Synthesis, characterization, crystal structure and DFT studies on 1-acetyl-3-(2,4-dichloro-5-fluoro-phenyl)-5-phenyl-pyrazoline

Article abstract of DOI:10.1016/j.saa.2007.05.016

The title compound, 1-acetyl-3-(2,4-dichloro-5-fluoro-phenyl)-5-phenyl-pyrazoline, has been synthesized and characterized by elemental analysis, IR, UV-vis and X-ray single crystal diffraction. Density functional (DFT) calculations have been carried out f

Full text of DOI:10.1016/j.saa.2007.05.016

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Spectrochimica Acta Part A 69 (2008) 647–653
Synthesis, characterization, crystal structure and DFT studies on
1-acetyl-3-(2,4-dichloro-5-fluoro-phenyl)-5-phenyl-pyrazoline
Fangfang Jiana, Pusu Zhaoa,∗, Huanmei Guob, Yufeng Lia
a New Materials & Function Coordination Chemistry Laboratory, Qingdao University of
Science and Technology, Qingdao, Shandong 266042, PR China
b Department of Chemistry, Weifang University, Weifang, Shandong 261061, PR China
Received 8 February 2007; received in revised form 4 May 2007; accepted 7 May 2007
Abstract
The title compound, 1-acetyl-3-(2,4-dichloro-5-fluoro-phenyl)-5-phenyl-pyrazoline, has been synthesized and characterized by elemental ana-
lysis, IR, UV–vis and X-ray single crystal diffraction. Density functional (DFT) calculations have been carried out for the title compound by using
B3LYP method at 6-31G* basis set. The calculated results show that the predicted geometry can well reproduce the structural parameters. Predicted
vibrational frequencies have been assigned and compared with experimental IR spectra and they are supported each other. The theoretical electro-
nic absorption spectra have been calculated by using TD-DFT method. Molecular orbital coefficients analyses suggest that the above electronic
transitions are mainly assigned to n → ␲* and ␲ → ␲* electronic transitions. On the basis of vibrational analyses, the thermodynamic properties
of the title compound at different temperatures have been calculated, revealing the correlations between Cp0,m, Sm0 , Hm0 and temperatures.
© 2007 Elsevier B.V. All rights reserved.
Keywords: Synthesis; Crystal structure; Vibrational frequency; Electronic absorption spectra; DFT
1. Introduction
since it is computationally less demanding for inclusion of elec-
tron correlation. Detailed analyses [14–17] on the performance
of different DFT methods have been carried out particularly
for equilibrium structure properties of molecular systems, such
as geometry, dipole moment, vibrational frequency, etc. The
general conclusion from these studies is that DFT methods, par-
ticularly with the use of nonlocal exchange-correlation function,
can predict accurate equilibrium structure properties. With these
in mind, after the title compound of 1-acetyl-3-(2,4-dichloro-
5-fluoro-phenyl)-5-phenyl-pyrazoline was synthesized, we
performed DFT calculations on it. In this paper, we wish
to report the experimental values as well as the calculated
results.
Fluorescent probes are powerful tools in cell biology for the
non-invasive measurement of intracellular ion concentrations
[1]. They have found widespread applications, e.g., to gauge
intracellular calcium concentrations [2], to visualize labile zinc
[3,4]andironpools[5], oraspHsensors[6]. Amongvariouspos-
sible fluorescent probes, pyrazoline-based fluorophores stand
out since their simple structure and favorable photophysical pro-
perties such as large extinction coefficient and quantum yields
(Φf ≈ 0.6–0.8) [7]. Their attractive properties, including cation-
or pH-sensitive probes, have been described [8–10], and the
suitability of pyrazoline fluorophores as probes in a biologi-
cal environment is also explored [11]. Because of its modular
nature, the synthesis of 1,3,5-trisubstituted pyrazoline fluoro-
phores provides a high degree of structural flexibility [7,12]. On
the other hand, density functional theory (DFT) has long been
recognized as a better alternative tool in the study of organic che-
mical systems than the ab initio methods used in the past [13],
2. Experimental and theoretical methods
2.1. General method
Elemental analyses for carbon, hydrogen and nitrogen
were performed by a Perkin-Elmer 240C elemental instru-
ment. The melting points were determined on a Yanaco
MP-500 melting point apparatus. IR spectra (4000–400 cm−1),
as KBr pellets, were recorded on a Nicolet FT-IR spectro-
∗
Corresponding author. Tel.: +86 532 84022948; fax: +86 532 84023606.
E-mail address: zhaopusu@163.com (P. Zhao).
1386-1425/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2007.05.016

