Li3V4(OF3)3 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one F(15), one F(4), one F(6), and one F(9) atom. In the second Li site, Li(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one F(16) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(5), one O(6), one F(11), one F(14), one F(2), and one F(5) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(2), one O(4), one F(10), one F(13), one F(17), and one F(8) atom. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(5), one O(6), one F(2), one F(4), one F(5), and one F(6) atom. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(1), one F(1), one F(12), one F(18), one F(3), and one F(7) atom. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(10), one F(16), one F(18), one F(3), and one F(7) atom to form VOF5 octahedra that share corners with three equivalent V(2)O2F4 octahedra and corners with three equivalent V(8)OF5 octahedra. The corner-sharing octahedral tilt angles range from 35-47°. In the second V site, V(2) is bonded to one O(1), one O(3), one F(1), one F(12), one F(3), and one F(7) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 30-45°. In the third V site, V(3) is bonded to one O(2), one O(4), one F(11), one F(13), one F(17), and one F(8) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 35-45°. In the fourth V site, V(4) is bonded to one O(3), one F(1), one F(12), one F(15), one F(6), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 30-45°. In the fifth V site, V(5) is bonded to one O(2), one F(11), one F(14), one F(2), one F(5), and one F(8) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 36-43°. In the sixth V site, V(6) is bonded to one O(5), one O(6), one F(15), one F(4), one F(6), and one F(9) atom to form VO2F4 octahedra that share corners with three equivalent V(7)O2F4 octahedra and corners with three equivalent V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 35-43°. In the seventh V site, V(7) is bonded to one O(5), one O(6), one F(14), one F(2), one F(4), and one F(5) atom to form VO2F4 octahedra that share corners with three equivalent V(6)O2F4 octahedra and corners with three equivalent V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-43°. In the eighth V site, V(8) is bonded to one O(4), one F(10), one F(13), one F(16), one F(17), and one F(18) atom to form VOF5 octahedra that share corners with three equivalent V(3)O2F4 octahedra and corners with three equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 35-47°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(6), one V(1), and one V(2) atom to form distorted corner-sharing OLi2V2 tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(4), one V(3), and one V(5) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(4) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(4), one V(3), and one V(8) atom to form distorted corner-sharing OLi2V2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(3), one Li(5), one V(6), and one V(7) atom to form OLi2V2 trigonal pyramids that share  a cornercorner with one F(2)Li2V2 trigonal pyramid and  an edgeedge with one F(2)Li2V2 trigonal pyramid. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one V(6), and one V(7) atom. There are eighteen inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(6), one V(2), and one V(4) atom. In the second F site, F(2) is bonded to one Li(3), one Li(5), one V(5), and one V(7) atom to form FLi2V2 trigonal pyramids that share  a cornercorner with one O(5)Li2V2 trigonal pyramid and  an edgeedge with one O(5)Li2V2 trigonal pyramid. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(6), one V(1), and one V(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one V(6), and one V(7) atom. In the fifth F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one V(5), and one V(7) atom. In the sixth F site, F(6) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(5), one V(4), and one V(6) atom. In the seventh F site, F(7) is bonded in a T-shaped geometry to one Li(6), one V(1), and one V(2) atom. In the eighth F site, F(8) is bonded in a T-shaped geometry to one Li(4), one V(3), and one V(5) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Li(1), one V(4), and one V(6) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one V(8) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(5) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(6), one V(2), and one V(4) atom. In the thirteenth F site, F(13) is bonded in a T-shaped geometry to one Li(4), one V(3), and one V(8) atom. In the fourteenth F site, F(14) is bonded in a distorted T-shaped geometry to one Li(3), one V(5), and one V(7) atom. In the fifteenth F site, F(15) is bonded in a T-shaped geometry to one Li(1), one V(4), and one V(6) atom. In the sixteenth F site, F(16) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(8) atom. In the seventeenth F site, F(17) is bonded in a distorted trigonal planar geometry to one Li(4), one V(3), and one V(8) atom. In the eighteenth F site, F(18) is bonded in a distorted trigonal planar geometry to one Li(6), one V(1), and one V(8) atom.
