SYNTHESIS, CHARACTERIZATION, CRYSTAL STRUCTURE AND THEORETICAL STUDIES OF N-(2,4-DICHLOROBENZYLIDENE)-3-METHYLBENZENAMINE

Abstract

N-(2,4-dichlorobenzylidene)-3-methylbenzenamine (L6) was synthesized as single crystal and characterized by FT-IR, Raman, ¹H NMR, ¹³C NMR and UV-VIS spectroscopy. The thermal stability of the title compound was also studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) analyses. The optimized geometric parameters, conformational analysis, normal mode frequencies and corresponding vibrational assignments of L6 was theoretically examined by means of density functional theory (DFT) method using the Becke-3-Lee-Yang-Parr (B3LYP) exchange-correlation functional and the 6-311G++(d, p) basis sets. The DFT based nuclear magnetic resonance (NMR) calculations was also performed to use for assigning the ¹H and ¹³C NMR chemical shifts of L6. Reliable vibrational assignments were investigated by the potential energy distribution analysis and the highest occupied and the lowest unoccupied molecular orbitals (HOMO and LUMO) of L6 was predicted. A good consistency was obtained between the theoretically predicted structural parameters, vibrational frequencies and those obtained experimentally.

Keywords

• Nitrile
• Metallophthalocyanine
• Cyclotetramerization
• Macrocyclic

References

1. Blagus A, Cinčić D, Frisčić T, Kaitner B, Stilinović V. Schiff bases derived from hydroxyaryl aldehydes: molecular and crystal structure, tautomerism, quinoid effect, coordination compounds. Maced J Chem and Chem Eng 2010: 29(2); 117-138.
2. Dueke-Eze CU, Fasina TM, Idika N. Synthesis, electronic spectra and inhibitory study of some Salicylaldehyde Schiff bases of 2-aminopyridine. AJPAC 2011: 5(2); 13-18.
3. Khaloji AD, Mighani H, Gotoh K, Ishida H. Synthesis, Characterization, Structure, Ab Initio and DFT Calculations of 2-Amino-N-(3-phenylprop-2-enylidene)aniline. J Chem Crystallogr 2011: 41; 1154-1157.
4. Pramanik HAR, Das D, Paul PC, Mondal P, Bhattacharjee CR. Newer mixed ligand Schiff base complexes from aquo-N-(2′-hydroxy acetophenone) glycinatocopper(II) as synthon: DFT, antimicrobial activity and molecular docking study. Journal of Molecular Structure 2014: 1059; 309- 319.
5. Singh AK, Pandey SK, Pandey OP, Sengupta SK. Synthesis and spectral characterization of Zn(II) microsphere series for antimicrobial application. Journal of Molecular Structure 2014: 1074; 376-383. [6] Li ZZ, Gu Z, Yin K, Zhang R, Deng Q, Xiang JN. Synthesis of substituted-phenyl-1,2,4-triazol-3- thione analogues with modified d-glucopyranosyl residues and their antiproliferative activities. Eur. J. Med. Chem. 2009: 44; 4716-4720.
6. Li YG, Dong XW, Ai R, Xu XL, Zhu HL. Synthesis and Crystal Structure of a New Schiff Base Ligand and Its Cobalt(II) Complex1. Russian J Coord Chem 2011: 37; 523-527.
7. Khalaji AD, Chermahini AN, Fejfarova K, Dusek M. Synthesis, characterization, crystal structure, and theoretical studies on Schiff-base compound 6-[(5-Bromopyridin-2-yl)iminomethyl]phenol. Struc Chem 2010: 21; 153-157.
8. Magar BK, Kirdant AS, Chondhekar TK. Formation of N-salicylidene-p-methylaniline: A kinetic study. Der Chemica Sinica 2014: 5(1); 95-100.

