Synthesis, structural, spectral (FT-IR, 1H and 13C NMR and UV-Vis), NBO and first order hyperpolarizability analysis of N-(4-nitrophenyl)-2, 2-dibenzoylacetamide by density functional theory

Article abstract of DOI:10.1016/j.molstruc.2015.06.036

The title compound, C₂₂H₁₆N₂O₅, was synthesized and characterized by experimental techniques (FT-IR, ¹H NMR, ¹³C NMR, UV-Vis and X-Ray single crystal determination) and theoretical calculations. The molecular geometry, vibrational frequencies, molecular electrostatic potential (MEP), thermodynamic properties, the dipole moments, HOMO-LUMO energy has been calculated by using the Density Functional Theory (DFT) method with 6-311G(d,p) and 6-311++G(d,p) basis sets. ¹H and ¹³C NMR chemical shifts show good agreement with experimental values. According to calculated results, the 6-311G(d,p) and 6-311++G(d,p) basis sets have showed similar results. The optimized geometry can well reproduce the crystal structure parameters.

Full text of DOI:10.1016/j.molstruc.2015.06.036

Accepted Manuscript
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Synthesis, structural, spectral (FT-IR, H and C-NMR and UV-Vis), NBO and first
order hyperpolarizability analysis of N-(4-nitrophenyl)-2, 2-dibenzoylacetamide by
density functional theory
Şerife Pınar Yalçın, Ümit Ceylan, Ahmet Oral Sarıoğlu, Mehmet Sönmez, Muhittin
Aygün
PII:
S0022-2860(15)30061-2
10.1016/j.molstruc.2015.06.036
MOLSTR 21588
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 13 April 2015
Revised Date: 10 June 2015
Accepted Date: 11 June 2015
Please cite this article as: Ş.P. Yalçın, Ü. Ceylan, A.O. Sarıoğlu, M. Sönmez, M. Aygün, Synthesis,
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structural, spectral (FT-IR, H and C-NMR and UV-Vis), NBO and first order hyperpolarizability
analysis of N-(4-nitrophenyl)-2, 2-dibenzoylacetamide by density functional theory, Journal of Molecular
Structure (2015), doi: 10.1016/j.molstruc.2015.06.036.
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ACCEPTED MANUSCRIPT

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Synthesis, structural, spectral (FT-IR, 1H and 13C-NMR and UV-Vis), NBO and first
order hyperpolarizability analysis of N-(4-nitrophenyl)-2, 2-dibenzoylacetamide by
density functional theory
a
b
c
ꢀ
Şerife Pınar Yalçın , Ümit Ceylan , Ahmet Oral Sarıoğlu ,
Mehmet Sönmezc, MuhittinAygünd
aCentral Laboratory, Osmanbey Campus, Harran University, 63190 Şanlıurfa, TURKEY
bDepartment of Medical Services and Techniques, Vocational High School of Health Services, Giresun
University, 28100Giresun, TURKEY
cDepartment of Chemistry, Faculty of arts and Sciences, Gaziantep University, 27310, Gaziantep, TURKEY
dDepartment of Physics, Faculty of arts and Sciences, DokuzEylül University,Buca,35150, Izmir, TURKEY
Abstract
The title compound, C22H16N2O5, was synthesized and characterized by experimental
techniques (FT-IR, 1H-NMR, 13C-NMR, UV-Vis and X-Ray single crystal determination) and
theoretical calculations. The molecular geometry, vibrational frequencies, molecular
electrostatic potential (MEP), thermodynamic properties, the dipole moments, HOMO-LUMO
energy has been calculated by using the Density Functional Theory (DFT) method with 6-
311G(d,p) and 6-311++G(d,p) basis sets. 1H and 13C-NMR chemical shifts show good
agreement with experimental values. According to calculated results, the 6-311G(d,p) and 6-
311++G(d,p) basis sets have showed similar results. The optimized geometry can well
reproduce the crystal structure parameters.
Keywords: X-ray diffraction; Density functional theory; Quantum chemical calculations;
Carboxamide; Characterization.
ꢀCorresponding author Tel.: +90 505 313 51 57
E-mail: umit.ceylan@giresun.edu.tr (Ü. Ceylan); msonmez@gantep.edu.tr, (M. Sönmez)

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Introduction
The synthesis, study of structure and properties of amide compounds has been an
important research topic during the last several decades [1]. Pyridine carboxamide compounds
containing common carboxamide [-C(O)NH-] group in the main structure of proteins are
important for construction of metal complexes [2]. These compounds are widely used in the
many fields of science such as industrial, pharmacological and biological studies [3-4]. The
literature concerning the dibenzoyl acetic acid compounds with nitrophenyl amide is rich and
the papers published cover such subjects as synthesize [5], NMR and vibrational
characteristics [6,7].
Many important physicochemical properties of biological and chemical systems,
investigation of structural properties and theoretical modeling of drug functional material can
be predicted by various computational techniques [8,9]. The density functional theory (DFT)
and Becke’s three-parameter hybrid functional (B3LYP) has been used to determined of
molecular structure and vibrational spectra because of its accuracy and consistency with
experimental data [10-15].
In this study, the title compound was synthesized as different from the litarature [5], and
determined of the molecular geometry, vibrational spectra and assignments, electronic
absorption spectra, molecular electrostatic potential, thermodynamic properties. This structure
1
was compared with experimental by H-NMR, 13C-NMR, FT-IR and UV-Vis spectral
methods. In addition, molecular electrostatic potential (MEP), molecular orbital (MO)
andnatural bond orbital (NBO) analysis of the title compound were performed by the
B3LYP/6-311++G (d,p) level.
Experimental and Computational Methods
Materials and Methods
All the chemicals were obtained from commercial suppliers (Sigma-Aldrich, Merck) and
used without any further purification. Elemental analysis (C, H, N, S) was recorded on a
Thermo Scientific Flash 2000 elemental analyzer. FT-IR spectra were recorded on a Perkin–
Elmer FT-IR type 1650 spectrophotometer. Electronic absorption spectra were recorded in
DMF from 1100 to 190 nm range on a PG Instruments T80+UV/Vis spectrometer in ethanol
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and methanol. H-NMR and 13C-NMR spectra were recorded at 25 C using an Agilent-

