Experimental and DFT studies on the vibrational and electronic spectra of 9-p-tolyl-9H-carbazole-3-carbaldehyde

Article abstract of DOI:10.1016/j.saa.2014.06.103

The compound 9-p-tolyl-9H-carbazole-3-carbaldehyde (HCCD) was synthesized and characterized by X-ray diffraction, FT-IR, FT-Raman and UV-Vis spectra. The X-ray diffraction study showed that HCCD has a Z-configuration. The benzene ring including methyl is twisted from the mean plane of the carbazole group by 59.7(3)°, which is comparable with the calculated result 65° for B3LYP/6-311++G(d, p) method. Vibrational spectra and electronic spectra measurements were made for the compound. Optimized geometrical structure and harmonic vibrational frequencies were computed with B-based DFT (BLYP, B3LYP and cam-B3LYP) methods, and WB-based DFT (WB97, WB97X and WB97XD) methods and ab initio RHF method using 6-311++G(d, p) basis set. Assignments of the observed spectra were proposed. The equilibrium geometries computed by all of the methods were compared with X-ray diffraction results. The absorption spectra of the title compound were computed both in gas phase and in DMF solution using TD-(cam)B3LYP/6-311++G(d, p) and PCM-(cam)B3LYP/6-311++G(d, p) approaches, respectively. The calculated results provide good descriptions of the bands maxima in the observed electronic spectrum. Temperature dependence of thermodynamic parameters in the range of 100-1000 K was determined. The natural atomic hybrids were calculated and discussed.

Full text of DOI:10.1016/j.saa.2014.06.103

Accepted Manuscript
Experimental and DFT studies on the vibrational and electronic spectra of 9-p-
tolyl-9H-carbazole-3-carbaldehyde
Yiwei Wang, Yu Zhang, Haiwei Ni, Nana Meng, Kuirong Ma, Jianying Zhao,
Dunru Zhu
PII:
S1386-1425(14)01002-6
http://dx.doi.org/10.1016/j.saa.2014.06.103
SAA 12362
DOI:
Reference:
To appear in:
Spectrochimica Acta Part A: Molecular and Biomo-
lecular Spectroscopy
Received Date:
Revised Date:
Accepted Date:
10 February 2014
1 June 2014
16 June 2014
Please cite this article as: Y. Wang, Y. Zhang, H. Ni, N. Meng, K. Ma, J. Zhao, D. Zhu, Experimental and DFT
studies on the vibrational and electronic spectra of 9-p-tolyl-9H-carbazole-3-carbaldehyde, Spectrochimica Acta
Part A: Molecular and Biomolecular Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.2014.06.103
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Experimental and DFT studies on the vibrational and electronic spectra of
-p-tolyl-9H-carbazole-3-carbaldehyde
9
a,b
b*
b
b
b
Yiwei Wang , Yu Zhang , Haiwei Ni , Nana Meng , Kuirong Ma ,
b
a*
Jianying Zhao , Dunru Zhu
a
College of Chemistry and Chemical Engineering, Nanjing University of Technology,
Nanjing 210009, P. R. China
b
Huaian Key Laboratory for Photoelectric Conversion and Energy Storage Materials,
Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of
Chemistry and Chemical Engineering, Huaiyin Normal University, Huai’an 223300,
Jiangsu, P. R. China
Corresponding author at: Tel.: +86 517 83525311; fax: +86 517 83525313.
E-mail address: yuzhang@hytc.edu.cn (for Yu Zhang)
zhudr@njut.edu.cn (for Dunru Zhu)
Abstract
The compound 9-p-tolyl-9H-carbazole-3-carbaldehyde (HCCD) was synthesized
and characterized by X-ray diffraction, FT-IR, FT-Raman and UV-Vis spectra. The
X-ray diffraction study showed that HCCD has a Z-configuration. The benzene ring
◦
including methyl is twisted from the mean plane of the carbazole group by 59.7(3) ,
which is comparable with the calculated result 65º for B3LYP/6-311++G(d, p)
method. Vibrational spectra and electronic spectra measurements were made for the
compound. Optimized geometrical structure and harmonic vibrational frequencies
were computed with B-based DFT (BLYP, B3LYP and cam-B3LYP) methods, and
WB-based DFT, (WB97, WB97X and WB97XD) methods and ab initio RHF method
using 6-311++ G(d, p) basis set. Assignments of the observed spectra were proposed.
The equilibrium geometries computed by all of the methods were compared with
1

X-ray diffraction results. The absorption spectra of the title compound were computed
both in gas phase and in DMF solution using TD-(cam)B3LYP/6-311++G(d, p) and
PCM-(cam)B3LYP/6-311++G(d, p) approaches, respectively. The calculated results
provide good descriptions of the bands maxima in the observed electronic spectrum.
Temperature dependence of thermodynamic parameters in the range of 100-1000 K
was determined. The natural atomic hybrids were calculated and discussed.
Keywords: Density functional theory (DFT); vibrational spectra; electronic spectra;
NBO; 9-p-tolyl-9H-carbazole-3-carbaldehyde (HCCD)
1. Introduction
Carbazole is an aromatic heterocyclic organic compound. It was isolated firstly
from coal tar in 1872 by Graebe and Glazer [1] and was firstly synthesized by
Borsche [2] and Drechsel [3]. Carbazole compounds have been extensively
investigated for the following reasons: (1) the carbazole unit was known as a famous
hole-transporting and electroluminescent material [4,5]. (2) The carbazole units can
be easily modified at 3-, 6-, 9-positions and covalently linked to other molecular
groups to be a functional building block or substituent for the preparation of organic
photoconductors [6], non-linearoptic(NLO) materials [7], efficient dyes for solar cells
[
(
8], organic light-emitting devices(OLED) [9] and phosphorescence applications [10].
3) Carbazole is isoelectronic to diphenylamine, but it has a planar structure and can
be a rigid structure with a donor-rigidized residue improves electron delocalization. (4)
The thermal stability and the glass state durability of organic compounds can be
greatly improved by the introduction of organic carbazole group in the core structure
[
11].
Carbazole-3-carbaldehyde is an important organic synthesis intermediates, it has
been developed to synthesis important organic compounds with different organic
2

synthesis pathway, such as, (1) Wittig condensation: Hong-Ku Shim [12] et al
reported
the
synthesis
of
Poly-9-(2-ethylhexyl)-3,6-
Poly-9-(2-ethylhexyl)
carbazolevinylene-alt-2,6-napthalenevinylenex
and
-
3,6-carbazolevinylene-alt -1,4-napthalenevinylenex through the Wittig condensation
polymerization, these polymer maximum photoluminescence wavelengths of were
found at 498 and 545 nm, which correspond to the greenish–blue and the yellow
emission region, respectively. (2) Vilsmeier-Haack reaction: R. Renganathan [13]
reported the Vilsmeier–Haack formylation followed by multicomponent cyclization
reaction to form highly fluorescent imidazole–carbazole derivatives. (3) Schiff-base
reaction: Cun Li [14] reported a new carbazole-based Schiff-base as a multi-
3
+
2+
functional fluorescent chemosensor for selectively recognized Fe and Cu ions over
a number of other metal ions. (4) Heck reaction: Săckus [15] reported methodology
and the further condensation of these aldehydes with N-methyl-N-phenylhydrazine
and N,N-diphenylhydrazine, resulting in mono- and dihydrazones that act as effective
hole transporting materials.
Neither the molecular structure and complete vibrational spectra nor the quantum
mechanical calculations for the title compound have been reported, so far. Therefore,
we calculated the vibrational frequencies and geometric parameters of the title
compound in the ground state to distinguish the fundamentals from the experimental
vibrational frequencies and geometric parameters by ab initio RHF and B-based DFT
(
BLYP, B3LYP and cam-B3LYP) methods, and WB-based DFT, (WB97, WB97X
and WB97XD) methods with the standard 6-311++G(d, p) basis set. A detailed
interpretation of the vibrational spectra of the title compound was made on the basis
of the calculated potential energy distribution (PED). The absorption spectra were
calculated with the time-dependent density functional theory (TDDFT) at
3

