Li3VF5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), and two equivalent F(2) atoms to form distorted LiF4 trigonal pyramids that share corners with four equivalent V(1)F6 octahedra and edges with four equivalent Li(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 27-65°. In the second Li site, Li(2) is bonded to one F(1), one F(3), one F(4), and two equivalent F(2) atoms to form distorted LiF5 trigonal bipyramids that share corners with two equivalent V(1)F6 octahedra, corners with three equivalent Li(2)F5 trigonal bipyramids, edges with two equivalent V(1)F6 octahedra,  an edgeedge with one Li(2)F5 trigonal bipyramid, and edges with two equivalent Li(1)F4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 50-53°. V(1) is bonded to one F(1), one F(4), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra, corners with four equivalent Li(2)F5 trigonal bipyramids, corners with four equivalent Li(1)F4 trigonal pyramids, and edges with four equivalent Li(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 11°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(1) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(1) atom.
Li3VF5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), and two equivalent F(2) atoms to form distorted LiF4 trigonal pyramids that share corners with four equivalent V(1)F6 octahedra and edges with four equivalent Li(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 27-65°. The Li(1)-F(1) bond length is 1.88 Å. The Li(1)-F(4) bond length is 1.89 Å. Both Li(1)-F(2) bond lengths are 1.86 Å. In the second Li site, Li(2) is bonded to one F(1), one F(3), one F(4), and two equivalent F(2) atoms to form distorted LiF5 trigonal bipyramids that share corners with two equivalent V(1)F6 octahedra, corners with three equivalent Li(2)F5 trigonal bipyramids, edges with two equivalent V(1)F6 octahedra,  an edgeedge with one Li(2)F5 trigonal bipyramid, and edges with two equivalent Li(1)F4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 50-53°. The Li(2)-F(1) bond length is 2.04 Å. The Li(2)-F(3) bond length is 2.30 Å. The Li(2)-F(4) bond length is 1.95 Å. There is one shorter (2.08 Å) and one longer (2.12 Å) Li(2)-F(2) bond length. V(1) is bonded to one F(1), one F(4), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra, corners with four equivalent Li(2)F5 trigonal bipyramids, corners with four equivalent Li(1)F4 trigonal pyramids, and edges with four equivalent Li(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 11°. The V(1)-F(1) bond length is 2.13 Å. The V(1)-F(4) bond length is 2.12 Å. Both V(1)-F(2) bond lengths are 2.10 Å. Both V(1)-F(3) bond lengths are 2.10 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(1) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(1) atom.