Synthesis, spectroscopic (UV-vis and GIAO NMR), crystallographic and theoretical studies of triazine heterocyclic derivatives

Article abstract of DOI:10.1016/j.molstruc.2015.04.036

Abstract This work presents the synthesis and characterization of triazine heterocyclic derivatives. The spectroscopic properties like nuclear magnetic resonance [NMR, (¹H and ¹³C)] were recorded in CDCl₃ solution and Ultr

Full text of DOI:10.1016/j.molstruc.2015.04.036

Accepted Manuscript
Synthesis, spectroscopic (UV-vis and GIAO NMR), crystallographic and theo-
retical studies of triazine heterocyclic derivatives
Salman A. Khan, Abdullah Y. Obaid, Laila M. Al-Harbi, Muhammad Nadeem
Arshad, Onur Şahin, Cem Cüneyt Ersanlı, R.M. Abdel-Rehman, Abdullah M.
Asiri, Michael B. Hursthouse
PII:
S0022-2860(15)00379-8
DOI:
http://dx.doi.org/10.1016/j.molstruc.2015.04.036
MOLSTR 21490
Reference:
To appear in:
Journal of Molecular Structure
Received Date:
Revised Date:
Accepted Date:
15 January 2015
2 March 2015
27 April 2015
Please cite this article as: S.A. Khan, A.Y. Obaid, L.M. Al-Harbi, M.N. Arshad, O. Şahin, C.C. Ersanlı, R.M. Abdel-
Rehman, A.M. Asiri, M.B. Hursthouse, Synthesis, spectroscopic (UV-vis and GIAO NMR), crystallographic and
theoretical studies of triazine heterocyclic derivatives, Journal of Molecular Structure (2015), doi: http://dx.doi.org/
1
0.1016/j.molstruc.2015.04.036
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Synthesis, spectroscopic (UV-vis and GIAO NMR), crystallographic and theoretical
studies of triazine heterocyclic derivatives
a
a
a
Salman A. Khan *, Abdullah Y. Obaid , Laila M. Al-Harbi , Muhammad Nadeem
a,b,
c,
d
a
Arshad
Onur Şahin , Cem Cüneyt Ersanlı , R. M. Abdel-Rehman , Abdullah M.
a,b
e
Asiri and Michael B. Hursthouse
a
Chemistry Department, Faculty of Science, King Abdulaziz University P.O. Box 80203,
Jeddah 21589, Saudi Arabia
b
Centre of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz
University P.O. Box 80203, Jeddah 21589, Saudi Arabia
c
Scientific and Technological Research Application and Research Center, Sinop University,
57010 Sinop, Turkey
d
Department of Physics, Faculty of Arts and Sciences, Sinop University, 57010 Sinop, Turkey
School of Chemistry, University of Southampton, Southampton, SO17 1BJ, UK
e
Abstract
This work presents the synthesis and characterization of triazine heterocyclic derivatives. The
1
13
spectroscopic properties like nuclear magnetic resonance [NMR, ( H and C)] were recorded
in CDCl solution and Ultraviolet-Visible (UV-vis) absorption spectrums of compounds, 5,6-
diphenyl-[1,2,4]triazin-3-ylamine (1), (5,6-diphenyl-[1,2,4]triazin-3-yl)-hydrazine (2) and
,6-diphenyl-4H-[1,2,4]triazine-3-thione (3), were recorded in the range of 200-800 nm, using
3
5
chloroform as base solvent. Molecular geometry of compounds with triazine heterocyclic
derivative in the ground state have been calculated using the density functional theory (DFT)
with 6-31G(d,p) basis set and compared with the X-ray experimental data. The calculated
1

results show that the optimized geometry can well reproduce the crystal structures. Total
static dipole moment (μ), the average linear polarizability (α) and the first hyperpolarizability
(β) values of the investigated molecules have been computed using the same methods. The
energetic behavior of compounds in solvent media has been examined using B3LYP method
with the 6-31G(d,p) basis set by applying the polarizable continuum model (PCM). The total
energy of compounds decreases with increasing polarity of the solvent. Frontier molecular
1
13
orbitals and the molecular electrostatic potential (MEP), H-NMR, and C-NMR of three
triazine derivatives were investigated using theoretical calculations. The linear polarizabilities
and first hyperpolarizabilities of the studied molecules indicate that the compounds 1-3 can be
used as a good nonlinear optical material (NLO). Isotropic chemical shifts were calculated
using the gauge-invariant atomic orbital (GIAO) method. Comparison of the NMR chemical
shifts, absorption wavelengths with the experimental values revealed that DFT and time
dependent-density functional theory (TD-DFT) method produce generally closer to good
results.
Keywords: 1,2,4-Triazine; Crystal structure; DFT; Non-linear optical properties; HOMO-
LUMO; MEP
*
Corresponding authors: e-mail address: sahmad_phd@yahoo.co.in
1
. Introduction
The usefulness of organic ligands with heteroatoms N, O, S is well known. However when
these ligands are coordinated with a metal atom, they show a remarkable biological activities
like anti-microbial, anti-viral and anti-tumor etc. [1-3]. 1,2,4-Triazine derivatives of Pd(II)
and Pt(II) show monodentate and bidentate behavior [4] due to their tautomeric and
ambidentate nature. Derivatives of triazines were investigated for their antitumor, fungicidal,
herbicidal, insecticidal and activities [5]. Wide use of atrazine as herbicidal compounds
2

resulted in alarming threat for human health as well as environment [6]. Keeping in view the
positive and negative aspects of triazine based molecules Larif et al reported a detailed
research explaining the biological activities of various derivatives of triazines using DFT and
quantitative structure activity relationship (QSAR) studies [7]. We have recently reported the
synthesis and spectroscopic studies of 1,2,4-triazine complexes with Ru(II) [8].
In recent years, DFT has been a shooting star in theoretical modeling. The
development of better and better exchange-correlation functionals made it possible to
calculate many molecular properties with comparable accuracies to traditional correlated ab
initio methods, with more favorable computational costs [9]. Literature survey revealed that
the DFT has a great accuracy in reproducing the experimental values of in geometry, dipole
moment, vibrational frequency, etc [10-16]. It was noted that the experimental results belong
to solid phase and theoretical calculations belong to gas phase. In the solid state, the existence
of the crystal field along with the intermolecular interactions have connected the molecules
together, which result in the differences of bond parameters between the calculated and
experimental values. Despite the differences observed in the geometric parameters, the
general agreement is good and the theoretical calculations support the solid state structure.
In this present paper, we report the crystal structures and spectral characterizations of
triazine heterocyclic derivatives. Representing the synthesis of triazine derivatives is given in
Scheme 1. The properties of the structure geometry, NLO properties, FMO and MEP for
compounds 1-3 at the DFT/B3LYP/6-31G(d,p) level were studied for the first time. Besides
these, the experimental and calculated values are valuable for providing insight into NMR,
UV-vis spectrum and molecular parameters. The results obtained from theoretical calculations
and experiments were compared.
2. Experimental and computational method
2.1. Materials and methods
3

