Na2NbF6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Na(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NaF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Nb(1)F6 octahedra,  an edgeedge with one Na(1)F6 octahedra, and  an edgeedge with one Nb(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. Nb(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NbF6 octahedra that share corners with eight equivalent Na(1)F6 octahedra and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-48°. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Nb(1) atom. In the second F site, F(1) is bonded in a trigonal planar geometry to two equivalent Na(1) and one Nb(1) atom.
Na2NbF6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Na(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NaF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Nb(1)F6 octahedra,  an edgeedge with one Na(1)F6 octahedra, and  an edgeedge with one Nb(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. Both Na(1)-F(2) bond lengths are 2.32 Å. There are two shorter (2.21 Å) and two longer (2.29 Å) Na(1)-F(1) bond lengths. Nb(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NbF6 octahedra that share corners with eight equivalent Na(1)F6 octahedra and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-48°. Both Nb(1)-F(2) bond lengths are 1.97 Å. All Nb(1)-F(1) bond lengths are 2.03 Å. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Nb(1) atom. In the second F site, F(1) is bonded in a trigonal planar geometry to two equivalent Na(1) and one Nb(1) atom.