Crystal structure, spectral characterization, molecular modeling studies and structural effects of the proton transfer process for (E)-5-methoxy-2-[(3,4-dimethylphenylimino) methyl]phenol

Authors

  • Basak Kosar Kirca Sinop University
  • Gonca Ozdemir Tarı Ondokuz Mayıs University Vezirköprü Vocational School http://orcid.org/0000-0001-5919-1778
  • Cıgdem Albayrak Kastas Sinop University
  • Mustafa Odabasoglu Pamukkale University
  • Orhan Buyukgungor Ondokuz Mayıs University

DOI:

https://doi.org/10.20450/mjcce.2017.1295

Keywords:

Schiff base, prototropic tautomerism, intramolecular proton transfer, NLO, DFT

Abstract

The main purpose of this study is to characterize a new organic material, (E)-5-methoxy-2-[(3,4-dimethylphenylimino)methyl]phenol, which was synthesized and grown as a single crystal. The molecular structure and spectroscopic properties of the ortho-hydroxy Schiff base compound were determined by X-ray diffraction analysis, Fourier-transform infrared (FT-IR), ultraviolet-visible (UV-Vis) and nuclear magnetic resonance (NMR) spectroscopy techniques, experimentally and computationally with density functional theory (DFT) calculations. X-ray and UV-Vis studies show that the compound exists in an OH tautomeric form in the solid and solvent media. The gas phase geometry optimizations of two possible forms of the title compound, resulting from the prototropic tautomerism, were obtained using DFT calculations at the B3LYP/6-311G+(d,p) level of theory. A relaxed potential energy surface (PES) scan was performed based on the optimized geometry of the OH tautomeric form by varying the redundant internal coordinate, the O-H bond distance. According to the PES scan process, the molecular geometry is strongly affected by the intramolecular proton transfer. The calculated first hyperpolarizability indicates that the compound could be a good material for non-linear optical applications. 

Author Biographies

Basak Kosar Kirca, Sinop University

Department of physics

Gonca Ozdemir Tarı, Ondokuz Mayıs University Vezirköprü Vocational School

Department of Physics

Cıgdem Albayrak Kastas, Sinop University

department of chemistry

Mustafa Odabasoglu, Pamukkale University

chemical technology program

Orhan Buyukgungor, Ondokuz Mayıs University

department of physics

References

W. M. F. Fabian, L. Antonov, D. Nedeltcheva, F. S. Kanounah, P. J. Taylor, Tautomerism in hydroxynaphthaldehyde anils and azo analogues: a com-bined experimental and computational study, J. Phys. Chem., A108 (2004) 7603–7612. DOI: 10.1021/jp048035z

T. M. Krygowski, J. E. Zachara-Horegland, M. Palusiak, S. Pelloni, P. Lazzaretti, Relation between pi-electron localization/delocalization and H-bond strength in deriv-atives of o-hydroxy-Schiff bases, J. Org. Chem., 73 (2008) 2138–2145. DOI: 10.1021/jo7023174

V. Bertolasi, P. Gilli, G. Gilli, Crystal Chemistry and Prototropic Tautomerism in 2-(1-Iminoalkyl)- phenols (or naphthols) and 2-Diazenyl-phenols (or naphthols), Curr. Org. Chem., 13 (2009) 250–268.

DOI: 10.2174/138527209787314841

B. Kukawska-Tarnawska, A. Les, T. Dziembowska, Z. J. Rozwadowski, Tautomeric forms of N-(5-nitrosalicylidene)-2-butylamine: Experimental and theo-retical DFT study, J. Mol. Struct., 928 (2009) 25–31.

DOI: 10.1016/j.molstruc.2009.03.007

H. Ünver, K. Polat, M. Uçar, D. M. Zengin, Synthesis and keto-enol tautomerism in N-(2-hydroxy-1-naphthylidene)anils, Spect. Lett., 36 (4) (2003) 287–301.

DOI: 10.1081/SL-120024579

D. Maciejewska, D. Pawlak, V. Koleva, Hydrogen bonding and tautomerism of benzylideneanilines in the solid state, J. Phys. Org. Chem., 12 (1999) 875–880.

H. Karabıyık, H. Petek, N. Ocak-İskeleli, Ç. Albayrak, Structural and aromatic aspects for tautomerism of (Z)-6-((4-bromophenylamino)methylene)-2,3-dihydroxycy-clohexa-2,4-dienone, Struct. Chem. 20 (2009) 1055–1065. DOI: 10.1007/s11224-009-9509-x

H. Petek, Ç. Albayrak, M. Odabaşoğlu, İ. Şenel, O. Büyükgüngör, The proton transfer process observed in the structure analysis and DFT calculations of (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol, Struct. Chem., 21 (2010) 681–690.