All chemicals used in this study were purchased from Fluka and used without further
purification. The melting point was recorded on Stuart scientific SMP3 (Bibby, UK) melting
1
13
point apparatus and is reported as uncorrected. The H-NMR and C-NMR experiments were
performed in Brucker-AVANCE-III 600 MHz at 300K. The compounds were dissolved in
3
CDCl . Chemical shifts (δ) were reported in parts per million (ppm) relative to
1
13
1
13
tetramethylsilane (TMS) for H-NMR and C-NMR spectra. H-NMR and C-NMR spectra
were obtained at a base frequency of 150 and 600 MHz, respectively. The UV-vis absorption
spectrum of the title molecules were examined in the range 200-800 nm using Spectro UV-
VIS double beam PC scanning spectrophotometer UVD-2960 Labomed Inc. The UV patterns
-
4
-5
are taken from 1.69x10 molar solution of compound 1, 6.46x10 molar solution of
-4
compound 2, and 1.39x10 molar solution of compound 3, dissolved in chloroform.
2.2. Synthesis
2
.2.1. 5,6-Diphenyl-[1,2,4]triazin-3-ylamine (1)
Benzil (4g, 19.03 mmol) and aminoguanidine bicarbonate (2.58g, 4.76 mmol) in n-
butanol (100 ml) was refluxed for four hours. The reaction was monitored through thin layer
chromatography (TLC). The mixture was cooled. The solid obtained was filtered off and
recrystalized from ethanol to give yellow crystals. [17]
o
1
Yield: 4.09g; 85%; m.p. 160 C; H-NMR shifts (CDCl
3
, δ ppm): 7.30-7.44 (10H, aromatic),
1
3
5
1
2
.53 (2H, s, NH
2
); C-NMR shifts (CDCl
3
, δ ppm): 161.18, 157.24, 150.78, 136.04, 135.97,
30.37, 129.52, 129.38, 129.24, 128.53, 128.38; UV-vis data (nm): λmax = 345.
.2.2. (5,6-Diphenyl-[1,2,4]triazin-3-yl)-hydrazine (2)
A mixture of 5,6-diphenyl-4H-[1,2,4]triazine-3-thione (5g, 18.84 mmol) and
2
hydrazine hydrate (10 ml) in isopropyl alcohol was refluxed for 4-6 h, until no more H S
evolved. Acetic acid was added drop wise into mixture to remove the excess of hydrazine till
neutralization. The mixture was cooled. The solid obtained was filtered off and crystalized
from ethanol to give yellowish crystals [18]
4

o
1
Yield: 4.19g: 83.8%; m.p. 175-178 C; H-NMR shifts (CDCl
3
, δ ppm): 7.31-7.49 (10H,
); C-NMR shifts (CDCl , δ ppm): 162.20,
57.12, 151.21, 135.96, 135.92, 130.52, 129.56, 129.25, 128.62, 128.39, 128.38; UV-vis data
nm): λmax = 355.
1
3
aromatic), 6.64 (1H, s, NH), 4.18 (2H, s, NH
2
3
1
(
2
.2.3. 5,6-Diphenyl-4H-[1,2,4]triazine-3-thione (3)
Benzil (6g, 28.5 mmol) was dissolved in glacial acetic acid (150 ml) and added to the
solution of thiosemicarbazide (2.59g, 28.5 mmol) in hot water (100 ml). The mixture was
refluxed for 4 h, the precipitate appeared filtered until hot. The orange filtrate obtained was
recrystallized from ethanol to give reddish crystals [18].
o
1
Yield: 5.27g; 87.82%; m.p. 222-224 C; H-NMR shifts (CDCl
3
, δ ppm): 7.27-7.57 (10H,
, δ ppm): 179.24, 160.73, 146.66,
32.22, 130.28, 130.10, 129.86, 129.40, 128.74, 128.60, 128.39; UV-vis data (nm): λmax =
40.
1
3
aromatic). 11.78 (1H, b, NH); C-NMR shifts (CDCl
3
1
4
S
O
S
HN
N
N
O
NH2
H N
N
H
2
3
NH
NH2
N
.H CO
H N
2
2
3
H
H N
2
NH2
NH
N
N
N
N
N
N
1
2
Scheme 1. Representing the synthesis of triazine derivatives
2.3. Crystal structure determination
5

Diffraction data of compounds 1-3 were collected on Oxford Diffraction SuperNova
single source at offset) Eos diffractometer equipped with a graphite-monochromatic CuK
(
α
radiation at 296 K. The structures were solved by direct methods using SHELXS-97 and
refined by full-matrix least-squares method using SHELXL-97 [19]. All non-hydrogen atom
parameters were refined anisotropically and all H atoms except for H atoms bonded nitrogen
atoms were refined using a riding model with C-H distances of 0.93 Å. H atoms bonded
nitrogen atoms were located in a difference map and refined freely. The following procedures
were implemented in our analysis: program used for molecular graphics were as follow:
MERCURY programs [20]; supramolecular analyses: PLATON [21]; software used to
prepare material for publication: WinGX [22].
Table 1. Crystal data and structure refinement parameters for compounds 1-3.
Crystal data
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
1
2
3
C
15
H
12
N
4
C
15
H
13
N
5
15 11 3
C H N S
248.29
monoclinic
P2 /c
263.30
monoclinic
P2 /c
265.33
monoclinic
P2 /c
1
1
1
6.2975 (3)
8.3157 (3)
24.9646 (14)
99.577 (5)
5.7566 (1)
17.2204 (4)
13.6750 (3)
94.324 (2)
5.8906 (3)
15.2907 (7)
14.6629 (7)
100.100 (5)
b (Å)
c (Å)
β(º)
3
V (Å )
1289.13 (11)
4
1351.76 (5)
4
1300.24 (11)
4
Z
–3
D
c
(g cm )
1.279
1.294
1.355
–
1
μ (mm )
0.64
0.66
2.11
θ range (º)
3.6-76.8
10676
3.2-76.2
12294
2822
2.9-76.6
7131
Measured refls.
Independent refls.
2682
2730
R
int
0.026
0.025
0.023
S
1.05
1.05
1.05
R1/wR2
0.042/0.124
0.12/-0.14
0.035/0.102
0.17/-0.10
0.036/0.105
0.19/-0.21
–3
Δρ max/ Δρ min (eÅ )
6

