Vibrational spectroscopic and Hirshfeld surface analysis of N,N'-(azanediylbis(2,1-phenylene))bis(2-chloropropanamide) European Journal of Chemistry 10 (4) (2019) 386-402 European Journal of Chemistry View Journal Online View Article Online Vibrational spectroscopic and Hirshfeld surface analysis of N,N'-(azanediylbis(2,1-phenylene))bis(2-chloropropanamide) Aysegul Suzan Polat 1,*, Ilkay Gumus 2 and Hakan Arslan 1 1 Department of Chemistry, Faculty of Arts and Science, Mersin University, Mersin, 33343, Turkey aysegul.polat@mersin.edu.tr (A.S.P.), hakan.arslan@mersin.edu.tr (H.A.) 2 Department of Basic Sciences, Faculty of Maritime, Mersin University, Mersin, 33343, Turkey ilkay.gumus@mersin.edu.tr (I.G.) * Corresponding author at: Department of Chemistry, Faculty of Arts and Science, Mersin University, Mersin, 33343, Turkey. Tel: +90.533.5671703 Fax: +90.324.3610047 e-mail: aysegul.polat@mersin.edu.tr (A.S. Polat). 10.5155/eurjchem.10.4.386-402.1921 Received: 02 September 2019 Received in revised form: 22 October 2019 Accepted: 26 October 2019 Published online: 31 December 2019 Printed: 31 December 2019 The title molecule, N,N'-(azanediylbis(2,1-phenylene))bis(2-chloropropanamide) (LNNN) was synthesized and characterized by means of Hirshfeld surface analysis and vibrational (FT-IR and RAMAN) studies. Ab-initio Hartree-Fock (HF) and density functional theory (DFT; BLYP, B3LYP, B3PW91 and mPW1PW91) calculations were accomplished using 6-31G(d,p) and 6- 311G(d,p) basis sets. The comparison of calculated bond lengths and angles with X-ray crystal structure shows sufficient agreement. The solid phase FT-IR and FT-RAMAN spectra of LNNN have been recorded in the regions 4000-525 cm-1 and 4000-50 cm-1, respectively. A comparative analysis between the calculated and experimental vibrational frequencies was carried out and significant bands were assigned. The results indicated a good correlation between experimental and theoretical IR and RAMAN frequencies. A detailed analysis of the intermolecular interactions via Hirshfeld surface analysis and fingerprint plots revealed that supramolecular structure of the LNNN is stabilized mainly by the formation of H···H, C···H, Cl···H ve O···H intermolecular interactions. Vibration spectrum Ab initio calculations Infrared spectroscopy Redox active compound Density functional theory Hirshfeld surface analysis Cite this: Eur. J. Chem. 2019, 10(4), 386-402 Journal website: www.eurjchem.com 1. Introduction Recently, many of research groups focused on the development of highly efficient and selective catalysts [1-7]. The catalytic activity performance of metal complexes depends on the interaction of the metal center and its surrounding ligands. Redox non-innocent or redox active ligands, unlike classical ligands, are actively involved in redox processes [8-22]. So, they supply an opportunity to modify the reactivity of metal complexes. As an example, Smith et al. found that the metal-carbon bond formation for Negishi-like cross-coupling of alkyl halides with organozinc reagents can occur via metal-centered oxidative addition steps but without changing the d-electron configuration of the metal [23]. The required electrons were supplied by redox active ligands and so, redox active ligands offered selectivity to the metal complex for the catalytic activity. Considering the facts above, the intent of this study is to perform an experimental and computational work on a potential redox active compound, N,N'-(azanediylbis(2,1- phenylene))bis(2-chloropropanamide) (LNNN). The optimized geometric parameters and vibrational frequencies have been calculated using the HF method with 6-31G(d,p) and 6- 311G(d,p) basis sets and similarly with DFT (BLYP, B3LYP, B3PW91 and mPW1PW91) methods along with 6-31G(d,p) and 6-311G(d,p) basis sets. In addition, intermolecular interactions and packing modes present in the solid state of the title compound were visualized by means of the Hirshfeld surface analysis. 2. Experimental 2.1. Instrumentation The NMR spectra were recorded in CDCl3 solvent on Bruker Avance III 400 MHz NaNoBay FT-NMR spectrophoto- meter using tetramethylsilane as an internal standard. FT-IR and FT-RAMAN spectroscopy was used for the identification of vibrational modes in the LNNN molecule. The room- temperature-attenuated total reflection Fourier transform infrared (FT-IR ATR) spectrum of N,N'-(azanediylbis(2,1- phenylene))bis(2-chloropropanamide) compound was recor- ded using a Perkin Elmer Spectrum 100 series spectrometer with a ATR prism (4000-525 cm-1; number of scans: 250; resolution: 1 cm-1) (Figure 1). ABSTRACT RESEARCH ARTICLE KEYWORDS European Journal of Chemistry ISSN 2153-2249 (Print) / ISSN 2153-2257 (Online) – Copyright © 2019 The Authors – Atlanta Publishing House LLC – Printed in the USA. This work is published and licensed by Atlanta Publishing House LLC – CC BY NC – Some Rights Reserved. http://dx.doi.org/10.5155/eurjchem.10.4.386-402.1921 http://dx.doi.org/10.5155/eurjchem.10.4.386-402.1921 https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.10.4.386-402.1921&domain=pdf&date_stamp=2019-12-31 http://www.eurjchem.com/ http://dx.doi.org/10.5155/eurjchem.10.4.386-402.1921 mailto:aysegul.polat@mersin.edu.tr mailto:hakan.arslan@mersin.edu.tr mailto:ilkay.gumus@mersin.edu.tr mailto:aysegul.polat@mersin.edu.tr http://www.eurjchem.com/ https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.10.4.386-402.1921&domain=pdf&date_stamp=2019-12-31� Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 387 Figure 1. Experimental (a) and theoretical (b) FT-IR spectrum of LNNN compound. Figure 2. Experimental (a) and theoretical (b) FT-RAMAN spectrum of LNNN compound. Nicolet Spectrometer 6700 was used to record the FT- RAMAN spectrum of the title compound in the range of 4000- 50 cm-1 at room temperature. The wavelength of the used laser was 780 nm. Figure 2 demonstrates the recorded FT-RAMAN spectrum of the title compound. 2.2. Synthesis The solvents and chemicals used in the study were commercially obtained from Merck, Sigma-Aldrich and Alfa- Aesar companies and were used without further purification. Precursor materials bis(2-nitrophenyl)amine and bis(2- aminophenyl)amine were prepared according to the previously published method (Scheme 1) [24-28]. (a) (b) 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 388 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 Scheme 1 A solution of 2-chloropropionyl chloride (5 mmol) in acetonitrile (50 mL) was cooled to 0 °C under nitrogen atmosphere. Then, bis(2-aminophenyl)amine (10 mmol) and triethylamine (Et3N) (10 mmol) was slowly added to this cold solution over 3 h. The mixture was stirred at 0 °C for 1 hr and the mixture temperature were allowed to slowly rise to room temperature. Then, the mixture was stirred again at room temperature for 24 h and the solvent was removed under vacuum. The resulting solid was crystallized from dichloro methane/n-hexane mixture (1:1, v:v) (Scheme 1) [25,26]. N,N'- (Azanediylbis(2, 1-phenylene))bis(2-chloropropanamide) (LNNN): Color: White. Yield: 65%. 1H NMR (400 MHz, CDCl3, δ, ppm): 8.51 (s, 2H, NH(CO)), 7.69 (dd, 2H, Ar-H), 7.13 (td, 2H, Ar-H), 7.07 (m, 2H, Ar-H), 6.91 (dd, 2H, Ar-H), 5.74 (s, 1H, NH), 4.53 (q, 2H, CH), 1.71 (d, 6H, CH3). 13C NMR (100 MHz, CDCl3, δ, ppm): 168.30 (CO), 136.00 (Ar-C), 128.43 (Ar-C), 126.89 (Ar- C), 123.90 (Ar-C), 121.31 (Ar-C), 55.90 (CH), 22.44 (CH3), 22.41 (CH3). FT-IR (ATR, cm-1): 3397, 3099, 3060, 2980, 1690, 1662, 1651. LC-MS (+ESI, m/z): 380.2 [M+H]+, 279.2, 242.3, 130.2, 102.2. 2.3. Calculation details The theoretical calculations were carried out with the Gaussian 16W program packages [29]. The calculated results were visualized by means of GaussView 6.0 [30]. In the present work, we have calculated the vibrational frequencies and the geometric parameters of N,N'-(azanediylbis(2,1- phenylene))bis(2-chloropropanamide) in the ground state to compare the fundamentals from the experimental vibration frequencies and geometric parameters, by using the Hartree- Fock (HF) [31], the Density functional theory using Becke’s three parameter hybrid functionals [32] with Lee, Yang, and Parr correlation functional methods (B3LYP) [33], Becke’s exchange functional in combination with the Lee, Yang and Parr correlation functional methods (BLYP) [32,33], the Barone and Adamo’s Becke-style one-parameter functional using the modified Perdew-Wang exchange and Perdew-Wang 91 correlation method (mPW1PW91) [34,35], Becke’s three parameter exchange functionals with Perdew-Wang exchange functional with Perdew and Wang’s gradient correlated functional (B3PW91) [32,36] with the standard 6-31G(d,p) and 6-311G(d,p) basic sets. The frequency values computed at these levels contain known systematic errors [37]. Scaling factor values of 0.9614, 0.9679, 0.9573, 0.9631, 0.9945, 0.9934, 0.9500, 0.9567 0.8992 and 0.9051 for B3LYP/6- 31G(d,p), B3LYP/6-311G(d,p), B3PW91/6-31G(d,p), B3PW91/ 6-311G(d,p), BLYP/6-31G(d,p), BLYP/6-311G(d,p), mPW1 PW91/6-31G(d,p), mPW1PW91/6-311G(d,p), HF/6-31G(d,p) and HF/6-311G(d,p), respectively, can be used to correct these discrepancies [38-44]. Also, optimal scaling factors were calculated for all analyzed methods. The GaussView 6.0 graphical interface of the Gaussian program, which is an animation option that provides a visual representation of the shape of the modes of vibration, provides a way of assigning the calculated wavenumbers [30]. The SQM procedure has been widely used in the assignment of bands of vibrational spectra due to being a highly successful and well established technique in refining the computerized vibration frequencies to better match the experimental values [45]. So, the vibrational modes were determined according to the potential energy distribution analysis using the SQM program [46]. Using the PAVF 1.0 program, the performance of the used method was quantitatively characterized [47]. The population analysis has also been performed by the natural bond orbital method [48] at B3LYP, BLYP, B3PW91, mPW1PW91 and HF/6-31G(d,p) and 6-311G(d,p) level of theory using the natural bond orbital (NBO) program [49] under the Gaussian 16W program package. 