Synthesis, spectroscopic characterization and quantum chemical computational studies on 4-(3-methyl-3-phenylcyclobutyl)-2-(2-undecylidenehydrazinyl)thiazole

Journal of Molecular Structure 1076 (2014) 1–9

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Synthesis, spectroscopic characterization and quantum chemical computational studies on 4-(3-methyl-3-phenylcyclobutyl)-2-(2undecylidenehydrazinyl)thiazole Fatih Sß en a,⇑, Muharrem Dinçer b, Alaaddin Cukurovali c a b c

Kilis 7 Aralık University, Vocational High School of Health Services, Department of Opticianry, 79000 Kilis, Turkey Ondokuz Mayıs University, Arts and Sciences Faculty, Department of Physics, 55139 Samsun, Turkey Firat University, Sciences Faculty, Department of Chemistry, 23119 Elazig, Turkey

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 4-(3-Methyl-3-phenylcyclobutyl)-2-

(2-undecylidenehydrazinyl)thiazole (CYTHI).  A detailed interpretations of the geometric parameters, vibrational frequencies and chemical shifts of CYTHI were reported.  It was calculated frontier orbital energies and related molecular properties.

a r t i c l e

i n f o

Article history: Received 21 April 2014 Received in revised form 14 July 2014 Accepted 15 July 2014 Available online 22 July 2014 Keywords: Schiff base X-ray structure determination Molecular modelling IR and NMR spectroscopy Molecular electrostatic potential (MEP) Non-linear optical properties

a b s t r a c t The Schiff base compound, 4-(3-methyl-3-phenylcyclobutyl)-2-(2-undecylidenehydrazinyl)thiazole, (C25H37N3S), was synthesized and characterized combining several experimental techniques (X-ray, 1H NMR and 13C NMR) and theoretical methods. The compound crystallizes in the monoclinic space group P 21/c with a = 16.2306 (6) Å, b = 6.728 (2) Å, c = 26.1834 (10) Å, b = 120.687 (3), and Z = 4. The initial molecular geometry (X-ray coordinates) was optimized using Hartree–Fock (HF) and Density Functional Theory (DFT/B3LYP) method with the 6-31+G(d, p) basis set in ground state. From the optimized geometry of the molecule, geometric parameters, vibrational frequencies, gauge-independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the title compound have been calculated theoretically and compared with the experimental data. Data from theoretical calculations show excellent consistency with experimental results. Besides, molecular electrostatic potential (MEP) distribution, frontier molecular orbitals (FMOs) and non-linear optical (NLO) properties of the title molecule were investigated by theoretical calculations. Ó 2014 Elsevier B.V. All rights reserved.

Introduction In recent years, combining crystallography and molecular modelling studies have become popular. The molecular structure of a ⇑ Corresponding author. E-mail address: [email protected] (F. Sßen). http://dx.doi.org/10.1016/j.molstruc.2014.07.041 0022-2860/Ó 2014 Elsevier B.V. All rights reserved.

compound can be brought to light by X-ray diffraction and its geometrical parameters can be obtained with high precision. In the same way, the molecular geometry of a molecule can be calculated by molecular modeling methods. The success of calculation methods is expressed with consistent experimental results. Hartree–Fock and Density Functional Theory (DFT) modelling methods are widely used in theoretical modeling. Both methods give good

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results in calculations of molecular geometry. In addition to the molecular geometry, HF and DFT methods may be used to calculate a variety of molecular properties, including vibrational frequencies and chemical shifts. Physicists and chemists always were interested in Schiff base compounds. Over the past 10 years, many Schiff base compounds were synthesized and their structures were brought to light. Recently, there has been a great interest in Schiff base compounds because of their potential applications in medicine such as antitumor [1], anticancer [2], antifungal [3] and antimicrobial [4]. The Schiff base compounds have been also under investigation during last years because of their potential applicability in optical communications and many of them have NLO behavior [5–7]. These properties have further increased the relevance of Schiff base compounds and stimulated the interest in this class of compounds. In this study we describe the synthesis of a new Schiff base compound, (CYTHI), 4-(3-methyl-3-phenylcyclobutyl)-2-(2undecylidenehydrazinyl)thiazole, together data from spectroscopic and crystallographic analysis and quantum mechanical calculations for said compound. In the experimental study, the compound was prepared and characterized by 1H NMR, 13C NMR, IR and single-crystal X-ray diffraction methods. In theoretical study, the molecular geometry, vibrational frequencies, 1H and 13C NMR chemical shift values of the title compound in the ground state have been calculated using the Hartree–Fock (HF) and Density Functional method (DFT) (B3LYP) with 6-31+G(d, p) basis set. The calculated geometric parameters, theoretical scaled vibrational frequencies and chemical shifts values were compared with their experimental data.