2
.4. Computational procedures
In computational procedure, Gaussian 03 [23] program package and GaussView
visualization program [24] were used for DFT and Hartree-Fock (HF) calculations. Starting
geometries of compounds 1-3 were taken from X-ray refinement data. Full geometry
optimization of compounds 1-3 in the ground state were performed by using DFT method
with Becke’s three-parameters hybrid exchange-correlation functional (B3LYP) [25]
employing 6-31G(d,p) basis set [26]. As the first step of our DFT calculation for the
investigated compounds 1-3, the initial geometrical configurations taken from their
crystallographically obtained geometrical data with no constraint. Thus, the optimized
molecular geometry, total molecular energy and dipole moment calculations were obtained
from the optimization output by the computational process. Secondly, the average linear
polarizability and first hyperpolarizability properties of the compounds were obtained from
molecular polarizabilities based on theoretical calculations. Thirdly, in order to evaluate the
energetic behavior and dipole moments of compounds 1-3 in solvent media, theoretical
calculations in the four different kinds of solvent [benzene, ε=2.3; chloroform ε=4.9; ethanol,
ε=24.55; DMSO, ε=46.7] have been carried out by using PCM [27-30]. Fourthly, frontier
molecular orbitals (FMOs) were performed with B3LYP/6-31G(d,p) the optimized structure.
Fifthly, to investigate the reactive sites of the compounds the molecular electrostatic
potentials (MEPs) were evaluated using the same method. Sixthly, for NMR calculations, the
1
geometry of the compounds 1-3, together with that TMS, is fully optimized. H-NMR and
1
3
C-NMR chemical shifts were calculated within the Gauge-including atomic orbital (GIAO)
approach [31] applying the DFT and HF methods and the same basis set as used for geometry
1
13
optimization. After optimization, the H-NMR and C-NMR chemical shifts were converted
to the TMS scale by subtracting the calculated absolute chemical shielding of TMS (δ=Σ -Σ,
where δ is the chemical shift, Σ is the absolute shielding and Σ is the absolute shielding of
o
o
TMS), with values of 32.02 and 201.35 ppm for HF/6-31G(d,p) and 32.01 and 184.38 ppm
7

1
13
for B3LYP/6-31G(d,p), respectively. In addition, H-NMR and C-NMR chemical shifts are
calculated by B3LYP/6-31G(d,p) method in chloroform solution. Finally, the electronic
properties, such as HOMO-LUMO energies, absorption wavelengths and oscillator strengths
calculated using B3LYP method of the TD-DFT, basing on the optimized structure in
chloroform and spectra were calculated using the TD-DFT method in gas phase and
chloroform solution.
2.5. Supplementary data
Crystallographic data for the structural analysis have been deposited with the Cambridge
Crystallographic Data Centre, CCDC 936603 for 1, 936601 for 2 and 936602 for 3. Copies of
this information may be obtained free of charge from the Director, CCDC 12 Union Road,
Cambridge CB2 1EZ, UK. (Fax: +44 1223 336 033 or e-mail: deposit@ccdc.cam.ac.uk).
Table 2. Comparison of experimental and calculated selected bond lengths, angles and
dihedral angles for compounds 1-3 (Å, º).
X-ray
2
DFT/B3LYP with 6-31G(d,p)
2
1
3
1
3
Bond lengths (Å)
C1–N1
1.348 (2)
1.3505 (18)
1.3427 (18)
-
1.3468 (18)
1.3404 (15)
1.3478 (17)
-
1.357 (2)
1.365 (2)
-
1.352
1.341
1.363
-
1.355
1.338
1.365
-
1.388
1.370
-
C1–N3
C1–N4
C1–S1
1.6797 (16)
-
1.664
-
N4–N5
-
1.407 (2)
-
1.406
1.314
1.338
1.421
1.348
1.485
1.486
N1–N2
1.3332 (16)
1.3262 (17)
1.4120 (19)
1.3320 (18)
1.4842 (19)
1.4841 (19)
1.3309 (15)
1.3294 (15)
1.4140 (16)
1.3356 (14)
1.4863 (16)
1.4882 (14)
1.3383 (19)
1.315 (2)
1.447 (2)
1.310 (2)
1.486 (2)
1.479 (2)
1.319
1.335
1.424
1.344
1.486
1.487
1.332
1.313
1.464
1.314
1.484
1.484
C3–N3
C2–C3
C2–N2
C2–C4
C3–C10
Bond angle (º)
C1–N4–N5
Torsion angles (º)
N2–C2–C4–C9
N3–C3–C10–C11
-
123.01 (12)
113.86 (14)
-
-
122.82
-
135.34 (15)
122.92 (16)
57.1 (2)
138.09
140.95
138.82
140.29
38.83
150.42 (13) -143.30 (17)
8
-144.15

C4–C2–C3–C10
-2.5 (2)
9.9 (2)
-5.9 (2)
-13.82
-14.24
17.07
Dihedral angles (º)
A/B
A/C
B/C
43.49(6)
56.74(5)
55.34(4)
64.04(4)
27.58(6)
65.59(5)
59.81(5)
34.91(6)
63.85(4)
40.83
37.00
57.29
40.21
37.68
57.85
41.54
33.69
58.67
3
.
Results and discussion
.1. Description of the crystal structures
Details of data collection and crystal structure determinations are given in Table 1.
3
Selected bond lengths and angles are collected in Table 2, respectively. The molecular
structures of compounds 1-3 with the atom numbering schemes are shown in Fig. 1. The 5-
and 6-phenyl substituents of the 1,2,4-triazine ring are inclined to its mean plane with the
dihedral angle of 56.74 (5)° and 43.49 (6)° for compound 1, 27.58 (6)° and 64.04 (4)° for
compound 2 and 34.91 (6)° and 59.81 (5)° for compound 3, respectively. Each 1,2,4-triazine
ring is forced by the steric effect of these bulky groups in adjacent positions of the
heterocyclic system. These strong steric interaction causing the appearance of the strains in
the 1,2,4-triazine ring results in the distortion of its planarity with the displacements of the
1,2,4-triazine atoms from the best plane within 0.0106 Å for compound 1, 0.0157 Å for
compound 2 and 0.0273 Å for compound 3. In compounds, the C-N distances show no
noteworthy features, with values in the range 1.3404 (15)-1.365 (2) Å, which are shorter than
the single-bond length of 1.480 Å and longer than the typical C=N distance of 1.280 Å,
indicating partial double-bond character and suggesting conjugation in the heterocycle.
(
a)
(b)
(c)
9

Fig. 1. The molecular structure of compounds 1-3 [(a) for 1, (b) for 2 and (c) for 3] showing
the atom numbering scheme.
The molecules of compound 1 are linked into sheets by a combination of two N-H···N
hydrogen bonds, C-H···π and π···π interactions are however found absent. Atom N4 in the
molecule at (x, y, z) acts as hydrogen-bond donor, via atoms H1 and H2, respectively, to
2
2
atoms N3 at (-x+1, y+1/2, -z+1/2) and N1 at (-x+1, y-1/2, -z+1/2), so forming C(4) [R
(8)]
chains running parallel to the [010] direction [(Fig. S1) (supplementary material)].
Table 3. Hydrogen-bonds, N-H···π and C-H···π interactions parameters for compounds 1-3
Å, º).
(
D–H···A
D–H
H···A
Compound 1
2.48
D···A
D–H···A
i
N4–H1···N3
N4–H2···N1
0.91
0.97
3.3431 (18)
3.156 (2)
159
166
ii
2.20
Compound 2
2.095 (19)
2.66 (3)
2.98 (3)
2.82
i
N4–H4···N1
0.911 (19)
0.99 (3)
0.94 (3)
0.93
3.0019 (17)
3.508 (3)
173.6 (16)
143 (2)
140
ii
N5–H5B···N1
iii
N5–H5A···Cg2
3.759 (2)
iv
C13–H13···Cg2
3.6156 (15)
145
Compound 3
2.33
i
N1–H1···S1
0.98
0.93
3.2862 (14)
3.420 (2)
163
136
ii
C14–H14···Cg2
2.69
Symmetry codes: (i) -x+1, y+1/2, -z+1/2; (ii) -x+1, y-1/2, -z+1/2 for 1; (i) –x-1, -y+1, -z; (ii)
x, -y+1, -z; (iii) -x, 1/2+y, 1/2-z; (iv) 1+x, 1/2-y, 1/2+z; Cg2 = C4-C9 for 2; (i) -x+1, -y+1,
-
−
z+2; (ii) x-1, 3/2-y, z-1/2; Cg2 = C4-C9 for 3.
In compound 2, amino atom N5 in the reference molecule at (x, y, z) acts as a
hydrogen-bond donor, via H5B, to atom N1 in the molecule at (-x, -y+1, -z), so forming a
2
2
centrosymmetric R
(10) ring centered at (0, 1/2, 0). Similarly, atom N4 in the molecule at (x,
y, z) acts as a hydrogen-bond donor, via H4, to atom N1 in the molecule at (-x-1, -y+1, -z), so
10

