LiV6O7F5 crystallizes in the monoclinic P2 space group. Li(1) is bonded to one O(1), one O(4), one O(6), and one F(4) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one V(1)O3F3 octahedra,  a cornercorner with one V(6)O3F3 octahedra,  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one V(8)O4F2 octahedra,  an edgeedge with one V(4)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(3)O4F2 octahedra, and  an edgeedge with one V(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 57-70°. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(2), two equivalent O(6), one F(2), and two equivalent F(1) atoms to form VO3F3 octahedra that share corners with four equivalent V(3)O4F2 octahedra, corners with four equivalent V(7)O4F2 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(5) atoms to form VO4F2 octahedra that share corners with four equivalent V(4)O3F3 octahedra, corners with four equivalent V(5)O3F3 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(5), one F(2), and one F(4) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra,  an edgeedge with one V(2)O4F2 octahedra,  an edgeedge with one V(3)O4F2 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles range from 45-56°. In the fourth V site, V(4) is bonded to one O(1), one O(3), one O(6), one F(1), and two equivalent F(6) atoms to form VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra, corners with two equivalent V(7)O4F2 octahedra, corners with two equivalent V(8)O4F2 octahedra,  an edgeedge with one V(1)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles range from 47-53°. In the fifth V site, V(5) is bonded to one O(4), one O(5), one O(7), one F(4), and two equivalent F(5) atoms to form VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra, corners with two equivalent V(7)O4F2 octahedra, corners with two equivalent V(8)O4F2 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-56°. In the sixth V site, V(6) is bonded to one O(8), two equivalent O(5), one F(3), and two equivalent F(4) atoms to form VO3F3 octahedra that share corners with four equivalent V(3)O4F2 octahedra, corners with four equivalent V(7)O4F2 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent V(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-55°. In the seventh V site, V(7) is bonded to one O(4), one O(6), one O(7), one O(8), one F(1), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra,  an edgeedge with one V(7)O4F2 octahedra,  an edgeedge with one V(8)O4F2 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles range from 44-55°. In the eighth V site, V(8) is bonded to two equivalent O(4), two equivalent O(7), and two equivalent F(6) atoms to form VO4F2 octahedra that share corners with four equivalent V(4)O3F3 octahedra, corners with four equivalent V(5)O3F3 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent V(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-50°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(2), one V(3), and one V(4) atom to form a mixture of distorted edge and corner-sharing OLiV3 trigonal pyramids. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(2), one V(3), and one V(4) atom. In the fourth O site, O(4) is bonded to one Li(1), one V(5), one V(7), and one V(8) atom to form a mixture of distorted edge and corner-sharing OLiV3 trigonal pyramids. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one V(3), one V(5), and one V(6) atom. In the sixth O site, O(6) is bonded to one Li(1), one V(1), one V(4), and one V(7) atom to form a mixture of distorted edge and corner-sharing OLiV3 trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(5), one V(7), and one V(8) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one V(6) and two equivalent V(7) atoms. There are six 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(7) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one V(6) and two equivalent V(7) atoms. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one V(3), one V(5), and one V(6) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent V(5) atoms. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one V(8) and two equivalent V(4) atoms.
LiV6O7F5 crystallizes in the monoclinic P2 space group. Li(1) is bonded to one O(1), one O(4), one O(6), and one F(4) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one V(1)O3F3 octahedra,  a cornercorner with one V(6)O3F3 octahedra,  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one V(8)O4F2 octahedra,  an edgeedge with one V(4)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(3)O4F2 octahedra, and  an edgeedge with one V(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 57-70°. The Li(1)-O(1) bond length is 1.87 Å. The Li(1)-O(4) bond length is 1.89 Å. The Li(1)-O(6) bond length is 1.91 Å. The Li(1)-F(4) bond length is 1.86 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(2), two equivalent O(6), one F(2), and two equivalent F(1) atoms to form VO3F3 octahedra that share corners with four equivalent V(3)O4F2 octahedra, corners with four equivalent V(7)O4F2 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. The V(1)-O(2) bond length is 1.93 Å. Both V(1)-O(6) bond lengths are 2.03 Å. The V(1)-F(2) bond length is 2.08 Å. Both V(1)-F(1) bond lengths are 2.11 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(5) atoms to form VO4F2 octahedra that share corners with four equivalent V(4)O3F3 octahedra, corners with four equivalent V(5)O3F3 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. Both V(2)-O(1) bond lengths are 2.02 Å. Both V(2)-O(3) bond lengths are 2.01 Å. Both V(2)-F(5) bond lengths are 2.12 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(5), one F(2), and one F(4) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra,  an edgeedge with one V(2)O4F2 octahedra,  an edgeedge with one V(3)O4F2 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles range from 45-56°. The V(3)-O(1) bond length is 2.08 Å. The V(3)-O(2) bond length is 2.01 Å. The V(3)-O(3) bond length is 1.98 Å. The V(3)-O(5) bond length is 1.90 Å. The V(3)-F(2) bond length is 2.15 Å. The V(3)-F(4) bond length is 2.42 Å. In the fourth V site, V(4) is bonded to one O(1), one O(3), one O(6), one F(1), and two equivalent F(6) atoms to form VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra, corners with two equivalent V(7)O4F2 octahedra, corners with two equivalent V(8)O4F2 octahedra,  an edgeedge with one V(1)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles range from 47-53°. The V(4)-O(1) bond length is 2.01 Å. The V(4)-O(3) bond length is 1.95 Å. The V(4)-O(6) bond length is 2.02 Å. The V(4)-F(1) bond length is 2.08 Å. There is one shorter (2.09 Å) and one longer (2.10 Å) V(4)-F(6) bond length. In the fifth V site, V(5) is bonded to one O(4), one O(5), one O(7), one F(4), and two equivalent F(5) atoms to form VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra, corners with two equivalent V(7)O4F2 octahedra, corners with two equivalent V(8)O4F2 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-56°. The V(5)-O(4) bond length is 2.05 Å. The V(5)-O(5) bond length is 1.94 Å. The V(5)-O(7) bond length is 1.92 Å. The V(5)-F(4) bond length is 2.14 Å. There is one shorter (2.06 Å) and one longer (2.15 Å) V(5)-F(5) bond length. In the sixth V site, V(6) is bonded to one O(8), two equivalent O(5), one F(3), and two equivalent F(4) atoms to form VO3F3 octahedra that share corners with four equivalent V(3)O4F2 octahedra, corners with four equivalent V(7)O4F2 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent V(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-55°. The V(6)-O(8) bond length is 1.92 Å. Both V(6)-O(5) bond lengths are 1.98 Å. The V(6)-F(3) bond length is 2.10 Å. Both V(6)-F(4) bond lengths are 2.12 Å. In the seventh V site, V(7) is bonded to one O(4), one O(6), one O(7), one O(8), one F(1), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra,  an edgeedge with one V(7)O4F2 octahedra,  an edgeedge with one V(8)O4F2 octahedra, and  an edgeedge with one Li(1)O3F trigonal pyramid. The corner-sharing octahedral tilt angles range from 44-55°. The V(7)-O(4) bond length is 2.04 Å. The V(7)-O(6) bond length is 2.02 Å. The V(7)-O(7) bond length is 2.00 Å. The V(7)-O(8) bond length is 1.98 Å. The V(7)-F(1) bond length is 2.24 Å. The V(7)-F(3) bond length is 2.16 Å. In the eighth V site, V(8) is bonded to two equivalent O(4), two equivalent O(7), and two equivalent F(6) atoms to form VO4F2 octahedra that share corners with four equivalent V(4)O3F3 octahedra, corners with four equivalent V(5)O3F3 octahedra, corners with two equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent V(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-50°. Both V(8)-O(4) bond lengths are 2.03 Å. Both V(8)-O(7) bond lengths are 1.99 Å. Both V(8)-F(6) bond lengths are 2.14 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(2), one V(3), and one V(4) atom to form a mixture of distorted edge and corner-sharing OLiV3 trigonal pyramids. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(2), one V(3), and one V(4) atom. In the fourth O site, O(4) is bonded to one Li(1), one V(5), one V(7), and one V(8) atom to form a mixture of distorted edge and corner-sharing OLiV3 trigonal pyramids. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one V(3), one V(5), and one V(6) atom. In the sixth O site, O(6) is bonded to one Li(1), one V(1), one V(4), and one V(7) atom to form a mixture of distorted edge and corner-sharing OLiV3 trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(5), one V(7), and one V(8) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one V(6) and two equivalent V(7) atoms. There are six 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(7) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one V(6) and two equivalent V(7) atoms. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one V(3), one V(5), and one V(6) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent V(5) atoms. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one V(8) and two equivalent V(4) atoms.