Metal complexes: Preparation, magnetic, spectral, and biocidal studies of some mixed-ligand complexes with schiff bases containing NO and NN donor atoms

Article abstract of DOI:10.1081/SIM-120030440

Metal complexes of the types [M(SB¹)₂acphen] and [M(SB²)₂acphen] where M = Mn(II), Co(II), Ni(II), Cu(II), and Cd(II); HSB¹ = 5-chlorosalicylidene-p-anisidine and HSB ² = 5-bromosalicyliden

Full text of DOI:10.1081/SIM-120030440

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Metal Complexes: Preparation, Magnetic, Spectral,
and Biocidal Studies of Some Mixed‐Ligand
Complexes with Schiff Bases Containing NO and NN
Donor Atoms
Prakash P. Dholakiya a & M. N. Patel a
a Department of Chemistry , Sardar Patel University , Vallabh Vidyanagar, 388 120,
Gujarat, India
Published online: 16 Nov 2010.
To cite this article: Prakash P. Dholakiya & M. N. Patel (2004) Metal Complexes: Preparation, Magnetic, Spectral, and
Biocidal Studies of Some Mixed‐Ligand Complexes with Schiff Bases Containing NO and NN Donor Atoms, Synthesis and
Reactivity in Inorganic and Metal-Organic Chemistry, 34:3, 553-563, DOI: 10.1081/SIM-120030440
To link to this article: http://dx.doi.org/10.1081/SIM-120030440
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 34, No. 3, pp. 553–563, 2004
Metal Complexes: Preparation, Magnetic,
Spectral, and Biocidal Studies of Some
Mixed-Ligand Complexes with
Schiff Bases Containing NO
and NN Donor Atoms
*
Prakash P. Dholakiya and M. N. Patel
Department of Chemistry, Sardar Patel University,
Vallabh Vidyanagar, Gujarat, India
ABSTRACT
Metal complexes of the types [M(SB1)2acphen] and [M(SB2)2acphen]
where M ¼ Mn(II), Co(II), Ni(II), Cu(II), and Cd(II); HSB1 ¼
5-chlorosalicylidene-p-anisidine and HSB2 ¼ 5-bromosalicylidene-p-
anisidine have been prepared and characterized. Magnetic suscepti-
bility measurements, elemental analyses, electro-nic, and infrared
spectral data suggest six-coordinated octahedral structures for these
complexes. The mixed-ligand complexes show higher activity against
Saccharomyces cereuisae, Salmonella typhi, Fasarium oxysporum,
*
Correspondence: M. N. Patel, Department of Chemistry, Sardar Patel University,
Vallabh Vidyanagar, 388 120 Gujarat, India; E-mail: jeenenpatel@yahoo.co.in.
553
DOI: 10.1081/SIM-120030440
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Dholakiya and Patel
and Lasiodiplodia theobromae as compared to the ligand, metal salts,
and control.
Key Words: Metal complexes; Biocidal studies; Schiff bases; Electronic
spectra.
INTRODUCTION
Schiff bases containing the –RC55N– group have gained importance
because of their physiological and pharmacological activities.[1] They consti-
tute an interesting class of chelating agents capable of coordination with one
or more metal ions giving mononuclear as well as polynuclear metal com-
plexes, which serve as models for metalloproteins.[2] In continuation of earlier
work[3] we report in the present communication the preparation, magnetic,
spectral and biocidal studies of Mn(II), Co(II), Ni(II), Cu(II), and Cd(II)
complexes with 5-chlorosalicylidene-p-anisidine or 5-bromosalicylidne-p-
anisidine as primary ligands and bis(acetophenone)ethylenediamine as a
secondary ligand.
The structures of the ligands are shown in Fig. 1.
Figure 1. Structures of the ligands.