2.4. Hirshfeld surfaces analysis Analysis of Hirshfeld surfaces and their associated two dimensional fingerprint plots of LNNN compound were calculated by using the CrystalExplorer17 [50]. The Hirshfeld surfaces are mapped with different properties dnorm, shape index and curvedness. The dnorm is a normalized contact distance, defined in terms of de, di and the vdW radii of the atoms. The combination of de and di in the form of a 2D fingerprint plot displays the summary of intermolecular contacts in the crystal. 3. Results and discussion 3.1. Molecular geometry The molecular structure of N,N'-(azanediylbis(2,1- phenylene))bis(2-chloropropanamide) obtained by the single crystal X-ray diffraction method has been previously reported [25,26]. The compound crystallizes triclinic, space group P-1 (no. 2), a = 9.4053(6) Å, b = 10.8925(8) Å, c = 18.5490(13) Å, α = 76.134(2)°, β = 80.859(2)°, γ = 79.963(2)°, V = 1803.0(2) Å3, Z = 4, T = 99.99 K, μ(MoKα) = 0.377 mm-1, Dcalc = 1.401 g/cm3, 149948 reflections measured (5.956° ≤ 2Θ ≤ 50.238°), 6409 unique (Rint = 0.1130, Rsigma = 0.0328) which were used in all calculations. The final R1 was 0.0411 (I > 2σ(I)) and wR2 was 0.0989 (all data). The optimized geometry parameters were performed by theoretical calculations using the HF and DFT (B3LYP, BLYP, B3PW91, mPW1PW91) methods with 6- 31G(d,p) and 6-311G(d,p) basis sets. Full geometry optimi- zation of structure was carried out without any restrictions. The stability of the optimized geometries was confirmed by the absence of imaginary frequencies in the vibrational spectra. The title compound belongs to C1 point group symmetry. The comparative optimized structural parameters such as bond lengths and bond angles are presented in Table 1 in accordance with the atom numbering scheme illustrated in Figure 3. In addition, the correlation values of theoretical and experimental geometric parameters are presented at the end of Table 1. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 389 Table 1. Optimized and experimental geometries of H3LNNN molecule in the ground state *. Parameter Experimental, Å Calculated, Å B3LYP B3PW91 BLYP mPW1PW HF 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 Bond lengths C1-C2 1.505(15) 1.516 1.514 1.512 1.510 1.525 1.523 1.509 1.508 1.515 1.514 C2-Cl3 1.778(8) 1.847 1.845 1.825 1.825 1.880 1.879 1.820 1.818 1.814 1.817 C2-C4 1.520(3) 1.538 1.537 1.535 1.533 1.550 1.549 1.532 1.530 1.530 1.529 C4-O5 1.219(3) 1.222 1.214 1.220 1.213 1.235 1.228 1.217 1.210 1.195 1.189 C4-N6 1.345(3) 1.373 1.373 1.369 1.369 1.388 1.388 1.366 1.366 1.357 1.358 N6-C7 1.426(3) 1.417 1.416 1.410 1.410 1.425 1.425 1.408 1.407 1.418 1.418 C7-C8 1.385(3) 1.401 1.401 1.401 1.399 1.415 1.412 1.397 1.397 1.389 1.388 C7-C12 1.404(3) 1.417 1.412 1.412 1.409 1.427 1.425 1.411 1.407 1.397 1.395 C8-C9 1.385(3) 1.392 1.389 1.389 1.387 1.401 1.398 1.388 1.385 1.381 1.379 C9-C10 1.385(3) 1.394 1.393 1.394 1.391 1.406 1.403 1.391 1.389 1.385 1.385 C10-C11 1.382(3) 1.391 1.388 1.388 1.386 1.400 1.397 1.387 1.384 1.380 1.379 C11-C12 1.393(3) 1.403 1.398 1.399 1.396 1.412 1.410 1.399 1.394 1.393 1.392 C12-N13 1.399(3) 1.407 1.416 1.411 1.410 1.427 1.425 1.399 1.409 1.403 1.405 N13-C14 1.397(3) 1.398 1.414 1.409 1.408 1.425 1.423 1.390 1.405 1.399 1.402 C14-C15 1.392(3) 1.407 1.398 1.399 1.396 1.412 1.409 1.402 1.393 1.393 1.392 C14-C19 1.406(3) 1.415 1.413 1.413 1.411 1.428 1.425 1.410 1.409 1.398 1.397 C15-C16 1.381(3) 1.392 1.391 1.392 1.389 1.403 1.400 1.388 1.388 1.383 1.383 C16-C17 1.383(3) 1.396 1.393 1.394 1.391 1.406 1.403 1.392 1.389 1.384 1.383 C17-C18 1.379(3) 1.392 1.391 1.392 1.389 1.403 1.400 1.388 1.388 1.383 1.382 C18-C19 1.390(3) 1.395 1.396 1.397 1.394 1.410 1.407 1.391 1.392 1.383 1.382 C19-N20 1.425(3) 1.424 1.416 1.410 1.409 1.425 1.426 1.416 1.407 1.421 1.421 N20-C21 1.344(3) 1.351 1.346 1.343 1.343 1.359 1.360 1.345 1.340 1.339 1.339 C21-O22 1.222(2) 1.237 1.235 1.239 1.233 1.256 1.248 1.232 1.230 1.210 1.205 C21-C23 1.518(3) 1.534 1.535 1.531 1.530 1.547 1.546 1.527 1.527 1.527 1.527 C23-C24 1.514(10) 1.528 1.525 1.523 1.520 1.537 1.535 1.521 1.518 1.526 1.524 C23-Cl25 1.813(3) 1.835 1.834 1.814 1.815 1.866 1.869 1.809 1.808 1.803 1.806 C26-C27 1.537(15) 1.516 1.514 1.512 1.510 1.525 1.523 1.509 1.508 1.515 1.514 C27-Cl28 1.756(5) 1.847 1.845 1.825 1.825 1.880 1.879 1.820 1.818 1.814 1.817 C27-C29 1.517(3) 1.538 1.537 1.535 1.533 1.550 1.549 1.532 1.530 1.530 1.529 C29-O30 1.226(2) 1.222 1.214 1.220 1.213 1.235 1.228 1.217 1.210 1.195 1.189 C29-N31 1.352(3) 1.373 1.373 1.369 1.369 1.388 1.388 1.366 1.366 1.357 1.358 N31-C32 1.428(3) 1.417 1.416 1.410 1.410 1.425 1.425 1.408 1.407 1.418 1.418 C32-C33 1.385(3) 1.401 1.401 1.401 1.399 1.415 1.412 1.397 1.397 1.389 1.388 C32-C37 1.401(3) 1.417 1.412 1.412 1.409 1.427 1.425 1.411 1.407 1.397 1.395 C33-C34 1.386(3) 1.392 1.389 1.389 1.387 1.401 1.398 1.388 1.385 1.381 1.379 C34-C35 1.375(3) 1.394 1.393 1.394 1.391 1.406 1.403 1.391 1.389 1.385 1.385 C35-C36 1.386(3) 1.391 1.388 1.388 1.386 1.400 1.397 1.387 1.384 1.380 1.379 C36-C37 1.393(3) 1.403 1.398 1.399 1.396 1.412 1.410 1.399 1.394 1.393 1.392 C37-N38 1.400(3) 1.407 1.416 1.411 1.410 1.427 1.425 1.399 1.409 1.403 1.405 N38-C39 1.400(3) 1.398 1.414 1.409 1.408 1.425 1.423 1.390 1.405 1.399 1.402 C39-C40 1.397(3) 1.407 1.398 1.399 1.396 1.412 1.409 1.402 1.393 1.393 1.392 C39-C44 1.398(3) 1.415 1.413 1.413 1.411 1.428 1.425 1.410 1.409 1.398 1.397 C40-C41 1.380(3) 1.392 1.391 1.392 1.389 1.403 1.400 1.388 1.388 1.383 1.383 C41-C42 1.383(3) 1.396 1.393 1.394 1.391 1.406 1.403 1.392 1.389 1.384 1.383 C42-C43 1.385(3) 1.392 1.391 1.392 1.389 1.403 1.400 1.388 1.388 1.383 1.382 C43-C44 1.385(3) 1.395 1.396 1.397 1.394 1.410 1.407 1.391 1.392 1.383 1.382 C44-N45 1.427(3) 1.424 1.416 1.410 1.409 1.425 1.426 1.416 1.407 1.421 1.421 N45-C46 1.336(3) 1.351 1.346 1.343 1.343 1.359 1.360 1.345 1.340 1.339 1.339 C46-O47 1.218(3) 1.237 1.235 1.239 1.233 1.256 1.248 1.232 1.230 1.210 1.205 C46-C48 1.514(3) 1.534 1.535 1.531 1.530 1.547 1.546 1.527 1.527 1.527 1.527 C48-C49 1.554(15) 1.528 1.525 1.523 1.520 1.537 1.535 1.521 1.518 1.526 1.524 C48-Cl50 1.766(6) 1.835 1.834 1.814 1.815 1.866 1.869 1.809 1.808 1.803 1.806 r 0.9931 0.9929 0.9932 0.9933 0.9901 0.9906 0.9939 0.9936 0.9962 0.9959 Bond angles C1-C2-Cl3 111.30(11) 109.99 109.93 110.17 110.11 109.69 109.66 110.23 110.17 110.23 110.15 C1-C2-C4 114.80(10) 111.90 112.18 111.63 111.95 112.12 112.41 111.60 111.85 112.18 112.43 Cl3-C2-C4 108.80(4) 108.11 107.20 107.36 107.16 107.25 107.19 108.25 107.10 108.25 108.04 C2-C4-O5 123.34(19) 121.12 121.27 121.20 121.37 121.26 121.40 121.18 121.37 121.04 121.20 C2-C4-N6 113.48(17) 113.65 113.38 113.49 113.24 113.47 113.29 113.53 113.23 114.13 113.84 O5-C4-N6 123.20(2) 125.21 125.35 125.31 125.39 125.27 125.30 125.27 125.40 124.81 124.94 C4-N6-C7 125.14(17) 125.92 126.70 126.52 126.67 126.98 126.98 125.67 126.57 124.34 124.54 N6-C7-C8 121.42(19) 121.88 122.00 122.03 122.07 122.00 121.94 121.92 122.15 120.96 121.00 N6-C7-C12 118.37(18) 118.62 118.76 118.73 118.71 118.83 118.88 118.54 118.61 119.18 119.20 C8-C7-C12 120.21(19) 119.50 119.23 119.23 119.22 119.16 119.18 119.53 119.24 119.86 119.79 C7-C8-C9 120.80(2) 120.67 120.53 120.52 120.53 120.55 120.60 120.65 120.45 120.77 120.79 C8-C9-C10 119.10(2) 120.01 120.32 120.34 120.33 120.38 120.30 120.00 120.38 119.56 119.59 C9-C10-C11 120.70(2) 119.90 119.61 119.59 119.59 119.61 119.67 119.91 119.58 120.15 120.06 C10-C11-C12 120.70(2) 121.01 121.01 120.98 120.98 121.04 121.07 120.96 120.91 120.87 120.92 C7-C12-C11 118.45(19) 118.89 119.27 119.31 119.32 119.22 119.14 118.94 119.40 118.78 118.84 C7-C12-N13 117.71(18) 120.11 121.32 121.36 121.25 121.54 121.39 120.03 121.14 120.29 120.50 C11-C12-N13 123.79(19) 120.93 119.38 119.30 119.41 119.19 119.43 120.97 119.43 120.86 120.60 C12-N13-C14 129.42(18) 126.37 122.60 122.19 122.37 122.73 123.35 126.03 122.12 125.19 124.64 N13-C14-C15 123.90(19) 123.11 123.12 123.14 123.12 123.05 122.95 123.14 123.22 123.37 123.38 N13-C14-C19 117.80(18) 118.93 118.10 118.03 118.05 118.22 118.37 118.85 117.91 118.46 118.40 C15-C14-C19 118.24(19) 117.95 118.78 118.83 118.83 118.73 118.68 118.00 118.86 118.16 118.22 C14-C15-C16 120.50(2) 120.81 120.66 120.58 120.62 120.63 120.70 120.77 120.58 120.76 120.80 C15-C16-C17 121.10(2) 120.69 120.16 120.15 120.15 120.20 120.21 120.70 120.17 120.61 120.54 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 390 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 Table 1. Continued. Parameter Experimental, Å Calculated, Å B3LYP B3LYP B3LYP B3LYP B3LYP 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 Bond angles C16-C17-C18 119.20(2) 119.30 120.11 120.18 120.13 120.19 120.09 119.30 120.14 119.18 119.18 C17-C18-C19 120.50(2) 120.47 120.00 119.91 119.98 119.93 120.06 120.44 119.94 120.58 120.63 C14-C19-C18 120.49(19) 120.76 120.23 120.28 120.22 120.25 120.21 120.78 120.24 120.67 120.60 C14-C19-N20 119.26(18) 118.36 116.27 116.06 116.12 116.32 116.62 118.22 115.95 118.54 118.48 C18-C19-N20 120.25(19) 120.85 123.44 123.59 123.60 123.34 123.08 120.97 123.76 120.76 120.89 C19-N20-C21 123.45(17) 125.56 129.11 129.06 129.21 129.30 129.20 125.38 129.18 124.94 125.13 N20-C21-O22 123.60(2) 124.24 124.80 124.64 124.81 124.63 124.85 124.18 124.76 124.51 124.62 N20-C21-C23 114.63(18) 118.02 117.90 117.91 117.65 117.97 117.83 117.91 117.67 118.28 118.21 O22-C21-C23 122.76(19) 117.69 117.29 117.43 117.53 117.36 117.29 117.87 117.57 117.11 117.09 C21-C23-C24 112.30(5) 111.32 111.45 111.08 111.32 111.70 111.87 110.99 111.28 110.48 110.73 C21-C23-Cl25 110.46(16) 113.30 113.68 113.79 113.72 113.37 113.55 113.42 113.70 113.79 113.73 C24-C23-Cl25 110.70(5) 109.71 109.57 109.80 109.68 109.48 109.28 109.92 109.70 110.06 109.93 C26-C27-Cl28 107.00(10) 109.99 109.93 110.17 110.11 109.69 109.66 110.23 110.17 110.23 110.15 C26-C27-C29 105.50(9) 111.90 112.18 111.63 111.95 112.12 112.41 111.60 111.85 112.18 112.43 Cl28-C27-C29 109.90(3) 108.11 107.20 107.36 107.16 107.25 107.19 108.25 107.10 108.26 108.04 C27-C29-O30 122.12(19) 121.12 121.26 121.20 121.37 121.26 121.40 121.18 121.37 121.04 121.20 C27-C29-N31 114.45(18) 113.65 113.38 113.49 113.24 113.47 113.29 113.53 113.23 114.13 113.84 O30-C29-N31 123.40(2) 125.21 125.35 125.31 125.39 125.27 125.30 125.27 125.40 124.81 124.94 C29-N31-C32 123.35(17) 125.92 126.70 126.52 126.67 126.98 126.98 125.67 126.57 124.34 124.54 N31-C32-C33 119.61(18) 121.88 122.00 122.03 122.07 122.00 121.94 121.92 122.15 120.96 121.00 N31-C32-C37 119.55(18) 118.62 118.77 118.73 118.71 118.83 118.88 118.54 118.61 119.17 119.20 