Isolation, characterization and X-ray structure determination of the Schiff base ligand: 5-methyl-2-phenyl-4-[phenyl-(4-phenyl-thiazol-2-ylamino)-methylene]-2,4-dihydro-pyrazol-3-one

Article abstract of DOI:10.17159/0379-4350/2015/v68a6

The structure of the amine tautomer of the new Schiff base derived from 4-benzoyl-5-methyl-2-phenyl-2,4-dihydro-pyrazol-3-one (2) and 4-phenyl-thiazol-2-ylamine (3) was confirmed by means of single crystal X-ray diffraction. The title compound (4) was synthesized and crystals were grown from a mixture of dichloromethane and n-hexane (1:3). Single crystal X-ray diffraction analysis show that the structure is primarily stabilized by strong intramolecular N3-H3A...O1 hydrogen bonds [N3-H3A = 0.883(19) ?, H3A...O1=1.925(18) ?, N3...O1=2.6901(13) ?, with an angle for N3-H3A...O1=144.1(17) °] and this leads to the formation of a pseudo nine-membered hydrogen bonded pattern. Elemental analysis, FTIR andNMRanalyses have been employed to characterize the crystal.

Full text of DOI:10.17159/0379-4350/2015/v68a6

RESEARCH ARTICLE
A.S. Thakar, H.B. Friedrich, K.T. Joshi and G.E.M. Maguire,
S. Afr. J. Chem., 2015, 68, 39–44,
39
<http://journals.sabinet.co.za/sajchem/>.
Isolation, Characterization and X-ray Structure
Determination of the Schiff Base Ligand:
5-Methyl-2-phenyl-4-[phenyl-(4-phenyl-thiazol-2-ylamino)-
methylene]-2,4-dihydro-pyrazol-3-one
Amit S. Thakara, Holger B. Friedricha, Krishnalal T. Joshib and Glenn E.M. Maguireb,
*
aSchool of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban, 4000, South Africa.
bDepartment of Chemistry, Navjivan Science College, Dahod, Gujarat, 389 151, India.
Received 12 June 2014, revised 20 December 2014, accepted 23 December 2014.
ABSTRACT
The structure of the amine tautomer of the new Schiff base derived from 4-benzoyl-5-methyl-2-phenyl-2,4-dihydro-pyrazol-
3-one (2) and 4-phenyl-thiazol-2-ylamine (3) was confirmed by means of single crystal X-ray diffraction. The title compound (4)
was synthesized and crystals were grown from a mixture of dichloromethane and n-hexane (1:3). Single crystal X-ray diffraction
analysis show that the structure is primarily stabilized by strong intramolecular N3–H3A···O1 hydrogen bonds [N3–H3A =
0.883(19) Å, H3A···O1 = 1.925(18) Å, N3···O1 = 2.6901(13) Å, with an angle for N3–H3A···O1 = 144.1(17) °] and this leads to the for-
mation of a pseudo nine-membered hydrogen bonded pattern. Elemental analysis, FTIR and NMR analyses have been employed
to characterize the crystal.
KEYWORDS
Pyrazolone, thiazole, Schiff base, tautomer, X-ray structure.
1. Introduction
3-one (1) was obtained from Prima Chemicals, Ahmedabad,
The chemistry of pyrazolone derivatives has attracted much India. Methanol and dioxane were obtained from SD’s Fine
attention because of their interesting structural properties and Chemical Ltd., India. Absolute alcohol was obtained from
applications in diverse areas.1 They can be used in laser materials, Baroda Chem. Industry Ltd. and was used after distillation.
as 1H NMR shift reagents, in chromatographic studies and in the Calcium hydroxide and benzoyl chloride were obtained from
petrochemical industry.2 Furthermore, they are useful reagents Samir Tech. Chem. Pvt. Ltd. All the chemicals used were of AR
for the extraction and separation of various metal ions.3 More- grade. Solvents used in this study were purified following standard
over, particular interest exists due to the ability of these compounds procedures. For the synthesis of compound 2, the benzoylation
to exhibit several tautomeric forms: keto-imine, imine-ol and step was carried out in the presence of calcium hydroxide as per
keto-amine.4 These Schiff base ligands have been studied exten- a literature method.8
sively due to their ease of synthesis and their ability to be readily
varied both sterically and electronically. On the other hand, the
aminothiazole ring system is a useful structural element in
medicinalchemistry.5 Wehavereportedsubstitutedpyrazolones
with various amino thiazoles and their molecular structures
were determined.6 The ligands can exist in three tautomeric
forms but the keto-amine form is predominant in the solid state.7
In Schiff base compounds, the imine nitrogen can act as an inter-
or intramolecular hydrogen bond acceptor. We are interested in
exploring the essence of inter- and intra-molecular interactions
of the ligand in metal stabilization, extraction and florescence
effects in green chemistry.
As a part of our ongoing studies into the structure and utility of
Schiff base ligands synthesized from pyrazolone and thiazole,
we report the synthesis (Scheme 1), spectral properties, crystal
structure, tautomerism (Scheme 2), and weak interactions of the
Schiff base prepared from the condensation of 4-benzoyl-5-
methyl-2-phenyl-2,4-dihydro-pyrazol-3-one (2) and 4-phenyl-
thiazol-2-ylamine (3).
The elemental analysis was obtained by using a Flash Elemental
Analyzer-1112. Infrared spectra (IR) were measured with a
PerkinElmer Precisely 100 FTIR spectrometer. 1H and 13C NMR
spectra were measured at 400.22 and 100.63 MHz, respectively,
with a Bruker Avance III 400 MHz spectrophotometer by using
TMS (tetramethylsilane) as the internal reference. Melting
points were recorded on an Ernst Leitz Wetzlar hot stage melting
point apparatus. Reactions were monitored by thin layer chro-
matography (TLC) on aluminum-backed plates coated with
Merck Kieselgel 60 F254 silica gel. TLC plates were visualized by
UV radiation at a wavelength of 254 nm. Crystals suitable for
X-ray diffraction were obtained by slow evaporation of the title
compound in a combination of dichloromethane with n-hexane
(1:3) at room temperature. The data collection and cell refine-
ment were achieved by using Bruker APEX2 and SAINT-Plus
respectively.9 The data reduction was performed with SAINT-Plus
and XPREP.9 The program used to solve and refine the structure
was SHELXS 97.10 For molecular graphics ORTEP-311 and
OLEX212 were employed to prepare the material for publica-
tion.12
2. Experimental
2.1. Materials and Measurements
The compound 5-methyl-2-phenyl-2,4-dihydro-pyrazol-
2.2. Synthesis of Schiff Base Ligand
5-Methyl-2-phenyl-2,4-dihydro-pyrazol-3-one (1) (2 g,
11.5 mmol) was dissolved in hot dioxane (20 mL) in a flask
* To whom correspondence should be addressed. E-mail: maguireg@ukzn.ac.za
ISSN ISSN 0379-4350 Online / ©2015 South African Chemical Institute / http://saci.co.za/journal
DOI: http://dx.doi.org/10.17159 /0379-4350/2015/v68a6

