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Department of Chemistry, Zakir Husain Delhi College, University of Delhi, JLN-Marg, New Delhi 110002, India
Department of Chemistry, School of Sciences, IGNOU, Maidan Garhi, New Delhi 110068, India
Dairy Microbiology Division, National Dairy Research Institute, Karnal 132001, Haryana, India
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Synthesis of 2-aminobenzamide
a r t i c l e
i n f o
Article history:
Received 25 October 2014
Received in revised form 19 December 2014
Accepted 4 February 2015
Available online 13 February 2015
Keywords:
Schiff base
Ni(II)
Co(II) and Cu(II) complexes
Spectroscopic studies
Antimicrobial activity
DFT calculations
a b s t r a c t
A series of two biologically active Schiff base ligands L1, L2 have been synthesized in equimolar reaction of
2-aminobenzamide with pyrrol-2-carboxaldehyde and furan-2-carboxaldehyde. The synthesized Schiff
bases were used for complexation with different metal ions like Co(II), Ni(II) and Cu(II) by using a molar
ratio of ligand: metal as 2:1. The characterization of newly formed complexes was done by 1H NMR, UV
Vis, TGA, IR, mass spectrophotometry, EPR and molar conductivity studies. The thermal studies suggested
that the complexes are more stable as compared to ligand. In DFT studies the geometries of Schiff bases
and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On
the basis of the spectral studies an octahedral geometry has been assigned for Co(II) and Ni(II) complexes
and distorted octahedral geometry for Cu(II) complexes. All the synthesized compounds, were studied for
their in vitro antimicrobial activities, against four bacterial strains and two fungal strains by using serial
dilution method. The data also revealed that the metal complexes showed better activity than the ligands
due to chelation/coordination.
2015 Elsevier B.V. All rights reserved.
Introduction
In medicinal chemistry, benzamides derivatives are widely used
as antimicrobial agents. Benzamides derivatives are well known to
Corresponding author.
http://dx.doi.org/10.1016/j.saa.2015.02.027
1386-1425/ 2015 Elsevier B.V. All rights reserved.
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
NH2
O
O
+
NH2
Reflux Ethanol
NH2
O
N
L1, L2
N
H2N
N
M
NH2
H2N
O
O
O
O
NH2
X2
7-12
1-6
L1: R=
H
N
, L2: R=
(m, 1H, Ar AH), 7.68 (d, 1H, J = 7.96 Hz, Ar AH), 7.89 (d, 1H,
J = 4.8 Hz, furan AH), 8.09 (s, 2H, D2O exchangeable, ANH2),
8.19(d, 1H, J = 8 Hz, Ar AH), 8.97 (s, 1H, N@CH). Anal. Calcd. for
C12H10N2O2 (214.22): C: 67.28; H: 4.71; N: 13.08; Found: C:
67.33%; H: 4.75%; N: 13.11%. Mass spectrum (ESI) [M]+ = 214.2.
General procedure for the synthesis of metal complexes 112
Preparation of Co(II) complexes with (E)-2-(((1H-pyrrol-2yl)methylene)amino)benzamide L1 (1).
Hot ethanolic solution (15 mL) of CoCl26H2O (2 mmol) was
added drop wise to a magnetically stirred solution of (E)-2-(((1Hpyrrol-2-yl)methylene)amino)benzamide L1 (4 mmol) in ethanol
(20 mL) (Scheme 1). The resultant mixture was reuxed for 10 h.
On keeping the resulting mixture overnight at 0 C, the product
was separated out, which was ltered off, washed with cold ethanol, ether and dried under vacuum over P4O10. The same method
was used for the preparation of other metal complexes. Physical,
analytical and spectral data of ligand and metal complexes are
given in Table 1.
Analysis
The carbon and hydrogen were analyzed on Carlo-Erba 1106
elemental analyzer. The nitrogen content of the complexes was
determined using Kjeldahls method. Molar conductance was measured on the ELICO (CM82T) conductivity bridge. ESI-MS spectra
were obtained using a VG Biotech Quattrro mass spectrometer
equipped with an elctrospray ionization source in the mass range
of m/z 100 to m/z 1000. IR spectra (CsBr) were recorded on FTIR
spectrum BX-II spectrophotometer. NMR spectra were recorded
with a model Bruker Advance DPX-300 spectrometer operating at
400 MHz using DMSO-d6 as a solvent and TMS as internal standard. The electronic spectra were recorded in DMSO on Shimadzu
UV mini-1240 spectrophotometer. Thermogravimetric analysis
(TGA) was carried out in dynamic nitrogen atmosphere
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
Table 1
Physical measurements and analytical data of the ligand (L1, L2) and metal complexes (112).
