Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

A novel one-pot synthesis of heterocyclic compound (4-benzoyl-

5-phenyl-2-(pyridin-2-yl)-3,3a-dihydropyrazolo[1,5-c]pyrimidin-7(6H)-
one): Structural (X-ray and DFT) and spectroscopic (FT-IR, NMR, UV-Vis
and Mass) characterization Studies
Mecit Özdemir a,⇑, Mehmet Sönmez b, Fatih Sß en c, Muharrem Dinçer d, Namık Özdemir d
a
Kilis 7 Aralık University, Arts and Sciences Faculty, Department of Chemistry, 79000 Kilis, Turkey
b
Gaziantep University, Arts and Sciences Faculty, Department of Chemistry, 27310 Gaziantep, Turkey
c
Kilis 7 Aralık University, Vocational High School of Health Services, Department of Opticianry, 79000 Kilis, Turkey
d
Ondokuz Mayıs University, Arts and Sciences Faculty, Department of Physics, 55139 Samsun, 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

 A novel pyrazole molecule was

synthesized.
 The compound was characterized by
IR–NMR and X-ray single crystal
diffraction.
 Structural parameters, vibrational
assignments and chemical shifts were
investigated by DFT calculations.
 It was calculated frontier orbital
energies and related molecular
properties.
 Non-linear optical properties of the
title compound have been calculated.

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the title compound named as 4-benzoyl-5-phenyl-2-(pyridin-2-yl)-3,3a-dihydropyrazol-

Received 20 April 2014 o[1,5-c]pyrimidin-7(6H)-one (C24H18N4O2) was both experimentally and theoretically investigated. The
Received in revised form 27 August 2014 compound was synthesized and characterized by FT-IR, NMR (1H NMR, 13C NMR and HETCOR-NMR),
Accepted 31 August 2014
Mass spectroscopies and single-crystal X-ray diffraction methods. The compound crystallizes in the
monoclinic space group P21/n with a = 6.1402 (3) Å, b = 21.4470 (15) Å, c = 15.0049 (8) Å and
b = 97.407 (4)°. The molecular geometry was obtained from the X-ray structure determination optimized
Keywords:
using density functional theory (DFT/B3LYP) method with the 6-31+G(d, p) basis set in ground state.
Pyrazole
Pyrimidine
From the optimized structure, geometric parameters, vibrational wavenumbers and chemical shifts of
One-pot synthesis molecule were obtained. Experimental measurements were compared with its corresponding the calcu-
X-ray diffraction lated data. An excellent harmony between the two data was ascertained. Besides, molecular electrostatic
Density functional theory (DFT) potential (MEP), frontier molecular orbitals (FMOs) and non-linear optical (NLO) properties of the title
molecule were investigated by theoretical calculations at the B3LYP/6-31+G(d, p) level.
Ó 2014 Elsevier B.V. All rights reserved.

⇑ Corresponding author.
E-mail address: ozdemirm46@gmail.com (M. Özdemir).

http://dx.doi.org/10.1016/j.saa.2014.08.131
1386-1425/Ó 2014 Elsevier B.V. All rights reserved.
 M. Özdemir et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314 1305