2
forming a centrosymmetric R
hydrogen bonds generates a chain of edge-fused R
100] direction [(Fig. S2) (supplementary material)]. Compound 2 also contain C-H···π and N-
2
(8) ring centered at (-1/2, 1/2, 0). The combination of N-H···N
2
2
2
2
(8)R (10) rings running parallel to the
[
H···π interactions. Details of these interactions are given in Table 3. These C-H···π and N-
H···π interactions play a major role in constructing network [(Fig. S3) (supplementary
material)].
The molecules of compound 3 interacts with the protonated nitrogen atom through a
2
2
N-H···S hydrogen bond forming centrosymmetric R
(8) ring motif with an adjacent cation
sulphur atom. In compound 3, there is also C-H···π interaction between C14-H14 and centroid
Cg2 (Cg2 = C4-C9). Details of this interaction are given in Table 3. All of these
intermolecular interactions give two-dimensional framework results [(Fig. S4) (supplementary
material)].
3.2. Optimized geometry and electronic structure
The optimized parameters of compounds 1-3 have been obtained by using the
B3LYP/6-31G(d,p) level by DFT method. The computational results for compounds 1-3 were
listed together with corresponding X-ray experimental values in Table 2. As seen from Table
2, the optimized bond lengths and the bond angles are slightly different than the X-ray
experimental values. We noted here that the experimental results belong to the solid phase and
theoretical calculations belong to the gas phase. In the solid state, the existence of a crystal
field along with the intermolecular interactions connects the molecules together, which results
in the differences in bond parameters between the calculated and experimental values.
According to X-ray and DFT studies, the dihedral angles between the mean planes of
A (N1-N3/C1-C3), B (C4-C9) and C (C10-C15) rings for compounds 1-3 are given Table 2.
A logical method for globally comparing the structures obtained with the theoretical
calculations (red) is by superimposing the molecular skeleton with that obtained from X-ray
diffraction (blue), giving a RMSE of 0.232 Å for compound 1, 0.226 Å for compound 2 and
0
.177 Å for compound 3 (Fig. 2). These differences are due to intermolecular interactions.
11

These studies indicate that the B3LYP calculation reproduce the geometry of the compounds
well.
(a)
(b)
(
c)
Fig. 2. Atom-by-atom superimposition of the calculated structures (red) over the X-ray
structures (blue) for the synthesized compounds 1-3 [(a) for 1, (b) for 2 and (c) for 3].
Hydrogen atoms have been omitted for clarity.
3.3. Non-linear optical effects
Non-linear optical (NLO) effects arise from the interactions of electromagnetic fields
in various media to produce new fields altered in phase, frequency, amplitude or other
propagation characteristics from the incident fields [32]. NLO is at the forefront of current
research because of its importance in providing the key functions of frequency shifting,
optical modulation, optical switching, optical logic, and optical memory for the emerging
technologies in areas such as telecommunications, signal processing, and optical
interconnections [33-35]. In order to investigate the relationships among photocurrent
generation, molecular structures and NLO, the polarizabilities and hyperpolarizabilities of
compounds 1-3 was calculated.
12

The total static dipole moment (μ), the average linear polarizability (α) and, the first
hyperpolarizability (β) can be calculated using the following the Eqs. (1)-(3), respectively
[
33]. There are x, y and z components:
2
x
2
y
2
z
µ= µ +µ +µ
(1)
(2)
(3)
αxx + αyy + αzz
α=
3
2
2
2
β= (βxxx +βxyy +βxzz ) + (β +βxxy +βyzz ) + (β +βxxz +βyyz
)
yyy
zzz
DFT has been extensively used as an effective method to investigate the organic NLO
materials [36]. In order to investigate the NLO properties of structures, μ, α, and β
components for compounds 1-3 in gas phase were calculated at the B3LYP/6-31G(d,p) level
using polar = ENONLY input to Gaussian 03W program package listed in Table 4. In our
present work, the corresponding results of μ, α and β are given directly here, 2.807 D, 27.5889
3
-30
5
3
-30
Å and 5.5930x10 cm /e.s.u. for compound 1, 4.031 D, 26.2836 Å and 3.2817x10
5
3
-30
5
cm /e.s.u. for compound 2, and 7.355 D, 28.4596 Å and 7.2968x10 cm /e.s.u. for
compound 3, respectively. Although the calculated values of α and β are smaller than that of
(Z)-4-methyl-N-[2-((2-oxonaphthalen-1(2H)-ylidene)methylamino)ethyl]benzenesulfonamide
3
-30
5
(
α = 39.117 Å and β = 13.011x10 cm /e.s.u. calculated with B3LYP/6-31G(d,p) method)
3
[
37] and (E)-1-((4-phenoxyphenylimino)methyl)naphthalen-2-olate (α = 45.34 Å and β =
-
30
5
3
9.01x10 cm /e.s.u. calculated with B3LYP/6-31G(d,p) method) [38]. Urea is one of the
prototypical molecules used in the study of the NLO properties of molecular systems.
Therefore it was used frequently as a threshold value for comparative purposes. The
3
-30
5
calculated values of α and β for compounds 1-3 are, 27.5889 Å and 5.5930x10 cm /e.s.u.,
3
-30
5
3
-30
5
2
6.2836 Å and 3.2817x10
cm /e.s.u. and 28.4596 Å and 7.2968x10
cm /e.s.u.,
3
respectively, which are greater than those of urea (the α and β of urea are 3.831 Å and
-
30
5
0
.3728x10 cm /e.s.u. obtained by B3LYP/6-31G(d,p) method). So that, these results
indicate that compounds 1-3 are good candidate NLO materials.
13

