A New Family of Layered Bismuth Oxohalides

D. O. Charkin*, O. A. Dityatiev*, A. B. Rakounov*, V. A. Dolgikh*, and P. Lightfoot**

* Moscow State University, Vorob’evy gory, Moscow, 119899 Russia

** School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST, United Kingdom

Received April 29, 2002

Abstract—A series of layered bismuth oxohalides, belonging to three new structural types, have been predicted
and synthesized. In all cases, the fluorite-like [Bi₂O₂] layers are alternatively separated by metal–halide layers
of the CsCl type and perovskite-like sheets of varied width. The structural motifs of the new compounds have
been confirmed by X-ray crystallography for Bi₄NdTi_1.6Nb_0.4Cs_0.6O₁₁Br₂ (space group P4/mmm, a =
3.8571(1)Å, c = 25.280(1) Å, R_wp = 0.092, R_p = 0.063) and Bi₄Nd₂Ti_2.4Fe_0.6Cs_0.6O₁₄Cl₂ (space group P4/mmm,
a = 3.8424(1) Å, c = 26.622(1) Å, R_wp = 0.062, R_p = 0.043). These results are compared with the data on the
related layered family BIPOX. The possibilities of further development of different families of layered bismuth
oxohalides containing fluorite-like metal–oxygen layers are discussed.

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