JCPR 2014 6 4 1225 1231

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Journal of Chemical and Pharmaceutical Research, 2014, 6(4):1225-1231

Research Article
ISSN : 0975-7384
CODEN(USA) : JCPRC5

1225
HC
N
N
O
N
H
H
N
H
CH
3
O
O
OH
CH
3 S
H
3
C
CH
3
HO
Synthesis, characterization and antimicrobial activities of [Fe(II), Co(II),
Ni(II),Cu(II) and Zn(II)] mixed ligand complexes schiff base derived from
amoxicillin drug and 4-(dimethylamino)benzaldehyde with nicotinamide

*Taghreed H. Al-Noor, Manhel Reemon Aziz and Ahmed T. AL- Jeboori

Department of Chemistry, Ibn -Al-Haithem College of Education for Pure Science, Baghdad University-Iraq
_____________________________________________________________________________________________

ABSTRACT

New Schiff base ligand (E)-6-(2-(4-(dimethylamino)benzylideneamino)-2-(4-hydroxyphenyl)acetamido)-3,3-
dimethyl-7-oxo-4-thia-1- azabicyclo[3.2.0]heptane-2-carboxylic acid = (HL) was synthesized via condensation of
Amoxicillin and 4(dimethylamino)benzaldehyde in methanol. Figure -1 Polydentate mixed ligand complexes were
obtained from 1:1:2 molar ratio reactions with metal ions and HL, 2NA on reaction with MCl
2
.nH
2
O salt yields
complexes corresponding to the formulas [M(L)(NA)
2
Cl],where M=Fe(II),Co(II),Ni(II),Cu(II),and Zn(II),
A=nicotinamide .

Figure (1): The proposed molecular structure and 3D of (HL)

The
1
H-NMR, FT-IR, UV-Vis and elemental analysis were used for the characterization of the ligand. The complexes
were structurally studied through AAS, FT-IR, UV-Vis, chloride contents, conductance, and magnetic susceptibility
measurements. All complexes are non-electrolytes in DMSO solution. Octahedral geometries have been suggested
for each of the complexes. the Schiff base ligands function as tridentate and the deprotonated enolic form is
preferred for coordination. In order to evaluate the effect of the bactericidal activity, these synthesized complexes, in
comparison to the un complexed Schiff base has been screened against six bacterial species, Staphylococcus aureus,
Escherichia coli. Klebsiella pneumonia, Acinetobacter baumannii, Salmonella and Acinetobacter baumanni and the
results are reported.

Key words: Amoxicillin drug, Nicotinamide, mixed ligand) Complexes, Antibacterial activities, and spectral
studies.
_____________________________________________________________________________________________

INTRODUCTION

Amoxicillin, an acid stable, semisynthetic drug belongs to a class of antibiotics called the Penicillin (lactam
antibiotics). It is shown to be effective against a wide range of infections caused by wide range of Gram positive
and Gram negative bacteria in both human and animals[14]. It is a congener of ampicillin (a semisynthetic amino
penicillin) differing from the parent drug only by hydroxylation of the phenyl side chain. It has found a niche in the
treatment of ampicillinresponsive infections after oral administration. Chemically amoxicillin is (2S, 5R, 6R) 6-
[[(2R)-2-Amino-2, 3, 3-dimethyl-7-oxo- 4-thia-1-azabicyclo[3.2.0]heptanes-2-carboxylic acid [1].

Compounds containing an azomethine group (imine) are a class of important compounds in medicinal and
pharmaceutical field. The biological applications of these compounds have attracted remarkable attention. Some
Schiffbases were exhibits antibiotic, antiviral and antitumor agents because of their specific structure. The wide use
of antibiotics resulted in the serious medical problem of drugs resistance and public health concern. The synthesis of
new derivatives of antibiotics has become an important task to cope with drug resistance problems. [1].

Due to the activities associated with amoxicillin and imines, an attempt was made to generate new derivatives
containing imine and amoxicillin in the same molecules. All the synthesized compounds were further characterized
Taghreed H. Al-Noor et al J. Chem. Pharm. Res., 2014, 6(4):1225-1231
______________________________________________________________________________
1226
and evaluated for antibacterial activities. There are many interesting studies on the Schiff bases compounds and their
complexes derived from antibiotics [2]. Naz and Iqbal [3] found that the Schiff base complexes derived from
amoxicillin having good antibacterial activity in good range when comparison to control (Amoxicillin).

In 2009 El-Said and co-workers [4], Synthesized Mixed ligand complexes of Zn(II) and Cd(II) containing
ceftriaxone (Naceftria) or cephradine (Hcefphr) antibiotics and other ligands have been prepared and characterized
by elemental analysis, spectral, biological and thermal studies. The complexes have the general formulas
[Cd
2
(cephr)(diamine)Cl
3
(H
2
O)].xH
2
O [Cd
3
(cephr)(HL)Cl
5
(H
2
O)].
2
H
2
O where diamine=2,2'-bipyridyl or o-
phenanthroline; M= Cd(II) or Zn(II), L=glycine, proline or methionine and x=0-6.

