LiV4O5F7 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one O(1), one O(6), one O(8), and one F(5) atom. In the second Li site, Li(2) is bonded in a distorted trigonal planar geometry to one O(10), one O(4), one O(7), and one F(9) atom. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), one O(6), one F(11), one F(5), and one F(8) atom to form VO3F3 octahedra that share  a cornercorner with one V(6)O2F4 octahedra,  a cornercorner with one V(2)O3F3 octahedra, corners with two equivalent V(3)O2F4 octahedra, and corners with two equivalent V(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 18-35°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one F(1), one F(4), and one F(6) atom to form VO3F3 octahedra that share  a cornercorner with one V(4)O2F4 octahedra,  a cornercorner with one V(1)O3F3 octahedra, corners with two equivalent V(7)O2F4 octahedra, and corners with two equivalent V(8)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 18-35°. In the third V site, V(3) is bonded to one O(4), one O(6), one F(2), one F(3), one F(5), and one F(7) atom to form VO2F4 octahedra that share  a cornercorner with one V(7)O2F4 octahedra,  a cornercorner with one V(8)O3F3 octahedra, corners with two equivalent V(4)O2F4 octahedra, and corners with two equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 29-44°. In the fourth V site, V(4) is bonded to one O(1), one O(4), one F(12), one F(14), one F(2), and one F(9) atom to form VO2F4 octahedra that share  a cornercorner with one V(6)O2F4 octahedra,  a cornercorner with one V(2)O3F3 octahedra, corners with two equivalent V(3)O2F4 octahedra, and corners with two equivalent V(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 29-44°. In the fifth V site, V(5) is bonded to one O(5), one O(7), one O(9), one F(12), one F(8), and one F(9) atom to form VO3F3 octahedra that share  a cornercorner with one V(7)O2F4 octahedra,  a cornercorner with one V(8)O3F3 octahedra, corners with two equivalent V(4)O2F4 octahedra, and corners with two equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 18-35°. In the sixth V site, V(6) is bonded to one O(10), one O(8), one F(10), one F(11), one F(13), and one F(14) atom to form VO2F4 octahedra that share  a cornercorner with one V(4)O2F4 octahedra,  a cornercorner with one V(1)O3F3 octahedra, corners with two equivalent V(7)O2F4 octahedra, and corners with two equivalent V(8)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 29-44°. In the seventh V site, V(7) is bonded to one O(7), one O(8), one F(10), one F(4), one F(6), and one F(7) atom to form VO2F4 octahedra that share  a cornercorner with one V(3)O2F4 octahedra,  a cornercorner with one V(5)O3F3 octahedra, corners with two equivalent V(6)O2F4 octahedra, and corners with two equivalent V(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 29-44°. In the eighth V site, V(8) is bonded to one O(10), one O(2), one O(9), one F(1), one F(13), and one F(3) atom to form VO3F3 octahedra that share  a cornercorner with one V(3)O2F4 octahedra,  a cornercorner with one V(5)O3F3 octahedra, corners with two equivalent V(6)O2F4 octahedra, and corners with two equivalent V(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 18-35°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(8) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(5), and one V(7) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one V(6), and one V(7) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(5) and one V(8) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(6), and one V(8) atom. There are fourteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(2) and one V(8) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(3) and one V(8) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(7) atom. In the fifth F site, F(5) is bonded in a distorted bent 150 degrees geometry to one Li(1), one V(1), and one V(3) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(7) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(7) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one Li(2), one V(4), and one V(5) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(6) and one V(7) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one V(1) and one V(6) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one V(4) and one V(5) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one V(6) and one V(8) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one V(4) and one V(6) atom.
LiV4O5F7 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one O(1), one O(6), one O(8), and one F(5) atom. The Li(1)-O(1) bond length is 2.10 Å. The Li(1)-O(6) bond length is 2.09 Å. The Li(1)-O(8) bond length is 1.93 Å. The Li(1)-F(5) bond length is 2.50 Å. In the second Li site, Li(2) is bonded in a distorted trigonal planar geometry to one O(10), one O(4), one O(7), and one F(9) atom. The Li(2)-O(10) bond length is 2.10 Å. The Li(2)-O(4) bond length is 1.94 Å. The Li(2)-O(7) bond length is 2.09 Å. The Li(2)-F(9) bond length is 2.51 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), one O(6), one F(11), one F(5), and one F(8) atom to form VO3F3 octahedra that share  a cornercorner with one V(6)O2F4 octahedra,  a cornercorner with one V(2)O3F3 octahedra, corners with two equivalent V(3)O2F4 octahedra, and corners with two equivalent V(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 18-35°. The V(1)-O(3) bond length is 1.68 Å. The V(1)-O(5) bond length is 1.97 Å. The V(1)-O(6) bond length is 1.99 Å. The V(1)-F(11) bond length is 2.06 Å. The V(1)-F(5) bond length is 1.97 Å. The V(1)-F(8) bond length is 1.96 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one F(1), one F(4), and one F(6) atom to form VO3F3 octahedra that share  a cornercorner with one V(4)O2F4 octahedra,  a cornercorner with one V(1)O3F3 octahedra, corners with two equivalent V(7)O2F4 octahedra, and corners with two equivalent V(8)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 18-35°. The V(2)-O(1) bond length is 1.99 Å. The V(2)-O(2) bond length is 1.69 Å. The V(2)-O(3) bond length is 1.98 Å. The V(2)-F(1) bond length is 1.96 Å. The V(2)-F(4) bond length is 2.07 Å. The V(2)-F(6) bond length is 1.96 Å. In the third V site, V(3) is bonded to one O(4), one O(6), one F(2), one F(3), one F(5), and one F(7) atom to form VO2F4 octahedra that share  a cornercorner with one V(7)O2F4 octahedra,  a cornercorner with one V(8)O3F3 octahedra, corners with two equivalent V(4)O2F4 octahedra, and corners with two equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 29-44°. The V(3)-O(4) bond length is 1.86 Å. The V(3)-O(6) bond length is 1.73 Å. The V(3)-F(2) bond length is 2.11 Å. The V(3)-F(3) bond length is 1.95 Å. The V(3)-F(5) bond length is 2.05 Å. The V(3)-F(7) bond length is 1.98 Å. In the fourth V site, V(4) is bonded to one O(1), one O(4), one F(12), one F(14), one F(2), and one F(9) atom to form VO2F4 octahedra that share  a cornercorner with one V(6)O2F4 octahedra,  a cornercorner with one V(2)O3F3 octahedra, corners with two equivalent V(3)O2F4 octahedra, and corners with two equivalent V(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 29-44°. The V(4)-O(1) bond length is 1.73 Å. The V(4)-O(4) bond length is 1.86 Å. The V(4)-F(12) bond length is 1.95 Å. The V(4)-F(14) bond length is 2.10 Å. The V(4)-F(2) bond length is 1.99 Å. The V(4)-F(9) bond length is 2.05 Å. In the fifth V site, V(5) is bonded to one O(5), one O(7), one O(9), one F(12), one F(8), and one F(9) atom to form VO3F3 octahedra that share  a cornercorner with one V(7)O2F4 octahedra,  a cornercorner with one V(8)O3F3 octahedra, corners with two equivalent V(4)O2F4 octahedra, and corners with two equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 18-35°. The V(5)-O(5) bond length is 1.69 Å. The V(5)-O(7) bond length is 1.99 Å. The V(5)-O(9) bond length is 1.97 Å. The V(5)-F(12) bond length is 2.06 Å. The V(5)-F(8) bond length is 1.96 Å. The V(5)-F(9) bond length is 1.97 Å. In the sixth V site, V(6) is bonded to one O(10), one O(8), one F(10), one F(11), one F(13), and one F(14) atom to form VO2F4 octahedra that share  a cornercorner with one V(4)O2F4 octahedra,  a cornercorner with one V(1)O3F3 octahedra, corners with two equivalent V(7)O2F4 octahedra, and corners with two equivalent V(8)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 29-44°. The V(6)-O(10) bond length is 1.74 Å. The V(6)-O(8) bond length is 1.86 Å. The V(6)-F(10) bond length is 2.09 Å. The V(6)-F(11) bond length is 1.95 Å. The V(6)-F(13) bond length is 2.04 Å. The V(6)-F(14) bond length is 1.99 Å. In the seventh V site, V(7) is bonded to one O(7), one O(8), one F(10), one F(4), one F(6), and one F(7) atom to form VO2F4 octahedra that share  a cornercorner with one V(3)O2F4 octahedra,  a cornercorner with one V(5)O3F3 octahedra, corners with two equivalent V(6)O2F4 octahedra, and corners with two equivalent V(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 29-44°. The V(7)-O(7) bond length is 1.73 Å. The V(7)-O(8) bond length is 1.86 Å. The V(7)-F(10) bond length is 1.98 Å. The V(7)-F(4) bond length is 1.95 Å. The V(7)-F(6) bond length is 2.04 Å. The V(7)-F(7) bond length is 2.11 Å. In the eighth V site, V(8) is bonded to one O(10), one O(2), one O(9), one F(1), one F(13), and one F(3) atom to form VO3F3 octahedra that share  a cornercorner with one V(3)O2F4 octahedra,  a cornercorner with one V(5)O3F3 octahedra, corners with two equivalent V(6)O2F4 octahedra, and corners with two equivalent V(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 18-35°. The V(8)-O(10) bond length is 1.99 Å. The V(8)-O(2) bond length is 1.98 Å. The V(8)-O(9) bond length is 1.69 Å. The V(8)-F(1) bond length is 1.96 Å. The V(8)-F(13) bond length is 1.96 Å. The V(8)-F(3) bond length is 2.07 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(8) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(5), and one V(7) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one V(6), and one V(7) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(5) and one V(8) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(6), and one V(8) atom. There are fourteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(2) and one V(8) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(3) and one V(8) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(7) atom. In the fifth F site, F(5) is bonded in a distorted bent 150 degrees geometry to one Li(1), one V(1), and one V(3) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(7) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(7) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one Li(2), one V(4), and one V(5) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(6) and one V(7) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one V(1) and one V(6) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one V(4) and one V(5) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one V(6) and one V(8) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one V(4) and one V(6) atom.