Novel transition metal complexes of 4-hydroxy-coumarin-3- thiocarbohydrazone: Pharmacodynamic of Co(III) on rats and antimicrobial activity

Article abstract of DOI:10.1016/j.saa.2011.05.035

A new series of stable transition metal complexes of the formula M(L)X·S, where M = Cu(II), Ni(II), Co(III), Cr(III) and Fe(III) and L is the deprotonated ligand of 4-hydroxy-coumarin-3-thiocarbohydrazone, X = Cl ^-, NO₃^- or CH₃COO^- and S = H₂O and/or EtOH. The HL ligand was prepared by the reaction of 3-formyl-4-hydroxy-coumarine with thiocarbohydrazide in the molar ratio 1:1. The HL ligand and its metal complexes were characterized by elemental analysis, ¹H NMR, IR and electronic spectra, and molar conductance and magnetic measurements and thermal gravimetric analysis (TGA). The HL ligand acts as a monobasic tridentate ONS donor in all metal complexes, and coordinated through the phenolic OH, azomethine nitrogen and thione sulfur. Electronic spectra with magnetic moments suggested varieties of geometries around the central metal atoms. Thermal gravimetric analysis indicates that the complexes are stable up to 300 °C, and release the uncoordinated and/or coordinated H ₂O/solvent molecules, which is accompanied by a color change. The formed complexes after releasing the solvent were investigated and their structures are suggested to have square planar or octahedral arrangement. Pharmacodynamic of cobalt(III) complex on some biochemical parameters and histological studies in serum and heart tissue in rats have been studied. Although the complexes demonstrated a significant effect at low dose than the high dose, the ligand showed significant good effects in both high and low doses on the biochemical analysis in serum and heart tissue. Cobalt complex was screened in order to evaluate its antifungal activity against the filamentous fungi Aspergillus niger, Aspergillus fumigatus, and Aspergillus flavus, and antibacterial activity against the Candida albicans, Escherichia coli, Klebseilla pneumoniae and Pseudomonas aeruginosa.

Full text of DOI:10.1016/j.saa.2011.05.035

Spectrochimica Acta Part A 81 (2011) 35–43
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Novel transition metal complexes of
4-hydroxy-coumarin-3-thiocarbohydrazone: Pharmacodynamic
of Co(III) on rats and antimicrobial activity
A.I. Mosaa,∗, Adel A.A. Emarab,c, J.M. Yousefa, A.A. Saddiqd
a Department of Chemistry, Girl’s Collage of Education, King Abdul Aziz University, Jeddah 21453, Saudi Arabia
b Department of Chemistry, University College in Mekkah, Umm Al-Qura University, Mekkah 21955, Saudi Arabia
c Department of Chemistry, Faculty of Education, Ain Shams University, Roxy, Cairo 11711, Egypt
d Department of Plant, Faculty of Science (Girl’s Branch), Microbiology, King Abdul Aziz University, Jeddah 21453, Saudi Arabia
a r t i c l e i n f o
a b s t r a c t
Article history:
A new series of stable transition metal complexes of the formula M(L)X·S, where M = Cu(II), Ni(II), Co(III),
Cr(III) and Fe(III) and L is the deprotonated ligand of 4-hydroxy-coumarin-3-thiocarbohydrazone, X = Cl−,
Received 29 November 2010
Received in revised form 20 April 2011
Accepted 16 May 2011
−
NO3 or CH3COO− and S = H2O and/or EtOH. The HL ligand was prepared by the reaction of 3-formyl-
4-hydroxy-coumarine with thiocarbohydrazide in the molar ratio 1:1. The HL ligand and its metal
complexes were characterized by elemental analysis, 1H NMR, IR and electronic spectra, and molar con-
ductance and magnetic measurements and thermal gravimetric analysis (TGA). The HL ligand acts as
a monobasic tridentate ONS donor in all metal complexes, and coordinated through the phenolic OH,
azomethine nitrogen and thione sulfur. Electronic spectra with magnetic moments suggested varieties
of geometries around the central metal atoms. Thermal gravimetric analysis indicates that the complexes
are stable up to 300 ◦C, and release the uncoordinated and/or coordinated H2O/solvent molecules, which
is accompanied by a color change. The formed complexes after releasing the solvent were investigated
and their structures are suggested to have square planar or octahedral arrangement. Pharmacodynamic
of cobalt(III) complex on some biochemical parameters and histological studies in serum and heart tissue
in rats have been studied. Although the complexes demonstrated a significant effect at low dose than
the high dose, the ligand showed significant good effects in both high and low doses on the biochemi-
cal analysis in serum and heart tissue. Cobalt complex was screened in order to evaluate its antifungal
activity against the filamentous fungi Aspergillus niger, Aspergillus fumigatus, and Aspergillus flavus, and
antibacterial activity against the Candida albicans, Escherichia coli, Klebseilla pneumoniae and Pseudomonas
aeruginosa.
Keywords:
Transition metal complexes
4-Hydroxy-coumarin-3-thiocarbo-
hydrazone
Pharmacodynamic of Co(III)
Antimicrobial activity
© 2011 Elsevier B.V. All rights reserved.
1. Introduction
Some derivatives of thiosemicarbazone have activity against proto-
zoan parasite Trypanosoma cruzi [2]. Also, they can enhance tumor
Ligands with potential sulfur and nitrogen donors, such as
thiosemicarbazone and its derivatives are quite interesting which
have gained special attention in the last decade, not only because
of the structural chemistry and their importance in medical chem-
istry, but also because these materials are used as drugs and
they are reported to possess a wide variety of biological activities
against bacteria, fungi and certain type of tumors. They are also
become a useful model for bioinorganic processes, which has many
biochemical and pharmacological properties. Thiosemicarbazone
derivatives and their metal complexes appear to be increases the
ability as antifungal, antimicrobial and antitumor properties [1].
cells radiosensitivity in vitro and in vivo which have inhibition for
DNA repair [3].
The present work is dealing with the preparation of Cu(II), Ni(II),
Co(III), Cr(III) and Fe(III) complexes with 3-hydroxy-coumarin-3-
thiocarbohydrazone, HL, ligand in the molar ratio 1:1. The newly
prepared metal complexes of this ligand were identified by differ-
ent physicochemical and spectroscopic techniques. Investigation of
the reaction of the HL ligand with cobalt(II) chloride showed that
cobalt(II) ion of the formed complex is oxidized to Co(III). This was
investigated by the paramagnetism of cobalt complex and the elec-
tronic spectrum of the complex. The HL ligand acts as monobasic
with ONS-tridentate sites and can coordinate with one metal ion to
form mononuclear complexes. The coordination sites are through
the phenolic OH, azomethine nitrogen and thione sulfur. Electronic
spectra with magnetic moments suggested that copper(II) complex
∗
Corresponding author. Tel.: +966 0503393776.
