Berkesi, Ottó

Körtvélyesi, Tamás

Németh, Cs.

Pálinkó, István

Berkesi Ottó

Körtvélyesi Tamás

Németh Csaba

Pálinkó István

SZTE Publicatio Repozitórium - SZTE - Repository of Publications

Hydrogen bonding interactions of a benzylidene type Schiff base in the solid state

Repository of the Academy's Library

EIGHTEENTHINTERNATIONAL CONFERENCE ONRAMAN SPECTROSCOPY(rcoRs 2002)Proceedings of theEighteenth International Conference onRaman Spectroscopy25-30 August, 2002Budapest, HungaryEdited byJiinos MinkUniversity of Veszpr6mChemical Research Center, Hungarian Academy of SciencesGydrgy JalsovszkyChemical Research Center, Hungarian Academy of SciencesGr4bor KereszturyChemical Research Center, Hungarian Academy of SciencesJOHN WILEY & SONS, LTDCopyright €) 2002 John Wiley & Sons Ltd, The Atrium, Southem Gate, Chichester,W-est Sussex POl9 8SQ, EnglandTelephone (+44) 1243 719771Email (for orders and customer service enquiries): cs-books@wiley.co.ukVisit our Home Page on www.wileyeurope.com or www.rviley.comAll Rights Reserved. No part of this publication may be reproduced, stored in a retrievalsystem or transmitted in any form or by any nleans, electronic, mechanical, photocopying,recording, scanning or otherwise, except under the terms of the Copyright, Designs andPatents Act 1988 or under the terms of a licence issued by the Copyright Licensing AgencyLtd, 90 Tottenham Court Road, London WIT 4LP, UK, without the permission in writing ofthe Publisher. Requests to the Publisher should be addressed to the Permissions Department,John Wiley & Sons Ltd, The Atrium, Southern Gare, Chichester, West Sussex POl9 8SQ,England, or emailed to permreq@wiley.co.uk, or faxed to (+44) 1243 7'10571.This publication is designed to provide accurate and authoritative information in regard tothe subject matter covered. It is sold on the understanding that the Publisher is not engagedin rendering professional services. If professional advice or other expert assistance isrequired, the services of a competent professional should be sought.Other Wiley Editoial OficesJohn Wiley & Sons Inc., I I I River Street, Hoboken, NJ 07030, USAJossey-Bass, 989 Market Street, San Francisco, CA 94103-1741, USAWiley-VCH Verlag GmbH, Boschstr. 12, D-69469 Weinheim, GermanyJohn Wiley & Sons Australia Ltd, 33 Park Road, Milton, Queensland 4064, AustraliaJohn Wiley & Sons (Asia) Pte Ltd,2 Clementi Loop #02-01, Jin Xing Distripark, Singapore 129809John Wiley & Sons Canada Ltd,22 Worcester Road, Etobicoke, Ontario, Canada M9W lLlBritish Library Cataloguing in Publication DstaA catalogue record for this book is available from the British LibraryISBN 0 47t 49t89 6Produced from pdf files supplied by the conference organizcrsPrinted and bound in Great Britain by Antony Rowe Ltd, Chippenham, WiltshireThis book is printed on acid-free paper responsibly manufactured from sustainable forestryin which at least two trees are planted for each one used for paper production.THE SOLID STATEHYDROGEN BONDING INTERACTIONS OF A BENZYLIDENE TYPE,SCHIFF BASE IN THE SOLID STATEO. Berkesi', T. Korrrr6lyesi', Cs. N6meth2 and I. Pelink6r'lDepartment of Physical Chemistry, University of Szeged, Szeged, Rerrich B. terl, Szeged, H-6720 Hungary; E-mail: berkesi@chem.u-szeqed.hu2Department of Medicinal Chemistry, University of Szeged, Szeged, Dom ter B,Szeged, H-6720 Hungary3Department.of Organic Chemistry, (lniversity of Szeged, Szeged, Dom tdr B,Szeged, H-6720 Hungary; E-mail: palinko@chem.u-szeged.huSchiff bases of the benzylidene type are widely sfudied molecules, however, thosecontaining OH groups in the ring(s) are out of the focus of researchers. It is somewhatsurprising, since the presence of OH groups provides the possibility of H-bondinginteractions, which may gretaly influence the physical and spectroscopic properties ofthe compounds [1]. If the OH groups are in appropriate positions relative to the C:Nfunctionality, both intramolecular and intermolecular H-bonds may appear. In this work2-hydroxybenzylidene 