B3LYP/6-311++G(d, p) level associated with the polarized continuum model (PCM).
Thermodynamic properties of the title compound at different temperatures have also
been calculated and they reveal the correlation between heat capacity, entropy,
enthalpy and Gibbs free energy and temperatures.
2
2
2
. Experimental and computational
.1 Experimental
.1.1 Synthesis of HCCD
Carbazole (16.703 g, 0.1 mol), 4-bromotoluene (20.401 g, 0.12 mol) and
potassium carbonate (27.602 g, 0.2 mol) were dissolved in p-xylene (120 mL), stirring
for 1 h under the protection of nitrogen. Then KI (20.013 g, 0.12 mol),
1,10-phenanthroline (1.802 g, 0.01 mol) and CuI (1.910 g, 0.01 mol) were added, after
reacting 30 minutes, slowly heated to reflux for 48 h [16]. The product was cooled to
room temperature, filtration, extracted with dichloromethane. The extracted solution
was concentrated under reduced pressure and the white needle crystal product
1
(
9-p-tolyl-9H-carbazole) was obtained from ethanol (yield: 80%). HNMR (400 MHz,
CDCl3): δ (ppm) 8.14 (d, 2H, Ar), 7.43 (d, 2H, Ar), 7.39 (d, 4H, Ar), 7.27 (t, 4H, Ar),
2
.48 (s, 3H, CH
-p-tolyl-9H-carbazole (1.14 g, 4.4 mmol) was dissolved in 20 mL
,2-dichloroethane, which was named solution A. POCl (4.8 mL, 52 mmol) was
3
). ES-MS [m/z]: 256.3 [M+1].
9
1
3
added dropwise into 20 mL DMF in ice bath, after reacting 30 minutes at room
temperature, then the solution A was added. The mixture was stirred and heated to
85℃ for 24 h under nitrogen atmosphere. Upon cooling, the mixture was poured into
60 mL ice-water and extracted with chloroform, purified with ethyl acetate, finally got
1
9
-p-tolyl-9H-carbazole-3-carbaldehyde (yield: 72%) [17]. HNMR (400 MHz,
CDCl3): δ (ppm) 10.12 (s, 1H, CHO), 8.67 (s, 1H, Ar), 8.19 (d, 2H, Ar), 7.94 (d, 2H,
4

Ar), 7.46 (t, 2H, Ar), 7.39 (d, 4H, Ar), 2.50 (s, 3H, CH
.1.2 X-ray diffraction measurements
X-ray diffraction measurements of the crystal were performed on a Bruker Smart
3
). ES-MS [m/z]: 286.1 [M+1].
2
Apex CCD diffractometer at 296 K. The intensity data was collected using graphite
monochromated Mo-Kα radiation (λ= 0.71073 Å). The data collection 2θ range was
2.90~50.00º. No significant decay was observed during the data collection. The raw
data was processed to give structure factors using the SAINT-plus program [18].
Empirical absorption corrections were applied to the data sets using the SADABS
[
19]. The structure was solved by direction method and refined by full matrix
2
least-squares against F for all data using SHELXTL software [20]. All non-hydrogen
atoms in the compound were anisotropically refined. All hydrogen atoms were
included in the calculated positions and refined using a riding model with isotropic
thermal parameters 1.2 times larger than those of the parent atoms. The crystal data,
further details of the experimental conditions and the structure refinement parameters
for the compound are given in Table 1 and the atomic numbering scheme are shown
in Fig. 1.
The FT-IR spectrum of the title compound was measured on AVATAR360
−1
spectrophotometer in the range of 400–4000 cm at room temperature using KBr
pellet technique. The Raman spectra was recorded on Bruker RFS 100/S FT-Raman
−1
spectrometer in the 400–2500 cm region with diode-pumped air-cooled cw
Nd–YAG laser source giving 785 nm as exciting line at 75 mW power. The UV–Vis
spectrum was recorded on UV–Vis 916 spectrophotometer in the region 270–500 nm
using DMF as solvent.
2.2 Methods of calculation
The most important step of the theoretical calculations is geometry optimization.
5

This procedure proceeded in two steps; firstly, the initial geometry was constructed by
+
MM molecular modeling in HyperChem 6.0 package [21]. Then the geometry was
optimized by ab initio restrict Hartree–Fock (RHF) method and the B-based density
functional theory (DFT) (BLYP [22,23], B3LYP [24,25], cam-B3LYP [26] and
WB-based DFT WB97 [27], WD97X [27] and WB97XD [28] methods with
6
-311++G(d, p) basis set. Time-dependent density functional theory (TDDFT) [29]
excited-state calculations were determined both in gas phase and in DMF solution.
The polarizable continuum model (PCM) [30] was used to calculate the excitation
energy considering the solvent effect. All calculations were performed using Gaussian
0
3
3
9W program package [31].
Results and discussion
.1 The geometrical structure of HCCD
The crystal data, further details of the experimental conditions and the structure
refinement parameters for the compound are given in Table 1 and the atomic
numbering scheme are shown in Fig. 1(a). The compound belongs to triclinic, space
group P2(1)/n, a = 8.3170(16) Å, b = 13.740(3) Å and c = 13.745(3) Å, α = 90.00º, β
=
107.166(2)º and γ = 90.00º and Z = 4.
The selected experimental bond lengths and angles are listed in Table 2. All the
bond lengths and angles are normal and comparable to those observed in a similar
compound 9-Ethyl-9H-carbazole-3-carbaldehyde [32].
The molecule (Fig. 1) lies approximately in a plane besides the benzene ring
including methyl are tilted with respect to the plan by 65º (∠C8N9C14C17 with
B3LYP/6-311++ G(d, p) method). There is a minor displacement between the plane
of the carbazole ring (1.0º for ∠C2C3C7C10 with B3LYP/6-311++ G(d, p) method).
The difference between the two N-C bonds, N9-C8 and N9-C6, is 0.043 Å, which is
6

