Li4V5O9F crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), two equivalent O(5), and two equivalent O(9) atoms to form LiO6 octahedra that share  a cornercorner with one V(2)O5F octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent V(4)O6 octahedra, and edges with three equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), two equivalent O(6), and one F(1) atom to form LiO5F octahedra that share  a cornercorner with one V(2)O5F octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(3)O4F2 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O5F octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent V(3)O4F2 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the third Li site, Li(3) is bonded to one O(6), one O(9), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one V(5)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O5F octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the fourth Li site, Li(4) is bonded to one O(5), one O(7), two equivalent O(4), and two equivalent O(8) atoms to form LiO6 octahedra that share  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(2)O5F octahedra, corners with two equivalent V(5)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent V(2)O5F octahedra, and edges with three equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-25°. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O5F octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent V(3)O4F2 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with three equivalent Li(2)O5F octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. In the second V site, V(2) is bonded to one O(4), two equivalent O(7), two equivalent O(8), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(2)O5F octahedra,  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent V(3)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(5)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. In the third V site, V(3) is bonded to one O(6), one O(7), two equivalent O(2), and two equivalent F(1) atoms to form VO4F2 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Li(2)O5F octahedra, edges with two equivalent V(3)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(1)O6 octahedra, and edges with three equivalent Li(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-25°. In the fourth V site, V(4) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O5F octahedra,  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. In the fifth V site, V(5) is bonded to one O(8), one O(9), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one V(1), and two equivalent V(4) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(9)Li3V3 octahedra,  a cornercorner with one O(2)Li2V3 square pyramid, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with three equivalent O(3)Li3V3 octahedra, and edges with three equivalent O(9)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the second O site, O(2) is bonded to two equivalent Li(2), one V(1), and two equivalent V(3) atoms to form OLi2V3 square pyramids that share  a cornercorner with one O(1)Li3V3 octahedra, corners with two equivalent O(6)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with three equivalent O(6)Li3V3 octahedra, and edges with two equivalent O(2)Li2V3 square pyramids. The corner-sharing octahedral tilt angles are 1°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(3), one V(4), and two equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(5)Li3V3 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(6)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(9)Li3V3 octahedra, edges with three equivalent O(1)Li3V3 octahedra, edges with three equivalent O(6)Li3V3 octahedra, and edges with two equivalent O(2)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(4), one V(2), and two equivalent V(5) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra, corners with two equivalent O(5)Li3V3 octahedra, corners with two equivalent O(8)Li2V3 square pyramids, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(9)Li3V3 octahedra, edges with three equivalent O(5)Li3V3 octahedra, and edges with three equivalent O(8)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-2°. In the fifth O site, O(5) is bonded to one Li(4), two equivalent Li(1), one V(4), and two equivalent V(5) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(9)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with three equivalent O(4)Li3V3 octahedra, edges with three equivalent O(9)Li3V3 octahedra, and edges with two equivalent O(8)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 0-3°. In the sixth O site, O(6) is bonded to one Li(3), two equivalent Li(2), one V(3), and two equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(9)Li3V3 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(2)Li2V3 square pyramids, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with three equivalent O(3)Li3V3 octahedra, and edges with three equivalent O(2)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-3°. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(4), one V(3), and two equivalent V(2) atoms. In the eighth O site, O(8) is bonded to two equivalent Li(4), one V(5), and two equivalent V(2) atoms to form OLi2V3 square pyramids that share  a cornercorner with one O(9)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with two equivalent O(8)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-7°. In the ninth O site, O(9) is bonded to one Li(3), two equivalent Li(1), one V(5), and two equivalent V(4) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(6)Li3V3 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(5)Li3V3 octahedra,  a cornercorner with one O(8)Li2V3 square pyramid, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(9)Li3V3 octahedra, edges with three equivalent O(1)Li3V3 octahedra, and edges with three equivalent O(5)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), and two equivalent V(3) atoms.
Li4V5O9F crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), two equivalent O(5), and two equivalent O(9) atoms to form LiO6 octahedra that share  a cornercorner with one V(2)O5F octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent V(4)O6 octahedra, and edges with three equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. The Li(1)-O(1) bond length is 2.22 Å. The Li(1)-O(4) bond length is 2.16 Å. Both Li(1)-O(5) bond lengths are 2.17 Å. Both Li(1)-O(9) bond lengths are 2.22 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), two equivalent O(6), and one F(1) atom to form LiO5F octahedra that share  a cornercorner with one V(2)O5F octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(3)O4F2 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O5F octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent V(3)O4F2 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. The Li(2)-O(3) bond length is 2.20 Å. Both Li(2)-O(2) bond lengths are 2.17 Å. Both Li(2)-O(6) bond lengths are 2.19 Å. The Li(2)-F(1) bond length is 2.07 Å. In the third Li site, Li(3) is bonded to one O(6), one O(9), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one V(5)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O5F octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. The Li(3)-O(6) bond length is 2.29 Å. The Li(3)-O(9) bond length is 2.13 Å. Both Li(3)-O(1) bond lengths are 2.18 Å. Both Li(3)-O(3) bond lengths are 2.21 Å. In the fourth Li site, Li(4) is bonded to one O(5), one O(7), two equivalent O(4), and two equivalent O(8) atoms to form LiO6 octahedra that share  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent V(2)O5F octahedra, corners with two equivalent V(5)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent V(2)O5F octahedra, and edges with three equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-25°. The Li(4)-O(5) bond length is 2.31 Å. The Li(4)-O(7) bond length is 2.23 Å. Both Li(4)-O(4) bond lengths are 2.24 Å. Both Li(4)-O(8) bond lengths are 2.14 Å. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(2)O5F octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent V(3)O4F2 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with three equivalent Li(2)O5F octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. The V(1)-O(1) bond length is 2.05 Å. The V(1)-O(2) bond length is 2.05 Å. Both V(1)-O(3) bond lengths are 2.07 Å. Both V(1)-O(6) bond lengths are 2.07 Å. In the second V site, V(2) is bonded to one O(4), two equivalent O(7), two equivalent O(8), and one F(1) atom to form VO5F octahedra that share  a cornercorner with one Li(2)O5F octahedra,  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent V(3)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(5)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. The V(2)-O(4) bond length is 2.07 Å. Both V(2)-O(7) bond lengths are 2.00 Å. Both V(2)-O(8) bond lengths are 2.06 Å. The V(2)-F(1) bond length is 2.20 Å. In the third V site, V(3) is bonded to one O(6), one O(7), two equivalent O(2), and two equivalent F(1) atoms to form VO4F2 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Li(2)O5F octahedra, edges with two equivalent V(3)O4F2 octahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(1)O6 octahedra, and edges with three equivalent Li(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-25°. The V(3)-O(6) bond length is 2.07 Å. The V(3)-O(7) bond length is 1.97 Å. Both V(3)-O(2) bond lengths are 2.00 Å. Both V(3)-F(1) bond lengths are 2.15 Å. In the fourth V site, V(4) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O5F octahedra,  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. The V(4)-O(3) bond length is 2.07 Å. The V(4)-O(5) bond length is 2.03 Å. Both V(4)-O(1) bond lengths are 2.08 Å. Both V(4)-O(9) bond lengths are 2.07 Å. In the fifth V site, V(5) is bonded to one O(8), one O(9), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent V(2)O5F octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. The V(5)-O(8) bond length is 2.02 Å. The V(5)-O(9) bond length is 2.06 Å. Both V(5)-O(4) bond lengths are 2.07 Å. Both V(5)-O(5) bond lengths are 2.08 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one V(1), and two equivalent V(4) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(9)Li3V3 octahedra,  a cornercorner with one O(2)Li2V3 square pyramid, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with three equivalent O(3)Li3V3 octahedra, and edges with three equivalent O(9)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the second O site, O(2) is bonded to two equivalent Li(2), one V(1), and two equivalent V(3) atoms to form OLi2V3 square pyramids that share  a cornercorner with one O(1)Li3V3 octahedra, corners with two equivalent O(6)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with three equivalent O(6)Li3V3 octahedra, and edges with two equivalent O(2)Li2V3 square pyramids. The corner-sharing octahedral tilt angles are 1°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(3), one V(4), and two equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(5)Li3V3 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(6)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(9)Li3V3 octahedra, edges with three equivalent O(1)Li3V3 octahedra, edges with three equivalent O(6)Li3V3 octahedra, and edges with two equivalent O(2)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(4), one V(2), and two equivalent V(5) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(1)Li3V3 octahedra, corners with two equivalent O(5)Li3V3 octahedra, corners with two equivalent O(8)Li2V3 square pyramids, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(9)Li3V3 octahedra, edges with three equivalent O(5)Li3V3 octahedra, and edges with three equivalent O(8)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-2°. In the fifth O site, O(5) is bonded to one Li(4), two equivalent Li(1), one V(4), and two equivalent V(5) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, corners with two equivalent O(9)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with three equivalent O(4)Li3V3 octahedra, edges with three equivalent O(9)Li3V3 octahedra, and edges with two equivalent O(8)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 0-3°. In the sixth O site, O(6) is bonded to one Li(3), two equivalent Li(2), one V(3), and two equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(9)Li3V3 octahedra, corners with two equivalent O(3)Li3V3 octahedra, corners with two equivalent O(2)Li2V3 square pyramids, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with three equivalent O(3)Li3V3 octahedra, and edges with three equivalent O(2)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-3°. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(4), one V(3), and two equivalent V(2) atoms. In the eighth O site, O(8) is bonded to two equivalent Li(4), one V(5), and two equivalent V(2) atoms to form OLi2V3 square pyramids that share  a cornercorner with one O(9)Li3V3 octahedra, corners with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with two equivalent O(8)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-7°. In the ninth O site, O(9) is bonded to one Li(3), two equivalent Li(1), one V(5), and two equivalent V(4) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(6)Li3V3 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(5)Li3V3 octahedra,  a cornercorner with one O(8)Li2V3 square pyramid, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(9)Li3V3 octahedra, edges with three equivalent O(1)Li3V3 octahedra, and edges with three equivalent O(5)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), and two equivalent V(3) atoms.