No.
L
L2
1
2
3
4
5
6
7
8
9
10
11
12
a
C12H11N3O [213.2]
C12H10N2O2 [214.2]
[Co(L1-H)2] [483.2]
C24H20CoN6O2
[Ni(L1-H)2] [483.1]
C24H20N6NiO2
[Cu(L1-H)2] [488.01]
C24H20N6CuO2
[Co(L1-H)2] [483.2]
C24H20CoN6O2
[Ni(L1-H)2] [483.1]
C24H20N6NiO2
[Cu(L1-H)2] [488.01]
C24H20N6CuO2
[Co(L2)2]Cl2 [558.2]
C24H20Cl2CoN4O4
[Ni(L2)2]Cl2.H2O [576.06]
C24H22Cl2N4NiO5
[Cu(L2)2]Cl2 [562.8]
C24H20Cl2CuN4O4
[Co(L2)2](NO3)2 [611.4]
C24H20CoN6O10
[Ni(L2)2](NO3)2 [611.1]
C24H20N6NiO10
[Cu(L2)2](NO3)2 [616]
C24H20CuN6O10
m/z
MP (C)
Yield (%)
Ma
213.21
214.24
483.32
178
184
230
82
77
69
67.45 (67.59)
67.24 (67.28)
59.60 (59.63)
5.17 (5.20)
4.73 (4.71)
4.15 (4.17)
19.76 (19.71)
13.11 (13.08)
17.35 (17.39)
12.17 (12.19)
483.43
232
76
59.62 (59.66)
4.16 (4.17)
17.26 (17.39)
12.13 (12.15)
487.98
237
70
59.04 (59.07)
4.14 (4.13)
17.20 (17.22)
12.98 (13.01)
483.41
228
68
59.58 (59.63)
4.18 (4.17)
17.33 (17.39)
12.13 (12.19)
483.35
225
65
59.60 (59.66)
4.12 (4.17)
17.35 (17.39)
12.10 (12.15)
488.20
242
60
59.01 (59.07)
4.09 (4.13)
17.15 (17.22)
13.01 (13.02)
558.71
220
72
51.60 (51.63)
3.55 (3.61)
9.98 (10.04)
10.53 (10.56)
576.08
231
64
50.12 (50.04)
3.90 (3.85)
9.78 (9.73)
10.21 (10.19)
563.23
236
65
51.17 (51.21)
3.60 (3.58)
9.91 (9.95)
11.25 (11.29)
611.36
231
68
47.12 (47.15)
3.28 (3.30)
13.78 (13.75)
9.61 (9.64)
610.93
219
70
47.16 (47.17)
3.32 (3.30)
13.71 (13.75)
9.55 (9.60)
616.23
227
62
46.72 (46.80)
3.25 (3.27)
13.68 (13.64)
10.28 (10.32)
DFT calculations
Preparation of dilutions
In all, for ligands L1, L2, their metal complexes (112) and standard antimicrobial i.e., Ciprooxacin for antibacterial and Fluconazole for antifungal, 28 tubes of 5 mL capacity were arranged in ve
rows with each row containing 6 tubes. 1.9 mL of brain heart infusion broth was added in the rst tube in each row and then 1 mL in
the remaining tubes. Now, 100 lL of antimicrobial suspension dissolved in dimethyl sulfoxide was added to the rst tube in each
row and then after mixing the content, 1 mL was serially transferred from these tubes to the second tube in each of the rows.
The contents of the second tube of each of the rows were mixed
and transferred to the third tube in each of the rows. This serial
dilution was repeated till the last tube in each of the rows. This
provided antimicrobial compounds concentrations of 50, 25, 12.5,
6.25, 3.125, 1.5625 mg/mL in the rst to sixth tube separately in
each row. Finally, 1 mL of 105 cfu/mL of pathogenic strains suspension was added to the rst, second, third, fourth and fth rows of
tubes respectively. Additionally with the test samples and standard
drug (Ciprooxacin/Fluconazole), the inoculum control (without
antimicrobials) and broth control (without antimicrobials and
inoculum) were also prepared. All the test tubes were then incubated for 18 h at 37 C.
