Li2VOF4 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(4), one F(7), and two equivalent F(5) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(8), and two equivalent F(6) atoms. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(3), one F(6), and two equivalent F(8) atoms. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(4), one F(5), and two equivalent F(7) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), one F(1), one F(4), one F(5), and one F(8) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles are 14°. In the second V site, V(2) is bonded to two equivalent O(1), one F(2), one F(3), one F(6), and one F(7) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles are 14°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), and two equivalent V(2) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), and two equivalent V(1) atoms. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one V(1) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(2), one Li(4), and one V(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one V(2) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one V(1) atom. In the fifth F site, F(5) is bonded to one Li(4), two equivalent Li(1), and one V(1) atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids. In the sixth F site, F(6) is bonded to one Li(3), two equivalent Li(2), and one V(2) atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids. In the seventh F site, F(7) is bonded to one Li(1), two equivalent Li(4), and one V(2) atom to form a mixture of distorted corner and edge-sharing FLi3V tetrahedra. In the eighth F site, F(8) is bonded to one Li(2), two equivalent Li(3), and one V(1) atom to form a mixture of distorted corner and edge-sharing FLi3V tetrahedra.
Li2VOF4 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(4), one F(7), and two equivalent F(5) atoms. The Li(1)-O(2) bond length is 2.56 Å. The Li(1)-F(1) bond length is 2.30 Å. The Li(1)-F(4) bond length is 1.92 Å. The Li(1)-F(7) bond length is 2.08 Å. Both Li(1)-F(5) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(8), and two equivalent F(6) atoms. The Li(2)-O(1) bond length is 2.56 Å. The Li(2)-F(2) bond length is 2.30 Å. The Li(2)-F(3) bond length is 1.92 Å. The Li(2)-F(8) bond length is 2.08 Å. Both Li(2)-F(6) bond lengths are 1.97 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(3), one F(6), and two equivalent F(8) atoms. The Li(3)-O(2) bond length is 2.43 Å. The Li(3)-F(1) bond length is 1.92 Å. The Li(3)-F(3) bond length is 1.94 Å. The Li(3)-F(6) bond length is 2.42 Å. There is one shorter (2.04 Å) and one longer (2.07 Å) Li(3)-F(8) bond length. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(4), one F(5), and two equivalent F(7) atoms. The Li(4)-O(1) bond length is 2.43 Å. The Li(4)-F(2) bond length is 1.92 Å. The Li(4)-F(4) bond length is 1.94 Å. The Li(4)-F(5) bond length is 2.41 Å. There is one shorter (2.05 Å) and one longer (2.07 Å) Li(4)-F(7) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), one F(1), one F(4), one F(5), and one F(8) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles are 14°. There is one shorter (1.71 Å) and one longer (2.01 Å) V(1)-O(2) bond length. The V(1)-F(1) bond length is 1.90 Å. The V(1)-F(4) bond length is 1.92 Å. The V(1)-F(5) bond length is 2.00 Å. The V(1)-F(8) bond length is 2.04 Å. In the second V site, V(2) is bonded to two equivalent O(1), one F(2), one F(3), one F(6), and one F(7) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles are 14°. There is one shorter (1.72 Å) and one longer (2.00 Å) V(2)-O(1) bond length. The V(2)-F(2) bond length is 1.90 Å. The V(2)-F(3) bond length is 1.92 Å. The V(2)-F(6) bond length is 2.00 Å. The V(2)-F(7) bond length is 2.03 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), and two equivalent V(2) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), and two equivalent V(1) atoms. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one V(1) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(2), one Li(4), and one V(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one V(2) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one V(1) atom. In the fifth F site, F(5) is bonded to one Li(4), two equivalent Li(1), and one V(1) atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids. In the sixth F site, F(6) is bonded to one Li(3), two equivalent Li(2), and one V(2) atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids. In the seventh F site, F(7) is bonded to one Li(1), two equivalent Li(4), and one V(2) atom to form a mixture of distorted corner and edge-sharing FLi3V tetrahedra. In the eighth F site, F(8) is bonded to one Li(2), two equivalent Li(3), and one V(1) atom to form a mixture of distorted corner and edge-sharing FLi3V tetrahedra.