Li3VF5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one F(1), one F(2), and two equivalent F(4) atoms. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form LiF5 trigonal bipyramids that share corners with four equivalent V(1)F6 octahedra and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-63°. V(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra, corners with four equivalent Li(2)F5 trigonal bipyramids, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 35°. 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(2), two equivalent Li(1), and one V(1) atom. In the second F site, F(2) is bonded in a trigonal pyramidal geometry to one Li(2), two equivalent Li(1), and one V(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(2) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted see-saw-like geometry to one Li(2), two equivalent Li(1), 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 in a rectangular see-saw-like geometry to one F(1), one F(2), and two equivalent F(4) atoms. The Li(1)-F(1) bond length is 2.04 Å. The Li(1)-F(2) bond length is 1.89 Å. There is one shorter (1.92 Å) and one longer (1.96 Å) Li(1)-F(4) bond length. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form LiF5 trigonal bipyramids that share corners with four equivalent V(1)F6 octahedra and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-63°. The Li(2)-F(1) bond length is 1.98 Å. The Li(2)-F(2) bond length is 2.02 Å. The Li(2)-F(3) bond length is 1.94 Å. Both Li(2)-F(4) bond lengths are 2.06 Å. V(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra, corners with four equivalent Li(2)F5 trigonal bipyramids, and  an edgeedge with one Li(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 35°. The V(1)-F(1) bond length is 2.12 Å. The V(1)-F(2) bond length is 2.09 Å. There is one shorter (2.12 Å) and one longer (2.17 Å) V(1)-F(3) bond length. Both V(1)-F(4) bond lengths are 2.13 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(2), two equivalent Li(1), and one V(1) atom. In the second F site, F(2) is bonded in a trigonal pyramidal geometry to one Li(2), two equivalent Li(1), and one V(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(2) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted see-saw-like geometry to one Li(2), two equivalent Li(1), and one V(1) atom.