Li2V2F7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(3), and one F(7) atom to form distorted LiF4 trigonal pyramids that share corners with two equivalent V(2)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and  an edgeedge with one Li(2)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 39-64°. In the second Li site, Li(2) is bonded to one F(1), one F(5), one F(6), and one F(7) atom to form distorted LiF4 trigonal pyramids that share corners with two equivalent V(1)F6 octahedra, corners with four equivalent V(2)F6 octahedra, and  an edgeedge with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 40-58°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(2), one F(4), one F(5), one F(7), and two equivalent F(3) atoms to form VF6 octahedra that share  a cornercorner with one V(2)F6 octahedra, corners with two equivalent Li(2)F4 trigonal pyramids, corners with four equivalent Li(1)F4 trigonal pyramids,  an edgeedge with one V(1)F6 octahedra, and  an edgeedge with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles are 15°. In the second V site, V(2) is bonded to one F(1), one F(2), one F(4), one F(5), and two equivalent F(6) atoms to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra, corners with two equivalent Li(1)F4 trigonal pyramids, corners with four equivalent Li(2)F4 trigonal pyramids,  an edgeedge with one V(1)F6 octahedra, and  an edgeedge with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles are 15°. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a linear geometry to one V(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent V(2) atoms. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom.
Li2V2F7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(3), and one F(7) atom to form distorted LiF4 trigonal pyramids that share corners with two equivalent V(2)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and  an edgeedge with one Li(2)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 39-64°. The Li(1)-F(1) bond length is 1.95 Å. The Li(1)-F(2) bond length is 1.95 Å. The Li(1)-F(3) bond length is 1.92 Å. The Li(1)-F(7) bond length is 1.86 Å. In the second Li site, Li(2) is bonded to one F(1), one F(5), one F(6), and one F(7) atom to form distorted LiF4 trigonal pyramids that share corners with two equivalent V(1)F6 octahedra, corners with four equivalent V(2)F6 octahedra, and  an edgeedge with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 40-58°. The Li(2)-F(1) bond length is 1.89 Å. The Li(2)-F(5) bond length is 1.96 Å. The Li(2)-F(6) bond length is 1.90 Å. The Li(2)-F(7) bond length is 1.90 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(2), one F(4), one F(5), one F(7), and two equivalent F(3) atoms to form VF6 octahedra that share  a cornercorner with one V(2)F6 octahedra, corners with two equivalent Li(2)F4 trigonal pyramids, corners with four equivalent Li(1)F4 trigonal pyramids,  an edgeedge with one V(1)F6 octahedra, and  an edgeedge with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles are 15°. The V(1)-F(2) bond length is 2.11 Å. The V(1)-F(4) bond length is 2.01 Å. The V(1)-F(5) bond length is 2.11 Å. The V(1)-F(7) bond length is 1.98 Å. There is one shorter (2.07 Å) and one longer (2.09 Å) V(1)-F(3) bond length. In the second V site, V(2) is bonded to one F(1), one F(2), one F(4), one F(5), and two equivalent F(6) atoms to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra, corners with two equivalent Li(1)F4 trigonal pyramids, corners with four equivalent Li(2)F4 trigonal pyramids,  an edgeedge with one V(1)F6 octahedra, and  an edgeedge with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles are 15°. The V(2)-F(1) bond length is 1.98 Å. The V(2)-F(2) bond length is 2.07 Å. The V(2)-F(4) bond length is 1.98 Å. The V(2)-F(5) bond length is 2.08 Å. There is one shorter (2.06 Å) and one longer (2.07 Å) V(2)-F(6) bond length. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a linear geometry to one V(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent V(2) atoms. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom.