Synthesis, characterization, antimicrobial activities, and structural studies of Lanthanide (III) complexes with 1-(4-Chlorophenyl)-3-(4-fluoro/ hydroxyphenyl)prop-2-en-1-thiosemicarbazone

Article abstract of DOI:10.1080/10426500902797483

Twelve coordinate lanthanide (III) complexes with the general composition [Ln L₃X_n(H₂O)_n] where Ln = Pr(III), Sm(III), Eu (III), Gd (III), Tb (III), Dy (III), X = Cl^-1, NO3 ^-2, n = 2-7, and

Full text of DOI:10.1080/10426500902797483

This article was downloaded by: [National Sun Yat-Sen University]
On: 08 January 2015, At: 21:41
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the
Related Elements
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gpss20
Synthesis, Characterization,
Antimicrobial Activities, and Structural
Studies of Lanthanide (III) Complexes
with 1-(4-Chlorophenyl)-3-(4-
fluoro/hydroxyphenyl)prop-2-en-1-
thiosemicarbazone
a
a
a
Chandra K. Oza , Meenakshi Jain , Neelima Jain & Dinesh Verma
a
a
Centre of Advanced Studies, Department of Chemistry , University
of Rajasthan , Jaipur, India
Published online: 03 Feb 2010.
To cite this article: Chandra K. Oza , Meenakshi Jain , Neelima Jain & Dinesh Verma (2010) Synthesis,
Characterization, Antimicrobial Activities, and Structural Studies of Lanthanide (III) Complexes with
1-(4-Chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone, Phosphorus, Sulfur,
and Silicon and the Related Elements, 185:2, 377-386
To link to this article: http://dx.doi.org/10.1080/10426500902797483
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“
Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Phosphorus, Sulfur, and Silicon, 185:377–386, 2010
Copyright ꢀ
Taylor & Francis Group, LLC
C
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500902797483
SYNTHESIS, CHARACTERIZATION, ANTIMICROBIAL
ACTIVITIES, AND STRUCTURAL STUDIES
OF LANTHANIDE (III) COMPLEXES
WITH 1-(4-CHLOROPHENYL)-3-(4-FLUORO/
HYDROXYPHENYL)PROP-2-EN-1-THIOSEMICARBAZONE
Chandra K. Oza, Meenakshi Jain, Neelima Jain,
and Dinesh Verma
Centre of Advanced Studies, Department of Chemistry, University of Rajasthan,
Jaipur, India
Twelve coordinate lanthanide (III) complexes with the general composition [Ln
−
1
L3Xn(H2O)n] where Ln = Pr(III), Sm(III), Eu (III), Gd (III), Tb (III), Dy (III), X = Cl
,
−2
NO3 , n = 2–7, and L is 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-
thiosemicarbazone have been prepared. The lanthanide complexes (5) were derived
from the reaction between 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-
1-thiosemicarbazone (4) with an aqueous solution of lanthanide salt. Chalcone
thiosemicarbazone ligand (4) was prepared by the reaction of [1-(4-chlorophenyl)-3-(4-
fluoro/hydroxyphenyl)]prop-2-enone (chalcone) (3) with thiosemicarbazide in the presence
of hot ethanol. All the lanthanide-ligand 1:3 complexes have been isolated in the solid state,
are stable in air, and characterized on the basis of their elemental and spectral data.
Thiosemicarbazone ligands behave as bidentate ligands by coordinating through the
sulfur of the isocyanide group and nitrogen of the cyanide residue. The probable structure
for all the lanthanide complexes is also proposed. The chalcone thiosemicarbazone ligands
and their lanthanide complexes have been screened for their antifungal and antibacterial
studies. Some of the synthesized lanthanide complexes have shown enhanced activity
compared with that of the free ligand.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental
file.
Keywords Antimicrobial activities; 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-
en-1-thiosemicarbazone; lanthanide complexes; spectral studies
Received 4 June 2008; accepted 2 February 2009.
We would like to thank the late Prof. Vijai N. Pathak, Department of Chemistry, Centre of Advance Studies,
University of Rajasthan, Jaipur, India, who was instrumental in our research work, and we extend our deepest
warm regards to him. We express our sincere gratitude to Dr. K. P. Madhusudnan, Deputy Director and Head, SAIF,
Central Drug Research Institute (CDRI), Lucknow, India, for elemental analyses and spectral (IR, NMR, and FAB
mass) data, and also thanks to Prof. V. M. Rao, Department of Botany, University of Rajasthan, Jaipur, India, for
biological activity. The authors are thankful to the Coordinator of Centre of Advanced Studies, Department of
Chemistry, University of Rajasthan, for providing chemicals and other facilities.
Address correspondence to Chandra K. Oza, Centre of Advanced Studies, Department of Chemistry, Uni-
versity of Rajasthan, Jaipur 302 004, India. E-mail: drneelimajain@yahoo.com
3
77