In 2011Sunil, and co- workers [5], synthesis and characterized some new Schiff bases derived from Amoxicillin
trihydrate with Cinnamaldehyde and p-Chlorobenzaldehyde and their complexes with bivalent transition metal ions
viz. Co(II), Zn(II), Ni(II), and Mn(II), have been synthesized. The ligand and their metal complexes were
characterized on the basis of elemental analysis and micro analytical datas. Shift in the characteristic spectral
frequency of the metal complexes, confirms the coordination through metal ion with azomethine group. They were
screened for antibacterial activity against several bacterial strains namely E. coli(-), S. aureus(+) M. luteus(+) and B.
lichenformis(+) (ATCC), the metal complexes showed enhanced antibacterial activity compared to uncomplexed
ligand.

In 2013 Tghreed and co-workers [6], Synthesis a New Schiff base ligand (Z)-7-(2-(4-(dimethylamino)
benzylideneamino)-2-phenylacetamido)-3-methyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid =
(HL)was prepared via condensation of Cephalexin and 4(dimethylamino)benzaldehyde in methanol. Polydentate
mixed ligand complexes were obtained from 1:1:2 molar ratio reactions with metal ions and HL, 2NA on reaction
with MCl2 .nH2O salt yields complexes corresponding to the formulas [M(L)(NA)
2
Cl], where M =
Fe(II),Co(II),Ni(II),Cu(II),and Zn(II) and NA= nicotinamide.

The work presented in this paper concerns the Preparation , Characterization and Antimicrobial activities of
Fe(II),Co(II),Ni(II),Cu(II), and Zn(II)}Mixed Ligand Complexes Schiff base derived from Amoxicillin drug and
4dimethylamino benzaldehyde with Nicotinamide in 1:1:2(M:L:2NA) ratio.

EXPERIMENTAL SECTION

1-Chemicals
All chemicals used were of reagent grade (supplied by either Merck or Fluka, and used as received, ethanol
methanol and dimethylforamaide, and KBr, from (B.D.H). amoxicillin tri hydrate powder) and 4-(dimethylamino)
benzaldehyde from Riedial-Dehaen DSM (Spain).

2-Instrumentation
UV-Vis spectra were recorded on a (Shimadzu UV- 160A) Ultra Violet-Visible Spectrophotometer. IR- spectra were
taken on a (Shimadzu, FTI R- 8400S) Fourier Transform Infrared Spectrophotometer (4000- 400) cm
-1
with samples
prepared as KBr discs. Elemental micro analysis for the ligand was performed on a (C.H.N.S.O) Perkin Elemar
2400. While metal contents of the complexes were determined by atomic absorption(A.A) technique using a
Shimadzu AA 620G atomic absorption spectrophotometer. The Chloride contents of complexes were determined by
potentiometric titration method using (686-Titro processor-665. Dosimat Swiss) Molecular weight determined by
Rast Camphor method, confirming the monomeric nature of the compounds. Conductivities were measured for 10
-
3
M of complexes in DMSO at 25C using (conductivity meter, Jewnwary, model 4070). Magnetic measurements
were recorded on a Bruker BM6 instrument at 298K following the Faradys method .Nuclear magnetic resonance
spectrum
1
H NMR for ligand was recorded in DMSO-d
6
using a Bruker 300 MHz instrument with a tetra methyl
silane (TMS) as an internal standard. The samples were recorded at Queen Mary, university of Al-Albeit, Jordon,
Amman. In addition melting points were obtained using (Stuart Melting Point Apparatus).The proposed molecular
structure of the complexes was drawing by using chem.office prog, 3DX (2006).

2.3- preparation of ligand (HL): [7]
A solution of (Amoxi) (0.419 gm, mmole) in methanol (5 ml) was added to a solution of (4DMAB) (0.149 gm, m
mole) in methanol (10 ml). The mixture was refluxed for (5 hours) with stirring. The resulting was an orange
solution allowed to cool and dried at room temperature, then re-crystallization to the precipitate with ethanol, orange
solid was obtained by evaporation of ethanol during (24 hours) Scheme (1), m. p (146-152 C). Anal. Calcd for
ligand ( HL), C = 60.47%, H = 5.68%, N = 11.28 %. = Found: C = 59.30%, H = 6.37%, N = 10.40%.

