1-Formyl-3-phenyl-5-(4-isopropylphenyl)-2-pyrazoline: Synthesis, characterization, antimicrobial activity and DFT studies

Article abstract of DOI:10.1016/j.molstruc.2016.05.043

The structure of 1-formyl-3-phenyl-5-(4-isopropylphenyl)-2-pyrazoline synthesized as single crystal was investigated by FTIR, NMR, XRD. Experimental data were complemented by quantum mechanical calculations. XRD data show that the compound crystallizes in

Full text of DOI:10.1016/j.molstruc.2016.05.043

Journal of Molecular Structure 1121 (2016) 46e53
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
1
-Formyl-3-phenyl-5-(4-isopropylphenyl)-2-pyrazoline: Synthesis,
characterization, antimicrobial activity and DFT studies
a
b
c
c
d
Assia Sid , Amel Messai , Cemal Parlak , Nadide Kazancı , Dominique Luneau ,
e
f
g
f, *
Gürkan Ke s¸ an , Lydia Rhyman , Ibrahim A. Alswaidan , Ponnadurai Ramasami
Laboratoire des Sciences Analytiques Mat ꢀe riaux et Environnement (LSAME), Larbi Ben M’Hidi University, Oum El Bouaghi, 04000, Rue de Constantine,
a
Algeria
b
Laboratoire d’Ing ꢀe nierie et Sciences des Mat ꢀe riaux Avanc ꢀe s (ISMA), Institut des Sciences et Technologie Abb ꢁe s Laghrour University Khenchela, 40000,
Algeria
c
Department of Physics, Science Faculty, Ege University, Izmir, 35100, Turkey
Laboratoire des Multimat ꢀe riaux et Interfaces (UMR 5615), Universit ꢀe Claude Bernard Lyon 1, 69622, Villeurbanne Cedex, France
Institute of Physics and Biophysics, Faculty of Science, University of South Bohemia, Brani ꢂs ovsk aꢀ 31, Cesk ꢀe Bud ꢂe jovice, 370 05, Czech Republic
Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, R ꢀe duit, 80837, Mauritius
Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh, 11451, Saudi Arabia
d
e
f
ꢂ
g
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 2 March 2016
Received in revised form
The structure of 1-formyl-3-phenyl-5-(4-isopropylphenyl)-2-pyrazoline synthesized as single crystal was
investigated by FTIR, NMR, XRD. Experimental data were complemented by quantum mechanical cal-
culations. XRD data show that the compound crystallizes in the triclinic system (Pꢀ1) via trans isomer
12 May 2016
ꢁ
ꢁ
(
a ¼ 6.4267(4) Å, b ¼ 10.9259(12) Å, c ¼ 12.4628(9) Å and
a
¼ 102.894(8) ,
b
¼ 102.535(6) ,
Accepted 12 May 2016
Available online 13 May 2016
ꢁ
g
¼ 101.633(7) ). Anti-microbial screening results indicate that the compound shows promising activity.
The theoretically predicted and experimentally obtained parameters reveal further insight into pyr-
azoline systems.
Keywords:
Pyrazolines
©
2016 Elsevier B.V. All rights reserved.
Crystal structure
Hydrogen-bonding
Antimicrobial activity
1
. Introduction
thiocarbamoyl-3-phenyl-5-thienyl-2-pyrazolines [10] have signifi-
cant anti-convulsant and anti-depressant activities based on the
Porsolt forced swimming test [11]. In addition, they are extensively
useful as synthons in organic chemistry [12].
In 2011, the compound was synthesized by some of us [13] by
reacting the appropriate chalcone with hydrazine hydrate. In the
present study, the structure was confirmed by FTIR, NMR and
single-crystal XRD. Hydrogen bonding interactions and antimicro-
bial activity of the compound were also investigated. As a supple-
ment to the experimental investigations, density functional theory
method in conjunction with the B3LYP functional and 6-31G(d,p)
basis set was used to predict the structural and spectroscopic data
of the compound in different medium.
a,b-unsaturated ketones especially chalcones as templates for
the combinatorial assembly of heterocyclic compounds have been
of research interests [1]. Pyrazolines have been widely used in the
industry. They are employed as optical brightening agents, carrier
transporting or emitting materials for textile, paper and fabrics. 2-
Pyrazolines have higher hole-transport efficiency and some
photoelectron characteristics. They are typical heterocyclic transi-
tion molecular crystals and have large molecular hyper-
polarizability. This means that the photofractivity of the two-
dimensional-array can be constructed with their nanoparticles in
an applied optical field [2,3].
