LiNb(OF)2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(2), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiOF4 trigonal bipyramids that share corners with four equivalent Nb(1)O4F2 octahedra, corners with four equivalent Li(1)OF4 trigonal bipyramids, and  an edgeedge with one Nb(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-65°. Nb(1) is bonded to two equivalent O(1), two equivalent O(2), one F(1), and one F(2) atom to form distorted NbO4F2 octahedra that share corners with four equivalent Nb(1)O4F2 octahedra, corners with four equivalent Li(1)OF4 trigonal bipyramids, and  an edgeedge with one Li(1)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 37-43°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent Nb(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Nb(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Nb(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Nb(1) atom.
LiNb(OF)2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(2), two equivalent F(1), and two equivalent F(2) atoms to form distorted LiOF4 trigonal bipyramids that share corners with four equivalent Nb(1)O4F2 octahedra, corners with four equivalent Li(1)OF4 trigonal bipyramids, and  an edgeedge with one Nb(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-65°. The Li(1)-O(2) bond length is 2.22 Å. There is one shorter (2.04 Å) and one longer (2.27 Å) Li(1)-F(1) bond length. There is one shorter (1.95 Å) and one longer (2.03 Å) Li(1)-F(2) bond length. Nb(1) is bonded to two equivalent O(1), two equivalent O(2), one F(1), and one F(2) atom to form distorted NbO4F2 octahedra that share corners with four equivalent Nb(1)O4F2 octahedra, corners with four equivalent Li(1)OF4 trigonal bipyramids, and  an edgeedge with one Li(1)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 37-43°. There is one shorter (1.92 Å) and one longer (1.95 Å) Nb(1)-O(1) bond length. There is one shorter (1.85 Å) and one longer (2.19 Å) Nb(1)-O(2) bond length. The Nb(1)-F(1) bond length is 2.04 Å. The Nb(1)-F(2) bond length is 2.08 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent Nb(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Nb(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Nb(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Nb(1) atom.