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VNMRS-400 spectrometer operating at 400 MHz and 100 MHz respectively. Melting points
were measured on a RY-1 micro melting point apparatus.
Synthesis of the N-carboxamide Ligand (H2L):
A mixture of dibenzoyl acetic acid-N-carboxy alkyl amide [8] (339 mg, 1 mmol) and 4-
°
nitroaniline (135 mg, 1 mmol) was stirred at 100 C for further 3 h in toluene (20 mL). The
toluene was removed under vacuum. 50 mL of dry diethyl ether was added to the residue. The
solid was filtered, washed with diethyl ether and recrystallized from a mixture of n-
BuOH/THF. Anal.Calc. for C22H16N2O5: C, 68.04; H, 4.15; N, 7.21. Found: C, 67.81; H, 4.39;
N, 7.17. LC-MS/MS (m/z): 389.1 [M+H]+.
Crystal structure determination
The data of the title single crystal was collected via a Agilent Diffraction Xcalibur [16]
diffractometer by the ω-scanning technique using graphite-monochromatic MoKα radiation
(λ=0.71073 Å). The intensity symmetries indicate the monoclinic P121/c1 space group with a
= 10.023 (2) Å, b = 21.587 (5) Å, c= 9.401 (2) Å and β = 110.29 (3)°, and Z = 4 in the unit
cell. Intensity data were collected in the θ range 5.96-52.72° at 296 K. The structure was
solved by direct methods using SHELXS-97 [17] implement in WINGX [18] program suite.
The program ORTEP-3 for Windows [19] was used in the preparation of the molecular
graphics. The refinement was carried out by full-matrix least-squares method on the positional
and anisotropic temperature parameters of the non-hydrogen atoms using SHELXL-97
[20].All H atoms were positioned geometrically and treated using a riding model, fixing the
bond lengths at 0.86 and 0.93 Å for NH and CH atoms, respectively. The crystal structure was
refined to R=0.097 by the condition of the I>2σ(I) threshold. The crystal data, some details
data collection conditions and parameters of the refinement process are listed in Table 1,
whereas selected bond lengths, bond angles, and torsion angles are shown in Table 2. Full
crystallographic data are available as supplementary material.
(Table 1)
Computational details
All theoretical calculations were conducted using Density Functional Theory (DFT)
[21,22] as implemented in the Gaussian 03Wquantum chemistry programs [23,24]. Geometry

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optimization was performed to obtain the stable conformers. Initial calculations were
performed using the restricted B3LYP exchange and correlation functional and the 6-
311G(d,p) and 6-311++G(d,p) [25,26] basis sets for all atoms. Default SCF and geometry
convergence criteria were used and no symmetry constraints were imposed [27], harmonic
frequency analysis based on analytical second derivates was used to characterize the
optimized geometry as global minimum on the potential energy surface of the title molecule
[28].
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Geometry optimization of the molecule, molecular energy, H-NMR, C-NMR and FT-
IR spectrum, UV-Vis spectrum, Mulliken charges and dipole moments were calculated by
using the same method [29-33]. The obtained frequencies were scaled by 0.984 and 0.979 for
6-311G(d,p) and 6-311++G(d,p), respectively [34]. GIAO (Gauge-Independent Atomic
Orbital) method was used to determine NMR chemical shift values [35,36]. The obtained
NMR frequencies were scaled by 31.99 ppm and 31.97 ppm for H atom and 184.79 ppm and
184.66 ppm for C atom in 6-311G(d,p) and 6-311++G(d,p), respectively [37].
Results and discussion
N-(4-nitrophenyl)-2, 2-dibenzoylacetamide (NPDBA) is description in Scheme S1
(supplementary materials). The title compound was prepared by the reaction of dibenzoyl
acetic acid-N-carboxy ethyl amide and 4-nitroaniline and obtained in 65 % yield as colorless
solid. The experimental data was obtained and compared with calculated values. The
observed and calculated values of the title compound were found to be in well-agreement with
each other.
Crystal structure description of the compound
The molecular structure and Ortep-3 view of the title compound, C22H16N2O5, is given in
Figure 1a and b. According to crystallographic data for the title compound (Table 1), the title
compound belongs to monoclinic crystal system with space group P121/c1 which have the
following dimensions; a=10.023 (2) Å, b=21.587 (5) Å, c=9.401 (2) Å and β =110.29 (3)°.
The molecular structure of the compound is not planar with a dihedral angle N1—C7—C8—
C16 of -148.1 (3) Å and N1—C7—C8—C9 of 90.9 (4) Å. The N1—C1 and N1—C7 distance
has been observed as 1.409 (4) Å and 1.339 (4) Å. Selected optimized and experimental
geometries parameters of the title compound in ground state was given in Table 2.

