LiNb3O7F crystallizes in the monoclinic Pm space group. Li(1) is bonded to one O(2), two equivalent O(4), and two equivalent O(5) atoms to form LiO5 trigonal bipyramids that share corners with four equivalent Li(1)O5 trigonal bipyramids and edges with four equivalent Nb(2)O6 octahedra. There are three inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. In the second Nb site, Nb(2) is bonded to one O(3), one O(6), two equivalent O(4), and two equivalent O(5) atoms to form distorted NbO6 octahedra that share  a cornercorner with one Nb(3)O4F2 octahedra, corners with four equivalent Nb(2)O6 octahedra, and edges with four equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-30°. In the third Nb site, Nb(3) is bonded to one O(1), one O(6), two equivalent O(7), and two equivalent F(1) atoms to form NbO4F2 octahedra that share  a cornercorner with one Nb(2)O6 octahedra and corners with four equivalent Nb(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Nb(1) and one Nb(3) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(1) and two equivalent Nb(1) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Nb(2) and two equivalent Nb(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(1), one Nb(1), and two equivalent Nb(2) atoms to form distorted corner-sharing OLi2Nb3 trigonal bipyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Nb(2) atoms. In the sixth O site, O(6) is bonded in a linear geometry to one Nb(2) and one Nb(3) atom. In the seventh O site, O(7) is bonded in a linear geometry to two equivalent Nb(3) atoms. F(1) is bonded in a linear geometry to two equivalent Nb(3) atoms.
LiNb3O7F crystallizes in the monoclinic Pm space group. Li(1) is bonded to one O(2), two equivalent O(4), and two equivalent O(5) atoms to form LiO5 trigonal bipyramids that share corners with four equivalent Li(1)O5 trigonal bipyramids and edges with four equivalent Nb(2)O6 octahedra. The Li(1)-O(2) bond length is 1.96 Å. Both Li(1)-O(4) bond lengths are 2.04 Å. There is one shorter (2.06 Å) and one longer (2.07 Å) Li(1)-O(5) bond length. There are three inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. The Nb(1)-O(1) bond length is 1.84 Å. The Nb(1)-O(4) bond length is 2.43 Å. Both Nb(1)-O(2) bond lengths are 2.04 Å. Both Nb(1)-O(3) bond lengths are 2.05 Å. In the second Nb site, Nb(2) is bonded to one O(3), one O(6), two equivalent O(4), and two equivalent O(5) atoms to form distorted NbO6 octahedra that share  a cornercorner with one Nb(3)O4F2 octahedra, corners with four equivalent Nb(2)O6 octahedra, and edges with four equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-30°. The Nb(2)-O(3) bond length is 2.34 Å. The Nb(2)-O(6) bond length is 1.86 Å. Both Nb(2)-O(4) bond lengths are 2.02 Å. Both Nb(2)-O(5) bond lengths are 2.03 Å. In the third Nb site, Nb(3) is bonded to one O(1), one O(6), two equivalent O(7), and two equivalent F(1) atoms to form NbO4F2 octahedra that share  a cornercorner with one Nb(2)O6 octahedra and corners with four equivalent Nb(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. The Nb(3)-O(1) bond length is 2.04 Å. The Nb(3)-O(6) bond length is 2.01 Å. There is one shorter (1.91 Å) and one longer (2.00 Å) Nb(3)-O(7) bond length. Both Nb(3)-F(1) bond lengths are 2.02 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Nb(1) and one Nb(3) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(1) and two equivalent Nb(1) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Nb(2) and two equivalent Nb(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(1), one Nb(1), and two equivalent Nb(2) atoms to form distorted corner-sharing OLi2Nb3 trigonal bipyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Nb(2) atoms. In the sixth O site, O(6) is bonded in a linear geometry to one Nb(2) and one Nb(3) atom. In the seventh O site, O(7) is bonded in a linear geometry to two equivalent Nb(3) atoms. F(1) is bonded in a linear geometry to two equivalent Nb(3) atoms.