A new bismuth subiodide Bi16I4 was synthesized by hightemperature synthesis. Its structure was determined by single-crystal X-ray diffraction analysis [C2/m (No. 12), a = 25.948(6) angstrom, b = 4.354(1) angstrom, c = 13.259(3) angstrom, beta = 104.48(2)circle, Z = 2, R-1 = 0.041, wR(all)(F-2) = 0.109]. The compound belongs to the BimI4 (m = 14, 16, 18) family of low-dimensional subhalides that feature one-dimensional bismuth stripes of varying width, terminated by iodine atoms. Ab initio calculations at the I)FT level were performed on 31) structures of all three BimI4 compounds of the family. According to the computational data all three compounds are expected to exhibit metallic behavior and Pauli paramagnetism, with a directional anisotropy of the properties indicated by the calculated band structures. The molecular packing in bismuth subiodides has been analyzed in detail and two homologous series - Bi8+4nI4 and Bi10+4nI4 (n = 0, 1, 2, ...) - are suggested to describe existing and possible structures of the compounds of the BimI4 family. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
2008. no 33, 5196-5202 p.