E-mail address: mosa ai@yahoo.com (A.I. Mosa).
1386-1425/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2011.05.035

36
A.I. Mosa et al. / Spectrochimica Acta Part A 81 (2011) 35–43
FT-IR spectra (4000–400 cm−1) were recorded as KBr discs using
Perkin Elmer Spectrophotometer 1650. Electronic spectra were car-
ried out with UV–vis spectrophotometer Shimadzu model 1601
with one centimeter quartz cell. 1H NMR measurements were car-
ried out on Brucker 250 MHz spectrophotometer. The chemical
shifts were measured with respect to TMS which used as internal
standard. Magnetic susceptibilities of the complexes were mea-
sured by the Gouy method at room temperature using a magnetic
susceptibility balance (Johnson Matthey, Alfa product, Model No.
(MKI)) using HgCo(NSC)4 as reference. Effective magnetic moments
were calculated from the expression ꢀeff = 2.828 (ꢁMT)1/2 B.M.,
where ꢁM is the molar susceptibility corrected using Pascal’s con-
stants for the diamagnetism of all atoms in the compounds and T
is the absolute temperature [7]. Thermal analysis was performed
using Shimadzu-TAG-50 under nitrogen 20◦C/min. Molar conduc-
tance of 1 × 10−3 M in DMF solution was measured on the WTW.
D8120 Weilheim L.F.42 conductivity meter (Germany).
has square planar geometry, while Ni(II), Co(III), Cr(III) and Fe(III)
have octahedral geometry around the central metal atoms [4].
Thermal gravimetric analysis indicates that the complexes are
stable up to 300 ◦C, with release the uncoordinated and/or coor-
dinated H2O/solvent molecules, which is accompanied by a color
change due to the change of the geometry and/or the coordina-
tion sites of the Cl−, CH3COO− and NO3 counter anion associated
−
with the complex. The formed complexes after releasing the sol-
vent were investigated using physicochemical and spectroscopic
techniques and their structures are suggested to have either square
planar or octahedral arrangement.
The pharmacodynamic activity on Co(III) complex was studied
on rats. The antifungal activity was studies against the filamentous
fungi Aspergillus niger, Aspergillus flavus, and Aspergillus fumiga-
tus. The antibacterial investigation was studied against the Candida
albicans, Escherichia coli, Klebseilla pneumoniae and Psuedomonas
aeruginosa.
2. Experimental
2.2. Biochemical analysis
2.1. Inorganic Preparation
2.2.1. Subject
Eighty male Wister Albino rats, weighing 100–150 g were main-
tained in clean cages. The rats were fed with commercial pelleted
diet obtained from King Fahad Medical Research Center in Jed-
dah. Time of the experiment is 12 days. Rats were divided into
six groups, group (A) is a control group takes ethanol 25 mg/kg,
group (B) is a control group takes ethanol 5 mg/kg, group (C) takes
[Co(L)(H2O)Cl2]·EtOH complex (4) 25 mg/kg, group (D) takes the HL
ligand 25 mg/kg, group (E), takes [Co(L)(H2O)Cl2]·EtOH complex (4)
5 mg/kg, group (F) takes the HL ligand 5 mg/kg. All groups injected
by i.p. from the first day to the end of the experiment [8]
2.1.1. Materials
4-Hydroxy-coumarine, phosphorus oxytrichloride, hydrazine
hydrate 80%, carbon disulfide, DMF, dioxane are Merck. Copper(II)
chloride (CuCl2·2H2O), copper(II) nitrate (Cu(NO3)2·3H2O),
copper(II)
acetate
(Cu(OAc)2·H2O),
nickel(II)
chloride
(NiCl2·6H2O), nickel(II) nitrate (Ni(NO3)2·6H2O), nickel(II) acetate
(Ni(OAc)2·4H2O), cobalt(II) chloride (CoCl2·6H2O), cobalt(II)
nitrate (Co(NO3)2·6H2O), chromium(III) chloride (CrCl3·9H2O) and
iron(III) chloride (FeCl3·9H2O) salts are Merck or BDH.
2.1.2. Preparation of ligand
3-Formyl-4-hydroxy coumarine was prepared by the literature
method using the reaction of POCl3 with 4-hydroxy coumarine [5].
Also, thiocarbohydrazide was prepared by the literature method
using the reaction of CS2 and NH2NH2·H2O in DMF [6].
2.2.2. Methods
After 3, 6 and 12 days of the experiment, rats anesthetized
with ether, blood were collected to determine some biochemical
parameters, include bilirubin [9], cholesterol [10], triacylglycerols
[11], which were measured by Diminsion (DAD BEHRING Company,
Germany). The rats were killed by cervical decapitation, and used
for the determination of glucose [12], lactate dehydrogenase (LDH)
[13] and creatine phosphokinase (CPK) [14]. Collected data were
calculated by t-test and ANOVA using SPSS program version 15.
4-Hydroxycoumarin-3-thiocarbohydrazone, HL, ligand was
prepared by addition of 3-formyl-4-hydroxy-coumarine (2.78 g,
10.00 mmol) dissolved in hot ethanol gradually to thiocarbohy-
drazide (1.06 g, 10.00 mmol) in the molar ratio 1:1 (70%/30%, v/v)
H2O with stirring for 1 h. The orange yellow precipitate was filtered
off and washed several times with small portions of ethanol/ether
and dried under vacuum. The melting point was 205 ◦C.
2.3. Antimicrobial screening
2.1.3. Preparation of complexes
Transition metal complexes of HL were prepared in the molar
ratio 1:1 (M:HL). The metal chloride (10.00 mmol) of Cu(II), Ni(II),
Co(II), Cr(III) and Fe(III), metal acetate (10.00 mmol) of Cu(II) and
Ni(II), and metal nitrates (10.00 mmol) of Cu(II), Ni(II) or Co(II) were
dissolved in 30 mL ethanol. Each solution was added gradually with
stirring to (10.00 mmol) of HL in 100–150 mL dioxane, then each
reaction was heated to reflux for 2 h, where reaction tube was
closed with dry CaCl2. Chromium(III) complex was formed after
raising the pH values using 0.5 mL of ethanolic 1% KOH. The formed
complexes were washed with ethanol, dioxane then dried under
vacuum. The nitrate and acetate complexes were heated under
vacuum for 5 h at 80 ◦C in a water bath to avoid lattice molecules.