RESEARCH ARTICLE
A.S. Thakar, H.B. Friedrich, K.T. Joshi and G.E.M. Maguire,
S. Afr. J. Chem., 2015, 68, 39–44,
40
<http://journals.sabinet.co.za/sajchem/>.
Scheme 1
Synthetic pathway for the Schiff base ligand.
Scheme 2
The possible tautomeric forms of the Schiff base.
equipped with a stirrer, separating funnel and reflux condenser. (1.2 g, 77 %), mp. = 199 °C. IR (cm–1): 3153, 1616, 1591, 1540, 1516,
Calcium hydroxide (1.7 g, 23 mmol) was added to this solution, 1490, 1385, 1353, 1209, 1196, 839, 821, 724, 688; dH (400 MHz,
followed by benzoyl chloride (3.23 g, 11.5 mmol) added CDCl3): 13.73 (0.5H, s, NH), 7.97 (2H, d, J = 7.84 Hz, ArH), 7.71
dropwise with precaution, as this reaction was exothermic. (2H, d, J = 7.28 Hz, ArH), 7.57 (3H, m, ArH), 7.44 (2H, d, J = 7.24
During this addition the reaction mass was converted into a Hz, ArH), 7.36 (2H, t, J = 7.92 Hz, ArH), 7.32 (2H, t, J = 7.42 Hz,
thick paste. After the complete addition, the reaction mixture ArH), 7.25 (2H, d, J = 7.16 Hz, ArH), 7.12 (t, J = 6.36 Hz, ArH), 6.84
was refluxed for half an hour and then it was poured into dilute (1H, s, CH), 4.71 (0.5H, s, OH), 1.48 (3H, s, CH3) ppm; dC
hydrochloric acid (50 mL, 2 M). The crude product 4-benzoyl- (100 MHz, CDCl3): 165.04, 160.88, 159.27, 153.04, 147.55, 138.42,
5-methyl-2-phenyl-2,4-dihydro-pyrazol-3-one (2) obtained was 136.09, 134.47, 131.15, 129.47, 129.34, 126.04, 119.39, 107.58,
separated by filtration and recrystallized from n-hexane to give a 103.39, 15.97 ppm.
bright yellow crystalline solid (2.5 g, 80 %).
A solution of 2 (1 g, 3.6 mmol) in methanol (30 mL) was added 3. Results and Discussion
to another solution of 4-phenyl-thiazol-2-ylamine (3) (0.63 g,
3.6 mmol) in methanol (20 mL) under an inert atmosphere. The 3.1. Characterization of the Ligand
reaction mixture was refluxed for three hours. Completion of the
The compound was stable at room temperature, non-hygro-
reaction was monitored by TLC using hexane/ethyl acetate (8:2). scopic, insoluble in n-hexane, petroleum ether and toluene,
The reaction was allowed to cool to room temperature and and soluble in chloroform, dichloromethane and ethyl acetate.
stirred overnight. A yellow precipitate formed which was then Analytical data are shown in Table 1.
filtered and washed with methanol (10 mL). The crude product
The general structure of these ligands is such that they can
was purified by crystallization from ethanol to give brown crystals exist in three tautomeric forms as shown in Scheme 2. Detailed
of the desired product 5-methyl-2-phenyl-4-[phenyl-(4-phenyl- solution and solid-state studies of the ligand were carried out to
thiazol-2-ylamino)-methylene]-2,4-dihydro-pyrazol-3-one (4) establish the predominant tautomer.
Table 1 Analytical data of the Schiff base and precursor.
Compound
M.F.
M.Wt.
Yield/%
M.p./°C
Elemental analysis/% (found/calcd.)
C
H
N
S
2
4
C17H14N2O2
C26H20N4OS
278.31
436.53
80
77
85
199
73.28 (73.37)
77.67 (77.54)
5.12 (5.07)
4.59 (4.62)
10.13 (10.07)
12.80 (12.83)
–
7.31 (7.35)
M.F. - molecular formula, M.Wt. - molecular weight, M.p. - melting point.

