Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 816–827

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Spectrochimica Acta Part A: Molecular andBiomolecular Spectroscopy

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Synthesis, spectroscopic and theoretical studies of ethyl(2E)-3-amino-2-({[(4-benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]amino}carbonothioyl)but-2-enoate butanol solvate

1386-1425/$ - see front matter � 2013 Elsevier B.V. All rights reserved.http://dx.doi.org/10.1016/j.saa.2013.09.068

⇑ Corresponding author. Tel.: +90 354 242 1021; fax: +90 354 242 1022.E-mail address: i_koca@yahoo.com (_I. Koca).

_Irfan Koca a,⇑, Yusuf Sert b, Mehmet Gümüs� a, _Ibrahim Kani c, Çagrı Çırak d

a Department of Chemistry, Faculty of Art & Sciences, Bozok University, Yozgat, Turkeyb Department of Physics, Faculty of Art & Sciences, Bozok University, Yozgat, Turkeyc Department of Chemistry, Faculty of Sciences, Anadolu University, Eskis�ehir, Turkeyd Department of Physics, Faculty of Art & Sciences, Erzincan University, Erzincan, Turkey

h i g h l i g h t s

� New pyrazole-3-carboxamidederivative was prepared in good yieldvia one pot reaction.� IR, Raman, NMR, elemental analysis,

and XRD methods were used forcharacterization.� The FT-IR and Laser-Raman spectra of

the title compound were recorded insolid phase.� The optimized geometry and

vibrational frequencies werecalculated for the first time.� The HOMO–LUMO energies and

related molecular properties wereevaluated.

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

a r t i c l e i n f o

Article history:Received 15 May 2013Received in revised form 6 September 2013Accepted 26 September 2013Available online 8 October 2013

Keywords:PyrazolePyrazole-3-carboxamideHFDFTVibrational study

a b s t r a c t

We have synthesized ethyl (2E)-3-amino-2-({[(4-benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]amino}carbonothioyl)but-2-enoate (2) by the reaction of 4-benzoyl-1,5-diphenyl-1H-pyrazole-3-car-bonyl chloride (1), ammonium thiocyanate and ethyl 3-aminobut-2-enoate and then characterized byelemental analyses, IR, Raman, 1H NMR, 13C NMR and X-ray diffraction methods. The experimental andtheoretical vibrational spectra of 2 were investigated. The experimental FT-IR (4000–400 cm�1) andLaser-Raman spectra (4000–100 cm�1) of the molecule in the solid phase were recorded. Theoreticalvibrational frequencies and geometric parameters (bond lengths, bond angles) were calculated usingAb Initio Hartree Fock (HF), Density Functional Theory (B3LYP) methods with 6-311++G(d,p) basis setby Gaussian 09W program. The computed values of frequencies are scaled using a suitable scale factorto yield good coherence with the observed values. The assignments of the vibrational frequencies wereperformed by potential energy distribution (PED) analysis by using VEDA 4 program. The theoretical opti-mized geometric parameters and vibrational frequencies were compared with the corresponding exper-imental X-ray diffraction data, and they were seen to be in a good agreement with each other. Also, thehighest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) ener-gies were calculated.

� 2013 Elsevier B.V. All rights reserved.

_I. Koca et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 816–827 817

Introduction

Pyrazole derivatives are well established in the literatures asimportant biologically effective heterocyclic compounds [1]. Dur-ing the past decades, considerable evidence has been accumulatedto demonstrate the efficacy of pyrazole derivatives including anti-bacterial [2,3], antiinflammatory [4], antiviral [5], anticonvulsant[6], antitumor [7], antihistaminic [8] and antidepressant [9] activ-ities. Morever, pyrazole-3-carboxamide are of great significanceand have been extensively used for different therapeutics such ascannabinoid (CB) receptor ligands [10], estrogen receptor antago-nist [11] and Aurora-A kinase inhibitors [12].

In the present study, we synthesized novel pyrazole-3-carbox-amide derivative by the addition of ethyl 3-aminobut-2-enoate to4-benzoyl-1,5-diphenyl-1H-pyrazole-3-carbonyl isothiocyanate.The structures of the synthesized compound (2) were character-ized by IR, Raman, 1H NMR, 13C NMR, X-ray diffraction and elemen-tal analysis. And also the theoretical and experimental studieswere performed to give a detailed description of the molecularstructure and vibrational harmonic spectra of 2.

Materials and methods

General remarks

Melting point is uncorrected and recorded on Electrothermal9200 digital melting point apparatus. IR spectra were measuredwith Perkin Elmer Spectrum Two Model FT-IR Spectrophotometerusing ATR method with a resolution of 4 cm�1 at room tempera-ture and its scan number is 100 and its form is solide phase andregion 4000–400 cm�1. Raman spectrum was recorded by the useof an Renishaw Model Raman spectrophotometer with a resolutionof 1 cm�1 at room temperature and its scan number is 100 and itsform is solide phase and region 4000–100 cm�1. The 1H and 13CNMR spectra were obtained with Bruker Avance III 400 MHzspectrometer using CDCl3 solvent. Leco-932 CHNS-O ElementalAnalyzer was used for elemental analysis. Reaction was monitoredby TLC (Silica gel, aluminum sheets 60 F254, Merck).

X-ray crystallography

Diffraction data for the compounds were collected with BrukerSMART APEX CCD diffractometer equipped with a rotation anodeat 100 K using graphite monochrometed Mo K radiation(0.71073 Å). SAINT, SHELXTL, and SHELXS 97 [13,14] were usedfor cell refinement, data reduction and structure solving, andrefinement of structure. Molecular graphics and publication mate-rials were prepared using SHELXTL. 2 Crystallographic data andstructure refinements parameters are listed in Table 1. Hydrogenatoms were added to the structure model on calculated positions.Geometric calculations were performed with Platon [15]. Therefinement converged with residuals summarized in Table 1.The structure of compound 1 has been deposited at CCDC withthe deposition number 924122. Copies of data can be obtained,free of charge (deposit@ccdc.cam.ac.uk).