In vitro cytotoxicity
In vitro cytotoxic activity of synthesized ligands L1, L2 and their
metal complexes 112 were studied using the protocol of Meyer
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
H NMR spectra
The 1H NMR spectra have been recorded for ligand L1 and L2.
The spectra of ligand L1 (Fig. 2) displayed azomethine (AHC@N)
proton as a singlet at 8.93 ppm. The pyrrole protons appeared as
a set of doublet and multiplet in the region 7.146.32 ppm.
Similarly, aromatic protons appears as a set of doublets and multiplets in the range 8.157.30 ppm. Pyrrole ANH proton appear as a
singlet in 11.91 ppm for the ligand L1. Similarly, in the spectra of
the ligand L2 the azomethine (AHC@N) proton appeared as a singlet at 8.97. The appeared signals of all the protons of the ligand
L1, L2 were found as to be in their expected region.
IR spectra
The characteristic bands of IR spectra of ligands L1, L2 and their
metal(II) complexes are reported in order to conrm the binding
mode of the Schiff base ligands to the corresponding metal ion.
Both ligands possessed potential donor sites like azomethine linkage (AC@N), amide group (ACONH2), furan (O) and pyrrole (ANH)
groups which have tendency to coordinate with metal ions
(Table 2). Peak corresponding to m(C@O) stretching vibrations
was absent in IR spectra of L1 and, instead, a new band assigned
to azomethine m(HC@N) linkage appeared at 1612 cm1 conrming
the formation of Schiff base [24]. Similarly, the peak at 1615 cm1
in L2 corresponds to m(HC@N) linkage. The IR spectrum of the L1, L2
shows peaks in range 32103240 due to the ANH2 vibrations [25].
The peak at 3112 cm1 in ligand L1 is assigned to (ANH) group of
pyrrole ring [26]. Similarly, the band at 1022 cm1 in ligand L2 corresponds m(CAOAC) stretching vibration of the furan ring [27]. The
comparison of the IR spectra of Schiff base ligands with corresponding metal complexes gave clue of binding modes of the Schiff
base ligand to the corresponding metal ion. The IR band due to
azomethine AN shifts to lower frequency (1422 cm1) 1590
1601 cm1, representing the coordination of azomethine AN in
the complex formation [28]. This is also conrmed by the appearance of new band in spectra of metal complexes in the range of
468492 cm1, which has been assigned to the m(MAN) bond
[29]. The m(C@O) stretching vibration of amide group at
16681670 cm1 in free ligands shifts to a lower side (1652
1658 cm1) in all metal complexes, indicating the coordination of
H
N
m/z 92.10
m/z 106.13
Mass spectra
The ESI mass spectrum of ligand showed a molecular ion peak
at m/z = 231.2 amu corresponding to [M]+, which conrms the proposed formula [C12H11N3O]+ and its base peak was observed at m/z
198. Similarly the molecular ion peak of ligand L2 shows a molecular ion peak at 214.1 and its base peak was observed at m/z 199.
Fragmentation pattern of ligand L1 is shown as Fig. 1. The mass
spectrum of the ligand L1 (Fig. 2) shows a series of peaks at
233.2, 214, 186, and 130 corresponding to various fragments. The
intensities of these peaks give the idea of the stability of the fragments. The fragmentation pattern followed the cleavage of C@N,
CAN and CAC bonds. The mass spectrum of the metal complexes
112 showing the fragmentation model beside the m/z peak value
are given in Table 1.
H
N
O
NH2
NH2
H
N
N
m/z 148.16
m/z 213.24
m/z 52.08
N
m/z 198.23
H
N
H
N
m/z 170.22
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
Fig. 2. (a) NMR spectra of L1 and (b) mass spectrum of ligand L1.
Table 2
Important infrared spectral bands (cm1) and their assignments.
