LiVF6 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to one F(2), one F(4), one F(5), one F(6), and two equivalent F(1) atoms to form distorted LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, 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 32-51°. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VF6 octahedra that share corners with four equivalent Li(1)F6 octahedra and  an edgeedge with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 32-48°. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a single-bond geometry to one V(1) atom. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.
LiVF6 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to one F(2), one F(4), one F(5), one F(6), and two equivalent F(1) atoms to form distorted LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, 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 32-51°. The Li(1)-F(2) bond length is 2.00 Å. The Li(1)-F(4) bond length is 2.05 Å. The Li(1)-F(5) bond length is 2.13 Å. The Li(1)-F(6) bond length is 2.00 Å. There is one shorter (2.05 Å) and one longer (2.41 Å) Li(1)-F(1) bond length. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VF6 octahedra that share corners with four equivalent Li(1)F6 octahedra and  an edgeedge with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 32-48°. The V(1)-F(1) bond length is 1.87 Å. The V(1)-F(2) bond length is 1.83 Å. The V(1)-F(3) bond length is 1.76 Å. The V(1)-F(4) bond length is 1.84 Å. The V(1)-F(5) bond length is 1.80 Å. The V(1)-F(6) bond length is 1.82 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a single-bond geometry to one V(1) atom. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.