Li2VOF4 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 O(1), one F(3), and two equivalent F(4) atoms to form LiOF3 trigonal pyramids that share corners with four equivalent V(1)OF5 octahedra and corners with two equivalent Li(1)OF3 trigonal pyramids. The corner-sharing octahedral tilt angles range from 33-64°. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to two equivalent O(1), one F(2), and two equivalent F(3) atoms. V(1) is bonded to one O(1), one F(2), one F(3), one F(4), and two equivalent F(1) atoms to form distorted VOF5 octahedra that share corners with two equivalent V(1)OF5 octahedra and corners with four equivalent Li(1)OF3 trigonal pyramids. The corner-sharing octahedral tilt angles are 21°. O(1) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Li(2), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the third F site, F(3) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted corner-sharing FLi3V tetrahedra. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom.
Li2VOF4 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 O(1), one F(3), and two equivalent F(4) atoms to form LiOF3 trigonal pyramids that share corners with four equivalent V(1)OF5 octahedra and corners with two equivalent Li(1)OF3 trigonal pyramids. The corner-sharing octahedral tilt angles range from 33-64°. The Li(1)-O(1) bond length is 2.08 Å. The Li(1)-F(3) bond length is 1.95 Å. There is one shorter (1.98 Å) and one longer (2.20 Å) Li(1)-F(4) bond length. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to two equivalent O(1), one F(2), and two equivalent F(3) atoms. There is one shorter (2.07 Å) and one longer (2.34 Å) Li(2)-O(1) bond length. The Li(2)-F(2) bond length is 1.87 Å. There is one shorter (1.98 Å) and one longer (2.32 Å) Li(2)-F(3) bond length. V(1) is bonded to one O(1), one F(2), one F(3), one F(4), and two equivalent F(1) atoms to form distorted VOF5 octahedra that share corners with two equivalent V(1)OF5 octahedra and corners with four equivalent Li(1)OF3 trigonal pyramids. The corner-sharing octahedral tilt angles are 21°. The V(1)-O(1) bond length is 1.68 Å. The V(1)-F(2) bond length is 1.91 Å. The V(1)-F(3) bond length is 1.95 Å. The V(1)-F(4) bond length is 1.99 Å. There is one shorter (1.96 Å) and one longer (2.15 Å) V(1)-F(1) bond length. O(1) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Li(2), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the third F site, F(3) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted corner-sharing FLi3V tetrahedra. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom.