Li3V4O7F5 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one F(1), one F(3), and one F(4) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(6), one O(7), one F(2), and one F(5) atom. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(7), and one F(3) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(6), one O(7), one F(1), one F(2), and one F(5) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 31-41°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one F(3), and one F(4) atom. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one F(1), and one F(4) atom. In the fourth V site, V(4) is bonded to one O(1), one O(4), one O(7), one F(2), one F(3), and one F(5) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 31-41°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Li(3), one V(2), and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one V(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(3) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one V(4) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(3) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one V(4) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(2), and one V(4) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1), 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(2), one V(1), and one V(4) atom.
Li3V4O7F5 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one F(1), one F(3), and one F(4) atom. The Li(1)-O(2) bond length is 2.04 Å. The Li(1)-O(3) bond length is 2.20 Å. The Li(1)-O(5) bond length is 2.16 Å. The Li(1)-F(1) bond length is 2.08 Å. The Li(1)-F(3) bond length is 2.00 Å. The Li(1)-F(4) bond length is 2.10 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(6), one O(7), one F(2), and one F(5) atom. The Li(2)-O(1) bond length is 2.02 Å. The Li(2)-O(4) bond length is 2.19 Å. The Li(2)-O(6) bond length is 2.09 Å. The Li(2)-O(7) bond length is 2.36 Å. The Li(2)-F(2) bond length is 2.37 Å. The Li(2)-F(5) bond length is 1.98 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(7), and one F(3) atom. The Li(3)-O(1) bond length is 2.23 Å. The Li(3)-O(3) bond length is 2.08 Å. The Li(3)-O(4) bond length is 2.01 Å. The Li(3)-O(5) bond length is 2.29 Å. The Li(3)-O(7) bond length is 2.19 Å. The Li(3)-F(3) bond length is 2.23 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(6), one O(7), one F(1), one F(2), and one F(5) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 31-41°. The V(1)-O(2) bond length is 2.02 Å. The V(1)-O(6) bond length is 2.04 Å. The V(1)-O(7) bond length is 1.91 Å. The V(1)-F(1) bond length is 2.00 Å. The V(1)-F(2) bond length is 2.03 Å. The V(1)-F(5) bond length is 2.02 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one F(3), and one F(4) atom. The V(2)-O(1) bond length is 1.94 Å. The V(2)-O(3) bond length is 1.70 Å. The V(2)-O(4) bond length is 1.88 Å. The V(2)-O(5) bond length is 2.08 Å. The V(2)-F(3) bond length is 2.35 Å. The V(2)-F(4) bond length is 2.00 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one F(1), and one F(4) atom. The V(3)-O(2) bond length is 1.73 Å. The V(3)-O(3) bond length is 2.24 Å. The V(3)-O(5) bond length is 1.74 Å. The V(3)-O(6) bond length is 1.72 Å. The V(3)-F(1) bond length is 2.13 Å. The V(3)-F(4) bond length is 2.13 Å. In the fourth V site, V(4) is bonded to one O(1), one O(4), one O(7), one F(2), one F(3), and one F(5) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 31-41°. The V(4)-O(1) bond length is 1.85 Å. The V(4)-O(4) bond length is 1.90 Å. The V(4)-O(7) bond length is 1.84 Å. The V(4)-F(2) bond length is 2.00 Å. The V(4)-F(3) bond length is 2.01 Å. The V(4)-F(5) bond length is 2.11 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Li(3), one V(2), and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one V(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(3) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one V(4) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(3) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one V(4) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(2), and one V(4) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1), 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(2), one V(1), and one V(4) atom.