Introduction in a 100-mL two-necked flask fitted with a condenser was slowly

added a solution of 2.91 g (10 mmol) of N-aminopyrimidine in
In the recent years pyrazoles and pyrimidines have attracted 25 mL of absolute ethanol. This mixture was heated to reflux with
much interest due to their pharmacological and biological proper- stirring and under a nitrogen atmosphere for 18 h, after cooling the
ties. Pyrazole derivatives exhibit important biological properties solution, the resulting precipitate was filtered and washed with
such as antitumor [1], anticoagulant [2], anti-hyperglycemic, anal- diethyl ether and methanol dried under reduced pressure to afford
gesic, anti-inflammatory, anti-pyretic, antibacterial, hypoglycemic compound as a honey-yellow solid. Schematic representation of
and sedative-hypnotic activity [3–5]. In addition, these derivatives the synthesis route of the compound shown in Scheme 1. Its purity
have attracted significant attention because of the application in was checked with the TLC.Yield: 2.77 g (70%); M.p.: 254 °C. Anal.
drug development [6]. Similarly, pyrimidines have been used in Calcd. (%) For C24H18N4O2: C, 73.08; H, 4.60; N, 14.20. Found: C,
syntheses for many years due to their importance about structural 72.43; H, 4.59; N, 14.10.
diversities and medicinal properties such as antibacterial, anti-
fungal, antitumour, antimicrobial, antiviral activities [7–9]. This
General remarks
title compound synthesized via cycloaddition reaction method
can further be used as a chelator for metal ions owing to its donor
All of the precursor chemicals and solvents were purchased
atoms that two nitrogens and one oxygen (NNO) carries a lone pair
commercially available reagent grade from Merck, Aldrich or Fluke
of electrons. Those of characteristics make pyrimidine and pyrazole
and used without purification. They were 2-formylpyridine and
rings containing compounds upgrade remarkable heterocyclic
methanol, ethanol, chloroform, dichloromethane, n-hexane and
ligand. Eventually, a novel compound containing heterocycles such
ethyl acetate used as organic solvents. 1H-pyrimidine-2-one(N-
as pyrazole and pyrimidine have successfully been added to the
aminopyrimidine) was synthesized as described in the literature
literature.
[11].
Nowadays, theoretical and experimental comparison of mole-
To the characterization of the synthesized compound was based
cules has become popular. The success of a theoretical method is
on the analysis of 2-D HETCOR NMR techniques, NMR, ESI-MS,
related to compatible with experimental findings. The density
FT-IR, Elemental, Melting point and UV/Vis spectra. A HETCOR
functional theory (DFT) has been the shooting star in theoretical
calculations and it was used in numerous studies. DFT method cal-
culates a great variety of molecular properties such as molecular
structures, vibrational frequencies, chemical shifts, non-linear Table 1
optical effects, molecular electrostatic potential, frontier molecular Crystal data and structure refinement parameters for the title compound.
orbitals and thermodynamic properties.
CCDC deposition no. 995206
The title compound, 4-benzoyl-5-phenyl-2-(pyridin-2-yl)-3,3a- Chemical formula C24H18N4O2
dihydropyrazolo [1,5-c]pyrimidin-7(6H)-one (C24H18N4O2), was Formula weight 394.42
prepared by the reaction of N-aminopyrimidine with 2-acetylpyri- Temperature (K) 296
dine. This title compound has been elucidated both experimentally Wavelength (Å) 0.71073
Crystal system Monoclinic
and theoretically. In experimental studies, the molecule was char-
Space group P 21/n
acterized by FT-IR, 1H NMR, 13C NMR, HETCOR-NMR, UV–Vis, Mass Unit cell parameters
spectroscopies and single-crystal X-ray diffraction method. Addi- a – b – c (Å) 6.1402 (3), 21.4470 (15), 15.0049 (8)
tion, the molecular geometry, vibrational frequencies, 1H and 13C a = c – b (°) 90, 97.407 (4)
Volume (Å3) 1959.5 (2)
NMR chemical shift values, UV–Vis absorption frequencies of the
Z 4
title compound in the ground state have been calculated using Calculated density (Mg/m3) 1.337
the density functional method (DFT) (B3LYP) with 6-31+G(d, p) l (mm1) 0.09
basis set. The calculated geometric parameters, theoretical scaled F000 824
vibrational frequencies, chemical shifts and absorption frequencies Crystal size (mm) 0.560  0.297  0.100
hmin, hmax 7, 7
have been compared with their experimental data.
kmin, kmax 26, 23
lmin, lmax 18, 18
Experimental and theoretical methods Theta range for data collection (°) 26.0, 1.7
Measured reflections 20,046
Independent/observed reflections 3867
Synthesis and characterization of the compound Refinement method Full-matrix least-squares on F2
wR(F2) 0.096
The compound was synthesized according to a procedure chan- Goof = S 0.893
Rint 0.100
ged from that explained in the literature [10]. To a solution of
Dqmax, Dqmin (e/Å3) 0.14, 0.12
1.22 g (10 mmol) of 2-acetylpyridine in 25 mL of absolute ethanol

Scheme 1. Schematic representation of the synthesis route of the compound.

1306 M. Özdemir et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314

Scheme 2. The proposed mechanism for cycloaddition reaction over an intermediate Schiff base compound to obtain a novel heterocyclic compound.

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).
 M. Özdemir et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314 1307

collection was performed on a STOE IPDS II diffractometer by the

x scan technique using graphite-monochromatic Mo Ka, radiation
(k = 0.71073 Å) at 296 K. A total of 20,046 reflections with
[1.7° < h < 26°] were collected in the rotation mode and cell param-
eters were determined by using X-AREA software [12]. Absorption
correction (l = 0.09 mm1) was achieved by the integration
method via X-RED software [12]. The structure was solved by
direct methods using SHELXS-97 [13] implemented in the WinGX
[14]. All non-hydrogen atoms were refined anisotropically by the
full-matrix least squares procedure based on F2 using SHELXL-97
[15]. All H atoms were positioned geometrically and treated using
a riding model, fixing the bond lengths at 0.86, 0.93 and 0.97 Å for
NH, CH and CH2 atoms, respectively. The general purpose crystal-
lographic tool PLATON [16] was used for the structure analysis
and presentation of the results. Details of the data collection con-
ditions and the parameters of the refinement process are given in
Table 1.