9. Jadhav SM, Shelke VA, Munde AS, Shankarwar SG, Chondhekar TK. Synthesis, characterization, potentiometry, and antimicrobial studies of transition metal complexes of a tridentate ligand. J Coord Chem 2010: 63(23); 4153-4164.
10. Shelke VA, Jadhav SM, Shankarwar SG, Munde AS, Chondhekar TK. Synthesis and Characterization of Tetradentate N2O2 Schiff Base Ligand and its Rare Earth Metal Complexes. J Korean Chem Soc 2011: 55(3); 436-443.
11. Patel PR, Zele S. Preparation and characterization of some lanthanide complexes involving a heterocyclicβ-diketone. Ind. Chem 1999: 38A; 563-567.
12. ChemBioDraw Ultra 14 Individual ASL SN Win., Download Individual Two Year Term English Windows, 2014.
13. Dennington RD, Keith TA, Millam JM, GaussView 5.0.8, Gaussian Inc., Wallingford CT 2008.
14. Becke AD. Density‐functional thermochemistry. III. The role of exact Exchange, J Chem Phys 1993: 98; 5648-5652.
15. Lee C, Yang W, Parr RG. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, Phys. Rev. B 1988: 37; 785–789.
16. Jamróz, M.H. Vibrational Energy Distribution Analysis: VEDA 4 Program, Warsaw, 2004.
17. Sundaraganesan N, Ilakiamani S, Salem H, Wojciechowski PM, Michalska D. FT-Raman and FT-IR spectra, vibrational assignments and density functional studies of 5-bromo-2-nitropyridine. Spectrochim. Acta A 2005: 61; 2995-3001.
18. Sundaraganesan N, Ilakiamani S, Subramani P, Dominic Joshua B. Comparison of experimental and ab initio HF and DFT vibrational spectra of benzimidazole. Spectrochimica Acta Part A 2007: 67; 628-635.
19. Jamróz MH. Vibrational energy distribution analysis (VEDA): Scopes and limitations. Spectrochimica Acta Part A 2013: 114; 220-230.
20. Bürgi HB, Dunitz JD. Molecular conformation of benzylideneanilines; relation to electronic structure and spectra. J. Chem. Soc. D, 1969: 472-473.
21. Bernstein J. Conformational Studies. Part 111.l Crystal and Molecular Structures of N- (2,4-D ichlorobenzylidene)aniline. J Chem Soc Perkin Trans 1972: 2; 946-950.
22. Vergoten G, Fleury G. Vibrational Spectroscopy Of Liquid Crystals 2. Normal Coordinate Analysis Of Benzaniline: Basis Structure For Some Liquid Crystals, Journal of Molecular Structure 1976: 30(2); 347-359.
23. Bernstein J, Schmidt GMJ. Conformational Studies. Part 1V.l Crystal and Molecular Structure of the Metastable Form of N-(p-Chlorobenzv1idene)-p-chloroaniline, a Planar Anil, J Chem Soc Perkin Trans 1972: 2; 951-955.
24. Udhayakala P, Jayanthi A, Rajendiran TV, Gunasekaran S. Computation and interpretation of vibrational spectra, thermodynamical and HOMO-LUMO analysis of 2-chloro-4-nitroaniline. Int J ChemTech Res 2011: 3(4); 1851-1862.
25. Prasad JV, Rai SB, Thakur SN. Overtone spectroscopy of benzene derivatives using thermal lensing. Chemıcal Physıcs Letters 1989: 164(6); 629-634.
26. Hayd H, Savin H, Stoll A, Preuss H, Becker G. Influence of substituents on bond lengths. Journal of Molecular Structure (Theochem) 1988: 165; 87-97.
27. Gough KM, Henry BR. CH Stretching Overtone Spectra of Nltrobenzene and Its Deuterated Derivatives. Assignment of the Ortho CH. J Phys Chem 1989: 87; 3804-3805.
28. Mizugai Y, Katayama M, Nakagawa N. Substituent Effect on the Fifth Overtones of the Aryl C-H Stretching Vibrations in Disubstituted Benzenes. J Am Chem Soc 1981: 103; 5061-5063.
29. Traetteberg M, Hilmo I, Abraham RJ, Ljunggren S. The Molecular Structure Of N-Benzylıdene- Anılıne. Journal of Molecular Structure 1978: 48; 395-405.
30. Rukiah M, Lefebvre J, Descamps M, Hemon S, Dzyabchenko A. Ab initio structure determination of m-toluidine by powder X-ray diffraction. J Appl Cryst 2004: 37; 464-471.
31. Stuart B. Infrared Spectroscopy: Fundamentals and Applications. 2004: John Wiley & Sons, Inc. ISBNs: 0-470-85427-8 (HB); 0-470-85428-6 (PB).
32. Varsanyi G. Assignments of Vibrational Spectra of Seven Hundred Benzene Derivatives. Adam Hilger Ed. 1974: Vol. 1-2.
33. Silverstein M, Clayton Basseler G, Morill C. Spectrometric Identification of Organic Compounds. 2001: Wiley New York.
34. Kozhevina LI, Prokopenko EB, Rybachenko VI, Titov EV. Investıgatıon Of Azomethıne Group Vıbratıons In Aromatıc Schıff Bases And Theır N-Oxıdes By Vıbratıonal Spectroscopy Methods. Journal of Structural Chemistry 1995: 36; 276-280.
35. Suydam FH. The C-N Stretching Frequency in Azomethines. Analytical Chemistry, 1963: 35(2); 193-195.
36. Meić Z, Baranović G. Vibrational Spectra of trans-N-Benzylideneaniline and Its Isotopomers. Pure &Appl. Chem 1989: 61(12); 2129-2138.
37. Campagnaro GE, Wood JL. The vibrational spectra and origin of torsional barriers in some aromatic systems. Journal of Molecular Structure 1970: 6; 117-132.
38. Figueroa AK, Peña CR, Campos-Vallette MM. Valence Force Constants of N- Benzylideneanilines. Z Naturforsch 1989: 44b; 923-927.
39. Tyagi P, Chandra S, Saraswat BS, Sharma D. Design, spectral characterization, DFT and biological studies of transition metal complexes of Schiff base derived from 2-aminobenzamide, pyrrole and furan aldehyde. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2015: 143; 1-11.
40. APEX2 and Saint, Bruker AXS 2007: Madison, Wisconsin, USA.
41. Sheldrick GM. SHELXS-97, Phase annealing in SHELX-90: direct methods for larger structures. Acta Crystallogr 1990: 46; 467-473.
42. Spek AL. Platon-A Multipurpose Crystallographic Tool Utrecht; Utrecht University 2005: The Netherlands.
43. Macrae CF, Edgington PR, McCabe P, Pidcock E, Shields GP, Taylor R, Owler M Van de Streek. Mercury: visualization and analysis of crystal structures. J Appl Crystallogr 2006: 39; 453-457.