Synthesis and Antibacterial Activities of Some mixed ligand complexes

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, µeff (B.M) as well as the conductivity measurements (Λm ). 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].

It’s 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 Λm 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 ν(NH2) and υ(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 υ(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 υ(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 [ν(C-OH ) and ν(C-Cl)] respectively[24-25], and the bands at 1608cm-1and1361cm1were attributed to [υ(COO)asym] asymmetric and to [υ(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 Δν -COO-)asym –ν(-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 [ν(C=C) and ν(C-H)] aromatic stretching, respectively . [26].The appearance of new

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Transactions on Engineering and Sciences 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 υ(N→M str) and υ(O→M str), υ(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 (π –π*) electronic transition[27-28].The electronic spectrum of (CSA) appeared peak at 301 nm attributed to(π –π*) 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 6A1g→4T2g(G) and 6A1g→4T1g(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., Δo =10 Dq=13037 cm-1 (first spin-allowed transition}, Δo= ΔE= 13037 x 0.01196=155.92 kJ/ moL ΔE = Δo =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 (λmax) 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

υ(NH2) + (υ OH)(

υasy(COO)

υsym(COO)

υ(M-N)

υ(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

λmax (nm)

Wave number (cm-1)

€max (L.mol-1.cm-1)

Λm (S.cm2.mol-1) in DMSO (10-3M)

µeff (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 185873 134222 130371 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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