was cooled to room temperature and then made alkaline with an aqueous solution of NH3 (5%), and the white precipitate separated by suction, washed with aqueous NH3 solution several times and dried in air. Suitable single crystals for crystal structure determination were obtained by slow evaporation of its ethanol solution. Overall yield: 71%, melting point: 377 K. Crystallography The single-crystal X-ray data were collected on a STOE IPDS II image plate diffractometer at 296 K. Graphite-monochromated Mo Ka radiation (k = 0.71073 Å) and the w-scan technique were used. The structure of title CYTHI was solved by direct methods using SHELXS-97 [10] and refined through the full-matrix leastsquares method using SHELXL-97 [11], implemented in the WinGX [12] program suite. Non-hydrogen atoms were refined with anisotropic displacement parameters. All H atoms were located in a difference Fourier map and were refined isotropically. Data collection: Stoe X-AREA [13], cell refinement: Stoe X-AREA [13], data reduction: Stoe XRED [13]. The general-purpose crystallographic tool PLATON [14] was used for the structure analysis and presentation of the results. The structure was refined to Rint = 0.062 with 3455 observed reflections using I > 2r (I) threshold. The ORTEP-3 program for Windows was used for preparation of figures. Details of the data collection conditions and the parameters of the refinement process are given in Table 1. Computational details All the calculations were performed by using Gaussian 03 package [15] and Gauss-View molecular visualization software [16] on the personal computer without restricting any symmetry for the title. For modeling, the initial guess of the CYTHI was first obtained from the X-ray coordinates and the structure was optimized by Hartree–Fock (HF) and Density Functional Theory (DFT)/B3LYP methods [17,18] with 6-31+G(d, p) as basis set. The vibrational frequencies and chemical shifts for optimized molecular structures have been calculated.

Experimental and theoretical methods General remarks All chemicals were of reagent grade and used as commercially purchased without further purification. The melting point was determined by Gallenkamp melting point apparatus. The IR spectrum of the tittle compound was recorded in the range 4000–400 cm1 using a Mattson 1000 FT-IR spectrometer with KBr pellets. The 1H and 13C Nuclear Magnetic Resonance (NMR) spectra were recorded on a Varian-Mercury-Plus 400 MHz spectrometer using TMS as internal standard and CDCl3 (chloroform) as solvent.

Results and discussion Molecular geometry The atomic numbering scheme for the X-ray structure (C25H37N3S) and theoretical geometric structure of the title CYTHI are shown in Fig. 1. X-ray diffraction analysis has revealed that the title compound crystallizes in monoclinic system with space group P 21/c. The unit cell dimensions are a = 16.2306 (6) Å, b = 6.728 (2) Å, c = 26.1834 (10) Å and V = 2458.8 (7) Å3. To the best of our knowledge, experimental and theoretical data on the geometric structure of the CYTHI are not available in the literature. The molecule has ‘‘C1’’ symmetry and is composed of a thiazole ring, with an (E)-undecylidenehydrazine group connected to the 2position of the ring and a (1,3-dimethylcyclobutyl)benzene in the 4-position. In the crystal structure, the mesitylene and thiazole rings are in cis positions with respect to the cyclobutane ring.

Synthesis of the title compound The compound was synthesized as in Scheme 1 according to a reported literature procedure [8] as following. A solution of undecanal (1.7029 g, 10 mmoL) and thiosemicarbazide (0.9114 g, 10 mmoL) in 20 mL of absolute ethanol was refluxed for 2 h. The course of the reaction was monitored by IR. Then the reaction mixture was cooled to room temperature, and a solution of 2-chloro-1(3-methyl-3-phenylcyclobutyl)ethanone [9] (2.2271 g, 10 mmoL) in 10 mL of absolute ethanol was added dropwise with stirring. After the addition of the a-haloketone, the temperature was raised to 323–328 K and kept at this temperature for 2 h. The solution

H3C

(CH 2)9

CHO + H2N NH C

NH2

S

H3C

Ethanol

C H2C

O Cl

N

H3C S

NH N CH (CH2)9

Scheme 1. Synthetic pathway for the synthesis of the target compound.