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The crystal packing of the title compound is shown in Figure 2. In the crystal structure,
molecules are linked together by intermolecular N—H···O and intramolecular C—H···O
interactions with symmetry code (i) 2-x, -y, -z; (ii) x, 1/2-y, 1/2+z. This hydrogen bond
generates an intramolecular S(6) ring motif through C—H···O. Details of these bonds and
interactions are given in Table 3.
Optimized geometries
The optimized structure parameters of the title compound were calculated by DFT–
B3LYP levels with the 6-311G(d,p) and 6-311++G(d,p) basis sets. The selected bond lengths,
bond angles and torsion angles were compared with the experimental data of the title
compound (Table 3). X-ray crystallographic data and molecular calculations of the title
compound have not been reported to best of our knowledge. All calculated geometrical
parameters are in good agreement with the experimental structural parameters.
In benzene ring, all carbon-carbon bond lengths were calculated in the range of 1.392—
1.403 Å for B3LYP and observed in the range of 1.343—1.395 Å for XRD data. In phenyl
ring, C—C bond lengths were observed 1.359—1.389 Å and calculated 1.383—1.406 Å in
range. N2—O4, N2—O5, C1—N1 and C7—N1 bond distances were observed as 1.191,
1.178, 1.409 and 1.339 Å, respectively. The experimental bond lengths are in agreement with
the theoretical values (1.225, 1.225, 1.401, and 1.364 Å, respectively). These data can be
comparable with literature data [38].
The bond angles, C7—C8—C16, C7—C8—C9, C8—C9—C10, C8—C16—C17 and
C1—N1—C7 , was observed as 109.3°, 107.9°, 120.9°, 118.7° and 127.8°, whereas these
values were calculated as and 108.2°, 116.5°, 118.7°, 118.5° and 128.4°, respectively. N1—
C7—O3 bond distances in amide group was observed as 125.3°. The bond angles C17–C16–
O2, C8–C16–O2, C10–C9–O1 and C8–C9–O1 were observed as 121.8°, 119.5°, 120.8° and
118.3°, this bond angles were calculated as 122.1, 119.4, 120.5 and 120.8, respectively. These
values are in agreement with literature data [39].
The torsion angles τ1 (N1—C7—C8—C16) were observed as 80.4° for theoretically and
as -148.1° for experimentally. Furthermore, (N1—C7—C8—C9) was observed as -41.4° and
-90.9° for theoretically and experimentally, respectively. The torsion angles τ1 (O1—C9—
C8—C7) and τ1 (O3—C7—C8—C9) are 33.4° and 141.2° for B3LYP, respectively. These
torsion angles are in agreement with the XRD data (12.3° and -88.0°).

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Using the root mean square (RMS) error, experimental and theoretical data were
compared (Figure3). It was found that the B3LYP/6-311G(d,p) calculation provide the lowest
RMSE value of 0.025 Å and 1.738 for bond lengths and bond angles respectively.
Consequently the B3LYP calculation with 6-311G(d,p) basis set predicts the best geometry
when compared the calculation with 6-311++G(d,p) levels.
(Figure 1)
(Table 2)
(Figure 2)
(Figure 3)
(Table 3)
Vibrational frequency
In order to facilitate assignment of the observed peaks, we have analyzed some bands and
compared calculated results with the experimental ones. Experimental FT-IR spectrum of the
title compound is given in Figure S1 (supplementary materials). As seen from Table 4, the
FT-IR spectra contain some characteristic bands NH, CH, CO and NO groups. The
carboxyamide ligand stated the formation of proposed structure by the appearance of new
absorption bands at 3281 cm-1 (NH), 3070 (sym) and 3104 (asym) cm-1 (Ar-CH), 1689, 1675,
-1
1659 cm-1 (C=O), 1595-1507 cm (C=C), 1448,1409 cm-1(Ph-NO2). Di substitue and mono
substitue phenyl ring were observed at 804 and 666-686 cm-1, respectively. The high
frequency region above 3000 cm-1 is the characteristic region for identification phenyl C H
stretching vibrations [40]. In the present case, υCH modes of the phenyl rings are observed at
3070 cm−1 in the IR spectrum. The region 1700-500 cm-1 has very strong and sharp peaks. All
the calculated spectra are in good agreement with the experimental data.
(Table 4)
1H NMR (DMSO-d6, δ ppm):
1H NMR (400 MHz, DMSO-d6): δ, ppm 11.04 (s, 1H, NH), 8,25(d, 2H, J=9.2 Hz, B ring
C1-ArH), 7.99 (d, 4H, J= 7.6 Hz, A ring C3-ArH),7.79 (d, 2H, J= 9.2 Hz, B ring C2-ArH),