The antimicrobial properties of HL and [Co(L)(H2O)Cl2]·EtOH
complex containing coumarine (heterocyclic ring) and thiocarbo-
hydrazone moieties were evaluated against four Gram-negative
bacteria; C. albicans, E. coli, K. pneumoniae and P. aeruginosa and
three fungi; A. niger, A. flavus and A. fumigatus.
2.3.1. Antibacterial screening
The agar disc diffusion method [15] was employed to
test the presence of antibacterial activities in both HL and
[Co(L)(H2O)Cl2]·EtOH complex (4). Suspension of the tested bac-
teria (108 CFU/␮L) was spread on Mueller Hinton Agar (Oxioid) for
bacteria. The bacteria species used were C. albicans, E. coli, K. pneu-
moniae and P. aeruginosa. The tested solutions were prepared in
DMF. Then filter paper discs (6 mm in diameter) were soaked with
20 ␮L of the stock solutions and placed on the incubated plates.
After keeping at 2 ◦C for 2 h, the Petri dishes were incubated at 37 ◦C
for 24 h for growing bacteria. The diameter of the inhibition zones
was measured in millimeters. The antibacterial effects are listed in
Table 6.
2.1.4. Physical measurements
Elemental analysis was performed by elemental analyzer
Electro-therm 1900. Analyses of metal ions was performed after
the dissolution of the solid complex in hot concentrated nitric acid,
HNO3, then diluting with distilled water and filtering to remove
the precipitated organic ligand. The solution was neutralized with
ammonia solution and the metal ions were then titrated with EDTA.

A.I. Mosa et al. / Spectrochimica Acta Part A 81 (2011) 35–43
37
Ar–H), ␦ 8.0–8.40 (s, 2H, NH2, amino), ␦ 9.68 (s, H, OH, phenolic),
␦ 9.9 (s, H, CH, azomethine), ␦ 10.29 (s, H, NH, imin), ␦ 13.67 (s, H,
NH, imin), 12.9 (s, H, NH, imin) [18].
Electronic spectrum of the HL ligand showed absorption bands
at 280, 300 nm which are assigned to ␲–␲* transitions within the
coumarine moiety [18]. The bands at 350 and 360 nm attributed to
n–␲* transitions of the C N (azomethine) and thio-amid group in
thiocarbohydrazide; respectively. The absorption bands at 280 and
390 nm were assigned to CT transitions to visible region [19].
Scheme 1. Structure of the thiocarbohydrazone, HL, ligand.
3.2. The metal complexes
2.3.2. Antifungal screening
The thiocarbohydrazone,
HL,
ligand
and
its
The ligand reacted with Cu(II), Ni(II), Co(II), Cr(III) and Fe(III)
metal ions to give their corresponding metal complexes of the for-
mula MLX·S where L = 4-hydroxycoumarin-3-thiocarbohyrazone,
X = Cl−, NO3−, CH3COO− and S = H2O and/or EtOH. All prepared
complexes insoluble in most organic solvents and partially solu-
ble in DMSO and DMF, decomposed above 300 ◦C without melting,
which indicate their polymeric nature. Table 1 lists the analytical
and physical data of the HL ligand and its metal complexes.
[Co(L)(H2O)Cl2]·EtOH complex (4) were also evaluated for
their antifungal activity by the agar-well diffusion method [16].
The fungi (A. niger, A. flavus and A. fumigatus) were incubated
in Malt Extract Broth (Difco) for 48 h. In the agar-well diffusion
fungi (103–104 per mL) for 24 h, by using a sterilized cork borer
(7 mm diameter), wells were dug in the culture plates. Compounds
dissolved in DMF were left at 4 ◦C for 2 h and then the plates
were incubated at 25 ◦C (72 h). At the end of incubation of the
period, inhibition zones formed on the medium were evaluated
as millimeters (mm) diameter. The control samples contain DMF
only.
3.2.1. Infrared spectra
The spectra of the M(L)X·S complexes showed a frequency shift
in the vibration of ꢂ(C N), ꢂ(C–S) and ꢂ(C–O) to lower frequency
indicating that coordination occurred via azomethine nitrogen,
thione sulfur, and phenolic oxygen atom which supported by shift
of ꢂ(N–N) to lower frequency. Thus, the ligand acts as monobasic
tridentate, coordinated in thione form, this supported by appear-
3. Results and discussion
3.1. 4-Hydroxy-coumarin-3-thiocarbohydrazone ligand
ance of ꢂ(M–O), ꢂ(M–N) at 416–449 cm−1 and 464–576 cm−1
;
Schiff base thiocarbohydrazone, HL, ligand was prepared by
the reaction of one mole of thiocarbohydrazide with one mole
of 3-formyl-4-hydroxycoumarine. The structure of the HL lig-
and is identified by elemental analysis, infrared, UV–visible, 1H
NMR spectra. Table 1 lists the physical and analytical data of
the 4-hydroxy coumarin-3-thiocarbohydrazone, HL, ligand and its
transition metal complexes. From the investigation, the HL ligand
can be represented as in Scheme 1.
The infrared spectrum is consistent with the formation of HL
ligand. The vibrational assignments were aided by comparison
with the vibrational frequencies of the related compounds, such as,
thiocarbohydrazone of salicyldehyde and 2-hydroxyacetophenone
[17]. The fundamental stretching mode of the azomethine moiety,
ꢂ(–C N–), is readily assigned by comparison with the infrared spec-
tra of thiocarbohydrazide and 3-formyl-4-hydroxycoumarine. The
absorption bands of the C O of the formyl group in the 3-formyl-
4-hydroxycoumarine disappeared while the other ꢂ(C O) in the
aromatic ring still persist, and the absorption band of the NH2 in
the thiocarbohydrazide, still persists, which may be due to the con-
densation of one NH2 has occurred while the other NH2 still as it
is. The most intense band at 1691 cm−1 is assigned to the –C N–
stretching frequency of the HL ligand and is characterized for the
azomethine moiety of most Schiff base compounds. The band at
1112 cm−1 is assigned to the ꢂ(C S) stretching frequency.
respectively. The IR of the M(L)Cl·S complexes showed stretching
vibration at 899–902 cm−1 and is assigned to ꢂ(M-Cl). This indi-
cates that Cl− ion attached directly to the metal ion which supports
the non- electrolytic nature of the complexes [20]. The IR spectra of
the nitrate complexes [M(L)(NO3)(S)] reveals spitted sharp bands
at 750–740 cm−1 which is characteristic in-plane bending vibra-
tion band ␥4. This supports the coordination nature of the nitrate
ion. The ꢂ(N–H) vibration of the ligand disappears in the spectra
of the complexes indicating coordination of ligand with metal ion
incorporated in the thiol form. The presence of ꢂ(H–N) vibration
indicates that the ligand coordinated in thione form. In the complex,
M(L)(OAc)·2H2O participation of the OAc− in complex formation
was an evidence from the appearance of bands at 1706, 1589 and
1422 cm−1 due to ꢂ(C O), ꢂ(COO)asym and ꢂ(COO)sym [20]. The IR
spectra of most complexes show intense band at 3430 cm−1 which
is due to ꢂ(OH) of the H2O and/or EtOH solvent molecules accom-
panied with the complex formation [21].
