Transactions on Engineering and Sciences

Volume 4, Issue 2, April-June 2016

ISSN: 2347-1964 (Online) 2347-1875 (Print)

Synthesis and Antibacterial Activities of Some

mixed ligand complexes
Shatha M.H.Al Naimi1

Alia.S.kindeel2

Amer J.Jarad3

Taghreed H. Al-Noor4

Department of Chemistry, Ibn -Al-Haithem College of Education for pure science, Baghdad University,
Baghdad, Iraq.
Abstract: New complexes of M(II) with mixed ligand of 5-Chlorosalicylic acid (CSA) C7H5ClO3 as
primary ligand and L- Valine (L-Val) C5H11NO2 as a secondary ligand were prepared and characterized
by elemental analysis (C.H.N), UV., FT-IR, magnetic susceptibility, eff (B.M) as well as the conductivity
measurements (m ). In the complexes, the 5-chlorosalicylic acid is bidentate in all complexes
coordinating through OH- and COO- groups; also L-Valine behaves as a bidentate ligand in all
complexes through NH2 and COO- groups. These five mixed ligand complexes formulated as
Na3[M(CSA)2(L-Val)]. The proposed molecular structure for all complexes is octahedral geometries. The
synthesis complexes were tested in vitro for against four bacteria (2-gram +ve) and (2gram -ve)
showing activity similar to that of (L-Val).
Keywords: L- Valine ,5- Chlorosalicylic acid, mixed ligand complexes
I.

INTRODUCTION

In recent years, the rational design and synthesis of metal-carboxylate complexes are one of the
most attraction areas of materials research. salicylic derivatives have attracted considerable attention not
only for their structural varieties but also for their biological uses and spectroscopic .[1-2]. These are
widespread in nature and are of considerable commitment in bio chemistry [3]. In 5-chlorosalicylic acid
C7H5ClO3 (abbreviated for CSA) the carboxylate (-COO_) group and Hydroxyl (-OH) can partly or entirely
be deprotonated, which makes it possible to coordinate to the metal ion or participate in hydrogen bonding
interactions [4].
Its well known and most widely used drug aspirin reduces the risk of many diseases associated with
aging and is also used in the different pain and for the prevention of thrombosis in the vascular system. In
the search of literature, it was revealed that there are many studies which deal with salicylic acid chelate of
many metal ions [5-10]. Amino acids (L-AA) are well known complexing agents with multifunctional
groups and are biologically significance and metabolic enzymatic activities, show considerable interest in
their metal complexes [11-17].
L-Valine (abbreviated for Val) is one of the 20 protein genic amino acids, found on almost all known
proteins. [18-20]. Specially, the mixed ligand complexes derived from the ligands containing N,O donor
binding sites with M(II) ions are used in a number of fields like biological, agricultural, industrial,
therapeutic applications and analytical [21-22].
The present investigation deals with the preparation, spectroscopic studies of the complexes obtained
during the reaction of 5-chlorosalicylic acid (CSA) as primary ligand and L-Valine (L-Val) as a secondary
ligand with [ Mn (II), Co(II), Zn(II), Cd(II) and Hg(II)] ions with the aim of investigating the coordination
mode of 5-chlorosalicylic acid and L- Valine. In vitro antibacterial evaluation of the two ligands and their
metal complexes were
carried against E. coli (G-ev)
, Pseudomonas(G-ev), Bacillus(G+ev) and
Staphylococcus(G+ev) , by measuring diameter of zone of inhibition (ZI) in (mm) to know the potentiality of
such compounds.
II.

EXPERIMENTAL

A. Chemical:
All chemicals used in this investigation were of analytical grade and used without further purification.
(L-Val) and (CAS) were parchased from (Merck and B.D.H.), metals chloride and solvents from (B.D.H.,
Riedel and Merck).
B. Synthesis of the metal complexes:
The following general procedure was adopted for the synthesis of the complexes:
Sodium Valinate solution: Dissolve [0.117gm,1mmol] of (L-Val) with [0.04gm,1mmol] solution of sodium
hydroxide in 50% ethanol(10mL) was deprotonated according to the following reaction. Scheme I.

