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Synthesis and Reactivity in


Inorganic and Metal-Organic
Chemistry
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Synthesis, Characterization
and Scavenger Effect on
of Copper(II) and Zinc(II)
Complexes Derived from
Thiosemicarbazide
a a a
Zhu Xinde , Wang Chenggang , Le Zhifeng , Mei
a a a
Shangyun , Yen Zhenhuan & Wu Zishen
a
Department of Chemistry , Huazhong Normal
University , Wuhan, Hubei, P. R. China
Published online: 17 Feb 2007.

To cite this article: Zhu Xinde , Wang Chenggang , Le Zhifeng , Mei Shangyun , Yen
Zhenhuan & Wu Zishen (1991) Synthesis, Characterization and Scavenger Effect on
of Copper(II) and Zinc(II) Complexes Derived from Thiosemicarbazide, Synthesis
and Reactivity in Inorganic and Metal-Organic Chemistry, 21:9, 1365-1373, DOI:
10.1080/15533179108020457

To link to this article: http://dx.doi.org/10.1080/15533179108020457

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SYNTH. REACT. INORG. MET.-ORG. CHEM., 21(9), 1365-1373 (1991)

SYNTHESIS, CHARACTERIZATION AND SCAVENGER EFFECT


ON 0; OF COPPER(I1) AND ZINC(I1) COMPLEXES
DERIVED FROM THIOSEMICARBAZIDE
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Zhu Xinde, Wang Chenggang, Le zhlfeng,


Mei Shangyun , Yen Zhenhuan and Wu Zishen *

Department of Chemistry, Huazhong Normal University,


Wuhan. Hubei, P. R. china

ABSTRACT
Copper(l1) and zinc(1I) complexes with the Schiff base derived from 3.4-dhydroxy
benzaldehyde and thiosemicarbazide were synthesized. These compounds have been character
ized by elemental analyses, conductivity measurements, infra - red and electronic spectra.
The Schiff base Ligand has been further characterized by 'H NMR and Ius. The results suggest
that the Schiff base acts as a bidentate Ligand which bonds to metal ions through the imino nitro
gen and sulphur atom. All the complexes are non-electrolytes. These complexes are superox
idefree radical 0; scavengers.

INTRODUCTION
A lot of investigations on the synthesis and biological activity of thiosemicarbazide
derivatives have been done recently. The investigations show that these compounds are active a
gainst bacteria, viruses and cancer'-7. In our earlier publicationssse, 2, 4 -dihydroxyben
zaldehyde thiosemicarbazone and its complexes with 3--metals were reported to show strong

1365

Copyright 0 199 I by Marcel Dekker, Inc.


1366 ZHU ET AL.

antibacterial and scavenging effects on 0


:. In this paper, we present the synthesis, characteri
zation and scavenging effect on 0;of 3,4 -dihydroxybenzaldehyde thiosemicarbazone and its
complexes with copper(I1) and zinc(I1).

EXPERIMENTALS
Materials
All chemicals used in this work were of reagent grade. Thiosemicarbazide was recrystal
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lized from ethanol prior to use.

Preparation of the Schiff Base Ligand


The ethanolic solution (20 mL) of 3,4-dihydroxybenzaldehyde (1.38 g, 10 mmol)
was added dropwise to a 50% ethanolic solution (10 mL) of thiosemicarbazide (0.94 g, 10
mmol). 'Ihe mixture was stirred magnetically at 60 'C on a water bath for 1. 5 h. The solvent
was evaporated to 1/3 and the concentrated reaction mixture was allowed to cool in a refrigera
tor. The product was filtered and recrystallized in 50% ethanol.

Preparation of Metal Complexes


The alcoholic solution of copper chloride (0.67 g, 5 mmol) or zinc acetate (0.92 g , 5
mmol) was mixed with the ligand in 1 1 and 1 : 2 molar ratio, respectively. The mixture
was stirred magnetically at 60 *C on a water bath for two hours. The precipitate was collected
by filtration and recrystallized from 95% ethanol.

Physical Measurements
C , H and N analyses were obtained using a Perkin-Elmer 240B elemental analysis in
strument. Copper was determined by icdometry and zinc by EDTA titration. H 2 0 analyses
were camed out by heating a sample to constant weight at 120 'C. Melting points were ob
tained using a Eeijing X4 microscopic melting point apparatus. All conductivity measurements
were performed in methanol using a Shanghai DDG-11A apparatus at 25 %.The concentra
tion of the solution was 10-3mol L-'.
Infra-red spectra were measured in KBr pellets on a Perkin-Elmer 983 spectropho
tometer in the range 200-4000 cm-I. Electronic spectra from 200 to 900 nm were obtained
in methanol on a Perkin-Elmer Lambda 7 spectrophotometer. 'H N M R spectra were recorded
in deuterated dimethyl sulfoxide with a Varian XL-200 NMR spectrometer using TMS as the
internal standard. The mass spectrum of the Schiff base ligand was obtained using a VG-
707E mass spectrometer. The electron impact excitation energy was 70 eV.
COPPER(I1) AND ZINC(I1) COMPLEXES 1367

