The occurrence of a first-order paraelectric-ferroelectric phase trans
ition at T(C) = 315(5) K in CuInP2S6 is revealed by calorimetry, X-ray
powder diffraction, and dielectric measurements. This is the first ob
servation of such a phenomenon in a thiophosphate of the lamellar MPS3
family. The data are consistent with the polar character of the room-
temperature structure attributable to the acentric positions of the Cu
(I) and In(III) ions and may be related to the probable T dependence o
f the site-occupation ratios for the former cation and displacement of
the latter. Results of the dielectric measurements are suggestive of
a two-component phase transition.