2.4- Synthesis of [Cu(L)(NA)
2
Cl] complex:[7]
A solution of (HL) (0.496gm, 1 mmole) in methanol (10 ml) and a solution of (NA) (0.244 gm, 2mmole) in
methanol (10ml), were added to a stirred solution of Cu

(II) chloride dihydrate (0.17 gm, 1mmole) in methanol (5
ml).The resulting mixture was heated under reflux for (5 hours). Then the mixture was filtered and the precipitation
was washed with an excess of ethanol and dried at room temperature during (24 hours). A green solid was obtained,
m.p (260-266 C).

2.5-Synthesis of[Fe(L)(NA)
2
Cl], [Co(L)(NA)
2
Cl], [Ni(L)(NA)
2
Cl, and [Zn(L)(NA)
2
Cl] complexes
The method used to prepare these complexes was similar method to that mentioned in preparation of
[Cu(L)(NA)
2
Cl] complex in paragraph above.

2.6-Preparation of Microorganism suspension
A) The microorganism suspension was prepared by taking 24 colonies from all the studied microorganism. Then
it was inserted in the physiological solution in 0.85% concentration and was compared with Macferr land tube
number 0.5 which is equal to 1.5108 cell/mm. It is used for Petri dish preparation for the examination of biological
activity against the under studied chemical compound.
______________________________________________________________________________
1227
B) Inhibition Activity Selection for the complexes in studied Microorganism The agar well diffusion method was
used to see the effect of under studied chemical complexes on the microorganism growth. This is done by using 20
25 ml from Nutrient agar medium for each Petri dish. The dish was incubated in incubator for 24 hours at (37C) to
make sure that no contamination would occur in the dish .Bore was made on the cultured medium surface by using
cork borer. The chemical complexes were made as 100 m ml per bore and left the central bore containing only
DMF. The biological activity for the complexes was defined by measuring the diameter of the inhibition area
surrounding each bore in millimeters. [8]

C
CH3
O
H
N
H3C
3 H2O
N
H
N
S
CH3
HO
NH2
O
H
CH3
O
O
OH
MeOH
NH
H
O
CH3
H3C
CH3
HC
N
O N
H
CH3
O
OH
S
HO
N
.
+
amoxicilin
Reflux 5 hours
4-(dimethylamino)benzaldehyde
HL

Scheme (1): Schematic representation of synthesis of the ligand (HL)

RESULTS AND DISCUSSION

3. 1-Physical Properties
Ligand (HL) is soluble in( N,N-dimetylformamide (DMF), dimetylsulphoxide (DMSO), methanol (Me OH), ethanol
(EtOH), acetone (C
3
H
6
O), 2-propanol (C
3
H
8
O) and completely insoluble in water (H
2
O),carbon tetra chloride
(CCl
4
), benzene(C
6
H
6
), Petroleum ether and chloroform (CHCl
3
).

3. 2- Characterization of Metal Complexes:
Generally, the complexes were prepared by reacting the respective metal salts with the ligands using 1:1:2 mole
ratio, i.e. one mole of metal salt : one mole of HL and two moles of nicotinamide. The formula weights and melting
points are given in(Table 1 based on the physicochemical characteristics, it was found that all the complexes were
non-hygroscopic, stable at room temperature and appears as powders with high melting points. The solubility of the
complexes of ligands was studied in various solvents. They are not soluble in water .All complexes are soluble in
(DMF) and (DMSO) solvents. The complexes were analyzed for their metal by atomic absorption measurements and
chloride contents were determined by standard methods. (Table-1) for all complexes gave approximated values for
theoretical values. Molar conductance values of the soluble complexes in DMSO show values
(9.4-12.3
-1
cm
2
mol
-1
) indicating that they are all non-electrolytic in nature [9].

FT-IR spectrum of the ligand (HL):
The (FT-IR) spectrum for the starting material amoxicillin , the band at (3456) cm
-1
due to (NH) primary amine
stretching vibration, and (3525) cm
-1
for (-OH), and amoxicillin major peak absolved at (3176) cm
-1
(amide NH)
and phenol OH stretch). The band at (3039) cm
-1
benzene ring (CH) stretching vibration. The band at (1774) cm-
1
is due to (C=O) -Lactam group, (1452) cm
-1
(NH) bend (CN) stretch combination and (NH
3
+
) symmetric
deformation. The bands at (1585), and (1396) cm
-1
were assigned to stretching vibration (COO
-
) asymmetric and
symmetric stretching vibration, respectively., (COO
-
)
asym
- (COO
-
)
sym
=189 cm
-1
. The bands at (1519) cm
-1
, (3039)
cm
-1
, (1178) cm
-1
, and (2970) cm
-1
were assigned to (C=C) aromatic, (CH) aromatic, (CC) aliphatic, and (C
C) stretching vibration respectively. The band at (1282) cm
-1
is due to (CN) cm
-1
stretching vibration. The band at
(1249) cm
-1
was assigned to (CO) stretching vibration. The band at (557) cm
-1
was assigned to (CS) stretching
vibration.

