Infrared and Raman Characteristic Group Frequencies Contents List of Charts and Figures xi " / Stretching Vibrations Alkene C=C 68 / , List of Tables xiii Alkene C-H Stretching Vibrations 69 Alkene C-H Deformation Vibrations 69 Symbols Used xvi Alkene Skeletal Vibrations 69 o ,,, I ' " 'd' 78 xlmes. C=N-OH. mmes. /C=N- , AmI mes, Preface xvii / " N-C=N- . etc, 1 Introduction 1 / Spurious Bands in Infrared and Raman Spectra 4 Azo Compounds. -N=N- 80 Spurious Bands at Any Position 5 References 81 Spurious Bands at Specific Positions 9 Positive and Negative Spectral Interpretation 9 Negative Spectral Interpretation 10 4 Triple Bond Compounds: -C=:=C-, -C-N, -N=:=C, 82 Positive Spectral Interpretation 10 -N=:=N Groups Regions for Preliminary Investigation 10 Alkyne Functional Group, -C=:=C- 82 Preliminary Regions to Examine 10 Alkyne C==C Stretching Vibrations 82 Confirmation 14 Alkyne C-H Vibrations 82 Chemical Modification 14 Alkyne Skeletal Vibrations 82 Collections of Reference Spectra 14 Nitriles, -C==N 84 Final Comment 48 Isonitriles, -N==C 85 References 48 Nitrile N-oxides, -C==N + 0 85 , , 2 Alkane Group Residues: C-H Group CyanamIdes, N-C=N 86 50 / Alkane Functional Groups 50 Diazonium Salts. Aryl-N==N+X- 86 Alkane C- H Stretching Vibrations 50 References 86 Alkane C-H Deformation Vibrations 51 Alkane C-C Vibrations: Skeletal Vibrations 53 References 67 5 Cumulated Double-bond Compounds: X= Y= Z 88 Group 3 Alkenes, Oximes, Imines, Amidines, Azo Compounds: 68 " / Allenes. C=C=C 88 C=C, C=N, N=N Groups / , , ,,/ Isocyanates. -N=C=O, and Cyanates 88 Alkene Functional Group. /C=C, 68 Isothiocyanates. -N=C=S 89 VI 6 7 8 9 Thiocyanates, -S-C==N Selenocyanates and Isoselenocyanates Azides, -N=N+=N- Diazo Compounds, "C=N+ N- / Carbodi-imides, -N=C=N- References Hydroxyl Group Compounds: O-H Group Alcohols, R-OH Alcohol O-H Stretching Vibrations Alcohol C-O Stretching Vibrations Alcohol O-H Deformation Vibrations Phenols References Ethers: G 1 -0-G2 Group References Peroxides and Hydroperoxides: -O-O-Group References Amines, Imines, and Their Hydrohalides Amine Functional Groups Amine N- H Stretching Vibrations Amine N- H Deformation Vibrations Amine C-N Stretching Vibrations , , Amine N-CH 3 and N-CH z - Absorptions / / Other Amine Bands Amine Hydrohalides, -NH 3 +, 'NHz+, ~NH+ and / / Imine Hydrohalides, "C=NH+- / Amine Hydrohalide N-H+ Stretching Vibrations Amine Hydrohalide N-H+ Deformation Vibrations Amine and Imine Hydrohalides: Other Bands References 89 90 90 90 93 93 94 94 94 94 95 99 99 101 104 105 106 107 107 107 107 107 108 108 108 108 109 113 113 10 The Carbonyl Group: C=O Introduction " Ketones, C=O / Ketone C=O Stretching Vibrations Methyl and Methylene Deformation Vibrations in Ketones Ketone Skeletal and Other Vibrations o Quinone. Q ond &0 o Aldehydes, -CHO Aldehyde C=O Stretching Vibrations Aldehydic C-H Vibrations Other Aldehyde Bands Carboxylic Acids, -COOH Carboxylic Acid O-H Stretching Vibrations Carboxylic Acid C=O Stretching Vibrations Other Vibrations of Carboxylic Acids Carboxylic Acid Salts Carboxylic Acid Anhydrides, -CO-O-CO- Carboxylic Acid Halides, -CO-X Diacyl Peroxides, R-CO-O-O-CO-R, (Acid Peroxides), and Peroxy Acids, -CO-OO-H Esters, -CO-O-, Carbonates, -O-CO-O-, and Haloformates, -O-CO-X Ester C=O Stretching Vibrations Ester C-O-C Stretching Vibrations Other Ester Bands L "rt~Sr actones, C- C -CO / , n / Amides, -CO-N , Amide N-H Stretching Vibrations Amide C=O Stretching Vibrations: Amide I Band Amide N-H Deformation and C-N Stretching Vibrations: Amide II Band Other Amide Bands Hydroxamic Acids, -CO-NHOH Hydrazides, -CO-NH-NH z and -CO-NH-NH-CO- Contents 115 115 117 117 117 117 122 122 122 122 123 125 125 125 125 129 130 130 130 