Li4V3OF11 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(10), one F(3), one F(4), one F(5), and one F(6) atom to form distorted LiF5 trigonal bipyramids that share  a cornercorner with one V(2)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra,  a cornercorner with one V(1)OF6 pentagonal bipyramid,  an edgeedge with one V(2)OF5 octahedra, and  an edgeedge with one V(1)OF6 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 46-53°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(10), one F(4), one F(6), one F(7), one F(8), and one F(9) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(1), one F(3), one F(5), one F(7), one F(8), and one F(9) atom. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one F(11), one F(5), one F(6), one F(8), and one F(9) atom. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(11), one F(3), one F(4), one F(6), and one F(9) atom to form distorted VOF6 pentagonal bipyramids that share  a cornercorner with one V(2)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid,  an edgeedge with one V(2)OF5 octahedra,  an edgeedge with one V(3)OF5 octahedra, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 39-46°. In the second V site, V(2) is bonded to one O(1), one F(2), one F(3), one F(4), one F(5), and one F(8) atom to form distorted VOF5 octahedra that share corners with two equivalent V(3)OF5 octahedra,  a cornercorner with one V(1)OF6 pentagonal bipyramid,  a cornercorner with one Li(1)F5 trigonal bipyramid,  an edgeedge with one V(1)OF6 pentagonal bipyramid, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 47-48°. In the third V site, V(3) is bonded to one O(1), one F(1), one F(10), one F(11), one F(2), and one F(7) atom to form VOF5 octahedra that share corners with two equivalent V(2)OF5 octahedra,  a cornercorner with one V(1)OF6 pentagonal bipyramid,  a cornercorner with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one V(1)OF6 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 47-48°. O(1) is bonded in a trigonal non-coplanar geometry to one V(1), one V(2), and one V(3) atom. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(3) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one V(2) and one V(3) atom. In the third F site, F(3) is bonded to one Li(1), one Li(3), one V(1), and one V(2) atom to form distorted FLi2V2 tetrahedra that share  a cornercorner with one F(4)Li2V2 tetrahedra,  a cornercorner with one F(5)Li3V tetrahedra, corners with two equivalent F(8)Li3V trigonal pyramids,  an edgeedge with one F(4)Li2V2 tetrahedra,  an edgeedge with one F(5)Li3V tetrahedra, and  an edgeedge with one F(9)Li3V tetrahedra. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one V(1), and one V(2) atom to form distorted FLi2V2 tetrahedra that share  a cornercorner with one F(3)Li2V2 tetrahedra, corners with two equivalent F(5)Li3V tetrahedra, corners with two equivalent F(9)Li3V tetrahedra,  an edgeedge with one F(3)Li2V2 tetrahedra, and  an edgeedge with one F(8)Li3V trigonal pyramid. In the fifth F site, F(5) is bonded to one Li(1), one Li(3), one Li(4), and one V(2) atom to form FLi3V tetrahedra that share  a cornercorner with one F(3)Li2V2 tetrahedra, corners with two equivalent F(4)Li2V2 tetrahedra, corners with two equivalent F(9)Li3V tetrahedra,  a cornercorner with one F(8)Li3V trigonal pyramid,  an edgeedge with one F(3)Li2V2 tetrahedra, and  an edgeedge with one F(8)Li3V trigonal pyramid. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one V(1) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one V(3) atom. In the eighth F site, F(8) is bonded to one Li(2), one Li(3), one Li(4), and one V(2) atom to form distorted FLi3V trigonal pyramids that share  a cornercorner with one F(5)Li3V tetrahedra,  a cornercorner with one F(9)Li3V tetrahedra, corners with two equivalent F(3)Li2V2 tetrahedra,  an edgeedge with one F(4)Li2V2 tetrahedra,  an edgeedge with one F(5)Li3V tetrahedra, and  an edgeedge with one F(9)Li3V tetrahedra. In the ninth F site, F(9) is bonded to one Li(2), one Li(3), one Li(4), and one V(1) atom to form FLi3V tetrahedra that share corners with two equivalent F(4)Li2V2 tetrahedra, corners with two equivalent F(5)Li3V tetrahedra,  a cornercorner with one F(8)Li3V trigonal pyramid,  an edgeedge with one F(3)Li2V2 tetrahedra, and  an edgeedge with one F(8)Li3V trigonal pyramid. In the tenth F site, F(10) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(3) atom. In the eleventh F site, F(11) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one V(3) atom.
