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Title: Crystal and molecular structure of a series of 15-crown-5-containing styryl heterocycles and their dimethoxy substituted analogues

Abstract

A comparative study of the molecular geometry and crystal packing of crown-containing styryl heterocycles and their dimethoxy substituted analogues is performed. It is established that all the compounds exhibit an identical type of distortions of the geometry of the central styryl fragment. These are the localization of the {pi}-electron density at the ethylene bond and the bond alternation in a half of the phenyl ring due to the conjugation of lone electron pairs of the oxygen substituents with the chromophore system of the molecule. A comparative analysis of the crystal packings of the compounds reveals extended separate hydrophilic and hydrophobic regions. The hydrophilic regions are built of crown ether fragments, and the hydrophobic regions consist of {pi}-conjugated and aromatic molecular fragments. The hydrophobic regions are characterized by a wide variety of packing motifs, among which stacking packing is absent. For two compounds, the formation of sandwich dimers that are preorganized to enter into the photochemical [2 + 2]cycloaddition reaction is observed.

Authors:
 [1]; ; ; ; ;  [2]
  1. Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation), E-mail: kuzmina@igic.ras.ru
  2. Russian Academy of Sciences, Photochemistry Center (Russian Federation)
Publication Date:
OSTI Identifier:
21091479
Resource Type:
Journal Article
Resource Relation:
Journal Name: Crystallography Reports; Journal Volume: 51; Journal Issue: 3; Other Information: DOI: 10.1134/S1063774506030126; Copyright (c) 2006 Nauka/Interperiodica; Article Copyright (c) 2006 Pleiades Publishing, Inc; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CROWN ETHERS; CRYSTALS; ELECTRON DENSITY; ELECTRON PAIRS; ETHYLENE; MOLECULAR STRUCTURE; PHOTOCHEMISTRY

Citation Formats

Kuz'mina, L. G., Fedorova, O. A., Andryukhina, E. N., Mashura, M. M., Gromov, S. P., and Alfimov, M. V. Crystal and molecular structure of a series of 15-crown-5-containing styryl heterocycles and their dimethoxy substituted analogues. United States: N. p., 2006. Web. doi:10.1134/S1063774506030126.
Kuz'mina, L. G., Fedorova, O. A., Andryukhina, E. N., Mashura, M. M., Gromov, S. P., & Alfimov, M. V. Crystal and molecular structure of a series of 15-crown-5-containing styryl heterocycles and their dimethoxy substituted analogues. United States. doi:10.1134/S1063774506030126.
Kuz'mina, L. G., Fedorova, O. A., Andryukhina, E. N., Mashura, M. M., Gromov, S. P., and Alfimov, M. V. Mon . "Crystal and molecular structure of a series of 15-crown-5-containing styryl heterocycles and their dimethoxy substituted analogues". United States. doi:10.1134/S1063774506030126.
@article{osti_21091479,
title = {Crystal and molecular structure of a series of 15-crown-5-containing styryl heterocycles and their dimethoxy substituted analogues},
author = {Kuz'mina, L. G. and Fedorova, O. A. and Andryukhina, E. N. and Mashura, M. M. and Gromov, S. P. and Alfimov, M. V.},
abstractNote = {A comparative study of the molecular geometry and crystal packing of crown-containing styryl heterocycles and their dimethoxy substituted analogues is performed. It is established that all the compounds exhibit an identical type of distortions of the geometry of the central styryl fragment. These are the localization of the {pi}-electron density at the ethylene bond and the bond alternation in a half of the phenyl ring due to the conjugation of lone electron pairs of the oxygen substituents with the chromophore system of the molecule. A comparative analysis of the crystal packings of the compounds reveals extended separate hydrophilic and hydrophobic regions. The hydrophilic regions are built of crown ether fragments, and the hydrophobic regions consist of {pi}-conjugated and aromatic molecular fragments. The hydrophobic regions are characterized by a wide variety of packing motifs, among which stacking packing is absent. For two compounds, the formation of sandwich dimers that are preorganized to enter into the photochemical [2 + 2]cycloaddition reaction is observed.},
doi = {10.1134/S1063774506030126},
journal = {Crystallography Reports},
number = 3,
volume = 51,
place = {United States},
year = {Mon May 15 00:00:00 EDT 2006},
month = {Mon May 15 00:00:00 EDT 2006}
}
  • The transformations of hydrogen-poor hydrocarbyls (C[sub n]H[sub x], x [le] n) on multimetallic sites are of interest in connection with the study of surface cokes and carbides formed during catalytic reactions of hydrocarbons or CO on metal surfaces. The authors have shown previously that an [alpha]-substituted alkyne complex is a convenient precursor to a metal-stabilized carbo-cation upon reaction with protic acids. During studies of the deprotonation reactions of dimolybdenum alkyne complexes, Green et al. published the results of their thorough investigation on this topic. In this paper, the authors report on the structure and fluxional behavior of the [sigma],[pi]-acetylide formedmore » by the deprotonation of the [alpha]-substituted alkyne complex. The structure features an interesting chelate-type coordination of the counterion, Na(15-crown-5)[sup +], and the diasteriotopic methylene protons in the [sigma],[pi]-acetylide gives additional information on the nature of the fluxional process that these complexes exhibit. 31 refs., 3 figs., 1 tab.« less
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