C33-C32-C37 120.84(19) 119.50 119.23 119.23 119.22 119.16 119.18 119.53 119.24 119.86 119.79 C32-C33-C34 120.30(2) 120.67 120.53 120.52 120.53 120.55 120.60 120.65 120.45 120.77 120.79 C33-C34-C35 119.30(2) 120.01 120.32 120.34 120.33 120.38 120.30 120.00 120.38 119.56 119.59 C34-C35-C36 121.00(2) 119.90 119.61 119.59 119.59 119.61 119.67 119.91 119.58 120.15 120.06 C35-C36-C37 120.50(2) 121.01 121.01 120.98 120.98 121.04 121.07 120.96 120.91 120.87 120.92 C32-C37-C36 118.07(19) 118.89 119.27 119.31 119.32 119.22 119.14 118.94 119.40 118.78 118.84 C32-C37-N38 117.71(18) 120.11 121.32 121.36 121.25 121.54 121.39 120.03 121.14 120.29 120.50 C36-C37-N38 124.20(2) 120.93 119.38 119.30 119.41 119.19 119.43 120.97 119.43 120.86 120.60 C37-N38-C39 128.16(18) 126.37 122.59 122.19 122.37 122.73 123.35 126.03 122.12 125.19 124.63 N38-C39-C40 123.80(2) 123.11 123.12 123.14 123.12 123.05 122.95 123.14 123.22 123.37 123.38 N38-C39-C44 118.17(19) 118.93 118.11 118.03 118.05 118.22 118.37 118.85 117.92 118.46 118.40 C40-C39-C44 118.00(2) 117.95 118.78 118.83 118.83 118.73 118.68 118.00 118.86 118.16 118.22 C39-C40-C41 120.60(2) 120.81 120.66 120.58 120.62 120.63 120.70 120.77 120.58 120.76 120.80 C40-C41-C42 121.00(2) 120.69 120.16 120.16 120.15 120.20 120.21 120.70 120.17 120.61 120.54 C41-C42-C43 119.10(2) 119.30 120.11 120.18 120.13 120.19 120.09 119.30 120.14 119.18 119.18 C42-C43-C44 120.30(2) 120.47 120.00 119.91 119.98 119.93 120.06 120.44 119.94 120.58 120.63 C39-C44-C43 121.10(2) 120.76 120.23 120.28 120.22 120.25 120.21 120.78 120.24 120.67 120.60 C39-C44-N45 118.91(18) 118.36 116.27 116.06 116.12 116.32 116.62 118.22 115.95 118.54 118.48 C43-C44-N45 120.00(2) 120.85 123.44 123.59 123.60 123.34 123.08 120.97 123.76 120.76 120.89 C44-N45-C46 122.10(17) 125.56 129.11 129.06 129.21 129.30 129.20 125.38 129.18 124.94 125.13 N45-C46-O47 122.10(2) 124.24 124.80 124.65 124.81 124.63 124.85 124.18 124.76 124.51 124.62 N45-C46-C48 115.30(18) 118.02 117.90 117.91 117.65 117.97 117.83 117.91 117.67 118.28 118.21 O47-C46-C48 122.50(2) 117.69 117.29 117.43 117.53 117.36 117.29 117.87 117.57 117.11 117.09 C46-C48-C49 110.70(10) 111.32 111.45 111.08 111.32 111.70 111.87 110.99 111.28 110.48 110.73 C46-C48-Cl50 110.20(3) 113.30 113.68 113.79 113.72 113.37 113.55 113.42 113.70 113.79 113.73 C49-C48-Cl50 111.60(11) 109.71 109.57 109.80 109.68 109.48 109.28 109.92 109.70 110.06 109.93 r 0.9175 0.8450 0.8419 0.8444 0.8451 0.8525 0.9192 0.8424 0.9101 0.9035 * 6-31: 6-31G(d,p); 6-311: 6-311G(d,p); The atom numbering scheme given in Figure 3(a). On Table 1, it can be seen that, the theoretical and experimental structure parameters obtained in this study were found to be both in harmony with each other and experimental one. In the bond length calculations, the best correlation (r = 0.9962) was found for the HF/6-31G(d,p) method, and the maximum difference between the theoretical and experimental bond lengths (C27-Cl28) was 0.058 Å. In the bond angle calculations, the best correlation (r = 0.9192) was found for the mPW1PW91/6-31G(d,p) method, and the maximum difference between the theoretical and experi- mental bond angles (C26-C27-C29) was 6.10°. We discovered some minor differences between the experimental (solid phase) and the theoretical (gas phase) structure parameters of the title compound. The experimental structure parameters of title compound are obtained from solid phase and it is clear, that the solid phase of the compounds includes various crystal interactions [25,26,39-44]. 3.2. Vibrational assignments The theoretical calculations were performed to obtain the harmonic frequencies, RAMAN activities and IR intensities required for the vibrational assignment of the experimental spectra of the title compound. The theoretical values were calculated via the HF and DFT (B3LYP, B-LYP, B3PW91, mPW1PW91) methods with the 6-31G (d, p) and 6-311G(d, p) basis sets. The title compound molecule possesses no symmetry elements and belongs to the C1 point group symmetry. The title molecule consists of 88 (2×44) atoms, which undergo 258 normal modes of vibration. The calculated frequencies, measured RAMAN and IR band positions and their assignments along with corresponding potential energy distribution (PED) contributions are summarized in Table 2. Based on the normal coordinate analysis (NCA) IR and RAMAN spectral wavenumbers have been assigned. The vibrational assignments for different functional groups have been discussed below. The recorded FT-IR and FT-RAMAN spectra of the compound are also presented with the calculated frequencies in Figure 1 and 2, respectively. The vibrational band assignments have been made by using both the animation option of the GaussView 6.0 graphical interface for the Gaussian 16W program [29,30] and the SQM 2.0 program [46]. All the calculated spectra were found to be in good accordance with the experimental ones. Considering Table 2, it can be concluded that experimental bases better aligned with the scaled fundamentals and have a better correlation with B3LYP/6-31G(d,p) than the other calculation methods. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 https://www.sciencedirect.com/topics/biochemistry-genetics-and-molecular-biology/vibration https://www.sciencedirect.com/topics/chemistry/normal-coordinate-analysis Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 391 (a) (b) Figure 3. The optimized geometry of LNNN molecule calculated at B3LYP/6-31G(d,p) level (a) and a view of the molecular structure of LNNN molecule with displacement ellipsoids drawn at the 50% probability level [25] (b). Overall better performance of the used calculation methods can be quantitatively characterized by using the mean absolute percentage error, mean absolute error, root mean square values (RMS) and coefficients of correlation (r) between the theoretically calculated and experimentally observed vibration frequencies (Table 3). All these values were calculated in this study by the PAVF 1.0 program [47] according to Scott and Radom [38]. The r values for all DFT methods were greater than 0.9993. We calculated the optimal scaling factors, which are crucial for IR spectral predictions, using the PAVF 1.0 program [47]. Without accounting for different vibrations, only single-uniform scaling factors were calculated. The values obtained are 0.9615, 0.9675, 0.9595, 0.9647, 0.9922, 0.9970, 0.9524, 0.9585, 0.9023 ve 0.9078 for the B3LYP/6-31G(d,p), B3LYP/6-311G(d,p), B3PW91/6- 31G(d,p), B3PW91/6-311G(d,p), B-LYP/6-31G(d,p), B-LYP/6- 311G(d,p), mPW1PW91/6-31G(d,p), mPW1PW91/6-311G (d,p), HF/6-31G(d,p) and HF/6-311G(d,p), methods, respect- tively. They are very close to those recommended by Scott and Radom [47] for the same level of theory. The N-H stretching vibrations of aromatic amines arise in the range of 3340-3520 cm-1 [51]. The symmetric and anti- symmetric stretching modes (Observed: 3413, 3404, 3397 cm- 1, Calculated: 3462, 3422, 3363 cm-1) are assigned in the spectra of the title compound in the appropriate range. The difference between calculated and observed N-H stretching modes can be explained by the hydrogen bonds which occur in the solid phase. The C=O stretching vibrations arise in the region 1710- 1680 cm-1 [52]. In the IR spectrum of title compound, the C=O stretching vibrations are found at 1690, 1662 and 1651 cm-1 and were calculated at 1720, 1656 and 1646 cm-1. In general, an aromatic C-H stretching vibrations occurs in the region 3100-3000 cm-1 [53-55] and they are affected by the nature of substituent. The title compound has two aromatic groups which have eight C-H adjacent moieties. These C-H stretching modes contributed to five different bands in the RAMAN spectrum of the title compound, located at 3136, 3109, 3092, 3074 and 3069 cm-1 and five bands in the IR spectrum at 3136, 3118, 3099, 3076 and 3060 cm-1 which were in agreement with the calculated ones. The PED contribution of these stretching modes was calculated as 73- 100%, meaning that these local coordinates fully explain the C- H aromatic vibration modes. The symmetric (νsCH3) and asymmetric (νasCH3) stretching modes are usually observed in the range between 3050 and 2950 cm-1 [56]. Our theoretical calculations for the title compound locate these modes for methyl group at the following wavenumbers: νasCH3: 3048, 3036, 3029, 3016 and 3015, and νsCH3: 3013, 2949 and 2944 cm-1. They agree well with the experimental values (Table 2). 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 392 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 Table 2. Vibrational wavenumbers obtained for LNNN at 6-31G(d,p) level. No Exp. IR (cm-1) RAMAN (cm-1) B3LYP Assignments, PED (%) Unscaled (cm-1) Scaled (cm-1) Scaled (cm-1) IR Int. (km/mol) RAMAN activity (A4/amu) 1 3413 3407 3601 3462 3462 165.36 0.01 νNHring, 100 2 3413 3407 3601 3462 3462 0.01 572.86 νNHring, 97 3 3404 3407 3559 3421 3422 0.01 166.41 νNHCarb, 97 4 3404 3407 3558 3421 3422 135.07 0.01 νNHCarb, 96 5 3397 3397 3498 3363 3363 709.45 0.02 νNHCarb, 90 6 3397 3397 3497 3362 3363 0.03 462.97 νNHCarb, 91 7 3136 3136 3263 3137 3137 0.22 140.03 νCHarom, 100, sym 8 3136 3136 3263 3137 3137 2.26 13.35 νCHarom, 99, sym 9 3118 3109 3232 3108 3108 2.28 2.11 νCHarom, 89, sym 10 3118 3109 3232 3108 3108 0.01 399.95 νCHarom, 88, sym 11 3099 3092 3224 3100 3100 9.00 0.05 νCHarom, 83, sym 12 3099 3092 3224 3100 3100 0.01 176.26 νCHarom, 82, sym 13 3099 3092 3216 3092 3092 16.18 0.01 νCHarom, 83, sym 14 3099 3092 3216 3092 3092 0.01 237.82 νCHarom, 82, sym 15 3076 3074 3209 3085 3086 0.01 279.89 νCHarom, 77, asym 16 3076 3074 3209 3085 3086 29.47 0.01 νCHarom, 77, asym 17 3076 3074 3205 3082 3082 0.01 436.27 νCHarom, 73, asym 18 3076 3074 3205 3082 3082 54.32 0.01 νCHarom, 73, asym 19 3060 3069 3192 3068 3069 0.01 166.92 νCHarom, 78, asym 20 3060 3069 3192 3068 3069 9.19 0.07 νCHarom, 78, asym 21 3060 3069 3189 3066 3066 5.63 0.02 νCHarom, 83, asym 22 3060 3069 3189 3066 3066 0.01 140.03 νCHarom, 83, asym 23 3045 3045 3171 3048 3049 11.23 0.01 νCHmetil, asym, 80 + νCH, 15 24 3045 3045 3171 3048 3048 0.01 81.72 νCHmetil, asym, 80 + νCH, 15 25 3045 3045 3158 3036 3037 10.60 0.04 νCHmetil, asym, 44 + νCH, 43 26 3045 3045 3158 3036 3037 0.01 128.03 νCH, 44 + νCHmetil, asym, 43 27 3045 3045 3151 3029 3029 0.01 95.64 νCHmetil, asym, 80 + νCH, 17 28 3045 3045 3151 3029 3029 9.61 0.01 νCHmetil, asym, 80 + νCH, 17 29 3018 3029 