Synthesis

0.387 g (1 mmol) 4-benzoyl-1,5-diphenyl-1H-pyrazole-3-car-bonyl chloride (1) and 0.084 g (1.1 mmol) ammonium thiocyanatein 15 mL acetone were refluxed for 30 min. The resulting solid(NH4Cl) was removed by filtration. Then to this solution ethyl3-aminobut-2-enoate (1 mmol) in 10 mL acetone was added dropwise, the mixture was stirred under reflux for 3 h. The solventwas removed under reduced pressure. The obtained residue was

treated with 2-propanol to give the crude product, which werefiltered off, recrystallized from butanol yielded a pure product,ethyl (2E)-3-amino-2-({[(4-benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]amino}carbonothioyl)but-2-enoate (2) (Scheme 1), asred crystals (76%). M.p.: 177 �C. Elemental analysis calculated forC30H26N4O4S (538.62): C, 66.90; H, 4.87; N, 10.40; S, 5.95. Found:C, 66.98; H, 5.06; N, 10.15; S, 5.80%.

Computational details

Hartree–Fock is the most basic ab initio molecular orbital ap-proach. The Hartree–Fock approximation underlies the most com-mon method for calculating electron wave functions of atoms andmolecules. For small atoms and molecules, not to mention solids,the Schrödinger equation cannot be solved, neither analyticallynor numerically. For the purpose of assessing wave functions,approximations to the wave function become necessary in one orthe other form. The primary interest at the moment is to describethe electron ground state. The idea of the Hartree–Fock method forthis purpose is to construct an approximation of the many electronwave function from single particle wave functions. It is the bestapproximation to the true wave function where each electron isoccupying an orbital, the picture that most chemists use to ratio-nalize chemistry. The Hartree–Fock approximation is, furthermore,the usual starting point for more accurate calculations.

Density functional theory (DFT) is an approach to the electronicstructure of atoms and molecules and states that all the ground-state properties of a system are function of the charge density.So, DFT calculations cannot be considered a pure ab initio method.In DFT, the electron density is the basic variable, instead of thewave function. This reduces the computational burden of treatingelectron–electron interaction terms, which are treated explicitlyas a functional of the density. The DFT approach combines thecapacity to incorporate exchange–correlation effects of electronswith reasonable computational costs and high accuracy. The pastfew years has seen a rapid increase in the use of DFT methods indifferent types of applications, particularly since the introductionof accurate non-local corrections. In density functional theory,the exchange–correlation energy is the main issue among all ofthe approximations; therefore, the accuracy of DFT is depended di-rectly by the approximate nature of the exchange–correlation en-ergy functional. The DFT methods employed in the present paperare representative in aspect of the exchange–correlation energyand were commonly used in numerous theoretical studies [16–24].

Initial atomic coordinates can be generally taken from any data-base or experimental XRD results. We have used experimental XRDdata and GaussView software database to determine initial atomiccoordinates and to optimize the input structure. After the optimi-zation, we have used the most stable optimized structure for othertheoretical analysis. In this study, initial atomic coordinates thattaken from GaussView database [16] have given most stable struc-ture after optimization.

The molecular structure of 2 in the ground state (in gas phase)was optimized by HF and DFT (B3LYP) methods with6-311++G(d,p) basis set level, and the optimized structure wasused in the vibrational frequency calculations. The calculated har-monic vibrational frequencies were scaled by 0.9051 (HF) and0.9614 (B3LYP) for 6-311++G(d,p) level [17]. The molecular geom-etry was not restricted, and all the calculations (vibrational wave-numbers, geometric parameters and other molecular properties)were performed by using Gauss View molecular visualization pro-gram [16] and Gaussian 09W program package on a computingsystem [18]. Additionally, the calculated vibrational frequenciesare clarified by means of the potential energy distribution (PED)analysis of all the fundamental vibration modes by using VEDA 4program [19]. VEDA 4 program has been used in previous studies

Table 1Data collection and structure refinement for compound 2.

Chemical formula C32H31N4O4.50SFormula weight 575.67Temperature 107(2) KWavelength 0.71073 ÅCrystal size 0.19 � 0.27 � 0.47 mmCrystal system MonoclinicSpace group P 1 21/n 1Unit cell dimensions a = 14.1529(4) Å a = 90�

b = 17.2113(5) Å b = 94.0000(10)�c = 24.3008(6) Å c = 90�

Volume 5905.0(3) Å3

Z 8Density (calculated) 1.295 Mg/cm3

Absorption coefficient 0.155 mm�1

F (000) 2424Theta range for data

collection1.45–28.33�

Index ranges �18 6 h 6 18, �22 6 k 6 22,�26 6 l 6 31

Reflections collected 67,605Independent

reflections13,741 [R(int) = 0.0456]

Max. and min.transmission

0.9711 and 0.9307

Structure solutiontechnique

Direct methods

Structure solutionprogram

SHELXS-97 (Sheldrick, 2008)

Refinement method Full-matrix least-squares on F2

Refinement program SHELXL-97 (Sheldrick, 2008)Function minimized R w(F2

o � F2c )2

Data/restraints/parameters

13,741/0/768

Goodness-of-fit on F2 1.027D/rmax 0.002Final R indices 9341 data; I > 2r(I) R1 = 0.0442,

wR2 = 0.1017All data R1 = 0.0801,

wR2 = 0.1242Weighting scheme w = 1/

[r2(F2o ) + (0.0598P)2 + 1.0266P]

Where P = (F2o + 2F2

c )/3Largest diff. peak and

hole0.293 and �0.308 e�3

R.M.S. deviation frommean

0.060 e�3

818 _I. Koca et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 816–827

by many researchers [20–24]. All the vibrational assignments havebeen made at B3LYP/6-311++G(d,p) level.

Results and discussion

Characterization of compound 2

The synthetic sequence leading to the pyrazole-3-carboxamideis outlined in Scheme 1. The starting material 4-benzoyl-1,5-diphenyl-1H-pyrazole-3-carbonyl chloride (1) were prepared asdescribed earlier [25]. Compound 1 was converted into

Scheme 1. The formation o

corresponding acyl thiocyanate by treatment with ammoniumthiocyanate. In the same reaction vessel, pyrazolyl acyl thiocyanatewas reacted with ethyl 3-aminobut-2-enoate to obtain the targetcompound in good yield. Compound 2 is soluble in DMF, acetoni-trile, dichloromethane, acetone, THF and benzene, and insolublein hexane and alcohol derivatives. The final product was character-ized by elemental analyses, IR, Raman, 1H NMR, 13C NMR and X-raydiffraction methods.

