Structure, Phonon Properties, and Order–Disorder Transition in the Metal Formate Framework of [NH4][Mg(HCOO)3]

We report the synthesis, crystal structure, thermal, dielectric, IR, and Raman studies of [NH4]­[Mg­(HCOO)3] formate. Single-crystal X-ray diffraction shows that it crystallizes in the hexagonal space group P6322, with orientationally disordered NH4+ ions located in the cages of the network. Upon cooling, [NH4]­[Mg­(HCOO)3] undergoes a phase transition at around 255 K to the ferroelectric P63 structure. Raman and IR spectra show a strong increase in intensity of the N–H stretching bands as well as narrowing of the bands related to the NH4+ ions upon cooling. These changes indicate that the phase transition is due to orientational ordering of the NH4+ ions. Analysis of the Raman data show, however, that the rotational and translational motions of NH4+ do not freeze completely at the phase transition but exhibit further slowing down below 255 K, and the motional freezing becomes nearly complete below 140 K.