3
Table 4. The calculated static dipole moments (D), linear polarizability (Å ) and first
hyperpolarizability components (a.u.) for compounds 1-3 in gas phase.
1
2
3
1
2
3
μ
μ
x
y
1.3035
2.4799
-0.1726
3.1918
-1.0752
4.0305
-2.2562
6.7337
1.9149
β
β
β
β
β
β
β
xxx
xxy
xyy
yyy
xxz
xyz
yyz
-365.4869
258.0666
143.2967
-328.0198
-31.4658
7.8488
-119.7117
138.4988
96.8056
387.5222
-238.1375
-68.3260
560.9760
327.1541
-343.1309
258.2515
127.3559
-196.8959
12.0348
μ
z
-553.2536
-152.3444
145.1642
71.18243
-130.4859
112.8170
-90.8921
α
xx
α
xy
α
yy
α
xz
α
yz
35.2489
-2.1673
32.1889
3.1412
24.8951
0.1285
26.7226
-7.3773
38.5578
4.3371
34.8663
6.5570
4.6281
β
β
β
xzz
yzz
zzz
-30.3930
25.2420
4.0966
2.7383
-2.2591
19.0894
5.4078
α
zz
15.3292
20.0985
3.4. Total energies and dipole moments in solvent media
The total energy, energy gap and dipole moment have an effect on the stability of a
molecule [39]. We have done optimization in order to evaluate the energetic behavior and
dipole moments of the compounds 1-3 in solvent media; we carried out calculations in gas
phase and four different kinds of solvent (benzene, chloroform, ethanol and DMSO). The total
molecular energies, the highest occupied molecular orbital (HOMO) and the lowest
unoccupied molecular orbital (LUMO) energies, dipole moments and chemical hardness (η)
have been calculated with the PCM using B3LYP/6-31G(d,p). Results obtained from solvent
and gas phase are listed in Table 5. The chemical hardness is quite useful to rationalize the
relative stability and reactivity of chemical species. Hard species having large HOMO-LUMO
gap will be more stable and less reactive than soft species having small HOMO-LUMO gap
[40]. As seen from Table 5, we can infer that the obtained total molecular energies and energy
gap (ΔE) between HOMO and LUMO of compounds 1-3 by PCM method and chemical
hardness decrease with the increasing polarity of the solvent while the dipole moments rise
with the increase of polarity of the solvent for compounds 1-2. Solvent effects improve the
charge delocalized in the molecules, therefore, inducing the dipole moments to be raised.
Ground-state dipole moment is an important factor in measuring the solvent effect. A large
14

ground-state dipole moment gives rise to strong solvent polarity effects [41, 42]. However, we
can conclude that the total molecular energies obtained by PCM method decrease with the
increasing polarity of the solvent, while the dipole moments and chemical hardness will
increase with the increase of the polarity of the solvent for compound 3. According to these
results, the stability of compound 3 increases in going from the gas phase to the solution
phase.
3.5. Frontier molecular orbital energies
Energies HOMO and LUMO are popular quantum mechanical descriptors [43].
According to the investigation on the FMO energy levels of the compounds, which play
important roles in interactions between the molecules as well as in electronic spectra of
molecule [44], we can find that the corresponding electronic transfer happened between
HOMO and LUMO, respectively. The energies of the HOMO are directly related to the
ionization potential and characterize the susceptibility of the molecule towards attack of
electrophiles. The energy of LUMO is directly related to the electron affinity and
characterizes the susceptibility of the molecule attack of nucleophiles. The concept of hard
and soft nucleophiles and electrophiles has been also directly related to the relative energies
of the HOMO and LUMO orbitals. Hard nucleophiles have a low energy HOMO, soft
nucleophiles have a high energy HOMO, hard electrophiles have a high energy LUMO and
soft electrophiles have a low energy LUMO. Hard species having large HOMO-LUMO gap
will be more stable and less reactive than soft species having small HOMO-LUMO gap [45].
The atomic orbital compositions of the frontier molecular orbitals with energy values, which
computed at B3LYP/6-31G(d,p) level for compounds 1-3 in gas phase are shown in Fig. 3.
The positive phase is red and the negative one is green. As seen from Fig. 3, in the HOMO:
the main electronic transition is occurred at partly phenyl ring and C3 atom, while in LUMO
the charge density accumulated at a part of phenyl ring for compound 1. In compound 2, it is
clear from the figure that while the HOMO is mainly delocalized over the structure, LUMO is
delocalized on the whole structure other than hydrazinly group and phenyl ring. In the
15

HOMO, the charge density is mainly localized on C atom of triazine group and S atom
attached to triazine group of molecule for compound 3. However, in case of the LUMO, more
charge density moves to the triazine ring part and S1 atom. Both the HOMO and LUMO are
mostly the π-antibonding type orbitals for compounds 1-3. As can be seen from Table 5, the
magnitude of the energy separations between the HOMO and LUMO (transition from HOMO
to LUMO) are 6.232, 4.187 and 3.211 eV for compounds 1, 2 and 3, respectively, in gas
phase. In our present study compound 3 with low chemical hardness 1.6055 eV compared
with other compound 1-2 have a low energy gap. Normally, the inhibitor with the least value
of chemical hardness is expected to have the highest inhibition efficiency [46]. These large
HOMO-LUMO gaps automatically mean high excitation energies for many of excited states,
a good stability and a high chemical hardness for the compounds 1-3.
LUMO (-0.262 eV)
HOMO (-6.494 eV)
(
a)
LUMO (-1.931 eV)
HOMO (-6.118 eV)
(b)
16

LUMO (-1.798 eV)
HOMO (-5.009 eV)
(c)
Fig. 3. Molecular orbital surfaces and energy levels given in parentheses for the HOMO and
LUMO synthesized compounds 1-3 [(a) for 1, (b) for 2 and (c) for 3] computed at B3LYP/6-
31G(d,p) level.
17

Table 5. Calculated energies, frontier orbital energies, chemical hardness and dipole moments of structures for four different solvents.
Gas phase (ε =1)
Benzene (ε = 2.3)
Chloroform (ε = 4.9)
1
2
3
1
2
3
1
2
3
E
E
E
total (Hartree)
HOMO (eV)
LUMO (eV)
-797.8311
-852.8783 -1140.4349 -797.8396 -853.1576 -1140.6669
-797.8459
-853.1643
-5.903
-1.887
4.016
-1140.6749
-6.076
-2.656
3.420
-6.494
-0.262
6.232
-6.118
-1.931
4.187
-5.009
-1.798
3.211
-5.892
-1.765
4.127
-5.890
-1.860
4.030
-5.926
-2.634
3.292
-5.927
-1.809
4.118
ΔE (eV)
η(eV)
μ (D)
3.1160
2.807
2.0935
4.031
1.6055
7.355
2.0635
3.330
2.0150
4.044
1.6460
8.277
2.0590
3.712
2.0080
4.495
1.7100
9.450
Ethanol (ε = 24.55)
DMSO (ε = 46.7)
1
2
3
1
2
3
E
E
E
total (Hartree)
HOMO (eV)
LUMO (eV)
-797.8520
-5.971
-1.854
4.117
-853.1707 -1140.6827 -797.8526 -853.1714 -1140.6837
-5.874
-1.865
4.009
-6.192
-2.679
3.513
-5.974
-1.858
4.116
-5.892
-1.891
4.001
-6.203
-2.680
3.523
ΔE (eV)
η(eV)
μ (D)
2.0585
4.088
2.0045
4.768
1.7565
10.550
2.0580
4.132
2.0005
4.834
1.7615
10.693
18