The spectrum for the starting material 4(dimethylamino)benzaldehyde (DMBA) which exhibits a band due to (C
N) were observed in the (1371) cm
1
.The bands at (1165) cm
1
and (2796) cm
1
were assigned to the (CC) and
(CH) aliphatic stretching vibration. The very strong bands due to carbonyl group (C=O) stretching of (DMBA)
were observed in the (1662 -1600) cm
-1
regions, while the bands at (1548) cm
1
and (2819) cm
1
were assigned to
the (C=C) aromatic and (CH) aromatic stretching vibration respectively.

The (FT-IR) spectrum for the ligand (HL),Figure (1),the band at (3298) cm
-1
due to (NH) secondary amine
stretching vibration and disappeared the band for the (NH) primary amine stretching vibration. The spectrum
displays a new band at (1658) cm
-1
is due to azomethine group (-HC=N-) stretching vibrations of the ligand. The
band at (1735) cm
-1
is due to (C=O) cm
-1
stretching vibration for (COOH).The band at (1658) cm
-1
stretching
vibration is due to (C=O) for -Lactam group overlapping with (-HC=N-) stretching vibrations. The bands at
Taghreed H. Al-Noor
______________________________________________________________________________
(1597) cm
-1
, and (1377) cm
vibration, respectively. The bands at (1546) cm
aromatic, (CH) aromatic,
is due to (CN) cm
-1
stretching vibration. The band at (1230) cm
The band at (555) cm
-1
was assigned to
due to (OH) hydroxyl group overlapping with
assignment of the characteristic bands for the starting materials, intermediate compounds and the ligand are
summarized in Table (2).

1
H NMR spectrum for the ligand (H
In 1H NMR spectrum of the ligand (HL) in DMSO
at ( 3.031) ppm (
2CH3
) and (2CH
doublet due one proton of aromatic ring of phenyl. The signal obtained at (
one proton of -CH=N linkage in the ligand. This confirms the formations of imine ligand. This observation was also
supported by the FTIR data of the ligand discussed earlier. One group of four resonance signals attributed to (S
CH) on the dihydrothiazine ring was observed in the (
(COCH) and (NCH) on the
respectively. single peak attributed to hydroxyl group appeared at (

FT-IR of spectral data for the Schiff base mixed ligands complexes
[Fe(L)(NA)
2
Cl](1),[Co(L)(NA)
The spectrum of the (HL) displays a new band at (1658) cm
stretching vibrations of the ligand [5,6],on complexation these band has been shifted to higher frequencies (1624),
(1624), (1624), (1630), and (1630) cm
compounds revealed the presence of wide strong bands between (3541
(O-H) and (N-H) in accord with the results in found it difficult to get reasonable resolution between bands due to
OH and NH, hence abroad band between (3500
(1597),and (1377) cm
-1
were assigned to stretching vibration
vibration, respectively. on complexation these
(1604), (1604), and (1620) cm
(1363) cm
-1
, for (-COO)
sy
occurred through the oxygen atom of carboxylate ion. The overlap band at (1658) cm
(C=O) for -Lactam group, these band has been shifted to higher frequency at (1670
showing that the coordination is through the Oxygen atom of
Noor et al J. Chem. Pharm. Res., 2014, 6(4):
______________________________________________________________________________
1228
, and (1377) cm
-1

(COOH) asymmetric and symmetric stretching
vibration, respectively. The bands at (1546) cm
-1
,(2962) cm
-1
, (1168) cm
H) aromatic, (CC) aliphatic and (CC) stretching vibration respectively. The band at (1315) cm
stretching vibration. The band at (1230) cm
-1
was assigned to
was assigned to (CS) stretching vibration. The band at (3298)
OH) hydroxyl group overlapping with (NH) secondary amine stretching vibration [9
H NMR spectrum for the ligand (HL):
In 1H NMR spectrum of the ligand (HL) in DMSO-d6 Figure (2), single peaks attributed to methyl groups appeared
) and (2CH
3
) ( 1.56) ppm. The signal obtained in range (
doublet due one proton of aromatic ring of phenyl. The signal obtained at (
CH=N linkage in the ligand. This confirms the formations of imine ligand. This observation was also
ted by the FTIR data of the ligand discussed earlier. One group of four resonance signals attributed to (S
CH) on the dihydrothiazine ring was observed in the ( 3.421 - 3.660) ppm, Three groups of double peaks given by
CH) on the -lactam ring and (NH sec.) amide appeared at (
respectively. single peak attributed to hydroxyl group appeared at ( 9.67) ppm (17).
Figure (2): 1H NMR spectrum of the ligand (HL) in DMSO
Figure (3): FT-IR spectrum of (HL)
IR of spectral data for the Schiff base mixed ligands complexes
Cl](1),[Co(L)(NA)
2
Cl](2),[Ni(L)(NA)
2
Cl](3),[Cu(L)(NA)
The spectrum of the (HL) displays a new band at (1658) cm
-1
is due to
(1624), (1624), (1630), and (1630) cm
-1
for complexes (1), (2), (3), (4),(5).Infra red spectra
compounds revealed the presence of wide strong bands between (3541
H) in accord with the results in found it difficult to get reasonable resolution between bands due to
NH, hence abroad band between (3500 - 2500) cm
-1
is definitely due to OH and NH stretching. The bands at

