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 5-coordinate geometry to one O(1), one O(2), one F(2), one F(5), and one F(9) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one F(2), one F(3), and one F(9) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), one F(1), one F(4), one F(6), and one F(8) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(3), one F(6), one F(7), and one F(9) atom to form VOF5 octahedra that share corners with two equivalent V(4)O2F4 octahedra and corners with four equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 32-44°. In the second V site, V(2) is bonded to one O(1), one F(3), one F(4), one F(5), one F(6), and one F(7) atom to form VOF5 octahedra that share corners with two equivalent V(3)O2F4 octahedra and corners with four equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 32-44°. In the third V site, V(3) is bonded to one O(2), one O(3), one F(2), one F(4), one F(5), and one F(8) atom to form VO2F4 octahedra that share corners with two equivalent V(2)OF5 octahedra and corners with four equivalent V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-46°. In the fourth V site, V(4) is bonded to one O(2), one O(3), one F(1), one F(2), one F(8), and one F(9) atom to form VO2F4 octahedra that share corners with two equivalent V(1)OF5 octahedra and corners with four equivalent V(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 34-46°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(3), and one V(4) atom to form distorted OLi3V2 trigonal bipyramids that share edges with two equivalent F(2)Li2V2 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one V(3), and one V(4) atom. There are nine 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(4) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one V(3), and one V(4) atom to form distorted FLi2V2 trigonal pyramids that share edges with two equivalent O(2)Li3V2 trigonal bipyramids. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(3), one V(2), and one V(3) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Li(3), one V(3), and one V(4) atom. In the ninth F site, F(9) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(4) 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 5-coordinate geometry to one O(1), one O(2), one F(2), one F(5), and one F(9) atom. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(2) bond length is 2.24 Å. The Li(1)-F(2) bond length is 1.96 Å. The Li(1)-F(5) bond length is 2.05 Å. The Li(1)-F(9) bond length is 2.14 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one F(2), one F(3), and one F(9) atom. The Li(2)-O(2) bond length is 1.97 Å. The Li(2)-O(3) bond length is 2.16 Å. The Li(2)-F(2) bond length is 2.28 Å. The Li(2)-F(3) bond length is 2.05 Å. The Li(2)-F(9) bond length is 2.00 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), one F(1), one F(4), one F(6), and one F(8) atom. The Li(3)-O(2) bond length is 2.37 Å. The Li(3)-O(3) bond length is 1.96 Å. The Li(3)-F(1) bond length is 1.95 Å. The Li(3)-F(4) bond length is 2.55 Å. The Li(3)-F(6) bond length is 2.00 Å. The Li(3)-F(8) bond length is 2.22 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(3), one F(6), one F(7), and one F(9) atom to form VOF5 octahedra that share corners with two equivalent V(4)O2F4 octahedra and corners with four equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 32-44°. The V(1)-O(1) bond length is 1.86 Å. The V(1)-F(1) bond length is 2.05 Å. The V(1)-F(3) bond length is 2.05 Å. The V(1)-F(6) bond length is 2.04 Å. The V(1)-F(7) bond length is 2.00 Å. The V(1)-F(9) bond length is 2.09 Å. In the second V site, V(2) is bonded to one O(1), one F(3), one F(4), one F(5), one F(6), and one F(7) atom to form VOF5 octahedra that share corners with two equivalent V(3)O2F4 octahedra and corners with four equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 32-44°. The V(2)-O(1) bond length is 1.86 Å. The V(2)-F(3) bond length is 2.07 Å. The V(2)-F(4) bond length is 1.98 Å. The V(2)-F(5) bond length is 2.04 Å. The V(2)-F(6) bond length is 2.09 Å. The V(2)-F(7) bond length is 2.01 Å. In the third V site, V(3) is bonded to one O(2), one O(3), one F(2), one F(4), one F(5), and one F(8) atom to form VO2F4 octahedra that share corners with two equivalent V(2)OF5 octahedra and corners with four equivalent V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 33-46°. The V(3)-O(2) bond length is 1.95 Å. The V(3)-O(3) bond length is 1.92 Å. The V(3)-F(2) bond length is 2.10 Å. The V(3)-F(4) bond length is 2.01 Å. The V(3)-F(5) bond length is 2.12 Å. The V(3)-F(8) bond length is 2.05 Å. In the fourth V site, V(4) is bonded to one O(2), one O(3), one F(1), one F(2), one F(8), and one F(9) atom to form VO2F4 octahedra that share corners with two equivalent V(1)OF5 octahedra and corners with four equivalent V(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 34-46°. The V(4)-O(2) bond length is 1.94 Å. The V(4)-O(3) bond length is 1.92 Å. The V(4)-F(1) bond length is 2.05 Å. The V(4)-F(2) bond length is 2.04 Å. The V(4)-F(8) bond length is 2.04 Å. The V(4)-F(9) bond length is 2.10 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(3), and one V(4) atom to form distorted OLi3V2 trigonal bipyramids that share edges with two equivalent F(2)Li2V2 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one V(3), and one V(4) atom. There are nine 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(4) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one V(3), and one V(4) atom to form distorted FLi2V2 trigonal pyramids that share edges with two equivalent O(2)Li3V2 trigonal bipyramids. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(3), one V(2), and one V(3) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Li(3), one V(3), and one V(4) atom. In the ninth F site, F(9) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one V(1), and one V(4) atom.