3.6. Molecular electrostatic potential
The molecular electrostatic potential (MEP) V(r), is related to the electronic density
and is a very useful descriptor in determining the sites for electrophilic and nucleophilic
reactions as well as hydrogen bonding interactions [47, 48]. Being a real physical property,
V(r) can be determined experimentally by diffraction or by computational methods [44].
MEP maps of the compounds 1-3 were calculated by using the geometry obtained from DFT
method at the B3LYP/6-31G(d,p). The negative (red and yellow) and the positive (blue)
regions in the MEP were related to electrophilic reactivity and nucleophilic reactivity,
respectively (Fig. 4). As can be seen from the Fig. 4, In compounds 1-3, negative electrostatic
potential regions (red color) are mainly localized over 1,2,4-triazine ring atoms. In such a way
that, the most negative regions are on the N2 and N1 atoms in compounds 1-2 and V(r) values
are -0.058 and -0.056 a.u. for compound 1, -0.059 and -0.057 a.u. for compound 2. In
compound 3, the negative V(r) values are -0.060 and -0.058 a.u. S1 and N3 atoms,
respectively, which is the most negative regions. However, for the possible nucleophilic
reactions, the most positive regions (blue color) in MEP maps are on the hydrogen atoms
bonded to N4 for compound 1 and N4 and N5 for compound 2. The maximum positive
regions are located on the H1 and H2 atoms bonded to N4 with V(r) values of 0.041 and
0.046 a.u. for compound 1, the latter positive sites are localized over the H4 and H5A
hydrogen atoms bonded to N4 and N5 atoms with values of 0.032 and 0.042 a.u. for
compound 2, respectively. In compound 3, a maximum positive region is associated with the
N1-H1 bond indicating a possible site for nucleophilic attack with maximum value of 0.048
a.u. In regard to these calculated results, the MEP map indicates that the negative potential
sites are on nitrogen atoms as the positive potential sites are around the hydrogen atoms.
These regions give knowledge about intermolecular interactions.
19

(a)
(b)
(c)
Fig. 4. Molecular electrostatic potential maps of the synthesized compounds 1-3 [(a) for 1, (b)
for 2 and (c) for 3] calculated at B3LYP/6-31G(d,p) level.
3
.7. NMR analysis
The isotropic chemical shifts are frequently used as an aid in identification of reactive organic
as well as ionic species. It is recognized that accurate predictions of molecular geometries are
essential for reliable calculations of magnetic properties [49]. Therefore, full geometry
optimization of compounds 1-3 were performed by using the HF and B3LYP methods with 6-
1
13
3
1G(d,p) basis set. Then, GIAO H and C chemical shift calculations of the compounds 1-3
1
13
have been by the same methods. The H-NMR and C-NMR chemical shifts were measured
in gas phase and a less polar (CDCl ) solvent. The results obtained via experimental (in
chloroform) and theoretical calculations (in gas phase and chloroform) are tabulated in Table
. The molecule 1 contains twelve protons, out of these, 10 are aromatic and two are amino.
There is very clear sharp singlet peak at 5.53 ppm with the intensity of two protons
representing the protons (H & H ) of amino group. The corresponding values we obtained
3
6
1
2
through HF & B3LYP method are 4.30-4.59 & 5.01-5.46, respectively. Since, we had one
dimensional proton spectrum so it is difficult to assign separate value for each aromatic
proton in experimental results. We have provided aromatic range for all three molecules and
these are well comparable with data obtained through theoretical calculations. Similarly for
molecule two there are two singlet’s appear at 6.64 and 4.18 ppm with the intensity of one
2
and two protons which help us to identify NH & NH protons. The third molecule had one N-
20

H proton which gave a broad peak at 11.78 ppm the corresponding HF and B3LYP values are
1
3
1
1.62 & 11.36 ppm. C-NMR data also gave very good characterization of all three
molecules, triazine ring in each molecule contain three carbon atoms C1, C2 & C3. C1 lies
between two carbon atoms and it appears at 161.18 ppm, the calculated theoretical values for
3
this signal are 159.23 & 148.23 ppm in CDCl through HF and B3LYP methods for molecule
nd
rd
1
. Similarly in 2 and 3 molecule this signal appears at 162.20 & 179.24 ppm. The variation
rd
in 3 molecule represents its different environment with other two molecules. The overall
assignments for triazine and aromatic carbon atoms are given in Table 6.
1
13
Table 6. Experimental and theoretical H-NMR and C-NMR isotropic chemical shifts (with
respect to TMS, all values in ppm) of compounds 1-3 in gas phase and chloroform.
Compound 1
Atom
Exp.
CDCl
5.53
HF
CDCl
4.59
4.30
8.1
B3LYP
Atom
Exp.
HF
B3LYP
CDCl
3
3
Gas
4.12
3.70
7.13
7.37
7.69
7.78
8.33
7.35
7.23
7.82
7.79
9.06
CDCl
5.46
5.01
8.70
8.03
7.84
7.61
7.37
7.60
7.60
7.94
8.06
8.70
3
Gas
4.93
4.36
8.70
7.83
7.61
7.49
7.26
7.54
7.37
7.67
7.81
8.60
CDCl
3
CDCl
3
Gas
3
Gas
H1
H2
C1
C2
161.18
150.78
157.24
135.97
128.38
129.24
128.53
129.24
129.38
136.04
128.38
129.52
130.37
129.52
128.38
159.23
148.17
163.31
134.95
128.30
126.19
126.04
124.57
128.41
132.73
129.40
123.76
129.30
125.38
129.14
158.16
147.87
161.03
135.58
128.77
126.06
125.39
124.20
128.38
133.58
129.45
123.57
128.22
126.05
129.02
148.23
142.40
145.52
126.19
116.50
116.45
115.50
114.74
117.47
125.56
118.38
114.60
118.14
126.39
118.38
147.02
142.37
143.60
126.55
127.18
116.27
114.96
114.28
117.49
126.23
118.41
114.21
117.12
115.95
118.58
5.53
H5
7.30
C3
H6
7.72
7.55
7.25
6.86
7.04
7.24
7.68
7.72
8.26
C4
H7
C5
H8
to
C6
H9
C7
H11
H12
H13
H14
H15
C8
C9
C10
C11
C12
C13
C14
C15
7.44
Compound 2
Atom
Exp.
CDCl
HF
B3LYP
Atom
Exp.
HF
B3LYP
3
CDCl
6.49
3
Gas
5.97
3.38
CDCl
3
Gas
6.38
3.53
CDCl
3
CDCl
3
Gas
CDCl
3
Gas
H4
6.64
4.18
6.93
C1
C2
162.20
151.21
168.20
153.78
167.28
153.40
151.22
141.84
H5A
3.69
3.79
21

