Li3V4O11F crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(10), one O(2), one O(3), one O(4), one O(8), and one O(9) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(6), one O(8), one O(9), and one F(1) atom. In the third Li site, Li(3) is bonded to one O(10), one O(11), one O(3), one O(4), one O(5), and one O(7) atom to form distorted LiO6 octahedra that share  a cornercorner with one V(4)O5F octahedra,  a cornercorner with one V(3)O6 octahedra,  an edgeedge with one V(4)O5F octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-28°. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(6), one O(8), one O(9), and one F(1) atom. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(3), one O(4), one O(5), and one O(7) atom. In the third V site, V(3) is bonded to one O(10), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form distorted VO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 28°. In the fourth V site, V(4) is bonded to one O(1), one O(11), one O(5), one O(6), one O(7), and one F(1) atom to form distorted VO5F octahedra that share  a cornercorner with one Li(3)O6 octahedra and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 21°. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(2), one V(1), and one V(4) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(2), and one V(3) atom to form edge-sharing OLi2V2 tetrahedra. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one V(4) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(3) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(3) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(3), one V(2), and one V(3) atom to form edge-sharing OLi2V2 trigonal pyramids. In the eleventh O site, O(11) is bonded in a T-shaped geometry to one Li(3), one V(2), and one V(4) atom. F(1) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one V(4) atom.
Li3V4O11F crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(10), one O(2), one O(3), one O(4), one O(8), and one O(9) atom. The Li(1)-O(10) bond length is 2.12 Å. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(3) bond length is 2.38 Å. The Li(1)-O(4) bond length is 1.93 Å. The Li(1)-O(8) bond length is 2.32 Å. The Li(1)-O(9) bond length is 2.15 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(6), one O(8), one O(9), and one F(1) atom. The Li(2)-O(1) bond length is 2.17 Å. The Li(2)-O(2) bond length is 2.12 Å. The Li(2)-O(6) bond length is 1.97 Å. The Li(2)-O(8) bond length is 2.52 Å. The Li(2)-O(9) bond length is 2.05 Å. The Li(2)-F(1) bond length is 1.96 Å. In the third Li site, Li(3) is bonded to one O(10), one O(11), one O(3), one O(4), one O(5), and one O(7) atom to form distorted LiO6 octahedra that share  a cornercorner with one V(4)O5F octahedra,  a cornercorner with one V(3)O6 octahedra,  an edgeedge with one V(4)O5F octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-28°. The Li(3)-O(10) bond length is 1.95 Å. The Li(3)-O(11) bond length is 2.02 Å. The Li(3)-O(3) bond length is 2.25 Å. The Li(3)-O(4) bond length is 2.15 Å. The Li(3)-O(5) bond length is 2.06 Å. The Li(3)-O(7) bond length is 2.30 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(6), one O(8), one O(9), and one F(1) atom. The V(1)-O(1) bond length is 1.73 Å. The V(1)-O(2) bond length is 2.30 Å. The V(1)-O(6) bond length is 1.82 Å. The V(1)-O(8) bond length is 1.74 Å. The V(1)-O(9) bond length is 2.03 Å. The V(1)-F(1) bond length is 2.02 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(3), one O(4), one O(5), and one O(7) atom. The V(2)-O(10) bond length is 2.05 Å. The V(2)-O(11) bond length is 1.82 Å. The V(2)-O(3) bond length is 1.68 Å. The V(2)-O(4) bond length is 1.87 Å. The V(2)-O(5) bond length is 2.35 Å. The V(2)-O(7) bond length is 1.92 Å. In the third V site, V(3) is bonded to one O(10), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form distorted VO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 28°. The V(3)-O(10) bond length is 1.79 Å. The V(3)-O(2) bond length is 1.75 Å. The V(3)-O(3) bond length is 2.33 Å. The V(3)-O(4) bond length is 1.97 Å. The V(3)-O(8) bond length is 2.02 Å. The V(3)-O(9) bond length is 1.77 Å. In the fourth V site, V(4) is bonded to one O(1), one O(11), one O(5), one O(6), one O(7), and one F(1) atom to form distorted VO5F octahedra that share  a cornercorner with one Li(3)O6 octahedra and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 21°. The V(4)-O(1) bond length is 2.04 Å. The V(4)-O(11) bond length is 1.90 Å. The V(4)-O(5) bond length is 1.67 Å. The V(4)-O(6) bond length is 1.92 Å. The V(4)-O(7) bond length is 1.79 Å. The V(4)-F(1) bond length is 2.31 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(2), one V(1), and one V(4) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(2), and one V(3) atom to form edge-sharing OLi2V2 tetrahedra. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one V(4) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(3) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(3) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(3), one V(2), and one V(3) atom to form edge-sharing OLi2V2 trigonal pyramids. In the eleventh O site, O(11) is bonded in a T-shaped geometry to one Li(3), one V(2), and one V(4) atom. F(1) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one V(4) atom.