Li3V4(OF3)3 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one F(15), one F(4), one F(6), and one F(9) atom. The Li(1)-O(3) bond length is 1.99 Å. The Li(1)-F(15) bond length is 2.17 Å. The Li(1)-F(4) bond length is 1.97 Å. The Li(1)-F(6) bond length is 2.28 Å. The Li(1)-F(9) bond length is 1.98 Å. In the second Li site, Li(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one F(16) atom. The Li(2)-O(1) bond length is 1.93 Å. The Li(2)-O(4) bond length is 1.92 Å. The Li(2)-F(16) bond length is 1.94 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(5), one O(6), one F(11), one F(14), one F(2), and one F(5) atom. The Li(3)-O(5) bond length is 1.96 Å. The Li(3)-O(6) bond length is 2.29 Å. The Li(3)-F(11) bond length is 1.99 Å. The Li(3)-F(14) bond length is 2.47 Å. The Li(3)-F(2) bond length is 1.96 Å. The Li(3)-F(5) bond length is 2.41 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(2), one O(4), one F(10), one F(13), one F(17), and one F(8) atom. The Li(4)-O(2) bond length is 1.96 Å. The Li(4)-O(4) bond length is 2.41 Å. The Li(4)-F(10) bond length is 2.03 Å. The Li(4)-F(13) bond length is 2.25 Å. The Li(4)-F(17) bond length is 2.02 Å. The Li(4)-F(8) bond length is 2.23 Å. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(5), one O(6), one F(2), one F(4), one F(5), and one F(6) atom. The Li(5)-O(5) bond length is 2.35 Å. The Li(5)-O(6) bond length is 1.96 Å. The Li(5)-F(2) bond length is 2.33 Å. The Li(5)-F(4) bond length is 2.51 Å. The Li(5)-F(5) bond length is 1.99 Å. The Li(5)-F(6) bond length is 1.98 Å. In the sixth Li site, Li(6) is bonded in a 6-coordinate geometry to one O(1), one F(1), one F(12), one F(18), one F(3), and one F(7) atom. The Li(6)-O(1) bond length is 2.23 Å. The Li(6)-F(1) bond length is 2.32 Å. The Li(6)-F(12) bond length is 1.95 Å. The Li(6)-F(18) bond length is 2.01 Å. The Li(6)-F(3) bond length is 2.04 Å. The Li(6)-F(7) bond length is 2.11 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(10), one F(16), one F(18), one F(3), and one F(7) atom to form VOF5 octahedra that share corners with three equivalent V(2)O2F4 octahedra and corners with three equivalent V(8)OF5 octahedra. The corner-sharing octahedral tilt angles range from 35-47°. The V(1)-O(1) bond length is 1.85 Å. The V(1)-F(10) bond length is 2.09 Å. The V(1)-F(16) bond length is 2.05 Å. The V(1)-F(18) bond length is 2.09 Å. The V(1)-F(3) bond length is 2.03 Å. The V(1)-F(7) bond length is 2.03 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one F(1), one F(12), one F(3), and one F(7) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 30-45°. The V(2)-O(1) bond length is 2.00 Å. The V(2)-O(3) bond length is 1.89 Å. The V(2)-F(1) bond length is 2.03 Å. The V(2)-F(12) bond length is 2.03 Å. The V(2)-F(3) bond length is 2.11 Å. The V(2)-F(7) bond length is 2.04 Å. In the third V site, V(3) is bonded to one O(2), one O(4), one F(11), one F(13), one F(17), and one F(8) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 35-45°. The V(3)-O(2) bond length is 1.86 Å. The V(3)-O(4) bond length is 1.97 Å. The V(3)-F(11) bond length is 2.09 Å. The V(3)-F(13) bond length is 2.08 Å. The V(3)-F(17) bond length is 2.12 Å. The V(3)-F(8) bond length is 2.04 Å. In the fourth V site, V(4) is bonded to one O(3), one F(1), one F(12), one F(15), one F(6), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 30-45°. The V(4)-O(3) bond length is 1.84 Å. The V(4)-F(1) bond length is 2.00 Å. The V(4)-F(12) bond length is 2.08 Å. The V(4)-F(15) bond length is 2.05 Å. The V(4)-F(6) bond length is 2.07 Å. The V(4)-F(9) bond length is 2.03 Å. In the fifth V site, V(5) is bonded to one O(2), one F(11), one F(14), one F(2), one F(5), and one F(8) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 