Li3VS4 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form distorted LiS5 trigonal bipyramids that share corners with three equivalent V(1)S4 tetrahedra, corners with two equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one V(1)S4 tetrahedra, and  an edgeedge with one Li(1)S5 trigonal bipyramid. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one S(2), one S(4), and two equivalent S(3) atoms. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one S(2), one S(3), and two equivalent S(4) atoms. V(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form VS4 tetrahedra that share corners with three equivalent Li(1)S5 trigonal bipyramids and  an edgeedge with one Li(1)S5 trigonal bipyramid. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(1) atom. In the second S site, S(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one V(1) atom to form distorted SLi4V trigonal bipyramids that share corners with two equivalent S(4)Li3V trigonal pyramids,  an edgeedge with one S(2)Li4V trigonal bipyramid, and  an edgeedge with one S(4)Li3V trigonal pyramid. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), and one V(1) atom. In the fourth S site, S(4) is bonded to one Li(2), two equivalent Li(3), and one V(1) atom to form SLi3V trigonal pyramids that share corners with two equivalent S(2)Li4V trigonal bipyramids, corners with two equivalent S(4)Li3V trigonal pyramids, and  an edgeedge with one S(2)Li4V trigonal bipyramid.
Li3VS4 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form distorted LiS5 trigonal bipyramids that share corners with three equivalent V(1)S4 tetrahedra, corners with two equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one V(1)S4 tetrahedra, and  an edgeedge with one Li(1)S5 trigonal bipyramid. The Li(1)-S(3) bond length is 2.63 Å. There is one shorter (2.48 Å) and one longer (2.76 Å) Li(1)-S(1) bond length. There is one shorter (2.60 Å) and one longer (2.74 Å) Li(1)-S(2) bond length. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one S(2), one S(4), and two equivalent S(3) atoms. The Li(2)-S(2) bond length is 2.57 Å. The Li(2)-S(4) bond length is 2.47 Å. There is one shorter (2.56 Å) and one longer (2.93 Å) Li(2)-S(3) bond length. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one S(2), one S(3), and two equivalent S(4) atoms. The Li(3)-S(2) bond length is 2.48 Å. The Li(3)-S(3) bond length is 2.92 Å. There is one shorter (2.44 Å) and one longer (2.54 Å) Li(3)-S(4) bond length. V(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form VS4 tetrahedra that share corners with three equivalent Li(1)S5 trigonal bipyramids and  an edgeedge with one Li(1)S5 trigonal bipyramid. The V(1)-S(1) bond length is 2.16 Å. The V(1)-S(2) bond length is 2.19 Å. The V(1)-S(3) bond length is 2.14 Å. The V(1)-S(4) bond length is 2.17 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(1) atom. In the second S site, S(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one V(1) atom to form distorted SLi4V trigonal bipyramids that share corners with two equivalent S(4)Li3V trigonal pyramids,  an edgeedge with one S(2)Li4V trigonal bipyramid, and  an edgeedge with one S(4)Li3V trigonal pyramid. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), and one V(1) atom. In the fourth S site, S(4) is bonded to one Li(2), two equivalent Li(3), and one V(1) atom to form SLi3V trigonal pyramids that share corners with two equivalent S(2)Li4V trigonal bipyramids, corners with two equivalent S(4)Li3V trigonal pyramids, and  an edgeedge with one S(2)Li4V trigonal bipyramid.