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7.71 (t, 2H, A rings C1-ArH), 7.59 (t, 4H, A rings C2-ArH), 6.90 (s, 1H, aliphatic C-H).The
1H-NMR spectra (Figure S2 (supplementary materials)) were in good agreement with the
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structure of N-(4-nitrophenyl)-2,2-dibenzoylacetamide. In the H-NMR spectrum of the
compound in DMSO-d6, the aromatic protons appeared as a broad band at 7.71-8.25 ppm, –
NH proton at 11.04 ppm and –CH proton among three carbonyl groups at 6.90 ppm.
13C NMR (DMSO-d6, δ ppm):
65.00 (aliphatic carbon-C(6)); 119.40 (B aromatic ring C(9)); 125.60 (B ring C(10)); 128.87
(A aromatic rings C(2)); 129.57 (A aromatic rings C(3)); 134.52 (A aromatic rings C(1)); 135.98
(A aromatic rings C(4)); 143.09 (B aromatic ring C(11)); 145.09 (B aromatic ring C(8)); 165.19
(amide carbonyl (C=O) C(7)); 192.70 (A aromatic ring benzoyl carbonyls (C=O) C(5)). The 13C
NMR spectrum of compound is analyzed carbonyl (-C=O) carbon resonance is observed
characteristic peaks sequentially at δ 165.19 carbonyl related to amide and 192.70 ppm
carbonyl related to benzoyl. In the compound, carbon atoms include one hydrogen in benzene
rings located at 119.4, 125.6, 128.87, 129.57, 134.52 and C H aliphatic carbon (C6) among
three carbonyl carbons at 65.00 ppm (Figure S3 (supplementary materials)). The carbons
atom without hydrogen in benzene rings observed at 135.98, 143.09 and 145.09 ppm.
Chemical shifts of the peaks of the carbon in the aromatic ring due to the effect substituents
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are compatible with the literature data [41]. As can be seen from Table 5, the theoretical H
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and C chemical shift results for the title compound are generally closer to the experimental
1H and 13C shift data. Both 6-311G(d,p) and 6-311++G(d,p) have showed good conformity.
(Table 5)
Electronic absorption spectra
Ultraviolet spectra analyses of N-(4-nitrophenyl)-2, 2-dibenzoylacetamite) (NPDBA)
have been investigated by experimentally and theoretically. The UV-Vis spectra of the title
compound in ethanol and methanol solvents were recorded within the 190-1100 nm range.
The maximum is observed at 320 nm related to n-π* transition of the amide and benzoyl
carbonyl groups (Figure S4 in supplementary materials). In addition, the maximum at 260 nm
is related to π-π* transition of phenyl rings. The calculated frontier orbital energies, absorption
wavelength (λ), excitation energies (E) and oscillator strength (f) for gas phase and solvent are
given in Table 6.

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(Table 6)
HOMO and LUMO analysis
The calculations indicate that the compound has 101 occupied molecular orbitals (MOs).
The energy gap between HOMO and LUMO of the molecule indicate that this molecule is
very stable [42]. Figure 4 shows the distributions and energy levels of the HOMO-1, HOMO,
LUMO and LUMO+1 orbitals computed at the B3LYP/6-311++G(d,p) level for the title
compound. The positive and negative phase has been seen in red and green color,
respectively. The energy gap between the highest occupied and the lowest unoccupied
molecular orbitals, is a critical parameter in determining molecular electrical transport
properties because it is a measure of electron conductivity.
HOMO energy = -6.9713eV
LUMO energy = -2.7494eV
HOMO-LUMO energy gap = 4.2219eV
The energy values of HOMO and LUMO are computed as -7.0254, -7.0186 and -6.9713
eV; -3.0251, -3.0264 and -2.7494 eV in ethanol, methanol and gas phase, respectively. The
energy gap values of the title compound are 4.0003, 3.9922 and 4.2219 eV in ethanol,
methanol and gas phase, respectively. According to Koopmans theorem, the values of
electronegativity, hardness, softness, electrophilicity index and dipole moment of the
molecule were calculated as 5.0252, 2.0001, 0.2499, 6.3128 eV and 13.7011 debye in ethanol,
respectively [43-46]. The electronic properties values for the molecules are shown in Table S1
(supplementary materials).
(Figure 4)
Molecular electrostatic potential
Molecular electrostatic potential is related to the electronic density and is a very useful
descriptor for determining sites for hydrogen bonding interactions as well as electrophilic
attack and nucleophilic reactions [47,48]. The electrostatic potential V(r) at any point in space
around a molecule by charge distribution is given by
V(r) = ∑ZA/|RA-r| - ∫ρ(rl)/|rl-r|drl

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where the summation runs over all the nuclei A in the molecule and polarization and
reorganization effect is neglected. ZA is the charge of the nucleus A, located at RA and ρ(rl) is
the electron density function of the molecule.
The different values of the electrostatic potential at the surface are represented by
different colors. The electrostatic potential increases in the order red < orange < yellow <
green < blue. The color code of these maps is in the range between -0.02573 a.u. (dark red)
and 0.02573 a.u. (dark blue) in compound. The negative (red color) regions of MEP were
related to electrophilic reactivity and the positive (blue color) ones to nucleophilic reactivity.
As seen from Figure 5, the negative potential regions (red) are over the O atom on the NO2
bonded to aromatic ring, amide carbonyl (C=O) and aromatic tile carbonyl (C=O) group. The
positive potential regions (blue) are over the H atom on the aliphatic (C-H) and aromatic tiles.
Considering these calculated results, the MEP map shows that the negative potential sites are
on electronegative O atoms as well as the positive potential sites are around the hydrogen
atoms, respectively.
(Figure 5)
Mulliken population analysis and natural population analysis
The calculated Mulliken atomic charges and natural population analysis (NPA) atomic
charges of N-(4-nitrophenyl)-2, 2-dibenzoylacetamite) (NPDBA) are presented in Table S2
(supplementary materials). The Mulliken population analysis and NPA are obtained from
optimized geometry and NBO [49] results, respectively. In all these compound among the
C17 atom has the highest positive charge (0.917 e-) due to highly electronegative Oxygen
atoms (O1 = -0.571 e- and O3 = -0.614 e-) present in the adjacent position. The charge of the
O3 (-0.614 e-) atom is the highest negative value at NPA. However, charge value for O4 and
O5 (-0.007 e-) atoms at Mulliken population analysis are nearly neutral. As can be seen in
Table S2 (supplementary materials), all the hydrogen atoms have a net positive charge and all
the oxygen atoms have a net negative charge. Natural Population Analysis shows that the H1
atom has maximum positive atomic charges (0.449 e-; 0.435 e-) than the other hydrogen
atoms. The total dipole moments were obtained as 10.88 and 10.88 Debye by using Mulliken
population analysis and NPA, respectively.
Natural bond orbital analysis (NBO)