648
F. Jian et al. / Spectrochimica Acta Part A 69 (2008) 647–653
Table 1
photometer. Electronic absorption spectra in EtOH solution
were measured on a Shimadzu UV3100 spectrophotome-
ter.
Crystal data and structure refinement
Empirical formula
C17H13Cl2 FN2O
Formula weight
351.19
2.2. Synthesis
Temperature
Wavelength
293(2) K
0.71073 A
˚
Crystal system, space group
Unit cell dimensions
Tetragonal, P-421c
All chemicals were obtained from a commercial source and
used without further purification.
˚
˚
a = 20.460(3) A, b = 20.460(3) A,
˚
c = 7.7246(15) A
The reaction path is shown in Scheme 1.
3
˚
Volume
3233.8(9) A
8, 1.443 Mg/m3
1-2,4-Dichloro-5-fluoro-phenyl-3-phenyl-2-propenyl-1-
ketone (0.01 mol) and hydrazine hydrate (0.015 mol) were
mixed in acetic acid (40 mL) and stirred in refluxing for 6 h,
then, the mixture was poured into ice-water to afford light-
yellow solids. The solids were filtrated and washed with water
until the pH of solution is about to 7. Finally, the light-yellow
solid crystals were dry under room temperature. Yield 87%,
mp 149–150 ◦C. Found: C, 58.01; H, 3.58; N, 7.88%. Calcd.
for C17H13Cl2FN2O: C, 58.14; H, 3.73; N, 7.98%. Electronic
absorption spectra in hexahydrobenzene (nm, log ε): λmax = 210
(1.70), λ = 236 (0.81), λ = 312 (1.19).
Z, Calculated density
Absorption coefficient
F(0 0 0)
θ range for data collection
Limiting indices
Reflections collected/unique
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
0.416
1440
1.41–25.00◦
−24 ≤ h ≤ 22, −21 ≤ k ≤ 24, −9 ≤ l ≤ 6
13068/2837 [Rin t = 0.0561]
Full-matrix least-squares on F2
2837/0/208
1.289
R1 = 0.0826, wR2 = 0.1466
R1 = 0.0930, wR2 = 0.1511
−3
˚
Largest diff. peak and hole
0.263 and −0.172 e A
2.3. Crystal structure determination
2.4. Theoretical methods
The diffraction data were collected on a Enraf-Nonius
DFT calculations with a hybrid functional B3LYP (Becke’s
three parameter hybrid functional using the LYP correlation
functional) at basis set 6-31G* by the Berny method [20] were
performed with the Gaussian 03 software package [21]. Vibra-
tional frequencies calculated ascertain the structure was stable
(no imaginary frequencies). The thermodynamic properties of
the title compound at different temperatures were calculated on
the basis of vibrational analyses. Natural bond orbital (NBO)
analyses and the time-dependent density functional theory (TD-
DFT) [22–25] calculations of electronic absorption spectra were
also performed on the optimized structure.
CAD-4 diffractometer with graphite-monchromated Mo K␣
˚
radiation (λ = 0.71073 A, T = 293 K). The technique used was
ω–2θ scan mode with limits 1.41–25.00◦. The structure
of the title compound was solved by direct methods and
refined by least squares on F2 by using the SHELXTL
[18] software package. All non-hydrogen atoms were ani-
sotropically refined. The hydrogen atom positions were
fixed geometrically at calculated distances and allowed to
ride on the parent carbon atoms. The final conventional
R = 0.0826 and Rw = 0.1466 for 2509 reflections with I > 2σ(I)
using the weighting scheme, w = 1/[σ(Fo2 + (0.0467P)2 +
1.6334P], where P = (Fo2 + 2Fc2)/3. The molecular graphics
were plotted using SHELXTL. Atomic scattering factors and
anomalous dispersion corrections were taken from Interna-
tional Tables for X-ray Crystallography [19]. A summary
of the key crystallographic information is given in Table 1.
Further details on the crystal structure investigation have
been deposited with the Cambridge Crystallographic Data
Centre as supplementary publication number CCDC 626447
for this paper. These data can be obtained free of charge
via http://www.ccdc.can.ac.uk/conts/retrieving.html (or from
the Cambridge Crystallographic Centre, 12 Union Road,
Cambridge CB21EZ, UK [Fax: +44 1223 336033; e-mail:
deposit@ccdc.cam.ac.uk]).
All calculations were performed on a DELL PE 2850 ser-
ver and a Pentium IV computer using the default convergence
criteria.
3. Results and discussions
3.1. Description of the crystal structure
For the title compound, the displacement ellipsoid plot with
the numbering scheme is shown in Fig. 1 and a perspective view
of the crystal packing in the unit cell is shown in Fig. 2. Selected
bond lengths and bond angles by X-ray diffraction are listed in
Table 2 along with the calculated bond parameters.
Scheme 1.