The NMR spectrum of 2 was recorded in CDCl3 at room temper-ature (Figs. 1 and 2). In the 1H NMR spectra, the NH proton was ob-served at 10.93 ppm as singlet. The phenyl protons of the 2 gavemultiplet in the range of 7.81–7.15 ppm. The methylene protonsof ester group were resonated at 3.95 ppm. A singlet arised at2.20 pmm due to methyl protons. And also the other methyl groupobserved at 1.10 ppm in the form of triplet. In the 13C NMR spectraof 2, carbonyl carbons observed at 191.0, 166.7, 155.4 ppm due topresence of benzoyl, ester and amide groups, respectively. Thechemical shift of C@S group was seen at 163.1 ppm. The peaks ofC@C and C@N which are attributed to phenyl and pyrazole ringsobserved in the range of 144.0–123.4 ppm. The resonance of threedifferent aliphatic carbons of compound 2 was observed at 59.9,23.2 and 14.3 ppm.

Description of the crystal structure of 2

We have determined the crystal structure of the compound 2which crystallizes with two independent but very similarmolecules in the unit cell. The crystal structure of the compound2, crystallizes in an monoclinic space group P 1 21/n 1, withZ = 8 for the formula unit, C32H31N4O4.50S. The final cellconstants of a = 14.1529(4) Å, b = 17.2113(5) Å, c = 24.3008(6) Å,b = 94.0000(10)�, volume = 5905.0(3) Å3, are based upon therefinement of the XYZ-centroids of reflections above 20r(I). Per-spective view the compound 2 is shown in Fig. 3, the crystallo-graphic data some selected bond distances and angles are givenin Tables 1 and 2, respectively.

The theoretical and experimental structure parameters (bondlengths and bond angles) of the molecule are tabulated in Table 2,in accordance with the atom numbering scheme given in Fig. 4.Compound 2 has C1 symmetry. From the theoretical geometry,we have found that most of the optimized bond lengths are slightlylonger or shorter than the experimental values at the both HF andDFT (B3LYP) levels, due to the fact that the theoretical calculationsbelong to isolated molecule in gaseous phase while the experimen-tal results belong to one in solid state. In addition, the comparisonof the theoretical bond lengths and bond angles at the HF andB3LYP levels as a whole shows that the calculated values atB3LYP level correlate well with the experimental ones. C9@N2bond length is all longer than and C7AN1 bond length is all shorterthan those found in similar structures [C@N�1.291–1.300 Å,CAN � 1.482–1.515 Å] [26], resulting from the conjugation of theelectrons of atom N with atom C. In this relation, these resultsare consistent with the respect to different pyrazole derivatives.The density functional calculation gives C8AC24 and C9AC10 bond

f the title compound.

Fig. 1. 1H NMR spectra of compound 2.

Fig. 2. 13C NMR spectra of compound 2.

_I. Koca et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 816–827 819

Fig. 3. The molecular structure of the title compound.

820 _I. Koca et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 816–827

lengths are longer than the normal CAC single bond length ofabout 1.47 Å since these bonds play a bridge role between carbox-amide and C@O groups. In the earlier literature [27], the bondlengths of C@O and CAO were 1.266 Å and 1.305 Å, respectively.In this study, the corresponding bond lengths are measuredO2@C15 = 1.223 Å and O3@C16 = 1.447 Å as experimentally, whichare calculated as 1.226 Å and 1.447 Å by B3LYP/6-311++G(d,p),respectively. For amide group, C10@O1 and N3AH6 bond lengthswere calculated 1.222 Å and 1.008 Å with B3LYP/6-311++G(d,p)by Sridevi et al. [28], respectively. These bond lengths were calcu-lated for our compound 1.214 Å and 1.015 Å with same method.Comparing bond angles for the title compound, O1@C10AN3 andH6AN3AC10 were calculated 125.6� and 115.1�, respectively.These bond angles by Sridevi et al. [28] were calculated 122� and119�, respectively. For ester group O3AC16AC17 bond angle wasfound 107.6� by Nagabalasubramanian et al. [29] for nicotinic acidethyl ester, this angle was found for our molecule experimentally107.2� and theoretically 107.4�.

To make comparison with experimental results, we present lin-ear correlation coefficients (R2) for linear regression analysis oftheoretical and experimental bond lengths and angles. These val-ues are 0.9805 and 0.9885 (for bond lengths), and 0.9804 and0.9810 (for bond angles) with HF and B3LYP levels, respectively.These coefficients can be seen in the last line of Table 2. From thesevalues it can easily be said that the geometric parameters calcu-lated with the B3LYP method are much closer to the experimentalresults. The largest differences between the calculated and experi-mental geometries are 0.144 Å (B3LYP) compared with 0.126 Å(HF) for the bond lengths and 2.8� (B3LYP) compared with 3.1�(HF) for the bond angles.

Vibrational analysis

A complete vibrational analysis of the 189 fundamental vibra-tional modes of 2 has been done on the basis of its experimentalinfrared and Raman spectra and HF and B3LYP/6-311++G(d,p)

quantum chemical calculations. The experimental FT-IR and Ra-man spectra of the molecule are shown in Fig. 5.

For comparative purpose the calculated IR and Raman spectraare shown in Figs. S1 and S2 (see supplementary file). The scaledcalculated harmonic vibrational frequencies at HF and B3LYP lev-els, observed vibrational frequencies, experimental IR intensities/Raman activities, and detailed PED assignments are tabulated inTable 3. To our knowledge, there are no theoretical studies onvibrational assignment of 2 in the literature. So, in order to intro-duce detailed vibrational assignments of 2, we have done thePED analysis of the molecule. VEDA4 software does not describethe vibrations under%10. But, poorlydefined modes were assignedby using Gauss View software in Table 3. These modes are t113,t124, t126, t132, t136, t138, t142, t166, t171, t177, t179 andt180.