similar with 9-ethyl-9H-carbazole-3-carbaldehyde and obviously different from that
of 9-ethyl-3,6-diformyl-9H-carbazole [33] and that of
,6-dibromo-9-ethyl-9H-carbazole [34].
We have investigated the title compound with quantum chemical methods in
3
order to explain the features of the molecular structure, FT-IR, FT-Raman. The
optimized geometry with atomic numbering scheme for the title compound is shown
in Fig. 1 (b). The selected bond lengths and angles are given in Table 2. It is found
that most of the optimized bond lengths are good agreement with the experimental
values. For example, the optimized C-C bond lengths of in cabazole ring falls in the
range (1.39-1.4478 Å), which are in good agreement with those of experimental bond
lengths (1.317-1.470 Å). The optimized C-C bond lengths for BLYP method are in
good agreement with the experimental bond lengths (1.414-1.558 Å). The
experimental N9-C8 (1.441 Å) and N9-C6 (1.398 Å) are typical single bonds which
are longer than the calculated values in all methods. The experimental C21=O22
(
1.194 Å) bond length is a typical C=O double bond and the calculated C=O bond
length 1.188 Å with RHF/6-311++G(d, p) theoretical level agrees well with the
experimental value. The experimental C11-C10 (1.392 Å) is longer than C3-C2
(
1.341 Å) in the cabazole ring because of the substitution. Similar results were found
in the calculations.
3.2. Vibrational assignments
The experimental IR and Raman spectra are shown in Fig. 2 (a) and Fig. 2 (c),
the calculated IR and Raman spectra are shown in Fig. 2 (b) and Fig. 2 (d),
respectively. The calculated vibrational frequencies, potential energy distribution
(
PED) and approximate descriptions of normal modes are listed in Table 3. Usually,
scaling factors are introduced to modify the calculated frequency values. In our
7

calculations, scaling factors for different methods were introduced and listed in the
Table 4. Gaussview program [35] and PED were used to assign the calculated
harmonic frequencies.
3.2.1 C-H vibrational modes
-1
In carbazole ring, an IR band observed at 3056 cm is assigned to CH stretching
-
1
vibration, the B3LYP/6-311++G(d, p) calculated value is 3097 and 3200 cm
(
unscaled), PED analysis found that this mode is almost pure CH (PED, 96-99%)
stretching vibration. The bending modes for CH in cabazole ring are observed at 1445
in IR spectrum and 1441, 1462 in Raman spectrum, these modes are strongly coupled
with CC stretching modes in cabazole ring. Vibrational mode 1240 in IR and 1242
-1
cm in Raman is the mixed vibrational modes for CH bending mode (PED, 42%) in
cabazole, CC stretching modes for R1 and R2 (PED, 16%) and the CN stretching
-1
modes (PED, 13%). The IR band observed at 1126 cm and corresponding Raman
-1
band at 1017 and 1138 cm are assigned to CH bending vibrational modes of
-
1
-1
carbazole (PED, 90%). The IR band observed at 914 cm and Raman band 943 cm
are assigned to wagging out of plane C(R1)H vibrational modes (PED, 86% and 87%,
respectively). The wagging out of plane C(R1)H vibrational mode is also observed at
-
1
-1
7
36 cm in Raman spectra, the B3LYP/6-311++G(d, p) calculated value is 761 cm
-
1
(
PED, 52%). In ring R3, the IR band observed at 1488 cm and corresponding Raman
band at 1493 are assigned to CH bending modes, the B3LYP/6-311++G(d, p)
-
1
calculated value is 1547 cm , the PED of these modes is 70%. The Raman bands
-
1
observed at 1285 and 1190 cm are assigned to C(R3)H bending modes, PED for
these modes are 59% and 35%, respectively, the former mode is coupled with C(R1)H
bending in plane mode (PED, 14%), the later is coupled with C17C20 stretching
-1
modes (PED, 33%). The IR band observed at 1176 cm and corresponding Raman
8

-1
band at 1173 cm are also assigned to C(R3)H bending in plane modes (PED, 53%),
these modes are coupled with C(R1)H bending in plane vibrational modes (PED,
23%). The IR band at 544 can be assigned to C(R3)H in plane bending mode too, but
this mode is strongly coupled with wagging in plane of ring R4 and R2. The observed
-1
-1
IR band at 488 cm and Raman bands at 702 and 796 cm are assigned to C(R3)H
wagging out of plane vibrational modes, PEDs for these modes are 65%, 45% and
77%, respectively, the former mode is mainly coupled with wagging in plane of R1
and R2 (PED, 25%), and the third is mainly coupled with C(R2)H wagging out of
plane vibrational modes (PED, 8%).
-1
For CH
3
, the IR bands observed at 2843 and 2913 cm are assigned to CH
stretching vibrational modes of methyl, the B3LYP/6-311++G(d, p) calculated values
-1
are 3025 and 3079 cm , respectively, the PED of these modes is 99%. The IR band
-
1
observed at 1354 and corresponding Raman band at 1367 cm are assigned to CH
-1
bending modes, the B3LYP/6-311++G(d, p) calculated value is 1416 cm , the PED of
-1
these modes is 72%. The IR band observed at 1013 cm and corresponding Raman
-
1
band at 1017 cm are assigned to CH wagging out of the plane vibrational modes, the
-
1
B3LYP/6-311++G(d, p) calculated value is 1062 cm , the PED of these modes is
4%.
CH stretching vibrational mode of C21H was observed at 2746 cm in IR
6
-1
-
1
spectrum, the B3LYP/6-311++G(d, p) calculated value is 2875 cm , PED for this
vibrational mode is 99%.
Compared with the experimental values, the RHF method overestimates the
frequencies with an error 4.7-14.7%, the B-based DFT methods overestimate the
frequencies with errors 0.2-6.8%, and the WB-based DFT methods overestimate the
frequencies with errors 1.8-8.3%.
9

3.2.2 C＝O and C-N modes
-
1
An IR band observed at 1686 cm and the corresponding Raman band at 1692
-1
cm are assigned to C＝O stretching vibrational modes, the B3LYP/6-311++G(d, p)
-1
calculated value is 1753 cm , PED analysis found that these modes are coupled with
bending vibrational mode of C11C21H (PED, 31%). An IR band observed at 1240
-1
-1
cm and the corresponding Raman band at 1242 cm are assigned to CN stretching
vibrational mode (PED, 33%).
Compared with the experimental values, the RHF method overestimates the
frequencies with an error 6.2-16.0%, the B-based methods overestimate the
frequencies with errors 1.8-7.0%, and the WB-based methods overestimate the
frequencies with errors less than 3.6-8.2%.
3.2.3 Ring modes
In the cabazole ring, the CC stretching vibrational modes are observed at
-1
-1
1
616cm , 1587, 1508 and 1312 cm in IR spectrum, the corresponding Raman band
-1
is 1630, 1595, 1518 and 1324 cm . The former mode is coupled with stretching
vibrational modes of R3 ring (PED, 13%), the second mode is coupled with wagging
in plane of ring R1H and R2H and the third mode is coupled with wagging in plane of
ring R2H and stretching vibrational modes of R3 ring. In the ring R3, the ring
-1
stretching vibrational mode is observed at 1267 cm in IR spectra. The mode is
coupled with the wagging in plane of ring R2H (PED, 25%). An IR band observed at
-1
7
50 cm is assigned to ring breath modes of cabazole ring, the B3LYP/6-311++G(d,
p) calculated value is 773, PED analysis found that this mode is coupled with CH
wagging out of plane modes of R3 (PED, 11%).
For above vibrational modes, computed frequencies at all levels are higher than
that of the experimental ones. The best value was achieved by B-based DFT methods,
1
0