Table I. Analytical Wta and Some Physical Roperties of Compounds

Yield Found ((3alcd. ) % COndUCtiVty


compMlnd color
(Formula) (%) c H N S M (Ohm-'an'ml-l)
LH light 45.04 3.97 19.72 14.87
88.6 9. 66
(CsHsNsOlS) 14 (45.50) (4.26) (19.90) (15.16)
cu(wa2-Ko 26.65 2.80 11.57 8.54 17. 15
black 68.2 8.63
(GHiiNsOSazCu) (26.41) (3.03) (11.55) (8.80) (17.45)
Zn(LH)(OAc)z*KO yellow 74. 34.66 3.96 10.59 7.94 16.17
5. 47
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(GzHuNsOlSZn) (34.92) (4.12) (10.18) (7.76) (15.85)


CuLI.2H20 37.03 3.54 15.98 11.96 12.32
black 73. 8 6.84
(CisHzoNs~z~) (36.96) (3.85) (16.17) (12.32) (12.23)
m.2HZo 36.35 3.68 16.15 12.74 12.87
yellow 80.5 6. 64
(CIEHZONKWZZ~) (36.83) (3.84) (16.11) (12.28) (12.54)

Table Ll. Thermogravimetriy Data of the Complexes


Content of HzO Melting
M a s of sample Loss of HzO
Compound (mol mol)
(P) calcd. found point( *C)

Cu(LH)Cl2. Hz0 0.5108 0.02564 1 1.02 >280


Zn(LH) (0Ac)z. HzO 0.4895 0.02156 1 1.01 >280
CULz * 2Hz0 0.5441 0. 03721 2 1.97 >280
ZnL * 2Hz0 0.5084 0.03480 2 1.98 >280

-
Tests for Scavenger Effect on 0;
The tests for the scavenger effect on $ were carried out using the Pyrogdlol-W
method".

RESULTS AND DISCUSSION


The reactions of the Schiff base ligand (LH) with the corresponding metal salt can be.
represented as follows.
MXZ+ LH ethanol M(LH)Xz-H20
(1)

Mh'2H20 + 2Hx
ethanol
MXz+ 2LH -
(II )
1368 ZHU ET AL.

Table LII. Mass Spectrum Data and Assignments


of the Schiff Base Ligand

Relative
Fragment
intensity

211 100 M+ CeHgN302S

136 68 M+ dissociatedNHmNH~

109 17 M+ dissociated CHNzHCSNHz


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77 29 C6&+

43 51 CH"H2'

All of the synthesized compounds are colored solids. The compounds are stable in air,
soluble in DMSO and methanol and pmrly soluble in water. The elemental analyses (see Table
I ) are in agreement with the chemical formula of the compounds. Molar conductivities in
methanol (see Table 1) indicate that all of the cornpounds behave as non-electrolytes'O. Ther
mcgravimetric data in Table I1 show that the complexes ( I ) have one molecule of water of crys
tallization and complexes (11) have two, respectively.

Mass Spectrum
Mass spectrum data and the assignments of fragments of the Schiff base ligand are pra
sented in Table Ill. The msl~sof the molecular ion of the ligand is 21 1, which is in agreement
S . of the other frag
with the empirical formulation C ~ H B N ~ O ZAll
ments are parts that compose the molecule and correlate with the molecular ion CeH9N302Sf.

'H N M R Spectrum of the Schiff Base Ligand


The 'H NMR spectrum of the Schiff base ligand was obtained. 'H NMR data and their
assignments are shown in Table 1V. The data support the proposed structure of the ligand (see
Fig. l ) g s 1 6 .

lnfra -red Spectra


The infra -red spectra of the Schiff base ligand and its complexes can provide an in
sight into the mode of bonding of the ligand to the metal ions. Assignments were made based on
typical group frequencies''. The strong and broad absorption (see Table V) in the region 3200
-3400 m-' of all the complexes substantiates the presence of water. 'zhe coordination of the
C O P P E R ( I 1 ) AND Z I N C ( I 1 ) COMPLEXES 1369

Table IV. 'H NMR Data (DmO--d0


.~

Compound Cnemid shift (b,ppm)


~ ~~~

9.64(OH,lH.s) 9.08(0H,lH.s) 8. lO(C=N,lH,s)


LH
7.82(NH,lH.s) 7.21(NH,2H.d) 7.10-6.78 (ring,3H)

H ~ = N - N H - C - N H ~
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II
HO S

Fig. 1. The ligand LH

TaMe V. Tntra-red spectral Data of Free Ligandand CMnplexs (an-')

