Li3V4(OF3)3 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one F(6) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one F(1), one F(3), one F(4), and one F(7) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(3), one F(1), one F(2), one F(4), one F(5), and one F(9) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(2), one F(3), one F(5), one F(6), and one F(8) atom to form VOF5 octahedra that share corners with three equivalent V(2)O2F4 octahedra and corners with three equivalent V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 34-47°. In the second V site, V(2) is bonded to one O(2), one O(3), one F(1), one F(2), one F(5), and one F(9) atom to form VO2F4 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 34-42°. In the third V site, V(3) is bonded to one O(1), one O(3), one F(1), one F(4), one F(7), and one F(9) atom to form VO2F4 octahedra that share corners with three equivalent V(2)O2F4 octahedra and corners with three equivalent V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 35-42°. In the fourth V site, V(4) is bonded to one O(1), one F(3), one F(4), one F(6), one F(7), and one F(8) 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 three inequivalent O sites. In the first O site, O(1) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one V(3), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(2), and one V(3) atom. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(2), and one V(3) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(4) atom. In the fourth F site, F(4) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(3), and one V(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(1), one V(1), 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 V(3), and one V(4) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the ninth F site, F(9) is bonded in a T-shaped geometry to one Li(3), one V(2), and one V(3) atom.
Li3V4(OF3)3 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one F(6) atom. The Li(1)-O(1) bond length is 1.96 Å. The Li(1)-O(2) bond length is 1.92 Å. The Li(1)-F(6) bond length is 1.93 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one F(1), one F(3), one F(4), and one F(7) atom. The Li(2)-O(1) bond length is 2.34 Å. The Li(2)-O(3) bond length is 1.99 Å. The Li(2)-F(1) bond length is 2.25 Å. The Li(2)-F(3) bond length is 2.05 Å. The Li(2)-F(4) bond length is 2.25 Å. The Li(2)-F(7) bond length is 2.02 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(3), one F(1), one F(2), one F(4), one F(5), and one F(9) atom. The Li(3)-O(3) bond length is 2.28 Å. The Li(3)-F(1) bond length is 2.01 Å. The Li(3)-F(2) bond length is 2.36 Å. The Li(3)-F(4) bond length is 1.96 Å. The Li(3)-F(5) bond length is 1.98 Å. The Li(3)-F(9) bond length is 2.08 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(2), one F(3), one F(5), one F(6), and one F(8) atom to form VOF5 octahedra that share corners with three equivalent V(2)O2F4 octahedra and corners with three equivalent V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 34-47°. The V(1)-O(2) bond length is 1.85 Å. The V(1)-F(2) bond length is 2.04 Å. The V(1)-F(3) bond length is 2.06 Å. The V(1)-F(5) bond length is 2.01 Å. The V(1)-F(6) bond length is 2.12 Å. The V(1)-F(8) bond length is 2.03 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one F(1), one F(2), one F(5), and one F(9) atom to form VO2F4 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 34-42°. The V(2)-O(2) bond length is 1.91 Å. The V(2)-O(3) bond length is 1.96 Å. The V(2)-F(1) bond length is 2.08 Å. The V(2)-F(2) bond length is 2.03 Å. The V(2)-F(5) bond length is 2.08 Å. The V(2)-F(9) bond length is 2.06 Å. In the third V site, V(3) is bonded to one O(1), one O(3), one F(1), one F(4), one F(7), and one F(9) atom to form VO2F4 octahedra that share corners with three equivalent V(2)O2F4 octahedra and corners with three equivalent V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 35-42°. The V(3)-O(1) bond length is 1.93 Å. The V(3)-O(3) bond length is 1.86 Å. The V(3)-F(1) bond length is 2.11 Å. The V(3)-F(4) bond length is 2.17 Å. The V(3)-F(7) bond length is 2.09 Å. The V(3)-F(9) bond length is 2.03 Å. In the fourth V site, V(4) is bonded to one O(1), one F(3), one F(4), one F(6), one F(7), and one F(8) 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(4)-O(1) bond length is 1.87 Å. The V(4)-F(3) bond length is 2.10 Å. The V(4)-F(4) bond length is 2.08 Å. The V(4)-F(6) bond length is 2.01 Å. The V(4)-F(7) bond length is 2.02 Å. The V(4)-F(8) bond length is 2.02 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one V(3), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(2), and one V(3) atom. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(2), and one V(3) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(4) atom. In the fourth F site, F(4) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(3), and one V(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(1), one V(1), 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 V(3), and one V(4) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the ninth F site, F(9) is bonded in a T-shaped geometry to one Li(3), one V(2), and one V(3) atom.