Compound
m(HC@N)
m(CAOAC)
m(C@O)
m(MAO)
m(MAN)
L1
L2
1
2
3
4
5
6
7
8
9
10
11
12
1612
1615
1594
1597
1592
1590
1601
1597
1594
1599
1595
1593
1590
1598
1022
1668
1670
1656
1654
1652
1658
1652
1654
1655
1658
1653
1655
1658
1652
474
468
482
488
492
476
486
485
487
475
479
480
490
1012
1008
1010
1014
1009
1008
512
516
502
518
522
524
514
517
520
518
522
524
the ligands through the oxygen of amide group. The same is also
supported by the appearance of band in region of 502524 cm1,
which corresponds to m(MAO) bond [30]. A noteworthy point in
the IR spectra of all metal complexes is the position of m(NAH)
stretching vibration of NH2 of amide group. Sharp bands at
32103240 cm1 for all complexes have been found to be unaltered and are in the same position as in ligand L1 and L2 [25], which
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
of the metal complexes and lower values shows their non-electrolytic nature. The molar conductance of the metal complexes in
DMF showed values indicating that complexes 16 (1114 ohm1
cm2 mol1) are non-electrolytes and complexes 712 (98
114.4 ohm1 cm2 mol1) are electrolytic in nature. The determined
magnetic moment (BM) values of all the metal complexes, 112 at
room temperature were recorded in Table 3. The magnetic
moment values of Co(II) complexes were found in the range of
4.824.99 BM suggesting the Co(II) complexes as high-spin with
three unpaired electrons in an octahedral environment. The Ni(II)
complexes exhibited magnetic moment values in the range of
2.912.98 BM representative of two unpaired electrons per Ni(II)
ion suggesting these complexes to have octahedral geometry
[31]. The obtained magnetic moment values 1.931.96 BM for
Cu(II) complexes are indicative of one unpaired electron per Cu(II)
ion for d9-system suggesting spin-free distorted octahedral
geometry.
Electronic spectra
The electronic absorption spectra of the Co(II), Ni(II) and Cu(II)
complexes in DMSO were recorded at room temperature and the
band positions of the absorption maxima, band assignments and
the proposed geometry are listed in Table 3. The electronic spectra
of Co(II) complexes generally showed three absorption bands in
the region at 97869892, 17,33417,759 and 29,726
30,150 cm1 which assigned to transitions 4T1g ? 4T2g(F), 4T1g ?
4
A2g(F) and 4T1g ? 4Tg(P), showing an octahedral geometry around
the Co(II) ion. The electronic spectral data of Ni(II) complexes
showed dd bands in the region 10,78511,580, 15,27516,365
and 23,21025,635 cm1 [25] respectively, to assigned the transitions 3A2g(F) ? 3T2g(F), 3A2g(F) ? 3T1g(F) and 3A2g(F) ? 3T2g(F),
which are characteristic of Ni(II) in octahedral geometry. Electronic
spectra of Cu(II) complexes show the dd transition bands in the
range 12,18815,479, 18,62119,132 and 24,40227,322 cm1
[24].These bands correspond to 2B1g ? 2A1g (dx2y2 ? dz2),
2
B1g ? 2B2g (dx2y2 ? dxy) and 2B1g ? 2Eg (dx2y2 ? dxz, dyz) transitions, respectively. On the basis of electronic transitions, a distorted octahedral geometry is suggested for Cu(II) complexes.
Thermal analysis
Thermal behavior of the complexes has been studied using
Thermogravimetric analysis from ambient temperature to 800 C
in nitrogen atmosphere. Based on the thermograms; decomposition stages, temperature ranges, decomposition product as well
as weight loss percentages of the complexes were calculated. The
TG curves were redrawn as% mass loss vs. temperature (TG) curves.
Typical TG curves for Co(II), Ni(II) and Cu(II) complexes (79) in
comparison to ligand L1 are presented in Fig. 3. The temperature
Table 3
Conductivity, magnetic, electronic spectra EPR spectra of metal complexes 112.
No.
BM (leff)
kmax (cm1)
gk
g\
1
2
3
4
5
6
7
8
9
10
11
12
11.2
13.8
12.6
14.2
12.8
13.2
99.4
98
112.2
108.6
114.4
110.8
4.78
2.93
1.94
4.72
2.91
1.93
4.89
2.98
1.95
4.83
2.93
1.96
2.297
2.232
2.185
2.242
2.098
2.065
2.052
2.075
3.03
3.56
3.55
3.22
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
Fig. 3. TGA curve of (a) ligand L1, (b) complex 7, (c) complex 8, and (d) complex 9.