F. Jian et al. / Spectrochimica Acta Part A 69 (2008) 647–653
649
Table 2
Selected structural parameters by X-ray and theoretical calculations
Experimental
Calculated
˚
Bond lengths (A)
Cl(1) C(15)
Cl(2) C(13)
F(1) C(12)
O(1) C(16)
N(1) C(16)
N(1) N(2)
N(1) C(7)
N(2) C(9)
C(14) C(15)
C(1) C(2)
C(4) C(5)
C(6) C(7)
C(7) C(8)
C(8) C(9)
C(9) C(10)
C(10) C(15)
C(12) C(13)
C(16) C(17)
1.730(5)
1.739(6)
1.339(6)
1.217(6)
1.340(6)
1.383(5)
1.457(6)
1.282(6)
1.379(7)
1.366(10)
1.376(9)
1.494(7)
1.540(7)
1.516(6)
1.457(7)
1.394(6)
1.361(8)
1.502(7)
1.750
1.741
1.341
1.222
1.364
1.387
1.485
1.294
1.395
1.395
1.394
1.518
1.553
1.525
1.466
1.417
1.394
1.514
Fig. 1. Molecular structure with the atomic numbering scheme for the title
compound.
The molecular structure of the title compound consists of
discrete [PhFCl2C3H3N2PhC2H3O] entities. All of the bond
lengths and bond angles in the phenyl rings are in the nor-
mal range. In the pyrazolinyl ring, the C N and C N bond
lengths are all shorter than those found in similar structures[C N
Bond lengths (◦)
N(2) N(1) C(7)
C(2) C(1) C(6)
C(3) C(4) C(5)
N(1) C(7) C(8)
N(2) C(9) C(8)
C(12) C(11) C(10)
C(14) C(13) C(12)
O(1) C(16) C(17)
C(9) N(2) N(1)
C(5) C(6) C(1)
C(4) C(5) C(6)
C(9) C(8) C(7)
C(15) C(10) C(11)
C(14) C(15) C(10)
O(1) C(16) N(1)
N(1) C(16) C(17)
113.1(4)
121.5(7)
120.6(7)
101.3(3)
112.6(4)
122.0(5)
119.8(5)
123.1(5)
109.0(4)
117.3(6)
120.5(6)
102.3(4)
115.9(5)
121.4(5)
119.6(5)
117.2(5)
114.1
120.6
120.1
100.7
112.7
122.1
119.7
124.3
109.4
119.0
120.5
102.8
116.4
121.3
119.4
116.2
˚
˚
1.291(2)–1.300(10) A, C N 1.482(2)–1.515(9) A] [11]. On the
contrary, the N N bond length is longer than those found in
˚
the above-cited structures [N N 1.373(2)–1.380(8) A] [11]. The
dihedral angles between the pyrazolinyl ring with the phenyl
rings at positions 3 and 5 of the pyrazoline are 3.87(2)◦ and
79.98(3)◦, respectively.
In the crystal lattice, there are two potentially weak inter-
molecular interactions (C H···Y, Y = O) [26,27]. The distances
˚
and angles between donor and acceptor are 3.3730(2) A and
141.93(2)◦ for C(4) H(4A)···O(1) [symmetry code: x, y, 1 + z],
◦
˚
and 3.3664(2) A and 163.72(2) for C(11)–H(11A)···O(1) [sym-
metry code: y, −x, −z], respectively. In the solid state, above
supramolecular interactions stabilize the crystal structures.
3.2. Optimized geometry
DFT calculations were performed on the title compound at
B3LYP/6-31G* level of theory. Some optimized geometric para-
meters are also listed in Table 2. Comparing the theoretical
values with the experimental ones indicates that all of the opti-
mized bond lengths are slightly larger than the experimental
values, as the theoretical calculations are performed for isola-
ted a molecule in gaseous phase and the experimental results
are for a molecule in a solid state. The geometry of the solid-
state structure is subject to intermolecular forces, such as van
der Waals interactions and crystal packing forces. The biggest
differences of bond lengths and bond angles between the experi-
˚
mental and the predicted values are −0.033 A for C(12) C(13)
bond distance and −1.7◦ for C(5) C(6) C(1) bond angle, which
suggests that the calculational precision is satisfactory [28] and
the B3LYP/6-31G* level of theory is suitable for the system
studied here. Based on the optimized geometries, electronic
spectra and thermodynamic properties of the title compound
are discussed as follows.
Fig. 2. A view of the crystal packing down the c axis for the title compound.