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Transactions on Engineering and Sciences

Volume 4, Issue 2, April-June 2016

ISSN: 2347-1964 (Online) 2347-1875 (Print)

Figure 1: Scheme I
Sodium 5-Chlorosalicylate solution : Dissolve [0.345gm,2mmol] of (CSA) with [0.08gm,2mmol] solution of
sodium hydroxide in 50% ethanol(10mL) was deprotonated according to the following reaction. Scheme II.

Figure 2: Scheme II
C. Synthesis of complexes:
The complexes were prepared by the addition of 50% ethanol(10mL) solution of the (2Na+ CSA-2) and
+
(Na Val-) to warm stirred 50% ethanol(10mL) solution of the respective metal (II) chloride of
MnCl2.4H2O[0.197gm, 1mmol], CoCl2.6H2O [0.273gm, 1mmol], ZnCl2 [0.136gm, 1mmol], CdCl2.H2O
[0.201gm, 1mmol],and HgCl2 [0.272gm, 1mmol] in the stoichiometric ratio metal : ligand [(M : 2(CSA):
(Val)]. The mixture was stirred for (1 hour at 700C). The resulting precipitate was filtered off and
recrystallized from is ethanolic solutions then dried at room temperature and tested using standard
methods.
D. Study of biological activity:
The antimicrobial activity of the all compounds were checked by nutrient agar well diffusion method.
The antibacterial activity of the ligands and the corresponding complexes were assayed simultaneously
against Gram positive bacteria (G+ve), (Staphylococcus and Bacillus) and Gram negative bacteria (G-ve),
(E.Coli and Pseudomonas). The DMSO solvent used for making test samples and control, which was
considered the best solvent in biological effects study [15, 22].
III.

RESULTS AND DISCUSSION

Based on the physicochemical characteristics (Table I), it was found that all the complexes were stable at
room temperature and non-hygroscopic, The (C.H.N), formula weights and melting points are given in
Table II. The (C.H.N) analysis with metal contents of these complexes were in good agreements with the
calculated values, the complexes soluble in H2O, CH3Cl, CH3OH , C2H5OH, (CH3)2CO, DMF and DMSO but
non soluble in CCl4 , C6H6 and (CH3CH)2O.The m in DMSO (10-3M) indicated the electrolyte type ratio
(1:3), [23]
The molar conductance values of these complexes indicated that the (CSA ) ligand was coordinated to
the M(II), ions as a doubly negative charged anions. Therefore it seems that the carboxylate (-COO-) group
and hydroxyl ( - OH) group can entirely be deprotonated, which makes it possible to coordinate to the metal
ion have been deprotonated and bonded to the metal ions as oxygen anions.
A. FT-IR Spectra :
IR spectra of all the synthesized complexes have been recorded in the range 400-4000 cm-1 and listed in
Table 2. The IR spectrum of (L-Val) exhibited band at 3124 cm-1 was assigned to (NH2) and (OH)
stretching frequency, on complexation a shifting with change in shape was observed from this band, while
increasing in intensity was noticed. The significant may be a result of coordination with metal ion [24 -26].
The bands in (L-Val)spectrum at 1504 cm-1 and 1361 cm-1 due to (COO) asymmetric and symmetric
vibration respectively, significant change in the intensity and in position were observed on complexation
with metal ion[15-16].The IR spectrum of (CSA) exhibited broad band at 3232 cm-1 was assigned to the
stretching vibration of (OH) group, absent this band in the spectra of all prepared complexes, which
indicated deprotonation and involvement of the enol O in chelation[18] Additinol beaks at 1226 cm-1 and 613
cm-1 were assigned to [(C-OH ) and (C-Cl)] respectively[24-25], and the bands at 1608cm-1and1361cm1were attributed to [(COO)asym] asymmetric and to [(COO) sym ]symmetric respectively[15,25], shifted
in position to higher and lower frequency in the spectra of all prepared complexes which indicated the
coordination with metal ion.The -COO-)asym (-COO-)sym) =
> 200, which is the evidence of
monodentate linkage of (-COO-) group [14]. The bands observed around (1449-1459 ) cm-1 and (2857-3107
)cm-1 were assigned to [(C=C) and (C-H)] aromatic stretching, respectively . [26].The appearance of new