Table 4
Thermal analysis data the ligand (L1) and metal complexes (79).
Comp. No.
Molecular formula
L1
C12H11N3O
[Co(L )2]Cl2
C24H20Cl2CoN4O4
[Ni(L2)2]Cl2H2O
C24H22Cl2N4NiO5
[Cu(L2)2]Cl2
C24H20Cl2CuN4O4
Stages
1st
2nd
1st
2nd
3rd
1st
2nd
3rd
1st
2nd
Temp (C)
155265
265480
150250
250415
415680
140220
220450
450715
160465
465690
out of the coordination plane and move far from Co(II) ion, which
results in the slight elongation of CoAN bond length. Similarly, the
C@O bond of the amide group moves out of the plane, which
results in increase of Co@O bond length. The CoAN and CoAO bond
lengths in complex 1 lies in the range of 2.0122.014 and 2.122
2.195 , respectively. This elongation in CoAN and CoAO bond
lengths caused a slight distortion from the regular octahedral
geometries. The bond angles in the coordination sphere of Co(II)
complexes are found approximately near to the perpendicular
value.
Similar bonding behavior is observed in case of complex 2 having Ni(II) as metal center. All the bond lengths and bond angles
have very close values as compared to complex 1. However, complex 3 having Cu(II) metal center shows a large degree of distortion
from the regular octahedral geometry. It is because of this
Decomposition species
C4H4N
C8H7N2O
Cl2
C8H8O2
C16H12N4O
HCl, 1/2 O2
C8H9O2
C16H12N4O
C10H8O2N2Cl2
C14H12N2O
Residual species
Calc.
100
100
CoO
13.46
13.42
NiO
13.04
12.96
CuO
14.22
14.13
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
Fig. 4. Geometry optimized structures of (a) ligand L1, (b) complex 7, (c) complex 8, and (d) complex 9 (colour code: H = White, C = Grey, N = Blue, O = red, Co = Grey,
Ni = Silver Grey, Cu = Pink). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)
C5
C6
C4
C3
C5
C7
C2
C8
N1
C1
C 10
C9
N2
H 2N
C11
C 12
H2 N
C2
C6
C4
C3
C7
O1
(a)
C 10
C8
C9
N1
O1
N2
C 12' N 2'
C 11'
C10'
C 9'
C11
C 12
NH2
O1 '
N 1'
C8 '
C1 '
C 2'
C7 '
C 6'
C3 '
C 4'
C 5'
(b)
Scheme 2. Numbering scheme of the optimized structures (a) ligand L1 and (b) complexes 79.
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
Antimicrobial study
Table 5
Optimized geometry of the ligand and metal complexes (bond lengths in Angstroms;
bond angles in degrees).
a
b
c
d
Parametersa
Ligand L1
Complex 1b
Complex 2c
Complex 3d
C1AC2
C1AN3
C1AO1
C2AC7
C7AN1
N1AC8
C8AC9
C9AN2
MAO1
MAN1
MAN2
MAO10
MAN10
MAN20
\N1MO1
\N1MN2
\O1MN20
\N10 MN20
\N2MO10
\N1MO10
\O1MO10
1.510
1.376
1.245
1.419
1.381
1.291
1.434
1.391
1.452
1.360
1.299
1.431
1.397
1.341
1.397
1.412
2.012
2.122
2.195
2.014
2.127
2.193
85.45
82.54
88.87
82.52
84.19
84.64
177.16
1.453
1.364
1.301
1.428
1.399
1.343
1.395
1.420
2.237
2.167
2.210
2.234
2.198
2.234
82.76
83.24
85.43
81.29
85.14
82.23
172.35
1.451
1.368
1.300
1.432
1.403
1.349
1.398
1.422
2.456
2.364
2.243
2.584
2.393
2.297
87.45
69.23
84.32
72.12
78.74
81.34
164.76
C5
C6
C4
C7
C3
C2
C1
H 2N
C 10
C8
C9
N1
N2
C10'
C6
C4
C7
C3
C 12
C2
C1
O1
C 12' N 2'
C 11'
C5
C11
C 9'
O1 '
N 1'
C8 '
NH2
C7 '
C 6'
1-6
H 2N
C1 '
C 2'
C 10
C8
C9
N1
O1
N2
C 12' N 2'
C3 '
C 11'
C 4'
C 5'
C10'
C 9'
C 12
NH2
O1 '
N 1'
C8 '
C11
X2.nH2O
C1 '
C 2'
C7 '
C 6'
C3 '
C 4'
C 5'
10
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
Table 6
MIC (minimum inhibitory concentration) values of L1, L2 and metal complexes 112 (mg/mL).