132 132 133 134 142 143 143 143 144 145 145 148 Infrared and Raman Characteristic Group Frequencies Tables and Charts Third Edition GEORGE SOCRATES Formerly of Brunel, The University of West London, Middlesex. UK JOHN WILEY & SONS, LTD Chichester. New York. Weinheim • Toronto. Brisbane. Singapore Copyright © 200I by George Socrates Published in 2001 by John Wiley & Sons Ltd, Baffins Lane, Chichester, West Sussex PO 19 IUD, England National 01243779777 International (+44) 1243779777 e-mail (for orders and customer service enquiries): cs-books@wiley.co.uk Visit our Home Page on http://www,wiley.co.uk or http://www.wiley.com Reprinted as paperback January and October 2004 All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency, 90 Tottenham Court Road, London, UK WI P 9HE, without the permission in writing of the Publisher. Other Wiley Editorial Offices John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, USA WILEY-VCH Verlag GmbH, Pappelallee 3, D-69469 Weinheim, Germany John Wiley & Sons Australia, 33 Park Road, Milton, Quhneensland 4064, Australia John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02-01, Jin Xing Distripark, Singapore 129809 John Wiley & Sons (Canada) Ltd, 22 Worcester Road, Rexdale, Ontario M9W ILl, Canada Library of Congress Cataloguing-in-Publication Data Socrates, G. (George) Infrared and Raman characteristic group frequencies: tables and charts / George Socrates. - 3rd ed. p. em. Rev. ed. of: Infrared and Raman characteristic group frequencies. 2nd ed. c1994. Includes bibliographical references and index. ISBN 0-471-85298-8 l. Infrared spectroscopy. 2. Raman spectroscopy. I. Socrates. G. (George). Infrared characteristic group frequencies. II. Title. QC457 .S69 2000 543'.08583 - dc21 British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 0 470 09307 2 Typeset in 10/ 12pt Times by Laser Words, Madras, India Printed and bound in Great Britain by Antony Rowe Limited, Chippenham, Wiltshire This book is printed on acid-free paper responsibly manufactured from sustainable forestry, in which at least two trees are planted for each one used for paper production. 00-032096 vii 149 Overtone and Combination Bands 168 C=C and C=N Stretching Vibrations 168 149 Ring C-H Deformation Vibrations 169 lSI Other Bands 169 Pyridine N-Oxides 169 154 Other Comments 169 154 Quinolines, 00,and Isoquinolines, 00 173 N 157 Pyrimidines, 0" 173 158 N 159 Quinazolines, 00 159 173 N N~)~) 160 Purines, ~ I ~ 173 161 N (XN:O 161 Phenazines, I 176 165 ~ "N ~ 165 Sym-triazines, N 0 N ~ jJ 177 N 165 NH 2 Melamines, N~N 179 A!l- H 2 N N NH2 References 179 167 13 Five-membered Ring Heterocyclic Compounds 181 168 Pyrroles, [J and Indoles, OJ 181 168 N ~ N 168 Pyrrolines, n 181 N References Lactams rNHi (Cyclic Amides) -C-(C)i1 CO Imides, -CO-NH-CO- "- / Ureas, N-CO-N (Carbamides) / "- "- Urethanes, N-CO-O- (Carbamates) / References 11 Aromatic Compounds Aromatic C-H Stretching Vibrations Aromatic In-plane C-H Defortnation Vibrations Aromatic Out-of-plane C-H Deformation Vibrations and Ring Out-of-plane Vibrations in the Region 900-650cm- J Aromatic C=C Stretching Vibrations Overtone and Combination Bands Aromatic Ring Deformation Below 700 cm- I Polynuclear Aromatic Compounds Naphthalenes, 00 Anthracenes, ~ and Phenanthrenes, <08 12 Six-membered Ring Heterocyclic Compounds Pyridine Derivatives, 0 N Aromatic C- H Stretching Vibrations Contents _ viii Contents Furans, 0 181 Organic SuI phones, "S02 215 0 / Thiophenes, 0 Sulphonyl Halides, S02-X 216 183 Sulphonamides, -SOo-N/ S 216 Imidazoles, rJ . " 187 Covalent Sulphonates, R-S0 2 -OR ' 218 N Organic Sulphates, -0-S02 -0- 219 Pyrazoles, n Sulphonic Acids, -S03H. and Salts, S03 -M+ 220 189 Thiocarbonyl Compounds, "C=S