CH3

F. Sßen et al. / Journal of Molecular Structure 1076 (2014) 1–9 Table 1 Crystal data and structure refinement parameters for the title compound. CCDC deposition no. Chemical formula Formula weight Temperature (K) Wavelength (Å) Crystal system Space group Unit cell parameters a – b – c (Å) a = c – b (°) Volume (Å3) Z Calculated density (Mg/m3) l (mm1) F000 Crystal size (mm) hmin, hmax kmin, kmax lmin, lmax Theta range for data collection (°) Measured reflections Independent/observed reflections Refinement method R[F2 > 2r(F2)] wR(F2) GooF = S Rint Dqmax, Dqmin (e/Å3)

997,014 C25H37N3S 411.64 296 0.71073 Mo Ka Monoclinic P 21/c 16.2306(6), 6.728(2), 26.1834(10) 90.00, 120.687(3) 1672.51(16) 4 1.112 0.15 896 0.57  0.447  0.22 20, 20 8, 8 32, 32 1.5 6 h 6 26.8 36,369 5245 Full-matrix least-squares on F2 0.070 0.167 0.99 0.062 0.93, 0.56

The dihedral angles between the phenyl plane A (C1AC6), the cyclobutane plane B (C8AC11), and the thiazole plane C (S1/N1/ C12AC14) are 37.26 (13)° (A/B), 47.9 (8)° (B/C) and 77.53 (8)° (A/ C). Cyclobutane ring adopts a puckered conformation. Although the value for the puckering of the cyclobutane ring found in the literature is 23.5° [19], there is a negligible puckering in the

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cyclobutane ring (torsion angles; C8AC9AC11AC10, C9AC11AC10AC8, C11AC10AC8AC9 and C10AC8AC9AC11; 19.13 (16)°, 19.07 (16)°, 19.12 (16)° and 19.04 (16)°, respectively). When the bond lengths and angles of the cyclobutane ring in the compound are compared with the previously reported cyclobutane derivatives [20–28], it is seen that there are no significant differences. In the thiazole ring, the S1AC13 and S1AC14 bond lengths are 1.725 (2) Å and 1.732 (2) Å. These values are shorter than the standard value for an SACsp2 single bond (1.76 Å) [29]. The C14@N1 bond length [1.303(3) Å] compares with a literature value of 1.285 (7) Å [30]. The thiazole ring is planar with a maximum deviation of 0.0033 Å. The determined value for the C@N (Schiff base) bond length was determined 1.258 (3) Å. This value is close to the corresponding value reported in literature value, 1.256 (2) Å [31]. The crystal structure of CYTHI shows two intramolecular and two intermolecular bond-interactions. In intramolecular hydrogen bondings, atom N3 acts as a donor to related C17 and C18 (Fig. 2). In intermolecular hydrogen bondings, two types of hydrogen bonds, CAH  N and NAH  N are observed in the structure. In the first of these intermolecular interactions, atom C11 acts as donor to the symmetry-related N1 at (x + 1, y + 2, z) [3.3568(3) Å]. In the second type, atom N2 acts as hydrogen bond donor to the symmetry-related N1 at (x + 1, y + 1, z) [3.065 (2) Å]. Also, molecular structure has a intermolecular NAHp (p-ring) stacking interaction. DAH, H  A, D  A lengths and DAH  A angles of this interactions in the crystal structure are listed in Table 2. The molecular structure of the title CYTHI was also studied theoretically. The starting coordinates were those obtained from the X-ray structure determination. The molecular geometry (X-ray coordinates) was optimized using Hartree–Fock (HF) and Density Functional Theory (DFT/B3LYP) method with the 6-31+G(d, p) basis

Fig. 1. (a) A view of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. (b) The theoretical geometric structure of the title compound (B3LYP/6-31+G(d, p) level).

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0.9801 for bond lengths, 0.9925, 0.9823 for bond angles, 0.9986, 0.9996 for torsion angles respectively. While the HF/6-31+G(d, p) method gave accurate results for the bond lengths and bond angles compared with the B3LYP/6-31+G(d, p), unlike B3LYP/6-31+G(d, p) method gave accurate results compared with the HF/6-31+G(d, p) method for the torsion angles. The calculated DAH, H  A, D  A and DAH  A values for C17AH19  N3 and C18AH21  N3 are 1.08 Å, 2.68 Å, 2.88 Å and 88.55°, and 1.08 Å, 2.76 Å, 3.33 Å and 112.4° for HF/6-31+G(d, p) and also 1.09 Å, 2.67 Å, 2.88 Å and 89.87°, and 1.09 Å, 2.74 Å, 3.32 Å and 112.97° for B3LYP/6-31+G(d, p). A global comparison was performed by superimposing the molecular skeletons obtained from X-ray diffraction and the theoretical calculations atom by atom (Fig. 3), obtaining RMSE values of 0.407 and 0.237 Å for HF/6-31+G(d, p) and B3LYP/6-31+G(d, p), respectively. According to these results, it may be seen that the B3LYP/6-31+G(d, p) calculation reproduce closely the geometry of CYTHI. It was noted here that the experimental results belong to solid phase and theoretical calculations belong to gaseous phase. In the solid state, the existence of the crystal field along with the intermolecular interactions has connected the molecules together, which result in the differences of bond parameters between the calculated and experimental values [32]. IR spectra The Fourier Transform Infrared Spectrum (FT-IR) of CYTHI was recorded employing a ‘‘Mattson 1000 FT-IR spectrometer’’ using Table 3 Randomly selected geometric parameters (Å, °). Geometric parameters

