The structure of Cs3Bi2I9 has been refined to R = 0.0165 on the basis of X-
ray diffraction measurements at T = 290 K (STOE IPDS diffractometer; MoKalp
ha-radiation; 296 nonequivalent reflection with I > 2 sigma(I)). The absorp
tion correction was accounted for by the Gaussian method. The parameters of
the hexagonal unit cell are: a = 8.409(1) Angstrom and c = 21.243(5) Angst
rom; space group P6(3)/mmc. The structure consists of identical perovskite-
like layer fragments described by the general formula A(3)B(2)X(9) (A = Cs,
B = Bi, X = I) With Ordered vacancies in the B-sublattice. These fragments
alternate along the c-axis and are related by mirror planes which contains
the shared faces of the BiI6 octahedra. The analysis of the intensities in
the temperature range 288 K to 190 K indicates a reversible phase transiti
on into a monoclinic phase at T = 218 K which is accompanied by twinning. N
o satellite or superstructure reflections were observed with the current re
solution of the diffractometer. The Xray results are compared wih the studi
es of the temperature dependence of the linear expansion coefficients, opti
cal characteristics, and the nuclear quadrupole spectra of Cs3Bi2I9.