3
78
C. K. OZA ET AL.
INTRODUCTION
The chemistry of chalcone thiosemicarbazones, hydrazones, and their allied deriva-
tives has aroused great interest due to their diverse pharmaceutical activities, i.e., their use
1
2–5
4
2,6–8
8,9
as anticholinesterase, antibacterial, antifungal, antimalarial,
antileukemic, anti-
and antiproliferative agents. Some of them have shown
and were found to possess increased activity when they were ad-
10
11–13
14
tuberculosis, antimicrobial,
biological activities1
5,16
1
7–19
ministered as corresponding metal complexes.
A significant correlation between the
chelating properties and antitumor activity of some heterocyclic aldehydic thiosemicar-
2
0–22
bazones in animal systems were also reported.
1
Extensive studies on some substituted
-benzoyl-4-phenylthiosemicarbazide metal ion complexes were also reported.23 Encour-
aged by these observations, we report in this article the synthesis and antimicrobial activities
of 12 new lanthanide complexes of 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-
en-1-thiosemicarbazone.
RESULTS AND DISCUSSION
Synthesis
[
1-(4-Chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-enone] (chalcones) (3) were
23
prepared by the method of Joshi and Jauhar. 1-(4-Chlorophenyl)-3-(4-fluoro/hydroxy
phenyl)prop-2-enones were then treated with thiosemicarbazide in hot ethanolic solution
by Campaigne and Archer’s method.24 A solution of 1-(4-chlorophenyl)-3-(4-fluoro/
hydroxyphenyl)prop-2-en-1-thiosemicarbazone was treated with an aqueous solution of
lanthanide salt Ln = Pr(III), Sm(III), Eu(III), Gd(III), Tb(III), and Dy(III) in a 3:1 molar ratio
with stirring to afford tris[1-(4-fluoro/hydroxyphenyl)-3-(4-chlorophenyl)prop-2-en-1-
thiosemicarbazone]praseodymium/samarium/europium/gadolinium/terbium/dysprosium
(
III) (5a–l) (Scheme 1). The structure of the synthesized lanthanide complexes was
1
established on the basis of their IR, H NMR, and FAB mass spectral studies. Physical and
analytical data of chalcone thiosemicarbazone ligands and their lanthanide complexes 4
and 5 are given in Tables I and II, respectively. The spectral data of synthesized chalcone
thiosemicarbazone ligands (4) and their lanthanide complexes (5a–l) are given in Table III.
Major mass fragments along with their relative intensities and m/z values of lanthanide
complexes are given in Table IV S (available online in the Supplemental Materials).
IR Spectra
The IR spectra of 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-enone
−1
(
chalcones) (3) showed absorption bands at 1680 cm , which is attributed to >C O
stretching vibration. In the IR spectra of 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)
−
1
prop-2-en-1-thiosemicarbazone (4), a >C O absorption band at 1680 cm disappeared
−1
−1
and new absorption bands appeared in the region 3304–3420 cm , 3150–3300 cm ,
−1
and 1175–1180 cm
due to NH2 absorption, >N H absorption, and >C S
stretching vibration, respectively. The IR spectra of lanthanide complexes of tris[1-(4-
chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone] (5) exhibited
−1
–
NH2 absorption in the region 3392–3440 cm , which remains unaltered, indicating
non-involvement of nitrogen of NH2 group on coordination with lanthanide ions in
complexation reactions, but slight displacement of these frequencies is due to increased