Quantum chemical calculations

All the calculations were performed by using Gaussian 03 pack-

Fig. 2. A packing diagram for compound, showing the N1AH1  O1 interactions
(dashed lines).
age [17] and Gauss-View molecular visualization software [18] on
the personal computer without restricting any symmetry for the
title. For modeling, the initial guess of the compound was first
obtained from the X-ray coordinates and this structure was
optimized by density functional theory (DFT)/B3LYP method with
6-31+G(d, p) as basis set. From the optimized geometry of the
molecule, geometric parameters (bond lengths, bond angles, and
torsion angles), vibrational assignments, chemical shifts and
UV–Vis absorption frequencies of the title compound have been

spectrum of compound, 150 mg in 1.0 mL CDCl3, was obtained on a

Bruker 400 MHz ultrashield spectrometer equipped with a 5 mm
Table 3
PABBO BB-inverse gradient probe. The NMR spectra were recorded Some selected geometric parameters (Å, °).
on a Bruker 400 MHz spectrometer (Bruker Daltonics GmbH, Swit-
Geometric Experimental Calculated
zerland) using chloroform (CDCl3-d) as a solvent. IR spectra were
parameters [X-ray Diffraction] [B3LYP/6-31+G(d, p)]
recorded on a Perkin–Elmer FT-IR type 1650 spectrophotometer.
Bond lengths (Å)
Elemental analysis was recorded on a Perkin–Elmer 240B micro
C6AO1 1.226 (2) 1.220
analyzer. The absorbance was measured at Perkin Elmer LAMBDA C6AN1 1.378 (3) 1.408
850 UV/Vis. Melting points were measured on a RY-1 micro melt- C6AN2 1.349 (3) 1.367
ing point apparatus. The electron impact (ESI) mass spectra (70 eV) N2AN3 1.385 (2) 1.372
was obtained on a Perkin–Elmer system. All other chemical sup- C1AC2 1.506 (3) 1.516
C2AC3 1.512 (3) 1.539
plies were of analytical grade and purchased from conventional
C3AC4 1.504 (3) 1.515
commercial sources. C4AC5 1.348 (3) 1.366
C1AC7 1.460 (3) 1.468
C7AN4 1.333 (3) 1.346
Crystal structure determination N4AC11 1.329 (4) 1.338
C4AC12 1.471 (3) 1.482
A block of single crystal with dimensions 0.560 mm  C12AO2 1.225 (2) 1.234
0.297 mm  0.100 mm was mounted on goniometer and data C12AC13 1.495 (3) 1.499
C13AC14 1.376 (3) 1.404
C5AC19 1.476 (3) 1.486
C19AC20 1.385 (3) 1.403
C20AC21 1.381 (3) 1.395
Table 2
C21AC22 1.369 (4) 1.397
Hydrogen-bond geometry (Å, °).
Bond angles (°)
DAH  A DAH H  A D  A DAH  A N1AC6AN2 111.73 (18) 110.74
C2AH2A  O2 0.97 2.70 3.023 (3) 100 N2AN3AC1 106.85 (18) 107.53
C2AH2B  N4 0.97 2.71 2.825 (3) 87 C1AC2AC3 102.34 (16) 100.79
C8AH8  N3 0.93 2.67 2.917 (4) 96 C3AC4AC5 115.75 (18) 116.08
C14AH14  O2 0.93 2.61 2.843 (3) 95 C4AC12AO2 120.6 (2) 118.29
C24AH24  N1 0.93 2.83 3.012 (3) 92 C4AC12AC13 119.90 (18) 121.99
C3AH3  O1i 0.98 2.42 3.233 (3) 140 C7AN4AC11 117.4 (2) 117.90
C20AH20  O1ii 0.93 2.77 3.576 (3) 145 Torsion angles (°)
N1AH1  O1iii 0.86 2.08 2.907 (2) 161 N3AC1AC2AC3 10.1 (3) 14.69
C22AH22  Cg1iv 0.93 2.95 3.399 (3) 111 N2AC6AN1AC5 18.7 (3) 17.68
N2AC3AC4AC5 38.5 (3) 35.65
Symmetry codes: (i) x  1, y, z; (ii) x + 1, y, z + 2; (iii) x + 2, y, z + 2;
C2AC3AC4AC5 152.44 (19) 150.65
(iv) 1/2 + x, 1/2  y, 1/2 + z.
1308 M. Özdemir et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314