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Natural bond orbital (NBO) analysis is a helpful tool for understanding the bond-antibond
stabilization energies within the title compound, interaction among bonds, and charge transfer
or conjugative interaction in molecular systems [50-53]. The Natural Bond Orbital (NBO)
calculations were performed via NBO 3.1 program [54] as implemented in the Gaussian 03W
package at the DFT-B3LYP/6-311++G(d,p) level. The second order perturbation approach is
used to evaluate the donor (i) and acceptor (j) interaction in the NBO basis [55].
In our study, this system shows some contribution to the π electron delocalization corresponds
to the donor–acceptor interactions which are π(C23—C32) →π*(O1—C22) (20.37 kcal/mol),
π*(C24—C26) (19.30 kcal/mol), π*(C28—C30) (17.84 kcal/mol); π(C24—C26) →π*(C23—
C32) (19.08 kcal/mol), π*(C28—C30) (21.74); π(C28—C30) →π*(C23—C32) (22.88
kcal/mol), π*(C24—C26) (17.36); π(C35—C44) →π*(O2—C34) (19.31 kcal/mol), π*(C36—
C38) (19.78 kcal/mol), π*(C40—C42) (17.74 kcal/mol); π(C36—C38) →π*(C35—C44)
(18.83 kcal/mol), π*(C40—C42) (21.62 kcal/mol); π(C40—C42) →π*(C35—C44) (22.82
kcal/mol), π*(C36—C38) (17.61 kcal/mol), while π(C9—C10) →π*(C12—C14) (25.31
kcal/mol), π*(C15—C17) (16.34 kcal/mol); π(C12—C14) →π*(O5—N8) (26.43 kcal/mol),
π*(C9—C10) (16.61 kcal/mol), π*(C15—C17) (22.01 kcal/mol); π(C15—C17) →π*(C9—
C10) (21.51 kcal/mol), π*(C12—C14) (17.30 kcal/mol) for the phenyl rings of the molecule.
The most important interaction energies are LP(1)N6 →π*(O3—C19) (63.22 kcal/mol) and
π*(C9—C10) (38.06 kcal/mol); LP(3)O4→π*(O5—N8) (160.60 kcal/mol). Finally, n(O1—
C22), n(O2—C34), n(O5—N8) lead to an enormous stabilization of 120.69, 128.68 and
17.57 kcal/mol, respectively. This strong stabilization denotes the larger delocalization. This
highest interaction around the ring can induce the large bioactivity in the compound [50]. The
hyper conjugative interaction and electron density transfer from lone electron pair of the O1
atom to the N6 H7 anti bonding orbital in the N6 H7···O1 system, O3 atom to C10 H11
and C44 H45 anti bonding orbital in C10 H11···O3 and C44 H45···O3 have been
predicted. This hydrogen bonding is formed by the orbital overlap between LP(2)O1 →
BD∗(1) N6 H7 (6.87 kcal/mol), LP(1) O3 → BD*(1) C10 H11 (0.53 kcal/mol ), LP(2)
O3→BD*(1) C10 H11 (1.10 kcal/mol) and LP (2) O3→BD*(1) C44 H45(0.61 kcal/mol)
which consequences inter and intra molecular charge transfer (ICT) causing stabilization of
the hydrogen bonded system. The results for title compound were presented in Table S3
(supplementary materials).