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555
EXPERIMENTAL
Preparation of the Schiff Bases
The preparation of 5-chlorosalicylidene-p-anisidine or 5-bromosali-
cylidene-p-anisidine was carried out by refluxing a solution 10 mmol of
p-anisidene (1.23 g) in 100 mL ethanol with a solution of 10 mmol of 5-chloro-
salicylaldehyde (1.56 g) or 5-bromosalicylaldehyde (2.00 g) in 100 mL etha-
nol for 2–3 hr. The reaction mixture was then allowed to cool to room
temperature overnight. The yellow crystals were collected and dried in air.
The preparation of bis(acetophenone)ethylenediamine was carried out by
refluxing a solution of 2 mmol of acetophenone (0.240 g) in 100 mL ethanol
and a solution of 1 mmol of ethylenediamine (0.06 g) in 100 mL ethanol
for 3–4 hr. The reaction mixture gave the Schiff base in the form of yellow
crystals. The product was filtered and washed with ether and dried in air.
Preparation of the Complexes
bis(5-Chlorosalicylidene-p-anisidine)diaquoM(II) or bis(5-bromosali-
cylideneaniline)diaquaM(II), [M ¼ Mn(II), Co(II), Ni(II), Cu(II), and
Cd(II)] were synthesized by a published procedure.[4] The preparation of the
mixed-ligand complexes of bis(5-chlorosalicylidene-p-anisidine)acphenNi(II)
or bis(5-bromosalicylidene-p-anisidine)acphenNi(II) was carried out by
refluxing a solution of bis(5-chlorosalicylidene-p-anisidine)diaquaNi(II)
(2mmol, 1.23 g) or bis(5-bromosalicylidene-p-anisidine)diaquaNi(II) (2mmol,
1.42g) with dimethylformamide (100mL) solution of bis(acetophenone)ethyl-
enediamine (2 mmol, 0.52 g) for an hour. The solution was then concentrated
to 15 mL, scratched and cooled in a refrigerator overnight. The obtained crys-
tals were collected and recrystallized from chloroform. Finally, the crystals
were dried in air. The complexes of Mn(II), Co(II), Cu(II), and Cd(II) were
prepared similarly.
Analytical Procedure
Elemental analyses for carbon, hydrogen, and nitrogen were analyzed
with a model 240 Perkin-Elmer elemental analyzer. Metal contents were
determined by EDTA titration. The electronic spectra were recorded on a
Beckman DK-2A spectrophotometer using MgO as a reference. The infrared
spectra were measured on a FT-IR Nicolet 400 D spectrophotometer in KBr
pellets. The melting points of the ligands and complexes were recorded in

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Dholakiya and Patel
open capillaries in a capillary melting point apparatus (Tempo Instruments
Co., Mumbai). The magnetic moments have been obtained in the solid state
by a model 7304 vibrating sample magnetometer.
RESULTS AND DISCUSSION
The analytical data, colours, yields, and melting points of the ligands
and complexes are presented in Table 1. The complexes were synthesized
following the general procedures outlined by the following equations.
H2O
MCI2 ꢀ nH2O þ 2HSB1 ꢁ!½MðSB1Þ2ðH2OÞ2ꢂ þ 2HCl
ð1Þ
EtOH; Reflux
½MðSB1Þ2ðH2OÞ2ꢂ þ acphen ꢁ!½MðSB1Þ2acphenꢂ þ 2H2O ð2Þ
1hour
H2O
MCI2 ꢀ nH2O þ 2HSB2 ꢁ!½MðSB2Þ2ðH2OÞ2ꢂ þ 2HCl
ð3Þ
EtOH; Reflux
½MðSB2Þ2ðH2OÞ2ꢂ þ acphen ꢁ!½MðSB2Þ2acphenꢂ þ 2H2O ð4Þ
1hour
Magnetic Measurements
The magnetic moment data are presented in Table 1. In the present
case the magnetic moment values of [Mn(SB1)2acphen] and [Mn(SB2)2
acphen] are 6.1 and 5.9 B.M., respectively, which is within the limits of
the spin-free value for five unpaired electrons, indicating that the complexes
are high-spin d5 system with an octahedral geometry.[5] The magnetic
moment data of [Co(SB1)2acphen] and [Co(SB2)2acphen] are 4.71 and
4.60 B.M., respectively,[6] suggesting an octahedral geometry. The magnetic
moment data of [Ni(SB1)2acphen] and [Ni(SB2)2acphen] are 2.88 and
2.81 B.M., respectively, which are in the usual range expected for similar
hexa-coordinated Ni(II) ions.[7] The magnetic moment data of [Cu(SB1)2
acphen] and [Cu(SB2)2acphen] are 1.75 and 1.76 B.M., respectively,
which are very close to the spin-only value (1.73 B.M.) expected for one
unpaired electron, which offers the possibility of an octahedral geometry.[8]
The magnetic moment determinations show that the Cd(II) complexes are
diamagnetic.