RESEARCH ARTICLE
A.S. Thakar, H.B. Friedrich, K.T. Joshi and G.E.M. Maguire,
S. Afr. J. Chem., 2015, 68, 39–44,
41
<http://journals.sabinet.co.za/sajchem/>.
Table 2 Crystal data and structure refinement of the new Schiff base.
3.2. IR and NMR Spectroscopy
The IR spectra of this family of ligands exhibit two characteristic
bands at 3135 and 1616 cm–1, which can either be assigned to u O
H and u C=N, respectively, for the tautomeric imine-ol form
(Scheme 2, I) or u N-H and u C=O respectively for the
keto-amine form (Scheme 2, III) of the ligand. We assigned these
two peaks to u N-H and u C=O, respectively, for the latter form
in conjunction with the information obtained from crystallo-
graphic studies (discussed below).
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system
Space group
C26H20N4OS
436.52
173(2) K
0.71073 Å
Monoclinic
P21/c
Unit cell dimensions
a = 13.9867(3) Å
b = 21.2378(4) Å, b= 95.7990(10)
c = 7.22470(10) Å
2135.09(7) Å3
1
The H and 13C NMR spectra of the ligand were recorded in
CDCl3 at room temperature and the data are presented in the
experimental section. The signals due to methyl protons appear
as singlets at d 1.48 ppm. Another singlet was observed at d 6.84,
which corresponds to the only proton of the thiazole ring. In the
aromatic region between d 7.13 and 7.98 ppm overlapping
doublets and multiplets are observed. One broad singlet, corre-
sponding to a single proton, is observed at d 13.73 ppm. This
signal disappeared when a D2O exchange experiment was
carried out and integrates exactly for one proton, which suggests
that only one tautomeric form of the ligand exists in solution
under the experimental conditions. Although no temperature
dependent experiments were carried out, comparing with the
solid state study, this signal was assigned to NH. However,
assignment of this peak to OH cannot be ruled out, provided the
solid state structural evidence is not considered. This assign-
ment is not without contention as several researchers have
reported the determination of the imine-ol (I) tautomer in solu-
tion. For example, in the case where an N-oxime derivative was
made, the imine-ol molecule is present exclusively. A mixture of
the two tautomers has also been reported in solution.13 However
it is important to note that in the vast majority of examples where
X-ray data are shown, the crystal structure is invariably the
keto-amine isomer (III).7,14
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
4
1.358 Mg/m3
0.179 mm–1
912
Crystal size
0.46 × 0.25 × 0.23 mm3
1.75–28.41
Theta range for data collection
Reflections collected
Independent reflections
Completeness to theta = 28.41 °
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
58780
5358 [R(int) = 0.0260]
99.9 %
Semi-empirical from equivalents
0.9600 and 0.9223
Full-matrix least-squares on F2
5358 / 0 / 294
1.035
R1 = 0.0373, wR2 = 0.0913
R1 = 0.0476, wR2 = 0.0978
0.572 d –0.285 e. Å–3
Largest diff. peak and hole
difference map. The bond between the C9 and C11 carbon
atoms is a double bond and it further concludes that the result-
ing Schiff base is present as a keto-amine (III in Scheme 2) tauto-
meric form, rather than the imine-ol (I in Scheme 2) in the solid
state. However, the N–H proton is clearly hydrogen bonded
with the O1 atom, the N3···O1 distance is 2.690(13) Å and the
N3–H3A···O1 angle is 144.1(17) ° (Table 3). The possibility of the
attachment of H3A with C9 (imine-one form-II) is ruled out on
the basis of the angles around C9. The summation of the three
angles C7–C9–C10, C7– C9–C11 and C10–C9–C11 is 359.91 and
is close to the ideal value of 360 expected from the coplanar C7,
C9, C10 and C11 atoms. Selected bond angles and bond lengths
are summarized in Table 4.
In the 13C NMR spectrum the carbon atom of the methyl group
appears at d 15.97 ppm. The singlet appearing at d 103.39 ppm is
assigned to the carbon atom of the C-N moiety; the significant
upfield shift is due to the electron donating phenyl group attached
to it. The signal appearing at d 107.58 ppm can be assigned to the
C-H of the thiazole ring. The correlation between carbon and
hydrogen can be seen from the HSQC data (see online supple-
ment). The carbon atoms of the three benzene rings exhibit sig-
nals in the range of d 119–139 ppm. In the low field region, five
signals were observed at d 147.55, 153.04, 159.27, 160.88 and
165.04 ppm, which are associated with the carbon atoms of the
heterocyclic ring. The most deshielded signal at d 165.04 ppm
can be assigned to the C=O carbon and the next signal at
d 160.88 ppm was assigned to the carbon of C=N.
Thus, the crystal structure study conclusively proves the exis-
tence of this compound in the keto-amine (III) form.
With the help of XRD analysis, the possible weak interactions
of the resulting Schiff base were also studied (Fig. 2). The molec-
ular structure is primarily stabilized by a strong intra molecular
N3–H3A···O1 hydrogen bond [N3–H3A = 0.883(19) Å, H3A···O1
= 1.925(18) Å, N3···O1 = 2.6901(13) Å, and the angle
N3–H3A···O1 = 144.1(17) °] and this leads to the formation of a
3.3. X-ray Crystallography Studies
Crystal data collection parameters are given in Table 2.
The molecular structure of the ligand (Fig. 1) was determined
from single crystal X-ray studies.
Table 3 Intramolecular hydrogen-bond distances (Å) and angles (°) for
the ligand in the crystal lattice.
This structure determination gives evidence for the existence
of the keto-amine form (in the solid state). An analysis of the
structural data shows that the C10-O1 distance in the pyra-
zolone moiety is 1.244(15) Å, which is significantly shorter than
the distances found for C OH in some pyrazolone derivatives,
1.341, 1.346 Å15 and 1.331 Å;16 however, they are close to the dis-
tances found for C=O in similar compounds, 1.262 Å.15 The
C10-N1 distance of the imine moiety is at 1.376(15) Å, which is
significantly longer than those found for C=N in pyrazolone
compounds, 1.298(2) Å17 and 1.383(2) Å,1i but similar to that
found for C-N (1.339(3) Å).18 It should also be noted that the
proton associated with N3 can be located from the Fourier
D H···A
D–H/Å
H···A/Å
D···A/Å
D –H···A/
N3–H3A···O1
C6–H6···O1
C2–H2···N2
C26–H26···N4
C17–H17···O1 a
C23–H23···N2 b
0.88
0.95
0.95
0.95
0.95
0.95
1.93
2.34
2.43
2.54
2.42
2.61
2.6901(13)
2.9626(15)
2.7706(16)
2.8728(16)
3.2954(16)
3.5437(16)
144.1
122
101
100
153
166
a
x, 2 – y, 2 + z, b –1 + x, 2 – y, 2 + z.
3
1
3
1

