LiV(OF)2 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded to one O(2), two equivalent F(1), and three equivalent F(2) atoms to form distorted edge-sharing LiOF5 octahedra. V(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), one F(1), and one F(2) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to two equivalent V(1) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to three equivalent Li(1) and one V(1) atom.
LiV(OF)2 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded to one O(2), two equivalent F(1), and three equivalent F(2) atoms to form distorted edge-sharing LiOF5 octahedra. The Li(1)-O(2) bond length is 2.00 Å. There is one shorter (2.03 Å) and one longer (2.04 Å) Li(1)-F(1) bond length. There are a spread of Li(1)-F(2) bond distances ranging from 1.96-2.37 Å. V(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), one F(1), and one F(2) atom. The V(1)-O(2) bond length is 1.60 Å. There is one shorter (1.81 Å) and one longer (1.82 Å) V(1)-O(1) bond length. The V(1)-F(1) bond length is 1.89 Å. The V(1)-F(2) bond length is 1.90 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to two equivalent V(1) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to three equivalent Li(1) and one V(1) atom.