Li4V3OF11 crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(12), one F(17), one F(18), and one F(4) atom. In the second Li site, Li(2) is bonded to one F(16), one F(21), one F(3), and one F(7) atom to form LiF4 tetrahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, corners with two equivalent Li(5)F4 tetrahedra, and  an edgeedge with one V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-66°. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one F(10), one F(18), one F(2), one F(4), and one F(8) atom. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(12), one F(4), and one F(8) atom. In the fifth Li site, Li(5) is bonded to one F(14), one F(20), one F(3), and one F(7) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-67°. In the sixth Li site, Li(6) is bonded to one F(13), one F(15), one F(19), and one F(6) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(2)O2F4 octahedra,  a cornercorner with one V(4)O2F4 octahedra, corners with three equivalent Li(8)OF4 trigonal bipyramids, and  an edgeedge with one V(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 57-71°. In the seventh Li site, Li(7) is bonded in a 4-coordinate geometry to one F(1), one F(10), one F(14), one F(17), one F(18), and one F(8) atom. In the eighth Li site, Li(8) is bonded to one O(2), one F(15), one F(19), one F(5), and one F(6) atom to form distorted LiOF4 trigonal bipyramids that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(5)F6 octahedra, corners with three equivalent Li(6)F4 trigonal pyramids,  an edgeedge with one V(2)O2F4 octahedra, and  an edgeedge with one V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(10), one F(14), one F(2), one F(3), and one F(8) atom to form VF6 octahedra that share corners with four equivalent V(6)F6 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  an edgeedge with one Li(5)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-53°. In the second V site, V(2) is bonded to one O(1), one O(2), one F(11), one F(12), one F(19), and one F(4) atom to form VO2F4 octahedra that share corners with four equivalent V(4)O2F4 octahedra,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one Li(8)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-42°. In the third V site, V(3) is bonded to one F(13), one F(21), one F(22), one F(5), one F(7), and one F(9) atom to form VF6 octahedra that share corners with four equivalent V(5)F6 octahedra,  a cornercorner with one Li(5)F4 tetrahedra,  a cornercorner with one Li(8)OF4 trigonal bipyramid,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-40°. In the fourth V site, V(4) is bonded to one O(1), one O(2), one F(11), one F(12), one F(17), and one F(6) atom to form VO2F4 octahedra that share corners with four equivalent V(2)O2F4 octahedra,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one Li(8)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-42°. In the fifth V site, V(5) is bonded to one F(13), one F(15), one F(20), one F(21), one F(22), and one F(9) atom to form VF6 octahedra that share corners with four equivalent V(3)F6 octahedra,  a cornercorner with one Li(2)F4 tetrahedra,  a cornercorner with one Li(5)F4 tetrahedra,  a cornercorner with one Li(8)OF4 trigonal bipyramid, and  an edgeedge with one Li(6)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 36-40°. In the sixth V site, V(6) is bonded to one F(1), one F(10), one F(14), one F(16), one F(18), and one F(2) atom to form VF6 octahedra that share corners with four equivalent V(1)F6 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  a cornercorner with one Li(5)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-53°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one V(2), and one V(4) atom to form distorted OLi2V2 tetrahedra that share  a cornercorner with one F(18)Li3V tetrahedra,  a cornercorner with one F(4)Li3V trigonal pyramid,  an edgeedge with one F(4)Li3V trigonal pyramid, and edges with two equivalent F(12)Li2V2 trigonal pyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Li(8), one V(2), and one V(4) atom. There are twenty-two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(7), one V(1), and one V(6) 