CAH vibrations in aromatic ringThe aromatic CAH stretching is normally found in the region

between 3100 and 3000 cm�1 [30]. In the present study, thearomatic CAH stretching vibrations are assigned in the region3041–3081 cm�1 (B3LYP) (mode nos: 4–18) which are in goodagreement with the literature values [31,32] and also find supportfrom observed FT-IR 3064 cm�1 and Raman 3063 cm�1 bands. Inaromatic compounds, the CAH in-plane bending frequenciesappear in the range 1000–1300 cm�1 and CAH out of plane bend-ing vibrations are in the range 750–1000 cm�1 [33,34]. From aboveliterature, the harmonic vibrations in the range 1005–1308 cm�1/B3LYP (mode nos: 58–60, 62, 63, 70, 72, 73, 75–77, 82, 84 and88–90) and 971–749 cm�1/B3LYP mode nos: 96–99, 101, 104–106, 110, 111 and 119 are assigned to CAH in-plane and CAHout of plane bending, respectively. The observed FT-IR bands1066, 1001 and 763 cm�1 are attributed to CAH in plane and outof plane bending, respectively, and their corresponding Ramancounterparts are 1066, 1002 and 770 cm�1. These assignmentsare found to be satisfactorily in agreement with theoretical andalready reported values [35,36]. Among the two computational

Table 2Experimental and calculated geometric parameters of compound 2 with 6-311++G(d,p).

Geometric parameters Exp. values Calculated values

Bond lenghts (Å) X-ray B3LYP HF

C1AC2 1.382 1.392 1.383C1AC6 1.384 1.394 1.384C1AH1 0.950 1.082 1.073C2AC3 1.366 1.394 1.385C2AH2 0.950 1.083 1.075C3AC4 1.366 1.393 1.384C3AH3 0.950 1.083 1.075C4AC5 1.390 1.392 1.384C4AH4 0.950 1.083 1.074C5AC6 1.381 1.394 1.382C5AH5 0.950 1.082 1.073C6AN1 1.436 1.432 1.428N1AC7 1.375 1.381 1.360N1AN2 1.349 1.343 1.321C7AC8 1.386 1.389 1.369C7AC18 1.473 1.476 1.483N2AC9 1.329 1.330 1.299C8AC9 1.410 1.416 1.412C8AC24 1.501 1.503 1.504C9AC10 1.473 1.486 1.490C10AO1 1.215 1.214 1.186C10AN13 1.381 1.389 1.377N3AH6 0.871 1.015 0.997N3AC11 1.387 1.385 1.368C11AS1 1.649 1.667 1.649C11AC12 1.457 1.469 1.481C12AC13 1.392 1.391 1.369C12AC15 1.463 1.468 1.467C13AC14 1.498 1.507 1.509C13AN4 1.335 1.345 1.338C14AH7 0.980 1.087 1.077C14AH8 0.980 1.092 1.083C14AH9 0.980 1.093 1.084N4AH10 0.880 1.017 0.995N4AH11 0.880 1.005 0.990C15AO2 1.223 1.226 1.198C15AO3 1.347 1.347 1.320O3AC16 1.447 1.447 1.423C16AH12 0.990 1.092 1.082C16AH13 0.990 1.092 1.082C16AC17 1.500 1.515 1.513C17AH14 0.980 1.092 1.084C17AH15 0.980 1.092 1.084C17AH16 0.980 1.093 1.086C18AC19 1.396 1.403 1.391C18AC20 1.390 1.401 1.389C19AC21 1.381 1.390 1.382C19AH17 0.950 1.083 1.074C20AC22 1.384 1.393 1.386C20AH18 0.950 1.082 1.073C21AC23 1.385 1.394 1.386C21AH19 0.950 1.084 1.075C22AC23 1.380 1.393 1.384C22AH20 0.950 1.084 1.075C23AH21 0.950 1.084 1.075C24AC25 1.486 1.491 1.495C24AO4 1.216 1.218 1.190C25AC26 1.394 1.399 1.387C25AC27 1.396 1.401 1.392C26AC28 1.387 1.392 1.386C26AH22 0.950 1.083 1.073C27AC29 1.385 1.388 1.380C27AH23 0.950 1.082 1.073C28AC30 1.388 1.393 1.383C28AH24 0.950 1.084 1.075C29AC30 1.381 1.396 1.388C29AH25 0.950 1.084 1.075C30AH26 0.950 1.084 1.075R2 0.9885 0.9805

Table 2 (continued)

Geometric parameters Exp. values Calculated values

Bond lenghts (Å) X-ray B3LYP HF

Bond angles (o)C2AC1AC6 119.1 119.3 119.4C2AC1AH1 120.5 121.0 120.8C6AC1AH1 120.5 119.5 119.7C1AC2AC3 120.7 120.3 120.2C1AC2AH2 119.6 119.5 119.5C3AC2AH2 119.6 120.1 120.1C2AC3AC4 119.9 119.8 119.8C2AC3AH3 120.0 120.0 120.0C4AC3AH3 120.0 120.0 120.0C3AC4AC5 120.4 120.3 120.2C3AC4AH4 119.8 120.1 120.1C5AC4AH4 119.8 119.4 119.5C4AC5AC6 118.7 119.3 119.3C4AC5AH5 120.6 120.5 120.4C6AC5AH5 120.6 120.1 120.1C1AC6AC5 121.2 120.7 120.8C1AC6AN1 117.7 118.9 118.9C5AC6AN1 121.0 120.2 120.2C6AN1AC7 130.4 129.1 129.3C6AN1AN2 117.3 118.6 118.8C7AN1AN2 112.1 112.1 111.7N1AC7AC8 106.3 105.9 106.4N1AC7AC18 124.3 124.0 123.9C8AC7AC18 129.3 129.8 129.6N1AN2AC9 105.0 105.6 106.4C7AC8AC9 104.4 104.7 104.1C7AC8AC24 126.9 126.7 127.0C9AC8AC24 128.4 128.4 128.8N2AC9AC8 112.2 111.4 111.2N2AC9AC10 120.9 121.5 121.7C8AC9AC10 126.6 126.8 126.9C9AC10AO1 121.5 121.3 120.5C9AC10AN3 113.4 113.0 113.3O1AC10AN3 125.1 125.6 126.1C10AN3AH6 – 115.1 115.4C10AN3AC11 128.8 130.0 130.1H6AN3AC11 – 114.4 114.3N3AC11AS1 117.3 116.9 117.1N3AC11AC12 118.3 118.8 119.2S1AC11AC12 124.2 124.1 123.5C11AC12AC13 121.8 121.3 121.4C11AC12AC15 118.2 119.2 118.0C13AC12AC15 119.9 119.3 120.4C12AC13AC14 123.9 124.0 123.8C12AC13AN4 121.5 121.7 122.9C14AC13AN4 114.5 114.1 113.2C13AC14AH7 109.5 112.3 112.6C13AC14AH8 109.5 110.0 109.3C13AC14AH9 109.5 109.6 109.2H7AC14AH8 109.5 107.3 108.0H7AC14AH9 109.5 108.8 108.7H8AC14AH9 109.5 108.5 108.7C13AN4AH10 119.9 118.2 119.8C13AN4AH11 120.0 119.8 119.6H10AN4AH11 120.0 121.0 119.8C12AC15AO2 126.2 125.3 125.1C12AC15AO3 112.1 113.2 112.9O2AC15AO3 121.5 121.3 121.8C15AO3AC16 115.8 116.5 118.0O3AC16AH12 110.3 108.5 108.8O3AC16AH13 110.3 108.7 108.9O3AC16AC17 107.2 107.4 107.5H12AC16AH13 108.5 107.9 108.2H12AC16AC17 110.3 112.0 111.6H13AC16AC17 110.3 111.9 111.5C16AC17AH14 109.5 111.0 110.8C16AC17AH15 109.5 111.0 110.9C16AC17AH16 109.5 109.5 109.5H14AC17AH15 109.5 108.5 108.5

