LiV6O7F5 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(4), one O(6), and one F(3) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(3)O4F2 octahedra, corners with two equivalent V(4)O3F3 octahedra,  an edgeedge with one V(3)O4F2 octahedra, and edges with two equivalent V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 60-68°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one F(1), and one F(5) atom to form VO4F2 octahedra that share corners with two equivalent V(4)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra, corners with four equivalent V(5)O3F3 octahedra,  a cornercorner with one Li(1)O3F trigonal pyramid, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(7), one F(3), and one F(4) atom. In the third V site, V(3) is bonded to one O(1), one O(4), one O(5), one O(6), one F(2), and one F(4) atom to form VO4F2 octahedra that share corners with two equivalent V(4)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with four equivalent V(6)O3F3 octahedra,  a cornercorner with one Li(1)O3F trigonal pyramid,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles range from 44-56°. In the fourth V site, V(4) is bonded to one O(3), one O(6), one O(7), one F(1), one F(3), and one F(4) atom to form VO3F3 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids,  an edgeedge with one V(5)O3F3 octahedra, and  an edgeedge with one V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. In the fifth V site, V(5) is bonded to one O(2), one O(5), one O(7), one F(1), one F(2), and one F(5) atom to form VO3F3 octahedra that share corners with two equivalent V(3)O4F2 octahedra, corners with four equivalent V(1)O4F2 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and  an edgeedge with one V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. In the sixth V site, V(6) is bonded to one O(1), one O(4), one O(6), one F(2), one F(3), and one F(5) atom to form VO3F3 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with four equivalent V(3)O4F2 octahedra,  an edgeedge with one V(4)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra, and edges with two equivalent Li(1)O3F trigonal pyramids. The corner-sharing octahedral tilt angles range from 44-56°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), one V(3), and one V(6) atom to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(5) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom. In the fourth O site, O(4) is bonded to one Li(1), one V(2), one V(3), and one V(6) atom to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one V(5) atom. In the sixth O site, O(6) is bonded to one Li(1), one V(3), one V(4), and one V(6) atom to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(2), one V(4), and one V(5) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one V(1), one V(4), and one V(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(3), one V(5), and one V(6) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one V(4), and one V(6) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(5), and one V(6) atom.
LiV6O7F5 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(4), one O(6), and one F(3) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(3)O4F2 octahedra, corners with two equivalent V(4)O3F3 octahedra,  an edgeedge with one V(3)O4F2 octahedra, and edges with two equivalent V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 60-68°. The Li(1)-O(1) bond length is 1.90 Å. The Li(1)-O(4) bond length is 1.87 Å. The Li(1)-O(6) bond length is 1.88 Å. The Li(1)-F(3) bond length is 1.82 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one F(1), and one F(5) atom to form VO4F2 octahedra that share corners with two equivalent V(4)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra, corners with four equivalent V(5)O3F3 octahedra,  a cornercorner with one Li(1)O3F trigonal pyramid, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. The V(1)-O(1) bond length is 2.03 Å. The V(1)-O(2) bond length is 2.00 Å. The V(1)-O(3) bond length is 1.99 Å. The V(1)-O(5) bond length is 2.03 Å. The V(1)-F(1) bond length is 2.13 Å. The V(1)-F(5) bond length is 2.15 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(7), one F(3), and one F(4) atom. The V(2)-O(2) bond length is 1.99 Å. The V(2)-O(3) bond length is 2.00 Å. The V(2)-O(4) bond length is 2.09 Å. The V(2)-O(7) bond length is 1.88 Å. The V(2)-F(3) bond length is 2.47 Å. The V(2)-F(4) bond length is 2.17 Å. In the third V site, V(3) is bonded to one O(1), one O(4), one O(5), one O(6), one F(2), and one F(4) atom to form VO4F2 octahedra that share corners with two equivalent V(4)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with four equivalent V(6)O3F3 octahedra,  a cornercorner with one Li(1)O3F trigonal pyramid,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles range from 44-56°. The V(3)-O(1) bond length is 2.07 Å. The V(3)-O(4) bond length is 2.01 Å. The V(3)-O(5) bond length is 1.94 Å. The V(3)-O(6) bond length is 2.04 Å. The V(3)-F(2) bond length is 2.25 Å. The V(3)-F(4) bond length is 2.16 Å. In the fourth V site, V(4) is bonded to one O(3), one O(6), one O(7), one F(1), one F(3), and one F(4) atom to form VO3F3 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids,  an edgeedge with one V(5)O3F3 octahedra, and  an edgeedge with one V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. The V(4)-O(3) bond length is 1.88 Å. The V(4)-O(6) bond length is 2.01 Å. The V(4)-O(7) bond length is 1.97 Å. The V(4)-F(1) bond length is 2.14 Å. The V(4)-F(3) bond length is 2.16 Å. The V(4)-F(4) bond length is 2.10 Å. In the fifth V site, V(5) is bonded to one O(2), one O(5), one O(7), one F(1), one F(2), and one F(5) atom to form VO3F3 octahedra that share corners with two equivalent V(3)O4F2 octahedra, corners with four equivalent V(1)O4F2 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and  an edgeedge with one V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. The V(5)-O(2) bond length is 1.96 Å. The V(5)-O(5) bond length is 1.97 Å. The V(5)-O(7) bond length is 1.97 Å. The V(5)-F(1) bond length is 2.08 Å. The V(5)-F(2) bond length is 2.17 Å. The V(5)-F(5) bond length is 2.09 Å. In the sixth V site, V(6) is bonded to one O(1), one O(4), one O(6), one F(2), one F(3), and one F(5) atom to form VO3F3 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with four equivalent V(3)O4F2 octahedra,  an edgeedge with one V(4)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra, and edges with two equivalent Li(1)O3F trigonal pyramids. The corner-sharing octahedral tilt angles range from 44-56°. The V(6)-O(1) bond length is 1.99 Å. The V(6)-O(4) bond length is 2.02 Å. The V(6)-O(6) bond length is 1.98 Å. The V(6)-F(2) bond length is 2.12 Å. The V(6)-F(3) bond length is 2.10 Å. The V(6)-F(5) bond length is 2.05 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), one V(3), and one V(6) atom to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(5) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom. In the fourth O site, O(4) is bonded to one Li(1), one V(2), one V(3), and one V(6) atom to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one V(5) atom. In the sixth O site, O(6) is bonded to one Li(1), one V(3), one V(4), and one V(6) atom to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(2), one V(4), and one V(5) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one V(1), one V(4), and one V(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(3), one V(5), and one V(6) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one V(4), and one V(6) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(5), and one V(6) atom.