LANTHANIDE (III) COMPLEXES
379
O
C
H
H
NaOH Cl
C
C
H3C
Cl
C
O
-
H2O
H
C
Y
Y
O
1
2
3
H2NNHCSNH2
-H2O
H
Cl
C
C
S
C
H
N
C
N
H
NH2
4
Cl
Cl
H
H
C
C
NH2
C
C
2H2O
C
C
H
N
C
S
H
N
S
N
Ln
N
Y
Y
S
C
NH2
N
C
X
Y
C
H2N
Cl
N
C
C
H
H
5
X
Y
Ln
Pr
X
Y
Ln
Pr
5
a
b
c
d
e
NO
3
3
F
F
F
F
F
F
5g
5h
5i
NO
3
3
OH
OH
OH
OH
OH
OH
5
5
5
5
Cl
Sm
Eu
Gd
Tb
Dy
Cl
Sm
Eu
Gd
Tb
Dy
NO
Cl
NO
Cl
5j
NO
3
3
5k
5l
NO
3
3
5f
NO
NO
Scheme 1
positive charge on the nitrogen atom arising because of donation of an electron pair from
sulfur of thioamide moiety, which is involved in chelation. A sharp >N H absorption
−1
in the range of 3150–3300 cm disappeared, indicating possible deprotonation on the
β-nitrogen after complexation with the lanthanide ion. This band undergoes a negative shift
−1
by ∼35 cm in the lanthanide complexes, and this shift is the consequence of drainage
of an electron of the terminal N atom of ( N N ) moiety, indicating the coordination
of at least one of the
N
groups to the central lanthanide ion. A very strong >C N

3
80
C. K. OZA ET AL.
Table I Physical data of 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone(4)
◦
Compd. No.
Y
Color
Mp C
Yield
Molecular formula
4
4
a
b
F
OH
Yellow
Yellow
>156
>180
92
74
C16H13N3ClFS
C16H14N3ClS
−
1
absorption was observed in the range of 1594–1642 cm of the free azomethine group
−1
in the ligand shifts to the lower frequency side (∼5–8 cm ) in the spectra of complex
indicating the coordination of the azomethine nitrogen to the lanthanide atom. The strong
−1
(
N N) absorption in the range of 835–843 cm in the ligand experiences a positive shift
−1
by ∼10–15 cm upon complexation, which confirms the involvement of one N atom
N N ) group in the bonding.
The IR spectra of these complexes do not display the S H mode at about 2600 cm ,
(
−1
indicating that in the solid state, these ligands remain in thio-keto form (Scheme 2).
Scheme 2
However, upon lanthanide complex formation, all these bands disappear, showing the
bonding of sulfur to the lanthanide atom by the loss of thiolic protons of ligands. A new
−1
absorption band in the lanthanide complexes at 477–499 cm assigned to Ln N confirms
the lanthanide nitrogen bond in the complexes. The appearance of a new Ln S absorption
−
1
band occurs in the range of 320–340 cm .
−1
The appearance of a broad band at 3285–3520 cm in the spectra of all lanthanide
complexes is associated with coordinated and/or lattice water molecules supported from
mass spectral data. These lanthanide complexes also show new bands at 1385–1399 cm
−1
−1
and 356–362 cm , which may be assigned to NO3 and Ln Cl absorptions, proving the
−
−
25
presence of NO3 and Cl as a free ion.
1H NMR Spectra
1
The H NMR spectra of 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-
1-thiosemicarbazone (4a) showed an additional broad signal at δ 3.07 ppm (2H), a sharp
singlet at δ 10.31 ppm (1H), and a multiplet at δ 6.82–7.12 ppm (12H) assigned to the NH2
proton, NH proton, and aromatic protons, respectively. The two olefinic protons constitute
an AB pattern and appeared as a pair of doublets. The doublet appeared at δ 5.42–6.03 ppm