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Nonlinear optical effects (NLO)
The polar properties of the title compound were calculated at the DFT-B3LYP/6-
311++G(d,p) level using Gaussian 03W program package. Urea is one of the prototypical
molecules used in the study of the Non Linear Optical (NLO) properties of molecular system.
As can be seen in Table S4 (supplementary materials), calculated values of µtot, αtot and βtot for
the title compound are, 4.281 debye, 45.800 Å3 and 2.283x10-29cm5/esu and the title molecule
is 61.2 times greater than those of urea (µtot and βtot of urea are 1.3732 debye and 0.3728x10-
30cm5/esu, respectively [50]. According to these results, the title compound is a good
candidate of NLO material.
Conclusion
N-(4-nitrophenyl)-2, 2-dibenzoylacetamite) (NPDBA), C22H16N2O5, was synthesized and
characterized by experimental (X-Ray, FT-IR, NMR and UV-Vis) and by theoretical methods
in DFT-B3LYP/6-311G(d,p) and B3LYP/6-311++G(d,p) levels. The crystal structure of the
title compound is stabilized by the C—H···O and N—H···O type hydrogen bonds. In order to
understand electronic transitions of compound, TD-DFT calculations on electronic absorption
spectra in gas phase and solvent (ethanol and methanol) were performed. Theoretical
1
calculations of 13C and H-NMR chemical shifts, FT-IR frequencies and geometrical
parameters contribute to a better understanding of the experimental spectra. The MEP map
shows that the negative potential sites are on electronegative O atoms as well as the positive
potential sites are around the hydrogen atoms. Frontier molecular orbital energies and
molecular electronic potential are calculated using B3LYP/6-311G(d,p) and 6-311++G(d,p)
level, and obtained small HOMO–LUMO energies show that charge transfer occurs in the
title compound. Electronic transition of the title compound has observed good chemical
stability with 4.24 eV value. Mulliken population analysis and natural population analysis
have showed maximum positive atomic charges around the C17 (Mulliken charges) atom. All
the hydrogen atoms have a net positive charge. Natural Population Analysis shows that the H1
atom has maximum positive atomic charges than the other hydrogen atoms. Nonlinear optical
properties of the title compound were found greater than those of urea. Natural bond orbital
(NBO) calculations reveals N6 H7···O1 and C10 H11···O3 hyper-conjugation interaction.
Supplementary data

12
ACCEPTED MANUSCRIPT
Crystallographic data for the structure reported in this article was deposited with the
Cambridge Crystallographic Data Centre as supplementary publication number CCDC
1042436. Copies of the data can be obtained free of charge on application to CCDC 12 Union
Road, Cambridge CB21 EZ, UK.
(Fax: (+44) 1223 336-033; e-mail: data_request@ccdc.cam.ac.uk).
Acknowledgment
This study was funded from Presidency of Scientific Research Projects of University
Gaziantep (FEF.10.08). The authors thank Harran University Chemistry Department and
Central Laboratory for IR and NMR, respectively; Dokuz Eylül University for XRD
measurement of the title compound.
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Figure Captions:
Figure 1 (a) Ortep 3 diagram of the title compound with the atom numbering scheme.
Displacement ellipsoids were drawn at the 50% probability. Dashed lines are show
the C–H···O intramolecular hydrogen bonds. (b) The theoretical geometric
structure of the title compound (B3LYP/6-311++G(d,p) level).
Figure 2 Packing diagram of the title compound along the b axis.
Figure 3 Atom-by-atom superimposition of the structures calculated (red) [a= B3LYP/6-
311G(d,p) and b= B3LYP/6-311++G(d,p)] over the X-ray structure (black) for the
title compound. Hydrogen atoms omitted for clarity.
Figure 4 The atomic orbital compositions of the frontier molecular orbital for N-(4-
nitrophenyl)-2, 2-dibenzoylacetamite) (NPDBA).
Figure 5 Molecular electrostatic potential map calculated as the B3LYP/6-311++G(d,p) level.

ACCEPTED MANUSCRIPT
Table 1 Crystallographic data for the title compound.
Formula Sum
C22H16N2O5
Crystal System
Space Group
Monoclinic
'P121/c1'
Formula weight
λ(Å)
388.37
0.71073
293(2)
1907.8 (7)
Temperature (0K)
Volume(Å3)
Z
4
a, b, c (Å)
10.023(2),21.587(5),9.401(2)
110.29(3)
1.352
0.097
β(0)
Calculated density (Mg/m3)
µ (mm-1)
F(000)
808.0
Crystal size (mm)
θ range for data collection(0)
Refinement method
Absorption correction
Limiting indices
Measured reflections
Independent reflections
Goodness -of-fit on F2
0.5241 × 0.2252 × 0.1561
5.96-52.72
Full-matrixleast-squares on F2
analytical
-10≤ h ≤12, -26≤k ≤17, -11≤ l≤11
8061
3900
1.002
2
w = 1/[σ2(Fo ) + (0.1548P)2 +
Weighting scheme
0.0000P]; P = (Fo + 2Fc2)/3
2
Rint
0.1027
0.0972, 0.3037
0.51and -0.58
R[F2>2σ(F2)], wR(F2)
Largest diff. Peak and hole (e Å−3)