calculated theoretically. Besides, the molecular electrostatic phenyl rings with a distance of 3.399 (3) Å between the ring
potential (MEP), frontier molecular orbital (FMOs) and non-linear centroids. The crystal structure is stabilized by these intra-
optical (NLO) properties of the title compound were investigated molecular and intermolecular interactions.
by theoretical calculation results. The molecular geometry of title compound was also investi-
gated theoretically. The starting coordinates were those obtained
Results and discussion from the X-ray structure determination and were optimized by
energy minimization with the density functional theory (DFT)
The general reaction and mechanism of cycloaddition reaction for a method. The X-ray and theoretical structure is shown in Fig. 1.
novel heterocyclic compound Based on B3LYP/6-31+G(d, p) optimized geometry, the total energy
and entropy of the title compound has been calculated by this
The proposed mechanism for the formation of 4-benzoyl-5- method, which are 1294.911 a.u. and 169.171 cal/mol-K,
phenyl-2-(pyridin-2-yl)-3,3a-dihydropyrazolo[1,5-c]pyrimidin- respectively.
7(6H)-one is depicted in Scheme 2. Previously, Schiff base 1 ligand For intramolecular bonds in the compound, the calculated DAH,
occurred by the condensation reaction of N-aminopyrimidine and H  A, D  A and DAH  A values 1.097 Å, 2.97 Å, 3.027 Å and
2-acetylpyridine at first step. At second step, hydronium ion acts 82.43° for C2AH2A  O2; 1.088 Å, 2.812 Å, 2.91 Å and 84.19°
as the electrophile attacks to Schiff base 2 producing compound C2AH2B  N4; 1.084 Å, 2.579 Å, 2.882 Å and 94.91° for
3. At the last step, compound 3 goes through a rearrangement to C8AH8  N3; 1.085 Å, 2.522 Å, 2.82 Å and 94.38° for C14AH14  O2;
yield a novel heterocyclic compound 4 via cycloaddition reaction 1.086 Å, 2.783 Å, 2.95 Å and 87.91° for C24AH24  N1.
takes place to give new five-membered part of compound 4 called
as a pyrazole ring. Subsequently, depending on the reaction
conditions, hydrogen exchange produces compound 4 over a
Table 4
ring-closing reaction. Comparison of the observed and calculated some vibrational assignments of the title
compound.
Structural description of the compound Assignment Experimental IR calculated (cm1)
With KBr B3LYP/6-31
The title compound, 4-benzoyl-5-phenyl-2-(pyridin-2-yl)-3,3a- (cm1) +G(d, p)
dihydropyrazolo[1,5-c]pyrimidin-7(6H)-one, shown in Fig. 1. The
mNAHPyrimidine 3330 3418
compound crystallized in space group P 21/n. From the single crys- msCAHaromatic – 3021
tal X-ray Diffraction data [Supplementary material], the crystal msCAHaromatic – 3019
belongs to monoclinic system with the following cell dimensions: masCAHaromatic 3059 3008
a = 6.1402 (3) Å, b = 21.4470 (15) Å, c = 15.0049 (8) Å, b = 97.407 masCAHaromatic 3025 3004
(4), Z = 4. masCAHaromatic 2928 2996
masCAH2pyrazole – 2974
The molecular structure of compound is containing heterocy- masCAH2pyrazole – 2865
cles such as pyrazole and pyrimidine. For the pyrazole and pyrim- msCAHpyrimidine+pyrazole – 2788
idine rings, bond lengths and bond angles are 1.506 (3) Å, 1.512 mC@Opyrimidine 1737 1686
(3) Å, 102.34 (16)° and 1.378 (3) Å, 1.349 (3) Å, 111.73 (18)° for mC@Obenzoyl 1693 1578
mC@Npyrazole + mC@Cpyrazole 1611 1529
C1AC2AC3 and N1AC6AN2, respectively.
aCAH2pyrazole 1403 1388
The dihedral angles between the pyrazole plane A (N2/N3/C1- cCAHpyrimidine+pyrazole 1266 1261
C3) and the pyrimidine plane B (N1/N2/C3AC6) are 24(12)° (A/B). xCAH2pyrazole + cCAHpyrimidine+pyrazole 1172 1186
Also, these rings are planar with a maximum deviation of 0.067 dCAH2pyrazole 1075 1075
and 0.175 Å. Vibrational modes: m, stretching; a, scissoring; c, rocking; x, wagging; d, twisting.
Perspective view of the crystal packing in the unit cell is shown Abbreviations: s, symmetric; as, asymmetric.
in Fig. 2. In the crystal structure, many intramolecular and
intermolecular interactions are observed. The geometry of these
interactions are listed in Table 2. Moreover, there is a CAH  p
stacking interactions between the atom C22 and (C13AC18)

Fig. 3. Atom-by-atom superimposition of the structures calculated (red) [B3LYP/6-

31+G(d, p)] over the X-ray structure (black) for the title compound. Hydrogen
atoms omitted for clarity. (For interpretation of the references to color in this figure Fig. 4. Simulated [at B3LYP/6-31+G(d, p) level] and experimental FT-IR spectra of
legend, the reader is referred to the web version of this article.) the title compound.
 M. Özdemir et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314 1309

