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Department of Chemistry, College of Education and Pure Science, UniversityofKerbala, Karbala, Iraq.
2Department of Chemistry, College of Education and Pure Science, University of Kerbala, Karbala, Iraq.
ABSTRACT
The amideligand type N2S2 have been prepared through one step. Included the reaction between one equivalent of ethylene di amine and oneequivalent of mercapto acetic acid compound. the Mn+2, Zn+2,Fe+3from there action of theligand Complexes were preparedwith metalions (1:1) ratio, the prepared compounds were characterized by (FT-IR, UV-Vis,
1HNMR) for the ligand and complexes,(C.H.N)-spectoscopies, as well as the molar conductivity and magnetic successptibility for preparedcomplexes. Thesemeasurements showsallthecomplexes have octahedral shape.and make biological study with two types of bacteria(grampositive and gramnegative).
KEYWORDS
Mercepto Acetic Acid, Ethylene Di Amine,Spectra Measurements,Biological Study.
Introduction
complexcompoundschemistry havebig importancein coordinationchemistry. it knownas coordinationcomplexes or complexescompounds,whichhavecentralmetal atom or ion surroundedby number of molecules or ions couldligands which linked by coordinationwithcentral atom.[1]Thesecompoundshavebig role in menyfildes like industry, agriculture,medicine and engineering [2], N2S2 compounds is basicimportance among organic compounds, some of them have biological role as antitumor [3], anti faver, anti fugnal, anti bacterial, anti HIV and as β- lactamase inzyem inhibitors in biological reactions [4-5].Studys mention that compounds have nitrogen and sulphate as donating atoms used as catalystfor several chemical reactions [6] and used in another applications as photocraphicmaterelase, reagents [7-8], mimics for meny biological systems and used these ligands in Radio pharmaceulrical [9].In anotherhandamidesare organic compounds containe active group could amideNH2– C=Osynthysidefromcarbonylgroup–C=Olinkwith amine –NH2.amides have two types, aliphatic and aromatic and divided to (primary, secondary, tertiary), aromatic amides less active than aliphatic one because of resonance between pair of electrons on nitrogen atom and π- electrons on carbonyl group.Most amides are solid but the simplest one formamide is liquid and have high fusion degrees. these compounds synthesizedby manyprosegers as react alcohol with amines, Easters with amines, but in this studywe react the carboxyl acid with amine with loss aqua molecule [10-13].
Material andEquipment
All chemicals used from Merck andhave enoughpurification. Meltingpointweremeasuredby (electro thermal) melting pointapparatusFT-IR spectrameasuredwith Shimadzu FT-IR-4800Sinfraredspectrophotometer by using KBrdisk,1H- NMR spectra by used Broker-400 MHz –Germany with DMSO-d6solvent. UV-Visible spectrarecorded by UV- Visiblespectrophotometer-1800 Shimadzu, and Digital Conductivity meter–WT-720–in lab(Germany) was used to measure the electrical conductivity.
Synthesis ofLigand
Add (1.6×10-2mol, 1.11 ml) from ethylene di amine to (3.2×10-2 mol, 2.2 ml) mercapto acetic acid in ice bath(0-5)°C with stirring,a gelatin compound will synthesis, then add30 mlofhotmethanol( 30° C), we noticewhiteparticipate, filter and wash twice with coldethanolandether [14], after dry give 1.586 gm, 46.4%, MP: (101-103) °C, formula : C6H12N2S2O2,M.wt :208.29 gm/ mol, C:34.60,H:5.81, N:13.45, found C:34.51,H:5.61,N:13.36.
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Fig. 1. Synthesis of ligand Synthesis ofLFeComplex
Add (0.75×10-3,0.25 gm) from FeCl3.6H2O dissolve in 15ml ofD.W to (1×10-3 mol,0.18gm) from ligand dissolve in 15ml ofethanol with reflux to (60-70)°Cwithstirring, for two hours, we noticeblackparticipate, filter and washtwicewithcoldethanolandether, after dry give 0.31 gm,77.5 %, MP: (299-300) °C, formula : C6H10N2S2O2Fe(H2O)2Cl,M.wt :351.62 gm/mol, C:20.50,H:4.59, N:7.97, found C:20.44,H:4.13,N:8.03
Synthesis ofLMnComplex
Add (0.76×10-3 mol,0.25 gm) from MnCl2.2H2O dissolve in 15ml ofD.W to (1×10-3 mol,0.18 gm) from ligand dissolve in 15ml ofethanol with reflux to (60-70)°Candstirring, for two hours, we noticeoff -whiteparticipate, filter and wash twice with coldethanolandether, after dry give 0.34 gm,85 %,MP:dec. (294) °C, formula : C6H10N2S2O2Mn(H2O)2,M.wt:330.12 gm/mol: C: 21.70,H:3.04, N:8.44, found C:21.60,H:3.12,N:8.51.