3137 3016 3016 23.02 0.01 νCHmetil, asym, 78 + νCH, 13 30 3018 3029 3137 3016 3016 0.01 191.34 νCHmetil, asym, 78 + νCH, 13 31 3018 3020 3136 3015 3015 0.01 175.43 νCHmetil, asym, 56 + νCH, 23 32 3018 3020 3136 3015 3015 7.24 0.11 νCH, 45 + νCHmetil, asym, 34 33 3018 3020 3134 3013 3013 8.02 1.70 νCHmetil, sym, 73 + νCH, 18 34 3018 3020 3134 3013 3013 0.04 308.73 νCHmetil, sym, 72 + νCH, 18 35 2980 2982 3067 2949 2949 0.01 213.32 νCHmetil, sym, 76 36 2980 2982 3067 2949 2949 13.4 0.17 νCHmetil, sym, 76 37 2927 2929 3062 2944 2944 19.44 0.01 νCHmetil, sym, 71 38 2927 2929 3062 2944 2944 0.01 213.99 νCHmetil, sym, 71 39 1690 1691 1789 1720 1720 0.01 72.49 νCO, 71 40 1690 1691 1789 1720 1720 457.77 0.01 νCO, 73 41 1662 1666 1723 1656 1656 855.44 0.01 νCO, 74 42 1651 1651 1712 1646 1646 0.01 119.58 νCO, 73 43 1597 1608 1663 1599 1599 33.23 0.01 νCCarom, 86 44 1597 1608 1662 1598 1598 0.01 635.52 νCCarom, 96 45 1593 1594 1657 1593 1593 0.01 132.25 νCCarom, 72 + δCNH, 12 46 1593 1594 1656 1592 1593 340.93 0.01 νCCarom, 76 + δCNH, 14 47 1589 1584 1651 1587 1587 77.99 0.01 νCCarom, 56 + δCNH, 25 48 1589 1584 1649 1586 1586 0.01 177.08 νCCarom, 81 + δCNH, 10 49 1576 1582 1637 1573 1573 62.71 0.01 νCCarom, 75 + δCNH, 11 50 1576 1582 1636 1573 1573 0.01 161.34 νCCarom, 78 + δCNH, 10 51 1524 1531 1585 1524 1524 474.82 0.01 δCNH, 48 + νCCarom, 21 52 1524 1531 1584 1523 1523 0.01 80.12 δCNH 47 + νCCarom, 20 53 1518 1520 1574 1513 1513 591.1 0.01 νNCCarb, 41 + δCNH, 31 + νCCarom, 17 54 1518 1520 1569 1508 1508 0.01 140.82 νNCCarb, 42 + δCNH, 30 + νCCarom, 14 55 1506 1489 1550 1490 1491 0.01 68.76 δCNH, 58 + δNCH, 26 + νCCarom, 11 56 1506 1489 1550 1490 1490 786.90 0.01 δCNH, 57 + δNCH, 18 + νCCarom, 11 57 1460 1463 1530 1471 1471 11.11 0.01 δCHarom, ipb, 81 + δCNH, 11 58 1460 1463 1530 1471 1471 0.01 122.68 δCHarom, ipb, 80 + δCNH, 11 59 1455 1450 1508 1450 1450 5.40 0.01 δCHmetil, scis, 59 + δCHarom, ipb, 14 60 1455 1450 1508 1449 1450 0.01 26.79 δHCHmetil, scis, 63 + δCHarom, ipb, 16 61 1447 1444 1504 1446 1446 73.93 0.01 δCHarom, ipb, 69 + δHCHmetil, scis, 11 62 1447 1444 1504 1446 1446 0.01 46.25 δCHarom, ipb, 68 + δHCHmetil, scis, 10 63 1440 1437 1500 1442 1442 0.01 13.56 δHCHmetil, scis, 48 + δCHarom, ipb, 32 + δCNH, 12 64 1440 1437 1500 1442 1442 278.73 0.01 δHCHmetil, scis, 44 + δCHarom, ipb, 35 + δCNH, 18 65 1440 1437 1499 1441 1441 62.26 0.01 δCHmetil, scis, 52 + δCHarom, ipb, 21 66 1440 1437 1499 1441 1441 0.01 19.77 δCHmetil, scis, 56 + δCHarom, ipb, 20 67 1436 1431 1497 1440 1440 36.64 0.01 δCHmetil, scis, 59 + δCHarom, ipb, 14 68 1436 1431 1496 1438 1438 0.01 38.79 δCHmetil, scis, 48 + δCHarom, ipb, 18 69 1433 1431 1494 1436 1436 0.01 25.47 δCHmetil, scis, 54 70 1433 1431 1494 1436 1436 37.44 0.01 δCHmetil, scis, 46 71 1423 1425 1480 1423 1423 0.01 113.16 δCHarom, ipb, 42 + δNH, 22 72 1423 1425 1479 1422 1422 185.52 0.01 δCHarom, ipb, 43 + δNH, 22 73 1374 1379 1425 1370 1371 0.01 8.34 δCHmetil, umbr, 79 74 1374 1379 1425 1370 1370 24.73 0.01 δCHmetil, umbr, 79 75 1363 1362 1423 1368 1368 4.40 0.01 δCHmetil, umbr, 91 76 1363 1362 1423 1368 1368 0.01 6.11 δCHmetil, umbr, 90 77 1331 1336 1392 1339 1339 0.01 81.98 νCCmetil, 27 + νCCCarb, 18 + δCHmetil, wagg, 17 + δCH, 11 78 1331 1336 1392 1339 1339 29.00 0.01 νCCmetil, 26 + νCCCarb, 17 + δCHmetil, wagg, 17 + δCH, 13 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 393 Table 2. Continued. No Exp. IR (cm-1) RAMAN (cm-1) B3LYP Assignments, PED (%) Unscaled (cm-1) Scaled (cm-1) Scaled (cm-1) IR Int. (km/mol) RAMAN activity (A4/amu) 79 1321 1311 1360 1308 1308 121.43 0.01 νCCarom, 66 + δCHarom, ipb, 15 80 1321 1311 1360 1307 1307 0.01 110.82 νCCarom, 65 + δCHarom, ipb, 17 81 1289 1289 1351 1299 1299 51.96 0.01 νCCarom, 44 + νCN 24 + δCH, 10 82 1289 1289 1351 1299 1299 0.01 139.64 νCCarom, 45 + νCN 24 + δCH, 11 83 1289 1289 1336 1285 1285 21.35 0.01 δCHarom, ipb, 70 84 1289 1289 1336 1284 1285 0.01 26.98 δCHarom, ipb, 76 85 1271 1271 1331 1279 1280 137.60 0.01 δCHarom, ipb, 64 + δCH, 12 86 1271 1271 1331 1279 1279 0.01 49.19 δCHarom, ipb, 60 + δCH, 14 87 1265 1266 1329 1278 1278 65.77 0.01 δCHarom, ipb, 41 + δCH, 34 88 1265 1266 1328 1277 1277 0.01 27.66 δCHarom, ipb, 42 + δCH, 37 89 1255 1258 1303 1253 1253 107.04 0.01 δCHarom, ipb, 24 + νCN, 23 + δNH, 15 + νCCarom, 12 90 1255 1258 1303 1253 1253 0.01 162.52 δCHarom, ipb, 25 + νCN 24 + δNH, 15 + νCCarom, 14 91 1246 1246 1299 1249 1249 0.01 447.27 νNCarom, 52 + δNH, 18 + δCHarom, ipb, 11 92 1246 1246 1299 1248 1249 117.56 0.01 νNCarom, 53 + δNH, 16 + δCHarom, ipb, 11 93 1238 1238 1281 1232 1232 46.98 0.01 δHCCl, 76 94 1238 1238 1281 1232 1232 0.01 16.11 δHCCl, 76 95 1215 1220 1276 1227 1227 0.01 11.91 δHCCl, 61 + δCHmetil, 12 96 1215 1220 1275 1226 1226 79.13 0.01 δHCCl, 62 + δCHmetil, 12 97 1208 1208 1262 1214 1214 35.51 0.01 νNCCarb, 61 + δNH, 16 + δCHarom, ipb, 12 98 1208 1208 1261 1212 1213 0.01 26.43 νNCCarb, 64 + δCHarom, ipb, 15 + δNH, 15 99 1189 1191 1234 1186 1186 0.01 42.18 δCHarom, ipb, 76 + δNH, 14 100 1189 1191 1234 1186 1186 73.74 0.01 δCHarom, ipb, 82 + δNH, 11 101 1180 1177 1225 1177 1177 1.81 0.01 δCHarom, ipb, 72 + νCCarom, 11 102 1180 1177 1224 1177 1177 0.01 8.93 δCHarom, ipb, 69 + νCCarom, 14 103 1162 1161 1208 1162 1162 0.01 22.08 δCHarom, ipb, 62 + δNH, 15 + δCH, 12 104 1162 1161 1208 1162 1162 135.30 0.01 δCHarom, ipb, 59 + δNH, 10 + δCH, 10 105 1157 1158 1193 1147 1147 0.01 57.68 δCHarom, ipb, 64 106 1157 1158 1193 1147 1147 2.38 0.01 δCHarom, ipb, 67 107 1148 1148 1191 1145 1145 4.09 0.01 δCHarom, ipb, 65 108 1148 1148 1191 1145 1145 0.01 57.25 δCHarom, ipb, 66 109 1108 1109 1138 1094 1094 21.87 0.01 δCHarom, ipb, 46 + δCHmetil, 13 + νCC, 11 110 1108 1109 1137 1094 1094 0.01 6.78 δCHarom, ipb, 48 + νCC, 13 + δCHmetil, 12 111 1092 1091 1132 1088 1088 8.68 0.01 δCHarom, ipb, 66 + νCCarom, 21 112 1092 1091 1132 1088 1088 0.01 4.19 δCHarom, ipb, 66 + νCCarom, 22 113 1073 1074 1114 1071 1071 0.01 9.09 δCHarom, ipb, 34 + νCCarom, 25 + νCC, 14 114 1073 1074 1113 1070 1070 7.41 0.01 δCHarom, ipb, 35 + νCCarom, 26 + νCC, 12 115 1051 1051 1097 1054 1054 14.54 0.01 δCHmetil, wagg, 47 + δCH, 12 116 1051 1051 1097 1054 1054 0.01 14.82 δCHmetil, wagg, 45 + δCH, 13 117 1051 1051 1095 1053 1053 9.82 0.01 δCHmetil, wagg, 57 + δCH, 14 118 1051 1051 1095 1053 1053 0.01 9.73 δCHmetil, wagg, 53 + δCH, 18 119 1051 1051 1092 1050 1050 0.01 2.14 δCHmetil, wagg, 59 + δCH, 23 120 1051 1051 1092 1050 1050 39.92 0.01 δCHmetil, wagg, 58 + δCH, 21 121 1040 1039 1080 1039 1039 0.01 112.10 νCCarom, ring breating, 66 + δCHarom, ipb, 24 122 1040 1039 1080 1039 1039 21.54 0.01 νCCarom, ring breating, 65 + δCHarom, ipb, 23 123 1037 1039 1074 1032 1032 0.01 28.78 νCCarom, ring breating, 57 + δCHarom, ipb, 18 124 1037 1039 1074 1032 1032 7.81 0.01 νCCarom, ring breating, 56 + δCHarom, ipb, 19 125 995 996 1006 967 967 26.92 0.01 δCH, 56 + δCHmetil, wagg, 23 126 995 996 1006 967 967 0.01 4.63 δCH, 54 + δCHmetil, wagg, 25 127 968 968 995 956 957 28.97 0.01 νCC, 27 + δCHmetil, wagg, 19 + δCH, 18 128 968 968 994 956 956 0.01 7.66 νCC, 28 + δCHmetil, wagg, 19 + δCH, 16 129 950 951 986 948 948 0.01 1.42 δCHarom, opb, 60 130 950 951 986 948 948 1.31 0.01 δCHarom, opb, 59 131 942 943 978 940 940 0.01 0.41 δCHarom, opb, 65 132 942 943 978 940 940 2.58 0.01 δCHarom, opb, 65 133 925 929 965 928 928 2.47 0.01 δCHarom, opb, 42 134 925 929 964 927 927 0.01 2.62 δCHarom, opb, 41 135 918 917 952 915 915 4.48 0.01 δCHarom, opb, 67 136 918 917 951 915 915 0.01 1.54 δCHarom, opb, 69 137 900 899 943 906 906 0.01 16.43 δCHarom, opb, 54 + νCC, 15 + δNCO, 12 138 900 899 941 904 905 19.48 0.01 δCHarom, opb, 52 + νCC, 16 + δNCO, 13 139 894 899 933 897 897 15.16 0.01 δNCO, 22 + δCHarom, opb, 22 + δCHmetil, twist, 12 140 894 899 933 897 897 0.01 6.25 δCHarom, opb, 22 + δNCO, 20 + δCHmetil, twist, 12 141 869 870 904 869 869 33.31 0.01 δCCCring, 81 142 869 870 903 868 868 0.01 7.71 δCCCring, 80 143 851 853 885 851 851 1.83 0.01 δCHarom, opb, 50 + τCC, 14 144 851 853 885 851 851 0.01 8.99 δCHarom, opb, 52 + τCC, 13 145 829 829 868 835 835 2.49 0.01 δCHarom, opb, 49 + τCC, 10 146 829 829 868 835 835 0.01 5.69 δCHarom, opb, 54 147 829 829 863 830 830 1.64 0.01 δCCCring, 71 148 829 829 863 830 830 0.01 63.87 δCCCring, 72 149 815 817 841 808 808 0.01 14.83 δCCCring, 65 + νCN, 21 150 815 817 840 807 807 3.75 0.01 δCCCring, 68 + νCN, 22 151 802 795 832 800 800 6.42 0.01 νCCarom, 52 + δCCCring, 24 + δCNC, 21 152 802 795 832 800 800 0.01 30.57 νCCarom, 54 + δCNC, 24 + δCCCring, 23 153 779 771 794 763 764 0.01 31.58 γNH, 30 + γC-CCarb, 27 154 779 771 794 763 763 34.18 0.01 γNH, 30 + γC-CCarb, 31 155 741 747 774 744 744 0.01 8.50 δCHarom, opb, 32 + τCCring, 31 + τCC, 31 156 741 747 773 743 743 33.28 0.01 δCHarom, opb, 31 + τCCring, 30 + τCC, 27 157 741 747 767 738 738 176.36 0.01 τCCring, 27 + τCC, 27 + δCHarom, opb, 22 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 394 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 Table 2. Continued. No Exp. IR (cm-1) RAMAN (cm-1) B3LYP Assignments, PED (%) Unscaled (cm-1) Scaled (cm-1) Scaled (cm-1) IR Int. (km/mol) RAMAN activity (A4/amu) 158 741 747 766 737 737 0.01 3.42 τCCring, 35 + τCC, 25 + δCHarom, opb, 23 159 726 724 753 724 724 0.01 7.40 γCCarb, 33 + δCHmetil, wagg, 13 + δCHarom, opb, 12 160 719 718 749 720 720 10.10 0.01 γCCarb, 38 + δCHarom, opb, 13 + δCHmetil, wagg, 10 161 719 718 744 715 715 48.25 0.01 γNH, 42 + γC-CCarb, 20 + δCHarom, opb, 11 162 719 718 742 713 713 0.01 8.03 γNH, 41 + γC-CCarb, 21 + δCHarom, opb, 14 163 701 705 730 702 702 8.87 0.01 γCring, 76 164 701 705 730 701 701 0.01 9.23 γCring, 74 165 697 699 728 700 700 7.69 0.01 γC, 68 + γCring, 12 166 697 699 727 699 699 0.01 4.05 γCring, 74 167 691 689 713 685 685 56.42 0.01 νCCl, 61 + δCHmetil, wagg, 10 168 691 689 712 684 684 0.01 14.12 νCCl, 62 + δCHmetil, wagg, 10 169 678 671 705 678 678 0.01 10.36 νCCl, 60 + δCHmetil, wagg, 15 170 678 671 704 677 677 43.90 0.01 νCCl, 64 + δCHmetil, wagg, 18 171 649 653 677 651 651 0.01 39.03 γCN, 44 172 649 653 676 650 650 43.40 0.01 γCN, 45 173 638 638 663 637 637 4.33 0.01 δCCCring, 28 + γC, 21 + δCHmetil, wagg, 11 174 638 638 662 636 636 0.01 4.61 δCCCring, 27 + γC, 20 + δCHmetil, wagg, 13 175 614 614 642 618 618 0.01 24.24 δCCCring, 75 + δNH, opb, 13 176 614 614 642 617 617 15.66 0.01 δCCCring, 74 + δNH, opb, 14 177 581 592 608 584 584 8.34 0.01 δCCCring, 44 + δCCN, 20 178 581 592 607 584 584 0.01 16.30 