Abstract
The i.r. spectra of interlamellar kaolinite complexes with formamide, N-methylformamide and dimethylformamide have been examined. The spectra show that the amides hydrogen-bond, through the C=O group of the amide to the inner surface kaolinite hydroxyls and decrease the intensity of the kaolinite ν(OH) bands. Hydrogen-bonded kaolinite hydroxyl bands appear at lower frequencies and these have been correlated to the original kaolinite ν (OH) bands. Other kaolinite bands in the complexes show smaller perturbations of the kaolinite vibrations. Each amide hydrogen-bonds to different groups of hydroxyls. Formamide hydrogen-bonds to the 3690 and 3664 cm−1 hydroxyls, N-methylformamide to the 3690 and 3648 cm−1 hydroxyls. The interpretation for the dimethylformamide complex is less clear. The ν(NH) frequencies of formamide and N-methylformamide in the complexes are intermediate between that in dilute non-polar solution and in the liquid. This could arise from either or both a degree of intermolecular association of the amide when between the kaolinite lamellae, or to weak N—H … O hydrogen bonds to the tetrahedral oxygen sheet of the lamellae.
Résumé
Les spectres i.r. des complexes interlamellaires de la kaolinite avec la formamide, la N-méthylformamide et la diméthylformamide ont été étudiés. Les spectres montrent que les amides sont liés par une liaison hydrogène qui s’établit entre le groupe C=0 de l’amide et les hydroxyles de la surface interne de la kaolinite, ce qui entraîne une diminution de l’intensité des bandes ν(OH) de la kaolinite. Les bandes des hydroxyles pontés de la kaolinite apparaissent à des fréquences plus basses, qui ont été reliées aux bandes ν(OH) de la kaolinite originelle. Dans les complexes, d’autres bandes de la kaolinite montrent de petites perturbations des vibrations de la kaolinite. Chaque amide établit des liaisons hydrogène avec différents groupes d’hydroxyles. La formamide établit une liaison hydrogène avec les hydroxyles à 3690 et 3664 cm−1, et la N-méthylformamide avec les hydroxyles à 3690 et 3648 cm−1. L’interprétation du complexe avec la diméthylformamide est moins évidente. Les fréquences ν(NH) de la formamide et de la N-méthylformamide dans les complexes, sont intermédiaires entre celles d’une solution diluée en milieu non polaire et celles du liquide. Ceci pourrait provenir soit, ou à la fois d’une certain degré d’association intermoléculaire de l’amide lorsqu’elle est entre les feuillets de kaolinite, soit de liaisons hydrogène faibles N—H…O s’établissant avec la couche des atomes d’oxygène tétraédriques du feuillet.
Kurzreferat
Die Ultrarotspektren interlamellarer Kaolinitkomplexe mit Formamid, N-Methylformamid und Dimethylformamid wurden untersucht. Die Spektren zeigen, dass die Amide eine Wasserstoffbrücke über die C=0 Gruppe des Amids zu den Hydroxylgruppen an der inneren Oberfläche des Kaolinits bilden und die Intensität der Kaolinit ν(OH) Banden vermindern. Wasserstoffbrücken-Kaolinit Hydroxybanden erscheinen bei niedrigeren Frequenzen, und diese sind mit den ursprünglichen Kaolinit ν(OH) Banden in Beziehung gebracht worden. Andere Kaolinitbanden in den Komplexen zeigen geringere Störungen der Kaolinitschwingungen. Jedes Amid bildet eine Wasserstoffbrücke zu verschiedenen Gruppen von Hydroxylen, und zwar bildet Formamid Wasserstoff brücken zu den 3690 und 3664 cm−1 Hydroxylen, und N-Methylformamid zu den 3690 und 3648 cm−1 Hydroxylen. Die Ausdeutung ist weniger klar für den Dimethyjformamidkomplex. Die ν(NH) Frequenzen des Formamids und des N-Methylformamids in den Komplexen nehmen eine Zwischenstellung ein zwischen den Werten in verdünnter, nichtpolarer Lösung und in der Flüssigkeit. Das kann seine Ursache in einer oder beider der folgenden Erscheinungen haben: nämlich ein bestimmtes Mass intermolekularer Assoziation des Amids wenn es sich zwischen den Kaolinitlamellen befindet, oder aber schwache N—H … O Wasserstoffbrücken zum tetraedrischen Sauerstoffblatt der Lamellen.
