LiV6O7F5 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(3), one O(5), one F(1), and one F(2) atom to form distorted LiO2F2 trigonal pyramids that share  a cornercorner with one V(2)O3F3 octahedra,  a cornercorner with one V(6)O3F3 octahedra,  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one V(5)O4F2 octahedra,  an edgeedge with one V(2)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 61-68°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(6), one O(7), one F(1), and one F(5) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(4)O3F3 octahedra, corners with three equivalent V(2)O3F3 octahedra, corners with three equivalent V(6)O3F3 octahedra,  an edgeedge with one V(3)O4F2 octahedra,  an edgeedge with one V(5)O4F2 octahedra, and  an edgeedge with one Li(1)O2F2 trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-57°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(4) atom to form VO3F3 octahedra that share corners with two equivalent V(5)O4F2 octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(3)O4F2 octahedra,  a cornercorner with one Li(1)O2F2 trigonal pyramid,  an edgeedge with one V(4)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  an edgeedge with one Li(1)O2F2 trigonal pyramid. The corner-sharing octahedral tilt angles range from 42-56°. In the third V site, V(3) is bonded to one O(2), one O(3), one O(4), one O(5), one F(2), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent V(6)O3F3 octahedra, corners with three equivalent V(2)O3F3 octahedra, corners with three equivalent V(4)O3F3 octahedra,  a cornercorner with one Li(1)O2F2 trigonal pyramid,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one V(5)O4F2 octahedra, and  an edgeedge with one Li(1)O2F2 trigonal pyramid. The corner-sharing octahedral tilt angles range from 42-52°. In the fourth V site, V(4) is bonded to one O(4), one O(5), one O(6), 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 three equivalent V(3)O4F2 octahedra, corners with three equivalent V(5)O4F2 octahedra,  an edgeedge with one V(2)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  an edgeedge with one Li(1)O2F2 trigonal pyramid. The corner-sharing octahedral tilt angles range from 42-56°. In the fifth V site, V(5) is bonded to one O(1), one O(4), one O(5), one O(7), one F(4), and one F(5) atom to form VO4F2 octahedra that share corners with two equivalent V(2)O3F3 octahedra, corners with three equivalent V(4)O3F3 octahedra, corners with three equivalent V(6)O3F3 octahedra,  a cornercorner with one Li(1)O2F2 trigonal pyramid,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. In the sixth V site, V(6) is bonded to one O(1), one O(6), one O(7), one F(2), one F(3), and one F(5) atom to form VO3F3 octahedra that share corners with two equivalent V(3)O4F2 octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(5)O4F2 octahedra,  a cornercorner with one Li(1)O2F2 trigonal pyramid,  an edgeedge with one V(2)O3F3 octahedra, and  an edgeedge with one V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(2), one V(5), and one V(6) atom. 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(3) atom. In the third O site, O(3) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(3), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a distorted see-saw-like geometry to one Li(1), one V(3), one V(4), and one V(5) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(1), one V(5), and one V(6) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one V(4) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(1), one V(2), one V(3), and one V(6) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one V(3), 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(4), and one V(5) 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(3), one O(5), one F(1), and one F(2) atom to form distorted LiO2F2 trigonal pyramids that share  a cornercorner with one V(2)O3F3 octahedra,  a cornercorner with one V(6)O3F3 octahedra,  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one V(5)O4F2 octahedra,  an edgeedge with one V(2)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 61-68°. The Li(1)-O(3) bond length is 1.87 Å. The Li(1)-O(5) bond length is 1.88 Å. The Li(1)-F(1) bond length is 1.86 Å. The Li(1)-F(2) bond length is 1.91 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(6), one O(7), one F(1), and one F(5) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(4)O3F3 octahedra, corners with three equivalent V(2)O3F3 octahedra, corners with three equivalent