RESEARCH ARTICLE
A.S. Thakar, H.B. Friedrich, K.T. Joshi and G.E.M. Maguire,
S. Afr. J. Chem., 2015, 68, 39–44,
42
<http://journals.sabinet.co.za/sajchem/>.
Figure 1 ORTEP diagram of the ligand showing the atom numbering scheme (50 % probability factor for the thermal ellipsoids).
pseudo nine-membered (N1-N2-C7-C9-C11-N3-H3A···O1-C10)
hydrogen bonded pattern, thus locking the molecular confor-
mation and eliminating conformational flexibility. However,
intermolecular interaction involves C–H···O interactions [the
C17–H17···O1, C···O distance being 3.2954(16) Å, and the
C–H···O angle being 153 °, Fig. 2] which stabilize the packing.
Table 4 show the intramolecular and intermolecular hydrogen
bond geometry, respectively, for the ligand.
Table4 Summaryofselectedbondlengths(Å)andbondangles(°)ofligand.
Bond
Bond length
Bond
Bond angle
C1–N1
N3–H
N1–N2
C10–O1
C10–N1
C7–C8
C9–C11
C11–N3
C18–N3
S1–C18
1.4165(15)
0.883(19)
N2–C7–C9
N2–C7–C8
C9–C7–C8
C7–C8–H(8A)
C7–C9–C10
N3–C11–C9
C11–N3–C18
C11–N3–H(3A)
C19–S1–C18
111.46(10)
119.56(10)
128.94(11)
109.5
105.19(10)
117.68(11)
130.59(11)
113.7(12)
88.32(6)
1.4086(14)
1.2441(15)
1.3762(15)
1.4940(16)
1.3799(16)
1.3499(15)
1.3919(15)
1.7316(13)
4. Conclusion
There are three possible tautomers for this broad family of
compounds. The Schiff bases produced by the reaction between
4-benzoyl-5-methyl-2-phenyl-2,4-dihydro-pyrazol-3-one (2)
and 4-phenyl-thiazol-2-ylamine (3) are shown to exist in the
Figure 2 Intramolecular and intermolecular hydrogen-bond for the ligand in the crystal lattice.

RESEARCH ARTICLE
A.S. Thakar, H.B. Friedrich, K.T. Joshi and G.E.M. Maguire,
S. Afr. J. Chem., 2015, 68, 39–44,
43
<http://journals.sabinet.co.za/sajchem/>.
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bonding between the amine hydrogen and the pyrazolone C10
carbonyl oxygen helps to stabilize the structures of these com-
pounds in the keto-amine form.
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Supplementary material
1
Copies of H NMR, 13C NMR, HSQC, HMBC, COSY and IR
spectra are given in the online supplement. CCDC 953343 con-
tains the supplementary crystallographic data for this paper.
These data can be obtained free of charge at www.ccdc.cam.ac.
uk/conts/retrievel.html or from the Cambridge Crystallographic
Data Center, 12 Union Road, Cambridge CB2 1EZ, UK; fax +44
1223/336 033; e-mail: deposit@ccdc.ac.uk.
5
Acknowledgements
The authors wish to thank Mr. Kamlesh Modi, Prima Chemicals,
for providing pyrazolone. The authors are also thankful to Dr.
Bernard Owaga from the University of KwaZulu-Natal for
assistance with the data collection and refinement, and
c*change for financial support.
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1691–1692.

Supporting Information
Isolation, characterization and X-ray structure determination of Schiff base ligand: 5-
Methyl-2-phenyl-4-[phenyl-(4-phenyl-thiazol-2-ylamino)-methylene]-2,4-dihydro-pyrazol-
3-one
Amit S. Thakar1, Holger B. Friedrich1, Krishnalal T. Joshi2 and Glenn E.M. Maguire1*
1School of Chemistry and Physics, University of KwaZulu-Natal, Durban, 4000, South Africa,
2Department of Chemistry, Navjivan Science College, Dahod, Gujarat, 389 151, India
* E-mail: maguireg@ukzn.ac.za; Tel.: +27 31 260 1113; Fax: +27 31 260 3091
Table of content
1. Experimental
S3
S3
S3
S3
S4
S5
S5
S6
S6
S7
S7
S8
S8
S8
1.1 Materials
1.2 Physical measurements
1.3 Synthesis of Schiff base ligand
2. Scheme S1. Synthetic pathway of Schiff base ligand
3. Figure S1. 1H NMR spectra of Schiff base ligand
4. Figure S2. 13C NMR spectra of Schiff base ligand
5. Figure S3. HSQC spectra of Schiff base ligand
6. Figure S4. HMBC spectra of Schiff base ligand
7. Figure S5. COSY spectra of Schiff base ligand
8. Figure S6. IR spectra of Schiff base ligand
9. X-ray crystallography data of Schiff base ligand
Figure S7. ORTEP diagram showing atom numbering scheme
Table S1. Crystal data and structure refinement
Table S2. Atomic coordinates and equivalent isotropic displacement parameters S9
Table S3. Bond lengths [Å] and angles [°]
S10
S1

Table S4. Anisotropic displacement parameters
Table S5. Hydrogen coordinates and isotropic displacement parameters
Table S6. Torsion angles [°]
S15
S16
S17
S19
Table S7. Hydrogen bonds [Å and °]
1. Experimental
1.1 Materials
The compound 5-methyl-2-phenyl-2,4-dihydro-pyrazol-3-one 1 was obtained from Prima
chemicals, Ahmedabad, India. Methanol, dioxane, was obtained from SD’s fine chemical Ltd.,
India. Absolute alcohol was obtained from Baroda Chem. Industry Ltd. and was used after
distillation. Calcium hydroxide and benzoyl chloride were obtained from Samir Tech. Chem.
Pvt. Ltd. All the chemicals used were of AR grade. Solvents used in this study were purified
following the standard procedures.
1.2 Physical measurements
The elemental analysis was obtained from Flash Elemental Analyzer-1112. Infrared spectra (IR)
were measured using a Perkin Elmer Precisely Spectrometer100 FT-IR spectrometer. 1H and
13C NMR spectra were measured at 400.22 and 100.63 MHz, respectively, with a Bruker
Avance III 400 MHz spectrophotometer by using TMS (tetramethylsilane) as the internal
reference. Melting point is recorded on an Ernst Leitz Wetzlar hot stage melting point apparatus.
Reactions were monitored by thin layer chromatography (TLC) on aluminum-backed plates
coated with Merck Kieselgel 60 F254 silica gel. TLC plates were visualized by UV radiation at a
wavelength of 254 nm.
1.3 Synthesis of Schiff base ligand
5-Methyl-2-phenyl-2,4-dihydro-pyrazol-3-one 1 (2 g, 11.5 mmol) was dissolved in hot dioxane
(20 mL) in a flask equipped with a stirrer, separating funnel and reflux condenser. Calcium
hydroxide (1.7 g, 23 mmol) was added to this solution, followed by benzoyl chloride (3.23 g,
11.5 mmol) added drop wise with precaution, as this reaction was exothermic. During this
addition the whole mass was converted into a thick paste. After the complete addition, the
reaction mixture was refluxed for half an hour and then it was poured into dilute hydrochloric
acid (50 mL, 2 M). The colored crystals of 4-benzoyl-5-methyl-2-phenyl-2,4-dihydro-pyrazol-3-
S2