Numerous pyrazolines show various biological activities such as
anti-microbial [4], anti-fungal [5], anti-depressant [6] and
anti-convulsant [7]. 1-Thiocarbamoyl-3,5-diphenyl-2-pyrazolines
2. Experimental
[8] and their condensed analogs [9] and 1-n-substituted
2.1. Synthesis
*
Corresponding author.
E-mail address: ramchemi@intnet.mu (P. Ramasami).
Chemicals were obtained from commercial sources. They were
http://dx.doi.org/10.1016/j.molstruc.2016.05.043
022-2860/© 2016 Elsevier B.V. All rights reserved.
0

A. Sid et al. / Journal of Molecular Structure 1121 (2016) 46e53
47
Fig. 1. Synthesis of 1-formyl-3-phenyl-5-(4-isopropylphenyl)-2-pyrazoline.
ꢁ
used without further purification and the path of reaction is illus-
trated in Fig. 1. A mixture of hydrazine hydrate (50 mmol), chalcone
and formic acid (40 mL), prepared by aldol condensation of iso-
propyl benzaldehyde with acetophenone (10 mmol), was refluxed
for 24h by constant stirring. The final solution was poured in water
range of 3.0 <
q
< 29.2 . CrysAlis was used for unit cell determi-
nation and reduction of data [14]. 6713 reflections were collected of
which 3729 were independent while 2572 reflected with I > 2 (I).
Structure was solved by direct method with SIR2004 [15] and
s
2
refined by full-matrix least squares method on F with SHELXL-
(
100 mL) and allowed to stand. Crystals suitable for XRD were
1997 [16]. Both software are included within WinGX package
[17]. Non-hydrogen and hydrogen atoms were anisotropically
refined and located by Fourier map correspondingly. They were
fixed in computed positions with distance constraints of
CeH ¼ 0.93 Å. Refinements converged at conventional R factor of
obtained from ethanol-toluene (1:1) mixture by the slow evapo-
ration technique at room temperature (white crystal; yield 76%; mp
1
ꢁ
44e145 C).
0
.075 and Goodness-of-fit of 1.081. Maximum and minimum peaks
2
.2. Instrumentation
ꢀ3
in Fourier studies were 0.371 and ꢀ0.203 e Å . ORTEP-3 [18] and
MERCURY [19] were used to draw structural representations.
Analysis was performed by PLATON [20], as incorporated in the
A white block crystal of the compound with dimensions of
0
.07 ꢂ 0.12 ꢂ 0.09 mm was selected and mounted on an Oxford
ꢀ1
WinGX [17]. FTIR spectrum (4000-400 cm ) was recorded by a
Diffraction Xcalibur, Atlas, Gemini ultra diffractometer with Mo K
radiation (
a
1
13
NEXUS NICOLET Spectrometer by KBr pellet. H and C NMR
l
¼ 0.71073 Å) and using
f and j scans at 293 K in the
Figure 2. (a) Molecular view showing 50% probability thermal ellipsoids. Optimized structures of (b) trans and (c) cis isomers.

48
A. Sid et al. / Journal of Molecular Structure 1121 (2016) 46e53
Table 1
Energetic parameters in the gas phase and different solvents.
Table 2
Crystal parameters of the structure synthesized.
