Na2NbO4F5 crystallizes in the orthorhombic Aea2 space group. Na(1) is bonded to one O(2), two equivalent O(1), one F(1), one F(2), and one F(3) atom to form NaO3F3 octahedra that share corners with three equivalent Na(1)O3F3 octahedra and corners with four equivalent Nb(1)O2F5 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 53-71°. Nb(1) is bonded to two equivalent O(2), one F(3), two equivalent F(1), and two equivalent F(2) atoms to form distorted NbO2F5 pentagonal bipyramids that share corners with eight equivalent Na(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 30-54°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to two equivalent Na(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Nb(1), and one O(2) atom. There are three inequivalent F sites. In the first F site, F(2) is bonded in a bent 150 degrees geometry to one Na(1) and one Nb(1) atom. In the second F site, F(3) is bonded in a trigonal planar geometry to two equivalent Na(1) and one Nb(1) atom. In the third F site, F(1) is bonded in a bent 150 degrees geometry to one Na(1) and one Nb(1) atom.
Na2NbO4F5 crystallizes in the orthorhombic Aea2 space group. Na(1) is bonded to one O(2), two equivalent O(1), one F(1), one F(2), and one F(3) atom to form NaO3F3 octahedra that share corners with three equivalent Na(1)O3F3 octahedra and corners with four equivalent Nb(1)O2F5 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 53-71°. The Na(1)-O(2) bond length is 2.49 Å. There is one shorter (2.39 Å) and one longer (2.46 Å) Na(1)-O(1) bond length. The Na(1)-F(1) bond length is 2.31 Å. The Na(1)-F(2) bond length is 2.29 Å. The Na(1)-F(3) bond length is 2.42 Å. Nb(1) is bonded to two equivalent O(2), one F(3), two equivalent F(1), and two equivalent F(2) atoms to form distorted NbO2F5 pentagonal bipyramids that share corners with eight equivalent Na(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 30-54°. Both Nb(1)-O(2) bond lengths are 2.08 Å. The Nb(1)-F(3) bond length is 2.01 Å. Both Nb(1)-F(1) bond lengths are 1.98 Å. Both Nb(1)-F(2) bond lengths are 1.94 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to two equivalent Na(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Nb(1), and one O(2) atom. The O(2)-O(2) bond length is 1.39 Å. There are three inequivalent F sites. In the first F site, F(2) is bonded in a bent 150 degrees geometry to one Na(1) and one Nb(1) atom. In the second F site, F(3) is bonded in a trigonal planar geometry to two equivalent Na(1) and one Nb(1) atom. In the third F site, F(1) is bonded in a bent 150 degrees geometry to one Na(1) and one Nb(1) atom.