one 2 thus obtained were separated by filtration and recrystallized from n-hexane to give a bright
yellow crystalline solid (2.5 g, 80%).
A solution of 4-benzoyl-5-methyl-2-phenyl-2,4-dihydro-pyrazol-3-one 2 (1 g, 3.6 mmol) in
methanol (30 mL) was added to a another solution of 4-phenyl-thiazol-2-ylamine 3 (0.63 g, 3.6
mmol) in methanol (20 mL) under an inert atmosphere. The reaction mixture was refluxed for
three hours. Completion of the reaction was monitored by TLC using hexane/ethyl acetate (8:2).
The reaction was allowed to cool to room temperature and stirred overnight. A yellow precipitate
formed which was then filtered and washed with methanol (10 mL). The crude product, purified
by crystallization from ethanol to give brown crystals of the desired product 5-Methyl-2-phenyl-
4-[phenyl-(4-phenyl-thiazol-2-ylamino)-methylene]-2,4-dihydro-pyrazol-3-one 4 (1.2 g, 77%
yield).
3
N
O
Cl
H3C
H3C
N
H3C
N
S
O
H
N
H2N
N
O
S
O
N
N
O
N
N
methanol,
reflux
1,4-dioxane,
Ca(OH)2,
reflux
1
4
2
Scheme S1. Synthetic pathway of the Schiff base ligand
S3

Fig. 1 1H NMR spectra of Schiff base ligand
Fig. S2 13C NMR spectra of Schiff base ligand
S4

Fig. S3 1H-13C HSQC spectra of Schiff base ligand
Fig. S4 1H-13C HMBC spectra of Schiff base ligand
S5

Fig. S5 COSY spectra of Schiff base ligand
Fig. S6 IR spectra of Schiff base ligand
90.7
85
1740.42
1867.53
1938.92
459.22
389.26
80
75
70
65
60
55
50
45
40
35
30
25
3026.69
3059.81
2922.83
3135.58
599.49
474.83
421.28
901.33
1246.17
771.80
856.71
997.99
1067.18
551.53
1080.54
971.44
1151.24
506.30
1293.78
1418.36
1444.10
1028.18
1050.76
1120.95
1174.93
752.89
740.25
%T
1540.64
1012.82
839.12
821.21
1456.97
665.60
650.71
1196.35
1209.74
581.21
1516.27
1385.74
688.51
724.66
1591.541490.11
1616.09
18.9
1353.80
1400
4000.0
3600
3200
2800
2400
2000
1800
1600
1200
1000
800
600
380.0
cm-1
S6

9. X-ray crystallography data of Schiff base ligand
Fig. S7 ORTEP diagram showing atom numbering scheme.
Table S1 Crystal data and structure refinement
Identification code
Empirical formula
Formula weight
Temperature
13bo_hbf_at3_0ma
C26 H20 N4 O S
436.52
173(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Monoclinic
P21/c
Unit cell dimensions
b = 21.2378(4) Å
c = 7.22470(10) Å
a = 13.9867(3) Å
= 95.7990(10)°.
= 90°.
= 90°.
3
Volume
Z
2135.09(7) Å
4
3
Density (calculated)
1.358 Mg/m
S7

-1
Absorption coefficient
F(000)
0.179 mm
912
3
Crystal size
0.46 x 0.25 x 0.23 mm
1.75 to 28.41°.
Theta range for data collection
Index ranges
-17<=h<=18, -28<=k<=27, -9<=l<=9
58780
Reflections collected
Independent reflections
Completeness to theta = 28.41°
Absorption correction
Max. and min. transmission
5358 [R(int) = 0.0260]
99.9 %
Semi-empirical from equivalents
0.9600 and 0.9223
2
Refinement method
Full-matrix least-squares on F
Data / restraints / parameters
5358 / 0 / 294
2
Goodness-of-fit on F
1.035
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0373, wR2 = 0.0913
R1 = 0.0476, wR2 = 0.0978
-3
0.572 and -0.285 e.Å
Largest diff. peak and hole
4
2
Table S2 Atomic coordinates ( x 10 ) and equivalent isotropic displacement parameters (Å x
3
10 )
ij
U(eq) is defined as one third of the trace of the orthogonalized U tensor.
______________________________________________________________________________
x
y
z
U(eq)
______________________________________________________________________________
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
376(1)
-459(1)
-1022(1)
-769(1)
62(1)
6621(1)
6706(1)
6188(1)
5587(1)
5507(1)
6018(1)
8163(1)
8851(1)
7856(1)
7184(1)
2484(2)
3370(2)
3708(2)
3187(2)
2312(2)
1950(2)
2131(2)
2265(2)
1590(2)
1623(2)
15(1)
18(1)
22(1)
24(1)
23(1)
19(1)
15(1)
19(1)
15(1)
15(1)
637(1)
1232(1)
1029(1)
2077(1)
1861(1)
S8