Fig. 5. (a) 1H NMR spectrum, (b) pyridine (8.57–7.73 ppm) and aromatic group protons (7.05–7.55 ppm) regions and (c) 13
C NMR spectrum.
1310 M. Özdemir et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314
Fig. 5 (continued)
The X-ray and a theoretical geometry of the compound were
compared with the two methods. At the first step, it was calculated
correlation values for geometric parameters. Some selected geo-
metrical parameters experimentally obtained and theoretically
calculated are listed in Table 3. Comparing calculational and the
experimental data, we studied the relativity between the calcula-
tion and the experiments, and obtained that the linear function for-
mula is y = 1.0175x  0.0115 for bond lengths; where R2 is 0.9848;
y = 1.0501x  5.8665 for bond angles; where R2 is 0.9602;
y = 0.9774x + 0.9759 for torsion angles; where R2 is 0.9979.
At the second step, a global comparison was performed by
superimposing the molecular skeletons obtained from X-ray dif-
fraction and the theoretical calculations atom by atom (Fig. 3),
obtaining RMSE value of 0.317 Å for B3LYP/6-31+G(d, p).
For both methods, the calculated structure is in agreement with
X-ray structure. However, 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 mol-
ecules together, which result in the differences of bond parameters
between the calculated and experimental values [19].
Spectroscopic characterization
Vibrational spectra
The Fourier Transform Infrared Spectrum (FT-IR) of compound
was recorded employing a ‘‘Perkin–Elmer FT-IR type 1650 spec-
trophotometer’’ using 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 compound was also studied theoret-
ically. The theoretical harmonic frequencies have been calculated
with density functional theory (DFT/B3LYP) method 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 fac-
tor which is 0.9393 for B3LYP/6-31+G(d, p) is applied to all of
the calculated frequencies. Some observed and calculated vibra-
tional assignments are given in Table 4. Experimental and scaled
theoretical FT-IR spectra of the title compound are shown in
Fig. 4.
The NAH aromatic stretching vibrations were occured at 3300–
3500 cm1 [20]. In previous study, NAH stretching vibration was
founded at 3259 cm1[21]. In here, the NAH stretching vibration
is observed at 3330 cm1 as a very strong band in FT-IR spectrum
and its corresponding calculated frequency is 3481 cm1 B3LYP/6-
31+G(d, p) respectively.
The aromatic structure shows the presence of CAH stretching
vibrations in the range 3000–3100 cm1, which is the characteris-
tic region for mCAH stretching [22]. In our present work, the CAH
asymmetric stretching vibrations are observed at 3059, 3025 and
2928 cm1 in FT-IR spectrum and there is no peaks observed in
FT-IR spectrum for CAH symmetric stretching vibrations.
The IR spectrum of compound showed significant characteristic
stretching bands corresponding to the carbonyl groups mC@O of
benzoyl and pyrimidine structure. These bands observed at 1737
and 1693 cm1, also calculated at 1686 and 1578 cm1,
respectively.
In the pyrazole ring, the C@N and C@C stretching bands were
recorded at 1611 cm1 experimentally. These bands were deter-
mined at 1585 cm1 in the literature [23] and calculated at
1529 cm1 using B3LYP/6-31+G(d, p) methods. Also, the pyrazole
ring have scissoring CAH2 and twisting CAH2 vibrational modes
at 1403 and 1075 cm1 in FT-IR spectrum.
 M. Özdemir et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314 1311