compared with the experimental values, the RHF method overestimates the
frequencies with an error 9.6-15.5%, the B-based methods overestimate the
frequencies with errors 1.4-6.1%, and the WB-based methods overestimate the
frequencies with errors less than 3.5-10.1%.
3.3. Electronic properties
The energy levels of the frontier orbital of the compound are listed in Table 5.
The 3D plots of the HOMOs and LUMOs of the compound are shown in Fig. 3. The
experimental and simulated spectra are shown in Fig. 4. According to the
B3LYP/6-311++G(d, p) method, the energy level of HOMO is about -6.0 eV and the
LUMO is about -1.7 eV. As a result, the HOMO-LUMO gap in the title compound is
about 4.3 eV. The LUMO is mainly localized on the cabazole ring and the σ* bond of
N1C14, and the HOMO is localized on all molecules except for methyl.
The electronic absorption spectrum of the title compound in DMF solvent was
recorded within 225–500 nm range and representative spectrum is given in Fig. 4.
(
a) The observed low-intensity band at 324 nm in DMF solution was compared
with the theoretical data 335 nm for B3LYP and 332 nm for cam-B3LYP. The band
was defined as HOMO→LUMO(65.6%), HOMO-1→LUMO (18.4%) and
HOMO-1→LUMO+1 (16.6%) at B3LYP method with strengths 0.2406 and
HOMO→LUMO (66.4%), HOMO-1→LUMO (16.0%) and HOMO-1→LUMO+1
(
16.2%) at cam-B3LYP method with strengths 0.2537, respectively.
b) The experimental band at 291 nm in DMF solution was represented by state
(
in 298 nm for B3LYP and 291 nm for cam-B3LYP. The oscillator strength was
calculated between 0.1893 and 0.1887, and was classified as HOMO→LUMO,
HOMO-1→LUMO and HOMO→LUMO+1 transition.
(
c) The band observed at 275 nm in solution was compared with the theoretical
11

data in 275 nm for B3LYP and 273 nm for cam-B3LYP. These states of oscillator
strengths are 0.3229 and 0.2891, respectively. The band was classified as
HOMO→LUMO+2 and HOMO-1→LUMO+1 transition.
3.4. Molecular electrostatic potential
The electrostatic potential is related to the electronegativity and the partial
charges on the different atoms of the molecule, their study leads to the better
understanding of complex biological processes involving the charge–dipole,
dipole–dipole, and quadrupole–dipole interactions. The electrostatic potential of a
molecule is a good guide in assessing the molecules reactivity towards positively or
negatively charged reactants. A portion of a molecule that has a negative electrostatic
potential is susceptible to electrophilic attack—the more negative the better. The color
scheme for the MEP surface is as follows: red for electron rich, partially negative
charge; blue for electron deficient, partially positive charge; light blue for slightly
electron deficient region; yellow for slightly electron rich region; green for neutral;
respectively [36,37]. In other words, electrostatic potential increases in the order red <
orange < yellow < green < blue. In the title compound, the color code of these maps is
in the range between -0.05788 e (deepest red) to 0.05788 e (deepest blue). The
negative (red and yellow) regions of MEP are related to nucleophilic recognition and
the positive (blue) ones to electrophilic recognition shown in Fig. 5.
3.5. Thermodynamic Properties
The temperature dependence of the thermodynamic properties heat capacity at
constant volume (Cv), entropy (S), enthalpy (H) and Gibbs free energy (G) for the
title compound were also determined by B3LYP/6-311++G(d, p) method and were
listed in Table 6. It can be observed that these thermodynamic functions are
increasing with temperature ranging from 100 to 1000 K due to the fact that the
1
2

molecular vibrational intensities increase with temperature [38]. The correlation
equations between heat capacity, entropy, enthalpy and Gibbs free energy with
temperatures were filled by quadratic formulas, and the corresponding fitting factors
2
(
R ) for these thermodynamic properties are 0.99905, 0.99996, 0.99908 and 0.99994,
respectively. The corresponding fitting equations are as follows and the correlations
graphs are showed in Fig. 6.
-4 2
Cv=-2.42351+0.32331T-1.49131×10 T
-5 2
S=59.45984+0.31906T-7.16893×10 T
-
5 2
H=154.67142+0.03782T-7.95507×10 T
-4 2
G=161.33007-0.07741T-1.20507×10 T
3. 6. Natural bond orbital analysis
Natural bond orbital (NBO) analysis is an important technique for studying
hybridization and covalent effects in polyatomic wave functions, which based on local
block Eigen vector of the one-particle density matrix. We used the NBO analysis to
assign the hybridization of atomic lone pairs and the atoms involved in bond orbital to
interpret the deciphering of the molecular wave function, such as Lewis structures
charge, bond order, bond type, hybridization, resonance and donor-acceptor
interactions.
The bonding concepts (for example the bond orbital occupancies, contribution
from parent NBO, the natural atomic hybrids) were described in Table 7. The atom
x
label and the hybrid label showing the hybrid orbital (sp ) composition of HCCD
molecule determined by B3LYP/6-311++G(d, p) theoretical level. The occupancies of
NBOs in HCCD are reflecting their delicate dependence on chemical environment. In
1
3

Table 7, the bonding orbital C6-N9 with 1.97667 electrons has 37.09% C6 character
2
.68
2.06
in a sp hybrid and has 62.91% N9 character in a sp hybrid orbital of HCCD. The
2.61
bonding orbital for C8-N9 with 1.97732 electrons has 37.27% C8 character in a sp
2
.01
hybrid and has 62.73% N9 character in a sp
hybrid orbital. The C14-N9 with
2.73
1.98176 electrons has 37.10% C23 character in a sp
hybrid and has 62.90% N9
1.94
character in a sp hybrid orbital.
.7. Global and local reactivity descriptors
Depended on density functional descriptors, global chemical reactivity
3
descriptors of compounds such as hardness (η), softness (S), chemical potential (µ),
electronegativity (χ) and electrophilicity index (ω) as well as local reactivity
descriptors as the Fukui function and the philicity have been defined [39-43].
Using Koopman’s theorem for closed –shell compounds, η, µ, χ can be defined as:
η = (I-A)/2
µ = -(I+A)/2
χ = (I+A)/2
S= 1/η
I= -EHOMO and A= -ELUMO
Where, I and A are the ionization potential and electron affinity of the compound,
respectively. It is regard that the greater the ionization potential data, the more
difficult to lose electron of the ligand. Electron affinity is the capability of a ligand to
accept electron, the smaller the electron affinity data the easier to get the electron.
Hardness is half of the gap between the HOMO and LUMO, we all known that the
bigger the gap, the more stable the molecule, it is conceivable that “there seems to be
a rule of nature that molecules arrange themselves to be as hard as possible” as first
postulated by Pearson in 1978 [44]. Softness can measure the extent of chemical
1
4