C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
N(1)
2955(1)
3212(1)
3678(1)
3920(1)
3704(1)
3240(1)
2993(1)
4552(1)
6097(1)
5977(1)
6703(1)
7573(1)
8260(1)
8087(1)
7226(1)
6538(1)
947(1)
8089(1)
8770(1)
8985(1)
9616(1)
10030(1)
9817(1)
9185(1)
7766(1)
8094(1)
7461(1)
6979(1)
7149(1)
6699(1)
6071(1)
5894(1)
6345(1)
7154(1)
7757(1)
7672(1)
7275(1)
6734(1)
8489(1)
1200(2)
1367(2)
3045(2)
3238(2)
1773(2)
107(2)
15(1)
17(1)
21(1)
27(1)
31(1)
31(1)
24(1)
17(1)
22(1)
17(1)
18(1)
23(1)
26(1)
28(1)
29(1)
23(1)
15(1)
16(1)
18(1)
17(1)
19(1)
23(1)
-107(2)
276(2)
-555(2)
-442(2)
-743(2)
-1409(2)
-1700(2)
-1342(2)
-686(2)
-390(2)
2167(1)
2469(1)
745(2)
N(2)
N(3)
N(4)
O(1)
573(1)
3621(1)
5083(1)
2388(1)
5081(1)
28(2)
1290(1)
-58(1)
S(1)
______________________________________________________________________________
Table S3 Bond lengths [Å] and angles [°]
_____________________________________________________
C(1)-C(6)
C(1)-C(2)
C(1)-N(1)
C(2)-C(3)
C(2)-H(2)
C(3)-C(4)
C(3)-H(3)
C(4)-C(5)
C(4)-H(4)
C(5)-C(6)
C(5)-H(5)
C(6)-H(6)
C(7)-N(2)
C(7)-C(9)
C(7)-C(8)
C(8)-H(8A)
C(8)-H(8B)
1.3957(17)
1.3982(17)
1.4165(15)
1.3892(17)
0.9500
1.3865(19)
0.9500
1.3879(19)
0.9500
1.3918(18)
0.9500
0.9500
1.3038(16)
1.4390(16)
1.4940(16)
0.9800
0.9800
S9

C(8)-H(8C)
C(9)-C(11)
C(9)-C(10)
C(10)-O(1)
C(10)-N(1)
C(11)-N(3)
C(11)-C(12)
C(12)-C(17)
C(12)-C(13)
C(13)-C(14)
C(13)-H(13)
C(14)-C(15)
C(14)-H(14)
C(15)-C(16)
C(15)-H(15)
C(16)-C(17)
C(16)-H(16)
C(17)-H(17)
C(18)-N(4)
C(18)-N(3)
C(18)-S(1)
0.9800
1.3799(16)
1.4596(16)
1.2441(15)
1.3762(15)
1.3499(15)
1.4928(17)
1.3917(18)
1.3933(18)
1.3875(18)
0.9500
1.385(2)
0.9500
1.384(2)
0.9500
1.391(2)
0.9500
0.9500
1.3047(16)
1.3919(15)
1.7316(13)
1.3593(18)
1.7191(13)
0.9500
1.3864(15)
1.4726(17)
1.3930(18)
1.3998(17)
1.3858(19)
0.9500
1.384(2)
0.9500
1.3897(19)
0.9500
1.3888(19)
0.9500
C(19)-C(20)
C(19)-S(1)
C(19)-H(19)
C(20)-N(4)
C(20)-C(21)
C(21)-C(26)
C(21)-C(22)
C(22)-C(23)
C(22)-H(22)
C(23)-C(24)
C(23)-H(23)
C(24)-C(25)
C(24)-H(24)
C(25)-C(26)
C(25)-H(25)
C(26)-H(26)
N(1)-N(2)
0.9500
1.4086(14)
0.883(19)
N(3)-H(3A)
C(6)-C(1)-C(2)
C(6)-C(1)-N(1)
C(2)-C(1)-N(1)
C(3)-C(2)-C(1)
C(3)-C(2)-H(2)
C(1)-C(2)-H(2)
119.87(11)
121.35(11)
118.78(11)
119.56(12)
120.2
120.2
S10

C(4)-C(3)-C(2)
C(4)-C(3)-H(3)
121.02(12)
119.5
C(2)-C(3)-H(3)
119.5
C(3)-C(4)-C(5)
C(3)-C(4)-H(4)
119.07(12)
120.5
C(5)-C(4)-H(4)
120.5
C(4)-C(5)-C(6)
C(4)-C(5)-H(5)
121.01(12)
119.5
C(6)-C(5)-H(5)
119.5
C(5)-C(6)-C(1)
C(5)-C(6)-H(6)
119.48(12)
120.3
C(1)-C(6)-H(6)
120.3
N(2)-C(7)-C(9)
N(2)-C(7)-C(8)
C(9)-C(7)-C(8)
111.46(10)
119.56(10)
128.94(11)
109.5
C(7)-C(8)-H(8A)
C(7)-C(8)-H(8B)
H(8A)-C(8)-H(8B)
C(7)-C(8)-H(8C)
H(8A)-C(8)-H(8C)
H(8B)-C(8)-H(8C)
C(11)-C(9)-C(7)
C(11)-C(9)-C(10)
C(7)-C(9)-C(10)
O(1)-C(10)-N(1)
O(1)-C(10)-C(9)
N(1)-C(10)-C(9)
N(3)-C(11)-C(9)
N(3)-C(11)-C(12)
C(9)-C(11)-C(12)
C(17)-C(12)-C(13)
C(17)-C(12)-C(11)
C(13)-C(12)-C(11)
C(14)-C(13)-C(12)
C(14)-C(13)-H(13)
C(12)-C(13)-H(13)
C(15)-C(14)-C(13)
C(15)-C(14)-H(14)
C(13)-C(14)-H(14)
C(16)-C(15)-C(14)
C(16)-C(15)-H(15)
C(14)-C(15)-H(15)
C(15)-C(16)-C(17)
C(15)-C(16)-H(16)
C(17)-C(16)-H(16)
C(16)-C(17)-C(12)
109.5
109.5
109.5
109.5
109.5
131.68(11)
123.04(11)
105.19(10)
127.27(11)
128.22(11)
104.48(10)
117.68(11)
119.26(10)
122.96(11)
120.46(12)
121.20(11)
118.34(11)
119.39(12)
120.3
120.3
120.33(13)
119.8
119.8
120.21(13)
119.9
119.9
120.12(13)
119.9
119.9
119.48(13)
S11