δCCCring, 43 + δCCN, 20 179 570 582 600 577 577 0.01 24.29 δCCCring, 53 + δNH, opb, 12 180 570 582 600 576 576 8.48 0.01 δCCCring, 51 + δNH, opb, 11 181 567 567 577 554 555 79.83 0.01 δCCCring, 34 + νCCl, 30 + τCCring, 17 182 567 567 576 553 553 0.01 17.20 δCCCring, 34 + νCCl, 30 + τCCring, 17 183 537 540 555 533 533 0.01 2.56 τCCring, 87 184 537 540 555 533 533 6.45 0.01 τCCring, 87 185 533 540 552 530 530 12.50 0.01 γCring, 85 186 533 540 551 530 530 0.01 8.69 γCring, 84 187 - 484 508 488 488 0.01 3.98 δCCCring, 61+ γC, 21 + δCHmetil, twist, 13 188 - 484 508 488 488 19.32 0.01 δCCCring, 60 + γC, 22 + δCHmetil, twist, 15 189 - 464 475 456 456 0.01 3.13 τCCring, 63 190 - 464 474 456 456 8.02 0.01 τCCring, 64 191 - 464 473 455 455 28.29 0.01 τCCring, 62 192 - 464 473 454 454 0.01 11.91 τCCring, 82 193 - 442 468 450 450 42.20 0.01 τCCring, 71 194 - 442 466 448 448 0.01 0.65 γCring, 53 + δCCN, 20 195 - 425 434 417 417 18.37 0.01 δCCN, 41 + τCCring, 14 196 - 425 432 416 416 0.01 7.70 δCCN, 45 + τCCring, 15 197 - 401 417 401 401 131.59 0.01 γNH, 81 + τCCring, 11 198 - 401 416 400 400 0.01 20.39 γNH, 73 + τCCring, 12 199 - 391 408 392 392 49.26 0.01 γNH, 33 + νCCl, 29 200 - 391 403 388 388 0.01 15.90 γNH, 33 + νCCl, 12 201 - 372 386 372 372 117.05 0.01 γNH, 28 + δCCC, 21 202 - 372 381 367 367 0.01 14.85 γNH, 75 + δCCC, 13 203 - 320 335 322 322 0.01 2.92 δCCCl, 44 + τCCring, 30 204 - 320 334 321 321 9.14 0.01 δCCCl 44 + τCCring, 32 205 - 320 332 319 319 0.01 2.07 δCCC, 23 + τCCring, 21 206 - 320 331 318 318 6.66 0.01 δCNH, 30 + + τCCring 18 207 - 314 315 303 303 0.01 10.65 τCCring, 80 208 - 314 313 300 301 5.72 0.01 τCCring, 54 + δCCC, 10 209 - 298 308 296 296 5.68 0.01 τCCring, 63 + δCCC, 12 210 - 298 306 294 294 0.01 4.32 τCCring, 51 + δCCC, 11 211 - 298 303 292 292 0.01 6.78 τCCring, 40 + δCCCl, 22 + δCHmetil, rock, 15 212 - 298 302 290 290 12.04 0.01 δCCN, 30 + τCCring, 31 + δCHmetil, rock, 14 213 - 260 274 263 263 3.00 0.01 τCC, 25 + + δCCC, 25 + δCCN, 21 214 - 260 273 263 263 0.01 0.85 δCCC, 29 + τCC, 26 + δCCN, 21 215 - 251 265 255 255 18.16 0.01 τCC, 56 + δCHmetil, rock, 35 216 - 251 263 253 253 0.01 2.52 τCC, 68 + δCHmetil, rock, 31 217 - 238 247 237 237 6.71 0.01 τCC, 58 + δCHmetil, rock, 27 218 - 238 245 235 236 0.01 2.35 τCC, 28 + δCHmetil, rock, 20 219 - 227 235 226 226 0.01 2.14 τCC, 60 + τCHmetil, 21 220 - 227 235 226 226 7.18 0.01 τCC, 65 + τCHmetil, 24 221 - 220 227 218 218 20.89 0.01 τCHmetil, 24 + τCC, 21 + τCN, 12 222 - 216 225 216 216 0.01 6.57 τCHmetil, 21 + τCC, 21 + τCN, 11 223 - 186 199 192 192 7.89 0.01 τCC, 29 + τCHmetil, 14 + τNH, 13 224 - 186 198 190 190 0.01 5.24 τCC, 22 + τCHmetil, 15 + τNH, 12 225 - 179 182 175 175 0.01 1.68 τCC, 31 + τCN, 21 226 - 169 177 170 170 10.46 0.01 δCCN, 23 + τCC, 21 + τCN, 14 227 - 162 170 164 164 10.15 0.01 τCC, 22 + τCCring, 20 + δCCO, 16 228 - 162 170 164 164 0.01 4.09 τCCring, 26 + τCC, 20 + δCCO 19 229 - 155 165 158 158 7.58 0.01 τCCring, 52 + τCN, 21 230 - 155 163 157 157 0.01 2.66 τCCring, 51 + τCN, 31 231 - 131 130 125 125 0.01 6.99 τCCring, 31 + τCC, 30 + δCNC, 10 232 - - 129 124 124 1.95 0.01 τCCring, 31 + τCC, 29 + δCNC, 20 233 - - 107 103 103 0.01 17.58 τNCring, 23 + νO...H, 18 + τCCring, 17 234 - - 107 103 103 9.78 0.01 τNCring, 28 + τCCring, 20 235 - - 98 94 94 0.01 4.99 τNH...OC, 21 + δCCN, 20 236 - - 94 90 90 9.55 0.01 τNCring, 38 + τCC, 29 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 395 Table 2. Continued. No Exp. IR (cm-1) RAMAN (cm-1) B3LYP Assignments, PED (%) Unscaled (cm-1) Scaled (cm-1) Scaled (cm-1) IR Int. (km/mol) RAMAN activity (A4/amu) 237 - - 81 78 78 3.08 0.01 δCOH, 34 + τNCring, 22 + τCCring, 12 238 - - 79 76 76 0.01 7.22 τNCring, 38 + τCC, 29 239 - - 72 69 69 0.01 7.34 τNCring, 27 + τCN, 21 + τCC, 18 240 - - 70 67 67 6.83 0.01 δCCN, 32 + τNCring, 25 + τCCring, 13 241 - - 58 56 56 0.01 2.38 τNCring, 25 + τCC, 15 + τCCring, 13 242 - - 54 52 52 2.41 0.01 τCN, 34 + τCCring, 27 + τNCring, 26 243 - - 49 47 47 2.94 0.01 τNCring, 23 + τCC, 21 + τCN, 10 244 - - 48 46 46 0.01 4.36 τCN, 26 + τCCring, 22 245 - - 42 41 41 1.19 0.01 τCC, 35 + τCN, 28 246 - - 42 41 41 0.01 2.71 τCC, 36 + τCN, 21 247 - - 40 39 39 0.01 0.55 τCC, 43 248 - - 38 37 37 4.34 0.01 τCN, 31 + τCC, 22 249 - - 37 36 36 0.01 7.48 τCC, 30 + τCN, 11 250 - - 36 34 34 2.51 0.01 τCC, 40 251 - - 32 31 31 0.01 2.52 τCC, 21 + τCN, 10 252 - - 31 30 30 0.89 0.01 τCC, 38 253 - - 29 28 28 0.01 3.29 τCC, 20 + τCN, 12 + τCO, 10 254 - - 27 26 26 0.01 4.00 τCC, 26 + τCN, 19 255 - - 25 24 24 0.38 0.01 τCCring, 63 + τCC, 16 256 - - 16 16 16 0.98 0.01 τCC, 19 + δCOH, 15 + τCO...HN, 10 257 - - 14 13 13 0.01 2.49 τCC, 25 + τNCring, 10 258 - - 10 10 10 0.23 0.01 τCN, 16 + τCC, 13 r 0.9999 0.9999 0.9999 Mean absolute percentage error 3.9085 0.4836 0.4828 Mean absolute error 59.4301 6.7498 6.7434 RMS 59.4835 8.9128 8.9123 Scaling factor 1.0000 0.9614 0.9615 * ν, stretching; δ, in-plane bending; γ, out-of-plane bending; τ, torsion; ipb: in-plane bending; opb: out-of-plane bending; scis: scissoring; wagg: wagging; twist: twisting; rock: rocking; umbr: umbrella; sym, symmetric; asym, asymmetric; arom: aromatic; carb: carbonyl group; br: Between ring; SF: Scaling factor; CSF: Calculated scaling factor; PED less than 10% are not shown. Table 3. Statistical comparison of theoretical and experimental vibrational wavenumbers of LNNN molecule on the used method and basis set *. Method B3LYP B3LYP×SF B3LYP×CSF B3LYP B3LYP×SF B3LYP×CSF Basis set 6-31G(d,p) 6-311G(d,p) r 0.9999 0.9999 0.9999 0.9999 0.9999 0.9999 Mean absolute percentage error 3.9085 0.4836 0.4828 3.6402 0.7304 0.7250 Mean absolute error 59.4301 6.7498 6.7434 51.8010 8.1959 8.1867 RMS 59.4835 8.9128 8.9123 50.1132 9.0561 9.0357 Scaling factor 1.0000 0.9614 0.9615 1.0000 0.9679 0.9675 Method B3PW91 B3PW91×SF B3PW91×CSF B3PW91 B3PW91×SF B3PW91×CSF Basis set 6-31G(d,p) 6-311G(d,p) r 0.9999 0.9999 0.9999 0.9999 0.9999 0.9999 Mean absolute percentage error 4.3650 0.7509 0.7303 3.9508 0.7579 0.7670 Mean absolute error 63.9214 9.1326 8.7367 56.3114 8.8874 8.8026 RMS 62.6507 10.4008 9.8223 54.5543 10.1032 9.7999 Scaling factor 1.0000 0.9573 0.9595 1.0000 0.9631 0.9647 Method B-LYP B-LYP×SF B-LYP×CSF B-LYP B-LYP×SF B-LYP×CSF Basis set 6-31G(d,p) 6-311G(d,p) r 0.9999 0.9999 0.9999 0.9999 0.9999 0.9999 Mean absolute percentage error 0.8773 0.7574 0.7832 0.7355 0.8774 0.7446 Mean absolute error 13.7557 10.9979 10.7545 10.5338 11.2224 9.9809 RMS 16.7634 12.6458 12.1863 12.3226 12.6502 11.4966 Scaling factor 1.0000 0.9945 0.9922 1.0000 0.9934 0.9970 Method mPW1PW mPW1PW×SF mPW1PW×CSF mPW1PW mPW1PW×SF mPW1PW×CSF Basis set 6-31G(d,p) 6-311G(d,p) r 0.9999 0.9999 0.9999 0.9999 0.9999 0.9999 Mean absolute percentage error 4.9951 0.6182 0.5865 4.7233 0.8551 0.8722 Mean absolute error 74.9157 8.9412 8.4917 67.0145 9.9435 9.7613 RMS 74.0626 11.2626 10.6256 64.3573 11.1262 10.7601 Scaling factor 1.0000 0.9500 0.9524 1.0000 0.9567 0.9585 Method HF HF×SF HF×CSF HF HF×SF HF×CSF Basis set 6-31G(d,p) 6-311G(d,p) r 0.9994 0.9994 0.9994 0.9993 0.9993 0.9993 Mean absolute percentage error 11.9216 1.8079 1.9171 11.2904 1.9162 2.0199 Mean absolute error 170.3659 27.0687 27.5107 160.3598 28.0124 28.4236 RMS 161.4518 29.2392 28.8031 151.8008 29.7798 29.4472 Scaling factor 1.0000 0.8992 0.9023 1.0000 0.9051 0.9078 * SF: Scaling factor, CSF: Calculated scaling factor in this research. 3.3. Thermodynamic parameters and molecular properties The thermodynamic parameters namely energy, zero- point vibrational energy, rotational constants and entropy of the compounds have also been computed at the HF and DFT level using 6-31G(d,p) 6-311G(d,p) basis sets at 298.15 K in ground state. The results of the statistical thermos-chemical analysis of title compound are presented in Table 4. The thermodynamic data provides helpful information for further studies of the title compound. The standard thermodynamic functions can be used as reference thermodynamic values to calculate the changes of entropies and the changes of enthalpies of the reaction. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 396 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 Table 4. The calculated thermodynamic parameters of LNNN molecule. Thermodynamic parameters (298 K) B3LYP B3PW91 BLYP mPW1PW91 HF 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 SCF energy (a.u.) -3865.093 -3865.668 -3864.117 -3864.652 -3864.220 -3864.839 -3864.660 -3865.193 -3849.643 -3850.131 Total energy (Thermal) Etotal (kcal/mol) 468.778 466.929 470.147 468.100 455.715 453.766 472.870 470.936 498.299 495.644 Entropy, S (cal/mol.K) 303.739 299.180 298.494 299.637 304.474 308.323 302.180 298.549 297.962 300.663 Vibrational_enegry, Evib (kcal/mol) 467.000 465.151 468.370 466.323 453.938 451.988 471.093 469.159 496.521 493.867 Zero-point vib. energy, Eo (kcal/mol) 437.1447 435.5989 438.9418 436.8083 423.5659 421.4053 441.5041 439.8499 468.2872 465.5137 Rotational constant (GHz) A 0.07223 0.07642 0.07725 0.07756 0.07512 0.07356 0.07340 0.07858 0.07187 0.07192 B 0.03983 0.03437 0.03435 0.03448 0.03362 0.03381 0.04031 0.03475 0.03945 0.03916 C 0.03251 0.03081 0.03083 0.03096 0.03007 0.03006 0.03291 0.03128 0.03284 0.03279 Dipole moment (Debye) µx 0.0000 -0.0003 0.0003 0.0001 0.0002 0.0000 0.0000 -0.0005 0.0000 -0.0006 µy -0.0001 -0.0002 -0.0003 0.0000 0.0000 -0.0003 0.0000 -0.0003 0.0001 -0.0004 µz -0.0001 0.0005 0.0001 0.0001 -0.0002 -0.0001 0.0000 0.0000 0.0002 0.0003 µTotal 0.0001 0.0006 0.0004 0.0002 0.0002 0.0003 0.0000 0.0006 0.0002 0.0008 Entropy (cal/mol.K) Total 303.739 299.180 298.494 299.637 304.474 308.323 302.180 298.549 297.962 300.663 Translational 45.756 45.756 45.756 45.756 45.756 45.756 45.756 45.756 45.756 45.756 Rotational 39.372 39.515 39.505 39.492 39.578 39.594 39.332 39.461 39.376 39.384 Vibrational 218.611 213.908 213.233 214.389 219.139 222.973 217.092 213.332 212.829 215.523 * 6-31: 6-31G(d,p); 6-311: 6-311G(d,p). Atomic charges play an important role in quantum chemistry. The atomic natural charges have been calculated by natural bond orbital (NBO) method [57,58] for the title compound and the results are shown in Table 5. The charge distribution of the title molecule has an important influence on the vibrational spectra. The charges at the site of the C21 atom attached to the O22 atom are more positive than other carbon atoms due to the presence of the electron withdrawing nature of the oxygen atom (O22). Similar trends were observed for the other carbonyl groups. Mulliken atomic charge [59] populations give one of the simplest pictures of charge distribution and the Mulliken charges predict net atomic charges in the molecule (Table 6). Comparing the NBO and the Mulliken charges for the title compound, we can easily say that there is a general agreement for all atoms. 