reactivity of compound and it is the reciprocal of hardness. χ is defined by Iczkowski
and Margrave [45] as a generalization of the definition by Mulliken [46], because the
fundamental relationship to µ, χ is quite different from Pauling’s original meaning of
electronegativity, which is a property of an atom in a molecule. Here χ is a property of
the entire molecule [43]. Recently Parr et al [39] have defined a new descriptor to
quantity the global electrophilic power of the compound as electrophilicity index (ω),
which defines a quantitative classification of the global electrophilic nature of a
compound. Parr et al [39] have proposed electrophilicity index (ω) as a measure of
energy lowering due to maximal electron flow between donor and acceptor. They
defined electrophilicity index (ω) as follows:
2
ω =µ /2η
The electrophilicity is a descriptor of reactivity that allows a quantitative
classification of the global electrophilic nature of a molecule within a relative scale.
The usefulness of this new reactivity quantity has been recently demonstrated in
understanding the toxicity of various pollutants in terms of their reactivity and site
selectivity [47-52]. All the calculated values of HOMO-LUMO energy gap, ionization
potential, Electron affinity, hardness, potential, softness and electrophilicity index are
shown in Table 8.
4. Conclusions
The compound 9-p-tolyl-9H-carbazole-3-carbaldehyde (HCCD) was synthesized
and characterized by X-ray diffraction, FT-IR, FT-Raman and UV-Vis spectra. The
single crystal X-ray diffraction data and calculated geometrical parameters were
compared. The small difference between experimental and calculated geometrical
parameters can come from the difference of the state. Vibrational frequencies were
calculated using RHF and B-based DFT (BLYP, B3LYP and cam-B3LYP) methods,
1
5

and WB-based DFT (WB97, WB97X and WB97XD) methods with 6-311++G(d, p)
basis set, the maximum deviation for B-based DFT, WB-based DFT and ab initio
RHF method are 7.0%, 10.1% and 16.0%, respectively. The observed frequencies are
reproduced reasonably well by the B-based DFT methods. The predicted electronic
absorption spectra were achieved by TDDFT in gas phase and PCM-TDDFT in DMF
solution. The calculated the strongest band centered at 401.8 and 292.8 nm in gas
phase is closely agreement with the experimental values 396.1 and 289.7 nm,
respectively. The temperature dependence of thermodynamic parameters in the range
of 100–1000 K was determined and found that all thermodynamic properties increase
with rise in temperature. We found that the correlation equations between heat
capacity, entropy, enthalpy and Gibbs free energy with temperatures were filled by
2
quadratic formulas, and the corresponding fitting factors (R ) for these
thermodynamic properties are 0.99905, 0.99996, 0.99908 and 0.99994, respectively.
The bond orbital occupancies, contribution from parent NBO, the natural atomic
hybrids were discussed. The other molecular properties such as such as hardness (g),
softness (S), chemical potential (l), electronegativity (v) and electrophilicity index (x)
were described.
Acknowledgment
We thank the National Science Foundation of Educational Commission of
Jiangsu Province of China (Nos.12KJA150004) for financial support. The natural
science foundation of Jiangsu Province (Grant No. BK20131212) and Huaian key lab
for photoelectric conversion and energy storage materials for financial support for this
work.
1
6

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[
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2
0

Table 1 Crystal data and structure refinement for the title compound.
Empirical formula
Formula weight
Temperature
Radiation
Space group
a (Å)
b (Å)
c (Å)
α (◦)
C20H15ON
285.33
296(2)
Mo-Kα (λ = 0.71073 Å)
P2(1)/n
8.3170(16)
13.740(3)
13.745(3)
90.00
β (◦)
107.166(2)
γ (◦)
V (Å )
90.00
3694.1(13)
4
1.263
0.078
3
Z
-3
D
c
/(Mg . m )
-
1
µ/mm
F(000)
600
Crystal size (mm)
θ range for data collection
Index ranges
0.17×0.14×0.12
1.55~25.00
-9≤h≤9
-
16≤k≤15
-
16≤l≤16
Goof
0.857
Total reflections
10518
R indices [I > 2σ (I)]
R indices (all data)
Largest difference peak and hole
R
R
1
=0.0515 wR
=0.1328, wR
2
=0.0986
=0.1180
1
2
0.11/-0.16
Table 2 Optimized and experimental bond distances (Å) and bond angles (◦) for the
compound.
BLYP
1.401
1.413
1.408
1.429
1.455
1.402
1.404
1.413
1.434
1.402
1.399
1.411
1.439
1.410
1.424
1.479
1.393
B3LYP
1.390
1.404
1.398
1.416
1.448
1.391
1.395
1.400
1.420
1.393
1.387
1.402
1.428
1.398
1.413
1.472
1.383
cam-B3LYP WB97
WB97X
1.385
1.402
1.395
1.406
1.450
1.386
1.394
1.394
1.410
1.391
1.383
1.400
1.422
1.390
1.408
1.476
1.379
WB97XD RHF
Exp
R(1,2)
R(1,4)
R(2,3)
R(3,6)
R(3,7)
R(4,5)
R(5,6)
R(6,9)
R(7,8)
R(7,10)
R(8,9)
R(8,13)
R(9,14)
R(10,11)
R(11,12)
R(11,21)
R(12,13)
1.384
1.399
1.393
1.407
1.447
1.385
1.391
1.394
1.411
1.388
1.382
1.397
1.423
1.389
1.406
1.471
1.377
1.387
1.405
1.398
1.408
1.454
1.388
1.397
1.397
1.411
1.394
1.385
1.404
1.425
1.391
1.411
1.480
1.381
1.386
1.401
1.394
1.407
1.447
1.386
1.392
1.392
1.411
1.389
1.381
1.398
1.420
1.391
1.408
1.474
1.379
1.379
1.396
1.390
1.397
1.452
1.380
1.389
1.389
1.400
1.387
1.376
1.396
1.423
1.384
1.404
1.477
1.373
1.411(12)
1.408(10)
1.341(10)
1.450(9)
1.423(11)
1.407(11)
1.317(11)
1.398(9)
1.350(9)
1.383(10)
1.441(9)
1.401(11)
1.429(8)
1.392(12)
1.413(9)
1.470(10)
1.414(10)
2
1

