Li3VF5 is Aluminum carbonitride-like structured and crystallizes in the trigonal P3_121 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiF5 trigonal bipyramids that share corners with four equivalent Li(2)F4 tetrahedra and corners with five equivalent Li(1)F5 trigonal bipyramids. In the second Li site, Li(2) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form distorted corner-sharing LiF4 tetrahedra. V(1) is bonded in a 5-coordinate geometry to one F(3), two equivalent F(1), and two equivalent F(2) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form a mixture of edge and corner-sharing FLi3V tetrahedra. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form a mixture of distorted edge and corner-sharing FLi3V tetrahedra. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(1) atom.
Li3VF5 is Aluminum carbonitride-like structured and crystallizes in the trigonal P3_121 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiF5 trigonal bipyramids that share corners with four equivalent Li(2)F4 tetrahedra and corners with five equivalent Li(1)F5 trigonal bipyramids. The Li(1)-F(3) bond length is 1.95 Å. There is one shorter (2.06 Å) and one longer (2.15 Å) Li(1)-F(1) bond length. There is one shorter (1.96 Å) and one longer (1.98 Å) Li(1)-F(2) bond length. In the second Li site, Li(2) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form distorted corner-sharing LiF4 tetrahedra. Both Li(2)-F(1) bond lengths are 1.93 Å. Both Li(2)-F(2) bond lengths are 2.05 Å. V(1) is bonded in a 5-coordinate geometry to one F(3), two equivalent F(1), and two equivalent F(2) atoms. The V(1)-F(3) bond length is 2.24 Å. Both V(1)-F(1) bond lengths are 2.05 Å. Both V(1)-F(2) bond lengths are 2.09 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form a mixture of edge and corner-sharing FLi3V tetrahedra. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form a mixture of distorted edge and corner-sharing FLi3V tetrahedra. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(1) atom.