Medium
Sum of electronic and thermal Relative
free energy (Hartree) energy
kcal/mol)
Mole
fraction (%)
Parameter Compound
Empirical formula
Formula weight (gmolꢀ1)
Temperature (K)
Crystal system
19 20 2
C H N O
292.37
293(2)
(
Trans
Cis
Trans Cis
Trans Cis
Triclinic
Pꢀ1
Gas phase
n-Hexane
n-Heptane
Cyclohexane
ꢀ920.520974 ꢀ920.515543
ꢀ920.525484 ꢀ920.521012
ꢀ920.525574 ꢀ920.521143
ꢀ920.525840 ꢀ920.521576
ꢀ920.526279 ꢀ920.522201
ꢀ920.526409 ꢀ920.522353
ꢀ920.529028 ꢀ920.527163
ꢀ920.529413 ꢀ920.527463
ꢀ920.530804 ꢀ920.528498
0
3.41 100
2.81 100
2.78 100
2.68 100
2.56 100
2.55 100
1.17
1.22
1.45
1.50
1.47
1.45
1.44
1.41
1.39
1.39
1.38
0
0
0
0
0
Space group
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Hall symbol
Unit cell dimensions (Å,
-P 1
ꢁ
)
a
b
c
a
b
g
6.4267(4)
10.9259(12)
12.4628(9)
102.894(8)
102.535(6)
101.633(7)
803.44(12)
2
1,4-Dioxane
Benzene
0
Diethyl ether
Chloroform
Tetrahydrofuran
88
89
92
93
92
92
92
92
91
91
91
12
11
8
7
8
8
8
8
9
Dichloromethane ꢀ920.531256 ꢀ920.528867
3
Volume (A )
2
2
-Butanol
-Propanol
ꢀ920.532318 ꢀ920.529969
ꢀ920.532565 ꢀ920.530259
ꢀ920.532631 ꢀ920.530330
ꢀ920.532826 ꢀ920.530575
ꢀ920.533051 ꢀ920.530831
ꢀ920.533113 ꢀ920.530902
ꢀ920.533267 ꢀ920.531074
a
Z
3
Calculated density (g/cm )
Absorption coefficient (mm
F(000)
Crystal size (mm )
Colour
1.209
0.075
312
Acetone
Ethanol
Methanol
Acetonitrile
DMSO
ꢀ1
)
3
0.09 ꢂ 0.04 ꢂ 0.01
8
8
White
Shape
Block
Cell parameters from
6713
Wavelength (Mo K
a
) (Å)
0.71073
29.2 e3
ꢁ
ꢁ
q
max
e
q
min
spectra were reported in deuterated chloroform by Avance 400
Bruker spectrometer via TMS as internal standard.
Measured reflections
Independent reflections
Reflections with I > 2s(I)
6713
3729
2572
0.0309
R
int
2.3. Anti-microbial activity
Limiting indices
h
k
l
ꢀ8 / 8
Synthesized compound was screened in vitro for anti-bacterial
ꢀ15 / 14
ꢀ14 / 16
and anti-fungal activities against Escherchia coli, Salmonella typhi,
Staphylococcus aureus, Bacillus subtilis (200, 300, 400 500 g/mL)
and Aspergillus niger, Aspergillus flavus, Pencillium chrysogenum,
Fusirium moneliforme (100, 200, 300, 400 g/mL) via Agar Cup-Plate
Refinement method
Full-matrix least-squares on F2
m
Final R indicesb [F > 2
2
s
2
1 2
(F )] R , wR
2c
Goodness-of-fit on F
0.0750, 0.2474
1.081
3729/0/213
a constrained refinement
0.371, ꢀ0.203
m
Data/restraints/parameters
H atoms
diffusion technique correspondingly. Concentrations were selected
by detecting MIC of the molecule. DMSO diluted with water was
used as solvent. Müller-Hinton and Sabouraud agars were used as
the growth medium for the bacterial and fungal species corre-
spondingly. DMSO was also used as a control for microorganisms.
Activity against the strains of microorganisms was not showed at
Largest difference peak and hole (e Åꢀ3)
Drmax, Drmin
a
The asymmetric unit contains 0.5 of the chemical formula.
b
c
2
2
2 2
R
1
¼ P|F
o
-F
c
|/F
o
. wR
2
¼ {P[w(F
o
- F
c o
)2]/P[w(F ) ]}1/2.
2
2 2
GOF ¼ {P[w(F
o
- F
c
) ]/(Nobs ꢀ Nvar)}1/2.
ꢁ
the control. Results were obtained after 48 h of incubation at 35 C
ꢁ
and 28e30 C for anti-bacterial and anti-fungal tests, respectively.
3. Computational method
The zone of inhibition was measured in mm and they were
compared with penicillin and griseofulvin for anti-bacterial and
anti-fungal activities, respectively.
Computations were carried out using Gaussian 09 [21] program.
GaussView 5.0.8 was used for the structural and spectroscopic
Figure 3. (A) PES scan and (B) transition state structures of the compound.

