Li2VOF4 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one F(1), one F(2), one F(4), and two equivalent F(3) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one F(1), one F(2), one F(3), and two equivalent F(4) atoms. V(1) is bonded to two equivalent O(1), one F(1), one F(2), one F(3), and one F(4) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles are 14°. O(1) is bonded in a 2-coordinate geometry to one Li(1), one Li(2), and two equivalent V(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the third F site, F(3) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the fourth F site, F(4) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form a mixture of edge and corner-sharing FLi3V tetrahedra.
Li2VOF4 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one F(1), one F(2), one F(4), and two equivalent F(3) atoms. The Li(1)-O(1) bond length is 2.56 Å. The Li(1)-F(1) bond length is 2.32 Å. The Li(1)-F(2) bond length is 1.91 Å. The Li(1)-F(4) bond length is 2.14 Å. Both Li(1)-F(3) bond lengths are 1.94 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one F(1), one F(2), one F(3), and two equivalent F(4) atoms. The Li(2)-O(1) bond length is 2.48 Å. The Li(2)-F(1) bond length is 1.92 Å. The Li(2)-F(2) bond length is 1.94 Å. The Li(2)-F(3) bond length is 2.46 Å. Both Li(2)-F(4) bond lengths are 2.04 Å. V(1) is bonded to two equivalent O(1), one F(1), one F(2), one F(3), and one F(4) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles are 14°. Both V(1)-O(1) bond lengths are 1.83 Å. The V(1)-F(1) bond length is 1.90 Å. The V(1)-F(2) bond length is 1.93 Å. The V(1)-F(3) bond length is 2.01 Å. The V(1)-F(4) bond length is 2.04 Å. O(1) is bonded in a 2-coordinate geometry to one Li(1), one Li(2), and two equivalent V(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the third F site, F(3) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the fourth F site, F(4) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form a mixture of edge and corner-sharing FLi3V tetrahedra.