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Russian Journal of Coordination Chemistry

, Volume 31, Issue 9, pp 671–682 | Cite as

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

  • L. Kh. Minacheva
  • G. G. Aleksandrov
  • L. A. Lapkina
  • Yu. G. Gorbunova
  • S. V. Demin
  • V. E. Larchenko
  • V. S. Sergienko
  • A. Yu. Tsivadze
Article

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).

Keywords

Dihydrate Macrocycle Cyano Form Hydrogen Bond Bromo 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© MAIK "Nauka/Interperiodica" 2005

Authors and Affiliations

  • L. Kh. Minacheva
    • 1
  • G. G. Aleksandrov
    • 1
  • L. A. Lapkina
    • 1
  • Yu. G. Gorbunova
    • 1
  • S. V. Demin
    • 1
  • V. E. Larchenko
    • 1
  • V. S. Sergienko
    • 1
  • A. Yu. Tsivadze
    • 1
  1. 1.Kurnakov Institute of General and Inorganic ChemistryRussian Academy of SciencesMoscowRussia

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