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X-Ray Powder Structural Analysis of the Complexes of Benzo-15-Crown-5 with NaClO4 and KI: [C14H20O5]NaClO4 and [C14H20O5]2KI
Published online by Cambridge University Press: 10 January 2013
Abstract
X-ray powder diffraction analysis of the complex of Benzo-15-Crown-5 (B-15-Crown-5) with NaClO4 displays a monoclinic crystal system with refined unit cell parameters of a = 8.829(3)Å, b = 8.327(3)Å, c = 24.21(2)Å, ß = 99.18(1)Å, V = 1757.1(1)Å3, Z = 4, and Dx = 1.48 g/cm3. The space group, P21/c, and the unit cell dimensions, determined by a single crystal diffraction analysis, agree well with those of the powder analysis. X-ray powder diffraction analysis of the complex of B-15-Crown-5 with KI displays a tetragonal crystal system with refined unit cell dimensions of a = b = 17.869(3)Å, c = 9.761(3)Å, V = 3116.7(1)Å3, Z = 4, and Dx = 1.50 g/cm3. The space group, P4/n, and the unit cell dimensions, determined by a single crystal diffraction analysis, agree well with those of die powder diffraction analysis. The powder and single crystal analyses of the two complexes indicate that in the solid phase, B-15-Crown-5 forms a 1:1 complex with Na+ and a 2:1 complex with K+. The variation in the complexation mode of B-15-Crown-5 with different cations, partially explains the lack of selectivity of this crown ether towards Na+, while from considerations of the cavity size alone this crown ether was expected to be considerably selective towards this cation.
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