3.4. Hirshfeld surface analysis In this study, the Hirshfeld surface analyses revealing the nature of intermolecular interactions of the LNNN compound and the two-dimensional (2D) fingerprint plots associated with these surfaces were calculated using the Crystal Explorer17 program [50]. The X-ray single crystal analysis revealed two independent molecules in the asymmetric unit of LNNN (Mol A and Mol B). For this reason, Hirshfeld surface analyzes were performed for both molecules in the asymmetric unit and thus the structure similarities and differences between the independent molecules in the asymmetric unit were shown. Hirshfeld surfaces visualize intermolecular contacts by red-blue-white color-coding for short or long contacts and investigates the properties of all contacts within the crystal lattice. Hirshfeld surfaces of the molecules A and B mapped with different properties, i.e. dnorm, curvedness and shape index and were shown to be transparent to allow visualization of the molecular component in a similar orientation for all of the structures, around which they were calculated (Figure 4). dnorm surfaces were used to determine the normalized contact distance of the atoms, defined in terms of the di, de and van der Waals (vdW) radii. The dnorm value is positive or negative when intermolecular interactions are longer or shorter than vdW radii, respectively. The dnorm values are mapped on the Hirshfeld surface by using white-blue-red color scales. The white regions seen on the surface are equal to the sum of vdW radii, while the red and blue regions represent interactions at shorter and longer distances than vdW radii, respectively [60]. The shape index and curvedness surfaces are used to determine the characteristic packaging modes, planar stacking arrangements, and the manner in which neighboring molecules contact each other [61]. On the other hand, two- dimensional fingerprint maps were used to quantitatively determine intermolecular interactions in the compound. When the dnorm surfaces of molecules A and B are examined, a total of three red spots appear, which result from the interactions between A and B molecules in the asymmetric unit (Figure 4). The two large red spots on the surfaces are due to strong N–H⋯O hydrogen bonds between the A and B molecules, while the smaller red spot is caused by the weaker C-H⋯O interaction (Figure 5). These interactions continue between the ABABABAB molecules along the crystal lattice, causing the molecules to expand along the crystallographic axis (Figure 6). On the dnorm surface of the Mol A, two light red spots are also seen due to C-H⋯Cl interactions. The C-H⋯Cl interactions occur between the aromatic ring hydrogen atoms and the chlorine atoms of the 2-chloropropionyl moiety of adjacent the molecules A. These interactions are weaker than the N–H⋯O and C–H⋯O interactions (Figure 7). The C-H⋯π interactions contributing to the crystal clustering and three-dimensional structure of the synthesized LNNN compound were visualized by means of the Hirshfeld surface mapped by the shape index function. As shown in Figure 8, on the Hirshfeld surface mapped by the shape index function, the hollow orange (π⋯H) and swollen blue regions (H⋯π) correspond to C–H⋯π interactions (Figure 8). The 2D fingerprint plots associated with Hirshfeld surface analyzes of molecules A and B providing quantitative information for the intermolecular specific atom-to-atom contacts in the crystal lattice. The fingerprint plots were decomposed to highlight particular atom pairs in close contacts. Figure 9 shows the decomposed fingerprint plots of A and B molecules that are crystallographically independent. In the molecules A and B, the H⋯H (vdW) interactions have the highest contributions of the total Hirshfeld surface with 60.9 and 59.6%, respectively, and the contribution from the H⋯H contact is 1.3% more for molecule A compared to molecule B. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 397 Table 5. The natural charges of the atoms of LNNN molecule determined by natural bond analysis *. Atom Charge B3LYP B3PW91 BLYP mPW1PW91 HF 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 C1 -0.7037 -0.5888 -0.7298 -0.6024 -0.7007 -0.5961 -0.7299 -0.6012 -0.6561 -0.5096 C2 -0.2870 -0.2132 -0.3123 -0.2320 -0.2802 -0.2127 -0.3139 -0.2328 -0.2685 -0.1722 Cl3 -0.0978 -0.0940 -0.0762 -0.0812 -0.1010 -0.1015 -0.0810 -0.0794 -0.1063 -0.1163 C4 0.6812 0.6792 0.6765 0.6744 0.6372 0.6412 0.6877 0.6829 0.8372 0.8259 O5 -0.6024 -0.6080 -0.6011 -0.6042 -0.5739 -0.5825 -0.6053 -0.6091 -0.7005 -0.6906 N6 -0.6526 -0.6297 -0.6478 -0.6293 -0.6161 -0.6048 -0.6623 -0.6358 -0.7485 -0.7215 C7 0.1276 0.1374 0.1276 0.1339 0.1257 0.1328 0.1254 0.1356 0.1313 0.1414 C8 -0.2350 -0.2036 -0.2465 -0.2092 -0.2379 -0.2047 -0.2432 -0.2095 -0.1999 -0.1592 C9 -0.2470 -0.1996 -0.2494 -0.2043 -0.2383 -0.2010 -0.2567 -0.2035 -0.2527 -0.2037 C10 -0.2355 -0.1989 -0.2481 -0.2041 -0.2380 -0.1993 -0.2443 -0.2046 -0.2117 -0.1642 C11 -0.2712 -0.2192 -0.2622 -0.2249 -0.2507 -0.2213 -0.2819 -0.2241 -0.2733 -0.2297 C12 0.1412 0.1439 0.1273 0.1401 0.1241 0.1395 0.1402 0.1403 0.1861 0.1935 N13 -0.6368 -0.6619 -0.6757 -0.6613 -0.6485 -0.6381 -0.6442 -0.6656 -0.7177 -0.6953 C14 0.1570 0.1625 0.1418 0.1589 0.1371 0.1540 0.1557 0.1620 0.2057 0.2172 C15 -0.2797 -0.2353 -0.2758 -0.2418 -0.2626 -0.2310 -0.2903 -0.2446 -0.2876 -0.2473 C16 -0.2210 -0.1923 -0.2430 -0.1980 -0.2313 -0.1922 -0.2297 -0.1986 -0.2003 -0.1508 C17 -0.2570 -0.2023 -0.2513 -0.2079 -0.2389 -0.2020 -0.2666 -0.2097 -0.2616 -0.2156 C18 -0.2219 -0.2084 -0.2500 -0.2148 -0.2389 -0.2069 -0.2301 -0.2160 -0.1988 -0.1589 C19 0.1055 0.1276 0.1172 0.1233 0.1159 0.1249 0.1028 0.1231 0.1176 0.1287 N20 -0.6319 -0.5967 -0.6159 -0.5960 -0.5876 -0.5766 -0.6397 -0.6008 -0.7226 -0.6934 C21 0.7091 0.7012 0.7015 0.6964 0.6594 0.6609 0.7160 0.7063 0.8664 0.8557 O22 -0.6870 -0.7143 -0.6993 -0.7120 -0.6667 -0.6827 -0.6928 -0.7194 -0.7847 -0.7821 C23 -0.2958 -0.2174 -0.3197 -0.2361 -0.2883 -0.2155 -0.3213 -0.2374 -0.2789 -0.1787 C24 -0.6999 -0.5839 -0.7264 -0.5968 -0.6989 -0.5915 -0.7250 -0.5954 -0.6559 -0.5033 Cl25 -0.0855 -0.0859 -0.0664 -0.0732 -0.0907 -0.0946 -0.0697 -0.0718 -0.0972 -0.1097 C26 -0.7037 -0.5888 -0.7298 -0.6024 -0.7007 -0.5961 -0.7299 -0.6012 -0.6561 -0.5096 C27 -0.2870 -0.2132 -0.3123 -0.2320 -0.2802 -0.2127 -0.3139 -0.2328 -0.2685 -0.1722 Cl28 -0.0978 -0.0940 -0.0762 -0.0812 -0.1010 -0.1015 -0.0810 -0.0794 -0.1063 -0.1163 C29 0.6812 0.6792 0.6765 0.6744 0.6372 0.6412 0.6877 0.6829 0.8372 0.8259 O30 -0.6024 -0.6080 -0.6011 -0.6042 -0.5739 -0.5825 -0.6053 -0.6091 -0.7005 -0.6906 N31 -0.6526 -0.6297 -0.6478 -0.6293 -0.6161 -0.6048 -0.6623 -0.6357 -0.7485 -0.7215 C32 0.1276 0.1374 0.1276 0.1339 0.1257 0.1328 0.1254 0.1356 0.1313 0.1414 C33 -0.2350 -0.2036 -0.2465 -0.2092 -0.2379 -0.2047 -0.2432 -0.2095 -0.1999 -0.1592 C34 -0.2470 -0.1996 -0.2494 -0.2043 -0.2383 -0.2010 -0.2567 -0.2035 -0.2527 -0.2037 C35 -0.2355 -0.1989 -0.2481 -0.2041 -0.2380 -0.1993 -0.2443 -0.2046 -0.2117 -0.1642 C36 -0.2712 -0.2191 -0.2622 -0.2249 -0.2507 -0.2213 -0.2819 -0.2241 -0.2733 -0.2296 C37 0.1412 0.1439 0.1273 0.1401 0.1241 0.1395 0.1402 0.1403 0.1861 0.1935 N38 -0.6368 -0.6619 -0.6757 -0.6613 -0.6485 -0.6381 -0.6442 -0.6656 -0.7177 -0.6953 C39 0.1570 0.1625 0.1418 0.1589 0.1371 0.1540 0.1557 0.1619 0.2057 0.2172 C40 -0.2797 -0.2353 -0.2758 -0.2418 -0.2626 -0.2310 -0.2903 -0.2446 -0.2876 -0.2473 C41 -0.2210 -0.1923 -0.2430 -0.1980 -0.2313 -0.1922 -0.2297 -0.1986 -0.2003 -0.1508 C42 -0.2570 -0.2023 -0.2513 -0.2079 -0.2389 -0.2020 -0.2666 -0.2097 -0.2616 -0.2156 C43 -0.2219 -0.2084 -0.2500 -0.2148 -0.2389 -0.2069 -0.2301 -0.2160 -0.1988 -0.1589 C44 0.1055 0.1276 0.1172 0.1233 0.1159 0.1249 0.1028 0.1231 0.1176 0.1287 N45 -0.6319 -0.5967 -0.6159 -0.5960 -0.5876 -0.5766 -0.6397 -0.6008 -0.7226 -0.6933 C46 0.7091 0.7012 0.7015 0.6964 0.6594 0.6609 0.7160 0.7063 0.8664 0.8557 O47 -0.6870 -0.7143 -0.6993 -0.7120 -0.6667 -0.6826 -0.6928 -0.7194 -0.7847 -0.7821 C48 -0.2958 -0.2174 -0.3197 -0.2361 -0.2883 -0.2155 -0.3213 -0.2374 -0.2789 -0.1787 C49 -0.6999 -0.5839 -0.7264 -0.5968 -0.6989 -0.5915 -0.7250 -0.5954 -0.6559 -0.5033 Cl50 -0.0855 -0.0859 -0.0664 -0.0732 -0.0907 -0.0946 -0.0697 -0.0718 -0.0972 -0.1097 H51 0.2531 0.2087 0.2572 0.2135 0.2476 0.2119 0.2629 0.2128 0.2395 0.1880 H52 0.2446 0.2075 0.2577 0.2124 0.2482 0.2103 0.2534 0.2121 0.2281 0.1778 H53 0.2644 0.2247 0.2742 0.2297 0.2631 0.2262 0.2733 0.2294 0.2511 0.1997 H54 0.2735 0.2136 0.2782 0.2192 0.2668 0.2146 0.2834 0.2192 0.2668 0.1951 H55 0.4448 0.4194 0.4500 0.4233 0.4373 0.4141 0.4516 0.4252 0.4529 0.4171 H56 0.2715 0.2388 0.2815 0.2444 0.2706 0.2389 0.2801 0.2446 0.2557 0.2112 H57 0.2432 0.2042 0.2523 0.2091 0.2414 0.2046 0.2524 0.2093 0.2361 0.1899 H58 0.2418 0.2033 0.2509 0.2082 0.2399 0.2036 0.2510 0.2085 0.2342 0.1874 H59 0.2479 0.2111 0.2562 0.2174 0.2443 0.2113 0.2577 0.2178 0.2412 0.1978 H60 0.4362 0.4030 0.4427 0.4093 0.4306 0.4015 0.4445 0.4092 0.4408 0.3970 H61 0.2561 0.2224 0.2670 0.2290 0.2548 0.2216 0.2660 0.2299 0.2489 0.2066 H62 0.2461 0.2073 0.2558 0.2123 0.2446 0.2073 0.2553 0.2128 0.2376 0.1901 H63 0.2454 0.2076 0.2560 0.2125 0.2449 0.2075 0.2547 0.2132 0.2376 0.1919 H64 0.2529 0.2265 0.2701 0.2330 0.2584 0.2243 0.2615 0.2340 0.2460 0.2013 H65 0.4437 0.4235 0.4568 0.4273 0.4431 0.4175 0.4516 0.4287 0.4524 0.4136 H66 0.2924 0.2304 0.3027 0.2387 0.2873 0.2286 0.3040 0.2404 0.2828 0.2067 H67 0.2506 0.2056 0.2566 0.2107 0.2458 0.2079 0.2595 0.2105 0.2357 0.1825 H68 0.2571 0.2145 0.2657 0.2189 0.2561 0.2171 0.2661 0.2184 0.2441 0.1904 H69 0.2618 0.2291 0.2733 0.2334 0.2647 0.2325 0.2705 0.2326 0.2465 0.1953 H70 0.2531 0.2087 0.2572 0.2135 0.2476 0.2119 0.2629 0.2128 0.2395 0.1880 H71 0.2446 0.2075 0.2577 0.2124 0.2482 0.2103 0.2534 0.2121 0.2281 0.1778 H72 0.2644 0.2247 0.2742 0.2297 0.2631 0.2262 0.2733 0.2294 0.2511 0.1997 H73 0.2735 0.2136 0.2782 0.2192 0.2668 0.2146 0.2834 0.2192 0.2668 0.1951 H74 0.4448 0.4194 0.4500 0.4233 0.4373 0.4141 0.4516 0.4252 0.4529 0.4171 H75 0.2715 0.2388 