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_I. Koca et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 816–827 821

Table 2 (continued)

Geometric parameters Exp. values Calculated values

Bond lenghts (Å) X-ray B3LYP HF

H14AC17AH16 109.5 108.3 108.5H15AC17AH16 109.5 108.2 108.3C7AC18AC19 121.0 120.6 120.5C7AC18AC20 119.4 120.2 120.0C19AC18AC20 119.5 119.1 119.4C18AC19AC21 120.0 120.4 120.3C18AC19AH17 119.9 119.8 119.9C21AC19AH17 119.9 119.7 119.6C18AC20AC22 120.1 120.1 120.1C18AC20AH18 119.9 119.4 119.7C22AC20AH18 119.9 120.3 120.1C19AC21AC23 120.1 120.1 120.0C19AC21AH19 119.9 119.6 119.7C23AC21AH19 120.0 120.1 120.1C20AC22AC23 120.0 120.3 120.2C20AC22AH20 119.9 119.5 119.5C23AC22AH20 119.9 120.1 120.1C21AC23AC22 120.2 119.7 119.8C21AC23AH21 119.9 120.0 120.0C22AC23AH21 120.2 120.1 120.1C8AC24AC25 119.3 119.0 119.1C8AC24AO4 119.4 119.2 119.4C25AC24AO4 121.2 121.6 121.3C24AC25AC26 122.2 122.0 122.2C24AC25AC27 118.5 118.5 118.3C26AC25AC27 119.3 119.3 119.4C25AC26AC28 120.0 120.3 120.3C25AC26AH22 119.9 119.8 120.2C28AC26AH22 120.0 119.8 119.4C25AC27AC29 120.3 120.2 120.2C25AC27AH23 119.8 118.5 118.9C29AC27AH23 119.8 121.1 120.7C26AC28AC30 120.3 119.9 119.8C26AC28AH24 119.8 119.9 119.8C30AC28AH24 119.8 120.1 120.2C27AC29AC30 120.2 120.0 119.9C27AC29AH25 119.9 119.9 119.9C30AC29AH25 119.9 119.9 120.0C28AC30AC29 120.0 120.0 120.0C28AC30AH26 120.0 119.9 119.9C29AC30AH26 120.0 119.9 119.9R2 0.9810 0.9804

Fig. 4. Optimized structure

822 _I. Koca et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 816–827

methods DFT/B3LYP show excellent agreement with literaturevalues.

CAC vibrationsThere are six equivalent CAC bonds in benzene and conse-

quently there will be six CAC stretching vibrations. In addition,there are several in plane and out of plane bending vibrations ofthe ring carbons. However, due to high symmetry of benzene,many modes of vibrations are infrared inactive. In general, thebands around 1400–1650 cm�1 in benzene derivatives are as-signed to skeletal stretching CAC bands [37]. The bands observedas 1607, 1596, 1421 cm�1 in FT-IR and 1609, 1597 and 1456 cm�1

in Raman spectrum, respectively. These modes by Sundaraganesanet al. [38] have been observed at 1318, 1396, 1500 and 1565 cm�1

for 3-chloro-4-fluorobenzonitrile in FT-IR spectrum region. Thetheoretical scaled CAC stretching vibrations by B3LYP/6-311++G(d,p) are at 1580, 1576, 1574, 1572, 1569, 1556, 1553,1506, 1473 and 1420 cm�1 shows excellent agreement with re-corded spectral data. The ring breathing modes of 2 is assigned979 cm�1 in FT-IR and 966 cm�1 in Raman, respectively. This modehave been calculated as 979 cm�1 in B3LYP/6-311++G(d,p). Theo-retically calculated CACAC out of plane and CACAC in plane bend-ing modes are seen in the Table 3.

Amide group vibrationsThe secondary amide shows NAH stretch around 3300 cm�1

[36]. The strong infrared band at 3296 cm�1 in FT-IR spectrumis assigned to NAH stretching vibration. This vibration is pure;it does not mix with any other vibration with PED contribution99%. Amides show a very strong band for the C@O group that ap-pears in the range of 1680–1630 cm�1 [39]. A strong band at1669 cm�1 is assigned to C@O stretching mode (the amide Iband). This is also in agreement with the literature data [40].The secondary amides show NAH bending vibrations in the re-gion 1570–1515 cm�1 [40]. The FT-IR band at 1493 cm�1 is attrib-uted to NAH deformation mode (the amide II band). This bandresults from the interaction of NAH bending and the CANACACstretching.

of the title compound.