C(16)-C(17)-H(17)
C(12)-C(17)-H(17)
N(4)-C(18)-N(3)
N(4)-C(18)-S(1)
120.3
120.3
118.55(11)
115.67(9)
125.77(9)
111.16(9)
124.4
N(3)-C(18)-S(1)
C(20)-C(19)-S(1)
C(20)-C(19)-H(19)
S(1)-C(19)-H(19)
C(19)-C(20)-N(4)
C(19)-C(20)-C(21)
N(4)-C(20)-C(21)
C(26)-C(21)-C(22)
C(26)-C(21)-C(20)
C(22)-C(21)-C(20)
C(23)-C(22)-C(21)
C(23)-C(22)-H(22)
C(21)-C(22)-H(22)
C(24)-C(23)-C(22)
C(24)-C(23)-H(23)
C(22)-C(23)-H(23)
C(23)-C(24)-C(25)
C(23)-C(24)-H(24)
C(25)-C(24)-H(24)
C(26)-C(25)-C(24)
C(26)-C(25)-H(25)
C(24)-C(25)-H(25)
C(25)-C(26)-C(21)
C(25)-C(26)-H(26)
C(21)-C(26)-H(26)
C(10)-N(1)-N(2)
C(10)-N(1)-C(1)
N(2)-N(1)-C(1)
124.4
114.61(11)
126.01(11)
119.37(11)
118.50(12)
120.98(11)
120.52(12)
120.96(13)
119.5
119.5
119.93(12)
120.0
120.0
119.82(13)
120.1
120.1
120.24(13)
119.9
119.9
120.54(12)
119.7
119.7
111.85(9)
129.65(10)
118.48(9)
107.02(9)
130.59(11)
113.7(12)
115.7(12)
110.24(11)
88.32(6)
C(7)-N(2)-N(1)
C(11)-N(3)-C(18)
C(11)-N(3)-H(3A)
C(18)-N(3)-H(3A)
C(18)-N(4)-C(20)
C(19)-S(1)-C(18)
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
S12

2
3
Table S4 Anisotropic displacement parameters (Å x 10 )
The anisotropic displacement factor exponent takes the form: -2 [ h a* U + ... + 2 h k a* b*
12
2 2 2 11
U
]
______________________________________________________________________________
11 22 33 23 13 12
U
U
U
U
U
U
______________________________________________________________________________
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
14(1)
17(1)
17(1)
22(1)
24(1)
18(1)
17(1)
18(1)
15(1)
14(1)
15(1)
14(1)
21(1)
27(1)
37(1)
41(1)
27(1)
14(1)
15(1)
13(1)
14(1)
17(1)
16(1)
20(1)
27(1)
19(1)
14(1)
16(1)
14(1)
14(1)
17(1)
17(1)
16(1)
17(1)
23(1)
19(1)
16(1)
18(1)
16(1)
15(1)
15(1)
18(1)
16(1)
15(1)
20(1)
24(1)
16(1)
20(1)
21(1)
19(1)
24(1)
22(1)
23(1)
24(1)
32(1)
30(1)
23(1)
25(1)
13(1)
14(1)
16(1)
19(1)
16(1)
17(1)
15(1)
21(1)
28(1)
31(1)
29(1)
21(1)
14(1)
24(1)
15(1)
13(1)
14(1)
22(1)
22(1)
31(1)
42(1)
33(1)
23(1)
17(1)
28(1)
16(1)
16(1)
28(1)
33(1)
34(1)
37(1)
27(1)
18(1)
18(1)
24(1)
19(1)
24(1)
36(1)
2(1)
1(1)
2(1)
2(1)
-2(1)
-1(1)
0(1)
-1(1)
0(1)
1(1)
0(1)
-2(1)
-1(1)
-8(1)
-3(1)
6(1)
1(1)
0(1)
2(1)
0(1)
-1(1)
-3(1)
-6(1)
-4(1)
3(1)
2(1)
0(1)
0(1)
-1(1)
-1(1)
-1(1)
3(1)
1(1)
4(1)
7(1)
5(1)
4(1)
4(1)
2(1)
5(1)
2(1)
2(1)
1(1)
5(1)
2(1)
2(1)
9(1)
5(1)
1(1)
3(1)
7(1)
2(1)
1(1)
6(1)
8(1)
7(1)
11(1)
9(1)
4(1)
3(1)
5(1)
3(1)
6(1)
9(1)
-2(1)
1(1)
-2(1)
-6(1)
-1(1)
0(1)
1(1)
1(1)
1(1)
-1(1)
0(1)
-1(1)
-3(1)
-5(1)
-5(1)
2(1)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
N(1)
1(1)
-2(1)
-2(1)
-1(1)
1(1)
-2(1)
-1(1)
6(1)
3(1)
0(1)
1(1)
2(1)
N(2)
N(3)
N(4)
O(1)
-2(1)
-1(1)
2(1)
S(1)
-1(1)
______________________________________________________________________________
S13