Q(LH)CI~-HZO 3340-3230(s,b) 1600(s) 978(m) 850(m) 495 389


Zn(LH)(OAch .H20 3320-3200(s,b) 1600(s) 980(m) 850W 504 415
CuL2.2HzO 3350-3200(s,b) 1600(s) 978(m) 625(m) 535 468
ZnLn *2&0 3360-3180(s,b) 1608cs) 982(m) 628(m) 513 422

s = strong, b = broad, m = medium

metal ion to the imino nitrogen can be inferred from the shift of U ( ~ - - N ) from 1625 to 1600
cm-I.
The UW.S) is decreased slightly from 855 to 850 an-'for CU(LH)CIZ-HzO and Zn(LH) ( O A C ) ~
- HzO showing the involvement of coordination of thion sulphur. On the other hand, a marked
change occures in the 855 cn-' band. It is shifted almost 225 cm-' to lower frequencies in
CULZ.2H20 and 2Hz0. m e change indicates that the C=S double bond is converted to a
single bond such as would result from the formation of a strong metal-sulphur bond. At lower
frequencies, a band in the 495-535 cm-' region and another in the 389 to 468 an-' region are
attributed to UWN) and U(HS), respectively. IR bands observed between 234 and 256 an-]can
be assigned to U(~KI)for CU(LH)CIZ.HZO, and between 256 and 292 cm-' tou(,,(carboxy
late oxygen) for Z~(LH)(OA~)Z-HZO~'.
1370 ZHU ET AL.

Table W. Electronic Spectral Data (in methanol)

LH 225(15455) 248(8764) 292(16364) 365(10745)


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CU(LH)CIZ H 2 0 226(17108) 241(15436) 279(9436) 350(5877)


Zn(LH)(OAc)z HzO 222(12815) 245(15436) 352(6049)
CULz 2Hz0 228(21120) 248(18851) 294(10412) 358(7882)
Z n L z 2Hz0 226(11969) 244 (101 47) 348(5338)

Table VII. Scavenging Effect on 0;

-lgC 5.2596 5.5607 5.8617 6.1627


LH
ASR"(%) 42.40 31.84 23.21 11.27

-43c 5.2757 5.5768 5.8794 6.1805


Cu(LH)Ciz. HzO
ASR(%) 51.21 38.75 21.04 13.68

Zn(LH) (OAC)~.Hz0
-w 5.0757 5.3770 5.6778 5.9586
ASR(%) 45.79 36.24 25.07 13.23

-kC 5.4943 5.7959 6.0970 6.3979


CuLz * 2Hz0
ASR(%) 53.97 42. 01 28.31 15.09

-kC 5.1871 5.4881 5.7825 6.1790


m * 2H20
ASR(%) 50.37 36.24 21.97 12.08

it C = molar concentration of corresponding compound


** ASR = average suppression ratio
COPPER(I1) AND ZINC(I1) COMPLEXES 1371

N H Z
/

HO
M
/ \
x x

Fig. 2. M(LH)Xz* HzO M = Cu(II), X = (2-


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M = Zn(II), X = OAC-

H~N’

Fig. 3. MLz.2Hz0 i

al
4J
(0
c
C
0
-A
m
m
al
c
a
a
I)
m I
1 I I I I I 1
5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4
-1ogc
1372 ZHU ET A L .

Electronic Spectra
The electronic spectral data for the free ligand and the complexes are shown in Table
V1. In the spectrum of the Schiff base, the tnnd of 365 nm is attributed to the azomethine
chromophore n - n' transition. The bands a t higher energies (225 and 248 nm) are associated
with the benzene n-n* transition. In the spectra of the complexes, the band of the azomethine
chromphore n -n' transition is shifted to about 350 nm indicating that the imino nitrogen is
involved in coordination to the metal ion. The ahsorption frequencies ascribed to the benzene
n -n* transition (at about 225 and 250 run) are nearly the same as that of the Ligand'*.
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From the above discussion it is seen that the metal ions in the complexes are bonded to
the ligand through the imino nitrogen and sulphur atom. If the complexes are presumed to be
four-coordinate, proposed coordination modes are shown in Fig. 2 and Fig. 3".

~ e t for
s Scavenger on 0;
The data of the scavenger effect on 0; of the Schiff base ligand and its complexes are
summarized in Table VII. The results indicate that all of the synthetic compounds possess some
degree of scavenging effect on 0
;. The suppression ratios of the complexes are mostly higher
than that of the Schiff base ligand. The ratios are proportional to the concentration of the corn
pounds (see Fig. 4). The suppression of this kind of compounds are similar to that of SOD (su
peroxide dism~tase)'~.The significance concerning this property will be reported latter.

ACKN0WLEM;EMENT
We thank Xu Wen hua for his help in the experimental work. Thanks are also due to
Mr. hang Eping, h4r. Zhong Chuanxue and Mr. Guo Peng, Hubei (hemistry Institute, for
recording the mass spectrum.

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COPPER(I1) AND ZINC(I1) COMPLEXES 1373

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R e c e i v e d : 8 November 1990 R e f e r e e I : D. L. R e g e r
A c c e p t e d : 26 J u n e 1 9 9 1 R e f e r e e 11: M . Yamauchi