_I. Koca et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 816–827 823

C@O and CAO vibrationsThe C@O stretch of carboxylic acids is identical to the C@O

stretch in ketones, which is expected in the region 1740–1660 cm�1 [41]. Krishnakumar et al. [42] observed very strongband at 1661 cm�1 in IR and 1648 cm�1 in Raman for 1-Naphtha-leneacetic acid (NAA) was assigned to C@O stretching vibrations.The C@O bond formed by Pp–Pp between C and O, internal hydro-gen bonding reduces the frequencies of the C@O stretching absorp-tion to a greater degree than does intermolecular H bondingbecause of the different electronegativities of C and O, the bondingare not equally distributed between the two atoms. In this presentstudy, a very strong band observed in FT-IR spectrum at 1661 cm�1

(mode no. 29) is assigned to C@O stretching vibrations which theB3LYP predicted value (1635 cm�1) shows a small deviation ofabout ca. 26 cm�1 with FT-IR data and the PED value of 72% as re-ported in Table 3. The CAO stretching vibration is assigned to848 cm�1 in FT-IR which has the TED value of 29%. Most of theCAO vibrations are mixed vibrations as shown in the TED valuesin Table 3. The remainders of the observed and calculated frequen-cies are accounted in Table 3. The above all conclusions are verygood agreement with literature values [43–46].

C@S vibrationsAccording to Silverstein and Webstor [47], spectra of com-

pounds in which C@S group is attached to an N atom show absorp-tion bands in broad region 1563–700 cm�1. In nitrogen containing

Fig. 5. (A) The experimental FT-IR spectrum of 2 in solid phase. (B) Theexperimental Laser-Raman spectrum of 2 in solid phase.

thiocarbonyl compounds, the assignment of the C@S stretching fre-quency has been controversial one [48,49]. Mani et al. [50]assigned from PED calculation, the medium intensity band at988 cm�1 in FT-IR to the C@S stretching vibration for phenylisoth-iocynate. In accordance with above conclusion, the band1142 cm�1 calculated by B3LYP method (mode no: 74) has beenassigned to C@S stretching vibration. However, there is no otherFT-IR and Raman bands were observed.

NAH vibrationsThe asymmetric tasNH2 and symmetric tsNH2 stretching vibra-

tions are easily identified in IR spectrum of the title molecule. Asseen from the Table 3, these two NAH stretching modes are calcu-lated to be 3547 and 3314 cm�1. These modes are observed at 3466and 3248 cm�1 in FT-IR spectrum, but not apparent in Raman spec-trum. Muthu et al. observed these modes at 3430 cm�1 (IR)/3440 cm�1 (R) and 3560 cm�1 (IR)/3575 cm�1 (R) for 2-ethylpyri-dine-4-carbothioamide [51]. In the IR spectrum of liquid aniline,these bands were reported at 3440 and 3360 cm�1, respectively[52]. As seen from PED analysis in Table 3, the NAH in plane bend-ing (dHNH) vibrations contributes to the two calculated modes at1572 and 1473 cm�1. These frequencies were not seen in FT-IRand Raman spectrum region in the experimental FT-IR and Ramanspectra shown in Fig. 5.

Pyrazole vibrationsPyrazole ring has several bands between 1530 cm�1 and

1013 cm�1 with different intensities arising from ring stretchingvibrations [53]. In the pyrazole ring of our system, CAC stretchingvibrations appeared at 1550 cm�1 in the FT-IR spectrum. The C@Nstretching vibration in the pyrazole rings was observed at1324 cm�1 and 1202 cm�1. The NAN stretching vibration occuredat 1187 cm�1. Orza et al. noted that the pyrazole in plane ringdeformations are observed in the region below 1000 cm�1 andout of plane pyrazole ring deformation modes in the region below700 cm�1 [54]. For the title compound, the band observed at 1001was assigned to dCCC in plane bending this study.

Energies, dipole moments and molecular orbital energies

The sum of electronic and zero point energies, the dipole mo-ments, HOMO and LUMO and HOMO–LUMO gap energy values ofthe molecule at HF and B3LYP/6-311++G(d,p) level are given inTable S1 (Supp. Inf.). According to the theoretical results the mol-ecule is most stable at B3LYP/6-311++G(d,p) level. Dipole momentis a measure of the asymmetry in the molecular charge distributionand is given as a vector in three dimensions. The values of dipolemoment were also calculated and listed in Table S1. The dipole mo-ment obtained at HF/6-311++G(d,p) is the biggest one 6.3434 De-bye. Therefore, it can be used used as descriptor to depict thecharge movement across the molecule depends on the centers ofpositive and negative charges. Dipole moments are strictly deter-mined for neutral molecules. For charged systems, its value de-pends on the choice of origin and molecular orientation [55–59].HOMO–LUMO gap has been used as a criterion for kinetic stabilityand chemical reactivity because of the fact that adding electrons toLUMO with higher energy level and removing electron from HOMOwith lower energy is energetically more unfavorable. It is clear thatincrease in LUMO energy level and decrease in HOMO energy levelresults in higher HOMO–LUMO gap. Higher HOMO–LUMO gap cor-responds to higher kinetic stability so lower chemical reactivityHOMO–LUMO plot at B3LYP/6-311++G(d,p) level is given inFig. S3 (Supp. Inf.). As seen from the figure, the HOMO is locatedon ester group, amide group, NH2 and thiocarbonyl groupespecially over the ester group and thiocarbonyl group, the LUMOis more focused on benzene but there is less concentration on

Table 3Observed and calculated vibrational frequencies of compound 2 with 6-311++G(d,p).

Modes Exp. IR/IR int. Exp. Raman/R act. B3LYP HF Assignmentsa

m1 3466/88.1 3547 3577 tNH(100) in the NH2 assym.m2 3296/86.3 3404 3455 tNH(99) in the amidem3 3248/88.6 3314 3431 tNH(93) in the NH2 symm.m4 3081 3052 tCH(96)m5 3081 3046 tCH(74)m6 3080 3046 tCH(97)m7 3078 3043 tCH(92)m8 3069 3040 tCH(93)m9 3068 3035 tCH(89)m10 3064/89.7 3063/5.18 3067 3032 tCH(75)m11 3061 3028 tCH(62)m12 3061 3027 tCH(81)m13 3058 3022 tCH(93)m14 3052 3018 tCH(94)m15 3051 3017 tCH(97)m16 3047 3011 tCH(87)m17 3043 3007 tCH(92)m18 3041 3005 tCH(99)m19 3032/90.4 3029 2999 tCH(94) in the C-CH3

m20 2999/89.8 2995 2960 tCH(96) in the esterm21 2983/89.7 2981 2941 tCH(100) in the esterm22 2978 2929 tCH(97) in the C-CH3

