LiVF5 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one F(1), one F(3), two equivalent F(2), and two equivalent F(4) atoms to form distorted LiF6 trigonal bipyramids that share corners with five equivalent V(1)F6 octahedra, corners with two equivalent Li(1)F6 trigonal bipyramids, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 5-55°. 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 five equivalent Li(1)F6 trigonal bipyramids, and  an edgeedge with one Li(1)F6 trigonal bipyramid. The corner-sharing octahedral tilt angles are 42°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to 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(1) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a linear geometry to one Li(1) and one V(1) atom.
LiVF5 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one F(1), one F(3), two equivalent F(2), and two equivalent F(4) atoms to form distorted LiF6 trigonal bipyramids that share corners with five equivalent V(1)F6 octahedra, corners with two equivalent Li(1)F6 trigonal bipyramids, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 5-55°. The Li(1)-F(1) bond length is 1.87 Å. The Li(1)-F(3) bond length is 2.48 Å. There is one shorter (1.95 Å) and one longer (1.96 Å) Li(1)-F(2) bond length. Both Li(1)-F(4) bond lengths are 1.98 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 five equivalent Li(1)F6 trigonal bipyramids, and  an edgeedge with one Li(1)F6 trigonal bipyramid. The corner-sharing octahedral tilt angles are 42°. The V(1)-F(1) bond length is 1.80 Å. The V(1)-F(2) bond length is 1.86 Å. There is one shorter (1.97 Å) and one longer (2.02 Å) V(1)-F(3) bond length. Both V(1)-F(4) bond lengths are 1.78 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to 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(1) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a linear geometry to one Li(1) and one V(1) atom.