Synthesis ofLZnComplex
Add (0.73 ×10-3 mol,0.25 gm) from ZnCl2dissolve in 15ml ofD.W to (1×10-3 mol,0.18 gm) from ligand with reflux to (60-70)°Cand stirring, for two hours, we noticewhiteparticipate, filter and wash twice with coldethanolandether, after dry give 0.34 gm,83 %, MP: (<300) °C, formula : C6H10N2S2O2Zn(H2O)2,M.wt : 342.56 gm/mol, C: 21.04,H:2.94, N:8.18, found C: 21.13,H: 2.83,N: 8.28.
Fig. 2. Synthesis of complexes
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between(1645-1510)cm-1, in other hand, new bands will appear like ʋ(O-H) for water between(4438- 4470) cm-1. plus ʋ(M-N), ʋ(M-S) between (412-434) cm-1 and (502-553) cm-1 respectivelythatprovecoordination.[16-17] as show in table (1).
Figure 3.IR spectra for liqand
Figure 4.IR spectra for MnL complex
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Figure 5.IR spectra for FeL complex
Figure 6.IR spectra for ZnL complex
Table 1.IR spectra for ligand and it complexes Compound ʋ (O-H)
Water
ʋ (N-H) ʋ(-CH2) alfatic
ʋ (S-H) ʋ(-C=O) ʋ (M-S) ʋ(M-N)
H2L ….. 3362 w 2914w 2760 w 1587 s ….. …..
MnL 3440 b 3309 w 2924w …… 1510 s 501w 412 m
FeL 3470 b 3325m 2937w …… 1645 s 515-553m 432-470 m
ZnL 3438 b 3385 s 2935w …… 1506 s 507 w 434-468m
b = broad, w = weak, m = middle, s = strong Ultraviolet- Visible
Theelectronicspectraofligandfigure (7) show wideband in (ʎ =234-275)nm belong to π - π٭andn -π*,[18-19] when we comparedit with UVspectrumofcomplexes havenoticed thedifferences, electronicspectraofMn(II) complex figure (8) show three bands at (ʎ=300) nm attributed to charge transition (C.T.) and (ʎ=472)nm, (ʎ=577)nm due to the d-d transitions type 6A1g-4A1g,6A1g -4Eg, Fe (III)figure (9)show two bands at (ʎ=310) nm belong to C.T., (ʎ=363) nm due to d-d transition type6A1g -4A1g,while ZnL complexfigure (10)show one band at(ʎ=308) nm belong to (C.T.), no d-d transition at visible region because Zn(II)has d10.[20]
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Figure 7.UV- Visible Spectrafor H2L
Figure 8.UV- Visible Spectrafor MnL complex
Figure 9.UV- Visible Spectrafor FeL complex
Figure 10.UV- Visible Spectrafor ZnL complex
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1H-NMR Spectrafor Ligand and Complexes
The 1H-NMR spectrum in DMSO – d10 (δ = 2.43-2.57 ppm) ofthe ligand Fig (11)displays the chemical shift at (δ = 8.1 ppm, 2H ) assigned to protons (N- H), the signals at (δ = 4.40 ppm, 2H) for tutomersumin amide bond(
), and (δ = 3.40 ppm, 4H) belong to protons (-CH2) for ethylene di amine and( δ
= 2.88 ppm, 4H) for protons (-CH2) next to (-SH) groupswhichhave(δ = 1.24 ppm, 2H ) shifting.[21], while the 1H- NMR spectra in DMSO – d10 (δ = 2.45 ppm) ofthe Complexes Figs (12),(13) and (14) show disappear shifting of (- SH) groupsbecauseofcoordination.[22] and appear chemical shifts at (δ = 8.1 ppm, 2H, δ = 8.6 ppm, 2H, δ = 8.5 ppm, 2H) assigned to protons (N-H) for Mn(II), Fe(III), Zn(II) complexes respectively. And signals for protons (- CH2) to ethylene di amine at (δ = 3.34-3.39 ppm, 4H, δ = 3.34-3.39 ppm, 4H, δ = 3.33-3.37 ppm, 4H)respectively.finally,displays the chemical shifts at (δ = 3.29 ppm, 4H, δ = 3.29 ppm, 4H, δ = 3.20 ppm,4H)respectively for protons (-CH2) next to(S) atoms.and (δ = 2.51ppm, 4H, δ = 2.51ppm,4H, δ = 2.38ppm, 4H) respectively for (H2O) protons.