vibration, respectively. on complexation these bands have been shifted to higher frequencies [(1599), (1600),
(1604), (1604), and (1620) cm
-1
for (-COO)asy], and lower frequencies [(1363), (1366), (1366), (1367), and
sy
] for the compounds (1) , (2) , (3) ,(4) , and (5), that
Lactam group, these band has been shifted to higher frequency at (1670
showing that the coordination is through the Oxygen atom of
J. Chem. Pharm. Res., 2014, 6(4):1225-1231
______________________________________________________________________________
, (1168) cm
-1
, and (2823) cm
-1
were assigned to (C=C)
etching vibration respectively. The band at (1315) cm
-1
was assigned to (CO) stretching vibration.
S) stretching vibration. The band at (3298) cm
-1
stretching vibration

is
H) secondary amine stretching vibration [9-14]. The
d6 Figure (2), single peaks attributed to methyl groups appeared
1.56) ppm. The signal obtained in range ( 6.71-7.70) ppm was assigned for
doublet due one proton of aromatic ring of phenyl. The signal obtained at ( 8.20) ppm was assigned for singlet due
ted by the FTIR data of the ligand discussed earlier. One group of four resonance signals attributed to (S
3.660) ppm, Three groups of double peaks given by
ring and (NH sec.) amide appeared at ( 4.8), ( 4.9) and ( 8.2) ppm,
9.67) ppm (17).
Figure (2): 1H NMR spectrum of the ligand (HL) in DMSO-d6
spectrum of (HL)
IR of spectral data for the Schiff base mixed ligands complexes
Cl](3),[Cu(L)(NA)
2
Cl](4), [Zn(L)(NA)
2
Cl](5):
is due to (HC=N-) group of the azomethine
for complexes (1), (2), (3), (4),(5).Infra red spectra for the prepared
compounds revealed the presence of wide strong bands between (3541-3317) cm
-1
due to the stretching vibration
bands have been shifted to higher frequencies [(1599), (1600),
COO)asy], and lower frequencies [(1363), (1366), (1366), (1367), and
] for the compounds (1) , (2) , (3) ,(4) , and (5), that the coordination with metal was
-1
stretching vibration is due to
Lactam group, these band has been shifted to higher frequency at (1670-1689) cm
-1
for complexes
showing that the coordination is through the Oxygen atom of -Lactam group. [6] .The bands at (497),
1231
______________________________________________________________________________
(C=C)
1

O) stretching vibration.
is
14]. The
d6 Figure (2), single peaks attributed to methyl groups appeared
m was assigned for
8.20) ppm was assigned for singlet due
3.660) ppm, Three groups of double peaks given by

8.2) ppm,
) group of the azomethine
for the prepared
due to the stretching vibration
bands have been shifted to higher frequencies [(1599), (1600),
COO)asy], and lower frequencies [(1363), (1366), (1366), (1367), and
the coordination with metal was
stretching vibration is due to
exes
.The bands at (497),
Taghreed H. Al-Noor
______________________________________________________________________________
(486),(470),(489), and (474) cm
to the carbocylic oxygen, and oxygen of
The bands at (540), (520),(578), (547) and (505) cm
(5), respectively , indicating that the nitrogen of (NA) is involved in coordination with metal ions.

(U.V-Vis) Spectrum for the Schiff base ligand:
Magnetic susceptibility was determined
correction of metal- ligand system was calculated using the Pascal's constant. .The magnetic moments of the
complexes shown in (Table
diamagnetic corrections .