R(14,15)
R(14,17)
R(15,16)
R(16,19)
R(17,18)
R(18,19)
R(19,20)
R(21,22)
A(2,1,4)
A(1,2,3)
A(2,3,6)
A(2,3,7)
A(6,3,7)
A(1,4,5)
A(4,5,6)
A(3,6,5)
A(3,6,9)
A(5,6,9)
A(3,7,8)
A(3,7,10)
A(8,7,10)
A(7,8,9)
A(7,8,13)
A(9,8,13)
A(6,9,8)
A(6,9,14)
A(8,9,14)
A(7,10,11)
A(10,11,12)
A(10,11,21)
A(12,11,21)
A(11,12,13)
A(8,13,12)
A(9,14,15)
A(9,14,17)
A(15,14,17)
A(14,15,16)
A(15,16,19)
A(14,17,18)
A(17,18,19)
A(16,19,18)
A(16,19,20)
A(18,19,20)
A(11,21,22)
1.406
1.406
1.402
1.409
1.402
1.410
1.519
1.229
120.7
119.1
119.3
133.9
106.8
121.4
117.6
121.9
108.8
129.3
106.9
134.0
119.1
108.9
121.8
129.3
108.6
125.6
125.8
119.7
120.2
119.2
120.7
121.4
117.9
120.2
120.2
119.6
119.9
121.3
119.9
121.3
117.9
121.1
121.0
125.7
1.395
1.396
1.392
1.399
1.392
1.400
1.509
1.214
120.7
119.1
119.5
133.9
106.6
121.4
117.6
121.8
108.9
129.3
106.8
134.0
119.2
109.0
121.8
129.2
108.6
125.6
125.8
119.5
120.3
119.2
120.5
121.4
117.9
120.2
120.2
119.6
119.9
121.3
119.9
121.3
118.0
121.1
120.9
125.5
1.389
1.389
1.387
1.393
1.386
1.393
1.505
1.207
120.6
119.0
119.6
133.8
106.6
121.4
117.6
121.8
109.0
129.2
106.7
134.0
119.3
109.1
121.8
129.1
108.6
125.6
125.8
119.4
120.5
119.3
120.2
121.3
117.8
120.2
120.2
119.7
119.9
121.2
119.9
121.2
118.1
121.0
120.9
125.2
1.393
1.394
1.392
1.397
1.390
1.398
1.509
1.211
120.6
118.9
119.7
133.7
106.5
121.5
117.4
121.8
109.1
129.2
106.7
134.0
119.3
109.1
121.9
128.9
108.6
125.7
125.7
119.2
120.6
119.3
120.1
121.3
117.6
120.0
120.1
119.8
119.8
121.2
119.8
121.2
118.2
121.1
120.7
124.9
1.391
1.391
1.389
1.394
1.388
1.395
1.506
1.208
120.6
118.9
119.7
133.8
106.5
121.5
117.5
121.8
109.1
129.2
106.7
134.0
119.3
109.1
121.9
129.0
108.6
125.7
125.7
119.2
120.6
119.3
120.1
121.3
117.7
120.1
120.1
119.8
119.8
121.2
119.8
121.2
118.2
121.0
120.8
125.0
1.390
1.391
1.388
1.395
1.388
1.395
1.506
1.207
120.7
118.9
119.7
133.8
106.5
121.5
117.4
121.8
109.0
129.1
106.7
134.0
119.3
109.1
121.9
129.0
108.7
125.7
125.7
119.3
120.5
119.2
120.3
121.3
117.7
120.0
120.1
119.8
119.8
121.2
119.8
121.2
118.2
121.0
120.9
125.2
1.387
1.382
1.382
1.392
1.387
1.388
1.510
1.188
120.5
119.0
119.7
134.0
106.3
121.5
117.5
121.8
109.2
129.0
106.5
134.1
119.4
109.3
121.8
128.8
108.6
125.6
125.8
119.5
120.2
119.4
120.4
121.4
117.7
120.2
120.3
119.6
120.0
121.1
120.1
121.1
118.2
120.5
121.4
125.2
1.392(11)
1.356(10)
1.393(9)
1.326(10)
1.399(9)
1.374(12)
1.558(9)
1.194(7)
117.6(7)
122.1(7)
118.2(8)
135.0(8)
106.6(7)
120.5(8)
119.8(8)
121.5(7)
107.8(7)
130.6(7)
109.0(7)
133.4(7)
117.5(8)
109.8(7)
126.2(7)
124.0(7)
106.8(6)
126.9(6)
126.0(7)
120.2(7)
121.2(7)
121.1(7)
117.7(8)
119.0(7)
115.8(7)
118.7(7)
121.2(7)
119.7(7)
118.8(7)
122.6(7)
118.5(8)
122.1(8)
117.7(7)
123.7(8)
118.6(8)
127.5(8)
−1
Table 3 Experimental and calculated vibrational frequencies (cm ) with different
methods.
BLYP
B3LYP cam-B3
LYP
WB9
7
WB9
7X
WB9
7XD
RHF
Exp.IR
Exp.Ram Assign.(PED)
an
3
7
36
34
36
40
49
34
48
52
74
32
40
50
73
28
42
49
72
17
ωR3(42)
ωC20H(99)
ωC20H(93)
ωR3(73)
4
4
4
0
2
8
40
41
49
21
39
47
2
2

ωC10C11C3O22(4
5)+ωC8N9C12C7(3
7
1
74
75
78
89
117
80
9)
1
16
121
130
123
132
124
133
123
133
122
132
131
140
ωR1(12)+ωR2(16)
1
27
ρR1(17)+ρR3(52)
ωC10C11C12O22(
1
39
144
145
142
142
141
155
5
7)
1
2
2
2
2
2
3
3
54
11
21
71
78
97
26
44
159
217
227
279
286
308
337
354
161
219
230
282
289
313
342
358
164
218
230
279
287
310
340
357
163
218
230
280
288
311
341
358
162
217
230
280
287
310
339
358
171
232
242
301
306
338
371
376
ωR3(70)
ωR1(27)+ωR2(44)
ρR1(13)+ρR2(41)
ωR1(5)+ωR2(72)
ωR1(7)+ωR2(42)
ωR1(6)+ωR2(58)
ωR3(55)
ρR3(24)
ρR1(12)+ρR2(36)+
ρR3(9)
ωR3CH(93)
ωR1CH(43)+ωR2C
H(51)
3
4
4
75
08
17
387
423
432
392
430
439
390
426
433
392
427
435
391
425
434
413
463
472
ωR1CH(42)+ωR2C
H(51)
ωR1CH(21)+ωR2C
4
4
29
35
443
452
450
461
443
457
444
459
443
456
483
496
H(58)
4
4
5
61
94
58
475
511
575
481
519
582
479
515
579
481
517
581
480
516
581
505
556
613
ρR1(26)+ρR2(29)
ωC(R3)H(65)
ρC(R3)H(23)
488
544
ωC(R1)H(49)+ωC(
R2)H(38)
ωC(R1)H(20)+ωC(
R2)H(80)
5
5
58
78
580
598
592
609
586
603
589
606
586
602
630
646
5
6
88
23
606
640
613
647
608
642
611
646
611
645
652
685
ρR2(19)+ρR3(41)
614
686
ρR1(49)+ρR2(36)
ρR1(20)+ρR2(8)+ρ
6
26
644
652
647
650
649
692
R3(51)
ρR3(54)
6
6
7
41
92
09
659
713
734
666
723
748
661
719
743
664
722
745
663
721
742
705
762
798
ρR1(32)+ρR2(34)
ωC(R3)H(98)
ωC(R1)H(48)+ωC(
R2)H(9)
ωC(R1)H(50)
702
736
7
7
7
17
30
50
745
761
773
761
780
783
757
776
779
757
777
782
751
770
781
821
822
838
750
ρCC(R1)(26)+ρCC(
R2)(40)
ωC(R1)H(21)+ωC(
R2)H(15)
7
55
786
805
801
803
796
858
7
8
83
02
808
833
822
849
822
850
822
850
818
845
861
909
ρCC(R3)(50)
ωC(R3)H(79)
796
ωC(R2)H(33)+ωC(
8
03
835
853
852
853
847
923
R3)H(12)
8
8
16
30
849
866
867
887
871
884
869
882
862
871
931
944
814
914
ωC(R3)H(90)
ωC(R1)H(84)
νC11C21(10)+νCC(
8
47
875
889
888
889
884
963
R2)(25)
8
8
9
70
97
07
907
929
949
931
944
975
935
943
971
935
945
973
930
941
960
1003
1018
1027
ωC5H(85)
ωC(R3)H(64)
ωC(R1)H(86)
2
3

