Na2HF4 crystallizes in the monoclinic P2/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form distorted edge-sharing NaF6 octahedra. In the second Na site, Na(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form edge-sharing NaF6 octahedra. H(1) is bonded in a linear geometry to two equivalent F(2) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Na(2) atoms. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one H(1) atom to form a mixture of distorted corner and edge-sharing FNa3H tetrahedra.
Na2HF4 crystallizes in the monoclinic P2/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form distorted edge-sharing NaF6 octahedra. Both Na(1)-F(1) bond lengths are 2.33 Å. All Na(1)-F(2) bond lengths are 2.25 Å. In the second Na site, Na(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form edge-sharing NaF6 octahedra. Both Na(2)-F(2) bond lengths are 2.22 Å. All Na(2)-F(1) bond lengths are 2.31 Å. H(1) is bonded in a linear geometry to two equivalent F(2) atoms. Both H(1)-F(2) bond lengths are 1.13 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Na(2) atoms. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one H(1) atom to form a mixture of distorted corner and edge-sharing FNa3H tetrahedra.