The electronic spectrum of the ligand has been measured in DMSO solution between 200
temperature .In the spectrum of the Schiff base ligand (HL),the absorption band observed at 232 nm (431
1
),and 336 nm(29761cm
-1
) which are assigned to benzene (

The UV-Visible Spectroscopy and Magnetic measurements
The absorption data for complexes are given in Table (3).
[Fe(L)(NA)
2
Cl]: The (U.V
=431 molar
-1
.cm
-1
) is due to the ligand field and, the second high peak at (345 nm)(28985 cm
1
.cm
-1
) is due to the (C.T), the third wea
(
5
T2g
5
Eg), transition , in an octahedral geometry. in an octahedral geometry.Also, the values of the magnetic
moments 3.77 B.M. may be taken as additional evidence for a high spin

[Co(L)(NA)
2
Cl]: The (U.V
1
)(
max
=1321 molar
-1
.cm
-1
), is due to the ligand field and (L.F), while the second third and fourth weak pe
nm)( (3=12048 cm
-1
)(
max
nm)(10080 cm
-1
)(
max
=9 molar
(
4
T
1
g(F) 4T2g(F) transition respectively ,[17]

2/ 1 =1.019, ,
1
/
2
=0. 98, , from Tanabe
10. 080 cm
-1
, The room temperature magnetic moment (
symmetry.[17-18,4]

[Ni(L)(NA)
2
Cl]: The (U.V
max
=1643 molar
-1
.cm
-1
), is due to the ligand field the second small peak at (345 nm)(28985 cm
1
.cm
-1
) is due to the (C.T), while the third fourth and fifth weak peaks at(412 nm)(24271 cm
1
), (770 nm)(12987 cm
-1
)(
to
3
A
2
g
3
T
2
g(
1
)

(dd),
3
A
2
g
3
T
1
g(F)(
2
) (d
values of the magnetic moments 3.11 B.M, may be taken as additional evidence for octahedral nickel (II) geometry .
[17-18]

[Cu(L)(NA)
2
Cl]: The (U.V
max
=2100 molar
-1
.cm
-1
) is due to the (C.T) , while the second weak broad peak at (974 nm)(10266 cm
molar
-1
.cm
-1
), which assigned
magnetic moment in 2.04 B.M .corresponding to one unpaired electron .

[Zn(L)(NA)
2
Cl]: The (U.V
molar
-1
.cm
-1
Noor et al J. Chem. Pharm. Res., 2014, 6(4):
______________________________________________________________________________
1229
(486),(470),(489), and (474) cm
-1
were assigned to (MO) for compounds (1), (2), (3), (4),and (5), indicating that
to the carbocylic oxygen, and oxygen of -Lactam group of the ligand are involved in coordination with metal ions.
The bands at (540), (520),(578), (547) and (505) cm
-1
were assigned to
(5), respectively , indicating that the nitrogen of (NA) is involved in coordination with metal ions.
Vis) Spectrum for the Schiff base ligand:
Magnetic susceptibility was determined at room temperature using solid sample by Gouy method.
ligand system was calculated using the Pascal's constant. .The magnetic moments of the
complexes shown in (Table-3)were calculated from the measured magnetic susceptib
The electronic spectrum of the ligand has been measured in DMSO solution between 200
temperature .In the spectrum of the Schiff base ligand (HL),the absorption band observed at 232 nm (431
) which are assigned to benzene (-*), and ( n
Visible Spectroscopy and Magnetic measurements:
The absorption data for complexes are given in Table (3).
The (U.V- Vis) spectrum, exhibits three peaks, the first middle peak at (286 nm)(34965 cm
) is due to the (C.T), the third weak peak at (815 nm)(12269 cm
moments 3.77 B.M. may be taken as additional evidence for a high spin
The (U.V- Vis) spectrum, exhibits four peaks , the first high intense peak at (267 nm)(37453 cm
), is due to the ligand field and (L.F), while the second third and fourth weak pe
max
=5 molar
-1
.cm
-1
), ((2=976 nm)(10245 cm
=9 molar
-1
.cm
-1
), which assigned to (
5
Eg
5
T
2
4T2g(F) transition respectively ,[17]
=0. 98, , from Tanabe-Sugano diagram for d
7
, The room temperature magnetic moment (
eff
= 4.52 B.M) corresponded to a high
The (U.V- Vis) spectrum, exhibits five peaks , the first high intense peak at (269 nm)(37174 cm
)(
max
=10 molar
-1
.cm
-1
), and (956 nm)(10460 cm
) (dd), and
3
A
2
g
3
T
1
g(P)(
3
) transition respectively in an octahedral geometry. Also, the
The (U.V- Vis) spectrum exhibits two peaks , the first high broad peak at (275 nm)(36363 cm
), which assigned to (
2
E
g
2
T
2g
), transition in a high spin octahedral geometry. The complex show a
magnetic moment in 2.04 B.M .corresponding to one unpaired electron .

