(β-Cyclodextrin)2·KI7·9 H2O. Spatial fitting of a polyiodide chain to a given matrix

TLDR: In this paper, the structure of β-cyclodextrin polyiodide was solved in C2 on the basis of 3022 absorption corrected CuKα (Ni-filter) X-ray intensities and refined by full matrix least squares toR=17%.

Abstract: α-Cyclodextrin, a torus shaped molecule with a 5 A wide central cavity, forms a number of deep green, blue and black crystals when complexed with iodine/metal iodide. In contrast, β-cyclodextrin, having a 6 A cavity produces only one type of reddish-brown crystal, no matter what metal iodide is used. The complex (β-cyclodextrin)2 ·KI7·9H2O displays space groupP21 (pseudo-C2) with cell constantsa=19.609(5),b=24.513(7),c=15.795(6)A, β=109.50(2)°,Z=4. The crystal structure was solved inC2 on the basis of 3022 absorption corrected CuKα (Ni-filter) X-ray intensities and refined by full matrix least squares toR=17%. This relatively highR-factor is due to many weak reflections (pseudo-C2) and considerable disorder exhibited by water and iodine. In the complex, β-cyclodextrin adopts a ‘round’ shape with O(2)...O(3) interglucose hydrogen bonds formed and all O(6) hydroxyls pointing away from the cavity. Two molecules are arranged head-to-head to produce a dimer, and dimers are stacked such that a slightly zigzagged cylinder with a 6 A-wide cavity is formed. In the cavity described by each dimer, an I 7 − ion composed of I2·I 3 − ·I2 units is located, with I2 and I 3 − perpendicular to each other. K+ ions and 9 H2O molecules are found in interstices between the β-cyclodextrin cylinders. This zigzag polyiodide contrasts with the linear form observed in the 5 A wide α-cyclodextrin channels. It explains differences in color of the crystals and suggests that β-cyclodextrin polyiodide is not a good model for blue starch-iodine.