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(6) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(5), and one V(1) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(3), one Li(4), and one V(2) atom to form distorted FLi3V trigonal pyramids that share  a cornercorner with one O(1)Li2V2 tetrahedra, corners with three equivalent F(12)Li2V2 trigonal pyramids,  an edgeedge with one O(1)Li2V2 tetrahedra, and  an edgeedge with one F(18)Li3V tetrahedra. In the fifth F site, F(5) is bonded in a distorted bent 120 degrees geometry to one Li(8) and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(6), one Li(8), and one V(4) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(5), and one V(3) atom. In the eighth F site, F(8) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(4), one Li(7), and one V(1) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the tenth F site, F(10) is bonded in a 4-coordinate geometry to one Li(3), one Li(7), one V(1), and one V(6) atom. In the eleventh F site, F(11) is bonded in a T-shaped geometry to one Li(1), one V(2), and one V(4) atom. In the twelfth F site, F(12) is bonded to one Li(1), one Li(4), one V(2), and one V(4) atom to form distorted FLi2V2 trigonal pyramids that share  a cornercorner with one F(18)Li3V tetrahedra, corners with three equivalent F(4)Li3V trigonal pyramids, and edges with two equivalent O(1)Li2V2 tetrahedra. In the thirteenth F site, F(13) is bonded in a distorted trigonal non-coplanar geometry to one Li(6), one V(3), and one V(5) atom. In the fourteenth F site, F(14) is bonded in a 4-coordinate geometry to one Li(5), one Li(7), one V(1), and one V(6) atom. In the fifteenth F site, F(15) is bonded in a trigonal planar geometry to one Li(6), one Li(8), and one V(5) atom. In the sixteenth F site, F(16) is bonded in a bent 120 degrees geometry to one Li(2) and one V(6) atom. In the seventeenth F site, F(17) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(7), and one V(4) atom. In the eighteenth F site, F(18) is bonded to one Li(1), one Li(3), one Li(7), and one V(6) atom to form distorted FLi3V tetrahedra that share  a cornercorner with one O(1)Li2V2 tetrahedra,  a cornercorner with one F(12)Li2V2 trigonal pyramid, and  an edgeedge with one F(4)Li3V trigonal pyramid. In the nineteenth F site, F(19) is bonded in a distorted trigonal planar geometry to one Li(6), one Li(8), and one V(2) atom. In the twentieth F site, F(20) is bonded in a bent 120 degrees geometry to one Li(5) and one V(5) atom. In the twenty-first F site, F(21) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(3), and one V(5) atom. In the twenty-second F site, F(22) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom.
Li4V3OF11 crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(12), one F(17), one F(18), and one F(4) atom. The Li(1)-O(1) bond length is 2.33 Å. The Li(1)-F(11) bond length is 2.34 Å. The Li(1)-F(12) bond length is 2.08 Å. The Li(1)-F(17) bond length is 1.96 Å. The Li(1)-F(18) bond length is 1.95 Å. The Li(1)-F(4) bond length is 2.16 Å. In the second Li site, Li(2) is bonded to one F(16), one F(21), one F(3), and one F(7) atom to form LiF4 tetrahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, corners with two equivalent Li(5)F4 tetrahedra, and  an edgeedge with one V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-66°. The Li(2)-F(16) bond length is 1.90 Å. The Li(2)-F(21) bond length is 1.99 Å. The Li(2)-F(3) bond length is 1.85 Å. The Li(2)-F(7) bond length is 2.03 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one F(10), one F(18), one F(2), one F(4), and one F(8) atom. The Li(3)-F(10) bond length is 2.00 Å. The Li(3)-F(18) bond length is 2.32 Å. The Li(3)-F(2) bond length is 2.10 Å. The Li(3)-F(4) bond length is 1.91 Å. The Li(3)-F(8) bond length is 1.92 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one F(12), one F(4), and one F(8) atom. The Li(4)-O(1) bond length is 2.05 Å. The Li(4)-O(2) bond length is 2.35 Å. The Li(4)-F(12) bond length is 2.38 Å. The Li(4)-F(4) bond length is 1.97 Å. The Li(4)-F(8) bond length is 1.92 Å. In the fifth Li site, Li(5) is bonded to one F(14), one F(20), one F(3), and one F(7) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-67°. The Li(5)-F(14) bond length is 2.14 Å. The Li(5)-F(20) bond length is 1.89 Å. The Li(5)-F(3) bond length is 1.91 Å. The Li(5)-F(7) bond length is 1.94 Å. In the sixth Li site, Li(6) is bonded to one F(13), one F(15), one F(19), and one F(6) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(2)O2F4 octahedra,  a cornercorner with one V(4)O2F4 octahedra, corners with three equivalent Li(8)OF4 trigonal bipyramids, and  an edgeedge with one V(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 57-71°. The Li(6)-F(13) bond length is 1.98 Å. The Li(6)-F(15) bond length is 2.04 Å. The Li(6)-F(19) bond length is 1.92 Å. The Li(6)-F(6) bond length is 1.93 Å. In the seventh Li site, Li(7) is bonded in a 4-coordinate geometry to one F(1), one F(10), one F(14), one F(17), one F(18), and one F(8) atom. The Li(7)-F(1) bond length is 2.01 Å. The Li(7)-F(10) bond length is 2.47 Å. The Li(7)-F(14) bond length is 2.49 Å. The Li(7)-F(17) bond length is 1.89 Å. The Li(7)-F(18) bond length is 1.93 Å. The Li(7)-F(8) bond length is 2.02 Å. In the eighth Li site, Li(8) is bonded to one O(2), one F(15), one F(19), one F(5), and one F(6) atom to form distorted LiOF4 trigonal bipyramids that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(5)F6 octahedra, corners with three equivalent Li(6)F4 trigonal pyramids,  an edgeedge with one V(2)O2F4 octahedra, and  an edgeedge with one V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. The Li(8)-O(2) bond length is 2.19 Å. The Li(8)-F(15) bond length is 1.92 Å. The Li(8)-F(19) bond length is 2.18 Å. The Li(8)-F(5) bond length is 1.89 Å. The Li(8)-F(6) bond length is 2.23 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(10), one F(14), one F(2), one F(3), and one F(8) atom to form VF6 octahedra that share corners with four equivalent V(6)F6 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  an edgeedge with one Li(5)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-53°. The V(1)-F(1) bond length is 2.09 Å. The V(1)-F(10) bond length is 2.18 Å. The V(1)-F(14) bond length is 2.09 Å. The V(1)-F(2) bond length is 2.12 Å. The V(1)-F(3) bond length is 2.04 Å. The V(1)-F(8) bond length is 2.13 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one F(11), one F(12), one F(19), and one F(4) atom to form VO2F4 octahedra that share corners with four equivalent V(4)O2F4 octahedra,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one Li(8)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-42°. The V(2)-O(1) bond length is 1.87 Å. The V(2)-O(2) bond length is 1.80 Å. The V(2)-F(11) bond length is 1.98 Å. The V(2)-F(12) bond length is 2.07 Å. The V(2)-F(19) bond length is 1.91 Å. The V(2)-F(4) bond length is 2.06 Å. In the third V site, V(3) is bonded to one F(13), one F(21), one F(22), one F(5), one F(7), and one F(9) atom to form VF6 octahedra that share corners with four equivalent V(5)F6 octahedra,  a cornercorner with one Li(5)F4 tetrahedra,  a cornercorner with one Li(8)OF4 trigonal bipyramid,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-40°. The V(3)-F(13) bond length is 2.05 Å. The V(3)-F(21) bond length is 2.06 Å. The V(3)-F(22) bond length is 1.96 Å. The V(3)-F(5) bond length is 1.90 Å. The V(3)-F(7) bond length is 1.95 Å. The V(3)-F(9) bond length is 1.96 Å. In the fourth V site, V(4) is bonded to one O(1), one O(2), one F(11), one F(12), one F(17), and one F(6) atom to form VO2F4 octahedra that share corners with four equivalent V(2)O2F4 octahedra,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one Li(8)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-42°. The V(4)-O(1) bond length is 1.98 Å. The V(4)-O(2) bond length is 2.04 Å. The V(4)-F(11) bond length is 2.04 Å. The V(4)-F(12) bond length is 2.08 Å. The V(4)-F(17) bond length is 2.00 Å. The V(4)-F(6) bond length is 1.92 Å. In the fifth V site, V(5) is bonded to one F(13), one F(15), one F(20), one F(21), one F(22), and one F(9) atom to form VF6 octahedra that share corners with four equivalent V(3)F6 octahedra,  a cornercorner with one Li(2)F4 tetrahedra,  a cornercorner with one Li(5)F4 