Figure 11.1H-NMRSpectrafor H2L Ligand
Figure 12.1H-NMRSpectrafor MnL complex
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Figure 13.1H-NMRSpectrafor FeL complex
Figure 14.1H-NMRSpectrafor ZnL complex Magnetic Susceptibility and Molar Conductivity
The magnetic properties of the prepared complexes were measured by Faradi methodshowsthe complexes Mn (II) and Fe (III) are paramagnetic with (B.M.) dueto existence offive unpaired electrons and dia magnetic ofZn(II) complex[23], and the molar conductivity of the complexes was recorded in DMSO solvent [24] appears the complexes Mn(II) and Zn(II) were non- electrolyte and Fe(III) was electrolyte with 1:1 ratio, supported with octahedral geometry for Mn (II), Fe (III) and Zn (II) complexes. as show in table (2).
Table 2.Magnetic susceptibility and molar conductivity forcomplexes
compound Magnetic susceptibility(B.M.) molar conductivity hypredization Proposed structure
MnL 5.81 10.3 Sp3d2 Octahedral
FeL 5.83 37.2 Sp3d2 Octahedral
ZnL diamagnatic 5.1 Sp3d2 Octahedral
The Antibacterial Activity
ThebacterialstrainEscherichia coli andStaphylococcus aureus were used in this work andthen cultured on muller-
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hinton medium andincubatedat 37 ºCfor 24 h the standardizedantimicrobial disc,[25] were preparedfrom (L, MnL, FeLand ZnL) by using sternal filter paper discsaturatedwith solution for each compoundsFor Staphylococcus aureus the highest inhibitoryeffect was observedin compoundZnL whichshowed low effect from bacteria and followedtheinhibitory effect is low from MnL to FeL andthelowesteffect can sow it in compoundLshowFigure (15).
For E. coli the highest inhibitory effectwas observed in compound ZnL followed by FeLand the lowest antibacterialactivity was observedwith compound MnL and then was no activity with L compound show Figure (16).
Figure 15.For Staphylococcus zone
Figure 16. For E. colizone
Table 3.Zone inhibition (Key of symbols: zone inhibition= mm) Compound Staphylococcus E. coli
H2L (1) 10 _
MnL (2) 12 9
FeL (3) 19 15
ZnL (4) 21 21
Conclusion
The molar conductivity and magnetic, as well as the biological activity the success stability. Suggested octahedralgeometry around themanganeseand iron and zincions.
References
[1] Shriver, D.F., Atkins, P.W., Oveton, T.L., Rourke, J.P., Weller, M.T., Salmon, T.F., Weber J.H., &
Armstrong, F.A. (2009). Inorganic chemistry. 6th Ed. New York.
[2] Dave, V.G., & Vyas, P.J. (2010). Synthesis,structuralelucidation andantimicrobialactivities of some complexes of Mg(II) having N2S2 potential donors in 18-24membered macrocyclic rings. International Journal of Chemistry and Applications,2(2),88-102.
[3] Sathisha, M.P., Shetti, U.N., Revankar, V.K., & Pai, K.S.R. (2008). Synthesis and antitumor studies on novel Co (II), Ni (II) and Cu (II) metal complexes of bis (3-acetylcoumarin) thiocarbohydrazone. European
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methyl and S-benzyldithiocarbazate and the X-crystal structure of the[Pd (mpasme)Cl] complexe.
Transition Metal Chemistry,31,79-87.
[6] Kennedy, A.R., Okoth, M.O., & Walsh, D. (2011). Cantena-poly [(nitrito – k 2 O,O' ) Silver (1)]-µ-1,2 - bis[1- (pyridine – 4-yl) ethylidene ] hydrazine –k2 N:N']. Metal-organic compounds, 67(8), 1138.