Chart (1) Chart of biological effects of some of the studied complexes

The (U.V- Vis) spectrum, two high peaks, the first high peak at
13
0 0 0
18
20
17
20
0
15
12
0 0
16
14
15
0 0 0
22
13
14
0
18
22
20
22
18
Ecoli Pseudomonas
Staphylococcus aureus Klebsiella pneumoniae
Salmonella Acinetobacter baumannii
J. Chem. Pharm. Res., 2014, 6(4):1225-1231
______________________________________________________________________________
O) for compounds (1), (2), (3), (4),and (5), indicating that
Lactam group of the ligand are involved in coordination with metal ions.
assigned to (MN)for compounds (1), (2), (3), (4), and
(5), respectively , indicating that the nitrogen of (NA) is involved in coordination with metal ions. [13-15]
at room temperature using solid sample by Gouy method. Diamagnetic
calculated from the measured magnetic susceptibilities after employing
The electronic spectrum of the ligand has been measured in DMSO solution between 200- 1100 nm at room
temperature .In the spectrum of the Schiff base ligand (HL),the absorption band observed at 232 nm (43103 cm
-
*), and ( n-*) transition, respectively. [10-11,17].
Vis) spectrum, exhibits three peaks, the first middle peak at (286 nm)(34965 cm
-1
)(
max
-1
)(
max
=1110 molar
-
k peak at (815 nm)(12269 cm
-1
)(
max
=9 molar
-1
.cm
-1
), which assigned to
moments 3.77 B.M. may be taken as additional evidence for a high spin octahedral Iron(II) geometry.[17]
Vis) spectrum, exhibits four peaks , the first high intense peak at (267 nm)(37453 cm
-
), is due to the ligand field and (L.F), while the second third and fourth weak peaks at(830
2=976 nm)(10245 cm
-1
)(
max
=6 molar
-1
.cm
-1
), and (1= 992
2
g) (3A
2
g 4T
1
g(P), (
4
T
1
g(F)
4
T
1
g), and
7
octahedral field the value of 10Dq equal to
= 4.52 B.M) corresponded to a high spin octahedral
Vis) spectrum, exhibits five peaks , the first high intense peak at (269 nm)(37174 cm
-1
)(
-1
)(
max
=153 molar
-
-1
)(
max
=20 molar
-1
.cm
-
), and (956 nm)(10460 cm
-1
)(
max
=8 molar
-1
.cm
-1
), which assigned
Vis) spectrum exhibits two peaks , the first high broad peak at (275 nm)(36363 cm
-1
)(
-1
)(
max
=42
magnetic moment in 2.04 B.M .corresponding to one unpaired electron . [6,17-18]
.
Chart (1) Chart of biological effects of some of the studied complexes
Vis) spectrum, two high peaks, the first high peak at (279 nm)(35842 cm
-1
)(
max
=998
-1
)(
max
=1700 molar
-1
.cm
-
5
0
7
19
5
0
6
16
0
5 5
0
5
10
15
20
25
Pseudomonas
Klebsiella pneumoniae
Acinetobacter baumannii
1231
______________________________________________________________________________
O) for compounds (1), (2), (3), (4),and (5), indicating that
Lactam group of the ligand are involved in coordination with metal ions.
N)for compounds (1), (2), (3), (4), and
Diamagnetic
ilities after employing
1100 nm at room
-
max

-
), which assigned to
-
aks at(830
1= 992
g), and
octahedral field the value of 10Dq equal to
spin octahedral
)(
-
-
), which assigned

)(
=42
=998
-
______________________________________________________________________________
12!
1
) is due to the (C.T) in an octahedral geometry. this diamagnetic complex show no appreciable absorptions in the
region below 26000 cm
-1
in DMSO solutions. In accordance with the d10 electronic configuration of Zn(II) .
[6,18,20]

Also, the values of the magnetic moment Table (3).may be taken as additional evidence332 for their octahedral
structure. Molecular weight determined by Rast Camphor method and were found in accordance with calculated
value the range of metal complexes (852-858) [6].

Antimicrobial activity:
The in vitro antimicrobial screening results are given in Table 4,Chart (1).On the basis of observed zones of
inhibition, all the metal-mixed ligand complexes are active against all six tested organisms which in fact is in
agreement with the literature [18-23]. The antibacterial results evidently show that the activity of the Schiff base
became more upon coordination to the metal atoms.

Table (1): The physical properties of the compounds

M. wt = Molecular Weight, m = Molar Conductivity, dec. = decomposition , Calc.= calculation

Table (2) FTIR spectral data of the Ligands and there complexes

*overlap

Table 3- Electronic Spectral data, magnetic moment, of the studied compounds

Cl%
Metal%
m
-1
cm
2
mol
-1

M .pc
(de) c theory (exp) Yield % Colour
M. wt
Rast method.
M. wt
Calc.
Compounds
4.27
(4.32)
6.72
7.10
9.4 172 Dec. 77 Grey Green 852.81 831.11
[Fe(L)(NA)2Cl]
C37H39ClFeN8O7S
4.25
(4.22)
7.06
7.96
10.2 300 Dec. 72 Brown 817.7 834.20
[Co(L)(NA)2Cl]
C37H39ClCoN8O7S
4.25
(4.19)
7.04
6.06
13.1 300 Dec. 80 Yellow 830.6 833.96
[Ni(L)(NA)2Cl]
C37H39ClN8NiO7S
4.23
(4.26)
7.58
7.06
10.1 260-266 81 Green 858.0 838.81
[Cu(L)(NA)2Cl]
C37H39ClCuN8O7S
4.22
(4.29)
7.78
8.06
12.3 234-140 74 Brown 853. 8 840.68
[Zn(L)(NA)2Cl]
C37H39ClN8O7SZn
C
o
m
p
o
u
n
d