650
F. Jian et al. / Spectrochimica Acta Part A 69 (2008) 647–653
Fig. 3. Experimental IR spectra and predicted spectrum at B3LYP/6-31G* level for the title compound.
3.3. Vibrational frequency
molecular interactions occurring on O(1) atoms, which finally
influence the C O stretch vibration frequency, while in the cal-
culations, the studied molecule is isolated in gas state and there
is no other interaction to be considered. In a word, the scaled
frequencies of the DFT calculation are close to the correspon-
ding FTIR vibration data and the DFT-B3LYP/6-31G* level can
predict the vibrational frequencies for the system studied here
on the whole.
The experimental IR spectra and the simulated IR spectra
are shown in Fig. 3, where the calculated intensity is plotted
against the harmonic vibrational frequencies. Vibrational fre-
quencies calculated at B3LYP/6-31G* level were scaled by 0.96
[29]. Some primary calculated harmonic frequencies are listed
in Table 3 and compared with the experimental data. The des-
criptions concerning the assignment have also been indicated in
the Table 3. Gauss-view program [30] was used to assign the cal-
culated harmonic frequencies. In Fig. 3, the predicted harmonic
vibration frequencies and the experimental data are very similar
toeachotherexceptforthepeakat3293 cm−1 inexperimentalIR
spectra, which is attributed to the νO–H of water molecules. Our
present experimental conditions cannot avoid this νO–H peak of
water. On the other hand, there is a bigger difference on the C O
stretch vibration frequency. The experimental νC O stretch is at
1660 cm−1, while the predicted value is at 1708 cm−1. The rea-
son may be that in the solid state, there are two potentially weak
3.4. Electronic absorption spectra
Experimental electronic spectra measured in hexahydroben-
zene solution along with the theoretical electronic absorption
spectra calculated on the B3LYP/6-31G* level optimized struc-
ture are listed in Table 4.
Seen from Table 4, both the experimental electronic spec-
tra and predicted electronic spectra have three absorption peaks,
with the latter having some blue shifts compared with the former.
In addition, the theoretical electronic spectra have a broad band