4
2
3
Table S5 Hydrogen coordinates ( x 10 ) and isotropic displacement parameters (Å x 10 )
______________________________________________________________________________
x
y
z
U(eq)
______________________________________________________________________________
H(2)
H(3)
H(4)
H(5)
-639
-1591
-1158
241
1202
996
7115
6246
5236
5096
5958
9041
9053
8912
8701
9766
10462
10103
9037
8293
7578
6821
5761
5464
6221
7276(9)
3739
4306
3425
1954
1345
1023
3078
2783
4048
4380
1912
-891
-1250
-868
-1664
-2144
-1544
-439
57
22
27
29
28
23
28
28
28
25
33
38
38
28
26
28
32
33
34
28
35(5)
H(6)
H(8A)
H(8B)
H(8C)
H(13)
H(14)
H(15)
H(16)
H(17)
H(19)
H(22)
H(23)
H(24)
H(25)
H(26)
H(3A)
1543
414
3829
4235
3875
3090
2676
6668
7694
8849
8555
7106
5951
3433(13)
780(20)
______________________________________________________________________________
Table S6 Torsion angles [°]
________________________________________________________________
C(6)-C(1)-C(2)-C(3)
N(1)-C(1)-C(2)-C(3)
C(1)-C(2)-C(3)-C(4)
C(2)-C(3)-C(4)-C(5)
C(3)-C(4)-C(5)-C(6)
C(4)-C(5)-C(6)-C(1)
C(2)-C(1)-C(6)-C(5)
N(1)-C(1)-C(6)-C(5)
N(2)-C(7)-C(9)-C(11)
C(8)-C(7)-C(9)-C(11)
N(2)-C(7)-C(9)-C(10)
C(8)-C(7)-C(9)-C(10)
C(11)-C(9)-C(10)-O(1)
-0.13(18)
-179.42(11)
0.3(2)
-0.1(2)
-0.2(2)
0.3(2)
-0.15(18)
179.11(11)
-176.26(12)
6.2(2)
0.22(14)
-177.33(12)
-1.6(2)
S14

C(7)-C(9)-C(10)-O(1)
C(11)-C(9)-C(10)-N(1)
C(7)-C(9)-C(10)-N(1)
C(7)-C(9)-C(11)-N(3)
C(10)-C(9)-C(11)-N(3)
C(7)-C(9)-C(11)-C(12)
C(10)-C(9)-C(11)-C(12)
N(3)-C(11)-C(12)-C(17)
C(9)-C(11)-C(12)-C(17)
N(3)-C(11)-C(12)-C(13)
C(9)-C(11)-C(12)-C(13)
C(17)-C(12)-C(13)-C(14)
C(11)-C(12)-C(13)-C(14)
C(12)-C(13)-C(14)-C(15)
C(13)-C(14)-C(15)-C(16)
C(14)-C(15)-C(16)-C(17)
C(15)-C(16)-C(17)-C(12)
C(13)-C(12)-C(17)-C(16)
C(11)-C(12)-C(17)-C(16)
S(1)-C(19)-C(20)-N(4)
S(1)-C(19)-C(20)-C(21)
C(19)-C(20)-C(21)-C(26)
N(4)-C(20)-C(21)-C(26)
C(19)-C(20)-C(21)-C(22)
N(4)-C(20)-C(21)-C(22)
C(26)-C(21)-C(22)-C(23)
C(20)-C(21)-C(22)-C(23)
C(21)-C(22)-C(23)-C(24)
C(22)-C(23)-C(24)-C(25)
C(23)-C(24)-C(25)-C(26)
C(24)-C(25)-C(26)-C(21)
C(22)-C(21)-C(26)-C(25)
C(20)-C(21)-C(26)-C(25)
O(1)-C(10)-N(1)-N(2)
C(9)-C(10)-N(1)-N(2)
O(1)-C(10)-N(1)-C(1)
C(9)-C(10)-N(1)-C(1)
C(6)-C(1)-N(1)-C(10)
C(2)-C(1)-N(1)-C(10)
C(6)-C(1)-N(1)-N(2)
-178.44(12)
176.60(11)
-0.26(12)
179.17(12)
3.22(18)
2.8(2)
-173.12(11)
96.12(15)
-87.59(16)
-84.03(15)
92.26(15)
0.17(19)
-179.69(12)
-0.3(2)
0.3(2)
-0.3(2)
0.2(2)
-0.2(2)
179.69(12)
0.33(15)
-178.77(10)
172.83(13)
-6.23(18)
-7.7(2)
173.23(11)
-0.4(2)
-179.90(12)
0.4(2)
-0.2(2)
0.0(2)
-0.1(2)
0.3(2)
179.73(13)
178.44(11)
0.24(13)
0.0(2)
-178.21(11)
-11.39(19)
167.88(12)
170.25(11)
-10.48(16)
-0.07(13)
177.73(10)
-0.11(13)
178.53(10)
179.47(12)
C(2)-C(1)-N(1)-N(2)
C(9)-C(7)-N(2)-N(1)
C(8)-C(7)-N(2)-N(1)
C(10)-N(1)-N(2)-C(7)
C(1)-N(1)-N(2)-C(7)
C(9)-C(11)-N(3)-C(18)
S15

C(12)-C(11)-N(3)-C(18)
N(4)-C(18)-N(3)-C(11)
S(1)-C(18)-N(3)-C(11)
N(3)-C(18)-N(4)-C(20)
S(1)-C(18)-N(4)-C(20)
C(19)-C(20)-N(4)-C(18)
C(21)-C(20)-N(4)-C(18)
C(20)-C(19)-S(1)-C(18)
N(4)-C(18)-S(1)-C(19)
N(3)-C(18)-S(1)-C(19)
-4.0(2)
174.79(12)
-6.4(2)
179.52(11)
0.57(14)
-0.57(15)
178.59(11)
-0.01(10)
-0.33(10)
-179.20(12)
________________________________________________________________
Symmetry transformations used to generate equivalent atoms:
Table S7 Hydrogen bonds [Å and °].
______________________________________________________________________________
D-H...A
d(D-H)
d(H...A)
d(D...A)
<(DHA)
Symmetry
operator
N(3)-H(3A)…O(1)
C(2)-H(2)…N(2)
C(6)-H(6)…O(1)
C(17)-H(17)…O(1)
C(23)-H(23)…N(2)
C(26)-H(26)…N(4)
0.883(19)
0.95
0.95
0.95
0.95
1.925(18)
2.43
2.34
2.42
2.61
2.6901(13) 144.1(17)
x, y, z
x, y, z
x, y, z
2.7706(16)
2.9626(15)
3.2954(16)
3.5437(16)
2.8728(16)
101
122
153
166
100
x, ½-y, ½+z
-1+x, ½-y, ½+z
x, y, z
0.95
2.55
______________________________________________________________________________
S16

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