Li3V4O11F crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(10), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form a mixture of distorted corner and edge-sharing LiO6 octahedra. In the second Li site, Li(2) is bonded to one O(10), one O(2), one O(5), one O(7), and one O(9) atom to form a mixture of distorted corner and edge-sharing LiO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 21-82°. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(4), one O(9), and one F(1) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(7) atom. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), one O(6), and one F(1) atom. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(6), one O(8), one O(9), and one F(1) atom. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(7), and one O(8) atom. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Li(3), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(4) atom. In the third O site, O(3) is bonded in a distorted water-like geometry to one Li(1), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(2), and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(3) and one V(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one Li(3), and one V(3) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(4) atom. F(1) is bonded in a trigonal non-coplanar geometry to one Li(3), one V(2), and one V(3) atom.
Li3V4O11F crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(10), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form a mixture of distorted corner and edge-sharing LiO6 octahedra. The Li(1)-O(10) bond length is 2.36 Å. The Li(1)-O(2) bond length is 2.07 Å. The Li(1)-O(3) bond length is 2.09 Å. The Li(1)-O(5) bond length is 2.29 Å. The Li(1)-O(6) bond length is 2.00 Å. The Li(1)-O(7) bond length is 2.11 Å. In the second Li site, Li(2) is bonded to one O(10), one O(2), one O(5), one O(7), and one O(9) atom to form a mixture of distorted corner and edge-sharing LiO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 21-82°. The Li(2)-O(10) bond length is 2.31 Å. The Li(2)-O(2) bond length is 2.03 Å. The Li(2)-O(5) bond length is 2.16 Å. The Li(2)-O(7) bond length is 2.08 Å. The Li(2)-O(9) bond length is 1.94 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(4), one O(9), and one F(1) atom. The Li(3)-O(1) bond length is 2.10 Å. The Li(3)-O(11) bond length is 1.92 Å. The Li(3)-O(4) bond length is 2.10 Å. The Li(3)-O(9) bond length is 2.03 Å. The Li(3)-F(1) bond length is 2.11 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(7) atom. The V(1)-O(10) bond length is 1.80 Å. The V(1)-O(11) bond length is 1.79 Å. The V(1)-O(2) bond length is 2.08 Å. The V(1)-O(3) bond length is 1.68 Å. The V(1)-O(5) bond length is 2.03 Å. The V(1)-O(7) bond length is 2.42 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), one O(6), and one F(1) atom. The V(2)-O(1) bond length is 1.65 Å. The V(2)-O(4) bond length is 1.94 Å. The V(2)-O(5) bond length is 1.77 Å. The V(2)-O(6) bond length is 1.88 Å. The V(2)-F(1) bond length is 2.04 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(6), one O(8), one O(9), and one F(1) atom. The V(3)-O(1) bond length is 2.54 Å. The V(3)-O(4) bond length is 1.77 Å. The V(3)-O(6) bond length is 1.87 Å. The V(3)-O(8) bond length is 1.80 Å. The V(3)-O(9) bond length is 1.71 Å. The V(3)-F(1) bond length is 2.15 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(7), and one O(8) atom. The V(4)-O(10) bond length is 1.96 Å. The V(4)-O(11) bond length is 1.97 Å. The V(4)-O(2) bond length is 1.83 Å. The V(4)-O(3) bond length is 2.49 Å. The V(4)-O(7) bond length is 1.70 Å. The V(4)-O(8) bond length is 1.87 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Li(3), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(4) atom. In the third O site, O(3) is bonded in a distorted water-like geometry to one Li(1), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(2), and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(3) and one V(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one Li(3), and one V(3) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(4) atom. F(1) is bonded in a trigonal non-coplanar geometry to one Li(3), one V(2), and one V(3) atom.