Nb3O7F crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(1), two equivalent O(2), and three equivalent O(3) atoms to form NbO6 octahedra that share  a cornercorner with one Nb(2)O4F2 octahedra, corners with four equivalent Nb(1)O6 octahedra, and edges with two equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-30°. In the second Nb site, Nb(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form NbO4F2 octahedra that share corners with two equivalent Nb(1)O6 octahedra and corners with four equivalent Nb(2)O4F2 octahedra. The corner-sharing octahedra are not tilted. There are four inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Nb(1) and one Nb(2) atom. In the second O site, O(2) is bonded in a linear geometry to two equivalent Nb(1) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to three equivalent Nb(1) atoms. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent Nb(2) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Nb(2) atoms. In the second F site, F(1) is bonded in a linear geometry to two equivalent Nb(2) atoms.
Nb3O7F crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(1), two equivalent O(2), and three equivalent O(3) atoms to form NbO6 octahedra that share  a cornercorner with one Nb(2)O4F2 octahedra, corners with four equivalent Nb(1)O6 octahedra, and edges with two equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-30°. The Nb(1)-O(1) bond length is 1.93 Å. Both Nb(1)-O(2) bond lengths are 1.99 Å. There are two shorter (2.02 Å) and one longer (2.24 Å) Nb(1)-O(3) bond length. In the second Nb site, Nb(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form NbO4F2 octahedra that share corners with two equivalent Nb(1)O6 octahedra and corners with four equivalent Nb(2)O4F2 octahedra. The corner-sharing octahedra are not tilted. Both Nb(2)-O(1) bond lengths are 1.96 Å. Both Nb(2)-O(4) bond lengths are 1.95 Å. Both Nb(2)-F(1) bond lengths are 1.99 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Nb(1) and one Nb(2) atom. In the second O site, O(2) is bonded in a linear geometry to two equivalent Nb(1) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to three equivalent Nb(1) atoms. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent Nb(2) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Nb(2) atoms. In the second F site, F(1) is bonded in a linear geometry to two equivalent Nb(2) atoms. Both F(1)-Nb(2) bond lengths are 1.99 Å.