المجلة العراقية الوطنية لعلوم الكيمياء-2011 المجلد الثالث والربعون Iraqi National Journal of Chemistry,2011,volume 43
Synthesis, Characterization and Biological Study of Cr(III), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) Complexes with a New Tetradentate Schiff Base Ligand
Rehab Abdul Mahdi A-Hasani Sinan Madhat Mohammed
College of Science, Al-Mustansiriyah University
Enaam Majeed Rasheed College of Science, Al-Mustansiriyah University
(NJC)
(Recevied on 26/12/2010 ) (Accepted for publication 19/ 7 /2011)
Abstract At this paper we describe the synthesis of new Schiff Base (L) : 3,3`-(benzene- 1,4-diyldinitrilo) bis (1,3-dihydro-2H-indol-2-one). The product (L) was characterized by (FT-IR), (UV-Vis) spectroscopy and elemental analysis (C. H. N). (L) has been used as aligand to prepare a number of metal complexes with Cr(III), Mn(II, Co(II), Ni(II), Cu(II) and Zn(II). The prepared complexes were isolated and characterized by (FT-IR) and (UV-Vis) spectroscopy, elemental analysis (C. H. N) flame atomic absorption technique, as well as magnetic susceptibility and conductivity measurement. The Schiff base (L) and its complexes, with different concentration, have been screened for their (In-Vitro) antibacterial on (E. coli) and (Bacillusubtilis) and antifungal (A. niger) and (P. chrysogenum) activities by using different concentration. الخلةصة يتضمن هذا البحث تحضير ليكاند قاعدة شف الجديدة (benzene-1,4-diyldinitrilo)bis (1,3-dihydro-2H-indol-2-one) (L)-`3,3 جرى تشخيص (L) بطرائق تحليل طيف الشعة تحت الحمراء (FT-IR) وطيف الشعة فوق البنفسجية المرئية والتحليل الدقيق للعناصر (C. H. N). وتم إستخدام (L) كاليكاند في تحضير معقدات اليونات الفلزية : الكروم( III) والمنغنيز(II) والكوبلت(II) والنيكل(II) والنحاس(II) والخارصين(II). عزلت المعقدات الجديدة وتم تشخيصها بإستخدام طيف الشعة الحمراء وطيف الشعة فوق البنفسجية المرئية وتقنية التحليل الدقيق للعناصر (C. H. N) وتقنية المتصاص الذري اللهيبي للعناصر إضافة إلى قياسات الحساسية المغناطيسية والتوصيلية الكهربائية. تم إجراء التقويم الحيوي لليكاند قاعدة شف(L) ومعقداتها وبإستخدام تراكيز مختلفة ضد البكتريا (E. coli) و (Bacillussubtilis)، كما وتم إجراء التقويم الحيوي للمركبات ضد الفطريات سبإستخدام (A.niger) و ( (P.chrysogenum
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Introduction and were uncorrected. FT-IR spectra Isatin derivatives have been were recorded using FT-IR 8300 shown to exhibit a wide range of Shimadzu at range (4000-200)cm-1 as biological activity like anti-bacterial(1), CSI disc. Electronic spectra were anti-inflammatory(2), analgesic(3), anti- obtained using UV-1650 PC. viral(4), antifungal(5), anti-tubercular(6) Shimadzu spectrophotometer at room and anti-depressant(7). Schiff bases are temperature. The measurements were important class of ligands due to their recorded using concentration (10-3M) synthetic fleribility, selectivity and of the complex in chloroform as a sensitivity towards the central metal solvent. Micro analytic data for (C. H. atom, structural similarities with N) were obtained by EA-034, mth. natural biological substances, and also, Conductivity measurements were obtained by corning conductivity meter N C due to presence of imine group ( 220. These measurements were ) which imports in elucidating the obtained in (DMF) as a solvent using mechanism of transformation and concentration (10-3M) at rasemination reaction in biological 25oC.Magnetic susceptibility system(8). Metal complexes with Schiff measurements were obtained at 25oCon base of isatin derivatives exhibited the solid state applying Faraday’s remarkable biological activity(9-11). The method by using Bruker BM6 present paper describes the preparation instrument. of a new Schiff base (L) derived from Synthesis of Schiff base Ligand (L) the reaction of isatin and P- The synthesis of Schiff base is phenylenediamine to be used as a schematically