Li4V3OF11 crystallizes in the triclinic P-1 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(6), and one F(9) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra, and  an edgeedge with one V(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 56-67°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(7), one F(8), and two equivalent F(4) atoms. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(2), one F(4), and two equivalent F(7) atoms. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one F(10), one F(5), one F(6), one F(8), and one F(9) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(11), one F(2), one F(6), one F(7), and one F(8) atom to form VOF5 octahedra that share corners with four equivalent V(3)OF5 octahedra and  a cornercorner with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-42°. In the second V site, V(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(5) atoms to form VF6 octahedra that share corners with four equivalent V(4)F6 octahedra and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-37°. In the third V site, V(3) is bonded to one O(1), one F(10), one F(11), one F(2), one F(4), and one F(8) atom to form VOF5 octahedra that share corners with four equivalent V(1)OF5 octahedra and  a cornercorner with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-42°. In the fourth V site, V(4) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(9) atoms to form VF6 octahedra that share corners with four equivalent V(2)F6 octahedra and edges with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-37°. O(1) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one V(3) atom. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the second F site, F(2) is bonded in a T-shaped geometry to one Li(3), one V(1), and one V(3) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(2), and one V(4) atom. In the fourth F site, F(4) is bonded to one Li(3), two equivalent Li(2), and one V(3) atom to form distorted FLi3V trigonal pyramids that share corners with two equivalent F(11)Li2V2 trigonal pyramids, corners with four equivalent F(7)Li3V trigonal pyramids,  an edgeedge with one F(11)Li2V2 trigonal pyramid, and  an edgeedge with one F(4)Li3V trigonal pyramid. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one Li(4) and one V(2) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Li(1), one Li(4), and one V(1) atom. In the seventh F site, F(7) is bonded to one Li(2), two equivalent Li(3), and one V(1) atom to form distorted FLi3V trigonal pyramids that share corners with four equivalent F(11)Li2V2 trigonal pyramids, corners with four equivalent F(4)Li3V trigonal pyramids, and  an edgeedge with one F(7)Li3V trigonal pyramid. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one V(1), and one V(3) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(4), and one V(4) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one V(3) atom. In the eleventh F site, F(11) is bonded to one Li(2), one Li(3), one V(1), and one V(3) atom to form a mixture of distorted edge and corner-sharing FLi2V2 trigonal pyramids.
Li4V3OF11 crystallizes in the triclinic P-1 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(6), and one F(9) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra, and  an edgeedge with one V(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 56-67°. The Li(1)-F(10) bond length is 1.96 Å. The Li(1)-F(3) bond length is 1.98 Å. The Li(1)-F(6) bond length is 1.92 Å. The Li(1)-F(9) bond length is 2.07 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(7), one F(8), and two equivalent F(4) atoms. The Li(2)-O(1) bond length is 2.01 Å. The Li(2)-F(11) bond length is 2.37 Å. The Li(2)-F(7) bond length is 1.96 Å. The Li(2)-F(8) bond length is 2.33 Å. There is one shorter (1.95 Å) and one longer (2.32 Å) Li(2)-F(4) bond length. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(2), one F(4), and two equivalent F(7) atoms. The Li(3)-O(1) bond length is 2.49 Å. The Li(3)-F(11) bond length is 2.01 Å. The Li(3)-F(2) bond length is 2.17 Å. The Li(3)-F(4) bond length is 2.00 Å. There is one shorter (1.93 Å) and one longer (2.29 Å) Li(3)-F(7) bond length. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one F(10), one F(5), one F(6), one F(8), and one F(9) atom. The Li(4)-F(10) bond length is 2.08 Å. The Li(4)-F(5) bond length is 1.88 Å. The Li(4)-F(6) bond length is 2.42 Å. The Li(4)-F(8) bond length is 2.12 Å. The Li(4)-F(9) bond length is 1.94 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(11), one F(2), one F(6), one F(7), and one F(8) atom to form VOF5 octahedra that share corners with four equivalent V(3)OF5 octahedra and  a cornercorner with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-42°. The V(1)-O(1) bond length is 1.90 Å. The V(1)-F(11) bond length is 2.08 Å. The V(1)-F(2) bond length is 2.03 Å. The V(1)-F(6) bond length is 1.92 Å. The V(1)-F(7) bond length is 2.03 Å. The V(1)-F(8) bond length is 2.08 Å. In the second V site, V(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(5) atoms to form VF6 octahedra that share corners with four equivalent V(4)F6 octahedra and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-37°. Both V(2)-F(1) bond lengths are 1.97 Å. Both V(2)-F(3) bond lengths are 2.04 Å. Both V(2)-F(5) bond lengths are 1.90 Å. In the third V site, V(3) is bonded to one O(1), one F(10), one F(11), one F(2), one F(4), and one F(8) atom to form VOF5 octahedra that share corners with four equivalent V(1)OF5 octahedra and  a cornercorner with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-42°. The V(3)-O(1) bond length is 1.88 Å. The V(3)-F(10) bond length is 1.93 Å. The V(3)-F(11) bond length is 2.08 Å. The V(3)-F(2) bond length is 2.04 Å. The V(3)-F(4) bond length is 2.00 Å. The V(3)-F(8) bond length is 2.11 Å. In the fourth V site, V(4) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(9) atoms to form VF6 octahedra that share corners with four equivalent V(2)F6 octahedra and edges with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-37°. Both V(4)-F(1) bond lengths are 1.94 Å. Both V(4)-F(3) bond lengths are 2.04 Å. Both V(4)-F(9) bond lengths are 1.93 Å. O(1) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one V(3) atom. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the second F site, F(2) is bonded in a T-shaped geometry to one Li(3), one V(1), and one V(3) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(2), and one V(4) atom. In the fourth F site, F(4) is bonded to one Li(3), two equivalent Li(2), and one V(3) atom to form distorted FLi3V trigonal pyramids that share corners with two equivalent F(11)Li2V2 trigonal pyramids, corners with four equivalent F(7)Li3V trigonal pyramids,  an edgeedge with one F(11)Li2V2 trigonal pyramid, and  an edgeedge with one F(4)Li3V trigonal pyramid. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one Li(4) and one V(2) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Li(1), one Li(4), and one V(1) atom. In the seventh F site, F(7) is bonded to one Li(2), two equivalent Li(3), and one V(1) atom to form distorted FLi3V trigonal pyramids that share corners with four equivalent F(11)Li2V2 trigonal pyramids, corners with four equivalent F(4)Li3V trigonal pyramids, and  an edgeedge with one F(7)Li3V trigonal pyramid. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one V(1), and one V(3) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(4), and one V(4) atom. In the tenth F site, F(10) is bonded in a trigonal planar geometry to one Li(1), one Li(4), and one V(3) atom. In the eleventh F site, F(11) is bonded to one Li(2), one Li(3), one V(1), and one V(3) atom to form a mixture of distorted edge and corner-sharing FLi2V2 trigonal pyramids.