Abstract
The products of 4′,5′-dibromobenzo-15-crown-5 (I) cyanation by the Rosenmund-Braun reaction are studied by the 1H NMR and IR spectroscopy methods. X-ray diffraction analysis of two isolated products, i.e., di(4′,5′-dicyanobenzo-15-crown-5) 1.6 hydrate {(CN)2B15C5}2 · 1.6H2O (IIa) and 4′,5′-dicyanobenzo-15-crown-5,4′-cyano-5′-cyano(bromo)benzo-15-crown-5 dihydrate (CN)3.85Br0.15(B15C5)2 · 2H2O (III) is performed. Crystals IIa are monoclinic, a = 15.882(2) Å, b = 11.412(2) Å, c = 18.484(3) Å, β = 100.717(3)°, V = 3291.7(9) Å3, Z = 4, space group P21/c, R = 0.0746 for 4775 reflections with I > 2σ(I). Crystals III are monoclinic, a = 15.956(3) Å, b = 11.425(2) Å, c = 18.865(4) Å, β = 99.32(3)°, V = 3394(1) Å3, Z = 4, space group P21/c, R = 0.0692 for 2070 reflections with I > 2σ(I). Compounds IIa and III have similar structures with two crystallographically independent molecules in each (A and B in IIa; C and D in III). Four of the five O atoms of a macrocycle in molecules A and C form hydrogen bonds with the water molecules. The latter molecules lie above and below the cycle plane at a distance of ∼2 Å from this plane. The A and C molecules have identical conformations (TTG TTG TTG TTG TTC) that differ from those of molecules B (TTG TGG STT SSG TTC) and D (TTC TSG STT SSG TTC).
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Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 9, 2005, pp. 707–718.
Original Russian Text Copyright © 2005 by Minacheva, Aleksandrov, Lapkina, Gorbunova, Demin, Larchenko, Sergienko, Tsivadze.
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Minacheva, L.K., Aleksandrov, G.G., Lapkina, L.A. et al. Rosenmund-Braun Reaction Products 4′,5′-Dicyanobenzo-15-crown-5 and 4′,5′-Dicyanobenzo-15-crown-5,4′-cyano-5′-cyano(bromo)benzo-15-crown-5 Hydrates: Spectroscopic Properties and Crystal Structure. Russ J Coord Chem 31, 671–682 (2005). https://doi.org/10.1007/s11173-005-0154-7
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DOI: https://doi.org/10.1007/s11173-005-0154-7