Li2VF4 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), and two equivalent F(4) atoms to form LiF4 tetrahedra that share corners with five equivalent V(1)F6 octahedra and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-74°. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(1), one F(2), one F(4), and two equivalent F(3) atoms. V(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form VF6 octahedra that share corners with four equivalent V(1)F6 octahedra and corners with five equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-42°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(2) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(1) atom. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form distorted corner-sharing FLi3V trigonal pyramids.
Li2VF4 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), and two equivalent F(4) atoms to form LiF4 tetrahedra that share corners with five equivalent V(1)F6 octahedra and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-74°. The Li(1)-F(2) bond length is 1.91 Å. The Li(1)-F(3) bond length is 1.93 Å. There is one shorter (1.92 Å) and one longer (1.95 Å) Li(1)-F(4) bond length. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(1), one F(2), one F(4), and two equivalent F(3) atoms. The Li(2)-F(1) bond length is 1.88 Å. The Li(2)-F(2) bond length is 2.39 Å. The Li(2)-F(4) bond length is 2.04 Å. There is one shorter (1.92 Å) and one longer (2.20 Å) Li(2)-F(3) bond length. V(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form VF6 octahedra that share corners with four equivalent V(1)F6 octahedra and corners with five equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-42°. The V(1)-F(3) bond length is 2.10 Å. The V(1)-F(4) bond length is 2.13 Å. There is one shorter (2.11 Å) and one longer (2.13 Å) V(1)-F(1) bond length. There is one shorter (2.15 Å) and one longer (2.17 Å) V(1)-F(2) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(2) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(1) atom. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form distorted corner-sharing FLi3V trigonal pyramids.