LiV3O3F7 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(10), one F(12), one F(6), and one F(7) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(5), one F(13), one F(2), and one F(3) atom. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(6), one F(1), one F(2), and one F(6) atom to form distorted VO3F3 octahedra that share  a cornercorner with one V(6)O2F4 octahedra, corners with two equivalent V(5)O2F4 octahedra, and corners with two equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 16-42°. In the second V site, V(2) is bonded to one O(2), one O(4), one F(11), one F(3), one F(7), and one F(8) atom to form VO2F4 octahedra that share  a cornercorner with one V(3)OF5 octahedra, corners with two equivalent V(4)O2F4 octahedra, and corners with two equivalent V(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 7-38°. In the third V site, V(3) is bonded to one O(3), one F(12), one F(5), one F(6), one F(8), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one V(2)O2F4 octahedra,  a cornercorner with one V(4)O2F4 octahedra, corners with two equivalent V(5)O2F4 octahedra, and corners with two equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 7-48°. In the fourth V site, V(4) is bonded to one O(2), one O(5), one F(10), one F(11), one F(4), and one F(9) atom to form VO2F4 octahedra that share  a cornercorner with one V(3)OF5 octahedra, corners with two equivalent V(2)O2F4 octahedra, and corners with two equivalent V(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 15-41°. In the fifth V site, V(5) is bonded to one O(1), one O(6), one F(12), one F(13), one F(14), and one F(5) atom to form distorted VO2F4 octahedra that share  a cornercorner with one V(6)O2F4 octahedra, corners with two equivalent V(1)O3F3 octahedra, and corners with two equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 13-48°. In the sixth V site, V(6) is bonded to one O(4), one O(5), one F(1), one F(14), one F(3), and one F(4) atom to form distorted VO2F4 octahedra that share  a cornercorner with one V(5)O2F4 octahedra,  a cornercorner with one V(1)O3F3 octahedra, corners with two equivalent V(2)O2F4 octahedra, and corners with two equivalent V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 13-41°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(5) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one V(4), and one V(6) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. There are fourteen inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one V(1) and one V(6) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(6) atom. In the fourth F site, F(4) is bonded in a linear geometry to one V(4) and one V(6) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the seventh F site, F(7) is bonded in a linear geometry to one Li(1) and one V(2) atom. In the eighth F site, F(8) is bonded in a linear geometry to one V(2) and one V(3) atom. In the ninth F site, F(9) is bonded in a linear geometry to one V(3) and one V(4) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one Li(1) and one V(4) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the twelfth F site, F(12) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one V(5) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one Li(2) and one V(5) atom. In the fourteenth F site, F(14) is bonded in a linear geometry to one V(5) and one V(6) atom.
LiV3O3F7 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(10), one F(12), one F(6), and one F(7) atom. The Li(1)-F(10) bond length is 1.94 Å. The Li(1)-F(12) bond length is 2.13 Å. The Li(1)-F(6) bond length is 2.07 Å. The Li(1)-F(7) bond length is 1.88 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(5), one F(13), one F(2), and one F(3) atom. The Li(2)-O(5) bond length is 2.25 Å. The Li(2)-F(13) bond length is 1.91 Å. The Li(2)-F(2) bond length is 1.90 Å. The Li(2)-F(3) bond length is 2.08 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(6), one F(1), one F(2), and one F(6) atom to form distorted VO3F3 octahedra that share  a cornercorner with one V(6)O2F4 octahedra, corners with two equivalent V(5)O2F4 octahedra, and corners with two equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 16-42°. The V(1)-O(1) bond length is 