3.2.2. Thermal analysis
All thermograms of the transition metal complexes of the thio-
carbohydrazone, HL, ligand are mainly identical. The TGA curves
showed several stages in the weight loss%. The first stage is the
weight loss at 80 ◦C which corresponds to the loss of lattice water
or EtOH molecules. The second stage at 130–210 ◦C corresponds
to the loss of coordinated water molecules and release of Cl2. The
last stage is due to the loss of thiocyanate up to 600 ◦C followed by
organic ligand at the end metal oxide were formed above 700 ◦C.
The metal oxide residues are nearly close to the calculated values.
On the other hand, other fundamental bands were assigned in
the infrared spectrum of the H2L ligand. The appearance of vibra-
tions of ꢂ(SH) and ꢂ(N–C S), at 2987, 1565 and 1465 cm−1. Also,
the vibrational bands of ꢂ(C–O), ꢂ(C–N), ꢂ(C–S) were observed at
1363, 1250 and 625 cm−1; respectively, which indicate the thionic
nature of the ligand in the solid state [18]. In addition the spectra
show symmetric and asymmetric stretching vibration ꢂ(NH2) at
3500–3000 cm−1 of –NH2 group in the side chain of the thiosemi-
carbohydrazone and ꢂ(OH) phenolic at 3500 cm−1. The broad band
at 3100–3162 cm−1 was assigned to ꢂ(NH) in H-bonding between
sulfur atom of thione group and hydrogen of N–H moiety.
The
thermograms
of
[Cu(L)Cl]·1.5EtOH
(1),
[Ni(L)(H2O)2Cl]·EtOH (2) and [Co(L)(H2O)Cl2]·EtOH (4), showed
several stages in the weight loss. The first stage in the weight
loss at 75–100 ◦C corresponds to loss of lattice ethanol molecule.
The second stage around 210 ◦C is due to the weight loss of the
coordinated water molecule. The third stage showed successive
weight loss and is corresponds to loss of thiocyanate and chloride
up to 600 ◦C. The last stage is due to the loss of the organic
ligand. The residue is metal oxide after 700 ◦C. The thermo-
1H NMR spectrum of the HL ligand in DMSO-d6: showed several
significant signals. There signal were assigned as; ␦ 7.2–8.0 (m, 4H,

Table 1
Elemental analysis and physical data of 4-hydroxy coumarin-3-thiocarbohydrazone, HL, ligand and its metal complexes.
Reaction/ligand/complexa
Molecular formula
(M.Wt.)
Weight; g (mmol)
Yield%(g) Color
Elemental analysis; found (calculated) %
Ligand
Metal salt
C
H
N
MOb
–
M
HL
C11H10N4O3S
278.258
–
–
98(2.62) Yellow orange
63(2.80) Green
47.81(47.48)
3.44(3.62)
19.98(20.13)
–
1
2
3
4
5
6
7
8
9
HL + CuCl2·3H2O → [Cu(L)Cl]·1.5EtOH
HL + NiCl2·6H2O → [Ni(L)(H2O)2Cl]·EtOH
[Ni(L)(H2O)2Cl]·EtOH → [Ni(L)Cl]c
HL + CoCl2·6H2O → [Co(L)(H2O)Cl2]·EtOH
HL + CrCl3·9H2O → [Cr(L)(H2O)Cl2]·H2O
HL + FeCl3·9H2O → [Fe(L)(EtOH)Cl2]
C
14H18N4O4.5SClCu
445.294
13H19N4O6SClNi
2.78(10.0)
2.78(10.0)
1.80(10.0)
2.37(10.0)
38.10(37.76)
34.66(35.06)
34.90(35.56)
35.84(35.81)
30.43(30.28)
34.66(34.68)
36.40(35.83)
30.20(30.11)
35.95(36.22)
4.97(4.05)
4.35(4.19)
2.61(2.43)
3.62(3.47)
2.77(2.98)
3.68(3.34)
3.59(3.68)
3.06(2.97)
3.91(3.72)
3.29(3.04)
3.19(3.00)
2.45(2.22)
3.10(3.32)
12.19(12.59)
12.17(12.36)
15.17(15.09)
12.52(12.86)
12.95(12.85)
12.80(12.45)
12.58(12.86)
15.83(15.97)
13.15(13.00)
13.89(14.19)
15.99(16.14)
17.20(17.28)
15.75(15.49)
17.53(17.85)
16.11(16.48)
20.41(20.11)
17.96(17.93)
17.21(17.42)
17.91(17.73)
18.90(18.24)
18.81(18.12)
17.20(17.33)
18.73(18.91)
17.55(17.21)
18. 58(18.77)
16.73(16.57)
13.97(14.26)
12.73(12.95)
15.65(15.80)
13.56(14.10)
11.64(11.92)
12.31(12.40)
14.73(14.57)
14.40(14.47)
13.98(13.62)
14.76(14.86)
13.08(13.53)
14.43(14.75)
13.16(13.03)
C
62(2.71) Brown yellow
88(3.26) Brown red
79(3.29) Brown red
89(3.88) Brown
453.385
C11H9N4O3SClNi
371.457
C13H15N4O4SCl2Co
435.698
C11H13N4O5SCl2Cr
436.260
2.78(10.0)
2.787(10.0)
2.77(10.0)
2.78(10.0)
2.78(10.0)
2.78(10.0)
2.37(10.0)
3.21(10.00)
3.24(10.00)
2.49(10.00)
2.40(10.00)
2.44(10.0)
C13H15N4O4SCl2Fe
450.082
61(2.75) Dark brown
60(2.62) Brown
HL + Cu(CH3COO)2·H2O → [Cu(L)(H2O)2(CH3COO)] C13H16N4O7SCu
435.783
C11H13N5O8SCu
438.770
HL + Cu(NO3)2·3H2O → [Cu(L)(H2O)2(NO3)]
55(2.42) Green
HL + Ni(CH3COO)2·4H2O → [Ni(L)(H2O)2(CH3COO)] C13H16N4O7SNi
67(2.88) Brown yellow
430.983
10 [Ni(L)(CH3COO)]·2H2O → [Ni(L)(CH3COO)]d
11 HL + Ni(NO3)2·6H2O → [Ni(L)(NO3)(H2O)2]
12 [Ni(L)(NO3)]·2H2O → [Ni(L)(NO3)]e
C13H12N4O5SNi
394.980
C11H13N5O8SNi
433.970
C11H9N5O6SNi
397.967
–
–
88(3.48) Reddish brown 40.05(39.53)
2.78(10.0)
2.78(10.0)
2.90(10.0)
2.90(10.0)
72(2.71) Green
78(3.10) Brick red
44(2.00) Red
30.21(30.44)
33.32(33.20)
29.40(29.22)
13 HL + Co(NO3)2·6H2O → [Co(L)(H2O)2(NO3)]·H2O
C11H15N5O9SCo
452.172
a
All reactions were heated to reflux for 2–4 h.