DOI: 10.1007/s11224-010-9598-6

A. D. Garnovski, A. L. Nivorozhki, V. I. Minkin, Ligand environment and the structure of Schiff base adducts and tetracoordinated metal-chelates, Coord. Chem. Rev., 126 (1993) 1–69. DOI: 10.1016/0010-8545(93)85032-Y

M. Calligaris, L. Randaccio, In: G. Wilkinson (Ed.), Compherensive Coordination Chemistry, Vol 2, Permagon Press, London, pp. 715–738, 1987.

R. H. Lozier, R. A. Bogomolni, W. Stoeckenius, Bacteriorhodopsin: A light-driven proton pump in Halobacterium halobium, Biophys. J., 15, (1975) 955–962.

DOI: 10.1016/S0006-3495(75)85875-9

A. Das, M. D. Trousdale, S. Ren, E. J. Lien, Inhibition of herpes simplex virus type 1 and adenovirus type 5 by heterocyclic Schiff bases of aminohydroxyguanidine tosylate, Antiviral Res., 44 (1999) 201–208.

DOI: 10.1016/S0166-3542(99)00070-4

S. Ren, R. Wang, K. Komatsu, P. Bonaz-Krause, Y. Zyrianow, C. E. McKenna, C. Osipke, Z. A. Tokes, E. J. Lien, Synthesis, biological evaluation, and quantitative structure-activity relationship analysis of new Schiff ba-ses of hydroxysemicarbazide as potential antitumor agents, J. Med. Chem., 45 (2002) 410–419.

DOI: 10.1021/jm010252q

S. Ren, Z. A. Tokes, C. Osipke, B. Zhou, Y. Yen, E. J. Lien, Inhibition of tumor cell growth by Schiff bases of hydroxysemicarbazide, Anticancer Res., 21 (2001) 3445–3451.

E. Hadjoudis, M. Vitterakis, I. Moustakali-Mavridis, Photochromism and thermochromism of Schiff-bases in the solid-state and in rigid glasses, Tetrahedron 43 (1987) 1345–1360.

DOI: 10.1016/S0040-4020(01)90255-8

E. Hadjoudis, Photochromic and thermochromic anils, Mol. Eng. 5 (4) (1995) 301–337.

DOI: 10.1007/BF01004014

A. P. Alivisatos, P. F. Barbara, A. W. Castleman, J. Chang, D. A. Dixon, M. L. Klein, G. L. McLendon, J. S. Miller, M. A. Ratner, P. J. Rossky, S. I. Stupp, M. E. Thomson, From molecules to materials: Current trends and future directions, Adv. Materials., 10 (16) (1998) 1297–1336.

L. Dalton, Polymers for photonics applications I, Adv. Polym. Sci., 158 (2002) 1–75.

DOI: 10.1007/3-540-44608-7

A. Koll, J. Janski, A. Karpfen, P. Wolschann, Bifunctional influence of 3-chloro substitution on struc-tural and energetic characteristics of N-methyl-salicylidene imines, J. Mol. Struct., 976 (2010) 19–29.

DOI: 10.1016/j.molstruc.2009.12.028

A. Senier, F. G. Shepheard, Studies in phototropy and thermotropy. Part 1. Arylidene and naphthylidene-amines, J. Chem. Soc., 95 (1909) 1943–1955.

DOI: 10.1039/CT9099501943

A. Filarowski, A. Kochel, K. Cieslik, A. Koll, Steric and aromatic impact on intramolecular hydrogen bonds in o-hydroxyaryl ketones and ketimines, J. Phys. Org. Chem., 18 (2005) 986–993. DOI: 10.1002/poc.942

G. Pavlovic, J. M. Sosa, A 3-[(2-Oxo-1-naphthylidene) methylamino]benzoic acid, Acta Cryst. C56 (2000) 1117–1119. DOI: 10.1107/S0108270100007290

R. Casasnovas, A. Salva, J. Frau, J. Donoso, F. Munoz, Theoretical study on the distribution of atomic charges in the Schiff bases of 3-hydroxypridine-4-aldehyde and alanine. The effect of the protonation state of the pyridine and imine nitrogen atoms, Chem. Phys., 355 (2009) 149–156. DOI: 10.1016/j.chemphys.2008.12.006

H. Ünver, M. Yıldız, Tautomerism in solution and solid state, spectroscopic studies and crystal structure of (Z)-1-[(4-amino-2,3,5,6-tetramethylphenylamino)methylene]-1, 8a-dihydronaphthalen-2(3H)-one, Spect. Lett., 43 (2010) 114–121. DOI: 10.1080/00387010903284646

T. Dziembowska, M. Szafran, A. Katrusrak, Z. Raqzwadowski, Crystal structure of and solvent effect on tautomeric equilibrium in Schiff base derived from 2-hydroxy-1-napthaldehyde and methylamine studied by X-ray diffraction, DFT, NMR and IR methods, J. Mol. Struct., 929 (2009) 32–42.