V(6)O3F3 octahedra,  an edgeedge with one V(3)O4F2 octahedra,  an edgeedge with one V(5)O4F2 octahedra, and  an edgeedge with one Li(1)O2F2 trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-57°. The V(1)-O(2) bond length is 2.01 Å. The V(1)-O(3) bond length is 2.03 Å. The V(1)-O(6) bond length is 1.91 Å. The V(1)-O(7) bond length is 1.98 Å. The V(1)-F(1) bond length is 2.42 Å. The V(1)-F(5) bond length is 2.18 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(2), and one F(4) atom to form VO3F3 octahedra that share corners with two equivalent V(5)O4F2 octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(3)O4F2 octahedra,  a cornercorner with one Li(1)O2F2 trigonal pyramid,  an edgeedge with one V(4)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  an edgeedge with one Li(1)O2F2 trigonal pyramid. The corner-sharing octahedral tilt angles range from 42-56°. The V(2)-O(1) bond length is 1.96 Å. The V(2)-O(2) bond length is 1.92 Å. The V(2)-O(3) bond length is 2.04 Å. The V(2)-F(1) bond length is 2.06 Å. The V(2)-F(2) bond length is 2.14 Å. The V(2)-F(4) bond length is 2.19 Å. In the third V site, V(3) is bonded to one O(2), one O(3), one O(4), one O(5), one F(2), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent V(6)O3F3 octahedra, corners with three equivalent V(2)O3F3 octahedra, corners with three equivalent V(4)O3F3 octahedra,  a cornercorner with one Li(1)O2F2 trigonal pyramid,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one V(5)O4F2 octahedra, and  an edgeedge with one Li(1)O2F2 trigonal pyramid. The corner-sharing octahedral tilt angles range from 42-52°. The V(3)-O(2) bond length is 2.00 Å. The V(3)-O(3) bond length is 2.02 Å. The V(3)-O(4) bond length is 1.97 Å. The V(3)-O(5) bond length is 2.04 Å. The V(3)-F(2) bond length is 2.23 Å. The V(3)-F(3) bond length is 2.09 Å. In the fourth V site, V(4) is bonded to one O(4), one O(5), one O(6), 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 three equivalent V(3)O4F2 octahedra, corners with three equivalent V(5)O4F2 octahedra,  an edgeedge with one V(2)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  an edgeedge with one Li(1)O2F2 trigonal pyramid. The corner-sharing octahedral tilt angles range from 42-56°. The V(4)-O(4) bond length is 1.95 Å. The V(4)-O(5) bond length is 2.00 Å. The V(4)-O(6) bond length is 1.93 Å. The V(4)-F(1) bond length is 2.23 Å. The V(4)-F(3) bond length is 2.12 Å. The V(4)-F(4) bond length is 2.06 Å. In the fifth V site, V(5) is bonded to one O(1), one O(4), one O(5), one O(7), one F(4), and one F(5) atom to form VO4F2 octahedra that share corners with two equivalent V(2)O3F3 octahedra, corners with three equivalent V(4)O3F3 octahedra, corners with three equivalent V(6)O3F3 octahedra,  a cornercorner with one Li(1)O2F2 trigonal pyramid,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. The V(5)-O(1) bond length is 1.96 Å. The V(5)-O(4) bond length is 1.99 Å. The V(5)-O(5) bond length is 2.06 Å. The V(5)-O(7) bond length is 2.01 Å. The V(5)-F(4) bond length is 2.32 Å. The V(5)-F(5) bond length is 2.18 Å. In the sixth V site, V(6) is bonded to one O(1), one O(6), one O(7), one F(2), one F(3), and one F(5) atom to form VO3F3 octahedra that share corners with two equivalent V(3)O4F2 octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(5)O4F2 octahedra,  a cornercorner with one Li(1)O2F2 trigonal pyramid,  an edgeedge with one V(2)O3F3 octahedra, and  an edgeedge with one V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. The V(6)-O(1) bond length is 1.99 Å. The V(6)-O(6) bond length is 2.00 Å. The V(6)-O(7) bond length is 1.93 Å. The V(6)-F(2) bond length is 2.13 Å. The V(6)-F(3) bond length is 2.08 Å. The V(6)-F(5) bond length is 2.10 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(2), one V(5), and one V(6) atom. 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(3) atom. In the third O site, O(3) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(3), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a distorted see-saw-like geometry to one Li(1), one V(3), one V(4), and one V(5) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(1), one V(5), and one V(6) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one V(4) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(1), one V(2), one V(3), and one V(6) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one V(3), 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(4), and one V(5) 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.