N/ 222 References / 189 Reviews 224 Organic Selenium Compounds 224 Selenoamides, " 14 Organic Nitrogen Compounds 191 N-CSe- 224 / Nitro Compounds, -N02 191 The Se=O Stretching Vibration 227 Nitroso Compounds, -N=O, (and Oximes, 193 The P=Se Stretching Vibration 227 ~C=N-OH) References 227 Covalent Nitrates, -ON0 2 195 Nitrites, -O-N=O 195 17 Organic Phosphorus Compounds References 197 229 P-H and P-C Vibrations 229 P-OH and p-o Vibrations 229 15 Organic Halogen Compounds P-O-C Vibrations 229 198 Organic Halogen Compounds, ~C-X (where X=F, p=o Vibrations 229 198 Other Bands 240 CI, Br, I) References 240 Organic Fluorine Compounds 198 Organic Chlorine Compounds 198 Organic Bromine Compounds 201 18 Organic Silicon Compounds 241 Organic Iodine Compounds 205 Si-H Vibrations 241 Aromatic Halogen Compounds 207 Methyl-Silicon Compounds, Si-CH3 241 References 207 Ethyl-Silicon Compounds 241 Alkyl-Silicon Compounds 241 Aryl-Silicon Compounds 241 16 Sulphur and Selenium Compounds 209 Si-O Vibrations 246 Mercaptans, -SH 209 Silicon- Nitrogen Compounds 246 C-S and S-S Vibrations: Organic Sulphides, ~S, Silicon-Halide Compounds 246 209 Hydroxyl-Silicon Compounds 246 Mercaptans, -SH, Disulphides, -S-S-, and References 246 Polysulphides, -( -S-S -)/1- Compounds containing S=O: Organic Sulphoxides, 211 "S=O, and Sulphites, -O-SO-O- 19 Boron Compounds 247 / References 253 Contents IX 20 The Near Infrared Region 254 Polyconjugated Molecules 272 Carbon-Hydrogen Groups 254 Resins 272 Oxygen - Hydrogen Groups 255 Coatings and Alkyd Resins 273 Carbonyl Groups 255 Elastomers 273 Nitrogen-Hydrogen Groups 255 Plasticisers 273 Polymers 257 Strongest Band(s) in the Infrared Spectrum 273 Biological, Medical, and Food Applications 257 Strongest bands near 2940cm- 1 (~3.40Ilm) and 274 References 258 1475cm- 1 (~6.78llm) Strongest band near 1000cm- 1 (~IO.OOllm) 274 Strongest band near llOOcm- 1 (~9.09Ilm) 274 21 Polymers - Macromolecules 259 Strongest band in the region 835-715 cm- 1 274 Introduction 259 (I 1.98-13.99 11m) Pretreatment of Samples 261 Characteristic Absorption Patterns of Functional 274 Sample Preparation 262 Groups Present in Plasticisers Basic Techniques - Liquid, Solution, Dispersion 262 Carbonyl groups 274 Dispersive Techniques 262 Carboxylic acids 274 Films, Solvent Cast, Hot Press. Microtome 262 Carboxylic acid salts 274 Attenuated Total Reflection, Multiple Internal 263 Ortho-Phthalates 274 Reflection and Other Reflection Techniques Aliphatic esters 275 Pyrolysis. Microscope, etc. 263 Aromatic esters 276 Other Techniques 263 Sulphonamides, sulphates and sulphonates 276 Theoretical Aspects - Simplified Explanations 263 Sulphonic acid esters 276 General Introduction 263 Characteristic Bands of Other Commonly Found 276 Crystalline Polymers 264 Substances Non-crystalline Polymers 265 Common Inorganic Additives and Fillers 276 Band Intensities 265 Carbonates 276 Applications - Some Examples 266 Sulphates 277 Introduction 266 Talc 277 Stereoregularity, Configurations and Conformations 267 Clays 277 Morphology - Lamellae and Spherulites 267 Titanium Dioxide 278 C=C Stretching Band 267 Silica 278 Thermal and Photochemical Degradation 268 Antimony Trioxide 278 Polyethylene and Polypropylene 268 Infrared Flowcharts 278 Polystyrenes 269 References 281 Polyvinylchloride, Polyvinylidenechloride, 269 Polyvinylfluoride, and Polytetrafluoroethylene Polyesters, Polyvinylacetate 270 22 Inorganic Compounds and Coordination Complexes 283 Polyamides and Polyimides 270 Ions 284 Polyvinyl Alcohol 271 Coordination Complexes 292 Polycarbonates 271 Isotopic Substitution 299 Polyethers 271 Coordination of Free Ions having Tetrahedral 299 Polyetherketone and Polyetheretherketone 271 Symmetry