3
81

3
82

3
83

3
84
C. K. OZA ET AL.
with coupling constant (J = 9.0 Hz) due to the α proton ( CH CH—C N), and a doublet
appeared at δ 7.84–7.92 ppm with coupling constant (J = 9.0 Hz) due to the β proton
(
CH CH C N). This strong downfield shift of these protons is due to an extended
conjugation with aromatic protons. The high value of the coupling constant suggests trans
1
geometry across the double bond. H NMR spectra of compounds 5a–l revealed the singlet
at δ 3.07–3.13 ppm (6H), a sharp double doublet at δ 6.80–7.84 (6H) ppm with coupling
constant 6.0–6.4 Hz (CH CH C N), and the doublet in the region δ 6.16–7.25 (6H) ppm
with coupling constant 6.0–6.3 Hz due to (CH = CH—C N) proton and a singlet at δ
8
.01–8.58 (3H) ppm due to NH2 protons, olefinic protons, and –OH protons, respectively.
1
H NMR spectra of lanthanide complex 5 exhibited multiplets due to aromatic protons in
the range of δ 7.01–7.97 (36H) ppm. The lattice and coordinated water molecules were
observed at δ 4.23–4.10 ppm and δ 4.39–4.48 ppm, respectively. All other NMR spectral
data are given in Table III.
The molar conductance of the complexs in nitrobenzene (10 m mol) indicates that
they are essentially non-electrolytes. The magnetic moments of the complexes at room
temperature (Table II) show little deviation from the Van Vleck values, indicating the
non-participation of the 4f electrons in bond formation in these complexes. The magnetic
−3
2
6,27
moments of these complexes are within the predicted range.
Electronic Spectra
The electronic spectra of the complexes in the visible region indicate a shift of
the bands. The magnitude of nephelauxetic effect is dependent on the change in elec-
tronic repulsion parameter. The nephelauxetic ratio (β), percentage covalency parameter
1/2
(
δ%), bonding parameter (b ), and the angular covalency (η) values, respectively, are
0.9797–0.9818, 0.9998–2.0823, 0.0092–0.0104, and 0.009207–0.010406.
The values are less than one, and the positive values of% and bonding between the
metal and ligands are covalent.2
8,29
Fast Atom Bombardment (FAB) Mass Spectra
+
All FAB mass spectra of synthesized lanthanide complexes exhibited M +1 peak
+
due to transfer of proton matrix. Lanthanide complexes 5a exhibited (M +1) peak at m/z
+
1
388/1390 of relative intensity of 13.23% and molecular ion peak (M ) at m/z 1387/1389
of relative intensity 14.89%. Lanthanide complex 5a exhibited a base peak at m/z 391
(
100.0%)/393 (100.0%) corresponding to the molecular formula.
+
Lanthanide complex 5i exhibited (M +1) peak at m/z at 1161 (15.0%)/1163 (5.0%)
+
and molecular ion peak (M ) at m/z 1160 (20.0%)/1162 (10.0%). FAB mass spectra of
+
lanthanide complexes 5 exhibited (M+1) peak and (M ) peak. Details are given in Table
IV S (available online in the Supplementary Materials).
EXPERIMENTAL
Melting points were determined in open glass capillaries and are uncorrected (Tempo
melting point apparatus). The purity of the synthesized lanthanide complexes was checked
by thin layer chromatography (TLC) on silica gel in various non-aqueous solvent systems.
IR spectra were recorded in KBr on a Perkin Elmer 557 spectrometer, PMR spectra were
recorded in CDCl3 on a Brucker spectrometer (200 MHz) using tetramethylsilane (TMS)

LANTHANIDE (III) COMPLEXES
385
as an internal reference, and FAB mass spectra were recorded on Jeol SX-102 (FAB)
spectrometer. Electronic spectra were recorded on a Elico CL-54, and magnetic moments of
the complexes were determined by the Gouy method at room temperature. The conductance
−3
measurements were carried out in nitrobenzene medium (−10 M) by a Systronics 303
conductivity meter.
Different 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-enone (chalcones)
23
were prepared by the method proposed by Joshi and Jauhar, and 1-(4-chlorophenyl)-3-(4-
fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazones were prepared by another method
given by Campaigne and Archer.24
Tris[1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-
thiosemicarbazone]lanthanide (III) Complexes (5a–l): Tris[1-(4-
chlorophenyl)-3-(4-hydroxyphenyl)prop-2-en-1-thiosemicarbazone]europium
(
III) (5i)
1-(4-Chlorophenyl)-3-(4-hydroxyphenyl) prop-2-en-1-thiosemicarbazone (3 mmol,
0.84 g) was dissolved in ethanol (20 mL) taken in 100 mL round bottomed flask and heated
on a water bath. This hot solution was stirred with an aqueous solution of lanthanide salt
Eu(NO3)3 5H2O (1 mmol, 0.428 g) in dropping funnel in 3:1 molar ratio. The resulting
mixture thus obtained was refluxed on a water bath for 2 h and left overnight to yield
the dark brown crystalline lanthanide complex, which was filtered off under suction and
repeatedly washed several times with water (4 × 50 mL) until the filtrate became colorless.
The solid was washed with diethylether and dried over anhydrous CaCl2 in a vacuum
desiccator. The complexes were found to be amorphous colored lanthanide complexes,
◦
stable at room temperature, and soluble in CDCl3. Yield 1.02 g (88%) 5i, mp >227 C. All
other lanthanide complexes (5a–l) were prepared using the same procedure and are given
in Table II along with their characteristics and analytical data.
Antibacterial and Antifungal Activities
Representative chalcone thiosemicarbazone ligands and their lanthanide complexes
were screened for their antibacterial activity against Gram-negative bacteria E. coli and
Gram-positive bacteria S. aureus at 100, 200, 500, and 1000 ppm concentrations. (See the
Supplemental Materials online, Tables VS and VIS).
REFERENCES
1. S. S. Tiwari, A. K. Sengupta, and J. Kumari, J. Indian Chem. Soc., L1, 402 (1974).
2
. D. L. Klayman, J. P. Scovill, J. F. Bartosevich, C. J. Mason, and T. S. Griffin, U. S. US 4, 317,
7
76 (Cl. 260–244.4; CO7D211/24), 02 Mar 1982, Appl. 4, 247, 04 Jan 1979; 7 pp; Chem. Abstr.,
96, 199538S (1982).
3. A. S. Dobek, D. L. Klayman, E. T. Dickson Jr., J. P. Scovill, and E. C. Tramont, Antimicrob.
Agents Chemother., 18(1), 27 (1980).
4. B. J. A. Jeragh and A. El-Dissouky, J. Coord. Chem., 58(12/15), 1029 (2005).
5. N. Siddiqui and O. Singh, Indian J. Pharma. Sci., 65(4), 423 (2003).
6. D. L. Klayman, J. P. Scovill, J. F. Bartosevich, and C. J. Mason, J. Med. Chem., 22(11), 1367
(1979).
7
. D. L. Klayman, J. P. Scovill, J. F. Bartosevich, and J. Bruce, J. Med. Chem., 26(1), 35 (1983).

