X-ray diffraction and spectroscopic verification of dimerization in hexasubstituted para-nitrosophenols


Тип публикации: статья из журнала

Год издания: 2011

Идентификатор DOI: 10.1016/j.molstruc.2010.10.040

Ключевые слова: Dimerization of nitrosocompounds, Hexasubstituted nitrosophenols, X-ray powder structure analysis, IR, H-1 NMR spectra, 1H NMR spectra, Benzene ring, Center of symmetry, Dimer formation, Green solution, H NMR spectra, H NMR spectroscopy, Interlayer spaces, MONTE CARLO, Nitrogen atom, Nitroso, Non-hydrogen atoms, Organic anions, Potassium salts, Structure refinements, X-ray diffraction studies, X-ray powder structure, Zigzag chains, Benzene, Crystal symmetry, Diffraction, Dimerization, Dimers, Nitrogen compounds, Nuclear magnetic resonance spectroscopy, Phenols, Positive ions, Rietveld method, Rietveld refinement, X ray diffraction, X ray powder diffraction, X rays, Crystal atomic structure

Аннотация: It has been established earlier that the brilliant-green solution of the potassium salt of 2,6-diethoxycarbonyl-3,5-dimethy1-4-nitrosophenol (C14H16KNO6) - (I) when treated with an acid yields a white precipitate of 2,6-diethoxycarbony1-3,5-dimethy1-4-nitrosophenol, presumably (C14H17NO6)(2) - (II). The crystal structures of both cПоказать полностьюompounds have been determined and dimer formation has been confirmed by X-ray powder diffraction. Modeling of the structures with 22 and 42 non-hydrogen atoms was carried out by the Monte-Carlo technique applying "rigid" and "soft" constraints. The Rietveld method was used for the structure refinement. The layers parallel to the plane (10-1) are distinguished in structure (I). The distance between the layers is equal to 9.28 angstrom. The interlayer space is filled by ethoxygroups. In the layer the zigzag chains of potassium cations are located at the distance 9.38 angstrom from each other, with the organic anions being embedded between them. The pi-conjugation between phenol- and nitroso-groups is observed in the anions (C14H16NO6)(-), resulting in a flat ion. Potassium cations have irregular sevenfold coordination. The pi-system of the nitroso-group participates in the potassium coordination. Dimerization in structure (II) is due to the interaction of the nitrogen atoms of the nitroso-groups, d(N-N) = 1.29 angstrom. The planes of the benzene rings form an angle of 23 degrees. The absence of the pi-conjugation makes the molecule flexible, which at the molecule packing into a crystal is subjected to the requirement of the closest packing with the loss of the possible center of symmetry. The results of the X-ray diffraction studies are consistent with the evidence of the IR and H-1 NMR spectroscopy. (c) 2010 Elsevier B.V. All rights reserved.

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Выпуск журнала: Vol. 985, Is. 2-3

Номера страниц: 184-190

ISSN журнала: 00222860

Место издания: AMSTERDAM



  • Alemasov Y.A.
  • Slaschinin D.G.
  • Tovbis M.S.
  • Kirik S.D. (Siberian Federal University, Svobodny Ave.79, Krasnoyarsk 660041, Russian Federation)