[7] Kumar, S., Dhar, D.N., &Saxena, P.N. (2009). ApplicationsofmetalComplexesofSciff-bases– A Review.
Journal of Scientific and Industrial Research, 68, 181-187.
[8] Reddy, P.R., & Reddy, A.M. (2002). Synthesis and characterization of Mixed Ligandcomplexes of Cu(II), Ni(II) and Co(II) with cytidine & amino acids. Indian Journal of Chemistry, 41, 2083-2087.
[9] Dua, R., Shrivastava,S., Sonwane, S.K., & Srivastava, S.K. (2011). Pharmacological significanceof synthetic Hetro cycles Scaffold. Journal of Advanced biological Research, 5(3),120-144.
[10] Gunanathan, C., Ben-David, Y., & Milstein, D. (2007). Direct synthesis of amides from alcohols and amines with liberation of H2. Science, 317(5839), 790-792.
[11] David, K. (2011). Organic chemistry.John wiley& Sons, 1003.
[12] Kim, B.B., Lee, H.G., Kang, S.B., & Yoon, Y.J. (2012). Effect of substrate Temperature onResidral stress ZnO Thin films prepred by Ion bea Deposition. Synthesis,8(1), 27-32.
[13] Boonen, J., Bronselaer, A., Nielandt, J., Veryser, L., De Tre, G., & De Spiegeleer, B. (2012). Alkamid database: Chemistry, occurrence and functionality of plant N-alkylamides. Journal of Ethnopharmacology, 142(3), 563-590.
[14] Jawad, S.H.A. (2014). Synthesis new macrocyclic ligands type N2S2 and theirmetalcomplexes and studying thermodynamic properties of complexes. M.Sc.thesis, Kerbala University.
[15] Zadeh, A.S., Mansoori, G.A., Hasemian, A.R., Eshghi, H., Sszgarnia, A., &Montazerabadi, A.R. (2010).
Dynemic Bio chemistry. Process Biotechnology and Molecular Biology, 4(1),6-12.
[16] Dawood, A.H., Kareem, E.T., &Madlool, A.M. (2012). Binuclear Divalent Complexes ofCobalt, Nickel And Copper with N2S Ligand Derived from 1,3,4-Thiadiazole 2,5-dithiolate Dipotassium Synthesized via Click Chemistry. International Journal of Chemical, 4(6), 64-74.
[17] Nakamoto, K. (1997). Infrared and Raman spectra of Inorganic Coordination.5thEd.Part B,Joh N Wiley &
Sons, New York.
[18] Abass, S.K., Al-Hilfi, J.A., Abbas, S.K., & Ahmed, L.M. (2020). Preparation, characterization and study the photodecolorization of mixed-ligand binuclear Co (II) complex of Schiff base by ZnO. Indonesian Journal of Chemistry, 20(2), 404-412.
[19] Sharma, R.K. (2007). Text Book of Coordination Chemistry. Discovery PublishingHouse.
[20] Gökce, H., &Bahçeli, S. (2013). Analysis of molecular structure, spectroscopic properties (FT-IR, micro- Raman and UV–vis) and quantum chemical calculations of free and ligand 2-thiopheneglyoxylic acid in metal halides (Cd, Co, Cu, Ni and Zn). Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 116, 242-250.
[21] Silverstein, R.M., &Webster, F.X. (1998). Spectrometric identification of organiccompounds.6th Ed. John wiley and Sons, New York.
[22] Mir, J.M., Maurya, R.C., Rajak, D.K., Malik, B.A., Jaget, P.S., & Jain, N. (2017). A novel Schiff base complex of brain fuel (sugar) coordinated with intelligence mineral (Zn): synthesis, conjoint DFT-
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experimental evaluation and super oxide dismutation. Karbala International Journal of Modern Science, 3(3), 153-164.
[23] Dilek, S. (2017). J. Biol. and chem, 45 (1), 67-80.
[24] Kettle, S.A. (1975). Coordination Compounds Thomas Nelson and Sons. London, 3(186), 212.
[25] Alnasrawi, T.H., Jawad, S.A., Salman, H.E., & Al-Haideri, M.R. (2020). Synthesis, Characterization and Study of Schiff Base Ligand Type N2 and Metal Complexes with Di Valence Nickel, Copper and Zinc. International Journal of Pharmaceutical Research, 1, 1246- 1251.