Polyethersulphone and Polyetherethersulphone 271 Coordination of Free Ions having Trigonal-Planar 299 x Contents Symmetry Coordination of Free Ions having Pyramidal Structure Coordinate Bond Vibration Modes Structural Isomerism Cis-trans isomerism Lattice Water and Aquo Complexes Metal-Alkyl compounds Metal Halides Metal-n-Bond and Metal-a-Bond Complexes - Alkenes, Alkynes, etc. Alkenes Alkynes Cyclopentadienes Metal-Cyano and Nitrile Complexes Ammine, Amido, Urea and Related Complexes Metal Carbonyl Compounds Metal-Acetylacetonato Compounds, Carboxylate Complexes and Complexes Involving the Carbonyl Group Carboxylate Complexes and other Complexes Involving Carbonyl Groups Nitro- (-N02) and Nitrito- (-ONO) Complexes Thiocyanato- (-SCN) and Isothiocyonato- (- NCS) Complexes Isocyanates, M- NCO Nitrosyl Complexes Azides, M-N3' Dinitrogen and Dioxygen Complexes and Nitrogen Bonds Hydrides Metal Oxides and Sulphides Glasses Carbon Clusters References 300 300 301 301 301 302 303 304 304 307 308 309 309 314 317 317 320 320 320 320 321 321 323 325 327 327 23 Biological Molecules - Macromolecules Introduction Sample Preparation Carbohydrates Cellulose and its Derivatives Amino Acids Free Amino Acid - NH 3 + Vibrations Free Amino Acid Carboxyl Bands Amino Acid Hydrohalides Amino Acid Salts Nucleic Acids "- Amido Acids, N-CO-"'COOH / Proteins and Peptides Lipids Bacteria Food, Cells and Tissues References Appendix Further Reading Index 328 328 328 328 329 329 332 332 332 332 333 333 333 335 338 339 340 341 343 List of Charts and Figures Chart 1.1 Regions of strong solvent absorptions in the 7 Chart 17.1 Infrared - characteristic bands of phosphorus 230 infrared compounds and groups Chart 1.2 Regions of strong solvent absorptions for Raman 9 Chart 20.1 Near infrared region 256 Chart 1.3 Regions of strong solvent absorptions in the near 10 Chart 21.1 Infrared - polymer flowchart I 279 infrared regions Chart 21.2 Infrared - polymer flowchart II 280 Chart 1.4 Negative correlation 13 Chart 22.1 Infrared - band positions of ions 284 Chart 1.5 Infrared - positions and intensities of bands 15 Chart 22.2 Infrared - band positions of hydrides 293 CharI 1.6 Infrared - characteristic bands of groups and 22 Chart 22.3 Infrared - band positions of complexes, ligands 295 compounds and other groups Chari I.7 Raman - positions and intensities of bands 35 Chari 22.4 Transition metal halides stretching vibrations 308 Chart 3.1 Infrared - band positions of alkenes 70 Chart 22.5 Infrared - band positions of metal oxides and 324 Chart 10.1 Infrared - band positions of carbonyl groups 118 sulphides Chart 11.1 Infrared - substituted benzenes 158 Chart 11.2 Raman - substituted benzenes 159 Figure 1.1 Vibration modes for CH2 2 Chart 16.1 Infrared - characteristic bands of sulphur 210 Figure 11.1 Characteristic aromatic bands 900-600 cm- 1 157 compounds and groups Figure 11.2 Overtone patterns of substituted benzenes 161 Figure 12.1 Overtone patterns of substituted pyridines 168 [...]... introduction to characteristic group frequencies so as to assist all who may need to interpret or examine infrared and Raman spectra The characteristic absorptions of functional groups over the entire infrared region, including the far and near regions, are given in tables as well as being discussed and amplified in the text A section dealing with spurious bands that may appear in both infrared and Raman spectra... The infrared and Raman data given in the correlation tables and charts have been derived empirically over many years by the careful and painstaking work of very many scientists The infrared or Raman spectrum of any given substance is interpreted by the use of these known group frequencies and thus it is possible