DOI: 10.1016/j.molstruc.2009.04.001

H. Petek, Ç. Albayrak, N. Ocak-İskeleli, E. Ağar, İ. Şenel, Crystallographic and conformational analyses of zwitterionic form of (E)-2-methoxy-6-[(2-morpholinoethyl¬imino)methyl]phenolate, J. Chem. Cryst., 37 (2007) 285–290. DOI: 10.1007/s10870-006-9175-4

G. Wojciechowski, M. Ratajczak-Sitarz, A. Katrusiak, W. Schilf, P. Przybylski, B. Brzezinski, Crystal structure of Schiff base derivative of gossypol with 3,6,9-trioxa-decylamine, J. Mol. Struct., 650 (2003) 191–199.

DOI: 10.1016/S0022-2860(03)00319-3

H. Petek, Ç. Albayrak, E. Ağar, H. Kalkan, (Z)-6-[(2-Fluorophenyliminio)methylene]-2,3-dihydroxyphenolate, Acta Cryst., E62 (2006) o3685-o3687.

DOI: 10.1107/S1600536806029606

Stoe & Cie, X-AREA (Version 1.18) and X-RED32 (Version 1.04), Darmstadt, Germany, 2002.

G. M. Sheldrick, A short history of SHELX, Acta Cryst. A64 (2008) 112–122.

DOI: 10.1107/S0108767307043930

C. Lee, W. Yang, R. G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, Phys. Rev., B37 (1988) 785–789.

DOI: 10.1103/PhysRevB.37.785

A. D. Becke, Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys., 98 (1993) 5648–5652. DOI: 10.1063/1.464913

M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgom-ery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Dan-iels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.

J. Tomasi, B. Mennucci, R. Cammi, Quantum mechanical continuum solvation models, Chem. Rev., 105 (2005) 2999–3093. DOI: 10.1021/cr9904009

D. Jacquemin, J. Preat, V. Wathelet, M. Fontaine, E. A. Perpete, Thioindigo Dyes: Highly Accurate Visible Spectra with TD-DFT, J. Am. Chem. Soc., 128 (2006) 2072–2083. DOI: 10.1021/ja056676h

N. Santhanamoorthi, K. Senthilkumar, P. Kolandaivel, Tautomerization and solvent effects on the absorption and emission properties of the Schiff base N,N′-bis(salicylidene)-p-phenylenediamine - A TDDFT study, Mol. Phys., 108 (14) (2010) 1817–1827.

DOI: 10.1080/00268976.2010.490796

J. P. Merrick, D. Moran, L. Radom, An evaluation of harmonic vibrational frequency scale factors, J. Phys. Chem., A111 (2007) 11683–11700.

DOI: 10.1021/jp073974n

L. J. Farrugia, ORTEP-3 for Windows - a version of ORTEP-III with a Graphical User Interface (GUI), J. Appl. Cryst., 30 (1997) 565.

DOI: 10.1107/S0021889897003117

I. Moustakali-Mavridis, E. Hadjoudis, A. Mavridis, Structure of thermochromic Schiff bases. II. Structures of N-salicylidene-3-aminopyridine and N-(5-methoxysalicy-lidene)-3-aminopyridine, Acta Cryst., B36 (1980) 1126–1130. DOI: 10.1107/S0567740880005432

Ç. Albayrak, G. Kaştaş, M. Odabaşoğlu, R. Frank, The prototropic tautomerism and substituent effect through strong electron withdrawing group in (E)-5-(diethyl-amino)-2-[(3-nitrophenylimino)methyl]phenol, Spectrochimica Acta Part A, 114 (2013) 205–213.

DOI: 10.1016/j.saa.2013.05.044

D. K. Dey, S. P. Dey, A. Elmalı, Y. Elerman, Molecular structure and conformation of N-2-[3'-(methoxy-salicylideneimino)benzyl]-3''-methoxysalicylideneimine, J. Mol. Struct., 562 (2001) 177–184.

DOI: 10.1016/S0022-2860(00)00970-4

J. Kruszewski, T. M. Krygowski, Definition of Aromaticity Basing on the Harmonic Oscillator Model, Tetrahedron Lett., 13 (1972) 3839–3842.

DOI: 10.1016/S0040-4039(01)94175-9

T. M. Krygowski, M. K. Cyrański, Structural Aspects of Aromaticity, Chem. Rev., 101 (2001) 1385–1419.

DOI: 10.1021/cr990326u

M. Yıldız, Z. Kılıç, T. Hökelek, Intramolecular hydrogen bonding and tautomerism in Schiff bases. Part 1. Structure of 1,8-di[N-2-oxyphenyl-salicylidene]-3,6-di-oxaoctane, J. Mol. Struct., 441 (1998) 1–10.

