Temperature-Induced Irreversible Phase Transition From Perovskite to Diamond But Pressure-Driven Back-Transition in an Ammonium Copper Formate.

The compound [CH3 CH2 NH3][Cu(HCOO)3] undergoes a phase transition at 357 K, from a perovskite to a diamond structure, by heating. The backward transition can be driven by pressure at room temperature but not cooling under ambient or lower pressure. The rearrangement of one long copper-formate bond, the switch of bridging-chelating mode of the formate, the alternation of N-H⋅⋅⋅O H-bonds, and the flipping of ethylammonium are involved in the transition. The strong N-H⋅⋅⋅O H-bonding probably locks the metastable diamond phase. The two phases display magnetic and electric orderings of different characters.