(
O
-
H
)

(
N
-
H
)

p
r
i
m
a
r
y

a
m
i
n
e

(
N
-
H
)

S
e
c
o
n
d
a
r
y

a
m
i
d
e

(
C
=
O
)

-
l
a
c
t
a
m

(
H
C
=
N
-
)

a
s

(
C
O
O
)

s

(
C
O
O
)

(
C
=
C

a
r
o
m
.
)

(
C
-
C

a
l
i
p
h
.
)

(
C
-
N
)

(
C
-
O
)

(
C
-
S
)

(
C
-
H
)

a
r
o
m
.

(
C
-
H
)

a
l
i
p
h
.

(
M
-
N
)

(
M
-
O
)

HL 3298* ------- 3298* 1658* 1658 1597 1377 1546 1168 1315 1230 555 2962 2823
----
-
-----
Nicotine amide ------
3367
3259
-------- ------- ------ ----- ------ 1593 1124 1201 ----- ------ 3061 2787
----
--
-----
[Fe(L)(NA)2Cl] 3464 3410 3232 1684* 1624* 1599 1363 1543 1166 1246 1230 553 3060 2970 540 497
[Co(L)(NA)2Cl] 3402 3317
3261,
3197
1684* 1624 1600 1366 1577 1199 1292 1230 552 3078 2754 520 486
[Ni(L)(NA)2Cl] 3406 3321
3267,
3213
1684* 1624 1604 1366 1581 1149 1246 1199 553 3078 2754 578 470
[Cu(L)(NA)2Cl] 3475 3402
3305,
3159
1670 1630 1604 1367 1550 1184 1300 1203 553 3062 2769 547 489
[Zn(L)(NA)2Cl] 3541 3471 3259 1689 1630 1620* 1363 1512 1130 1230 1180 552 2978 2885 505 474
Compound nm ABS cm
-1
max (molar
-1
.cm
-1
) Assignments eff (BM)
Amox.
277
330
0.732
0.057
36101
30303
732
57
*
n *
-
NA
220
261
1.548
1.104
45454
38314
1548
1104
*
*
-
4DMAB
208
342
336
0.338
0.493
1.961
48007
29239
29761
338
493
1961
*
n *
n *
-
H L
232
336
1.035
1.952
43103
29761
1035
1952
*
n *
-
[Fe(L)(NA)2Cl]
286
345
815
0.431
1.110
0.009
34965
28985
12269
431
1110
9
L-F
C-T
5
T2g
5
Eg
3.77
[Co(L)(NA)2Cl]
267
830
976
992
1.321
0.005
0.006
0.009
37453
12048
10245
10080
1321
5
6
9
L.f
3
A2g
4
T1g(P)
3
A2g
4
T1g(F)
3
A2g (F)
3
T1g(F)
4.52
[Ni(L)(NA)2Cl]
269
345
412
770
956
1.643
0.153
0.020
0.010
0.008
37174
28985
24271
12987
10460
1643
153
20
10
8
L-F
C-T
3
A2g (F)
3
T1g (P) (3)
3
A2g(F)
3
T1g(F) (2)
3
A2g(F)
3
T2g(F) (1)
3.11
[Cu(L)(NA)2Cl]
275
974
2.100
0.042
36363
10266
2100
42
L.F

2
Eg
2
T2g
2.04
[Zn(L)(NA)2Cl]
279
342
1.288
1.700
35842
29239
1288
1700
C-T
C-T
0.0
______________________________________________________________________________
121
Table(4):Biological activity of the Schiff bases mixed ligands complexes Zone of inhibition (mm)

Compound
E
coli
P
aeruginosa
Staphylococcus
aureus
Klebsiella
pneumoniae
Salmonella
Typhi
Acinetobacter
baumannii
Control 5 7 5 6 5 5
[Fe(L)(NA)2Cl] 0 19 0 16 0 18
[Co(L)(NA)2Cl] 13 18 15 14 22 22
[Ni(L)(NA)2Cl] 0 20 12 15 13 20
[Cu(L)(NA)2Cl] 0 17 0 0 14 22
[Zn(L)(NA)2Cl] 0 20 0 0 0 18

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3.660) ppm, Three groups of double peaks given by

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