Li3V2F9 crystallizes in the trigonal P3c1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted LiF6 octahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent V(1)F6 octahedra, edges with three equivalent V(2)F6 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-46°. In the second Li site, Li(2) is bonded to three equivalent F(1) and three equivalent F(3) atoms to form LiF6 octahedra that share corners with three equivalent V(1)F6 octahedra, corners with three equivalent V(2)F6 octahedra, edges with three equivalent Li(3)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. In the third Li site, Li(3) is bonded to three equivalent F(1) and three equivalent F(3) atoms to form LiF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent V(1)F6 octahedra, corners with three equivalent V(2)F6 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. There are two inequivalent V sites. In the first V site, V(1) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form VF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Li(3)F6 octahedra, and  a faceface with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-52°. In the second V site, V(2) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted VF6 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Li(3)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), and one V(2) atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids. In the second F site, F(2) is bonded in a T-shaped 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(2), one Li(3), and one V(1) atom.
Li3V2F9 crystallizes in the trigonal P3c1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted LiF6 octahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent V(1)F6 octahedra, edges with three equivalent V(2)F6 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-46°. All Li(1)-F(1) bond lengths are 2.18 Å. All Li(1)-F(2) bond lengths are 1.99 Å. In the second Li site, Li(2) is bonded to three equivalent F(1) and three equivalent F(3) atoms to form LiF6 octahedra that share corners with three equivalent V(1)F6 octahedra, corners with three equivalent V(2)F6 octahedra, edges with three equivalent Li(3)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. All Li(2)-F(1) bond lengths are 2.17 Å. All Li(2)-F(3) bond lengths are 1.99 Å. In the third Li site, Li(3) is bonded to three equivalent F(1) and three equivalent F(3) atoms to form LiF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent V(1)F6 octahedra, corners with three equivalent V(2)F6 octahedra, and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. All Li(3)-F(1) bond lengths are 2.13 Å. All Li(3)-F(3) bond lengths are 2.06 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form VF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Li(3)F6 octahedra, and  a faceface with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-52°. All V(1)-F(2) bond lengths are 2.07 Å. All V(1)-F(3) bond lengths are 1.92 Å. In the second V site, V(2) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted VF6 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Li(3)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and  a faceface with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. All V(2)-F(1) bond lengths are 1.95 Å. All V(2)-F(2) bond lengths are 2.03 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), and one V(2) atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids. In the second F site, F(2) is bonded in a T-shaped 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(2), one Li(3), and one V(1) atom.