A. Sid et al. / Journal of Molecular Structure 1121 (2016) 46e53
49
Table 3
Hydrogen bond lengths (Å) and angles ( ).
fractions of the individual conformers were calculated as described
earlier [24e26].
o
D-H…A
D-H
H…A
D…A
D-H…A
C4-H4B/O1 i
C10-H10/ O1
C21-H21/ N2
1.02(5)
0.9300
0.9900
2.48(4)
2.4700
2.5700
3.470(5)
3.398(4)
3.540(3)
164(3)
175.00
166.00
4
. Results and discussion
ii
iii
4.1. Energetic and structural analyses
Symmetry codes: (i) ꢀ1þx,y,z, (ii): 1ꢀx,1ꢀy,ꢀz, (iii):1ꢀx,1ꢀy,1ꢀz.
Energetic parameters are given in Table 1. For the gas phase, the
trans form is more stable than cis by 3.41 kcal/mol. The cis isomer
has been neglected for the computation of equilibrium constant as
energy difference is larger than 2 kcal/mol [24e26]. Hence, in the
gas phase, the title compound prefers trans form with almost 100%
probability. As can be observed from Fig. 3, the conformational
preference is in agreement with the result found from PES analysis.
Energy barriers for trans/cis forms to transition state structures
(TS1/TS2) are 19.98/63.61 kcal/mol. In accordance with the mole
fractions, the structure generally prefers the trans from with 100%
probability for the non-polar solvents whereas the compound
prefers cis and trans isomers in polar solvents with approximate
probabilities of 7e12% and 88e93%, respectively. These confor-
mational preferences are also agreement with the results obtained
illustrations [22]. The geometrical structures of the conformers
Fig. 2) were optimized, without imposing symmetry, by the B3LYP
(
functional together with 6-31G(d,p) basis set. In order to calculate
the barrier of rotation, the transition state for the interconversion
was also fully optimized. Further, potential energy surface (PES)
analysis was performed by the rotations of NNCO torsion angle,
ꢁ
ꢁ
scanning 360 with 10 increments.
Computations were carried out in the gas phase and different
solvents. Polarizable continuum model was used to evaluate the
solvent effect. Harmonic vibrational frequencies were computed
using the same functional and basis set to confirm the nature of the
ground state structure, and then scaled by 0.9627 [23]. Mole
Fig. 4. The structure fragment.

50
A. Sid et al. / Journal of Molecular Structure 1121 (2016) 46e53
Table 4
The structural parameters.
ꢁ
Bond lengths (A )
Experimental
Calculated
Bond lengths (A)
Experimental
Calculated
O1eC21
N1eN2
N1eC5
N1eC21
N2eC3
C3eC4
C3eC15
C4eC5
C5eC6
C6eC7
C6eC11
C7eC8
1.220(4)
1.385(3)
1.486(3)
1.334(4)
1.287(4)
1.510(4)
1.472(4)
1.536(5)
1.510(4)
1.386(5)
1.383(4)
1.384(5)
1.219
1.374
1.486
1.368
1.293
1.520
1.466
1.554
1.518
1.397
1.394
1.394
C8eC9
C9eC10
C9eC12
1.379(5)
1.398(5)
1.517(5)
1.388(4)
1.496(5)
1.498(6)
1.386(4)
1.387(4)
1.389(5)
1.355(6)
1.385(6)
1.374(5)
1.402
1.401
1.523
1.401
1.540
1.540
1.404
1.408
1.395
1.394
1.399
1.390
C10eC11
C12eC13
C12eC14
C15eC16
C15eC20
C16eC17
C17eC18
C18eC19
C19eC20
ꢁ
ꢁ
Bond angles ( )
Bond angles ( )
N2eN1eC5
N2eN1eC21
C5eN1eC21
N1eN2eC3
N2eC3eC4
N2eC3eC15
C4eC3eC15
C3eC4eC5
N1eC5eC4
N1eC5eC6
C4eC5eC6
C5eC6eC7
C5eC6eC11
C7eC6eC11
C6 eC7eC8
C7eC8eC9
113.3(2)
120.5(2)
126.3(2)
108.3(2)
113.6(3)
121.0(2)
125.5(3)
103.1(2)
100.7(2)
110.6(2)
115.2(3)
121.2(3)
121.6(3)
117.2(3)
121.8(3)
121.4(3)
124.6
120.9
124.6
108.9
113.2
121.9
124.9
102.9
100.6
112.5
114.8
120.5
121.1
118.4
120.8
121.1
C8eC9eC10
C8eC9eC12
117.0(3)
121.0(3)
122.0(3)
121.4(3)
121.2(3)
111.0(3)
112.6(3)
113.1(3)
119.8(2)
121.5(3)
118.8(3)
120.4(3)
120.2(3)
120.1(4)
120.2(3)
123.7(2)
117.7
121.6
120.7
121.3
120.6
111.9
111.8
111.1
120.6
120.7
118.7
120.6
120.2
119.7
120.4
123.4
C10eC9eC12
C9eC10eC11
C6eC11eC10
C9eC12eC13
C9eC12eC14
C13eC12eC14
C3eC15eC16
C3eC15eC20
C16eC15eC20
C15eC16eC17
C16eC17eC18
C17eC18eC19
C18eC19eC20
O1eC21eN1
ꢁ
ꢁ
Torsion angles ( )
Torsion angles ( )
C5eN1eN2eC3
C21eN1eN2eC3
N2eN1eC5eC4
N2eN1eC5eC6
C21eN1eC5eC4
C21eN1eC5eC6
N2eN1eC21eO1
C5eN1eC21eO1
N1eN2eC3eC4
N1eN2eC3eC15
N2eC3eC4eC5
C15eC3eC4eC5
N2eC3eC15eC16
N2eC3eC15eC20
C7eC8eC9eC12
C8eC9eC10eC11
C12eC9eC10eC11
C8eC9eC12eC13
C8eC9eC12eC14
C10eC9eC12eC13
C4eC3eC15eC16
C4eC3eC15eC20
ꢀ5.9(3)
173.8(3)
9.9(3)
ꢀ112.4(3)
ꢀ169.7(3)
68.0(4)
ꢀ2.9
169.8
5.1
ꢀ117.5
ꢀ167.3
70.0
C3eC4eC5eN1
C3eC4eC5eC6
N1eC5eC6eC7
N1eC5eC6eC11
C4eC5eC6eC7
ꢀ9.5(3)
109.5(3)
66.0(4)
ꢀ112.3(3)
ꢀ47.3(4)
134.4(3)
ꢀ177.7(3)
0.7(5)
178.6(3)
0.2(4)
ꢀ0.8(5)
ꢀ0.1(5)
60.0(5)
ꢀ1.1(5)
ꢀ179.6(3)
ꢀ0.2(5)
179.2(3)
ꢀ0.1(5)
0.3(5)
ꢀ0.2(5)
ꢀ0.1(6)
0.3(5)
ꢀ5.0
116.0
59.1
ꢀ121.5
ꢀ55.2
124.2
179.2
ꢀ0.3
C4eC5eC6eC11
C5eC6eC7eC8
C11eC6eC7eC8
C5eC6eC11eC10
C7eC6eC11eC10
C6eC7eC8eC9
C7eC8eC9eC10
C10eC9eC12eC14
C9eC10eC11eC6
C3eC15eC16eC17
C20eC15eC16eC17
C3eC15eC20eC19
C16eC15eC20eC19
C15eC16eC17eC18
C16eC17eC18eC19
C17eC18eC19eC20
C18eC19eC20eC15
ꢀ179.5(3)
ꢀ173.7
0.1(5)
ꢀ1.7
ꢀ1.3(4)
ꢀ0.9
ꢀ178.9
0.6
178.9(3)
7.4(4)
179.7
4.0
ꢀ0.1
ꢀ172.8(3)
176.4(3)
ꢀ2.9(5)
ꢀ176.6
179.1
ꢀ0.7
0.3
63.3
ꢀ0.4
ꢀ179.2(3)
1.0(5)
ꢀ179.6
0.3
ꢀ179.8
0.1
ꢀ179.9(3)
111.1(4)
ꢀ120.9(4)
ꢀ68.0(4)
ꢀ3.4(5)
179.9
ꢀ62.1
63.3
ꢀ62.1
ꢀ0.18
ꢀ180.0
179.8
ꢀ0.04
ꢀ0.03
0.01
ꢀ0.01
177.3(3)
0.03
from XRD analysis.