b
MO is the metal oxide residue from the pyrolysis of the complexes at >900 ◦C.
Complex obtained by heating 0.2 g [Cu(L)Cl]·1.5EtOH to 100 ◦C.
Complex obtained by heating 0.2 [Ni(L)(CH3COO)(H2O)2] to 100 ◦C.
Complex obtained by heating 0.2 g [Ni(L)(NO3)]·2H2O to 100 ◦C.
c
d
e

A.I. Mosa et al. / Spectrochimica Acta Part A 81 (2011) 35–43
39
bands due to the triplet states 3T1g and 3T2g are not observed. The
visible spectrum of complex (4) is consistent with the low spin com-
plex of Co(III) and thus this complex is diamagnetic, which indicate
oxidation of Co(II) with thiosemicarbazone moiety as to Co(III) [25].
The electronic spectrum of [Ni(L)(H2O)2Cl]·EtOH complex (2)
gram of [Cu(L)(CH3COO)(H2O)2] (7), [Ni(L)(CH3COO)(H2O)2]
(9), [Cu(L)(NO3)(H2O)2] (8), [Ni(L)(NO3)]·2H2O (11) and
[Co(L)(H2O)2(NO3)2]·H2O (13) showed three stages in their
weight loss. The first stage was at 110–200 ◦C which corresponds
to the coordinated water molecules without decomposition of the
complexes. The second stage showed gradual weight loss up to
550 ◦C which is due to the loss of the organic ligand. The residues
are the metal oxides which are detected at 780–850 ◦C. This mean
that the chloride derivative less stable than the nitrate and acetate.
The Ni(II) complexes showed color change when heated to 200 ◦C
in oven. This color changes the complex to a new compound with
significant change in magnetic moment values. This indicates
change in the geometry and coordinating sites. Elemental analysis
of the product indicates the stability of the complexes without
either coordinated H2O or lattice EtOH. Physical and analytical
data of the heated complexes to 200 ◦C is listed in Table 1.
3
3
shows
a
band at 14 300 cm−1 due to A1g → T2g transition
and magnetic moment value of 2.47 B.M. suggested octahe-
dral geometry. The low value indicates polymeric nature of the
complex through solvent molecule, while the electronic spec-
tra of [Cr(L)Cl2(H2O)]·H2O complex (5), show two bands at
4
4
17 150 cm−1 and 23 900 cm−1 due to A2g(F) → T2g (F) transi-
tion, in addition, to a higher frequency band at 38 100 cm−1
which may be due to the CT transition [24]. The electronic spec-
trum of [Co(L)(H2O)2(NO3)2]·H2O complex (13) gave two bands at
4
17 350 cm−1 and 21 330 cm−1 corresponding to 4T1g(F) → A2g and
4
4T1g(F) → T2g(P) transitions in addition to a band at 24 600 cm−1
The change of magnetic moment and the IR spectra of the
dehydrated complexes indicated the bidentate nature of CH3COO−
and NO3−. The Ni(II) complete 6-coordinate through association
of complex molecules via phenolic oxygen and thione sulfur of
coumarine ring. This color change of the Ni(II) complexes can be
which may be due to the charge transfer transition. These bands
with the magnetic moment value of 5.09 B.M. suggest forma-
tion of Oh geometry around Co(II) ion [25]. [Ni(L)(NO3)]·2H2O
complex (11) spectrum showed two bands at 16 950 cm−1 and
expressed by the following equations [22]:
-2H2O, -EtOH
[Ni(L)Cl(H2O)2].EtOH
Octahedral (2)
(μ = 2.47 B.M.)
Brown yellow
[Ni(L)Cl]
Square planar
(Dia; (μ = 0.0 B.M)
Brown red
[Ni(L)Cl]n
Octahedral
(μ = 3.30 B.M.)
Green
∆H < 210 °C
∆H < 100 °C
-2H2O
∆H < 200 °C
[Ni(L)(NO3)].2H2O
Octahedral
[Ni(L)(NO3)]
Octahedral
(μ = 3.20 B.M.)
Green
(μ = 2.90 B.M.)
Brick red
-2H2O
[Ni(L)(CH3COO)(H2O)2]
Octahedral
[Ni(L)(CH3COO)]
Octahedral
∆H < 200 °C
(μ = 3.00 B.M.)
Green Yellow
(μ = 2.85 B.M.)
Reddish brown
The suggested structure of the polymeric [Ni(L)Cl]n complex
results from the dehydration process of [Ni(L)Cl] complex at 200 ◦C
is depicted in Fig. 1.
3
3
19 950 cm−1 which may be due to A2g → T1g(P) transition and
the magnetic moment of 3.2 B.M. suggest the octahedral geometry.
While [Cu(L)(NO3)(H2O)2] complex (8) give a band at 18 100 cm−1
In addition, the complex where heated in often to 100 ◦C, ele-
mental analysis of the product indicate loss of lattice solvent
molecule. They also subjected to heating up to 700 ◦C in porcelain
crucible, pyrolysis, to form the oxides; the formed oxides are nearly
close to the calculated values.
which is corresponding to 2B1g → Eg transition, and a shoulder at
2
27 300 cm−1. This is may be due to a distorted octahedral around
Cu(II) ion. The magnetic moment value was 2.10 B.M. suggested
distorted octahedral geometry [26].
The molar conductance values of 1 × 10−3 M DMF solution are
in the range (11–28 Ohm−1 mol−1 cm−2) for all complexes which
indicate their non-electrolytic properties [27].
3.2.3. Electronic spectra, magnetic moment and molar
conductance of the transition metal complexes
From the interpretation of elemental analysis and infrared, elec-
tronic spectra, it is possible to draw up the tentative structures of
the transition metal complexes. Fig. 2 depicts the representative
structures of the metal complexes (Table 2).