Fig. 2. A view of the crystal structure of the title compound, showing the NAH  N and CAH  N interactions.

set in ground state. The values of the total energy and entropy for employing the 6-31+G(d, p) basis set are found to be 1529.13 a.u., 207.560 cal/mol K and 1537.66 a.u., 213.907 cal/mol K for HF and B3LYP respectively. Some optimized parameters of the title compound (bond lengths, bond angles and dihedral angles) by HF and B3LYP methods with 6-31+G(d, p) as the basis set are compared with the experimental data (Table 3). Theoretical values were correlated with corresponding values obtained from experimental analysis, and the correlation coefficient were 0.9832,

Table 2 Hydrogen-bond geometry (Å, °). DAH  A

DAH

H  A

D  A

DAH  A

C17AH17A  N3 C18AH18A  N3 C11AH11  N1a N2AH2 N  N1b C11AH11  Cg1c

0.97 0.97 0.98 0.86 0.97

2.64 2.81 2.91 2.24 2.86

2.872 (3) 3.317 (3) 3.568 (3) 3.065 (2) 3.733(3)

94 114 125 161 50

Symmetry codes: (a) x + 1, y + 2, z; (b) x + 1, y + 1, z; (c) 1  x, 1  y, 1  z. Cg1: the centroid of the thiazole ring.

Experimental Calculated (X-ray) HF/6-31+G(d, p) B3LYP/6-31+G(d, p)

Bond lengths (Å) C1AC2 C2AC3 C6AC8 C7AC8 C8AC9 C11AC12 C12AC13 C12AN1 C13AS1 S1AC14 C14AN2 N2AN3 N3AC15 C15AC16 C16AC17 C17AC18 C18AC19 C19AC20

1.390 1.348 1.518 1.527 1.547 1.487 1.341 1.395 1.725 1.732 1.356 1.379 1.258 1.485 1.510 1.504 1.506 1.479

Bond angles (°) C1AC2AC3 C8AC9AC11 C8AC10AC11 C10AC11AC12 C12AN1AC14 C12AC13AS1 N1AC14AS1 C14AN2AN3 N2AN3AC15 C15AC16AC17 Torsion angles (°) C9AC11AC12AN1 C1AC6AC8AC9 C5AC6AC8AC7 C1AC6AC8AC10 C10AC11AC12AN1 C8AC9AC11AC12 C2AC1AC6AC8

(4) (5) (3) (3) (3) (3) (3) (3) (2) (2) (3) (2) (3) (3) (4) (4) (4) (4)

1.387 1.387 1.518 1.536 1.554 1.496 1.341 1.386 1.746 1.737 1.364 1.359 1.253 1.504 1.531 1.530 1.529 1.529

1.393 1.393 1.516 1.538 1.563 1.495 1.359 1.386 1.753 1.757 1.370 1.352 1.275 1.502 1.534 1.534 1.532 1.533

119.9 (3) 89.04 (15) 89.09 (15) 119.41 (18) 109.81 (16) 111.49 (16) 115.89 (15) 115.89 (17) 117.51 (17) 116.6 (2)

120.24 88.89 89.06 120.35 110.91 110.31 115.79 118.71 118.27 116.21

120.19 88.89 89.22 120.31 110.7 110.75 115.89 121.06 118.58 116.14

72.0 (2) 144.2 (2) 93.3 (3) 41.9 (3) 176.94 (17) 141.76 (18) 179.8 (3)

66.72 143.35 89.70 40.84 172.95 142.04 177.81

69.31 142.82 89.23 40.27 175.8 141.62 177.92

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Table 4 Comparison of the observed and calculated vibrational spectra of the title compound. Assignment

Fig. 3. Atom-by-atom superimposition of the structures calculated (red) [B3LYP/631+G(d, p)] over the X-ray structure (black) for the title compound. Hydrogen atoms omitted for clarity. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