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Volume 4, Issue 2, April-June 2016

ISSN: 2347-1964 (Online) 2347-1875 (Print)

bands in the region of 408-497 cm-1 are tentatively assigned to (NM str) and (OM str), (O-M str)
(Metal-Ligand) stretching bands [14,15,26 ]. The IR data exhibited that the used [(CSA) and(L-Val)] ligands
behaving as bidentate ligands towards the M (II) ions.
B. Electronic spectra:
The UV-Vis spectra data for the free ligands and all metal complexes are listed in Table 3. The UVVis spectrum of the (L-Val) show peak at 349 nm assigned to ( *) electronic transition[27-28].The
electronic spectrum of (CSA) appeared peak at 301 nm attributed to( *) electronic transition[15,27].The
spectrum of Mn(II) complex appeared absorption peak at 304 nm was related to ligand felid, then other
peaks at (814 & 944 )nm were assigned to electronic transition type 6A1g4T2g(G) and 6A1g4T1g(G)
respectively[27]. The spectrum of Co(II) complex showed peaks at 279nm and 345nm due to ligand felid
and charge transfer respectively. Other three peaks at (538, 745 and 767) nm were found to be caused by (dd) electronic transition type 4T1g(f) 4T1g(p) , 4T1g(f) 4A2g(f) and 4T1g(f) 4T2g(f) respectively[27].
The ratios: 1/ 2 = 0. 97 and 2/ 1 = 1.29., o =10 Dq=13037 cm-1 (first spin-allowed transition},
o= E= 13037 x 0.01196=155.92 kJ/ moL
E = o =13037 x1.24 x 10-4 = 1.61eV
The spectra of [Zn(II), Cd(II) and Hg(II)] (d10 ) diamagnetic complexes showed absorption peaks at [272,
306 and 305] nm due to charg transfer (CT)transition. The high shift in the (max) gave a good indication
for complex formation, this is a good result for octahedral complex[27]. Studying complexes on bases of the
above analysis , the existence of Hexa coordinated Na3[M (CSA)2(Val)] were M(II)= Mn(II), Co(II), Zn(II),
Cd(II) and Hg(II) proposed models of the species were built with chem. Office shows in Figure. (1)
Table 1: Some Physical properties and analytical data of the Compounds
Analysis Calc (Found)
C%
H%
-

Compounds

M. wt.

Color

M.P
C

(L-Val)
(CSA)

117.15
172.57

White
White

295
172

Na3[Mn(CSA)2(L-Val)]

581.16

Deep
brown

>250

9.45
(8.61)

39.27
(38.33)

2.78
(2.01)

2.41
(1.64)

Na3[Co(CSA)2(L-Val)]

585.15

Rose

>250

10.07
(9.72)

39.00
(38.16)

2.78
(2.01)

2.39
(1.01)

Na3[Zn(CSA)2(L-Val)][(

591.61

White

>250

11.05
(10.90)

38.57
(37.55)

2.73
(1.69)

2.37
(1.81)

Na3[Cd(CSA)2(L-Val)][(

638.63

White

>250

17.60
(16.54)

35.73
(34.49)

2.53
(2.47)

2.19
(1.61)

Na3[Hg(CSA)2(L-Val)][(

726.81

Brown

>250

27.59
(26.35)

31.39
(30.83)

2.22
(2.12)

1.93
(1.70)

M%
-

N%
-

Table 2: FTIR - spectral data of the compounds (Cm-1)

Compounds

(NH2) + ( OH)(

asy(COO)

sym(COO)

(M-N)

(M-O)

(L-Val)
(CSA)

3124 br.
3232 br.

1504 sh.
1608 sh.

1361 sh.
1361 sh

Na3[Mn(CSA)2(Val)]

br.3425

1581 s.

1311 s.

482 w.

482
432 w.

Na3[Co(CSA)2(Val)]

br.3444
3372 br.

1581 s.

1315 s.

447 w.

447
428 w.

Na3[Zn(CSA)2(Val)]

3255br.
3147br.

1581 s.

1363 s.

497 w.

459 w.
408w

Na3[Cd(CSA)2(Val)]

3323br.
3236br.

1573 s.

1313 s.

487w.

410 w
439 w.

Na3[Hg(CSA)2(Val)]

3444br.
3190br.

1597 sh.

1315 sh.

443w.

480 w
439 w.

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Transactions on Engineering and Sciences

Volume 4, Issue 2, April-June 2016

ISSN: 2347-1964 (Online) 2347-1875 (Print)

Table 3: UV- Vis, magnetic susceptibility and conductance measurements data

Compounds

max
(nm)

Wave
number
(cm-1)

max
(L.mol-1.cm-1)

m
(S.cm2.mol-1)
in DMSO
(10-3M)

eff
(B.M)

(L-Val)

349

28653

18

2.82

(5-CSA)

301
304
814
944
279
345
538
745
767
272
473
306
411
305

33222
32894
12285
10593
35842
28985
185873
134222
130371
36363
21141
32679
24330
32786

2332
1679
33
29
2285
1673
82
25
24
2052
19
77
32
113

7.90

90.40

4.95

85.80

5.76

84.84

Diamagnetic

85.73

Diamagnetic

83.60

Diamagnetic

Na3[Mn(CSA)2(Val]

Na3[Co(CSA)2(Val)]

Na3[Zn(CSA)2(Val)]
Na3[Cd(CSA)2(Val)]
Na3[Hg(CSA)2(Val)]

Figure 3: The Proposed Structure of the Complexes Na3[M (CSA)2(Val)]

25
20
15
105
0

E.Coli
Pseudomonas
Bacillus
Staphlococ

Figure 4: Biological effect of compounds

C. Antibacterial study :
The results obtained for antibacterial study models studies by agar well diffusion bioassay revealed
biological activity of the ligands and metal complexes after 24h in [Table 4. Chart -1]. Generally,
Na3[Hg(CSA)2(Val)] and Na3[Cd(CSA)2(Val)]complexes have been shown to be, in most cases, more
effective than the free ligands and their
complexes.(15,28) .The highest (IZ) was observed by
Na3[Hg(CSA)2(Val)] complex against Pseudomonas. The activity of the mixed-ligand chelates may be due to
the effect of the metal ion on the normal cell.[15,28]

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Transactions on Engineering and Sciences

Volume 4, Issue 2, April-June 2016

ISSN: 2347-1964 (Online) 2347-1875 (Print)

Table 4: The Inhibition Circle Diameter in Millimeter for the Compounds

Compounds
Control (DMSO)
(L-Val)
(CSA)
Na3[Mn(CSA)2(Val]
Na3[Co(CSA)2(Val)]
Na3[Zn(CSA)2(Val)]
Na3[Cd(CSA)2(Val)]
Na3[Hg(CSA)2(Val)]

E. Coli (G-ev)
4
15
11
13
15
11
15
21

Pseudomonas (G-ev)
5
15
11
10
22
14
15
17
IV.

Bacillus (G+ev)
4
10
15
15
16
12
16
15

Staphylococcus (G+ev)
6
11
12
11
17

CONCLUSION

The complexes have been successfully synthesized and characterized. , IR and UV-V spectrometry
observations were used to elucidate the structure. The physio analytical data showed that all the complexes
are formed from the reaction of the ligands and the metal salts.
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