[27e30]. All the bond lengths and angles in the phenyl rings are in
the expected range. In the pyrazolinyl ring, the C]N, CeN and NeN
(1.287(4), 1.486(3) and 1.385(3)) Å bond lengths are all similar to
those found in analogous structures (C]N: 1.291(2)e1.300(10) Å,
CeN: 1.482(2)e1.515(9) Å and NeN: 1.373(2)e1.380(8) Å) [30,31].
Crystal packing is mainly consolidated by CeH … O and CeH … N
intra- or inter-molecular hydrogen bonds. Information of three
hydrogen bonds is given in the asymmetric unit (Table 3). Each O1
atom is connected to two adjacent discrete molecules through C4-
H4B … O1 (symmetry code: -1þx,y,z) hydrogen bond of 3.470(5) Å
and C10-H10 … O1 (symmetry code: 1ꢀx, 1ꢀy,ꢀz) hydrogen bond
of 3.398(4) Å. Packing suggests that rings show how the neigh-
boring moieties link to each other through the C4-H4B … O1 and
C10-H10 … O1 interactions. These rings are connected yielding to
infinite supramolecular cycles (Fig. 4). Further, the N2 atom is
involved in an intramolecular C21-H21 … N2 (symmetry code:
Crystal parameters of the structure are collected in Table 2.
Further, equivalent thermal parameters are presented in Table SI1
together with atomic coordinates. Molecular structure with atom-
numbering is illustrated in Fig. 2. Crystal packing view is also
given in Fig. SI1. The refinement details are available in the CCDC:
1
429353. Synthesized molecule consists of discrete [C
PhC CHOPh] entities. It crystallizes in triclinic system by P-1
space group. Unit cell parameters are
3 7
H -
3 2 2
H N
a
¼
6.4267(4) Å,
ꢁ
b ¼ 10.9259(12) Å, c ¼ 12.4628(9) Å and
a
¼ 102.894(8) ,
ꢁ
ꢁ
b
¼ 102.535(6) ,
g
¼ 101.633(7) . The compound exists in a trans
configuration (Fig. 2a). Average mean plane angles between the
pyrazolinyl ring with phenyl at positions 3 and 5 of pyrazoline are
ꢁ
ꢁ
ꢁ
5
6
.4 and 88.6 , correspondingly. The average mean plane angle is
.3 between the formyl group and pyrazoline ring. These values
compare satisfactorily to similar compounds in the literature

A. Sid et al. / Journal of Molecular Structure 1121 (2016) 46e53
51
Table 5
Some parameters of the compound (P (ε) ¼ (εꢀ1)/(εþ2)).
Medium
B3LYP/6-31G(d,p)
Trans isomer
P(ε)
Dipole moment
C]O bond length
n(C]O)
Scaled n(C]O)
Gas phase
n-Hexane
n-Heptane
Cyclohexane
e
4.10
4.77
4.79
4.83
4.91
4.93
5.36
5.42
5.63
5.70
5.86
5.89
5.91
5.94
5.97
5.98
6.00
1.219
1.221
1.221
1.221
1.222
1.222
1.224
1.224
1.225
1.225
1.226
1.226
1.226
1.226
1.226
1.226
1.226
1786.61
1775.00
1774.57
1773.65
1772.03
1771.55
1761.99
1760.75
1756.11
1754.66
1751.24
1750.41
1750.19
1749.56
1748.83
1748.63
1748.11
1719.97
1708.79
1708.38
1707.49
1705.93
1705.47
1696.27
1695.07
1690.61
1689.21
1685.92
1685.12
1684.91
1684.30
1683.60
1683.41
1682.91
0.227
0.239
0.253
0.287
0.298
0.519
0.553
0.682
0.726
0.833
0.859
0.867
0.888
0.913
0.920
0.939
1,4-Dioxane
Benzene
Diethyl ether
Chloroform
Tetrahydrofuran
Dichloromethane
2
2
-Butanol
-Propanol
Acetone
Ethanol
Methanol
Acetonitrile
DMSO
Table 6
Anti-bacterial screening results.
Compound
Escherchia coli
Salmonella typhi
Staphylococcus aureus
16
40
e
Bacillus subtilis
Bis-Pyr
Penicillin
DMSO
15
18
e
20
25
e
08
17
e
-: No antibacterial activity.