2-hydroxy-aniline was chosen as possible model for detectingboth kinds of interaction in the solid state./-'.,( r  ,  / - - 'v/OHHOr. l-,N--<', \\  - , ,Photoacoustic spectroscopy (PAS) and Raman spectroscopy were used as primaryexperimental tools. Molecular modeling was also applied to help visualising andrationalising experimental results obtained.Photoacoustic IR spectra (PAS) of solid samples were recorded using an MTEC-200detector on a Bio-Rad Digilab Division FTS-65A/896 Fourier Transform Infrared(FTIR) spectrometer. Raman spectra were taken on a Bio-Rad Digilab Division FourierTransform Raman spectrometer using the 1064 nm line of a T-10-106c fype Nd:YVO4laser from Spectra Physics. The laser power at the sample position was 500 mW.Molecular modeling of the possible dimers were performed by the PM3 t2lsemiempirical quantum chemical code implemented in the Hyperchem package [3].There are fwo types of functionalities in the molecules to take into considerationwhen association properties are concerned. One of them is the OH group. In thephotoacoustic spectra taken in the range of the vo*, vibrations, a broad band shiftedenorrnously to low vawenumbers relative to the position of the isolated OH group, wasobserved (Figure 1/a). It indicates strong hydrogen bond involving the OH group. The526 THE SOI.ID STATEother important functionality is the C:N part of the molecule. This part of the spectmmdisplayed unexpected feafures (Figure l/b). The band observed at 1636 cm-' is too highto be acceptable as C:N stretching mode, rather, it can be assigned to C:O stretchingmode. Further intriguing observation was the missing of a band in the 1580-1560 cm-'range, which could have been assigned to the skeletal mode of the aromatic ringconnected to the C atom of the C:N group [4, 5]. Its lack may indicate the possibledestruction of the benzoic structure of the ring. The comparison of the Raman and IR-PAS spectra for the molecules confirmed this assumption, since higher symmetryelement was found for our compound. The double bond region, displayed in Figure 1/c,indicated the presence of inversion centre in the structure. The pair of the band at1636 cm-r in the PAS-IR spectrum was found at 1625 cm-' in the Raman spectrum.Deconvolution of both spectra revealed another pair of bands, which showed theexclusion rule at 1614 cm-r in the PAS-IR and at 1610 cm-' in the Raman spectrum.Three pairs of bands in the aromatic C-C skeletal region appeared at the samewavenumbers showing that the interaction between the rings was too small.tu) rim ro'm rs'mWavenumbers / cril Wavenumbers,/Raman Shrn / cf i \Figure l. PAS-IR spectrum of 2-hydroxybenzylidene 2-hydroxy-aniline (a) in the 3600 - 2000 cm'range, (b) in the 1700 - 1500 cm-'range and (c) deconvoluted PAS-IR and Raman spectra in the1700 -  1550 cm'r  ranscMolecular modeling, in complete accordance with experimental results, revealedthat both infra- and intermolecular hydrogen bonding interactions are viable when thebenzylidene ring loses its aromaticity and a quinoidal structure is assumed. Then,intermolecular hydrogen bond is formed between the oxygen of the quinoidal carbonylgroup of one molecule with the proton of the OH group of the other. Two suchinteractions can be observed. Intramolecular hydrogen bond is formed between thecarbonyl oxygen and proton of the C-H bond in the bridge connecting the two rings.Once again two such interactions can be identified.1. J. Cs6szhr and M.N. Bizony, Magy.K6m. Foly. 103,29 (1997).2. J. J. P. Stewart, J. Comput Chem. 10,209,221 (1989).3. Hyperchem 6.02, Hypercube, Gainesvil le, Fla (1994).4. B. Ostrowska and A. Tramer, Acta Phys. Polonica 33, l l l  (1967).5. Z. Meic and G. Baranovic, Pure Appl. Chem. 61,2129 (1989).oocoDoe(c) 15501050 16m

Hydrogen bonding interactions of a benzylidene type Schiff base in the solid state

Abstract

Similar works

Full text

Available Versions

SZTE Publicatio Repozitórium - SZTE - Repository of Publications

Repository of the Academy's Library