H5B
H5
4.18
7.31
3.67
8.82
8.01
7.82
7.55
7.29
7.60
7.55
8.04
8.03
8.91
3.26
8.78
7.78
7.56
7.29
7.14
7.54
7.30
7.73
7.76
8.75
3.73
8.76
8.03
7.82
7.60
7.38
7.63
7.62
7.96
8.06
8.71
3.35
8.76
7.84
7.59
7.48
7.25
7.58
7.40
7.40
7.69
8.58
C3
C4
157.12
128.62
128.38
129.25
135.92
129.25
128.38
130.52
128.39
129.56
135.96
129.56
128.39
164.47
137.01
130.09
128.89
128.91
127.36
131.18
134.51
133.44
126.22
133.39
127.79
133.08
161.94
137.36
130.76
128.83
128.44
126.95
131.15
135.37
133.47
126.12
132.26
127.53
132.93
144.98
126.07
116.48
116.39
115.56
114.79
117.39
125.86
118.36
124.74
118.20
116.43
118.42
H6
C5
H7
C6
H8
C7
H9
to
C8
H11
H12
H13
H14
H15
C9
C10
C11
C12
C13
C14
C15
7.49
Compound 3
Atom
Exp.
CDCl
HF
B3LYP
Atom
Exp.
HF
B3LYP
CDCl
3
CDCl
3
Gas
10.65
7.13
7.37
7.69
7.78
8.33
7.35
7.23
7.82
7.79
9.06
CDCl
3
Gas
10.59
7.22
7.44
7.67
7.81
8.19
7.45
7.46
7.74
7.83
8.71
CDCl
3
CDCl
3
Gas
3
Gas
H1
H5
11.78
7.27
11.62
7.35
7.63
8.00
8.04
8.54
7.54
7.53
8.17
8.05
9.15
11.36
7.42
7.69
7.94
8.05
8.37
7.60
7.62
8.03
8.07
8.80
C1
C2
179.24
146.66
160.73
130.28
128.39
128.74
129.40
128.74
128.39
132.22
128.60
130.10
129.86
130.10
128.39
199.94
150.76
169.81
133.07
131.76
127.44
131.77
128.95
129.79
131.48
134.41
125.42
136.41
127.65
135.11
187.15
148.38
167.77
134.05
131.34
127.23
130.56
128.85
129.48
132.46
133.69
124.90
134.74
127.59
135.27
170.18
136.14
148.64
122.78
117.29
115.32
117.62
116.96
115.84
123.49
118.86
114.72
120.62
116.92
119.75
169.63
133.87
147.26
123.45
116.89
114.82
116.47
116.54
115.60
124.15
118.31
113.94
119.14
116.51
119.94
H6
C3
H7
C4
H8
C5
H9
to
C6
H11
H12
H13
H14
H15
C7
C8
C9
C10
C11
C12
C13
C14
C15
7.57
3.8. Electronic absorption spectra
In order to understand electronic transitions, electronic absorption spectra was calculated with
TD-DFT method, based on the B3LYP/6-31G(d,p) level optimized structure of compounds 1-
3. TD-DFT calculations of compounds 1-3 in gas phase and chloroform solvent were
performed by using PCM model. The experimental and computed electronic values, such as
22

absorption maxima of λ (which is a function of the electron availability) and Singlet A values
which are from CI expansion coefficients are used to calculate the percentage contribution of
the translations), excitation energies (E), and oscillator strengths (f) are reported Table S1
supplementary material). The major contributions of the transitions were designated with the
(
(
aid of SWizard program [50]. The electronic absorption spectra of the investigated
compounds show an electronic absorption band with maxima at 345, 355 and 440 nm for
compound 1, 2 and 3, respectively, these values are very close to calculated absorption peak.
These experimental bands at 345, 355 and 440 nm for compounds 1-3, respectively are
*
attributed mainly to a HOMO→LUMO transitions are predicted as π→π transitions. The
other wavelength, excitation energies, oscillator strengths and calculated counterparts with
major contributions in gas phase and solvent can be seen in Table S1 (supplementary
material).
4
. Conclusions
In this paper, we have synthesized compounds [C15
3)] including triazine heterocyclic derivative, and characterized it using structural (XRD)
12 4 13 5 11 3
H N (1), C15H N (2) and C15H N S
(
technique. The optimized parameters of compounds 1-3 have been obtained by using the
B3LYP/6-31G(d,p) level by DFT method. The X-ray structure is found to be very slightly
different from its optimized counterparts. It is noted here that the experimental results are for
the solid phase and the theoretical calculations are for the gas phase. In the solid state, the
existence of the crystal field together with the intermolecular interactions holds the molecules
together, which results in differences between X-ray experimental and calculated values for
the bond parameters. In spite of the differences observed in the geometric parameters, the
common agreement is good and the theoretical calculations support the solid-state structures.
Furthermore, the non-linear optical properties: total static dipole moment and the first
hyperpolarizability properties of compounds have been calculated in order to get insight into
compounds. And also the value of the ΔE explains the eventual charge transfer interaction
23

taking place within the molecule of compounds. The total energy of molecules decreases with
the increasing polarity of the solvent for compounds 1-3. Chemical hardness decrease with the
increasing polarity of the solvent while the dipole moments rise with the increase of polarity
of the solvent for compounds 1-2. However, dipole moments and chemical hardness have
been increased with the increase of the polarity of the solvent for compound 3. According to
these results, the stability of compound 3 increases in going from the gas phase to the solution
phase. To predict reactive sites for electrophilic and nucleophilic attack for the investigated
molecules, MEP studies were carried out. Thus, it would be predicted that the nitrogen atoms
will be the most reactive site for electrophilic attack and hydrogen atoms will be the reactive
site for nucleophilic attack. These sites give information about the possible areas for inter-
and intramolecular hydrogen bonds. The magnetic properties of the compounds 1-3 were
1
13
observed and calculated. The theoretical H-NMR and C-NMR chemical shift results of
1
13
compounds 1-3 are generally are closer to the experimental H-NMR and C-NMR shift data.
The electronic properties were also experimental and calculated electronic spectrum was
recorded with help of UV-vis spectrometer. The experimental bands at 345, 355 and 440 nm
for compounds 1-3, respectively are attributed mainly to a HOMO→LUMO transitions are
*
predicted as π→π transitions. The comparisons of the predicted bands with the experimental
bands were done and show an acceptable general agreement. The present quantum chemical
study may further play an important role in understanding of dynamics of these molecules.
In summary, very complete characterizations of studied novel compounds were given
in the present paper. We hope the results of this study will be helpful for the design and
synthesis new materials.
5. Acknowledgment
This paper was funded by the Deanship of Scientific Research (DSR), King Abdulaziz
University, under grant No. (50-3-1432/HiCi). The authors, therefore, acknowledge with
thanks DSR technical and financial support.
24