0.2815 0.2444 0.2706 0.2389 0.2801 0.2446 0.2557 0.2112 H76 0.2432 0.2042 0.2523 0.2091 0.2414 0.2046 0.2524 0.2093 0.2361 0.1899 H77 0.2418 0.2033 0.2509 0.2082 0.2399 0.2036 0.2510 0.2085 0.2342 0.1874 H78 0.2479 0.2111 0.2562 0.2174 0.2443 0.2113 0.2577 0.2178 0.2412 0.1978 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 398 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 Table 5. Continued. Atom Charge B3LYP B3LYP B3LYP B3LYP B3LYP B3LYP 6-31 6-31 6-31 6-31 6-31 6-31 6-31 6-31 6-31 6-31 H79 0.4362 0.4030 0.4427 0.4093 0.4306 0.4015 0.4445 0.4092 0.4408 0.3970 H80 0.2561 0.2224 0.2670 0.2290 0.2548 0.2216 0.2660 0.2299 0.2489 0.2066 H81 0.2461 0.2073 0.2558 0.2123 0.2446 0.2073 0.2553 0.2128 0.2376 0.1901 H82 0.2454 0.2076 0.2560 0.2125 0.2449 0.2075 0.2547 0.2132 0.2376 0.1919 H83 0.2529 0.2265 0.2701 0.2330 0.2584 0.2243 0.2615 0.2340 0.2460 0.2013 H84 0.4437 0.4235 0.4568 0.4273 0.4431 0.4175 0.4516 0.4287 0.4524 0.4136 H85 0.2924 0.2304 0.3027 0.2387 0.2873 0.2286 0.3040 0.2404 0.2828 0.2067 H86 0.2571 0.2145 0.2657 0.2189 0.2561 0.2171 0.2661 0.2184 0.2441 0.1904 H87 0.2506 0.2056 0.2566 0.2107 0.2458 0.2078 0.2595 0.2105 0.2357 0.1825 H88 0.2618 0.2291 0.2733 0.2334 0.2647 0.2325 0.2705 0.2327 0.2465 0.1953 * 6-31: 6-31G(d,p); 6-311: 6-311G(d,p). Table 6. Mulliken charges of the atoms of LNNN molecule *. Atom Charge B3LYP B3PW91 BLYP mPW1PW91 HF 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 C1 -0.2922 -0.2331 -0.3661 -0.2715 -0.2597 -0.2238 -0.3694 -0.2713 -0.3072 -0.1589 C2 -0.2844 -0.3820 -0.3494 -0.4424 -0.2508 -0.3667 -0.3599 -0.4467 -0.3205 -0.3625 Cl3 -0.0937 -0.1034 -0.0631 -0.0835 -0.1000 -0.1121 -0.0670 -0.0804 -0.0976 -0.1391 C4 0.6159 0.4233 0.6356 0.4499 0.5766 0.3813 0.6412 0.4586 0.7812 0.5969 O5 -0.4919 -0.3549 -0.4936 -0.3637 -0.4655 -0.3208 -0.4980 -0.3692 -0.5830 -0.4675 N6 -0.6653 -0.4782 -0.6947 -0.5170 -0.6024 -0.4327 -0.7095 -0.5268 -0.8377 -0.6314 C7 0.2705 0.1828 0.2843 0.2000 0.2789 0.1666 0.2689 0.2061 0.2478 0.1826 C8 -0.0882 -0.0630 -0.1211 -0.0673 -0.0794 -0.0620 -0.1164 -0.0625 -0.1004 -0.0293 C9 -0.1055 -0.0999 -0.1412 -0.1116 -0.0751 -0.0927 -0.1503 -0.1096 -0.1746 -0.1089 C10 -0.0925 -0.0862 -0.1293 -0.0947 -0.0648 -0.0794 -0.1350 -0.0921 -0.1431 -0.0721 C11 -0.1222 -0.0704 -0.1311 -0.0776 -0.0827 -0.0674 -0.1576 -0.0728 -0.1670 -0.1135 C12 0.2871 0.0857 0.2288 0.0802 0.2429 0.0930 0.2847 0.0710 0.2990 0.2086 N13 -0.7373 -0.5310 -0.7369 -0.5663 -0.6764 -0.4891 -0.7731 -0.5727 -0.8569 -0.6674 C14 0.3071 0.1251 0.2387 0.1227 0.2522 0.1184 0.3005 0.1248 0.3118 0.2627 C15 -0.1317 -0.0967 -0.1483 -0.1056 -0.0971 -0.0863 -0.1668 -0.1026 -0.1834 -0.1375 C16 -0.0878 -0.0857 -0.1320 -0.0961 -0.0677 -0.0753 -0.1289 -0.0972 -0.1374 -0.0612 C17 -0.1131 -0.1015 -0.1388 -0.1160 -0.0701 -0.0939 -0.1580 -0.1145 -0.1809 -0.1271 C18 -0.0762 -0.0588 -0.1184 -0.0621 -0.0784 -0.0556 -0.0992 -0.0603 -0.1095 -0.0462 C19 0.2245 0.1354 0.2609 0.1434 0.2595 0.1253 0.2136 0.1437 0.2218 0.1511 N20 -0.6166 -0.4318 -0.6547 -0.4675 -0.5582 -0.3891 -0.6597 -0.4753 -0.7895 -0.5899 C21 0.6319 0.4380 0.6501 0.4637 0.5729 0.3926 0.6633 0.4752 0.8042 0.5869 O22 -0.5484 -0.4521 -0.5623 -0.4637 -0.5150 -0.4082 -0.5617 -0.4729 -0.6631 -0.5577 C23 -0.2719 -0.3142 -0.3355 -0.3666 -0.2377 -0.3059 -0.3487 -0.3697 -0.3065 -0.2691 C24 -0.3100 -0.2551 -0.3855 -0.2953 -0.2843 -0.2431 -0.3861 -0.2952 -0.3349 -0.2000 Cl25 -0.0793 -0.1065 -0.0516 -0.0901 -0.0884 -0.1126 -0.0529 -0.0890 -0.0833 -0.1380 C26 -0.2922 -0.2331 -0.3661 -0.2715 -0.2597 -0.2238 -0.3694 -0.2713 -0.3072 -0.1589 C27 -0.2844 -0.3819 -0.3494 -0.4424 -0.2508 -0.3667 -0.3599 -0.4467 -0.3205 -0.3625 Cl28 -0.0937 -0.1034 -0.0631 -0.0835 -0.1000 -0.1121 -0.0670 -0.0804 -0.0976 -0.1391 C29 0.6159 0.4233 0.6356 0.4499 0.5766 0.3813 0.6412 0.4586 0.7812 0.5969 O30 -0.4919 -0.3549 -0.4936 -0.3637 -0.4655 -0.3208 -0.4980 -0.3692 -0.5830 -0.4675 N31 -0.6653 -0.4782 -0.6947 -0.5170 -0.6024 -0.4327 -0.7095 -0.5268 -0.8377 -0.6314 C32 0.2705 0.1828 0.2843 0.2000 0.2789 0.1666 0.2689 0.2061 0.2478 0.1827 C33 -0.0882 -0.0630 -0.1211 -0.0673 -0.0795 -0.0620 -0.1164 -0.0625 -0.1004 -0.0293 C34 -0.1055 -0.0999 -0.1412 -0.1116 -0.0751 -0.0927 -0.1503 -0.1096 -0.1746 -0.1089 C35 -0.0925 -0.0862 -0.1293 -0.0947 -0.0648 -0.0794 -0.1350 -0.0921 -0.1431 -0.0721 C36 -0.1222 -0.0703 -0.1311 -0.0776 -0.0827 -0.0674 -0.1576 -0.0728 -0.1670 -0.1134 C37 0.2871 0.0855 0.2288 0.0802 0.2428 0.0930 0.2847 0.0710 0.2990 0.2086 N38 -0.7373 -0.5309 -0.7369 -0.5663 -0.6764 -0.4891 -0.7731 -0.5727 -0.8569 -0.6674 C39 0.3071 0.1250 0.2387 0.1227 0.2522 0.1184 0.3005 0.1248 0.3118 0.2626 C40 -0.1317 -0.0967 -0.1483 -0.1056 -0.0971 -0.0863 -0.1668 -0.1026 -0.1834 -0.1375 C41 -0.0878 -0.0857 -0.1320 -0.0961 -0.0677 -0.0753 -0.1289 -0.0972 -0.1374 -0.0612 C42 -0.1131 -0.1015 -0.1388 -0.1160 -0.0701 -0.0939 -0.1580 -0.1145 -0.1809 -0.1270 C43 -0.0762 -0.0588 -0.1184 -0.0621 -0.0784 -0.0556 -0.0992 -0.0603 -0.1095 -0.0462 C44 0.2245 0.1355 0.2609 0.1434 0.2595 0.1253 0.2136 0.1437 0.2218 0.1511 N45 -0.6166 -0.4318 -0.6547 -0.4675 -0.5582 -0.3891 -0.6597 -0.4753 -0.7895 -0.5899 C46 0.6319 0.4380 0.6501 0.4637 0.5729 0.3926 0.6633 0.4753 0.8042 0.5869 O47 -0.5484 -0.4521 -0.5623 -0.4637 -0.5150 -0.4082 -0.5617 -0.4729 -0.6631 -0.5577 C48 -0.2719 -0.3142 -0.3355 -0.3666 -0.2377 -0.3059 -0.3487 -0.3697 -0.3065 -0.2691 C49 -0.3100 -0.2551 -0.3855 -0.2953 -0.2843 -0.2431 -0.3861 -0.2952 -0.3349 -0.2000 Cl50 -0.0793 -0.1065 -0.0516 -0.0901 -0.0884 -0.1126 -0.0529 -0.0890 -0.0833 -0.1379 H51 0.1275 0.1167 0.1468 0.1332 0.1081 0.1122 0.1575 0.1332 0.1418 0.1077 H52 0.1127 0.1253 0.1452 0.1406 0.1049 0.1202 0.1415 0.1409 0.1251 0.1056 H53 0.1530 0.1491 0.1808 0.1656 0.1418 0.1422 0.1802 0.1660 0.1640 0.1333 H54 0.1778 0.2140 0.2031 0.2368 0.1553 0.2062 0.2103 0.2381 0.2119 0.2038 H55 0.3014 0.2593 0.3114 0.2698 0.2662 0.2445 0.3260 0.2736 0.3591 0.2928 H56 0.1291 0.1335 0.1698 0.1477 0.1042 0.1221 0.1703 0.1457 0.1887 0.1207 H57 0.0883 0.0969 0.1263 0.1069 0.0624 0.0879 0.1306 0.1056 0.1542 0.0995 H58 0.0862 0.0949 0.1237 0.1051 0.0594 0.0857 0.1286 0.1038 0.1533 0.0993 H59 0.0987 0.1007 0.1313 0.1155 0.0643 0.0918 0.1429 0.1134 0.1666 0.1136 H60 0.2722 0.2357 0.3011 0.2493 0.2599 0.2251 0.2977 0.2495 0.3304 0.2566 H61 0.1103 0.1213 0.1483 0.1371 0.0821 0.1104 0.1540 0.1365 0.1772 0.1278 H62 0.0951 0.1031 0.1331 0.1129 0.0689 0.0939 0.1374 0.1116 0.1604 0.1050 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 399 Table 6. Continued. Atom Charge B3LYP B3LYP B3LYP B3LYP B3LYP 6-31 6-31 6-31 6-31 6-31 6-31 6-31 6-31 6-31 6-31 H63 0.0934 0.0979 0.1322 0.1072 0.0680 0.0892 0.1355 0.1055 0.1582 0.1053 H64 0.1154 0.1449 0.1550 0.1636 0.0891 0.1313 0.1545 0.1629 0.1844 0.1351 H65 0.2901 0.2650 0.3192 0.2749 0.2727 0.2507 0.3161 0.2770 0.3494 0.2833 H66 0.1928 0.2297 0.2233 0.2572 0.1714 0.2148 0.2314 0.2631 0.2236 0.2172 H67 0.1373 0.1286 0.1582 0.1448 0.1190 0.1231 0.1650 0.1456 0.1469 0.1177 H68 0.1381 0.1403 0.1636 0.1551 0.1243 0.1352 0.1674 0.1550 0.1541 0.1288 H69 0.1517 0.1574 0.1826 0.1755 0.1486 0.1530 0.1790 0.1746 0.1612 0.1353 H70 0.1275 0.1167 0.1468 0.1332 0.1081 0.1121 0.1575 0.1332 0.1418 0.1077 H71 0.1127 0.1253 0.1452 0.1406 0.1049 0.1202 0.1415 0.1409 0.1251 0.1056 H72 0.1530 0.1491 0.1808 0.1656 0.1418 0.1422 0.1802 0.1660 0.1640 0.1333 H73 0.1778 0.2140 0.2031 0.2368 0.1553 0.2062 0.2103 0.2381 0.2119 0.2038 H74 0.3014 0.2593 0.3114 0.2698 0.2662 0.2445 0.3260 0.2736 0.3591 0.2928 H75 0.1291 0.1335 0.1698 0.1477 0.1042 0.1221 0.1703 0.1457 0.1887 0.1207 H76 0.0883 0.0969 0.1263 0.1069 0.0624 0.0879 0.1306 0.1056 0.1542 0.0995 H77 0.0862 0.0949 0.1237 0.1051 0.0594 0.0857 0.1286 0.1038 0.1533 0.0993 H78 0.0987 0.1007 0.1313 0.1155 0.0643 0.0918 0.1429 0.1134 0.1666 0.1136 H79 0.2722 0.2356 0.3011 0.2493 0.2599 0.2251 0.2977 0.2495 0.3304 0.2566 H80 0.1103 0.1213 0.1483 0.1371 0.0821 0.1104 0.1540 0.1365 0.1772 0.1278 H81 0.0951 0.1031 0.1331 0.1129 0.0689 0.0939 0.1374 0.1116 0.1604 0.1050 H82 0.0934 0.0979 0.1322 0.1072 0.0680 0.0892 0.1355 0.1055 0.1582 0.1053 H83 0.1154 0.1449 0.1550 0.1636 0.0891 0.1313 0.1545 0.1629 0.1844 0.1351 H84 0.2901 0.2650 0.3192 0.2749 0.2727 0.2507 0.3161 0.2770 0.3494 0.2833 H85 0.1928 0.2297 0.2233 0.2572 0.1714 0.2148 0.2314 0.2631 0.2236 0.2172 H86 0.1381 0.1403 0.1636 0.1551 0.1243 0.1352 0.1674 0.1550 0.1541 0.1288 H87 0.1373 0.1286 0.1582 0.1448 0.1190 0.1231 0.1650 0.1456 0.1469 0.1177 H88 0.1517 0.1574 0.1826 0.1755 0.1486 0.1530 0.1790 0.1746 0.1612 0.1354 * 6-31: 6-31G(d,p); 6-311: 6-311G(d,p). Mol A dnorm Shape index Curvedness Mol B dnorm Shape index Curvedness Figure 4. Hirshfeld surfaces mapped with dnorm, shape index and curvedness for LNNN (Mol A and Mol B). Despite the high share of H⋯H interactions, the role of these interactions in the stabilization of the crystal structure is quite small in importance because H⋯H interactions are between the same species. The C⋯H contacts, which refer to the C-H⋯π interactions described previously, contribute 21.3 (for Mol A) and 23.6% (for Mol B) of the Hirshfeld surfaces with di + de ≈ 2.8 Å. On the other hands, although the contribution of H⋯O/O⋯H interactions to the Hirshfeld surface is 14.7% and 13.8%, respectively, these interactions are the strongest interactions with di + de ≈ 1.9 Å, and their roles in stabilizing the crystal structure is quite large. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 400 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 Figure 5. N–H⋯O and C-H⋯O interactions between A and B molecules on Hirshfeld surface mapped by dnorm function. Figure 6. Consequtive N–H⋯O and C-H⋯O interactions between the A and B molecules in the crystal lattice along the crystallographic [010] axis. Figure 7. C-H⋯Cl interactions between molecules A on Hirshfeld surface mapped by dnorm function. Figure 8. C–H⋯π interactions between two adjacent molecules on the Hirshfeld surface mapped by the shape index function. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 401 Mol A H···H 60.9% C···H/H···C 21.3% O···H/H···O 14.7% N···H/H···N 2.1% Mol B H···H 59.6% C···H/H···C 23.6% O···H/H···O 13.8% N···H/H···N 2.2% Figure 9. Decomposed 2D fingerprint plots of A and B molecules. 