KBr pellet technique. The spectrum was recorded in the range of 4000–400 cm1 in the mid IR region. The IR spectrum of the title CYTHI was also studied theoretically. The theoretical harmonic frequencies have been calculated with HF and DFT/B3LYP methods with the 6-31+G(d, p) basis set in ground state. In order to compare the theoretical results with experimental values of those, scaling factor which are 0.9007 and 0.9648 [33] for HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) is applied to all of the calculated frequencies, respectively. Experimental and scaled theoretical FT-IR spectra of the CYTHI are shown in Fig. 4. In the infrared spectra of the CYTHI, some observed and calculated assignments are given in Table 4. The vibrational bands assignments have been made by using Gauss View molecular visualization program [16]. In order to make comparison with experimental observations, we show correlation based on the calculations. Comparing calculational and the experimental data we studied the relativity between the calculations and the experiments, and obtained linear function formulas are y = 1.0465x + 0.0037 (R2 = 0.9938) and y = 1.0303x  21.652 (R2 = 0.9964) for HF/6-31+G(d, p) and B3LYP/6-31+G(d, p), respectively. The observed and the calculated spectra are found to be in good agreement with each other. Also, some experimentally obtained vibrational frequencies were supported by literature and theoretical frequencies.

Fig. 4. Simulated [HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) levels] and experimental FT-IR spectra of the title compound.

mNAH mCAHthiazole msCAHaromatic masCAHaromatic masCAHaromatic masCAH2cyclobutane masCAH2cyclobutane mCAH msCAHcyclobutane masCAH2 msCAH2cyclobutane msCAH2cyclobutane masCAH2 msCAH3cyclobutane msCAH2 msC@N msC@Cthiazole + msC@Nthiazole msC@Cthiazole + msC@Nthiazole msC@Cthiazole aCAH2 aCAH2cyclobutane xCAH2 cNAH + cCAH xCAH2cyclobutane dCAH2cyclobutane

CCAHaromatic hcyclobutane

mSAC CCAHthiazole

Experimental IR with KBr (cm1)

Calculated (cm1) HF/631+G(d, p)

B3LYP/631+G(d, p)

3178 3083 – 3065 3024 2929 2855 – – – – – 2927 2853 – 1638 1583 1583 1494 – 1436 1290 1370 1152 1102 1028 1010 791 699

3553 3212 3145 3133 3116 3049 2973 3004 3002 2999 2997 2989 2987 2963 2954 1807 1644 1630 – 1523 1499 1448 1400 1272 1078 1031 967 864 764

3384 3144 3075 3063 3057 2998 2990 2909 2935 2946 2945 2938 2915 2912 2862 1647 – – 1515 1464 1450 1354 1405 1191 1024 963 1114 820 687

Vibrational modes: m, stretching; a, scissoring; c, rocking; x, wagging; d, twisting; h, ring; breathing C, out-of-plane bending. Abbreviations: s, symmetric; as, asymmetric.

NAH vibrations The NAH stretching vibrations occur in the region 3300– 3500 cm1 [34]. The hetero aromatic molecule containing NAH group shows its stretching absorption in the region 3220– 3500 cm1 [35,36]. The NAH stretching vibration is recorded at 3178 cm1 as a very strong band in FT-IR spectrum and its corresponding calculated frequencies are 3553 and 3384 cm1 using HF/6-31+G(d, p) and B3LYP/6-31+G(d, p), respectively.

Aromatic CAH vibrations Usually the carbon hydrogen stretching vibrations give rise to bands in the region of 3100–3000 cm1 in all aromatic compounds [35,37]. In the title molecule, two bands have been observed at 3065 and 3024 (asymmetric stretching) cm1 assigned to CAH stretching vibrations. Also, out-of-plane bending vibration of aromatic ring observed at 1028 cm1 and calculated 1031 and 963 cm1 for HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) levels.

Cyclobutane vibrations In the title molecule, there are many cyclobutane ring vibrations. The asymmetric stretching CAH2 observed at 2929 and 2855 cm1 in FT-IR spectrum. There are no peaks observed in FTIR spectrum for CAH2 symmetric stretching vibrations but these vibrations calculated at 3049, 2973 and 2998, 2990 cm1 for HF/ 6-31+G(d, p) and B3LYP/6-31+G(d, p) levels, respectively. The asymmetric stretching CAH3, scissoring CAH2, wagging CAH2, twisting CAH2 and breathing vibrations observed at 2853, 1436, 1152, 1102 and 1010 cm1 in FT-IR spectrum for cyclobutane ring.

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Fig. 5. Experimental (a) 1H and (b)

13

C chemical shift spectra of the title compound.