3
86
C. K. OZA ET AL.
8
9
. J. P. Scovill, D. L. Klayman, and C. F. Franchino, J. Med. Chem., 25(10), 1261 (1982).
. D. L. Klayman, J. P. Scovill, C. J. Mason, J. F. Bartosevich, J. Bruce, and A. J. Lin, Arzneim-
Forsch. Drug Res., 33(7), 909 (1983).
1
1
1
1
1
1
0. F. M. Collins, D. L. Klayman, and N. E. Morrison, Am. Rev. Respir. Dis., 125(1), 58 (1982).
1. M. B. Halli and Z. S. S. Qureshi, Metal-Org. Nano-Metal Chem., 34(10), 1755 (2004).
2. G. Domagk et al., Naturwissenschaften, 33, 315 (1946).
3. D. B. Lovejoy and D. R. Richardson, Blood, 100(2), 666 (2002).
4. N. Ergenc, E. Ilhan, and G. Otuk, Pharmazie, 47(1), 59 (1992).
5. M. Baldini, M. Belicchi-Ferrari, F. Bisceglie, G. Pelosi, S. Pinelli, and P. Tarasconi, Inorg. Chem.,
42(6), 2049 (2003).
1
1
1
1
6. D. R. Williams, Chem. Rev., 72(3), 203 (1972).
7. A. Furst and R. T. Haro, Progr. Exp. Tumor Res., 12, 102 (1969).
8. F. P. Dwyer, E. Mayhew, E. M. F. Roe, and A. Shulman, Brit. J. Cancer, 19(1), 195 (1965).
9. F. A. French, E. J. Blanz Jr., S. C. Shaddin, and R. W. Brockman, J. Med. Chem., 17(2), 172
(
1974).
0. K. C. Agrawal, A. J. Lin, B. A. Booth, J. R. Wheaton, and A. C. Sartorelli, J. Med. Chem., 17(6),
31 (1974).
2
6
2
2
2
2
2
2
2
2
1. J. A. Crim, H. H. Buskirk, and H. G. Petering, Cancer Res., 27(1), 1109 (1967).
2. A. A. El-Asmy, J. Chim. Chem. Soc., 35(1), 29 (1988).
3. K. C. Joshi and A. K. Jauhar, Indian J. Chem., 4(6), 277 (1966).
4. E. Campaigne and W. L. Archer, J. Am. Chem. Soc., 74, 5801 (1952).
5. M. D.Gutierrez, R. Lopez, M. A. Romero, and J. M. Salas, Can. J. Chem., 66, 249 (1988).
6. J. H. Vanvleck and A. Frank, Phys. Rev., 34, 1494, 1625 (1929).
7. M. Shrivastava and G. S. Pandey, Indian J. Chem., 27(A), 447 (1988).
8. (a) K. K. Dahiya and N. K. Kaushik, Indian J. Chem., 27(A), 449 (1988); (b) T. R. Rao, I. A.
Khan, and R. C. Agarwal J. Indian Chem. Soc., 63, 380 (1986).
2
3
9. S. Ghosh and B. Pradhan J. Indian Chem. Soc., 72, 818 (1995).
0. M. C. Bryant, Antibiotics and Their Laboratory Control (Butterworth, London, 1968).