F. Jian et al. / Spectrochimica Acta Part A 69 (2008) 647–653
651
Table 3
Comparison of the observed and calculated vibrational spectra of the title compound
Assignments
Experimental IR (with KBr)
Calculated (B3LYP/6-31G*)
Phenyl ring C H str.
3098
3053
3027
2965
2919
1660
1590
1579
1496
1441
1417
1353
1316
1290
1260
1212
1153
1095
1064
1022
968
3112–3111
3053
3012
2986–2975
2939
1708
1587–1582
1570
1485
1445–1443
1435
1350
1313
1293
1265
1228
1154
1073
1064
1022
Methyl group C H str.
Methyl group C H str.
Pyrazolinyl ring C H str.
Pyrazolinyl ring C H bend
C
O str.
Phenyl ring C C str. + C N str.
Phenyl ring C C str. + C N str.
Phenyl ring C H bend
Methyl group C H bend
Methyl group C H bend
Pyrazolinyl ring C H bend
Phenyl ring C H bend
Phenyl ring C C str. + pyrazolinyl ring C H bend
Pyrazolinyl ring C H bend
Phenyl ring C H bend
Pyrazolinyl ring C H bend + N-Nstr.
All C H bend
Phenyl ring C C str. + pyrazolinyl ring C N str.
Methyl group C H bend
Phenyl ring C C str.
978
Phenyl ring C H twist.
899
890
Phenyl ring C H twist.
873
857
Phenyl ring str. + pyrazolinyl ring str.
Phenyl ring C H twist. + pyrazolinyl ring C H twist
Phenyl ring C C str.
764
733
700
762
745
711
Phenyl ring C H twist.
684
684
Skeleton deformation
625
618
(Cp0,m), entropy (Sm0 ) and enthalpy (Hm0 ) were obtained and listed
in Table 5. The scale factor for frequencies is still 0.96.
As observed from Table 5, all the values of Cp0,m, Sm0 and Hm0
increase with the increase of temperature from 100.0 to 700.0 K,
whichisattributedtotheenhancementofthemolecularvibration
while the temperature increases.
The correlations between these thermodynamic properties
and temperatures T are shown in Fig. 5. The correlation equa-
tions are as follows:
from 304 to 308 nm, which is different from the experimental
peak at 312 nm. Molecular orbital coefficients analyses based
on the optimized geometry indicate that the frontier molecular
orbitals are mainly composed of p atomic orbitals, so electro-
nic transitions corresponding to above electronic spectra are
mainly assigned to n → ␲* and ␲ → ␲* electronic transitions.
Fig. 4 shows the surfaces of the HOMO-1, HOMO, LUMO
and LUMO + 1 for the title compound. As seen from Fig. 4,
in the HOMO-1, electrons are mainly delocalized on the acetyl
group, pyrazolinyl ring and 5-position phenyl ring, while in the
LUMO + 1, electrons are all delocalized on 3-position phenyl
ring. So, the electronic spectra are corresponding to n → ␲* and
␲ → ␲* electronic transitions.
Cp0,m = 28.54 + 1.214T − 5.484 × 10−4T2 (R2 = 0.9995);
Sm0 = 290.68 + 1.389T − 3.861 × 10−4T2 (R2 = 0.99995);
Hm0 =−5.30+9.847×10−2T+3.942 × 10−4T2 (R2 = 0.9998)
3.5. Thermodynamic properties
These equations could be used for the further studies on the
titlecompound. Forinstance, whenweinvestigatetheinteraction
On the basis of vibrational analyses and statistical thermo-
dynamics, the standard thermodynamic functions: heat capacity
Table 5
Thermodynamic properties at different temperatures at B3LYP/6-31G* level
Table 4
T (K)
Cp0,m (J mol−1 K−1
)
Sm0 (J mol−1 K−1
)
Hm0 (kJ mol−1
)
Experimental and theoretical electronic absorption spectra values
Experimental
Calculated
100.0
200.0
300.0
400.0
500.0
600.0
700.0
149.04
243.76
340.36
429.05
502.55
561.13
607.82
423.73
556.01
673.15
783.53
887.46
984.47
1074.60
9.59
29.22
58.44
Wave length (nm)
log ε
Wave length (nm)
Oscillator strength
210
236
312
1.70
0.81
1.19
204.87
226.80
304.82
308.61
0.3307
0.0655
0.2645
0.3700
97.02
143.73
197.03
255.56

652
F. Jian et al. / Spectrochimica Acta Part A 69 (2008) 647–653
Fig. 4. Surfaces of HOMO-1, HOMO, LUMO and LUMO + 1 for the title compound.
Fig. 5. Correlation graphics of thermodynamic properties and temperatures for the title compound.

F. Jian et al. / Spectrochimica Acta Part A 69 (2008) 647–653
653
between the title compound and another compound, thermo-
dynamic properties Cp0,m, Hm0 and Sm0 could be obtained from
these equations and then used to calculate the change of Gibbs
free energy of the reaction, which will assist us to judge the
spontaneity of the reaction.
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4. Conclusions
1-Acetyl-3-(2,4-dichloro-5-fluoro-phenyl)-5-phenyl-
pyrazoline has been synthesized and characterized by elemental
analysis, IR, UV–vis and X-ray single crystal diffraction. DFT
calculations at B3LYP/6-31G* level for the title compound
show that the optimized geometry closely resemble the crystal
structure. The comparisons between the calculated vibrational
frequencies and the experimental IR spectra indicate they
are supported each other. The predicted electronic absorption
spectra have some blue shifts compared with the experimental
data and molecular orbital coefficients analyses suggest that
the electronic spectra are assigned to n → ␲* and ␲ → ␲*
electronic transitions. The correlations between the thermody-
namic properties Cp0,m, Sm0 and Hm0 and temperatures T are also
obtained.
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Acknowledgements
This work was supported by Natural Science Foundation
of Shandong Province (No. Y2005B04), PR China, Doctoral
Fund of Shandong Province, PR China (No. 2006BS01043) and
Doctoral Fund of Qingdao University of Science & Technology.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.saa.2007.05.016.
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