2.15 Å. The V(1)-O(3) bond length is 1.98 Å. The V(1)-O(6) bond length is 1.68 Å. The V(1)-F(1) bond length is 2.00 Å. The V(1)-F(2) bond length is 1.88 Å. The V(1)-F(6) bond length is 2.02 Å. In the second V site, V(2) is bonded to one O(2), one O(4), one F(11), one F(3), one F(7), and one F(8) atom to form VO2F4 octahedra that share  a cornercorner with one V(3)OF5 octahedra, corners with two equivalent V(4)O2F4 octahedra, and corners with two equivalent V(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 7-38°. The V(2)-O(2) bond length is 2.01 Å. The V(2)-O(4) bond length is 1.98 Å. The V(2)-F(11) bond length is 1.99 Å. The V(2)-F(3) bond length is 2.02 Å. The V(2)-F(7) bond length is 1.88 Å. The V(2)-F(8) bond length is 2.00 Å. In the third V site, V(3) is bonded to one O(3), one F(12), one F(5), one F(6), one F(8), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one V(2)O2F4 octahedra,  a cornercorner with one V(4)O2F4 octahedra, corners with two equivalent V(5)O2F4 octahedra, and corners with two equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 7-48°. The V(3)-O(3) bond length is 1.67 Å. The V(3)-F(12) bond length is 2.00 Å. The V(3)-F(5) bond length is 1.93 Å. The V(3)-F(6) bond length is 2.08 Å. The V(3)-F(8) bond length is 1.94 Å. The V(3)-F(9) bond length is 1.94 Å. In the fourth V site, V(4) is bonded to one O(2), one O(5), one F(10), one F(11), one F(4), and one F(9) atom to form VO2F4 octahedra that share  a cornercorner with one V(3)OF5 octahedra, corners with two equivalent V(2)O2F4 octahedra, and corners with two equivalent V(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 15-41°. The V(4)-O(2) bond length is 1.68 Å. The V(4)-O(5) bond length is 1.73 Å. The V(4)-F(10) bond length is 1.85 Å. The V(4)-F(11) bond length is 2.02 Å. The V(4)-F(4) bond length is 2.05 Å. The V(4)-F(9) bond length is 2.01 Å. In the fifth V site, V(5) is bonded to one O(1), one O(6), one F(12), one F(13), one F(14), and one F(5) atom to form distorted VO2F4 octahedra that share  a cornercorner with one V(6)O2F4 octahedra, corners with two equivalent V(1)O3F3 octahedra, and corners with two equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 13-48°. The V(5)-O(1) bond length is 1.68 Å. The V(5)-O(6) bond length is 2.13 Å. The V(5)-F(12) bond length is 2.02 Å. The V(5)-F(13) bond length is 1.88 Å. The V(5)-F(14) bond length is 2.00 Å. The V(5)-F(5) bond length is 1.97 Å. In the sixth V site, V(6) is bonded to one O(4), one O(5), one F(1), one F(14), one F(3), and one F(4) atom to form distorted VO2F4 octahedra that share  a cornercorner with one V(5)O2F4 octahedra,  a cornercorner with one V(1)O3F3 octahedra, corners with two equivalent V(2)O2F4 octahedra, and corners with two equivalent V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 13-41°. The V(6)-O(4) bond length is 1.69 Å. The V(6)-O(5) bond length is 1.99 Å. The V(6)-F(1) bond length is 1.94 Å. The V(6)-F(14) bond length is 1.94 Å. The V(6)-F(3) bond length is 2.14 Å. The V(6)-F(4) bond length is 1.94 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(5) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one V(4), and one V(6) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. There are fourteen inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one V(1) and one V(6) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(6) atom. In the fourth F site, F(4) is bonded in a linear geometry to one V(4) and one V(6) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(3) and one V(5) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the seventh F site, F(7) is bonded in a linear geometry to one Li(1) and one V(2) atom. In the eighth F site, F(8) is bonded in a linear geometry to one V(2) and one V(3) atom. In the ninth F site, F(9) is bonded in a linear geometry to one V(3) and one V(4) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one Li(1) and one V(4) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the twelfth F site, F(12) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one V(5) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one Li(2) and one V(5) atom. In the fourteenth F site, F(14) is bonded in a linear geometry to one V(5) and one V(6) atom.