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 4-coordinate geometry to one O(1), one F(2), one F(3), and one F(6) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to 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 2-coordinate geometry to 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 in a distorted linear geometry to one O(2), one F(2), one F(3), one F(5), and one F(8) atom. In the second V site, V(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one F(2), one F(5), and one F(9) atom. In the third V site, V(3) is bonded in a 3-coordinate geometry to one O(1), one O(3), one F(4), and one F(9) atom. In the fourth V site, V(4) is bonded in a 4-coordinate geometry to one O(1), one F(3), one F(4), and one F(8) atom. 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(3), and one V(4) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to 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 water-like geometry to one Li(2) and one Li(3) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one V(1), and one V(4) atom. In the fourth F site, F(4) is bonded in a 4-coordinate 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 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 distorted single-bond geometry to one Li(1) atom. In the seventh F site, F(7) is bonded in a 1-coordinate geometry to one Li(2) atom. In the eighth F site, F(8) is bonded in a bent 120 degrees geometry to one V(1) and one V(4) atom. In the ninth F site, F(9) is bonded in a 3-coordinate 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 4-coordinate geometry to one O(1), one F(2), one F(3), and one F(6) atom. The Li(1)-O(1) bond length is 2.28 Å. The Li(1)-F(2) bond length is 2.11 Å. The Li(1)-F(3) bond length is 2.47 Å. The Li(1)-F(6) bond length is 1.95 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(1), one F(3), one F(4), and one F(7) atom. The Li(2)-F(1) bond length is 1.81 Å. The Li(2)-F(3) bond length is 2.11 Å. The Li(2)-F(4) bond length is 2.19 Å. The Li(2)-F(7) bond length is 2.07 Å. In the third Li site, Li(3) is bonded in a 2-coordinate geometry to one F(1), one F(2), one F(4), one F(5), and one F(9) atom. The Li(3)-F(1) bond length is 1.90 Å. The Li(3)-F(2) bond length is 2.39 Å. The Li(3)-F(4) bond length is 2.37 Å. The Li(3)-F(5) bond length is 2.42 Å. The Li(3)-F(9) bond length is 1.90 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded in a distorted linear geometry to one O(2), one F(2), one F(3), one F(5), and one F(8) atom. The V(1)-O(2) bond length is 1.58 Å. The V(1)-F(2) bond length is 2.51 Å. The V(1)-F(3) bond length is 2.22 Å. The V(1)-F(5) bond length is 2.28 Å. The V(1)-F(8) bond length is 1.71 Å. In the second V site, V(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one F(2), one F(5), and one F(9) atom. The V(2)-O(2) bond length is 1.63 Å. The V(2)-O(3) bond length is 1.65 Å. The V(2)-F(2) bond length is 2.64 Å. The V(2)-F(5) bond length is 2.07 Å. The V(2)-F(9) bond length is 2.03 Å. In the third V site, V(3) is bonded in a 3-coordinate geometry to one O(1), one O(3), one F(4), and one F(9) atom. The V(3)-O(1) bond length is 1.98 Å. The V(3)-O(3) bond length is 1.56 Å. The V(3)-F(4) bond length is 1.92 Å. The V(3)-F(9) bond length is 2.34 Å. In the fourth V site, V(4) is bonded in a 4-coordinate geometry to one O(1), one F(3), one F(4), and one F(8) atom. The V(4)-O(1) bond length is 1.88 Å. The V(4)-F(3) bond length is 2.09 Å. The V(4)-F(4) bond length is 1.82 Å. The V(4)-F(8) bond length is 1.66 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(3), and one V(4) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to 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 water-like geometry to one Li(2) and one Li(3) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one V(1), and one V(4) atom. In the fourth F site, F(4) is bonded in a 4-coordinate 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 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 distorted single-bond geometry to one Li(1) atom. In the seventh F site, F(7) is bonded in a 1-coordinate geometry to one Li(2) atom. In the eighth F site, F(8) is bonded in a bent 120 degrees geometry to one V(1) and one V(4) atom. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one V(3) atom.