS6 octahedra that share corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent V(1)S4 tetrahedra, corners with six equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, edges with two equivalent Li(2)S4 tetrahedra, edges with two equivalent V(1)S4 tetrahedra, and faces with two equivalent Li(3)S4 trigonal pyramids. In the second Li site, Li(2) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form LiS4 tetrahedra that share corners with two equivalent Li(1)S6 octahedra, corners with two equivalent V(1)S4 tetrahedra, corners with eight equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, and  an edgeedge with one V(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. In the third Li site, Li(3) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form distorted LiS4 trigonal pyramids that share corners with three equivalent Li(1)S6 octahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with four equivalent V(1)S4 tetrahedra, corners with four equivalent Li(3)S4 trigonal pyramids, and  a faceface with one Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 19-52°. V(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form VS4 tetrahedra that share corners with two equivalent Li(1)S6 octahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with eight equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, and  an edgeedge with one Li(2)S4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one V(1) atom to form distorted SLi5V pentagonal pyramids that share corners with two equivalent S(1)Li5V pentagonal pyramids, corners with four equivalent S(3)Li4V trigonal bipyramids, and edges with four equivalent S(3)Li4V trigonal bipyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), two equivalent Li(3), and one V(1) atom. In the third S site, S(3) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one V(1) atom to form distorted SLi4V trigonal bipyramids that share corners with two equivalent S(1)Li5V pentagonal pyramids, corners with five equivalent S(3)Li4V trigonal bipyramids, and edges with two equivalent S(1)Li5V pentagonal pyramids.
Li4VS4 is Aluminum carbonitride-like structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted LiS6 octahedra that share corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent V(1)S4 tetrahedra, corners with six equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, edges with two equivalent Li(2)S4 tetrahedra, edges with two equivalent V(1)S4 tetrahedra, and faces with two equivalent Li(3)S4 trigonal pyramids. Both Li(1)-S(1) bond lengths are 2.58 Å. Both Li(1)-S(2) bond lengths are 2.89 Å. Both Li(1)-S(3) bond lengths are 2.60 Å. In the second Li site, Li(2) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form LiS4 tetrahedra that share corners with two equivalent Li(1)S6 octahedra, corners with two equivalent V(1)S4 tetrahedra, corners with eight equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, and  an edgeedge with one V(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. The Li(2)-S(1) bond length is 2.46 Å. The Li(2)-S(2) bond length is 2.46 Å. Both Li(2)-S(3) bond lengths are 2.46 Å. In the third Li site, Li(3) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form distorted LiS4 trigonal pyramids that share corners with three equivalent Li(1)S6 octahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with four equivalent V(1)S4 tetrahedra, corners with four equivalent Li(3)S4 trigonal pyramids, and  a faceface with one Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 19-52°. The Li(3)-S(1) bond length is 2.54 Å. The Li(3)-S(2) bond length is 2.45 Å. There is one shorter (2.43 Å) and one longer (2.57 Å) Li(3)-S(3) bond length. V(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form VS4 tetrahedra that share corners with two equivalent Li(1)S6 octahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with eight equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, and  an edgeedge with one Li(2)S4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. The V(1)-S(1) bond length is 2.24 Å. The V(1)-S(2) bond length is 2.22 Å. Both V(1)-S(3) bond lengths are 2.23 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one V(1) atom to form distorted SLi5V pentagonal pyramids that share corners with two equivalent S(1)Li5V pentagonal pyramids, corners with four equivalent S(3)Li4V trigonal bipyramids, and edges with four equivalent S(3)Li4V trigonal bipyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), two equivalent Li(3), and one V(1) atom. In the third S site, S(3) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one V(1) atom to form distorted SLi4V trigonal bipyramids that share corners with two equivalent S(1)Li5V pentagonal pyramids, corners with five equivalent S(3)Li4V trigonal bipyramids, and edges with two equivalent S(1)Li5V pentagonal pyramids.