Резюме
Изучены инфракрасные спектры межслоевых комплексов каолинита с формамидом, N-метилформамидом и диметилформамидом. Спектры показали, что амиды за счет своих групп С=O образуют водородные связи с внутренними гидроксильными поверхностями каолинитовых слоев и уменьшают интенсивность каолинитовых полос ОН. Полосы водородных связей, образованных гидроксилами каолинита, наблюдаются при более низких частотах; они могут быть сопоставлены с полосами ОН исходного каолинита. Другие каолинитовые полосы в комплексах обнаруживают лишь незначительные изменения каолинитовых вибраций. Каждая амидная группа связана водородной связью с различными группами ОН. Формамид образует водородную связь, отвечающую гидроксилам, которые дают полосы при 3690 и 3664 см−1, N-метилформамид — при 3690 и 3648 см−1. Интерпретация ИК-спектров комплексов с диметилформамидом менее ясна. Частота колебаний групп NH формамида и N-метилформамида в комплексах является промежуточной между частотой колебания в разбавленном неполярном растворе и в жидкости. Это может быть обусловлено либо степенью межмолекулярного взаимодействия амидов между слоями каолинита, либо слабыми водородными связями типа N—H…O с тетраэдрическими кислородными поверхностями каолинитовых слоев, либо двумя этими причинами.
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References
Alexander, R., Ko, E. C. F., Mac, Y. C. and Parker, A. J. (1967) Solvation of Ions. Solubility products and instability constants in water, methanol, formamide, dimethylformamide, dimethylacetamide, dimethyl sulphoxide, acetonitrile, and hexamethylphosphorotri- amide: J. Am. Chem. Soc. 89, 3703–3712.
Badger, R. M. and Rubalcova, H. (1954) The infrared association spectra of amides in solution and their relation to the spectra of polypeptides: Proc. Nat. Acad. Sci. U.SA. 40, 12–17.
Chalapathi, V. V. and Ramiah, K. V. (1965) Vibrational spectra of some tertiary amides: Current Sci. 34, 12–13.
Chalapathi, V. V. and Ramiah, K. V. (1968) Normal vibrations of N,N-Dimethylformamide and N,N-Dimethylacetamide: Proc. Ind. Acad. Sci. 68, 109–122.
Davies, M., Evans, J. C. and Jones, R. L. (1955) Molecular interaction and infrared absorption spectra - 4. Methyl acetamide: Trans. Faraday Soc. 51, 761–774.
De Graaf, D. E. and Sutherland, G. B. B. M. (1957) Vibrational spectrum of N-Methylformamide: J. Chem. Phys. 26, 716–717.
Dorris, K. L., Siddall, T. H., Stewart, W. E. and Good, M. L. (1967) Infrared spectra of some deuterated tertiary amides: Spectrochim. Acta 23A, 1657–1660.
Farmer, V. C. (1964) Infrared absorption of hydroxyl groups in kaolinite: Science 145, 1189–1190.
Farmer, V. C. and Russell, J. D. (1964) The infrared spectra of layer silicates: Spectrochim. Acta 20, 1149–1173.
Hayden, A. L., Brannon, W. L. and Yaciw, C. A. (1966) Infrared spectra of some compounds of pharmaceutical interest: J. Assoc. Off. Anal. Chem. 49, 1109–1153.
Jones, R. R. Lumley (1963) The infrared spectra of some simple N substituted amides in the vapour state: J. Molec. Spectra. 11, 411–421.
Krishnamurthy, S. S. and Soundararajan, S. (1967) Pyridine N-Oxide complexes of rare earth perchlorates: Can. J. Chem. 45, 189–191.
Ledoux, R. L. and White, J. L. (1964a) Infrared study of the OH groups in expanded kaolinite: Science 143, 244–246.
Ledoux, R. L. and White, J. L. (1964b) Infrared study of selective deuteration of kaolinite and halloysite at room temperature: Science 145, 47–49.
Ledoux, R. L. and White, J. L. (1966) Infrared studies of the hydroxyl groups in intercalated kaolinite complexes: Clays and Clay Minerals 13, 289–315.
Ledoux, R. L. and White, J. L. (1966a) Infrared studies of hydrogen bonding interaction between kaolinite surfaces and intercalated potassium acetate, hydrazine, formamide and urea: J. Colloid Interface Sci. 21, 127–152.