Li4V3OF11 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(10), one F(3), one F(4), one F(5), and one F(6) atom to form distorted LiF5 trigonal bipyramids that share  a cornercorner with one V(2)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra,  a cornercorner with one V(1)OF6 pentagonal bipyramid,  an edgeedge with one V(2)OF5 octahedra, and  an edgeedge with one V(1)OF6 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 46-53°. The Li(1)-F(10) bond length is 1.96 Å. The Li(1)-F(3) bond length is 2.25 Å. The Li(1)-F(4) bond length is 1.97 Å. The Li(1)-F(5) bond length is 2.02 Å. The Li(1)-F(6) bond length is 1.98 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(10), one F(4), one F(6), one F(7), one F(8), and one F(9) atom. The Li(2)-F(10) bond length is 2.00 Å. The Li(2)-F(4) bond length is 2.21 Å. The Li(2)-F(6) bond length is 2.28 Å. The Li(2)-F(7) bond length is 1.95 Å. The Li(2)-F(8) bond length is 2.27 Å. The Li(2)-F(9) bond length is 2.04 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(1), one F(3), one F(5), one F(7), one F(8), and one F(9) atom. The Li(3)-F(1) bond length is 2.07 Å. The Li(3)-F(3) bond length is 2.41 Å. The Li(3)-F(5) bond length is 1.99 Å. The Li(3)-F(7) bond length is 2.09 Å. The Li(3)-F(8) bond length is 2.37 Å. The Li(3)-F(9) bond length is 2.05 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one F(11), one F(5), one F(6), one F(8), and one F(9) atom. The Li(4)-F(11) bond length is 2.28 Å. The Li(4)-F(5) bond length is 1.97 Å. The Li(4)-F(6) bond length is 2.04 Å. The Li(4)-F(8) bond length is 1.89 Å. The Li(4)-F(9) bond length is 2.05 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(11), one F(3), one F(4), one F(6), and one F(9) atom to form distorted VOF6 pentagonal bipyramids that share  a cornercorner with one V(2)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra,  a cornercorner with one Li(1)F5 trigonal bipyramid,  an edgeedge with one V(2)OF5 octahedra,  an edgeedge with one V(3)OF5 octahedra, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 39-46°. The V(1)-O(1) bond length is 2.01 Å. The V(1)-F(1) bond length is 2.15 Å. The V(1)-F(11) bond length is 2.03 Å. The V(1)-F(3) bond length is 2.08 Å. The V(1)-F(4) bond length is 2.20 Å. The V(1)-F(6) bond length is 1.99 Å. The V(1)-F(9) bond length is 2.07 Å. In the second V site, V(2) is bonded to one O(1), one F(2), one F(3), one F(4), one F(5), and one F(8) atom to form distorted VOF5 octahedra that share corners with two equivalent V(3)OF5 octahedra,  a cornercorner with one V(1)OF6 pentagonal bipyramid,  a cornercorner with one Li(1)F5 trigonal bipyramid,  an edgeedge with one V(1)OF6 pentagonal bipyramid, and  an edgeedge with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 47-48°. The V(2)-O(1) bond length is 1.92 Å. The V(2)-F(2) bond length is 2.00 Å. The V(2)-F(3) bond length is 2.05 Å. The V(2)-F(4) bond length is 2.08 Å. The V(2)-F(5) bond length is 2.07 Å. The V(2)-F(8) bond length is 1.94 Å. In the third V site, V(3) is bonded to one O(1), one F(1), one F(10), one F(11), one F(2), and one F(7) atom to form VOF5 octahedra that share corners with two equivalent V(2)OF5 octahedra,  a cornercorner with one V(1)OF6 pentagonal bipyramid,  a cornercorner with one Li(1)F5 trigonal bipyramid, and  an edgeedge with one V(1)OF6 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 47-48°. The V(3)-O(1) bond length is 1.93 Å. The V(3)-F(1) bond length is 2.05 Å. The V(3)-F(10) bond length is 1.94 Å. The V(3)-F(11) bond length is 2.03 Å. The V(3)-F(2) bond length is 2.01 Å. The V(3)-F(7) bond length is 1.96 Å. O(1) is bonded in a trigonal non-coplanar geometry to one V(1), one V(2), and one V(3) atom. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(3) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one V(2) and one V(3) atom. In the third F site, F(3) is bonded to one Li(1), one Li(3), one V(1), and one V(2) atom to form distorted FLi2V2 tetrahedra that share  a cornercorner with one F(4)Li2V2 tetrahedra,  a cornercorner with one F(5)Li3V tetrahedra, corners with two equivalent F(8)Li3V trigonal pyramids,  an edgeedge with one F(4)Li2V2 tetrahedra,  an edgeedge with one F(5)Li3V tetrahedra, and  an edgeedge with one F(9)Li3V tetrahedra. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one V(1), and one V(2) atom to form distorted FLi2V2 tetrahedra that share  a cornercorner with one F(3)Li2V2 tetrahedra, corners with two equivalent F(5)Li3V tetrahedra, corners with two equivalent F(9)Li3V tetrahedra,  an edgeedge with one F(3)Li2V2 tetrahedra, and  an edgeedge with one F(8)Li3V trigonal pyramid. In the fifth F site, F(5) is bonded to one Li(1), one Li(3), one Li(4), and one V(2) atom to form FLi3V tetrahedra that share  a cornercorner with one F(3)Li2V2 tetrahedra, corners with two equivalent F(4)Li2V2 tetrahedra, corners with two equivalent F(9)Li3V tetrahedra,  a cornercorner with one F(8)Li3V trigonal pyramid,  an edgeedge with one F(3)Li2V2 tetrahedra, and  an edgeedge with one F(8)Li3V trigonal pyramid. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one V(1) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one Li(2), one Li(3), and one V(3) atom. In the eighth F site, F(8) is bonded to one Li(2), one Li(3), one Li(4), and one V(2) atom to form distorted FLi3V trigonal pyramids that share  a cornercorner with one F(5)Li3V tetrahedra,  a cornercorner with one F(9)Li3V tetrahedra, corners with two equivalent F(3)Li2V2 tetrahedra,  an edgeedge with one F(4)Li2V2 tetrahedra,  an edgeedge with one F(5)Li3V tetrahedra, and  an edgeedge with one F(9)Li3V tetrahedra. In the ninth F site, F(9) is bonded to one Li(2), one Li(3), one Li(4), and one V(1) atom to form FLi3V tetrahedra that share corners with two equivalent F(4)Li2V2 tetrahedra, corners with two equivalent F(5)Li3V tetrahedra,  a cornercorner with one F(8)Li3V trigonal pyramid,  an edgeedge with one F(3)Li2V2 tetrahedra, and  an edgeedge with one F(8)Li3V trigonal pyramid. In the tenth F site, F(10) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(3) atom. In the eleventh F site, F(11) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one V(3) atom.