presented at scheme (1). ligand that provide four potential donor Schiff base has been synthesized by sites to form complexes with some refluxing the reaction mixture of hot metal ions. The ligand (L) and its ethanolic solution of isatin (0.294g, complexes have been fully 2mmole) and hot ethanolic solution of characterized. P-phenylenediamine (0.11g, 1mmole) Experimental for 4hrs with few of glacial acetic acid. All chemicals were of highest The product obtained after the purity and used as received. evaporation of the solvent was filtered Physical measurement and analysis : and recrystallized from ethanol. Some Melting points were recorded on of the physical and chemical properties Gallenkamp melting point apparatus of the prepared ligand arelisted at table (1) O C
2 C O + H2N NH2
N C R H e f 3 l u C x O
H 4 O h H r s
C N N C N O O (L) N H Scheme -1 H
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Synthesis of Schiff base complexes formation in solution were listed at (A1-A6) table (1). Ethanolic solution (20ml) of In-Vitro antibacterial and antifungal each one of the following metal assay : chloride (1mmole), CrCl3.6H2O, The biological activities of MnCl2.4H2O, CoCl2.6H2O, synthesized Schiff base and its Cr(III), NiCl2.6H2O, CuCl2.2H2O and ZnCl2 Mn(II), Co(II), Ni(II), Cu(II) and was added to an ethanolic solution Zn(II) metal complexes have been (20ml) of (0.366g, 1mmole) of (L) studies for their antibacterial and with stirring. The mixture was heated antifungal activities by agar and potato under reflux for 2 hrs during this time a dextrose agar diffusion methods precipitate was formed. The product respectively(13). The antibacterial and was isolated by filtration, washed antifungal activities were done at 100, several times with hot ethanol and then 200 and 500 mg/ml concentrations in dried under vacuum. Some of the DMF solvent by using two kinds of physical and chemical data of the bacteria (E. coli and Bacillus subtilis) prepared complexes are shown at table and tow kinds of fungi (A. niger and (1). P. chrysogenum). These bacterial Study the complexes formation is the strains were incubated for 24hr at 37oC solution : and fungi strains were incubated for Complexes of (L) with metal 48hr at the same temperature. ions were studied in the solution using Results and Discussion the ethanol as a solvent in order to A- Elemental Analysis : determine [M:L] ratio in the complex The analytical data of Schiff following molar ratio method(12). A base ligand (L) and its metal series of solutions were prepared complexes are given at table (1), in a having a constant concentration [10- satisfactory agreement with the 3M] of the metal ion and (L). The calculated values. The suggested [M:L] ratio was determined from the molecular which are formulated and relationship between the absorption of supported by subsequent spectral and the absorbed light and the mole ratio of molar ratio as well as magnetic [M:L]. The results of complexes moment.
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B- Infrared Spectroscopic Study : complexes reveal that table (2) behaves The reaction of isatin with P- as a four dentate coordinating with ions phenylenediamine produced Schiff metal by oxygen of carbonyl and base (L). this reaction was followed by nitrogen of the azomethine groups, disappearance of absorption bands at therefore, the bands due to νC=O and -1 (3420-3365)cm due to νNH2 and νC=N were shifted to lower characteristic new band at 1653cm-1 of frequencies(16). These observations azomethine group νC=N are utilized to were further indicated by the confirm the structure of (L)(14, 15), table appearance of νM-O, νM-N and νM- (2). Clrespectively(16), as well as υ-OH for A comparison of the infrared some complexes between (3400- spectra of the free ligand and metal 3450)cm-1, table (2).