νC14C(8)+ρR1(31)
ρR2(16)
9
29
959
976
976
974
971
1062
+
9
9
33
37
971
980
994
993
992
984
997
1080
1081
ωC(R3)H(87)
1007
1008
1006
943
ωC(R1)H(87)
ωC(R1)H(8)+ωC(R
2)H(61)+ωC(R3)H(
9
42
983
1009
1011
1010
999
1096
2
3)
ωC(R2)H(26)+ωC(
9
46
987
1011
1012
1012
1003
1098
R3)H(65)
9
9
80
81
1009
1023
1017
1042
1014
1038
1016
1041
1018
1037
1099
1101
ωC20H(35)
ωC21H(57)
νC9C10(9)+ρR1H(
9
1
1
1
1
97
1029
1037
1045
1062
1123
1135
1144
1044
1050
1059
1075
1138
1142
1156
1039
1045
1060
1069
1134
1135
1148
1042
1048
1062
1072
1138
1139
1153
1038
1045
1059
1069
1137
1144
1153
1111
1119
1147
1162
1173
1198
1210
1
0)+ρR2H(24)
007
014
030
089
ρR3H(40)
νC9C10(11)+ρR1H
(
42)+ρR2H(13)
1013
1017
ωC20H(64)
ρR1H(39)+ρR2H(1
2
)
1
107
110
146
154
162
174
188
ρR3H(77)
ρR1H(17)+ρR2H(6
1
3
)
1
126
176
1138
1173
ρR1H(81)+ρR2H(8
1
1175
1190
1198
1206
1230
1250
1261
1313
1321
1333
1342
1180
1202
1209
1220
1250
1269
1281
1311
1332
1343
1357
1167
1197
1205
1215
1255
1268
1285
1290
1325
1332
1347
1175
1200
1207
1219
1254
1270
1287
1305
1329
1338
1357
1182
1201
1207
1219
1246
1268
1286
1319
1328
1339
1358
1230
1268
1281
1282
1289
1312
1318
1326
1381
1388
1434
)
ρR1H(29)+ρR2H(1
1
9
)+ρR3H(26)
ρR1H(13)+ρR2H(2
)+ρR3H(34)
ρR1H(9)+ρR2H(14
+ρR3H(53)
1
6
1
1
)
1
190
νC19C20(33)+ρR3
H(35)
νC3C6(10)+ρR2H(
1
1
1
1
1
1
1
204
218
277
287
297
302
4
2)
νC8C7(11)+ρR1H(
2) +νCN(13)
1
240
267
1242
4
1
νCC(R3)(35)+ρR2
H(25)
νCC(R3)(15)+ρR2
H(54)
1
285
ρR1H(14)+ρR3H(5
9
)
ρR1H(49)+ρR3H(2
7)
1
1
328
333
1372
1375
1371
1387
1358
1384
1364
1389
1374
1393
1438
1451
1312
1354
1324
1367
νCC(R1)(55)
νCC(R2)(48)
νN9C14(17)+νCC(
R1)(11)+
1
341
1389
1417
1416
1422
1421
1504
νCC(R2)(13)
ρC21H(72)
1
1
1
375
379
392
1416
1417
1437
1426
1428
1457
1422
1430
1459
1425
1430
1459
1423
1433
1454
1526
1539
1544
ωC20H(93)
νCC(R3)(15)
ρR1H(40)+ρR2H(1
1
1
420
435
1469
1486
1492
1498
1490
1493
1495
1495
1489
1497
1584
1605
7
)
νCC(R1)(13)+ρR2
H(24)
1
1
449
454
1491
1495
1504
1513
1501
1522
1505
1520
1505
1512
1610
1613
ωC20H (99)
ωC20H(90)
1445
1441
ρC(R1)H(22)+ρC(
R2)H(29)
ρC(R1)H(43)+ρC(
R2)H(15)
1
1
457
463
1505
1516
1535
1542
1546
1551
1543
1549
1533
1540
1631
1640
1
462
2
4

+
νCC(23)
1
1
492
530
1547
1596
1577
1638
1589
1660
1586
1654
1576
1637
1683
1743
1488
1508
1493
1518
ρC(R3)H(70)
νCC(R2)(50)
νCC(R1)(27)+νCC(
R3)(21)
νCC(R1)(23)+νCC(
R3)(26)
1
1
547
551
1611
1616
1650
1656
1671
1679
1664
1672
1648
1655
1756
1761
1
587
616
1595
νCC(R1)(20)+
νCC(R2)(30)
νCC(R3)(35)
νCC(R1)(19)+νCC(
R2)(14)+
1
1
566
579
1631
1648
1671
1690
1692
1716
1685
1708
1669
1690
1775
1802
1
1630
1692
1
589
1658
1701
1727
1719
1703
1812
νCC(R3)(13)
νC21O22(51)
νC21H(99)
1
2
2
3
3
3
3
3
3
3
3
662
768
950
000
027
079
084
085
087
096
106
1753
2875
3025
3079
3106
3160
3163
3165
3167
3175
3186
1804
2917
3053
3112
3136
3183
3187
3188
3190
3198
3208
1824
2949
3077
3155
3172
3193
3205
3205
3207
3211
3222
1822
2931
3069
3139
3158
3189
3199
3201
3201
3208
3218
1812
2901
3051
3118
3139
3182
3191
3193
3193
3201
3210
1972
3095
3167
3224
3247
3320
3323
3324
3325
3332
3346
1686
2764
2843
2913
νC20H(99)
νC20H(99)
νC20H(99)
νC10H(98)
νC(R3)H(97)
νC(R3)H(96)
νC(R1)H(98)
νC(R1)H(91)
νC(R2)H(92)
νC(R1H(37)+
νC(R3)H(60)
C(R1H(59)+νC(R3)
H(40)
3
3
109
111
3188
3189
3210
3211
3226
3228
3221
3223
3215
3216
3347
3348
3
3
3
112
118
120
3190
3197
3200
3212
3220
3223
3229
3235
3237
3225
3231
3232
3218
3224
3225
3349
3357
3368
νC(R3)H(93)
νC(R1H(96)
νC(R2)H(99)
3056
a
Abbreviation/symbols: ν, stretching; δ, bending in-plane; τ, torsion; ω, wagging out-of-plane; ρ,
wagging in-plane; R1: ring of C1C2C3C4C5C6, R2: ring of C7C8C10C11C12C13, R3: ring
of C14C15C16C17C18C19, PED: potential energy distribution
Table 4 Scaling factors for the different methods
Methods
BLYP B3LYP cam-B3LYP RHF
WB97
WB97X
0.9421
WB97XD
0.9461
Scaling
factor
0.9947 0.9598 0.9439
0.8856 0.943
2
5