Thiazole vibrations It was observed four vibrations are appeared in the CYTHI for thiazole ring. Firstly, CAH symmetric stretching vibration recorded at 3083 cm1. Secondly, there is a band at 1683 and 1540 cm1 for C@N and C@C symmetric stretching vibrations in FT-IR spectrum, respectively. When the vibration frequencies of the thiazole ring in the compound are compared with the previously reported thiazole derivatives [23,33], it is seen that there are no significant differences. Thirdly, CAH out-of-plane bending vibration of thiazole ring observed at 699 cm1 and calculated 764 and 687 cm1 for HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) levels. NMR spectra The experimental 1H and 13C NMR spectra of the CYTHI recorded using TMS as an internal standard and chloroform (CDCl3)

as solvent are shown in Fig. 5. The theoretical GIAO 1H and 13C chemical shift values (with respect to TMS) were calculated using the HF and DFT (B3LYP) method with the 6-31+G(d, p) basis set and compared with experimental 1H and 13C chemical shift values in Table 5. The 1H and 13C NMR chemical shifts are converted to the TMS scale by subtracting the calculated absolute chemical shielding of TMS (d = R0  R), where d is the chemical shift, R is the absolute shielding and R0 is the absolute shielding of TMS), whose values are 31.88 and 201.25 ppm for HF/6-31+G(d, p), 31.56 and 192.41 ppm for B3LYP/6-31+G(d, p), respectively. It is well known that the aromatic protons of a phenyl group are monitoring around at 7.2 ppm. These chemical shifts are observed to be in the range between 7.15–7.35, 7.25–7.57 and 6.89– 7.21 ppm for experimental, HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) methods. The ACHA, ACH2A signals of the cyclobutane and ACH3-attached to cyclobutane ring have presented the average of

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3.64, 2.42 and 1.57 ppm, respectively. The aliphatic CH2 hydrogen atoms are recorded at 1.25–1.39 ppm in 1H NMR spectra of the compound. These signals have been calculated 0.41–1.78 ppm and 0.58–2.22 ppm for HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) methods, respectively. We have calculated 13C chemical shift values (with respect to TMS) of 175.57–13.32 and 181.74–24.73 ppm for HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) levels however, the experimental results were observed to be 168.65–14.17 ppm. In the phenyl ring, chemical shifts for the C atoms of para, meta and ortho position show the signals at 125.31, 128.22 and 124.76 ppm, respectively. These signals have been calculated as 122.03, 126.61, 122.98 and 138.73, 141.85, 138.51 ppm for HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) levels, respectively. In 13C NMR spectra, it can be shown the three signals belonging to the cyclobutane ring at 38.85, 40.18 and 31.93 ppm due to atoms C9 and C10 have only a signal in same position (40.18 ppm). Also, The C atom of methyl group linked to the cyclobutane ring is observed at 29.19 ppm. There are signals at 168.65 and 152.32 ppm due to C atoms next to sulfur atom for thiazole. These signals have been calculated as 175.57, 154.9 and 181.74, 171.49 ppm for HF/6-31G+(d, p) and B3LYP/6-31+G(d, p) levels, respectively. Comparing theoretical and the experimental data, we studied the relativity between the theoretical and the experiments and obtained that the linear function formula is y = 0.9917x  0.8849 for HF; where R2 is 0.9952, and y = 1.0992x + 2.3476 for B3LYP; where R2 is 0.9884. According to these results, it is seen that, the results of HF method have shown better fit to experimental ones than B3LYP in evaluating 1H and 13C chemical shifts.

Table 5 Experimental and theoretical the title compound.

13

C and 1H average isotropic chemical shifts (ppm) for

Atom

Experimental (ppm) (CDCl3)

C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 H1 H2 H3 H4 H5 H7A H7B H7C H9A H9B H10A H10B H11 (j = 9.2 Hz) H13 H2N H15 H16A H16B H17A H17B H18A H18B H19A H19B H20A H20B H21A H21B H22A H22B H23A H23B H24A H24B H25A (j = 6.8 Hz) H25B (j = 6.8 Hz) H25C (j = 6.8 Hz)

124.76 128.22 125.31 128.22 124.76 145.84 29.19 38.85 40.18 40.18 31.93 152.32 101.54 168.65 156.1 22.72 29.35 29.61 29.56 30.16 30.85 29.42 32.19 26.7 14.17 7.18a 7.18a 7.18a 7.32a 7.32a 1.57a 1.57a 1.57a 2.32a 2.32a 2.51a 2.51a 3.64 6.2 1.57a 7.18a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 1.32a 0.91 0.91 0.91

Calculated (ppm) (in chloroform solvent) HF/6-31+G(d, p) B3LYP/6-31+G(d, p)