tetrahedra,  a cornercorner with one Li(8)OF4 trigonal bipyramid, and  an edgeedge with one Li(6)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 36-40°. The V(5)-F(13) bond length is 2.05 Å. The V(5)-F(15) bond length is 1.95 Å. The V(5)-F(20) bond length is 1.90 Å. The V(5)-F(21) bond length is 2.04 Å. The V(5)-F(22) bond length is 1.96 Å. The V(5)-F(9) bond length is 1.97 Å. In the sixth V site, V(6) is bonded to one F(1), one F(10), one F(14), one F(16), one F(18), and one F(2) atom to form VF6 octahedra that share corners with four equivalent V(1)F6 octahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  a cornercorner with one Li(5)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-53°. The V(6)-F(1) bond length is 2.01 Å. The V(6)-F(10) bond length is 2.00 Å. The V(6)-F(14) bond length is 2.00 Å. The V(6)-F(16) bond length is 1.89 Å. The V(6)-F(18) bond length is 2.03 Å. The V(6)-F(2) bond length is 1.98 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one V(2), and one V(4) atom to form distorted OLi2V2 tetrahedra that share  a cornercorner with one F(18)Li3V tetrahedra,  a cornercorner with one F(4)Li3V trigonal pyramid,  an edgeedge with one F(4)Li3V trigonal pyramid, and edges with two equivalent F(12)Li2V2 trigonal pyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Li(8), one V(2), and one V(4) atom. There are twenty-two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(7), one V(1), and one V(6) 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(6) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(5), and one V(1) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(3), one Li(4), and one V(2) atom to form distorted FLi3V trigonal pyramids that share  a cornercorner with one O(1)Li2V2 tetrahedra, corners with three equivalent F(12)Li2V2 trigonal pyramids,  an edgeedge with one O(1)Li2V2 tetrahedra, and  an edgeedge with one F(18)Li3V tetrahedra. In the fifth F site, F(5) is bonded in a distorted bent 120 degrees geometry to one Li(8) and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(6), one Li(8), and one V(4) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(5), and one V(3) atom. In the eighth F site, F(8) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(4), one Li(7), and one V(1) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the tenth F site, F(10) is bonded in a 4-coordinate geometry to one Li(3), one Li(7), one V(1), and one V(6) atom. In the eleventh F site, F(11) is bonded in a T-shaped geometry to one Li(1), one V(2), and one V(4) atom. In the twelfth F site, F(12) is bonded to one Li(1), one Li(4), one V(2), and one V(4) atom to form distorted FLi2V2 trigonal pyramids that share  a cornercorner with one F(18)Li3V tetrahedra, corners with three equivalent F(4)Li3V trigonal pyramids, and edges with two equivalent O(1)Li2V2 tetrahedra. In the thirteenth F site, F(13) is bonded in a distorted trigonal non-coplanar geometry to one Li(6), one V(3), and one V(5) atom. In the fourteenth F site, F(14) is bonded in a 4-coordinate geometry to one Li(5), one Li(7), one V(1), and one V(6) atom. In the fifteenth F site, F(15) is bonded in a trigonal planar geometry to one Li(6), one Li(8), and one V(5) atom. In the sixteenth F site, F(16) is bonded in a bent 120 degrees geometry to one Li(2) and one V(6) atom. In the seventeenth F site, F(17) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(7), and one V(4) atom. In the eighteenth F site, F(18) is bonded to one Li(1), one Li(3), one Li(7), and one V(6) atom to form distorted FLi3V tetrahedra that share  a cornercorner with one O(1)Li2V2 tetrahedra,  a cornercorner with one F(12)Li2V2 trigonal pyramid, and  an edgeedge with one F(4)Li3V trigonal pyramid. In the nineteenth F site, F(19) is bonded in a distorted trigonal planar geometry to one Li(6), one Li(8), and one V(2) atom. In the twentieth F site, F(20) is bonded in a bent 120 degrees geometry to one Li(5) and one V(5) atom. In the twenty-first F site, F(21) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(3), and one V(5) atom. In the twenty-second F site, F(22) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom.