Li4V2F9 is Ilmenite-like structured and crystallizes in the trigonal P-3c1 space group. There are two 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 LiF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)F6 octahedra, corners with three equivalent V(1)F6 octahedra, edges with three equivalent V(1)F6 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. In the second Li site, Li(2) is bonded to six equivalent F(2) atoms to form LiF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with six equivalent V(1)F6 octahedra, edges with three equivalent Li(2)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. V(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form VF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with six equivalent Li(2)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 47-58°. There are two inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with four equivalent F(1)Li2V2 trigonal pyramids, corners with eight equivalent F(2)Li3V trigonal pyramids, edges with two equivalent F(1)Li2V2 trigonal pyramids, and edges with two equivalent F(2)Li3V trigonal pyramids. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted FLi3V trigonal pyramids that share corners with four equivalent F(1)Li2V2 trigonal pyramids, corners with eight equivalent F(2)Li3V trigonal pyramids,  an edgeedge with one F(1)Li2V2 trigonal pyramid, and edges with three equivalent F(2)Li3V trigonal pyramids.
Li4V2F9 is Ilmenite-like structured and crystallizes in the trigonal P-3c1 space group. There are two 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 LiF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)F6 octahedra, corners with three equivalent V(1)F6 octahedra, edges with three equivalent V(1)F6 octahedra, and  a faceface with one Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. All Li(1)-F(1) bond lengths are 2.04 Å. All Li(1)-F(2) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to six equivalent F(2) atoms to form LiF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with six equivalent V(1)F6 octahedra, edges with three equivalent Li(2)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. There are three shorter (2.02 Å) and three longer (2.17 Å) Li(2)-F(2) bond lengths. V(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form VF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with six equivalent Li(2)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 47-58°. All V(1)-F(1) bond lengths are 2.11 Å. All V(1)-F(2) bond lengths are 1.99 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with four equivalent F(1)Li2V2 trigonal pyramids, corners with eight equivalent F(2)Li3V trigonal pyramids, edges with two equivalent F(1)Li2V2 trigonal pyramids, and edges with two equivalent F(2)Li3V trigonal pyramids. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted FLi3V trigonal pyramids that share corners with four equivalent F(1)Li2V2 trigonal pyramids, corners with eight equivalent F(2)Li3V trigonal pyramids,  an edgeedge with one F(1)Li2V2 trigonal pyramid, and edges with three equivalent F(2)Li3V trigonal pyramids.