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  • Title: Redetermination of the structure and dielectric properties of bis(thiourea) pyridinium iodide--a new ferroelectric inclusion compound.
    Author: Małuszyńska H, Czarnecki P, Fojud Z, Wasicki J.
    Journal: Acta Crystallogr B; 2008 Oct; 64(Pt 5):567-72. PubMed ID: 18799844.
    Abstract:
    The crystal structure of bis(thiourea) pyridinium iodide (T(2)PyI) was previously determined at 295 and 110 K [Prout, Heyes, Dobson, McDaid, Maris, Mueller & Seaman (2000). Chem. Mater. 12, 3561-3569] and the two phases were described in the space groups Cmcm and P2(1)cn, respectively. Because differential scanning calorimetry revealed two phase transitions, at 161 and 141 K, a redetermination of the structure of T(2)pyI at 295, 155 and 110 K has been undertaken, and the following sequence of space groups obtained: Cmcm (I) --> C2cm (II) --> P2(1)cn (III). The high- (I) and low-temperature (III) phases confirmed the results reported in the previous study. In the new intermediate phase II, the mirror plane perpendicular to the x axis vanishes and the crystal structure loses the centre of symmetry. In phases I and II the pyridinium cations are strongly dynamically disordered, while in the low-temperature phase III the cations are well ordered. In all three phases the thiourea-iodine hydrogen-bonded sublattice is very well ordered. Dielectric measurements show that the intermediate and low-temperature phases are ferroelectric and that 161 K is the Curie point of a new ferroelectric crystal.
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