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557
m

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Dholakiya and Patel
Electronic Spectra
The electronic spectra of the complexes were recorded in the solid phase at
room temperature. The electronic spectra of the Mn(II) complexes[9] gave three
bands at ꢀ15,000, ꢀ19,000 and ꢀ25,500 cm21. These bands may be assigned
4
4
4
to the 6A1g ! T1g(4G) (n1), 6A1g ! T2g(4G) (n2) and 6A1g ! A1g, 4Eg(4G)
(n3) transitions in order of increasing energy. The electronic spectra
of the Co(II) complexes exhibit three bands at ꢀ9,300, ꢀ18,000, and
ꢀ19,000 cm21, which may be reasonably assigned[10] to the T1g(F) !
4
4T2g(F) (n1), 4T1g(F) ! A2g(n), and 4T1g(F) ! T1g(P) (n3) transitions, con-
sistent with an octahedral geometry around the metal ion. The electronic spectra
of the Ni(II) complexes gave three bands at ꢀ10,500, ꢀ18,000 and
4
4
ꢀ24,000 cm21, which may be ascribed[11] to the 3A2g(F) ! T2g(F) (n1), 3A2g
3
(F) ! T1g(F) (n2) and 3A2g(F) ! T1g(P) (n3) transitions, respectively, corre-
sponding to an octahedral geometry of the Ni(II) ion. The electronic spectra of
the Cu(II) complexes exhibit one band at ꢀ15,000 cm21 assignable to the 2Eg -
3
3
! T2g(F) transition, corresponding[12] to an octahedral geometry of the Cu(II)
2
ion. The value of the ligand field splitting energy (Dq), Racah interelectronic
repulsion parameter (B), nephelauxetic ratio (b), and ratio y2/y1 for the
Ni(II) and Co(II) complexes are presented in Table 2.
Infrared Spectra
A comparision of the characteristic IR absorption bands of the ligands
with those of the corresponding Mn(II), Co(II), Ni(II), Cu(II), and Cd(II)
complexes reveals the following important features. In the infrared spectra
of the 5-chlorosalicylidene-p-anisidine and 5-bromosalicylidene-p-anisidine
ligands, a relatively sharp band appearing at ꢀ2700 cm21 may be assigned
to the y(OH) vibrations.[13] The absence of this band in the complexes indi-
cates the deprotonation of the phenolic groups and coordination of the oxygen
atoms to the metal ion. In the free ligand, a strong band at ꢀ1525 cm21 due to
n(C–O) (phenolic) shifts to higher energy by 5–10 cm21 in the complexes
indicating the coordination of the phenolic oxygen atom to the metal ion.[14]
This shift of the band to higher energy is expected due to the maintenance of
ring currents arising from the electron delocalization in the chelate ring.
The n(C ¼ N) frequency of the bis(acetophenone) ethylenediamine, 5-chloro-
salicylidene-p-anisidine, and 5-bromosalicylidene-p-ani- sidine ligands occur
at ꢀ1640 cm21. This band shifts to lower energy by 10–20 cm21 in the
mixed-ligand complexes indicating coordination through the azomethine
nitrogen.[15] The complexes of 5-chlorosalicylidene-p-anisidine exhibit a