Table 5 To make comparison with experimental observations, we calcu-

13
Experimental and theoretical C and 1H isotropic chemical shifts (ppm) for the title lated correlation values based on the calculations; giving correla-
compound.
tion value (R2) is 0.9924 B3LYP/6-31+G(d, p) level. This value is
Atom Experimental Calculated (ppm) an acceptable correlation between the theoretical and experimen-
(ppm) (CDCl3) DFT/B3LYP/6-31+G(d, p) tal chemical shift values.
C1 150 158.8
The HETCOR NMR spectra of title compound were also investi-
C2 39 40.8 gated. HETCOR experiments, all carried out on a 9.4 T magnet
C3 59 64.3 (400 MHz). Assignments of protonated carbons were made by
C4 110 112.5 two 2D-13C–1H HETCOR experiment using delay values which cor-
C5 146 144.7
responds to J(C, H) [24]. The HETCOR spectra of the title compound
C6 160 143.5
C7 147 149.3 is shown in Fig. 6. From HETCOR data pyrazole hydrogens(H2)/car-
C8 138 118.6 bon(C2) and pyrimidine hydrogen(H3)/carbon(C3) at 2.9–3.8/39
C9 136 133 (dH/dC) and 5.2/58 (dH/dC) were assigned, respectively. The signals
C10 133 120.8
from aromatic ring moiety were observed such 7.0–7.6/125–135
C11 148 146.7
C12 194 189.8
(dH/dC). Further, the signals from pyridine ring hydrogens were
C13 122.2 137.5 also seen 8.6/150, 8.1/121 and 7.9/137 (dH/dC), accordingly.
C14 125.6 126.1
C15 123.4 123.9 Mass spectra
C16 124.7 127.9
The mass spectrum of the synthesized compound was pre-
C17 125.3 124.1
C18 127.5 128 sented in Fig. 7. Fragment at m/z = 395.1 (base peak) was attributed
C19 128.9 133.2 to molecular ion peak [C24H18N4O2 + H]+. The another peak
C20 129.6 127.3 appeared in the mass spectra at m/z = 416.6 was attributed to addi-
C21 130.6 125.4
tion of a sodium cation and denoted [C24H18N4O2+Na]+. In addition,
C22 131.3 126.8
C23 132.4 126
another fragment at m/z = 388.9 was found a part of molecular ion
C24 133.8 124.3 peak [C24H18N4O2ACH3]+. In addition, such as m/z peaks 199 and
H1 5.3 6.54 157 respectively were ascertained [25].
H2A 4.04 2.87
H2B 4.04 4
UV–Vis spectra
H3 3.10 5.46
H8 8.24 8.7 The experimental and theoretical UV–Vis spectra of the com-
H9 7.73 8.04 pound in methanol was shown in Fig. 8. The electronic spectrum
H10 7.50 7.56 displayed two major bands at 238 nm (emax = 49,560 L mol1 cm1)
H11 8.58 8.83 and 309 nm (emax = 54,758 L mol1 cm1). The first band of free
H14 7.05 8.22
H15 7.10 7.61
ligand at higher energy in methanol solution was due to p–p⁄ tran-
H16 7.13 7.58 sition associated with aromatic ring. The second band at lower
H17 7.18 7.31 energy was attributed to n–p⁄ and p–p⁄ transitions related to car-
H18 7.21 7.51 bonyl groups and azomethine chromophore [26].
H20 7.25 7.34
H21 7.26 7.11
H22 7.28 7.53 Quantum-chemical studies
H23 7.30 7.62
H24 7.33 7.79 Molecular electrostatic potential (MEP)
The molecular electrostatic potential (MEP) was investigated by
theoretical calculations at the B3LYP/6-31+G(d, p) level. Molecular
electrostatic potential is related to the electronic density and is a
NMR spectra very useful descriptor in understanding sites for electrophilic
1
H NMR and 13C NMR spectra were obtained in CDCl3 was attack and nucleophilic reactions as well as hydrogen bonding
obtained using a Bruker Avance 400 MHz Spectrometer. The chem- interactions [27–29]. The negative (red1 color) regions of MEP were
ical shift (d) values of the different types of protons in the exam- related to electrophilic reactivity and the positive (blue color) ones
ined compound were reported in Fig. 5. In addition, theoretical to nucleophilic reactivity shown in Fig. 9. As can be seen in from
1
H and 13C NMR chemical shift values of the compound have been the figure, there are two possible sites on the title compound for
calculated on optimized geometry. The results of this calculation electrophilic attack. The negative regions are mainly localized on
are listed in Table 5 together with the experimental values. the O1 and O2 atoms. So, Fig. 9 confirms the existence of intramolec-
We have calculated 1H chemical shift values (with respect to ular and intermolecular interactions observed in the solid state.
TMS) of 2.87–8.83 ppm at the B3LYP/6-31+G(d, p) level, however,
the experimental results were observed to be 3.1–8.58 ppm. In HOMO and LUMO analysis
the pyrimidine ring, the ANAH signal was recorded at 5.3 ppm The distributions and energy levels of the HOMO and LUMO
experimentally. These signal were calculated at 6.54 ppm using orbitals computed at the B3LYP/6-31+G(d, p) level for the title
B3LYP/6-31G+(d, p) methods. The CAH signals of phenyl group compound shown in Fig. 10. The calculations indicate that the title
are deshielded at 7.05–8.58 ppm. The ACAH hydrogen of the pyr- compound has 103 occupied molecular orbitals and the value of
azole ring appears at 3.1 ppm, and is determined computationally the energy separation between the HOMO and LUMO is 3.92 eV
at 5.46 ppm. for at the same level, respectively.
13
C NMR spectral data of the titled compound exhibited charac- The HOMO and LUMO energies, the energy gap (DE), the ioniza-
teristic signal with respect to pyrimidine (C6) at the 160 ppm for tion potential (I), the electron affinity (A), the absolute electroneg-
pyrimidine ring. This signal has been calculated at 143.5 ppm for
B3LYP/6-31+G(d, p). Furthermore, the atoms C1, C2 and C3 of sig-
nals were observed 150, 39 and 39 ppm for pyrimidine ring and 1
For interpretation of color in Fig. 9, the reader is referred to the web version of
also these signals were calculated 158.8, 40.8 and 64.3 ppm. this article.
1312 M. Özdemir et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314

Fig. 6. (a) Heteronuclear chemical shift correlation (HETCOR) spectrum of titled compound and (b) HETCOR spectrum for the aromatic region of compound.