Compounds
L
L2
1
2
3
4
5
6
7
8
9
10
11
12
a
b
Pathogenic strains
P. aeruginosa
E. coli
S. typhi
B. cereus
C. albicans
A. niger
Ciprooxacina
Fluconazoleb
12.500
12.500
3.1250
6.2500
12.500
6.2500
6.2500
1.5625
3.1250
6.2500
3.1250
6.2500
12.500
3.1250
12.500
6.2500
1.5625
3.1250
6.2500
6.2500
0.1250
3.1250
3.1250
12.500
6.2500
1.5625
6.2500
1.5625
6.2500
6.2500
3.1250
6.2500
3.1250
3.1250
6.2500
3.1250
3.1250
6.2500
6.2500
3.1250
6.2500
3.1250
6.250
12.500
3.1250
1.5625
6.2500
3.1250
6.2500
3.1250
12.500
3.1250
1.5625
3.1250
6.2500
1.5625
12.250
12.250
12.500
12.500
6.2550
3.1250
6.2550
12.500
6.2550
6.2550
12.500
6.2550
12.500
6.2500
12.250
12.250
3.1250
6.2500
12.250
6.2500
3.1250
6.2500
6.2500
3.1250
12.250
6.2500
6.2500
3.1250
1.5625
3.1250
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
6.2550
6.2550
6.2550
3.1250
3.1250
6.2550
6.2550
3.1250
3.1250
6.2550
3.1250
3.1250
6.2550
3.1250
Table 7
Brine shrimp bioassay data of the ligands L1, L2 and their metal complexes 112.
Compounds
1
L
L2
1
2
3
4
5
LD50 (M/mL)
3
>2.16 10
>1.98 103
>2.94 104
>3.16 103
>2.99 104
>4.35 104
>3.23 104
Compounds
6
7
8
9
10
11
12
LD50 (M/mL)
3
>4.65 10
>4.12 104
>3.76 104
>2.78 104
>3.11 104
>3.23 104
>3.87 104
Conclusion
The newly synthesized Schiff bases ligands L1, L2 act as tridentate ligands, and all these are coordinated through the azomethineN, oxygen of amide and through nitrogen of pyrrole/oxygen of
furan to the metal ion. All the synthesized metal(II) complexes possessed an octahedral geometry except the Cu(II) complexes which
showed a distorted octahedral geometry. The reasonable agreement between the theoretical and experimental data reects to
the great extent the suitability of the applied basis set, 631+g(d,p) for this type of work and conrms the suggested structure. The ndings of antimicrobial studies indicated that the Schiff
base ligands possessed mostly moderate activity and metal(II)
complexes mostly possessed moderate to signicant activities
against different bacterial and fungal strains which might be due
to azomethine (AHC@NA) linkage and/or heteroatoms present in
these compounds. The biological activity results showed that
majority of the Schiff base ligands possessed increased activity
upon coordination with different metal ions. The improvement in
biological activity upon coordination may be explained on the
basis of Overtones concept and chelation theory. The cytotoxicities
values indicates that metal complexes displayed signicant cytotoxic activities, that might help in the development of potent
antimicrobial drugs. Further structural optimization studies might
thus represent a rationale for further investigation.
Acknowledgements
We thank the Principal, Zakir Husain Delhi College for providing
lab facilities, National Dairy Research Institute, Karnal for Antimicrobial activities. Authors are thankful to Defence Research &
Development Organisation, New Delhi, India, for nancial
assistance.
