β-ZrNCl reacts with excess NaF in the solid state (350−400 °C) via anion exchange to give metastable
Na
x
ZrNF1+
x
(x ≈ 0.3), the first fluoride structural analogue of the MNX system (M = Zr, Hf; X = Cl,
Br, I). The sodium-stabilized phase (P63/mmc; a = 3.654(1) Å, c = 18.266(8) Å) was characterized by
powder X-ray and neutron diffraction studies and was shown to contain successive FZr2N2F layers that
are shifted from the original ZrNCl parent structure, giving a two-layer unit cell. Partially occupied Na
and F sites create a stabilizing cluster effect between these layers. Heating the reaction mixture above
500 °C leads to the formation of the ZrN
x
F4
-
3
x
phase reported by Jung and Juza. Further heating results
in decomposition to several known sodium fluorozirconate phases.