Fig. 7. ESI-mass spectra of the title compound.

 M. Özdemir et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314
Fig. 8. Experimental and theoretical UV–Vis spectra of the title compound.
Fig. 9. Molecular electrostatic potential (MEP) map in gas phase of compound (a.u.).
ativity (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. By using HOMO and LUMO energy values for a molecule,
Fig. 10. The molecular orbitals and energies for the HOMO and LUMO of the title compound.
1313
Table 6
The calculated frontier orbital energies, electronegativity, hardness and softness of
compound using B3LYP/6-31+G(d, p) level.
Parameters (eV) B3LYP/6-31+G(d, p)
EHOMO 6.71
ELUMO 2.25
I 6.71
A 2.25
v 4.48
g 2.23
S 0.22
electronegativity and chemical hardness can be calculated as
follows:
v ¼ ðI þ AÞ=2 ðelectronegativityÞ;
g ¼ ðI  AÞ=2 ðchemical hardnessÞ;
S ¼ 1=2g ðchemical softnessÞ;
where I and A are ionization potential and electron affinity;
I = EHOMO and A = ELUMO, respectively [30].
Non-linear optical 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 [31], and DFT has been exten-
sively used as an effective method to investigate the organic NLO
materials [32]. In previous studies, the non-linear effects of some
organic molecules were theoretically examined [33–38]. In here,
the linear polarizability (atot) and first-order hyperpolarizability
(btot ) of the title compound were calculated at the B3LYP/6-
31G+(d, p) level. The calculated values of atot and btot are
4.89  1023 esu and 1.59  1029 esu. Urea is one of the prototyp-
ical 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
4.9  1024 esu and 5.14  1031 esu obtained by B3LYP/6-
31G+(d, p) method. Theoretically, the first-order hyperpolarizabil-
ity of the title compound is of 30.9 times magnitude of urea.
According to these results, the title compound is a good candidate
of NLO material.
1314 M. Özdemir et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 1304–1314
Conclusions
In summary, a novel N-heterocyclic compound (4-benzoyl-5-
phenyl-2-(pyridin-2-yl)-3,3a-dihydropyrazolo[1,5-c]pyrimidin-
7(6H)-one) prepared from 2-acetylpyridine and N-aminopyrimidine
with condensation reaction in ethanolic solution at acidic
conditions has successfully been elucidated. Both experimental
techniques and theoretical methods were used to determine the
structural and spectroscopic properties of compound. Also, molec-
ular electrostatic potential, frontier molecular orbitals (HOMO and
LUMO) and non-linear optical properties of compound were inves-
tigated by theoretical results. Molecular electrostatic potential
map confirms the existence of intramolecular and intermolecular
interactions. The predicted nonlinear optical (NLO) properties of
the complex are much greater than those of urea. The compound
is a good candidate as second-order nonlinear optical material,
N-heterocyclic ligand for transition metal ion chelation and useful
precursor compound for drug discovery.
Appendix A. Supplementary material
CCDC 995206 contains supplementary crystallographic data
(excluding structure factors) for the structure reported in this arti-
cle. These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/data_request/cif, by e-mailing data_re-
quest@ccdc.cam.ac.uk or by contacting The Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK;
fax: +44 1223336033. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/
10.1016/j.saa.2014.08.131.
References
[1] F. Wei, B.-X. Zhao, B. Huang, L. Zhang, C.-H. Sun, W.-L. Dong, D.-S. Shin, J.-Y.
Miao, Bioorg. Med. Chem. Lett. 16 (2006) 6342.
[2] Y. Xia, Z.-W. Dong, B.-X. Zhao, X. Ge, N. Meng, D.-S. Shin, J.-Y. Miao, Bioorg.
Med. Chem. 15 (2007) 6893.
[3] B. Cottineau, P. Toto, C. Marot, A. Pipaud, J. Chenault, Bioorg. Med. Chem. Lett.