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559
b

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Dholakiya and Patel
band at ꢀ725 cm21 due to n(C–Cl).[16] The complexes of 5-bromosalicylidene-
p-anisidine exhibit band at ꢀ690 cm21 due to n(C–Br).[17] The frequencies in
the range 2815–2830cm21 and 1370–1385cm21 are due to n(C–OCH3)[18]
and n(C–CH3),[19] respectively. The frequencies in the range 450–460 cm21
and 410–420 cm21 are attributed to n(M–N)[20] and n(M–O),[21] respectively.
The suggested structures of the complexes are shown in Fig. 2.
Antimicrobial Activity
The antimicrobial activity of the ligand, the metal salts and their corres-
ponding complexes were tested against Salmonella typhi (bacteria), Sacchar-
omyces cereuisae (yeast), and two fungal species Lasiodiplodia theobromae
and Fusarium oxysporum. The antimicrobial activities of the compounds
were tested against bacteria and yeast using the “Agar Diffusion Method”.[22]
The fungal activity of the complexes has been screened against Lasiodiplodia
theobromae and Fusarium oxysporum using the “Potato Dextrose Agar
Method”.[23] All of the compounds have significant antimicrobial activity at
5 ꢃ 1024 g mL21 against bacteria, yeast, and fungi. The compounds are sol-
uble in dimethylformamide. Therefore, the growth was compared with
dimethylformamide as the control and is expressed as percentage inhibition
Figure 2. Suggested structure of the complexes.

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561
Table 3. Antimicrobial activities of the complexes.a
% Inhibition
Fungi
Lasiodiplodia
theobromae
Bacteria—
Salmonella
typhi.
Yeast—
Saccharomyces
cereuisae
Fusarium
oxysporum
Compounds
.
MnCl2 4H2O
22.22
15.16
11.11
22.20
16.66
22.22
27.77
38.88
55.00
50.00
55.00
61.11
44.40
61.11
50.00
61.11
50.00
50.00
21.05
10.52
8.26
20.00
06.60
10.30
20.00
06.60
06.60
13.30
26.00
33.30
33.30
33.30
40.00
40.00
36.60
46.60
47.00
45.00
40.00
15.30
07.70
10.30
15.30
07.70
23.00
37.00
23.00
46.00
53.00
46.00
46.00
53.00
46.00
47.00
50.00
53.00
45.00
.
CoCl2 6H2O
.
NiCl2 6H2O
.
CuCl2 2H2O
15.78
08.26
15.78
26.31
10.50
57.89
68.42
57.89
63.15
63.15
57.89
47.36
52.63
52.63
52.89
.
CdCl2 2H2O
HSB1
HSB2
acphen
[Mn(SB1)2acphen]
[Co(SB1)2acphen]
[Ni(SB1)2acphen]
[Cu(SB1)2acphen]
[Cd(SB1)2acphen]
[Mn(SB2)2acphen]
[Co(SB2)2acphen]
[Ni(SB2)2acphen]
[Cu(SB2)2acphen]
[Cd(SB2)2acphen]
aHSB1, 5-chlorosalicylidene-p-anisidene; HSB2, 5-bromosalicylidene-p-anisidene.
vs. controls. The percentage inhibition of various compounds are recorded in
Table 3. The data represents the values of the five replicates. From the data it is
observed that the complexes show higher activity against bacteria, yeast, and
fungi as compared to the control (blank), the ligands and metal salts. The
results suggest that the changes in structure due to the coordination in the com-
plexes decreases the growth of microorganisms relative to the metal ion and
ligands. Hence, complexation increases the antimicrobial activity due to pre-
sence of two halogen and four azomethine (C55N) groups. The complexes
show higher activity against Salmonella typhi and Fusarium oxysporum as
compared to Saccharomyces cereuisae and Lasiodiplodia thebromae. The
complexes are more active against Fusarium oxysporum as compared to
Lasiodiplodia thebromae. The patterns of activity are complex and no clear
trend can be ascertained.

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Dholakiya and Patel
ACKNOWLEDGMENTS
The authors are thankful to the Head, Department of Chemistry, and
Head, Department of Bio-Sciences, Sardar Patel University, Vallabh Vidya-
nagar, India, for providing the necessary laboratory facilities.
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Received July 8, 2003
Accepted December 1, 2003
Referee I: S. L. Phillips
Referee II: D. E. Pennington

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