Quantum-chemical studies Molecular electrostatic potential (MEP) Molecular electrostatic potential maps shows electron acceptor and electron donor regions of molecule. These regions gives information about intra and intermolecular hydrogen-bonding. The negative (red1 color) regions were related to electrophilic reactivity and the positive (blue color) ones to nucleophilic reactivity shown in MEP. MEP maps of CYTHI were calculated by HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) methods (Fig. 6). The color code of these maps is in the range between 0.054 a.u. (red) to 0.054 a.u. (blue) for HF/6-31+G(d, p) and 0.048 a.u. (red) to 0.048 a.u. (blue) for B3LYP/6-31+G(d, p). The negative (red color) regions are locate on the atom N1 and the positive (blue color) regions on the atom N2. These locations and intermolecular bond N2AH2N  N1 in the crystal are confirmed each other. HOMO and LUMO analysis Electrons of opposite spins when placed in the orbitals, the highest energy filled orbital (highest occupied molecular orbital) and the lowest energy is called the orbital empty (lowest-lying unoccupied molecular orbital) are named as HOMO and LUMO, respectively. HOMO and LUMO orbitals of distributions and energies can be calculated on the optimized structures. By using HOMO and LUMO energy values for a molecule, electronegativity, chemical hardness and chemical softness can be calculated as follows:

v ¼ ðI þ AÞ=2ðelectronegativityÞ; a

122.98 126.61 122.03 126.62 122.87 153.24 28.4 33.25 35.52 31.25 26.89 154.9 94.45 175.57 140.94 28.02 21.54 26.11 28.27 28.08 28.04 28.29 29.38 21.36 13.32 7.34 7.57 7.29 7.53 7.25 0.83 1.36 0.84 1.65 2.19 2.02 2 2.97 5.69 7.63 7.1 1.78 1.6 1.35 0.69 1.22 0.41 0.73 0.62 0.68 0.62 0.67 0.64 0.64 0.62 0.63 0.62 0.73 0.73 0.66 0.45 0.45

138.51 141.85 138.73 141.83 138.57 171.19 41.68 53.53 53.79 48.01 43.7 171.49 116.51 181.74 153.3 45.18 36.91 42.54 45.12 45.29 45.2 45.44 46.61 37.74 24.73 7.01 7.21 7.04 7.15 6.89 0.81 1.45 0.81 2.21 1.63 2.07 2.05 3.24 5.73 7.87 6.9 1.91 2.22 1.64 0.94 1.51 0.58 0.99 1.17 0.91 0.85 0.91 1.2 0.88 0.91 0.83 0.85 0.94 0.97 0.44 0.45 0.74

Average.

g ¼ ðI  AÞ=2ðchemical hardnessÞ; S ¼ 1=2gðchemical softnessÞ

1 For interpretation of color in Fig. 6, the reader is referred to the web version of this article.

where I and A are ionization potential and electron affinity; I = EHOMO and A = ELUMO, respectively [38]. The distributions and energy levels of the HOMO and LUMO orbitals calculated at the HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) levels for the CYTHI shown in Fig. 7. The calculations indicate that the compound has 112 occupied molecular orbitals and the

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F. Sßen et al. / Journal of Molecular Structure 1076 (2014) 1–9

Fig. 6. Molecular electrostatic potential (MEP) map in gas phase of compound.

Table 7 Calculated polarizability and the first hyperpolarizability components (a.u.) for the title compound.

axx axy ayy axz ayz azz atot. bxxx bxxy bxyy byyy bxxz bxyz byyz bxzz byzz bzzz btot.

HF/6-31+G(d. p)

B3LYP/6-31+G(d, p)

319.99 42.58 309.65 4.19 29.72 304.1 311.24 261.23 101.02 26.28 76.15 30.99 42.67 24.08 28.1 11.03 18.35 319.67

351.76 62.4 331.76 11.37 36.59 309.8 331.1 107.75 3.43 210.59 332.03 17.21 35.65 72.63 8.02 7.28 11.47 348.09

Fig. 7. The molecular orbitals and energies for the HOMO and LUMO of the title compound.

value of the energy separation between the HOMO and LUMO are 9.62 and 4.78 eV for at the same levels. The HOMO and LUMO energies, the energy gap (DE), the ionization potential (I), the electron affinity (A), the absolute electronegativity (v), the absolute hardness (g) and softness (S) for molecule have been calculated at the same levels and the results are given in Table 6. Non-linear optical (NLO) effects The calculations of the mean linear polarizability (atot) and the mean first hyperpolarizability (btot) from the Gaussian output have been explained in detail previously [39]. The values of the polarizability a and the first hyperpolarizability b of Gaussian 03 output are reported in atomic units (a.u.). The linear polarizability (a) and first-order hyperpolarizability (b) of the CYTHI were calculated at the HF/6-31+G(d, p) and B3LYP/6-31+G(d, p) levels. The components of polarizability and the first hyperpolarizability of

Table 6 The calculated frontier orbital energies, electronegativity, hardness and softness of compound using B3LYP/6-31+G(d, p) level.

