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(1), one O(3), one O(4), one F(2), one F(4), and one F(5) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(5), one O(6), 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(2), one O(3), one O(6), one O(7), one F(1), 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(3), one O(4), one O(7), one F(1), and one F(3) atom to form distorted VO4F2 octahedra that share corners with three equivalent V(4)O3F3 octahedra and corners with three equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 18-43°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(7), one F(4), and one F(5) atom to form VO4F2 octahedra that share corners with three equivalent V(3)O3F3 octahedra and corners with three equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 18-38°. In the third V site, V(3) is bonded to one O(1), one O(5), one O(6), one F(2), one F(4), and one F(5) atom to form distorted VO3F3 octahedra that share corners with three equivalent V(4)O3F3 octahedra and corners with three equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 29-42°. In the fourth V site, V(4) is bonded to one O(2), one O(5), one O(6), one F(1), one F(2), and one F(3) atom to form VO3F3 octahedra that share corners with three equivalent V(3)O3F3 octahedra and corners with three equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-43°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(2), and one V(3) atom to form distorted OLi2V2 tetrahedra that share  a cornercorner with one O(2)Li2V2 trigonal pyramid, corners with two equivalent O(6)Li2V2 trigonal pyramids, and corners with three equivalent F(2)Li2V2 trigonal pyramids. In the second O site, O(2) is bonded to one Li(2), one Li(3), one V(1), and one V(4) atom to form OLi2V2 trigonal pyramids that share  a cornercorner with one O(1)Li2V2 tetrahedra,  a cornercorner with one O(6)Li2V2 trigonal pyramid,  an edgeedge with one O(6)Li2V2 trigonal pyramid, and  an edgeedge with one F(2)Li2V2 trigonal pyramid. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one V(3), and one V(4) atom to form OLi2V2 trigonal pyramids that share corners with two equivalent O(1)Li2V2 tetrahedra,  a cornercorner with one O(2)Li2V2 trigonal pyramid,  a cornercorner with one F(2)Li2V2 trigonal pyramid,  an edgeedge with one O(2)Li2V2 trigonal pyramid, and  an edgeedge with one F(2)Li2V2 trigonal pyramid. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(4) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one V(3), and one V(4) atom to form distorted FLi2V2 trigonal pyramids that share corners with three equivalent O(1)Li2V2 tetrahedra,  a cornercorner with one O(6)Li2V2 trigonal pyramid,  an edgeedge with one O(2)Li2V2 trigonal pyramid, and  an edgeedge with one O(6)Li2V2 trigonal pyramid. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(3), one V(1), 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 see-saw-like geometry to one Li(1), one Li(2), one V(2), and one V(3) 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(1), one O(3), one O(4), one F(2), one F(4), and one F(5) atom. The Li(1)-O(1) bond length is 2.25 Å. The Li(1)-O(3) bond length is 2.25 Å. The Li(1)-O(4) bond length is 1.99 Å. The Li(1)-F(2) bond length is 2.00 Å. The Li(1)-F(4) bond length is 2.14 Å. The Li(1)-F(5) bond length is 2.04 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(5), one O(6), one F(2), and one F(5) atom. The Li(2)-O(1) bond length is 2.08 Å. The Li(2)-O(2) bond length is 2.13 Å. The Li(2)-O(5) bond length is 1.97 Å. The Li(2)-O(6) bond length is 2.30 Å. The Li(2)-F(2) bond length is 2.26 Å. The Li(2)-F(5) bond length is 2.30 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(6), one O(7), one F(1), and one F(3) atom. The Li(3)-O(2) bond length is 2.15 Å. The Li(3)-O(3) bond length is 2.39 Å. The Li(3)-O(6) bond length is 2.05 Å. The Li(3)-O(7) bond length is 2.02 Å. The Li(3)-F(1) bond length is 1.99 Å. The Li(3)-F(3) bond length is 2.28 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), one O(7), one F(1), and one F(3) atom to form distorted VO4F2 octahedra that share corners with three equivalent V(4)O3F3 octahedra and corners with three equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 18-43°. The V(1)-O(2) bond length is 1.97 Å. The V(1)-O(3) bond length is 1.87 Å. The V(1)-O(4) bond length is 1.99 Å. The V(1)-O(7) bond length is 1.75 Å. The V(1)-F(1) bond length is 2.04 Å. The V(1)-F(3) bond length is 2.16 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(7), one F(4), and one F(5) atom to form VO4F2 octahedra that share corners with three equivalent V(3)O3F3 octahedra and corners with three equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 18-38°. The V(2)-O(1) bond length is 2.02 Å. The V(2)-O(3) bond length is 1.83 Å. The V(2)-O(4) bond length is 1.75 Å. The V(2)-O(7) bond length is 1.98 Å. The V(2)-F(4) bond length is 2.14 Å. The V(2)-F(5) bond length is 2.11 Å. In the third V site, V(3) is bonded to one O(1), one O(5), one O(6), one F(2), one F(4), and one F(5) atom to form distorted VO3F3 octahedra that share corners with three equivalent V(4)O3F3 octahedra and corners with three equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 29-42°. The V(3)-O(1) bond length is 1.76 Å. The V(3)-O(5) bond length is 1.83 Å. The V(3)-O(6) bond length is 1.90 Å. The V(3)-F(2) bond length is 2.16 Å. The V(3)-F(4) bond length is 2.00 Å. The V(3)-F(5) bond length is 2.16 Å. In the fourth V site, V(4) is bonded to one O(2), one O(5), one O(6), one F(1), one F(2), and one F(3) atom to form VO3F3 octahedra that share corners with three equivalent V(3)O3F3 octahedra and corners with three equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-43°. The V(4)-O(2) bond length is 1.81 Å. The V(4)-O(5) bond length is 1.89 Å. The V(4)-O(6) bond length is 1.87 Å. The V(4)-F(1) bond length is 2.15 Å. The V(4)-F(2) bond length is 2.07 Å. The V(4)-F(3) bond length is 1.94 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(2), and one V(3) atom to form distorted OLi2V2 tetrahedra that share  a cornercorner with one O(2)Li2V2 trigonal pyramid, corners with two equivalent O(6)Li2V2 trigonal pyramids, and corners with three equivalent F(2)Li2V2 trigonal pyramids. In the second O site, O(2) is bonded to one Li(2), one Li(3), one V(1), and one V(4) atom to form OLi2V2 trigonal pyramids that share  a cornercorner with one O(1)Li2V2 tetrahedra,  a cornercorner with one O(6)Li2V2 trigonal pyramid,  an edgeedge with one O(6)Li2V2 trigonal pyramid, and  an edgeedge with one F(2)Li2V2 trigonal pyramid. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one V(3), and one V(4) atom to form OLi2V2 trigonal pyramids that share corners with two equivalent O(1)Li2V2 tetrahedra,  a cornercorner with one O(2)Li2V2 trigonal pyramid,  a cornercorner with one F(2)Li2V2 trigonal pyramid,  an edgeedge with one O(2)Li2V2 trigonal pyramid, and  an edgeedge with one F(2)Li2V2 trigonal pyramid. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(4) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one V(3), and one V(4) atom to form distorted FLi2V2 trigonal pyramids that share corners with three equivalent O(1)Li2V2 tetrahedra,  a cornercorner with one O(6)Li2V2 trigonal pyramid,  an edgeedge with one O(2)Li2V2 trigonal pyramid, and  an edgeedge with one O(6)Li2V2 trigonal pyramid. In the third F site, F(3) is bonded in a T-shaped geometry to one Li(3), one V(1), 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 see-saw-like geometry to one Li(1), one Li(2), one V(2), and one V(3) atom.