m23 2956/89.7 2968 2929 tCH(96) in he esterm24 2929/89.6 2933/4.31 2935 2911 tCH(98) in the esterm25 2922 2886 tCH(91) in the C-CH3

m26 2918 2869 tCH(100) in the C-CH3

m27 1669/76.9 1670/29.72 1688 1784 tOC(73) in the amidem28 1650 1759 tOC(74)m29 1661/78.5 1633/66.33 1635 1713 tOC(72)m30 1607/72.5 1609/161.18 1580 1626 tCC(49) + dHCC(11)m31 1596/73.9 1597/152.242 1576 1622 tCC(37)m32 1574 1619 tCC(49) + dHCC(21)m33 1572 1617 dHNH(44) + tCC(15) + tNC(10)m34 1569 1607 tCC(48) + dCCC(12)m35 1556 1596 tCC(25)m36 1550/86.3 1545/47.25 1553 1594 tCC(40) + dCCC(10) in the pyrazolem37 1501/112.98 1506 1566 tCC(34)m38 1493/68.8 1496/99.83 1479 1545 dHNC(39)m39 1473 1517 tCC(25) + dHNH(22)m40 1469 1510 dHCC(37)m41 1462 1497 dHCH(79)m42 1460 1491 dHCC(21) + sHCOC(14)m43 1455/73.9 1456/77.04 1459 1491 dHCC(43)m44 1440 1467 dHCH(63) + sHCOC(14)m45 1436 1465 dHCH(60) + sHCCN(11)m46 1431 1462 dHCC(39)m47 1428 1457 dHCH(73) + sHCCO(17)m48 1421/77.2 1425/261.09 1420 1450 dHCC(48) + tCC(11)m49 1417 1443 dHCC(32)m50 1412 1442 dHCH(55) + sHCCN(10)m51 1410 1439 dCNN(17) + dCCN(15)m52 1393 1438 tNC(49) in the pyrazolem53 1369/84.6 1370/158.55 1372 1417 dHCH(30) + sHCOC(24)m54 1365 1399 dHCH(58)m55 1349 1379 dHCH(40)m56 1336 1376 dHCH(16) + sHCOC(14)m57 1324/69.2 1325/445.13 1333 1355 tNC(54) in the pyrazolem58 1308 1324 dHCC(67)m59 1301 1323 dHCC(75)m60 1298 1318 tCC(40) + dHCC(54)m61 1293 1313 tCC(28) + tNC(13)m62 1288 1299 dHCC(16) + tCC(14)m63 1283 1281 tCC(37) + dHCC(14)m64 1270 1269 tCC(33)m65 1263 1258 tCC(38)m66 1245/65.2 1249/363.63 1246 1208 dHCO(63) + sHCOC(16)m67 1217 1204 tCC(27) + tOC(23) + dOCO(11)m68 1202/73.4 1204/28.84 1206 1195 tNC(18) + tNN(14) + tCC(11) in the pyrazolem69 1187/74.1 1179 1191 tNN(26) + tCC(14) in the pyrazolem70 1163 1174 dHCC(48)m71 1152/65.7 1162/137.52 1154 1169 tNC(14) + dHNC(13)m72 1151 1163 dHCC(41)m73 1150 1163 dHCC(60) + tCC(15)m74 1142 1161 tNC(29) + tSC(11)

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Table 3 (continued)

Modes Exp. IR/IR int. Exp. Raman/R act. B3LYP HF Assignmentsa

m75 1139 1157 dHCC(62)m76 1137 1141 dHCC(62) + tCC(27)m77 1136 1118 dHCC(68)m78 1120/73.6 1122/45.49 1131 1106 sHCOC(49) + dHCO(32) + dHCH(10)m79 1107 1096 tOC(19) + dHNC(19)m80 1091 1086 sHCOC(39) + tCC(35) + dCCO(15) + dHCH(10)m81 1086 1082 tNC(12) + tCC(10)m82 1066/68.5 1066/55.13 1061 1061 tCC(39) + dHCC(38)m83 1060 1058 tCC(33)m84 1059 1057 dHCC(36) + tCC(11)m85 1033/76.0 1028/57.76 1040 1055 tNC(16)m86 1019 1045 tOC(23) + tCC(10)m87 1014 1041 sHCCN(51) + dHCH(12)m88 1011 1018 dHCC(10)m89 1006 1016 tCC(35) + dHCC(23) + dCCC(10)m90 1001/76.9 1002/330.32 1005 1013 tCC(20) + dCCC(12)m91 998 1013 sHCCN(36) + tCC(18) + tOC(11) + dHCH(10)m92 979/80.0 966/20.08 979 1012 tCC(28) + dCCC(51)m93 977 1010 tCC(23) + dCCC(10)m94 977 1009 dCCC(10)m95 977 1002 dCCC(20)m96 971 1000 sHCCC(72)m97 971 996 sHCCC(65)m98 967 995 sHCCN(74) + sCCCC(13)m99 957 982 sHCCC(66)m100 956 981 tCC(13) + dNNC(10)m101 956 980 sHCCC(63)m102 945/81.4 949 966 sHCCN(78)m103 926/81.8 928/60.39 930 958 tCC(47)m104 915 950 sHCCC(69)m105 911 941 sHCCC(15) + dOCC(10)m106 906 935 sHCCC(35) + sHCCN(11)m107 898 917 sHCCN(75) + cNCCC(10)m108 848/69.3 866/35.85 846 872 tOC(29) + sHCOC(19)m109 828 862 dOCN(15)m110 827 859 sHCCC(70)m111 824/159.43 825 852 sHCCC(60)m112 805/80.2 806/38.48 815 846 sHCCN(79)m113 798 822 cring + cCH + q pyrazole + d amidem114 783/78.8 784/63.02 785 813 sHCOC(60) + sHCCO(18)m115 775 807 dOCO(23)m116 770 790 cONCC(44)m117 768 789 cONCC(22)m118 754 781 sHCCN(28) + sCCCC(10)m119 763/73.1 760/63.90 749 777 sHCCN(19) + sHCCC(14)m120 733/74.2 724 739 sHNCC(78)m121 718/68.2 709/101.58 719 733 sHNCC(11)m122 711 726 sHNCC(57)m123 707 708 cONCC(17) + sHCCC(10)m124 697/63.3 697 696 qCH2 + qCH3