The visible spectrum of [Cu(L)Cl]·1.5EtOH (1) in DMF, shows
2
band at 15 115 cm−1 represents the 2Eg → T2g transition charac-
teristic of Cu(II) in Oh geometry. The magnetic moment value is 2.09
B.M. for complex (1). This value of the measured magnetic moment,
in practice, is in the range (1.9–2.2 B.M.). This can be used diagnos-
tically to identify the geometry of the Cu(II) complex (1) in the solid
state. From the elemental analysis, it is believed that the Cu(II) com-
plex (1) has a coordination number equal to four, which could be
either square planar or tetrahedral [23]. The change of geometry
from solid state to DMF solution can be explained in terms of sol-
vation of DMF molecules around Cu(II) ion. The absorption band at
24 210 cm−1 explained in terms of CT [24].
3.3. Pharmacodynamics
3.3.1. Biochemical parameters in serum
3.3.1.1. Comparison in one group at different duration. Table 3 shows
the changes between increase and decrease of biochemical param-
eters in each group at different duration. In group (A), the results
show decrease in the level of bilirubin in 6 and 12 days, a decrease
in the level of triacylglycerol at 6 days, but very highly significant
increase in 12 days. In group (B), the results show decrease in the
level of bilirubin in 6, 12 days, highly significant increase in the level
of cholesterol at 6 days but decrease in 12 days and very highly sig-
nificant decrease in the level of triacylglycerol at 6 days, but very
highly significant increase in 12 days. In group (C), the results show
The visible spectrum of [Co(L)(H2O)Cl2]·EtOH complex (4),
showed two bands of about equal intensities and corresponds to
the spin allowed transitions from the 1A1g ground state to the 1T1g
1
and T2g states in the octahedral geometry. The first transition is
broader and occurs in the visible region at 24 096 cm−1, while the
other transition has its band at 18700 cm−1. The two forbidden

40
A.I. Mosa et al. / Spectrochimica Acta Part A 81 (2011) 35–43
Fig. 1. Dehydration process of the nickel(II) complex (2): (A) complex (2) without heating, (B) complex (3) produced after heating complex (2) to 100 ◦C, and (C) polymeric
form produced after heating complex (2) to 200 ◦C.
decrease in the level of bilirubin in 6, 12 days, an increase in the
level of cholesterol at all duration, highly significant increase in the
level of triacylglycerol in 6 days. In group (D), the results show a
decrease in the level of bilirubin in 6 and 12 days, an increase in
the level of cholesterol in 6 days but decrease in 12 days and highly
significant increase in the level of triacylglycerol in both 6 and 12
days. In group (E), the results show slightly decrease in the level
of bilirubin in 6 and 12 days, an increase in the level of cholesterol
in 3, 6 and 12 days, and significant increase in the level of triacyl-
glycerol in 12 days but decrease in 6 days. In group (F), the results
show no change in the level of bilirubin in 3, 6 and 12 days, and an
increase in the level of cholesterol in 6, 12 days but decrease in the
level of triacylglycerol in 6, 12 days compared with 3 days. These
results are due to the presence of many components in the HL lig-
and and its complex which may have the new interaction between
it in different doses which have effect on the groups of these study.
increase in 6 days between A(D), A(E), A(F), B(D), B(E), B(F), C(D) and
C(E), also increase in 12 days in A(E), A(F), C(E), C(F), B(C), C(D), D(E)
and D(F). Significant decrease in 3 days between A(D), A(F) and C(D).
While decrease in 3 days between A(B), A(E), B(D), B(F), C(E), C(F)
and E(F). Additionally, decrease in 6 days between A(C) and B(C)
and in 12 days between A(B), A(C), B(D) and E(F). Similar results in
3 days between A(B) and A(E), also similar in 6 days between A(B),
D(E), D(F) and E(F) and in 12 days A(D).
A significant increase in the level of cholesterol at 3, 6 and 12
days between C(D) and B(F) respectively. An increase in 3 days
between A(B), A(D) and B(F), increase in 6 days between A(B) and
A(D) Additionally, increase in 12 days between B(C), B(D), B(E),
C(E), C(F), D(E) and D(F). But highly significant decrease in 12 days
between A(B). Significant decrease in 6 days between B(C) and B(E),
also significant decrease in 12 days between A(D). A decrease in 6
days between A(E), B(D), B(F), C(E), C(F), D(E), D(F) and E(F), also
decrease in 12 days between A(E), A(F), C(D). Decrease in all dura-
tion between A(C).
3.3.1.2. Comparison between groups at different duration.
Tables 3 and 4 illustrate the results before activities changed
and the levels of biochemical parameters between the groups at
different duration.
A significant increase in the level of bilirubin at 12 days between
B(E) an increase in 3 days between A(C), B(C), D(E) and D(F), an
A very highly significant increase in the level of triacylglycerol
at 3 days between A(B), B(C), B(D), B(E), B(F) and C(D). Very highly
significant increase in 6 days between A(D), B(E), C(D), D(E) and
D(F) and very highly significant increase in 12 days between A(B),
A(C), A(D), A(E), A(F), B(C), B(D), B(E), B(F) and C(D). Highly signif-
Fig. 2. Representative structures of the transition metal complexes of the HL ligand.

A.I. Mosa et al. / Spectrochimica Acta Part A 81 (2011) 35–43
41
Table 2
Electronic spectral data (cm−1)a, magnetic moment and molar conductance of the transition metal complexes of 4-hydroxy coumarin-3-thiocarbohydrazone, HL, ligand.
Complex
ꢂ (cm−1
)
d–d transition
2Eg 2T2g
ꢀeff (B.M.)