References
[
[
[
1] S.B. Padhye, G.B. Kaufman, Coord. Chem. Rev. 63 (1985) 127-160.
2] A.M. Asiri, S.A. Khan, Molecules 15 (2010) 4784-4791.
3] E. Bermejo, R. Carballo, A. Castineiras, R. Dominguez, C.M. Mossemer, J. Strahle, D.X.
West, Polyhedron 18 (1999) 3695-3702.
4] M. Ghassemzadeh, M. Mirza-Aghayan, B. Neumüller, Inorg. Chim. Acta 358 (2005)
057-2065.
5] C. Lee , S. Lo, J. Lim, V.C.P. da-Costa, S. Ramezani, O.K. Oz, G.M. Pavan, O.
Annunziata, X. Sun, E.E. Simanek, Mol. Pharmaceutics, 10 (2013)4452–4461
6] J.N. Hogarh, N. Seike, Y. Kobara, A. Habib, J.J. Namd, J.S. Lee, Qilu Li, X. Liu, Li Jun,
G. Zhang, S. Masunaga,. Chemosphere 86 (2012) 718-726.
7] M. Larif, A. Adad, R. Hmammouchi, A.I. Taghki, A. Soulaymani, A. Elmidaoui, M.
Bouachrine, T. Lakhlifi, Arabian Journal of Chemistry
http://dx.doi.org/10.1016/j.arabjc.2012.12.033.
[
2
[
[
[
[
(
[
[
[
[
[
[
[
[
[
8] A.M. Asiri, A.O. Baghlaf, R.M. Abdel-Rahman, S.A. Khan, M. Ishaq Asian J. Chem. 25
2013) 7779-7782.
9] F.D. Proft, P. Geerlings, Chem. Rev. 101 (2001) 1451-1464.
10] G. Fitzgerald, J. Andzelm, J. Phys. Chem. 95 (1991) 10531-10534.
11] T. Ziegler, Pure Appl. Chem. 63 (1991) 873-878.
12] J. Andzelm, E. Wimmer, J. Chem. Phys. 96 (1992) 1280-1303.
13] G.E. Scuseria, J. Chem. Phys. 97 (1992) 7528-7530.
14] R.M. Dickson, A.D. Becke, J. Chem. Phys. 99 (1993) 3898-3905.
15] B.G. Johnson, P.M.W. Gill, J.A. Pople, J. Chem. Phys. 98 (1993) 5612-5626.
16] N. Oliphant, R.J. Bartlett, J. Chem. Phys. 100 (1994) 6550-6561.
17] M.E. F. Braibante, H.T.S. Braibante, M.P. Uliana, C.C. Costa, M. Spenazzatto, J. Braz.
Chem. Soc. 19 (2008) 909-913.
25

[18]M.M. Mashaly, H.F. El-Shafiy, S.B. El-Maraghy, H.A. Habib, Spectrochimica Acta A:
61 (2005) 1853–1869
[
[
19]G.M. Sheldrick, Acta Cryst. A: Found. Crystallogr. 64 (2008) 112-122.
20] C.F. Macrae, P.R. Edgington, P. McCabe, E. Pidcock, G.P. Shields, R. Taylor, M.
Towler, J. van de Streek, J. Appl. Cryst. 39 (2006) 453-457.
[
[
[
21] A.L. Spek, Utrecht University, Utrecht, The Netherlands, 20 (2001).
22] L.J. Farrugia, J. Appl. Cryst. 32 (1999) 837-838.
23] 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,
Gaussian, Inc., Wallingford, CT, 2004.
[
24] R. Dennington II, T. Keith, J. Millam, GaussView, Version 4.1.2. Semichem Inc.,
Shawnee Mission, KS, 2007.
25] P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J. Frisch, J. Phys. Chem. 98 (1994)
1623-11627.
[
1
[26] R. Ditchfield, W.J. Hehre, J.A. Pople, J. Chem. Phys. 54 (1971) 724-728.
[27] S. Miertus, E. Scrocco, J. Tomasi, Chem. Phys. 55 (1981) 117-129.
[28] V. Barone, M. Cossi, J. Phys. Chem. A 102 (1998) 1995-2001.
26

[
[
[
[
29] M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Comput. Chem. 24 (2003) 669-681.
30] J. Tomasi, B. Mennucci, R. Cammi, Chem. Rev. 105 (2005) 2999-3093.
31] R. Ditchfield, J. Chem. Phys. 56 (1972) 5688-5691.
32] Y.X. Sun, Q.L. Hao, W.X. Wei, Z.X. Yu, L.D. Lu, X. Wang, Y.S. Wang, J. Mol. Struct.
9
04 (2009) 74-82.
33] C. Andraud, T. Brotin, C. Garcia, F. Pelle, P. Goldner, B. Bigot, A. Collet, J. Am. Chem.
Soc. 116 (1994) 2094-2102.
[
[
[
34] V.M. Geskin, C. Lambert, J.-L. Brédas, J. Am. Chem. Soc. 125 (2003) 15651-15658.
35] M. Nakano, H. Fujita, M. Takahata, K. Yamaguchi, J. Am. Chem. Soc. 124 (2002) 9648-
9
655.
[
36] D. Sajan, J. Hubert, V.S. Jayakumar, J. Zaleski, J. Mol. Struct. 785 (2006) 43-53.
37] G. Alpaslan, M. Macit, A. Erdönmez, O. Büyükgüngör, J. Mol. Struct. 1016 (2012) 22-
[
2
9.
[
[
[
[
(
[
[
[
38] G. Alpaslan, M. Macit, A. Erdönmez, O. Büyükgüngör, J. Mol. Struct. 997 (2011) 70-77.
39] R.G. Pearson, Coord. Chem. Rev. 24 (1994) 401.
40] N. Ozbek, G. Kavak, Y. Ozcan, S. Ide, N. Karacan, J. Mol. Struct. 919 (2009) 154-159.
41] A. Masternak, G. Wenska, J. Milecki, B. Skalski, S. Franzen, J. Phys. Chem. A 109
2005) 759-766.
42] Y. Le, J.F. Chen, M. Pu, Int. J. Pharm. Sci. 358 (2008) 214-218.
43] Z. Zhou, R.G. Parr, J. Am. Chem. Soc. 112 (1990) 5720-5724.
44] K. Fukui, Theory of Orientation and Stereoselection. Springer, Berlin Heidelberg New
York (1975).
45] I. Fleming, Frontier Orbital and Organic Chemical Reactions, John Wiley & Sons, New
York (1976).
46] N.O. Obi-Egbedi, I.B. Obot, M.I. El-Khaiary, S.A. Umoren, E.E. Ebenso, Int. J.
Electrochem. Sci. 6 (2011) 5649-5675.
47] P. Politzer, P. Lane, Struct. Chem. 1 (1990) 159-164.
[
[
[
27

[
[
48] E. Scrocco, J. Tomasi, Adv. Quantum Chem. 11 (1978) 115-193.
49] S. Sebastian, N. Sundaraganesan, B. Karthikeiyan, V. Srinivasan, Spectrochim. Acta A
7
8 (2011) 590-600.
50] S.I. Gorelsky, SWizard Program, Revision 4.5, University of Ottawa, Ottawa, Canada,
010, <http://www.sg.chem.net/>.
[
2
28

Highlights
►
►
Synthesis of triazine heterocyclic derivatives.
Molecular geometry of triazine heterocyclic derivative in the ground state using the density
functional theory (DFT) with 6-31G(d,p)
►
Crystal structure determination of triazine heterocyclic derivatives
29