LiV6O11F crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(3)O5F octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-70°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(3), one O(4), one O(7), and one F(1) atom to form VO5F octahedra that share corners with four equivalent V(5)O5F octahedra, corners with four equivalent V(4)O6 octahedra,  an edgeedge with one V(3)O5F octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. In the second V site, V(2) is bonded to one O(1), one O(10), one O(11), one O(2), one O(5), and one O(8) atom to form VO6 octahedra that share corners with four equivalent V(4)O6 octahedra, corners with four equivalent V(6)O6 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(3)O5F octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 44-52°. In the third V site, V(3) is bonded to one O(11), one O(2), one O(3), one O(6), one O(9), and one F(1) atom to form VO5F octahedra that share corners with four equivalent V(5)O5F octahedra, corners with four equivalent V(6)O6 octahedra, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one V(1)O5F octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(4), one O(5), one O(7), and one O(8) atom to form VO6 octahedra that share corners with four equivalent V(1)O5F octahedra, corners with four equivalent V(2)O6 octahedra, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one V(5)O5F octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. In the fifth V site, V(5) is bonded to one O(3), one O(4), one O(6), one O(7), one O(9), and one F(1) atom to form distorted VO5F octahedra that share corners with four equivalent V(1)O5F octahedra, corners with four equivalent V(3)O5F octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the sixth V site, V(6) is bonded to one O(11), one O(2), one O(5), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share corners with four equivalent V(3)O5F octahedra, corners with four equivalent V(2)O6 octahedra,  an edgeedge with one V(5)O5F octahedra,  an edgeedge with one V(4)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 44-52°. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one V(3), and one V(6) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one V(4), and one V(6) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(3), one V(5), and one V(6) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one V(4), and one V(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(3), one V(5), and one V(6) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one V(2), one V(3), and one V(6) atom. F(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one V(5) atom.
LiV6O11F crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(3)O5F octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-70°. The Li(1)-O(11) bond length is 1.85 Å. The Li(1)-O(2) bond length is 1.83 Å. The Li(1)-O(5) bond length is 1.81 Å. The Li(1)-O(8) bond length is 1.85 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(3), one O(4), one O(7), and one F(1) atom to form VO5F octahedra that share corners with four equivalent V(5)O5F octahedra, corners with four equivalent V(4)O6 octahedra,  an edgeedge with one V(3)O5F octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. The V(1)-O(1) bond length is 1.77 Å. The V(1)-O(10) bond length is 1.98 Å. The V(1)-O(3) bond length is 1.98 Å. The V(1)-O(4) bond length is 2.00 Å. The V(1)-O(7) bond length is 2.00 Å. The V(1)-F(1) bond length is 2.12 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(11), one O(2), one O(5), and one O(8) atom to form VO6 octahedra that share corners with four equivalent V(4)O6 octahedra, corners with four equivalent V(6)O6 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(3)O5F octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 44-52°. The V(2)-O(1) bond length is 2.08 Å. The V(2)-O(10) bond length is 2.02 Å. The V(2)-O(11) bond length is 2.08 Å. The V(2)-O(2) bond length is 2.02 Å. The V(2)-O(5) bond length is 2.00 Å. The V(2)-O(8) bond length is 2.00 Å. In the third V site, V(3) is bonded to one O(11), one O(2), one O(3), one O(6), one O(9), and one F(1) atom to form VO5F octahedra that share corners with four equivalent V(5)O5F octahedra, corners with four equivalent V(6)O6 octahedra, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one V(1)O5F octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The V(3)-O(11) bond length is 2.09 Å. The V(3)-O(2) bond length is 1.98 Å. The V(3)-O(3) bond length is 2.05 Å. The V(3)-O(6) bond length is 2.01 Å. The V(3)-O(9) bond length is 2.01 Å. The V(3)-F(1) bond length is 2.09 Å. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(4), one O(5), one O(7), and one O(8) atom to form VO6 octahedra that share corners with four equivalent V(1)O5F octahedra, corners with four equivalent V(2)O6 octahedra, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one V(5)O5F octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. The V(4)-O(1) bond length is 2.17 Å. The V(4)-O(10) bond length is 1.85 Å. The V(4)-O(4) bond length is 1.95 Å. The V(4)-O(5) bond length is 1.98 Å. The V(4)-O(7) bond length is 1.95 Å. The V(4)-O(8) bond length is 1.99 Å. In the fifth V site, V(5) is bonded to one O(3), one O(4), one O(6), one O(7), one O(9), and one F(1) atom to form distorted VO5F octahedra that share corners with four equivalent V(1)O5F octahedra, corners with four equivalent V(3)O5F octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The V(5)-O(3) bond length is 1.79 Å. The V(5)-O(4) bond length is 1.97 Å. The V(5)-O(6) bond length is 1.97 Å. The V(5)-O(7) bond length is 1.97 Å. The V(5)-O(9) bond length is 1.97 Å. The V(5)-F(1) bond length is 2.33 Å. In the sixth V site, V(6) is bonded to one O(11), one O(2), one O(5), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share corners with four equivalent V(3)O5F octahedra, corners with four equivalent V(2)O6 octahedra,  an edgeedge with one V(5)O5F octahedra,  an edgeedge with one V(4)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 44-52°. The V(6)-O(11) bond length is 1.87 Å. The V(6)-O(2) bond length is 2.10 Å. The V(6)-O(5) bond length is 2.04 Å. The V(6)-O(6) bond length is 1.94 Å. The V(6)-O(8) bond length is 2.04 Å. The V(6)-O(9) bond length is 1.94 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one V(3), and one V(6) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one V(4), and one V(6) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(3), one V(5), and one V(6) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one V(4), and one V(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(3), one V(5), and one V(6) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one V(2), one V(3), and one V(6) atom. F(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one V(5) atom.