to characterise the substance as one containing a given type of group or groups Although group. .. bonds and so the Raman spectrum can reveal information about the backbone of the structure of a molecule On the other hand, strong infrared bands are observed for polar groups 6 Bands of importance to a particular study may occur in regions where they are overlapped by the bands due to other groups, hence, by making use of the other technique (infrared or Raman) it is often possible to observe the bands... bands that are strong in infrared spectra are often weak in Raman spectra The opposite is also often true (Bands due to the stretching vibrations of symmetrical groups/molecules may be observed by using Raman, i.e infrared inactive bands may be observed by Raman The reverse is also true - Raman inactive bands may be observed by using infrared spectroscopy.) For many molecules, Raman activity tends to... Often bands which are weak or inactive in the infrared, such as those due to the stretching vibrations ofC=C, C-C, C=N, C-S, S-S, N=N and 0-0 functional groups, exhibit strong bands in Raman spectra Also, in Raman spectra, skeletal vibrations often give characteristic bands of medium-tostrong intensity which in infrared spectra are usually weak Although not always true, as a general rule, bands that... where the infrared spectrum of a sample gives weak bands for certain groups, or their vibrations may be infrared inactive, but, in either case, result in strong bands in the Raman spectra (For example, the C=C stretching vibration of acetylene is infrared inactive as there is no dipole change whereas a strong band is observed in Raman. ) Alternatively, it may be that strong, broad bands in the infrared. .. (confirmed by other information), or (b) although _ Infrared and Raman Characteristic Group Frequencies more than one type of the given functional group is present in the sample their absorption bands all coincide, or (c) although more than one type of the given functional group is present, all but one have an infrared inactive transition The shape of an absorption band can give useful information, such as indicating... the bands observed in the spectrum may vary in intensity with time Although all the bands may belong to the sample, and in that sense are not truly spurious, they can nonetheless still be baffling Infrared and Raman Characteristic Group Frequencies Crystal orientation In general the infrared radiation incident on a sample is partially polarised so that the relative intensities of absorption bands may... the sample and that of the known reference material If the absorption bands are the same (i.e in wavelength, relative intensities and shapes), or nearly so, then it is reasonable to assume that the sample and reference are either identical or very similar in molecular structure 10 Infrared and Raman Characteristic Group Frequencies Chart 1.3 Regions of strong solvent absorptions in the near infrared. .. amide I band Table 10.33 Ureas: other bands Table 10.34 Urethane N-H stretching vibrations Table 10.35 Urethane C=O stretching vibrations: amide I band Table 10.36 Urethane combination N-H deformation and C-N stretching vibrations (amide II band) and other bands Table 11.1 Aromatic =C-H and ring C=C stretching vibrations Table 11.2 Aromatic =C-H out-of-plane deformation vibrations and other bands in . (George) Infrared and Raman characteristic group frequencies: tables and charts / George Socrates. - 3rd ed. p. em. Rev. ed. of: Infrared and Raman characteristic. positions of hydrides 293 CharI 1.6 Infrared - characteristic bands of groups and 22 Chart 22.3 Infrared - band positions of complexes, ligands 295 compounds and other groups Chari I.7 Raman -