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The absolute configuration of α-LiIO3 crystals has been reinvestigated. The redetermination of the absolute configuration is in agreement with a report by Stadnicka, Glazer & Moxon [J. Appl. Cryst. (1985), 18, 237–240]. Special attention should be paid to the selection of Bijvoet pairs in these and similar crystals. The signs of the piezoelectric and pyroelectric coefficients have been verified and correlated with the spontaneous polarization. The pyroelectric coefficient p3 was −4.4 × 10−5 C m−2 K−1 at 180 K. The correlation between the optical activity and the morphology of the crystals is discussed.

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