1
ꢀx,1ꢀy, 1ꢀz) hydrogen bonding of 3.540(3) with forming a dimer
vibrational frequencies and their intensities are tabulated in
Table SI2.
(Fig. 4). The calculated parameters (H21$$$N2: 2.489 Å,
ꢁ
:
C21H21N2: 153.9 ) are in good agreement with the experimen-
The calculated carbonyl stretching frequencies of the compound
are collected in Table 5. As shown in Table 5, significant changes in
the carbonyl stretching modes of the compound are observed when
considering the solutions. For n-hexane, the C]O stretching is
computed at higher frequencies. Since there is no any remarkable
solute-solvent interaction for inert solvent n-hexane, it belongs to
the free monomer state for C]O. These bands are found at lower
frequency in polar solvents. The C]O bond lengths increase by
increasing dielectric constant of solvent. Therefore, the C]O
stretching frequency should decrease. It is definitely shown in
Table 5 that these requirements are fulfilled. The frequency shift is
clarified by positive character increased on O atom in polar sol-
vents. Further, there is linear correlation between the dipole
moment and dielectric constant.
ꢁ
tally observed values (H21…N2: 2.570 Å, :C21H21N2: 166.0 ) for
the intramolecular hydrogen bond.
The structural parameters are given in Table 4. In general, all
calculated parameters are in good agreement with the experi-
mental data. Largest difference between the experimental and
theoretical bond length (angle) is 0.044 Å; C12-C13 (11.3 ; N2-N1-
C5). Mean absolute deviations between the theoretical and exper-
imental bond lengths and angles are found to be 0.015 Å and 1.0 .
ꢁ
ꢁ
4.2. Spectroscopic studies
FTIR spectrum is carried out to analyze the chemical bonding
and structure (Fig. SI2). It shows a strong band for
n
(C]O) at
ꢀ1
In the 1H NMR spectrum, the tree H atoms attached to the C4
and C5 atoms of the heterocyclic ring have given an ABX spin
system and a doublet signal at 8.96 ppm. It refers to the presence of
N-formyl. The values of chemical shift and coupling constant
1658 cm . The theoretical value (n21 by B3LYP/6-31G(d,p)) is
ꢀ
1
calculated as 1720 cm . The carbonyl stretching frequency is
consistent with previously reported for 1-acetyl-3-(2,4-dichloro-5-
fluoro-phenyl)-5-phenyl-pyrazoline where the experimental band
ꢀ1
13
was observed as 1660 cm whereas the theoretical data (B3LYP/6-
measured prove 2-pyrazoline in structure. In the C NMR spectra
ꢀ1
31G(d)) was computed as 1708 cm [30]. C]N stretching vibra-
(Fig. SI3), chemical shifts of carbon atoms C3 at 155.85 ppm, C4 at
42.60 ppm and C5 at 58.80 ppm corroborate 2-pyrazoline structure
ꢀ1
tion is observed at 1596 cm whereas the NeN stretching band
together with the pyrazoline ring CH contribution is shown at
1
determined by H NMR. Chemical shift of C3 is consistent with
ꢀ1
2
1156 cm . The corresponding theoretical data (
n
26 and
n57) are
previously reported for 1-formyl-3-phenyl-
D
-pyrazoline as
ꢀ1
computed as 1565 and 1121 cm , respectively. All computed
157.34 ppm [29]. C5 is easily differentiated from C4. The C4 and C5
Table 7
Anti-fungal screening results.
Compound
Aspergillus niger
Aspergillus flavus
Pencillium chrysogenum
Fusirium moneliforme
Bis-Pyr
Greseofulvin
Control
e
e
þ
þ
e
þ
þ
e
þ
þ
e
þ

52
A. Sid et al. / Journal of Molecular Structure 1121 (2016) 46e53
Table 8
Gas phase molecular orbital energies (eV) and dipole moment (Debye).
Appendix A. Supplementary data
Parameters
Trans
Cis
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.molstruc.2016.05.043.
HOMO
LUMO
HOMO-LUMO Gap
Dipole moment
ꢀ5.82
ꢀ1.40
4.42
ꢀ5.77
ꢀ1.34
4.43
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