36-43°. The V(5)-O(2) bond length is 1.85 Å. The V(5)-F(11) bond length is 2.06 Å. The V(5)-F(14) bond length is 2.00 Å. The V(5)-F(2) bond length is 2.09 Å. The V(5)-F(5) bond length is 2.10 Å. The V(5)-F(8) bond length is 2.01 Å. In the sixth V site, V(6) is bonded to one O(5), one O(6), one F(15), one F(4), one F(6), and one F(9) atom to form VO2F4 octahedra that share corners with three equivalent V(7)O2F4 octahedra and corners with three equivalent V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 35-43°. The V(6)-O(5) bond length is 1.91 Å. The V(6)-O(6) bond length is 1.91 Å. The V(6)-F(15) bond length is 2.06 Å. The V(6)-F(4) bond length is 2.09 Å. The V(6)-F(6) bond length is 2.08 Å. The V(6)-F(9) bond length is 2.12 Å. In the seventh V site, V(7) is bonded to one O(5), one O(6), one F(14), one F(2), one F(4), and one F(5) atom to form VO2F4 octahedra that share corners with three equivalent V(6)O2F4 octahedra and corners with three equivalent V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-43°. The V(7)-O(5) bond length is 1.88 Å. The V(7)-O(6) bond length is 1.93 Å. The V(7)-F(14) bond length is 2.03 Å. The V(7)-F(2) bond length is 2.13 Å. The V(7)-F(4) bond length is 2.10 Å. The V(7)-F(5) bond length is 2.12 Å. In the eighth V site, V(8) is bonded to one O(4), one F(10), one F(13), one F(16), one F(17), and one F(18) atom to form VOF5 octahedra that share corners with three equivalent V(3)O2F4 octahedra and corners with three equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 35-47°. The V(8)-O(4) bond length is 1.85 Å. The V(8)-F(10) bond length is 2.11 Å. The V(8)-F(13) bond length is 1.99 Å. The V(8)-F(16) bond length is 2.07 Å. The V(8)-F(17) bond length is 2.01 Å. The V(8)-F(18) bond length is 2.09 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(6), one V(1), and one V(2) atom to form distorted corner-sharing OLi2V2 tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(4), one V(3), and one V(5) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(4) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(4), one V(3), and one V(8) atom to form distorted corner-sharing OLi2V2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(3), one Li(5), one V(6), and one V(7) atom to form OLi2V2 trigonal pyramids that share  a cornercorner with one F(2)Li2V2 trigonal pyramid and  an edgeedge with one F(2)Li2V2 trigonal pyramid. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one V(6), and one V(7) atom. There are eighteen inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(6), one V(2), and one V(4) atom. In the second F site, F(2) is bonded to one Li(3), one Li(5), one V(5), and one V(7) atom to form FLi2V2 trigonal pyramids that share  a cornercorner with one O(5)Li2V2 trigonal pyramid and  an edgeedge with one O(5)Li2V2 trigonal pyramid. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(6), one V(1), and one V(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one V(6), and one V(7) atom. In the fifth F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(5), one V(5), and one V(7) atom. In the sixth F site, F(6) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(5), one V(4), and one V(6) atom. In the seventh F site, F(7) is bonded in a T-shaped geometry to one Li(6), one V(1), and one V(2) atom. In the eighth F site, F(8) is bonded in a T-shaped geometry to one Li(4), one V(3), and one V(5) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Li(1), one V(4), and one V(6) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one V(8) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal planar geometry to one Li(3), one V(3), and one V(5) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(6), one V(2), and one V(4) atom. In the thirteenth F site, F(13) is bonded in a T-shaped geometry to one Li(4), one V(3), and one V(8) atom. In the fourteenth F site, F(14) is bonded in a distorted T-shaped geometry to one Li(3), one V(5), and one V(7) atom. In the fifteenth F site, F(15) is bonded in a T-shaped geometry to one Li(1), one V(4), and one V(6) atom. In the sixteenth F site, F(16) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(8) atom. In the seventeenth F site, F(17) is bonded in a distorted trigonal planar geometry to one Li(4), one V(3), and one V(8) atom. In the eighteenth F site, F(18) is bonded in a distorted trigonal planar geometry to one Li(6), one V(1), and one V(8) atom.