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Table 2 Selected optimized and experimental geometries parameters of the title compound in
ground state.
Parameters
Experimental
Calculated (B3LYP)
6-311G(d,p)
6-311++G(d,p)
Bond lengths (Å)
O1—C9
O2—C16
C8—C16
C9—C10
O3—C7
C10—C11
O4—N2
C10—C15
O5—N2
C11—C12
N1—C1
C12—C13
N1—C7
C13—C14
N2—C4
C14—C15
C1—C2
C16—C17
C1—C6
C17—C18
C2—C3
C17—C22
C3—C4
C18—C19
C4—C5
C19—C20
C5—C6
1.217 (5)
1.207 (5)
1.523 (5)
1.464 (5)
1.209 (4)
1.378 (6)
1.191 (6)
1.393 (6)
1.178 (6)
1.377 (7)
1.409 (4)
1.359 (9)
1.339 (4)
1.355 (9)
1.472 (6)
1.353 (7)
1.375 (5)
1.477 (5)
1.376 (5)
1.395 (6)
1.389 (6)
1.380 (6)
1.373 (6)
1.380 (7)
1.359(6)
1.343 (7)
1.371 (6)
1.363 (7)
1.535 (5)
1.381 (6)
1.524 (5)
1.218
1.210
1.562
1.492
1.218
1.403
1.225
1.401
1.225
1.387
1.401
1.395
1.364
1.392
1.471
1.391
1.404
1.492
1.406
1.403
1.388
1.401
1.390
1.387
1.392
1.396
1.383
1.393
1.547
1.392
1.532
0.025
0.008
1.219
1.211
1.563
1.492
1.219
1.404
1.227
1.402
1.226
1.387
1.401
1.396
1.363
1.393
1.470
1.392
1.404
1.492
1.406
1.404
1.389
1.402
1.391
1.388
1.393
1.396
1.383
1.393
1.548
1.392
1.533
0.026
0.008
C20—C21
C7—C8
C21—C22
C8—C9
RMSE*
Max. Difference*
Bond Angles (º)
C7—N1—C1
O1—C9—C10
O4—N2—C4
C10—C9—C8
O5—N2—O4
C11—C10—C9
O5—N2—C4
C2—C1—N1
C15—C10—C9
C2—C1—C6
127.8 (3)
120.8 (4)
118.1 (5)
120.9 (3)
123.1 (5)
118.3 (4)
118.7 (5)
123.5 (3)
122.7 (4)
119.9 (4)
128.4
120.5
117.7
118.7
124.6
117.4
117.7
123.5
123.5
119.6
128.5
120.6
117.8
118.6
124.4
117.5
117.8
123.6
123.4
119.6

ACCEPTED MANUSCRIPT
C12—C11—C10
C6—C1—N1
C13—C12—C11
C1—C2—C3
C14—C13—C12
C4—C3—C2
C15—C14—C13
C3—C4—N2
119.8 (5)
120.5
116.8
120.0
119.6
120.0
119.8
120.1
119.4
120.3
119.2
119.4
121.3
122.1
118.5
117.4
125.7
123.1
119.2
114.9
120.2
116.5
119.9
108.2
120.1
108.0
120.2
120.8
119.9
1.738
3.200
120.5
116.7
120.0
119.6
120.0
119.8
120.1
119.4
120.3
119.2
119.4
121.3
122.1
118.5
117.5
125.6
123.0
119.1
115.2
120.2
116.7
119.9
108.3
120.0
108.1
120.1
120.8
119.9
1.758
3.100
116.6 (3)
119.9(5)
119.5(4)
120.6 (5)
119.0 (4)
120.7 (6)
118.5(4)
120.0 (5)
119.6 (5)
119.5(4)
122.0 (4)
121.8 (4)
118.7 (3)
118.9 (4)
125.3 (3)
122.8 (4)
120.8 (3)
113.8 (3)
119.6 (5)
107.9 (3)
121.4 (3)
109.3 (3)
120.0 (5)
111.2 (3)
120.1 (5)
118.3 (3)
120.6 (4)
C14—C15—C10
C5—C4—N2
O2—C16—C8
C5—C4—C3
O2—C16—C17
C17—C16—C8
C18—C17—C16
O3—C7—N1
C22—C17—C16
O3—C7—C8
N1—C7—C8
C19—C18—C17
C9—C8—C7
C20—C19—C18
C16—C8—C7
C19—C20—C21
C16—C8—C9
C20—C21—C22
O1—C9—C8
C17—C22—C21
RMSE*
Max. Difference*
Torsion Angles (º)
O1—C9—C10—C11
O1—C9—C10—C15
O2—C16—C17—C18
O2—C16—C17—C22
O3—C7—C8—C9
O3—C7—C8—C16
O4—N2—C4—C3
O4—N2—C4—C5
O5—N2—C4—C3
O5—N2—C4—C5
N1—C1—C2—C3
N1—C1—C6—C5
N1—C7—C8—C9
N1—C7—C8—C16
N2—C4—C5—C6
C9—C8—C16—O2
7.8 (6)
-169.5 (4)
-7.2 (6)
171.8 (4)
-88.0 (4)
33.0 (5)
-175.9 (6)
3.2 (9)
-4.7
-4.8
174.1
-14.7
163.6
141.2
-96.8
-179.9
0.1
174.0
-15.5
162.8
141.8
-95.8
-179.9
0.1
7.1 (8)
0.1
0.1
-173.8 (6)
-179.4 (4)
-179.9 (4)
90.9 (4)
-148.1 (3)
-179.0 (5)
14.6 (5)
-179.9
179.3
-179.4
-41.4
80.4
-179.9
179.3
-179.4
-40.7
81.4
179.9
38.1
179.9
39.9
*RMSE and maximum differences between the bond lenghts and angles computed using
theoretical method and those obtained from X-ray diffraction.

