LiV6O11F crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(5) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O5F octahedra,  a cornercorner with one V(3)O5F octahedra, corners with two equivalent V(2)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-59°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(7), two equivalent O(4), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one V(3)O5F octahedra, and  an edgeedge with one V(2)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(2), one O(7), one O(8), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(3)O5F octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. In the third V site, V(3) is bonded to one O(2), one O(3), one O(8), two equivalent O(6), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one V(1)O5F octahedra, and  an edgeedge with one V(2)O6 octahedra. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(7), two equivalent O(4), and two equivalent O(5) atoms. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(3), two equivalent O(4), and two equivalent O(6) atoms. In the sixth V site, V(6) is bonded in a 5-coordinate geometry to one O(8), two equivalent O(5), and two equivalent O(6) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(1), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(1), one V(3), and one V(5) atom. In the fourth O site, O(4) is bonded in a 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 distorted rectangular see-saw-like 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 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 3-coordinate geometry to one V(1), one V(2), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one V(6) atom. F(1) is bonded in an L-shaped geometry to one V(1) and one V(3) atom.
LiV6O11F crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(5) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O5F octahedra,  a cornercorner with one V(3)O5F octahedra, corners with two equivalent V(2)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-59°. The Li(1)-O(1) bond length is 1.82 Å. The Li(1)-O(2) bond length is 1.87 Å. Both Li(1)-O(5) bond lengths are 1.96 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(7), two equivalent O(4), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one V(3)O5F octahedra, and  an edgeedge with one V(2)O6 octahedra. The V(1)-O(1) bond length is 1.85 Å. The V(1)-O(3) bond length is 2.10 Å. The V(1)-O(7) bond length is 2.14 Å. Both V(1)-O(4) bond lengths are 2.01 Å. The V(1)-F(1) bond length is 2.02 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(7), one O(8), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(3)O5F octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The V(2)-O(1) bond length is 1.92 Å. The V(2)-O(2) bond length is 2.07 Å. The V(2)-O(7) bond length is 2.05 Å. The V(2)-O(8) bond length is 2.03 Å. Both V(2)-O(5) bond lengths are 2.04 Å. In the third V site, V(3) is bonded to one O(2), one O(3), one O(8), two equivalent O(6), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one V(1)O5F octahedra, and  an edgeedge with one V(2)O6 octahedra. The V(3)-O(2) bond length is 1.73 Å. The V(3)-O(3) bond length is 2.02 Å. The V(3)-O(8) bond length is 2.08 Å. Both V(3)-O(6) bond lengths are 2.01 Å. The V(3)-F(1) bond length is 1.99 Å. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(7), two equivalent O(4), and two equivalent O(5) atoms. The V(4)-O(7) bond length is 1.76 Å. Both V(4)-O(4) bond lengths are 1.94 Å. Both V(4)-O(5) bond lengths are 2.03 Å. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(3), two equivalent O(4), and two equivalent O(6) atoms. The V(5)-O(3) bond length is 1.79 Å. Both V(5)-O(4) bond lengths are 1.94 Å. Both V(5)-O(6) bond lengths are 1.97 Å. In the sixth V site, V(6) is bonded in a 5-coordinate geometry to one O(8), two equivalent O(5), and two equivalent O(6) atoms. The V(6)-O(8) bond length is 1.79 Å. Both V(6)-O(5) bond lengths are 2.00 Å. Both V(6)-O(6) bond lengths are 1.93 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(1), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(1), one V(3), and one V(5) atom. In the fourth O site, O(4) is bonded in a 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 distorted rectangular see-saw-like 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 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 3-coordinate geometry to one V(1), one V(2), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one V(6) atom. F(1) is bonded in an L-shaped geometry to one V(1) and one V(3) atom.