Ledoux, R. L. and White, J. L. (1966b) Infrared studies of hydrogen bonding of organic compounds on oxygen and hydroxyl surfaces of layer lattice silicates: Proc. Inter. Clay Conf. 1, 361–374.
McLachlan, R. D. and Nyquist, R. A. (1964) An infrared study of some α-substituted secondary amides in solution: Spectrochim. Acta 20, 1397–1406.
Miyazawa, T., Shimanouchi, T. and Mizushima, S. (1958) Characteristic infrared bands of monosubstituted amides: J. Chem. Phys. 24, 408–418.
Miyazawa, T. (1960) The characteristic band of secondary amides at 3100 cm−1: J. Molec. Spectro. 4, 168–172.
Olejnik, S., Aylmore, L. A. G., Posner, A. M. and Quirk, J. P. (1968) Infrared spectra of kaolin mineral dimethyl sulfoxide complexes: J. Phys. Chem. 72, 241–249.
Olejnik, S., Posner, A. M. and Quirk, J. P. (1970) The intercalation of polar organic compounds into kaolinite. Clay Minerals In Press.
Parker, A. J. (1962) The effects of solvation on the properties of anions in dipolar aprotic solvents: Q. Review 16, 163–187.
Price, W. C. and Fraser, R. D. B. (1953) Infrared dichroism and protein structure: Proc. R. Soc. Lond. 141B, 66–67.
Puranik, P. G. and Ramiah, K. V. (1959) Infrared and raman spectroscopic studies of the association of formamide: J. Molec. Spectro. 3, 486–495.
Ramiah, K. V. and Chalapathi, V. V. (1963) Infrared spectroscopic studies of amides and anilides: Proc. Ind. Acad. Sci. 58A, 233–243.
Russell, R. A. and Thompson, H. W. (1956) Vibrational spectra and geometrical isomerism in amides: Spectrochim. Acta 3, 138–141.
Serratosa, J. M., Hidalgo, A. and Vines, J. M. (1962) Orientation of OH bands in kaolinite: Nature 195, 486–487.
Serratosa, J. M., Hidalgo, A. and Vines, J. M. (1963) Infrared study of the OH groups in kaolin materials: Proc. Inter. Clay Conf. Stockholm 1, 17–26.
Suzuki, I. (1962) Infrared spectra and normal vibrations of N-methylformamides HCONHCH3, HCONDCH3, DCONHCH3 and DCONDCH3: Bull. Chem. Soc. Japan 35, 540–551.
Wada, K. (1967) A study of hydroxyl groups in kaolin minerals utilizing selective deuteration and infrared spectroscopy: Clay Minerals 7, 51–61.
Weiss, A., Thielepape, W., Goring, G., Ritter, W. and Schafer, H. (1963) Kaolinite einlagerungs-verbindungen: Proc. Inter. Clay Conf. Stockholm 1, 287–305.
Weiss, A., Thielepape, W. and Orth, H. (1966) Neue kaolinite-einlagerungouerbindungen: Proc. Inter. Clay Conf. Jerusalem 1, 277–293.
References
Cruz, M., Laycock, A. and White, J. L. (1969) Perturbation of OH groups in intercalated kaolinite donoracceptor complexes—I. Formamide-, methyl formamide-, and dimethyl formamide-kaolinite complexes. Proc. Inter. Clay Conf. Tokyo 1, 775–789.
Tahoun, S. A. and Mortland, M. M. (1966a) Complexes of montmorillonite with primary, secondary, and tertiary amides—I. Protonation of amides on the surface of montmorillonite: Soil Sei. 102, 248–321.
Tahoun, S. A. and Mortland, M. M. (1966b) Complexes of montmorillonite with primary, secondary, and tertiary amides—II. Coordination of amides on the surface of montmorillonite: Soil Sei. 102, 314–321.
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Olejnik, S., Posner, A.M. & Quirk, J.P. The I.R. Spectra of Interlamellar Kaolinite-Amide Complexes—I. The Complexes of Formamide, N-Methylformamide and Dimethylformamide. Clays Clay Miner. 19, 83–94 (1971). https://doi.org/10.1346/CCMN.1971.0190204
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DOI: https://doi.org/10.1346/CCMN.1971.0190204