References
[1] (a) V. Alexander, Chem. Rev. 95 (1995) 273;
(b) A.D. Granvoskii, A.L. Nivorozhkin, V.I. Minkin, Coord. Chem. Rev. 126
(1993) 1.
[2] D. Carbonnelle, F. Ebstein, C. Rabu, J.Y. Petit, M. Gregoire, F. Lang, Eur. J.
Immunol. 35 (2005) 546.
[3] K. Suzuki, H. Nagasawa, Y. Uto, Y. Sugimoto, K. Noguchi, M. Wakida, K.
Wierzba, T. Terada, T. Asao, Y. Yamada, K. Kitazato, H. Hori, Bioorg. Med. Chem.
13 (2005) 4014.
[4] M.V. Simonini, L.M. Camargo, E. Dong, E. Maloku, M. Veldic, E. Costa, A.
Guidotti, Proc. Natl. Acad. Sci. U.S.A. 103 (2006) 1587.
[5] E.A. Sener, K.K. Bingol, I. Oren, O.T. Arpaci, I. Yacin, N. Altanlar, Farmaco 55
(2000) 469.
[6] Y.F. Xiang, C.W. Qian, G.W. Xing, J. Hao, M. Xia, Y.F. Wang, Bioorg. Med. Chem.
Lett. 22 (2012) 4703.
[7] Y. Nagaoka, T. Maeda, Y. Kawai, D. Nakashima, T. Oikawa, K. Shimoke, T.
Ikeuchi, H. Kuwajima, S. Uesato, Eur. J. Med. Chem. 41 (2006) 697.
[8] D.W. Young, Heterocyclic Chemistry, 1st ed., Longman group Ltd., London,
1975.
[9] (a) E.M. Hodnett, W.J. Dunn, J. Med. Chem. 13 (1970) 768770;
(b) D. Kessel, A.F.A. Sayyab, E.M.H. Jaffar, A.H.H.A. Lanil, Iraq. J. Sci. 22 (1981)
312;
(c) J. Chakraborty, R.N. Patel, J. Ind. Chem. Soc. 73 (1996) 191.
[10] A.P. Singh, N.K. Kaushik, A.K. Verma, R. Gupta, Ind. J. Chem. 50 (2011) 474.
[11] A.P. Singh, N.K. Kaushik, A.K. Verma, G. Hundal, R. Gupta, Eur. J. Med. Chem. 44
(2009) 1607.
[12] F. Lebon, M. Ledecq, Z. Benatallah, S. Sicsic, R. Lapouyade, O. Kahn, A. Garcon,
M.R. Ravaux, F. Durant, J. Chem. Soc. Perkin Trans. 2 (1999) 795.
[13] F. Lebon, M. Ledecq, M. Dieu, C. Demazy, J. Remacle, R. Lapouyade, O. Kahn, F.
Durant, J. Inorg. Biochem. 86 (2001) 547.
[14] F. Lebon, E. de Rosny, M. Reboud-Ravaux, F. Durant, Eur. J. Med. Chem. 33
(1998) 733.
[15] A. Mishra, N.K. Kaushik, A.K. Verma, R. Gupta, Eur. J. Med. Chem. 43 (2008)
21892196.
[16] M.A.D. Becke, Phys. Rev. A 38 (1988) 3098.
[17] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785.
[18] S.H. Vosko, L. Wilk, M. Nusair, Can. J. Chem. 58 (1980) 1200.
[19] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M.
Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y.
Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery, Jr., J.E. Peralta, F. Ogliaro,
M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J.
Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M.
Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo,
J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C.
Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth,
P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman,
J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian Inc., Wallingford, CT, 2009.
[20] F. Weinhold, J.E. Carpenter, The Structure of Small Molecules and Ions, Plenum,
New York, 1988. p. 227.
[21] NCCLS, Method for Dilution Antimicrobial Susceptibility Test for Bacteria that
Grow Aerobically. Approved Standards, 5th ed., National Committee for
Clinical Standards, Villanova, PA, 2000.
[22] Y. Lu, N. Yeung, N. Sieracki, N.M. Marshall, Design of functional
metalloproteins, Nature (2009).
[23] W.J. Geary, Coord. Chem. Rev. 7 (1971) 81.
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
[24]
[25]
[26]
[27]
[28]
[29]
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