DOI: 10.1016/S0022-2860(97)00291-3

A. Filarowski, A. Koll, T. Glowiak, Structure and hydrogen bonding in ortho-hydroxy ketimines, J. Mol. Struct., 644 (2003) 187–195.

DOI: 10.1016/S0022-2860(02)00489-1

M. Odabaşoğlu, Ç. Albayrak, R. Özkanca, F.Z. Aykan, P. Lonecke, Some polyhydroxy azo–azomethine deriva-tives of salicylaldehyde: Synthesis, characterization, spectroscopic, molecular structure and antimicrobial ac-tivity studies, J. Mol. Struct., 840 (2007) 71–89.

DOI: 10.1016/j.molstruc.2006.11.025

R. Dobosz, A. Skotnicka, Z. Rozwadowski, T. Dziembowska, Stability of N-(ortho-hydroxynaphthyl-methylene)methylamines and their tautomers, J. Mol. Struct., 979 (2010) 194–199.

DOI: 10.1016/j.molstruc.2010.06.024

K. Ogawa, J. Harada, Aggregation controlled proton tautomerization in salicylideneanilines, J. Mol. Struct., 647 (2003) 211–216.

DOI: 10.1016/S0022-2860(02)00526-4

S. I. Gorelsky, SWizard program, Revision 4.5. http://www.sg.chem.net/, University of Ottawa, Ottawa, Canada, 2010.

H. Nazır, M. Yıldız, H. Yılmaz, M. N. Tahir, D. Ülkü, Intramolecular hydrogen bonding and tautomerism in Schiff bases, J. Mol. Struct., 524 (2000) 241–250.

DOI: 10.1016/S0022-2860(00)00393-8

R. M. Silverstein, F. X. Webster, D. J. Kiemle, Spectro-metric Identification of Organic Compounds, 7th ed. John Wiley & Sons, New York, 2005.

DOI: 10.1021/ed039p546

B. Koşar, Ç. Albayrak, C. C. Ersanlı, M. Odabaşoğlu, O. Büyükgüngör, Molecular structure, spectroscopic inves-tigations, second-order nonlinear optical properties and intramolecular proton transfer of (E)-5-(diethylamino)-2-[(4-propylphenylimino)methyl]phenol: A combined experimental and theoretical study, Spectrochimica Acta Part A, 93 (2012) 1–9. DOI: 10.1016/j.saa.2012.03.004

D. Sajan, J. Hubert, V. S. Jayakumar, J. Zaleski, Struc-tural and electronic contributions to hyperpolarizability in methyl p-hydroxy benzoate, J. Mol. Struct., 785 (2006) 43–53. DOI: 10.1016/j.molstruc.2005.09.041

C. E. Powel, M. G. Humphrey, Nonlinear optical proper-ties of transition metal acetylides and their derivatives, Coord. Chem. Rev., 248 (2004) 725–756.

DOI: 10.1016/j.ccr.2004.03.009

K. S. Thanthiriwatte, K. M. Nalin de Silva, Non-linear optical properties of novel fluorenyl derivatives-ab initio quantum chemical calculations, J. Mol. Struct., Theochem 617 (2002) 169–175.

DOI: 10.1016/S0166-1280(02)00419-0

L. Fang, G. C. Yang, Y. Q. Qiu, Z. M. Su, Theoretical predication of third-order optical nonlinearities of [Al4MAI4]n- (n = 0–2, M = Ti, V and Cr) clusters, Theor. Chem. Account., 119 (2008) 329–333.

DOI: 10.1007/s00214-007-0388-1

Y. X. Sun, Q. L. Hao, W. X. Wei, Z. X. Yu, L. D. Lu, X. Wang, Y. S. Wang, Experimental and density functional studies on 4-(3,4-dihydroxybenzylideneamino)antipy¬rine, and 4-(2,3,4-trihydroxybenzylideneamino)antipy¬rine, J. Mol. Struct. Theochem., 904 (2009) 74–82.

DOI: 10.1016/j.theochem.2009.02.036

Downloads

Published

2017-12-20

How to Cite

Kosar Kirca, B., Ozdemir Tarı, G., Albayrak Kastas, C., Odabasoglu, M., & Buyukgungor, O. (2017). Crystal structure, spectral characterization, molecular modeling studies and structural effects of the proton transfer process for (E)-5-methoxy-2-[(3,4-dimethylphenylimino) methyl]phenol. Macedonian Journal of Chemistry and Chemical Engineering, 36(2), 265–278. https://doi.org/10.20450/mjcce.2017.1295

Issue

Section

Spectroscopy