Publication Date:
2017-09-13
Description:
Morpholinium tetrafluoroborate, [C4H10NO]+[BF4]−, belongs to a class of ferroelectric compoundsABX4. However, [C4H10NO]+[BF4]−does not develop ferroelectric properties because the incommensurate phase belowTc,I= 153 K is centrosymmetric with superspace groupPnam(σ100)00sand σ1= 0.42193 (12) atT= 130 K; the threefold superstructure belowTc,II= 117–118 K possesses the acentric but non-ferroelectric space groupP212121. At ambient conditions, [C4H10NO]+[BF4]−comprises orientationally disordered [BF4]−anions accommodated in cavities between four morpholinium cations. A structure model for the incommensurately modulated phase, which involves modulated orientational ordering of [BF4]−together with modulated distortions and displacements of the morpholinium ions is reported. A mechanism is proposed for the phase transitions, whereby at low temperatures morpholinium cations are shaped around the tetrafluoroborate anion in order to optimize the interactions with one orientation of this anion and, thus, forcing [BF4]−into this orientation. This mechanism is essentially different from a pure order–disorder phase transition. It is supported by consideration of the transition entropy. The difference in configurational entropy between the disordered and incommensurate phases has been computed from the structure models. It is shown to be much smaller than the experimental transition entropy reported by Owczareket al.[Chem. Phys.(2011),381, 11–20]. These features show that the order–disorder contribution is only a minor contribution to the transition entropy and that other factors, such as conformational changes, play a larger role in the phase transitions.
Print ISSN:
2052-5192
Electronic ISSN:
2052-5206
Topics:
Chemistry and Pharmacology
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Geosciences
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Physics
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