4. Conclusion The present investigation thoroughly analyzed both the vibrational spectra, infrared and RAMAN of the title compound. All the vibrational bands observed in the IR and RAMAN spectra of the investigated compound are assigned to various modes of vibration. The complete vibrational assign- ments of wavenumbers are made on the basis of potential energy distribution. The second aim of this work was to discover which method yields the most accurate results simultaneously for the IR and RAMAN frequencies as well as for the geometrical parameters of the title compound. The scaled B3LYP/6-31G(d,p) results are the best among the used methods. Thermodynamic properties such as energy, entropy, and enthalpy are also calculated. The presented structural and spectroscopic data of the title compound in this research can be used in the future in the analysis of similar compounds. In addition, the present quantum chemical study may lead to the understanding of properties and reactivity of redox active compounds. On the other hand, the 3D Hirshfeld surface analysis and 2D fingerprint plots revealed that the O⋯H/H⋯O interactions represent an important contribution of the Hirshfeld surface result of hydrogen-bonding interactions in the molecules A and B. Acknowledgements This study was supported by Research Fund of Mersin University in Turkey with Project Number: 2018-1-TP2-2800. Supporting information CCDC-1954366 contains the supplementary crystal- lographic data for this paper. These data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/, or by e-mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033. Disclosure statement Conflict of interests: The authors declare that they have no conflict of interest. Author contributions: All authors contributed equally to this work. Ethical approval: All ethical guidelines have been adhered. Sample availability: Samples of the compounds are available from the author. Funding Mersin University http://dx.doi.org/10.13039/501100004172 ORCID Aysegul Suzan Polat http://orcid.org/0000-0002-0281-4011 Ilkay Gumus http://orcid.org/0000-0002-9398-0057 Hakan Arslan http://orcid.org/0000-0003-0046-9442 References [1]. Lyaskovskyy, V.; Bruin, B. Am. Chem. Soc. Catal. 2012, 2, 270-279. [2]. Allgeier, A. M.; Mirkin, C. A. Angew. Chem., Int. Edit. 1998 37, 894-908. [3]. Wile, B. M.; Trovitch, R. J.; Bart, S. C.; Tondreau, A. M.; Lobkovsky, E.; Milsmann, C.; Bill, E.; Wieghardt, K.; Chirik, P. J. Inorg. Chem. 2009, 48(9), 4190-4200. [4]. Bart, S. C.; Lobkovsky, E.; Bill, E.; Chirik; P. J. J. Am. Chem. Soc. 2006, 128(16), 5302-5303. [5]. Tondreau, A. M.; Milsmann, C.; Patrick, A. D.; Hoyt, H. M.; Lobkovsky, E.; Wieghardt, K.; Chirik, P. J. J. Am. Chem. Soc. 2010, 132(42), 15046- 15059. [6]. Skabara, P. J.; Pozo-Gonzalo, C.; Lardies, M. N.; Laguna, M.; Cerrada, E.; Luquin, A.; Gonzalez, B.; Coles, S. J.; Hursthouse, M. B.; Harrington, R. W.; Clegg, W. Dalton Trans. 2008, 23, 3070-3079. [7]. Mukherjee, C.; Pieper, U.; Bothe, E.; Bachler, V.; Bill, E.; Weyhermuller, T.; Chaudhuri, P. Inorg. Chem. 2008, 47(19), 8943-8956. [8]. Zhu, D.; Thapa, I.; Korobkov, I.; Gambarotta, S.; Budzelaar, P. H. M. Inorg. Chem. 2011, 50, 9879-9887. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 https://www.ccdc.cam.ac.uk/structures/ mailto:data_request@ccdc.cam.ac.uk http://dx.doi.org/10.13039/501100004172 http://orcid.org/0000-0002-0281-4011 http://orcid.org/0000-0002-9398-0057 http://orcid.org/0000-0003-0046-9442 402 Polat et al. / European Journal of Chemistry 10 (4) (2019) 386-402 [9]. Dzik, W. I.; Van Der Vlugt, J. I.; Reek, J. N. H.; De Bruin, B. Angew. Chem., Int. Ed. 2011, 50, 3356-3358. [10]. Hindson, K.; De Bruin, B. Eur. J. Inorg. Chem. 2012, 3, 340-580. [11]. Kaim, W. Coord. Chem. Rev. 1987, 76, 187-235. [12]. Chirik, P.J. Inorg. Chem. 2011, 50(20), 9737-9914. [13]. Van der Vlugt, J. I., Eur. J. Inorg. Chem. 2012, 3, 363-375. [14]. Dzik, W. I.; Zhang, P. X.; de Bruin, B. Inorg. Chem. 2011, 50(20), 9896- 9903. [15]. Kaim, W. Coord. Chem. Rev. 2010, 254, 1580-1588. [16]. Nawn, G.; Waldie, K. M.; Oakley, S. R.; Peters, B. D.; Mandel, D.; Patrick, B. P.; McDonald, R.; Hicks, R. G. Inorg. Chem. 2011, 50, 9826-9837. [17]. Bowman, A. C.; Milsmann, C.; Hojilla, A. C. C.; Lobkovsky, E.; Wieghardt, K.; Chirik, P. J. J. Am. Chem. Soc. 2010, 132(5), 1676-1684. [18]. Bowman, C. A.; Milsmann, C.; Bill, E.; Lobkovsky, E.; Weyhermüller, T.; Wieghardt, K.; Chirik, P. J. Inorg. Chem. 2010, 49(13), 6110-6123. [19]. Manuel, T. D.; Rohde, J. U. Am. Chem. Soc. 2009, 131(43), 15582- 15583. [20]. Rolle, C. J.; Hardcastle, K. I.; Soper, J. D. Inorg. Chem. 2008, 47(6), 1892-1894. [21]. Vlcek, A. Coord. Chem. Rev. 2010, 254(13-14), 1357-1357. [22]. Ward, M. D.; McCleverty, J. A. J. Chem. Soc. Dalton Trans. 2002, 3, 275- 288. [23]. Smith, A. L.; Hardcastle, K. I.; Soper, J. D. J. Am. Chem. Soc. 2010, 132, 14358-14360. [24]. Arslan, H. Ligand design studies for metal catalyzed oxidation reactions, TUBITAK Project no: 112T322, 2012. [25]. Polat, A. S., MSc Thesis, Mersin University, Mersin, Turkey, 2019. [26]. Polat, A. S.; Gumus, I.; Arslan, H. Int. Eng. Nat. Sci. Conf. Book, Diyarbakir, Turkey, 2019. [27]. Aydogdu, S. I., MSc Thesis, Mersin University, Mersin, Turkey, 2019. [28]. Aydogdu, I.; Gumus, I.; Arslan, H. Int. Eng. Nat. Sci. Conf. Book, Diyarbakir, Turkey, 2019. [29]. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, J. A.; Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16, Revision C.01, Gaussian, Inc.; Wallingford CT, 2016. [30]. Dennington, R.; Keith, T. A.; Millam, J. M. GaussView, Version 6, Semichem Inc.; Shawnee Mission, KS, 2016. [31]. Moller, C.; Plesset, M.S. Phys. Rev. 1934, 46(7), 618-622. [32]. Becke, A.D. J. Chem. Phys. 1993, 98(7), 5648-5652. [33]. Lee, C.; Yang, W.; Parr, R.G. Phys. Rev. B 1988, 37(2), 785-789. [34]. Adamo, C.; Barone, V. J. Chem. Phys. 1998, 108(2), 664-675. [35]. Burke, K.; Perdew, J.P.; Wang, Y.; Dobson, J.F.; Vignale, G. M.P. Das (Eds.), Electronic Density Functional Theory: Recent Progress and New Directions, Plenum Press, New York, 1998. [36]. Predew, J.P.; Wang, Y. Phys. Rev. B 1992, 45(23), 13244-13249. [37]. Foresman, B.; Frisch, E. Exploring Chemistry with Electronic Structure Methods: a Guide to Using Gaussian, Gaussian Pitttsburg, PA, 1993. [38]. Scott, A. P.; Radom, L. J. Chem. 1996, 100, 16502-16513. [39]. Arslan, H.; Algul, O.; Dundar, Y. Vib. Spectrosc. 2007, 44, 248-255 [40]. Arslan, H.; Algul, O. Spectrochim. Acta A 2008, 70, 109-116 [41]. Yabalak, E.; Gunay, F.; Kasumov, V.; Arslan, H. Spectrochim. Acta A 2013, 110, 291-303 [42]. Arslan, H.; Mansuroglu, D.; Vanderveer, D.; Binzet, G. Spectrochim. Acta A 2009, 72, 561-571. [43]. Arslan, H.; Demircan, A. Int. J. Mol. Sci. 2007, 8, 1064-1082. [44]. Arslan, H.; Floerke, U.; Kulcu, N.; Binzet, G. Spectrochim. Acta A 2007, 68, 1347-1355. [45]. Panchenko, Y. N. J. Mol. Struct. 2001, 567-568, 217-230. [46]. Rauhut, G.; Pulay, P. J. Phys. Chem. 1995, 99(10), 3093-3100. [47]. Arslan, H. Performance Analysis of Vibrational Frequencies, 1.0, Mersin, Turkey, 2007. [48]. Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88(6), 899- 926. [49]. Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. J. Am. Chem. Soc. 1998, 120(46), 12051-12068. [50]. Turner, M. J.; McKinnon, J. J.; Wolff, S. K.; Grimwood, D. J.; Spackman, P. R.; Jayatilaka, D.; Spackman, M. A. CrystalExplorer17, University of Western Australia, http://hirshfeldsurface.net, 2017. [51]. Socrates, G. Infrared and Raman Characteristic Group Frequencies, John Wiley & Sons Ltd. Chichester, 2001. [52]. Silverstein, R.M.; Webster, F.X.; Kiemle, D.J.; Bryce, D.J. Spectrometric Identification of Organic Compounds, Wiley, 2014. [53]. Colt, N. B.; Daly, L. H.; Wiberly S. E. Introduction to Infrared and Raman Spectroscopy, 3th edition, Academic Press, Boston, 1990. [54]. Lebas, J. M.; Garrigou-Lagrange, C.; Josien, M. L. Spectrochim. Acta 1959, 15, 225-235. [55]. Wiberley, S. E.; Bunce, S. C.; Bauner, W. H. Anal. Chem. 1960, 32, 217- 221. [56]. Linvien, D.; Cothup, N.B.; Fateley, W.G.; Graselli, J.G., The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules, Academic Press, Boston, 1991. [57]. Beaula, T. J.; Joe, I. H.; Rastogi, V. K.; Jothy, V. B. Chem. Phys. Lett. 2015, 624, 93-101. [58]. Abraham, C. S.; Prasana, J. C.; Muthu, S. Spectrochim. Acta Mol. Biomol Spectrosc. 2017, 181, 153-163. [59]. Mulliken, R.S. J. Chem. Phys. 1955, 23, 1833-1840. [60]. Wang, J. W.; Zhang, Y. W.; Wang, M. X.; Luo, Y. H.; Sun, B. W. Polyhedron 2017, 124, 243-250. [61]. Spackman, M. A.; Jayatilaka, D. Cryst. Eng. Commun. 2009, 11, 19-32. Copyright © 2019 by Authors. This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at http://www.eurjchem.com/index.php/eurjchem/pages/view/terms and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License (http://creativecommons.org/licenses/by-nc/4.0). By accessing the work, you hereby accept the Terms. This is an open access article distributed under the terms and conditions of the CC BY NC License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited without any further permission from Atlanta Publishing House LLC (European Journal of Chemistry). No use, distribution or reproduction is permitted which does not comply with these terms. Permissions for commercial use of this work beyond the scope of the License (http://www.eurjchem.com/index.php/eurjchem/pages/view/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry). 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.386-402.1921 http://hirshfeldsurface.net/ http://www.eurjchem.com/index.php/eurjchem/pages/view/terms http://creativecommons.org/licenses/by-nc/4.0 http://www.eurjchem.com/index.php/eurjchem/pages/view/terms 1. Introduction 2. Experimental 2.1. Instrumentation 2.2. Synthesis 2.3. Calculation details 2.4. Hirshfeld surfaces analysis 3. Results and discussion 3.1. Molecular geometry 3.2. Vibrational assignments 3.3. Thermodynamic parameters and molecular properties 3.4. Hirshfeld surface analysis 4. Conclusion Acknowledgements Supporting information Disclosure statement Funding ORCID References PrintField10: PrintField11: PrintField12: PrintField13: PrintField14: PrintField15: PrintField16: PrintField17: PrintField18: PrintField19: PrintField110: PrintField111: PrintField112: PrintField113: PrintField114: PrintField115: PrintField116: PrintField20: PrintField21: PrintField22: PrintField23: PrintField24: PrintField25: PrintField26: PrintField27: PrintField28: PrintField29: PrintField210: PrintField211: PrintField212: PrintField213: PrintField214: PrintField215: PrintField216: