Nb5OF14 is alpha Rhenium trioxide-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form NbF6 octahedra that share  a cornercorner with one Nb(1)F6 octahedra, corners with two equivalent Nb(3)F6 octahedra, and corners with three equivalent Nb(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the second Nb site, Nb(2) is bonded to one O(1), one F(1), one F(2), one F(4), one F(7), and one F(8) atom to form NbOF5 octahedra that share  a cornercorner with one Nb(3)F6 octahedra, corners with two equivalent Nb(2)OF5 octahedra, and corners with three equivalent Nb(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third Nb site, Nb(3) is bonded to two equivalent F(3), two equivalent F(6), and two equivalent F(7) atoms to form NbF6 octahedra that share corners with two equivalent Nb(2)OF5 octahedra and corners with four equivalent Nb(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. O(1) is bonded in a linear geometry to two equivalent Nb(2) atoms. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Nb(1) and one Nb(2) atom. In the second F site, F(2) is bonded in a linear geometry to one Nb(1) and one Nb(2) atom. In the third F site, F(3) is bonded in a linear geometry to one Nb(1) and one Nb(3) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Nb(1) and one Nb(2) atom. In the fifth F site, F(5) is bonded in a linear geometry to two equivalent Nb(1) atoms. In the sixth F site, F(6) is bonded in a linear geometry to one Nb(1) and one Nb(3) atom. In the seventh F site, F(7) is bonded in a linear geometry to one Nb(2) and one Nb(3) atom. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent Nb(2) atoms.
Nb5OF14 is alpha Rhenium trioxide-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form NbF6 octahedra that share  a cornercorner with one Nb(1)F6 octahedra, corners with two equivalent Nb(3)F6 octahedra, and corners with three equivalent Nb(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. The Nb(1)-F(1) bond length is 2.11 Å. The Nb(1)-F(2) bond length is 2.09 Å. The Nb(1)-F(3) bond length is 2.10 Å. The Nb(1)-F(4) bond length is 2.08 Å. The Nb(1)-F(5) bond length is 2.09 Å. The Nb(1)-F(6) bond length is 2.10 Å. In the second Nb site, Nb(2) is bonded to one O(1), one F(1), one F(2), one F(4), one F(7), and one F(8) atom to form NbOF5 octahedra that share  a cornercorner with one Nb(3)F6 octahedra, corners with two equivalent Nb(2)OF5 octahedra, and corners with three equivalent Nb(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. The Nb(2)-O(1) bond length is 1.90 Å. The Nb(2)-F(1) bond length is 2.09 Å. The Nb(2)-F(2) bond length is 2.09 Å. The Nb(2)-F(4) bond length is 2.17 Å. The Nb(2)-F(7) bond length is 2.09 Å. The Nb(2)-F(8) bond length is 2.08 Å. In the third Nb site, Nb(3) is bonded to two equivalent F(3), two equivalent F(6), and two equivalent F(7) atoms to form NbF6 octahedra that share corners with two equivalent Nb(2)OF5 octahedra and corners with four equivalent Nb(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Nb(3)-F(3) bond lengths are 2.07 Å. Both Nb(3)-F(6) bond lengths are 2.08 Å. Both Nb(3)-F(7) bond lengths are 2.11 Å. O(1) is bonded in a linear geometry to two equivalent Nb(2) atoms. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Nb(1) and one Nb(2) atom. In the second F site, F(2) is bonded in a linear geometry to one Nb(1) and one Nb(2) atom. In the third F site, F(3) is bonded in a linear geometry to one Nb(1) and one Nb(3) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Nb(1) and one Nb(2) atom. In the fifth F site, F(5) is bonded in a linear geometry to two equivalent Nb(1) atoms. In the sixth F site, F(6) is bonded in a linear geometry to one Nb(1) and one Nb(3) atom. In the seventh F site, F(7) is bonded in a linear geometry to one Nb(2) and one Nb(3) atom. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent Nb(2) atoms.