LiV(OF)2 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded in a 5-coordinate geometry to two equivalent O(1), two equivalent O(2), and one F(2) atom. V(1) is bonded to one O(1), one O(2), one F(2), and two equivalent F(1) atoms to form corner-sharing VO2F3 trigonal bipyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to two equivalent Li(1) and one V(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.
LiV(OF)2 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded in a 5-coordinate geometry to two equivalent O(1), two equivalent O(2), and one F(2) atom. There is one shorter (2.10 Å) and one longer (2.49 Å) Li(1)-O(1) bond length. There is one shorter (1.99 Å) and one longer (2.58 Å) Li(1)-O(2) bond length. The Li(1)-F(2) bond length is 1.90 Å. V(1) is bonded to one O(1), one O(2), one F(2), and two equivalent F(1) atoms to form corner-sharing VO2F3 trigonal bipyramids. The V(1)-O(1) bond length is 1.66 Å. The V(1)-O(2) bond length is 1.67 Å. The V(1)-F(2) bond length is 1.87 Å. There is one shorter (1.95 Å) and one longer (1.98 Å) V(1)-F(1) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to two equivalent Li(1) and one V(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.