12 (2002) 2105.
[4] K.Y. Lee, J.M. Kim, J.N. Kim, Tetrahedron Lett. 44 (2003) 6737.
[5] Z.J. Jia, Y. Wu, W. Huang, P. Zhang, Y. Song, J. Woolfrey, U. Sinha, A.E. Arfsten,
S.T. Edwards, A. Hutchaleelaha, S.J. Hollennbach, J.L. Lambing, R.M.
Scarborough, B.-Y. Zhu, Bioorg. Med. Chem. Lett. 14 (2004) 1229.
[6] M.P. Donohue, D.A. Marchuk, H.A. Rockman, J. Am. Coll. Cardiol. 48 (2006)
1289.
[7] C.C. Cheng, Prog. Med. Chem. (1969) 67.
[8] R.P. Tripatri, A.R. Khan, B.S. Setty, A.P. Bhaduri, Acta Pharm. 46 (1996) 169.
[9] R.S. Varma, Green Chem. 1 (1999) 43–55.
[10] G. Ceyhan, M. Köse, M. Tumer, I. Demirtas, A.S. Yaglioglu, V. McKee, J. Lumin.
143 (2013) 623–634.
[11] Y. Akcamur, B. Altural, E. Saripinar, G. Kollenz, Monatsh. Chem. 120 (1989)
1015–1020.
[12] Stoe & Cie X-AREA (Version 1.18) X-RED32 (Version 1.04) Stoe & Cie,
Darmstadt, Germany, 2002.
[13] G.M. Sheldrick, SHELXS-97; Program for the Solution of Crystal Structures,
University of Gottingen, Germany, 1997.
[14] L.J. Farrugia, J. Appl. Crystallogr. 30 (1999) 837–838.
[15] G.M. Sheldrick, SHELXL-97; Program for Crystal Structures Refinement,
University of Gottingen, 1997.
[16] A.L. Spek, Acta Crystallogr., Sect. D: Biol. Crystallogr. 65 (2009) 148–155.
[17] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox,
H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E.
Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y.
Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S.
Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J.
Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L.
Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M.
Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A.
Pople, Gaussian 03, Revision E.01, Gaussian, Inc., Wallingford, CT, 2004.
[18] R. Dennington II, T. Keith, J. Millam, Gauss View, Version 4.1.2, Semichem Inc.,
Shawnee Mission, KS, 2007.
[19] F.F. Jian, P.S. Zhao, Z.S. Bai, L. Zhang, Struct. Chem. 16 (2005) 635.
[20] L.J. Bellamy, The Infrared Spectra of Complex Molecules, vol. 2, Chapman and
Hall, London, 1980.
[21] F. Sen, M. Dinçer, A. Çukurovalı, I. Yılmaz, J. Mol. Struct. 1046 (2013) 1–8.
[22] N.P.G. Roeges, A Guide to Complete Interpretation of Infrared Spectra of
Organic Structures, Wiley, New York, 1994.
[23] E. Inkaya, M. Dinçer, E. Korkusuz, I. Yıldırım, O. Büyükgüngör, J. Mol. Struct.
1027 (2012) 133–139.
[24] S. Braun, H.O. Kalinowski, S. Berger, 150 and More Basic Experiments, Wiley-
VCH, Weinheim, 1998.
[25] N. Raman, S. Sobha, M. Selvaganapathy, R. Mahalakshmi, Spectrochim. Acta,
Part A 96 (2012) 698–708.
[26] A. Bo1ttcher, T. Takeuchi, K.I. Hardcastle, T.J. Meade, H.B. Gray, Inorg. Chem. 36
(1997) 2498–2504.
[27] E. Scrocco, J. Tomasi, Adv. Quantum Chem. 11 (1978) 115–121.
[28] F.J. Luque, J.M. Lopez, M. Orozco, Theor. Chem. Acc. 103 (2000) 343–345.
[29] N. Okulik, A.H. Jubert, Internet electron, J. Mol. Des. 4 (2005) 17–30.
[30] R.G. Pearson, Proc. Natl. Acad. Sci. 83 (1986) 8440–8841.
[31] G.A. Babu, P. Ramasamy, Curr. Appl. Phys. 10 (2010) 214–220.
[32] Y.-X. Sun, Q.-L. Hao, Z.-X. Yu, W.-X. Wei, L.-D. Lu, X. Wang, Mol. Phys. 107
(2009) 223–235.
[33] E. Inkaya, M. Dinçer, Ö. Ekici, A. Cukurovali, J. Mol. Struct. 1026 (2012) 117–
126.
[34] E. Inkaya, M. Dinçer, E. Sßahan, I. Yıldırım, O. Büyükgüngör, J. Mol. Struct. 1030
(2012) 1–9.
[35] E. Inkaya, M. Dinçer, Ö. Ekici, A. Cukurovali, Spectrochim. Acta A 101 (2013)
218–227.
[36] E. Inkaya, S. Günnaz, N. Özdemir, O. Dayan, M. Dinçer, B. Çetinkaya,
Spectrochim. Acta A 103 (2013) 255–263.
[37] F. Sßen, B.G. Durdu, M. Oduncuoğlu, K. Efil, M. Dinçer, Am. J. Opt. Photonics 2 (1)
(2014) 7–11.
[38] M. Türkyılmaz, N. Özdemir, Y. Baran, Spectrochim. Acta A 82 (2011) 360–367.