m125 685/65.5 684 693 sHCCC(18) + sCCCC(11)m126 682 683 dCH in the benzene + tCC amine-C@Om127 671/76.1 676 681 sCCCC(25)m127 673 676 sHCCC(51) + sCCCC(10)m129 656 666 dCCC(14)m130 646/76.4 649/75.29 648 660 sCNNC(36) + cSNCC(11)m131 619/76.7 628/55.13 627 651 cSNCC(35) + sCNNC(12)m132 619/76.7 628/55.13 618 625 dCH in the benzenem133 608 611 dCCC(27)m134 606 609 dCCC(57)m135 603 606 dCCC(64)m136 580/70.6 583/49.88 588 596 dCH3 + dCH2

m137 564/71.1 560 571 cNCCC(35)m138 544 554 dCH in the benzene + tCN in the pyrazolem139 524/73.3 523/57.76 528 537 dCCC(14)m140 500 511 dNCC(18) + cNCCC(10)m141 490/77.1 495/61.27 487 495 cNCCC(17)m142 471 478 dCH in the benzenem143 448 455 sCCCC(13)m144 435 439 dCCO(22) + dOCC(13)m145 422/55.13 414 414 tCC(31) + dOCC(22) + dCCO(10)m146 407/56.01 402 413 sCCCC(57)m147 400 409 sCCCC(41)m148 398 408 sCCCC(44) + sHCCC(10)m149 394 400 sCCCC(22)

(continued on next page)

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Table 3 (continued)

Modes Exp. IR/IR int. Exp. Raman/R act. B3LYP HF Assignmentsa

m150 390 397 dCCN(10)m151 385 388 dCCC(10)m152 375 382 sHNCC(37)m153 371/60.39 371 341 sHNCC(22)m154 34861.27 339 321 dCCC(23) + dCOC(18) + dOCC(11)m155 328/64.77 316 319 dSNC(15) + dNCC(10) + dCCO(10)m156 310 313 dOCN(24) + dNCC(18)m157 298 303 dNCC(17)m158 279 278 dCCC(18)m159 256/69.16 249 258 sHCCO(32) + sHCOC(22) + sCOCC(10)m160 244 247 sCCCC(11)m161 237/70.03 235 239 cCCNC(11)m162 229 232 tCC(11)m163 220 221 cCCNC(11)m164 207/75.29 209 209 dCCC(24)m165 197 200 dCCC(18) + dSCN(15)m166 171 176 tCH2 symm.m167 157 159 sCCCC(11)m168 149/92.82 144 147 sHCCN(16) + sOCCC(15)m169 136 138 sHCCN(21)m170 135 135 sCCNC(18)m171 127 128 tCH3 asymm.m172 120 120 sCCCC(25) + sHCCN(13) + sOCCC(13)m173 108 104 dCCC(17)m174 92 89 sCOCC(17) + dCCC(13)m175 85 86 sCCNC(13)m176 75 80 cCCNC(13) + sCOCC(11)m177 72 74 tCH asymm.m178 65 65 dCCN(13)m179 62 55 tCH asymm. in the benzenem180 51 50 tCH asymm. in the benzenem181 43 42 sOCCC(27) + sCCOC(18)m182 39 39 sCNCC(43)m183 38 36 sCCCC(23) + sCNCC(19)m184 33 34 sCCOC(14)m185 31 30 dCCN(22)m186 23 24 sCCCN(18) + sCCCC(12) + cNCCN(10)m187 20 18 sCCCN(36)m188 14 12 sNCCC(56)m189 10 9 sNCCC(54) + sCCCN(20)R2 0.9995 0.9977

t, stretching; d, in-plane bending; c, out-of-plane bending; s, torsion q, rocking.a Potential energy distribution (PED), less than 10% are not shown. In the assignments column, the meaning of the numbers between parenthesis is values of PED and the

meaning of R2 is correlation factors between calculated and experimental data.

826 _I. Koca et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 816–827

pyrazole group. The highest occupied molecular orbital (HOMO)energies, the lowest unoccupied molecular orbital (LUMO)energies, and the gap energy value of HOMO–LUMO for 2 werecalculated at HF and B3LYP/6-311++G(d,p) level of theory, andare shown in Table S1. As a result, at HF/6-311++G(d,p) level,HOMO–LUMO gap value is more higher than B3LYP/6-311++G(d,p) level. The HOMO–LUMO gap in the DFT calculationsis smaller than in the HF case. This is a consequence of systematicpositive energy shifts in the occupied moleclular orbbital (MOs)and negative energy shifts in the virtual ones, due to the natureof the HF and Kohn–Sham (KS) [60–62]. The energy gap HOMO–LUMO explains the eventual charge transfer interaction withinthe molecule, which influences the biological activity of themolecule.

Conclusions

In conclusion, we have synthesized and characterized a novelpyrazole-3-carboxamide derivative via one pot reaction. Elementalanalysis, IR, Raman, 1H NMR, 13C NMR and X-ray diffraction meth-ods were used for characterization. For the vibrational analysis of 2we have taken the experimental IR and Raman spectra. And then,we have calculated the geometric parameters, vibrational har-monic frequencies, the molecular orbital energies by using HFand DFT(B3LYP) methods with 6-311++G(d,p) basis set. Complete

vibrational assignments were performed according to the PED.Our detailed PED% analysis of the molecule showed a good agree-ment with the experimental data. The results of B3LYP method inevaluating the vibrational harmonic frequencies have shown betterfit to the experimental data. Any discrepancies noted between theobserved and calculated frequencies are due to the fact that thecalculations have been actually performed on single (or isolated)molecule in the gaseous state. Thus some reasonable deviationsfrom the experimental vales seem to be justified. Molecular geom-etries were reproduced within the limits of accuracy of X-ray data.The molecular geometry of 2 shows slightly more consistency withB3LYP level than those of HF. The HOMO and LUMO and gap ener-gies of the molecule were also given.

Acknowledgement

The authors are grateful to the Scientific Research Projects Of-fice of Bozok University for financial support and Medicinal Plants,Drugs and Scientific Research Center of Anadolu University (AUBI-BAM) for the use of the X-ray diffractometer.

Appendix A. Supplementary material

Supplementary data associated with this article can be found, inthe online version, at http://dx.doi.org/10.1016/j.saa.2013.09.068.

_I. Koca et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 816–827 827

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