Table 5 The energy levels (eV) of the frontier orbitals of the title compound with
B3LYP/6-311++G(d, p) theoretical level
BLYP B3LYP cam-B3LYP WB97
WB97X
-10.9983 -10.7591 -10.2772 -11.3558
WB97XD RHF
HOMO-6 -7.0515 -8.1396 -9.7088
HOMO-5 -6.6621 -7.6338 -9.0865
HOMO-4 -6.4300 -7.3998 -8.8530
HOMO-3 -6.3914 -7.3606 -8.7856
HOMO-2 -5.5264 -6.9731 -8.7333
HOMO-1 -5.4782 -6.3674 -7.6610
-10.2495 -10.0565 -9.6329
-10.0606 -9.8489
-10.0454 -9.8032
-10.6533
-9.8160
-9.5393
-9.4704
-8.0803
-8.0397
0.8492
1.0623
1.2049
1.2410
1.3434
1.4783
1.6522
-9.4215
-9.3295
-9.2185
-8.2150
-7.8101
0.2166
0.4003
0.8563
0.8819
0.9355
1.1058
1.2375
-9.9243
-8.7377
-8.2901
0.6887
0.7888
0.9864
1.1915
1.2544
1.3412
1.3469
-9.7292
-8.5709
-8.1472
0.5379
0.6691
1.0492
1.1717
1.2149
1.2892
1.4185
HOMO
-5.2039 -6.0442 -7.2974
-2.2764 -1.6715 -0.3910
LUMO
LUMO+1 -1.9423 -1.4141 -0.2136
LUMO+2 -1.6574 -1.0351 0.1603
LUMO+3 -1.6527 -1.0269 0.2264
LUMO+4 -0.9105 -0.4604 0.2675
LUMO+5 -0.7486 -0.2460 0.4253
LUMO+6 -0.4599 -0.1856 0.5899
Table 6 Thermodynamic properties at different temperatures with
B3LYP/6-311++G(d, p) level of the title compound
T(K)
Cv (cal/mol⋅K) S (cal/mol⋅K)
H (kcal/mol)
G (kcal/mol)
1
2
2
3
4
5
6
7
8
9
1
00
00
98.15
00
00
00
00
00
00
29.533
53.983
80.325
80.806
104.634
123.604
138.361
149.98
159.297
166.883
173.133
91.291
160.8476
165.1828
171.9744
172.1276
181.6378
193.2893
206.6177
221.2571
236.9376
253.4597
270.6709
151.7176
141.1066
127.9496
127.6759
111.4915
92.64545
71.28977
47.59387
21.72532
-6.16026
-35.9242
120.37
147.645
148.156
175.349
201.266
225.524
248.066
268.989
288.438
306.564
00
000
Table 7. Bond orbital analysis of title compound with B3LYP/6-311++G(d, p) level of
theory
Bond
Occupancy Atom Contribution from
parent NBO (%)
Atomic hybrid
contributions (%)
Hybrid
s
p
1
1
1
1
1
1
2
.76
.75
.79
.76
.80
.71
.29
C1-C2
C1-C4
C2-C3
C3-C6
1.97728
1.97891
1.97257
1.95882
C1
C2
C1
C4
C2
C3
C3
49.49
50.51
49.91
50.09
48.46
51.54
49.92
36.21
36.41
35.84
36.19
35.64
36.86
30.36
63.74
63.55
64.12
63.77
64.32
63.11
69.59
sp
sp
sp
sp
sp
sp
sp
2
6

1
2
2
1
1
1
1
2
2
2
1
1
1
2
2
1
1
1
2
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
1
1
1
.93
.06
.03
.77
.74
.86
.59
.68
.06
.32
.94
.71
.77
.61
.01
.61
.89
.94
.73
.76
.88
.88
.82
.27
.59
.74
.72
.73
.80
.74
.80
.76
.79
.73
.90
.76
.79
.73
.91
.21
.19
.11
.40
.00
.00
C6
C3
C7
C4
C5
C5
C6
C6
N9
C7
C8
C7
C10
C8
N9
C8
C13
N9
C14
C10
C11
C11
C12
C11
C21
C12
C13
C14
C15
C14
C17
C15
C16
C16
C19
C17
C18
C18
C19
C19
C20
C21
O22
C21
O22
50.08
49.85
50.15
49.22
50.78
48.71
51.29
37.09
62.91
49.91
50.09
51.19
48.81
37.27
62.73
51.33
48.67
62.90
37.10
49.78
50.22
50.87
49.13
52.71
47.29
49.36
50.64
50.69
49.31
50.69
49.31
50.23
49.77
49.75
50.25
50.23
49.77
49.75
50.25
50.70
49.30
34.54
65.46
33.27
66.73
34.17
32.66
32.96
36.14
36.45
34.96
38.55
27.14
32.70
30.08
33.97
36.84
36.03
27.64
33.22
38.25
34.62
34.03
26.80
36.21
34.70
34.67
35.44
30.56
38.60
36.42
36.76
36.57
35.73
36.54
35.71
36.23
35.80
36.68
34.44
36.25
35.84
36.65
34.37
31.13
31.31
32.09
41.61
0.00
65.79
67.30
67.00
63.81
63.51
65.00
61.42
72.76
67.26
69.87
65.99
63.13
63.93
72.26
66.74
61.72
65.34
65.94
73.10
63.75
65.26
65.29
64.51
69.39
61.36
63.54
63.20
63.39
64.23
63.42
64.25
63.72
64.15
63.28
65.52
63.71
64.12
63.31
65.59
68.84
68.64
67.76
58.28
99.59
99.88
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
sp
C3-C7
C4-C5
C5-C6
C6-N9
C7-C8
C7-C10
C8-N9
C8-C13
N9-C14
1.96440
1.97438
1.97367
1.97667
1.95858
1.97244
1.97732
1.97364
1.98176
C10-C11 1.97290
C11-C12 1.97225
C11-C21 1.97804
C12-C13 1.97444
C14-C15 1.97155
C14-C17 1.97141
C15-C16 1.97426
C16-C19 1.97384
C17-C18 1.97429
C18-C19 1.97375
C19-C20 1.97893
C21-O22 1.99591
C21-O22 1.98011
0.00
Table 8. Global and local reactivity descriptors and related molecular properties of calculated
values.
Molecular Properties
Ionization potential (I)
Electron Affinity (A)
Global Hardness(η)
BLYP
B3LYP cam-B3LYP
WB97
8.2901
-0.6887
4.4894
0.2227
3.8007
-3.8007
1.6088
WB97X
8.1472
-0.5379
4.3426
0.2303
3.8046
-3.8046
1.6667
WB97XD
7.8101
-0.2166
4.0133
0.2492
3.7967
-3.7967
1.7959
RHF
5.2039 6.0442
2.2764 1.6715
7.2975
0.3910
3.4532
0.2896
3.8442
-3.8442
2.1398
8.0397
0.8492
3.5953
0.2781
4.4445
-4.4445
2.7471
1.4638
0.6832
3.7402
2.1863
0.4574
3.8578
Global Softness (s)
Electronegativity (χ)
Chemical potential (µ)
Global Electrophilicity(ω)
-3.7402 -3.8578
4.7784 3.4036
2
7

Fig. 1(a)
Fig 1(b)
Fig. 1 Molecular of the title compound. 1(a) ORTEP view. 1(b) Optimized structure of title
compound with B3LYP/6-311++G (d, p) level
a
00
b
0
1
8
6
4
2
0
0
0
0
0
1
2
3
4
00
00
00
00
4
000 3500 3000 2500 2000 1500 1000 500
4000 3500 3000 2500 2000 1500 1000 500
-1
-
1
Wavenumber(cm
)
Wavenumber(cm )
(
a)
(b)
2
9

c
d
0
-
2000
0
1
00
2
000
4000
000
000
0000
t
200
300
n
t
.
l
I
l
e
R
6
4
5
00
00
8
1
5
00
1000
1500
2000
2500
3000
1000
2000
3000
4000
Wavenumber(nm)
Wavelength(nm)
(c)
(d)
Fig 2 Experimental and calculated IR and Raman spectra. (a) Experimental IR; (b) Calculated IR; (c)
Experimental Raman; (d) Calculated Raman
Fig.3 Energy levels and the 3D plots of the HOMOs and LUMOs of the compound
3
0