Geometry
Molar conductance (ꢃ)b
1
[Cu(L)Cl]·1.5EtOH
15 115(0.85)
24 210(0.16)
14 300(0.11))
–
→
2.09
Octahedral
18.19
Charge transfer
2
3
4
[Ni(L)(H2O)2Cl]·EtOH
[Ni(L)Cl]
[Co(L)(H2O)Cl2]·EtOH
3A1g
–
→
3T2g
2.47
Diamagnetic
Diamagnetic
Octahedral
Square planar
Octahedral
13.30
14.83
16.64
24 096(0.02)
18 700(0.02)
38 100(0.14)
23 900(0.07)
17 150(0.09)
23 900(0.17)
17 391(0.87)
10 100(0.14)
27 300(sh)(0.08)
12 500(0.04)
15 620(0.07)
21 200(0.09)
–
16 950(0.09)
19 950(0.07)
–
17 350(0.06)
21 330(0.03)
24 600(0.08)
1A1g
1A1g
→
→
1T1g
1T1g
5
[Cr(L)Cl2(H2O)]·H2O
CT (L → M)
3.18
Octahedral
11.23
4A2g(F) → 4T2g(F)
6
7
8
[Fe(L)Cl2(EtOH)]
[Cu(L)(CH3COO)(H2O)2]
[Cu(L)(NO3)(H2O)2]
CT (L → M)
5.87
1.81
2.10
Octahedral
Octahedral
Octahedral
14.14
17.87
22.36
Eg
→
3T2g(G)
→
2B1g
2Eg
9
[Ni(L)(CH3COO)(H2O)2]
3A2g
3A2g
3A2g
–
→
→
→
3T2g
3.60
Octahedral
25.49
3T1g(F)
3T1g(P)
10
11
[Ni(L)(CH3COO)]
[Ni(L)(NO3)]·2H2O
Diamagnetic
3.2
Square planar
Octahedral
27.93
24.34
3A2g
→
3T1g(P)
12
13
[Ni(L)(NO3)]
[Co(L)(H2O)2(NO3)]·H2O
–
Diamagnetic
4.96
Square planar
Octahedral
22.01
23.45
4
4T1g(F) → A2g
4
4T1g(F) → T2g(P)
CT (L → M)
a
Electronic spectra in the visible region recorded in DMF and the values of εmax are in parentheses and multiplied by 10−4 (mol−1 cm−1). The electronic transition from
the ligands which observed in all metal complexes within the range (22 000–50 000 cm−1) is not cited in the table.
b
Molar conductance (ꢄ−1 cm−2 mol−1) was measured in (1 × 10−3 mol−1 cm−1) DMF solvent.
icant increase in 3 days between A(C) and C(F), in 6 days between
A(B) and B(D) and in 12 days in D(E). Significant increase in 3 days
between C(D), D(E) and E(F), in 6 days between B(C), C(E) and E(F),
and in 12 days between D(F).
C(D). Highly significant increase between A(D). Significant increase
between A(B), C(F) and E(F). An increase between A(F). Slightly
increase between B(D). A decrease between D(E) and D(F). Slightly
decrease between A(C), A(E) and B(F). Similar between C(E).
The results of this study demonstrated that the complex at low
dose has better effect than at high dose and the ligand has signifi-
cant effects at both high and low doses on the biochemical analysis
in serum and heart tissue.
3.3.2. Biochemical parameters in tissues
Table 5 shows some key enzymatic and non-enzymatic bio-
chemical parameters. A very highly significant increase in the
level of glucose between A(D) and C(D). Highly significant increase
between A(B) and B(D). An increase between A(C), A(F) and E(F).
Slightly increase between C(F). A very highly significant decrease
between D(E). Highly significant decrease between B(E) and D(F).
Decrease between A(E), B(C), B(F) and C(E). Very highly signifi-
cant increase in the activity of CPK between A(B), A(D), A(F), C(D),
E(F) and A(C). An increase between A(E) and B(D). A very highly
significant decrease between B(E), D(E), B(C) and D(F). Significant
decrease between B(F) and C(E). Similar results between C(F). Also,
very highly significant increase in the activity of LDH between
3.4. Microbiological activity
The HL and its [Co(L)(H2O)Cl2]·EtOH complex (4) yield clear
inhibition zones around the disc. These showed their activity
against Gram-negative bacteria; C. albicans, E. coli and K. pneumo-
niae and P. aeruginosa. The complex and the free HL ligand showed
significant activity for C. albicans, E. coli and weak activity against
P. aeruginosa and P. aeruginosa.
The results revealed that the free ligand is most effective
against E. coli and K. pneumoniae with 100 ␮g/ml while the
Table 3
Effect of HL ligand and its [Co(L)(H2O)Cl2]·EtOH complex on some biochemical parameters; bilirubin (mg/dl), cholesterol (mg/dl) and triacylglycerol (mg/dl) in serum of the
rat groups at different durations.
Parameters
Days
Groups
A
B
C
D
E
F
X
S.D.
X
S.D.
X
S.D.
X
S.D.
X
S.D.
X
S.D.
Bilirubin (mg/dl)
3 days
6 days
12 days
0.16 0.08
0.08 0.01
0.08 0.01
0.1 0.08
0.08 0.03
0.06 0.01
0.2 0.07
0.07 0.02
0.07 0.02
0.08 0.02
0.09 0.01
0.08 0.02
0.1 0.06
0.09 0.005
0.1 0.06
0.09 0.01
0.09 0.01
0.09 0.01
Cholesterol (mg/dl)
Triacyglycerol (mg/dl)
3 days
6 days
12 days
62.3 6.5
76.7 23
81.3 15.9
64.3 4.5
89.7 7b
54.3 16.3
58.3 4.9
71.3 7.1
68.0 9.6
77.7 4.2
80.3 10.5
63.3 3.8
65.7 4.2
67.3 8.7
70 1.7
69.7 7.8
73.3 4.7
72.7 9.1
3 days
6 days
12 days
65.3 4.7
52.7 8.7
223 12.8a
159 5.3
81 5.2b
35.0 5.6
61.7 6.5b
49.7 15.9
59.0 8.2
49 2.6
39.7 6.5
65.3 9.3
61.0 24.6
62.0 14.4
108.7 3.5a
84.0 18.4c
253.3 7.6a
51.7
8
(A) is a control group takes 25 mg/kg, (B) is a control group takes 5 mg/kg, (C) group is taking [Co(L)(H2O)Cl2]·EtOH 25 mg/kg, (D) is taking HL ligand 25 mg/kg, (E) group is
taking [Co(L)(H2O)Cl2]·EtOH 5 mg/kg and (F) group is taking HL ligand 5 mg/kg.
a
Very highly significant increase P < 0.001.
Highly significant increase P < 0.01.
Significant increase P < 0.05. X S.D. = mean standard deviation.
b
c

42
A.I. Mosa et al. / Spectrochimica Acta Part A 81 (2011) 35–43
Table 4
Effect of HL ligand and its [Co(L)(H2O)Cl2]·EtOH complex for the activity changes and the difference between the values of the two groups for bilirubin (mg/dl), cholesterol
(mg/dl) and triacylglycerol (mg/dl) in serum between the rate groups at different durations.
Bilirubin (mg/dl)
3 days
Cholesterol (mg/dl)
Triacyglycerol (mg/dl)
Duration
Groups
6 days
12 days
3 days
6 days
12 days
3 days
6 days
12 days
P
Sig.
N.S.