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Table 3 Hydrogen bond geometry (Å, º)
D—H···A
D—H(Å)
H···A(Å)
D···A(Å)
D—H···A(º)
C2—H2···O3
C3—H3···O5i
C6—H6···O1ii
C8—H8···O3ii
N1—H1···O3ii
0.93
0.93
0.93
0.98
0.86
2.28
2.45
2.42
2.46
2.13
2.8671
3.3603
3.2032
3.1585
2.9459
120
165
142
128
159
Note: Symmetry codes: (i) 2-x, -y,- z; (ii) x, 1/2-y, 1/2+z.
Table 4 Comparison of the experimental and calculated vibrational frequencies (cm-1).
Assignment*
Experimental
Calculated (B3LYP)
6-311G(d,p) 6-311++G(d,p)
ν(N-H)aliphatic
ν(C-H)
ν(C-H)
ν(C=O)benzoyl
ν(C=O) + ν(N-H)
ν(C=O)
γ(N-H)
γ(C=C)as
ν(NO2)as + γ(N-H)
ν(NO2)as + γ(N-H)
γ(C-H)s
3281
3104
3070
1689
1675
1659
1618
1595
-
3397
3139
3128
1735
1728
1695
1629
1616
1585
1550
1503
1456
1422
1354
1338
1252
1226
800
3376
3135
3122
1717
1707
1675
1616
1603
1566
1550
1494
1446
1412
1328
1328
1298
1217
792
1448
-
γ(C-H)benzoyl
-
α(C-H)
ν(NO2)as + γ(N-H)
β(ring)
γ(C-H)
γ(C-H)
ω(C-H)phenyl
ω(C-H)phenyl
γ(N-H)
-
1409
1334
1284
1239
804
751
686
770
716
762
712
ω(C-H)
679
696
687
* ν: Stretching, s: Symmetric, γ: rocking, ω: wagging, α: scissoring

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Table 5 Theoretical and experimental 1H-NMR and13C-NMRchemical shift (with respect to
TMS, all values ppm) for the title compound.
Experimental (ppm)
Calculated (ppm)
Atom
1H-NMR
(DMSO-d6)
6-311G(d,p)
6-311++G(d,p)
10.97
H1
H2
H3
H5
H6
H8
H11
H12
H13
H14
H15
H18
H19
H20
H21
H22
11.04
7.79
8.25
8.25
7.79
6.90
7.99
7.59
7.71
7.59
7.99
7.99
7.59
7.71
7.59
7.99
10.63
8.95
8.39
8.41
7.17
6.69
8.73
7.73
7.73
7.45
7.81
8.33
7.66
7.81
7.83
9.18
9.04
8.39
8.53
7.30
6.86
8.72
7.76
7.81
7.41
7.81
8.58
7.60
7.83
7.92
9.27
13C-NMR
C1
C2
C3
C4
C5
C6
C7
C8
145.09
119.40
125.60
143.09
125.60
119.40
165.19
65.00
151.21
123.28
131.71
151.80
130.66
122.71
165.93
70.13
152.45
124.57
133.36
152.12
131.91
123.28
167.33
71.08
C9
192.70
135.98
129.57
128.87
134.52
128.87
129.57
192.70
135.98
129.57
128.87
134.52
128.87
129.57
197.31
141.64
136.81
135.22
141.18
134.21
134.97
192.04
142.34
137.17
134.57
140.68
134.70
138.15
199.20
142.30
138.33
136.05
142.30
135.27
135.79
193.91
143.42
139.09
134.95
141.75
135.88
139.51
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22

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Table 6 Calculated energies values, chemical hardness, electronegativity, chemical potential,
electrophilicity index of N-(4-nitrophenyl)-2,2-dibenzoylacetamite) (NPDBA) UV-vis region.
TD-DFT/B3LYP
6-311++G(d,p)
Etotal (Hartree)
EHOMO (eV)
ELUMO (eV)
Gas Phase
(ε=1)
-1333.8911
-6.9713
-2.7494
4.2219
Ethanol
(ε=24.3)
-1333.9197
-7.0254
-3.0251
4.0003
Methanol
(ε=32.63)
-1333.9208
-7.0186
-3.0264
3.9922
ꢀEHOMO-LUMO
Chemical hardness (η)
Chemical softness (S)
Electronegativity (χ)
Chemical potential (µ)
Electrophilicity index (φ)
Dipole moment (Debye)
2.1109
0.2368
4.8603
-4.8603
5.5953
2.0001
0.2499
5.0252
-5.0252
6.3128
1.9961
0.2504
5.0225
-5.0225
6.3186
10.8806
13.7011
13.7599

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Highlights of paper
•
The vibrational frequencies of the compound have been calculated by B3LYP/6-
311G(d,p) and B3LYP/6-311++G(d,p) methods.
•
•
NLO and NBO analysis of the molecule were studied.
HOMO and LUMO energies, absorption wavelength and excitation energies were
calculated.

ACCEPTED MANUSCRIPT
Synthesis, structural, spectral (FT-IR, 1H and 13C-NMR and UV-Vis), NBO and first
order hyperpolarizability analysis of N-(4-nitrophenyl)-2, 2-dibenzoylacetamide by
density functional theory
a
b
c
ꢀ
Şerife Pınar Yalçın , Ümit Ceylan , Ahmet Oral Sarıoğlu ,
Mehmet Sönmezc, Muhittin Aygünd
aCentral Laboratory, Osmanbey Campus, Harran University, 63190 Şanlıurfa, TURKEY
bDepartment of Medical Services and Techniques, Vocational High School of Health Services, Giresun
University, 28100 Giresun, TURKEY
cDepartment of Chemistry, Faculty of arts and Sciences, Gaziantep University, 27310, Gaziantep, TURKEY
dDepartment of Physics, Faculty of arts and Sciences, Dokuz Eylül University,Buca,35150, Izmir, TURKEY
ꢀCorresponding author Tel.: +90 505 313 51 57
E-mail: umit.ceylan@giresun.edu.tr (Ü. Ceylan); msonmez@gantep.edu.tr, (M. Sönmez)