EHOMO (eV) ELUMO (eV) I (eV) A (eV) v (eV) g (eV) S (eV)

HF/6-31+G(d, p)

B3LYP/6-31+G(d, p)

8.03 1.59 8.03 1.59 3.22 4.81 0.1

5.49 0.71 5.49 0.71 2.8 2.4 0.2

the compound can be seen in Table 7. The calculated values of atot and btot are 311.24, 319.71 and 311.1, 348.09 a.u., respectively. Urea is one of the prototypical molecules used in the study of the NLO properties of molecular systems. Therefore it was used frequently as a threshold value for comparative purposes. The values of atot and btot of urea are 27.74, 15.56 a.u. and 33.1, 59.4 a.u. obtained at the same levels. As can be seen, theoretically, the first-order hyperpolarizability of the CYTHI is times 20.54 for HF/6-31+G(d, p) and 5.86 B3LYP/631+G(d, p), which first-order hyperpolarizability magnitude of urea, respectively. According to these results, the title compound is a good candidate of NLO material.

Conclusions In conclusion, a novel compound containing a Schiff base was synthesized. The structure of the compound in the crystalline phase was determined by X-ray diffraction. Also, the Infrared (IR) and Nuclear Magnetic Resonance (NMR) spectra were determined experimentally. To support experimental results and compare theoretical with experimental results, the molecular geometry obtained from the X-ray coordinates was optimized using Hartree–Fock (HF) and Density Functional Theory (DFT/B3LYP) method with the 6-31+G(d, p) basis set in ground state. Theoretical IR and NMR spectroscopies for optimized molecular structures was calculated. It can be seen the excellent harmony between the experimental findings and theoretical calculations. Both Hartree– Fock (HF) and Density Functional Theory (DFT) methods was given very good results.

F. Sßen et al. / Journal of Molecular Structure 1076 (2014) 1–9

Supplementary material CCDC 997014 contains supplementary crystallographic data (excluding structure factors) for the structure reported in this article. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif, by e-mailing [email protected] or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223336033. Acknowledgments We are grateful to Firat University Scientific Research Coordination Center (FUBAP Project No: FF:12:12) for financial support of this work. We also thank to Prof. Dr. Orhan Büyükgüngör for his help with the data collection and acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the STOE IPDS II diffractometer. References [1] Q. Zhao, C. Shen, H. Zheng, J. Zhang, Pengfei Zhang, Carbohydr. Res. 345 (2010) 437–441. [2] O. Bekircan, B. Kahveci, M. Küçük, Turk. J. Chem. 30 (2006) 29–40. [3] L. Shi, H. Ge, S. Tan, H. Li, Y. Song, H. Zhu, R. Tan, Eur. J. Med. Chem. 42 (2007) 558–564. [4] N.A. Ghanwate, A.W. Raut, A.G. Doshi, Orient. J. Chem. 24 (2008) 721–724. [5] M. Jalali-Heravi, A.A. Khandar, I. Sheikshoaie, Spectrochim. Acta A 55 (1999) 2537. [6] J.F. Nicoud, R.J. Twieg, in: D.S. Chemla, J. Zyss (Eds.), Nonlinear Optical Properties of Organic Molecules and Crystals, vol. 1, Academic Press, New York, 1987, p. 277. Chapter II-3. [7] M. Jalali-Heravi, A.A. Khandar, I. Sheikshoaie, Spectrochim. Acta Part A 56 (2000) 1575. [8] I. Yilmaz, A. Cukurovali, Heteroatom Chem. 14 (7) (2003) 617–621. [9] M.A. Ahmedov, I.K. Sardarov, I.M. Ahmedov, R.R. Kostikov, A.V. Kisin, N.M. Babaev, Zh. Org. Khim. 27 (7) (1991) 1434. [10] G.M. Sheldrick, SHELXS-97, Program for the Solution of Crystal Structures, University of Göttingen, Germany, 1997. [11] G.M. Sheldrick, SHELXL-97, Program for Crystal Structures Refinement, University of Göttingen, Germany, 1997. [12] L.J. Farrugia, J. Appl. Crystallogr. 30 (1999) 837–838. [13] Stoe, Cie, X-AREA Version 1.18 and X-RED32 Version 1.04, Stoe & Cie, Darmstadt, Germany, 2002.

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