P
Sig.
P
Sig.
P
Sig.
P
Sig.
P
Sig.
P
Sig.
P
Sig.
P
Sig.
**
***
**
**
***
***
***
***
***
***
***
***
***
***
A (B)
A (C)
A (D)
A (E)
A (F)
B (C)
B (D)
B (E)
B (F)
C (D)
C (E)
C (F)
D (E)
D (F)
E (F)
0.105
0.680
0.017
0.26
0.0028
0.22
0.918
0.757
0.836
0.606
0.757
0.836
0.757
0.537
0.680
0.606
0.411
0.537
0.757
1
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
0.537
0.836
1
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
0.810
0.631
0.072
0.684
0.381
0.473
0.116
0.873
0.523
0.025
0.381
0.179
0.155
0.340
0.631
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
0.125
0.523
0.660
0.266
0.689
0.033
0.266
0.010
0.056
0.033
0.284
0.631
0.125
0.403
0.473
N.S.
N.S.
N.S.
N.S.
0.002
0.116
0.036
0.179
0.301
0.107
0.284
0.066
0.033
0.576
0.810
0.576
0.425
0.266
0.749
0.000
0.002
0.480
0.074
1
0.000
0.000
0.000
0.000
0.010
0.124
0.002
0.036
0.480
0.074
0.003
0.318
0.000
0.152
0.354
0.036
0.004
0.000
0.031
0.000
0.018
0.941
0.000
0.000
0.022
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.823
0.173
0.001
0.018
0.250
N.S.
N.S.
N.S.
*
*
***
N.S.
N.S.
N.S.
0.122
0.836
0.680
0.537
0.036
0.411
0.836
0.086
0.680
0.128
0.836
0.185
N.S.
N.S.
N.S.
N.S.
N.S.
*
N.S.
N.S.
N.S.
*
***
*
N.S.
N.S.
N.S.
***
***
***
*
**
***
*
0.41
N.S.
N.S.
*
*
0.606
0.537
0.045
0.472
0.069
0.185
0.836
0.260
N.S.
*
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
*
*
*
***
*
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
N.S.
**
N.S.
N.S.
*
***
**
***
*
*
N.S.
*
0.836
N.S.
(A) is a control group takes 25 mg/kg, (B) is a control group takes 5 mg/kg, (C) group is taking [Co(L)(H2O)Cl2]·EtOH 25 mg/kg, (D) is taking HL ligand 25 mg/kg, (E) group is
taking [Co(L)(H2O)Cl2]·EtOH 5 mg/kg and (F) group is taking HL ligand 5 mg/kg.
***
The mean difference is very highly significant at P < 0.001
The mean difference is highly significant at P < 0.01.
The mean difference is significant at P < 0.05.
**
*
N.S. is not significant.
Table 5
Effect of HL ligand and its [Co(L)(H2O)Cl2]·EtOH complex on glucose (mg/g tissue), lactate dehydrogenase (LDH) (␮mol/min/mg protein) and creatine phosphokinase (CPK)
(␮mol/min/mg protein) of heart in (A, B, C, D, E, F) groups at different duration.
Parameters
Groups
A
B
C
D
E
F
X
S.D.
X
S.D.
X
S.D.
X
S.D.
X
S.D.
X
S.D.
Glucose (mg/g tissue)
LDH (␮mol/min/mg protein)
CPK (␮mol/min/mg protein)
3.9 0.5
1.7 0.2
0.1 0.03
5.0 0.6**
2.2 0.3*
4.3 0.5
1.6 0.3
0.2 0.01**
5.9 0.4
2.4 0.2**
0.3 0.02
3.8 0.4*
1.6 0.2
0.1 0.01
4.5 0.3
2.1 0.2
0.2 0.01*
0.24 0.02***
(A) is a control group takes 25 mg/kg, (B) is a control group takes 5 mg/kg, (C) group is taking [Co(L)(H2O)Cl2]·EtOH 25 mg/kg, (D) is taking HL ligand 25 mg/kg, (E) group is
taking [Co(L)(H2O)Cl2]·EtOH 5 mg/kg and (F) group is taking HL ligand 5 mg/kg. X S.D. = mean standard deviation.
*
Significant P < 0.05.
Highly significant P < 0.01.
Very highly significant P < 0.001.
**
***
Table 6
Antifungal and antibacterial effects of the HL and [Co(L)(H2O)Cl2]·EtOH complex (100 ␮m/cm).
Treatment
Inhibition zone (mm)
Fungi
Bacteria
A. niger
A. flavus
A. fumigatus
C. albicans
E. coli
K. pneumoniae
P. aeruginosa
Control (DMF)
HL
[Co(L)(H2O)Cl2]·EtOH
9
21
16
9
21
17
7
11
8
11
28
20
15
26
23
8
13
18
13
14
13
[Co(L)(H2O)Cl2]·EtOH complex (4) proved to be the best against
P. aerogenes, it could not reach the effectiveness of the ligand
[28]. At the same time HL and [Co(L)(H2O)Cl2]·EtOH complex
(4) were screened in order to evaluate their antifungal activity
against the filamentous fungi A. niger, A. flavus, and A. fumigatus.
Table 6 lists the antifungal and antibacterial effects of the HL and
[Co(L)(H2O)Cl2]·EtOH complex (4).
metal complexes were characterized by elemental analysis, differ-
ent spectral data, molar conductance and magnetic measurements
and thermal gravimetric analysis. The HL ligand acts as a monoba-
sic tridentate ONS donor in all metal complexes, and coordinated
through the phenolic OH, azomethine nitrogen and thione sulfur.
The complexes have varieties of geometrical structures. Pharma-
codynamic of cobalt(III) complex on some biochemical parameters
and histological studies in serum and heart tissue in rats have been
studied. Although the complexes demonstrated a significant effect
at low dose than the high dose, the ligand showed significant good
effects in both high and low doses on the biochemical analysis in
serum and heart tissue. Cobalt(III) complex was screened in order
to evaluate its antifungal activity against the filamentous Gram-
negative bacteria; C. albicans, E. coli, K. pneumoniae and P. aeruginosa
and fungi; A. niger, A. flavus, and A. fumigatus.
The HL ligand revealed that it is most effective in all cases than
the [Co(L)(H2O)Cl2]·EtOH complex (4).
4. Conclusion
A
new series of stable copper(II), nickel(II), cobalt(III),
chromium(III) and iron(III) complexes of 4-hydroxy-coumarin-3-
thiocarbohydrazone ligand were prepared. The HL ligand and its

A.I. Mosa et al. / Spectrochimica Acta Part A 81 (2011) 35–43
43
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