Nb5O12F crystallizes in the orthorhombic Pmma space group. There are three inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(1), one O(2), one O(6), one O(7), and two equivalent O(3) atoms to form NbO6 octahedra that share corners with three equivalent Nb(1)O6 octahedra,  a cornercorner with one Nb(2)O7 pentagonal bipyramid, corners with two equivalent Nb(3)O6F pentagonal bipyramids,  an edgeedge with one Nb(3)O6F pentagonal bipyramid, and  an edgeedge with one Nb(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 14-30°. In the second Nb site, Nb(2) is bonded to one O(2), two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms to form NbO7 pentagonal bipyramids that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O7 pentagonal bipyramids, edges with two equivalent Nb(1)O6 octahedra, and edges with two equivalent Nb(3)O6F pentagonal bipyramids. The corner-sharing octahedral tilt angles are 26°. In the third Nb site, Nb(3) is bonded to one O(1), one O(7), two equivalent O(5), two equivalent O(6), and one F(1) atom to form NbO6F pentagonal bipyramids that share corners with two equivalent Nb(1)O6 octahedra, corners with three equivalent Nb(3)O6F pentagonal bipyramids,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Nb(3)O6F pentagonal bipyramid, and  an edgeedge with one Nb(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 40-46°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Nb(1), one Nb(2), and one Nb(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Nb(2) and two equivalent Nb(1) atoms. In the third O site, O(3) is bonded in a linear geometry to two equivalent Nb(1) atoms. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent Nb(2) atoms. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent Nb(3) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Nb(1) and two equivalent Nb(3) atoms. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Nb(1), one Nb(2), and one Nb(3) atom. F(1) is bonded in a linear geometry to two equivalent Nb(3) atoms.
Nb5O12F crystallizes in the orthorhombic Pmma space group. There are three inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(1), one O(2), one O(6), one O(7), and two equivalent O(3) atoms to form NbO6 octahedra that share corners with three equivalent Nb(1)O6 octahedra,  a cornercorner with one Nb(2)O7 pentagonal bipyramid, corners with two equivalent Nb(3)O6F pentagonal bipyramids,  an edgeedge with one Nb(3)O6F pentagonal bipyramid, and  an edgeedge with one Nb(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 14-30°. The Nb(1)-O(1) bond length is 2.05 Å. The Nb(1)-O(2) bond length is 2.00 Å. The Nb(1)-O(6) bond length is 2.03 Å. The Nb(1)-O(7) bond length is 2.03 Å. Both Nb(1)-O(3) bond lengths are 1.96 Å. In the second Nb site, Nb(2) is bonded to one O(2), two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms to form NbO7 pentagonal bipyramids that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O7 pentagonal bipyramids, edges with two equivalent Nb(1)O6 octahedra, and edges with two equivalent Nb(3)O6F pentagonal bipyramids. The corner-sharing octahedral tilt angles are 26°. The Nb(2)-O(2) bond length is 2.32 Å. Both Nb(2)-O(1) bond lengths are 2.10 Å. Both Nb(2)-O(4) bond lengths are 1.95 Å. Both Nb(2)-O(7) bond lengths are 2.11 Å. In the third Nb site, Nb(3) is bonded to one O(1), one O(7), two equivalent O(5), two equivalent O(6), and one F(1) atom to form NbO6F pentagonal bipyramids that share corners with two equivalent Nb(1)O6 octahedra, corners with three equivalent Nb(3)O6F pentagonal bipyramids,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Nb(3)O6F pentagonal bipyramid, and  an edgeedge with one Nb(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 40-46°. The Nb(3)-O(1) bond length is 2.02 Å. The Nb(3)-O(7) bond length is 2.26 Å. Both Nb(3)-O(5) bond lengths are 1.95 Å. There is one shorter (2.03 Å) and one longer (2.09 Å) Nb(3)-O(6) bond length. The Nb(3)-F(1) bond length is 2.29 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Nb(1), one Nb(2), and one Nb(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Nb(2) and two equivalent Nb(1) atoms. In the third O site, O(3) is bonded in a linear geometry to two equivalent Nb(1) atoms. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent Nb(2) atoms. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent Nb(3) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Nb(1) and two equivalent Nb(3) atoms. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Nb(1), one Nb(2), and one Nb(3) atom. F(1) is bonded in a linear geometry to two equivalent Nb(3) atoms.