Table -2 : characteristic stretching vibration frequencies (cm-1) located at FT-IR of (L) and their metal complexes Comp. No. νC=O νC=N νM-N νM-O νM-Cl L 1741 1653 - - -
A1 1714 1647 500 420 387
A2 1729 1616 550 455 383
A3 1705 1647 530 443 366
A4 1699 1655 515 493 -
A5 1697-1728 1631 539 491 380
A6 1722 1633 535 445 -
C- Electronic spectra, magnetic moment and conductance studies : [A2] : The spectrum of dark orange The UV spectrum of Schiff Mn(II) complex showed two band at base (L) showed intense bands at (12562, 263158)cm-1 due to the 6 4 295nm and at 426 which belong to transitions A1g→ T2g and * * (14, 17) 6 4 π→π and n→π respectively , table A1g→ E1g, these assignmentswhen (3). compared with those published for The electronic spectra of the octahedral geometry(21). In addition to Schiff base and metal complexes were the measured magnetic moment of recorded for their solution in this complex which was found to be chloroform at range (200-1100)nm, (5.19B.M), this value refers to high- while the molar conductance were spin (d5) complex(22), table (3). measurement in (DMF) as solvent. Conductivity measurement in (DMF) showed a non-conductive behavior of [A1] : The solution of brown chromium this complex. complex show three absorption bands
appeared at (21739, 22172 and [A3] : The solution spectrum of the 34722)cm-1, following octahedral brownish-red Co(II) complex field with (d3) configuration(18). The showed three bands at (8930, 18588 -1 4 4 effective magnetic moment at room and 30697)cm due to T1g→ T2g(F), 4 4 4 4 temperature was found to be (3.83 T1g→ A2g(F), T1g→ T1g(P) these B.M) revealing to octahedral stereo bands correspond to those of chemistry of the ligand around octahedral geometry(8), magnetic Cr(III) metal ion(19,20). Conductivity in moment of the solidcomplex (4.81 (DMF) showed that complex was due B.M) showed a high-spin Co(II) to be ionic, table (3). complex(23,24). Conductivity
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measurement in (DMF) showed a non-conductive behavior of the [A5] : The electronic spectrum of this complex, table(3). complex showed one band at (16129cm-1) attributable to 2 2 [A4] : The solution of Ni(II) complex Eg→ T2g transition in the gave a light brown colour, which octahedral geometry(28,29). The refers to the presence of vaccant magnetic moment value was (1.82 coordination site on the metal B.M) corresponds to one unpaired ion.The new weak bands in the electron, table (3). The low visible region of Ni(II) complex at conductivity value in DMF showed (18867, 22271 and 24390)cm-1 are a non-conductive behavior. assigned as ligand field bands due to 1 1 the transitions A1g→ A2g, [A6] : Zn(II) complex show no 1 1 1 1 A1g→ B1g and A1g→ Eg absorption peak to rang (380- respectively(18 , 27). Moreover, the 1000)nm that is indicated no magnetic moment of the solid (d-d) electronic transition happened complex (0.00 B.M) indicating a (d10-system) in visible square planer geometry (25, 26) and the region that is a good result for Zn(II) conductivity in (DMF) showed that tetrahedral complex(30,31). the complex was to be ionic, table (3).
Table -3 : Electronic Spectra, Conductance in (DMF) and Magnetic Moment (B.M) of (L) and its metal complexes Molar Comp. Suggested Bands cm-1 Assignment cond. µeff B.M No. Structure MS.cm-1 23474 n→π* (L) - - - 33898 π→π* 4 4 21739 A2g→ T2g 4 4 [A1] 22172 A2g→ T1g(F) 78.68 3.83 O.h 4 4 34722 A2g→ T1g(P) 6 4 A1g→ T2g 12562 6 4 [A2] A1g→ Eg, 13.62 5.19 O.h 263158 4 A1g(G) 4 4 8930 T1g→ T2g(F) 4 4 [A3] 18588 T1g→ A2g(F) 16.33 4.81 O.h 4 4 30697 T1g→ T1g(P) 1 1 18867 A1g→ A2g 1 1 [A4] 22271 A1g→ B1g 62.91 Zero S.q 1 1 24390 A1g→ Eg 2 2 [A5] 16129 Eg→ T2g 16.02 1.82 O.h 229886 [A ] L→M 168.93 Zero T.h 6 317460 (C.T)
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D- In-Vitro antimicrobial assay : evident from the results that the The antimicrobial results are biological activity of some of the metal systemized at table (4). From complexes is higher than the ligand. It antibacterial studies it is inferred that is, however, known that the chelating Schiff base (L) was found to be tends to make Schiff base act as more potentially activity against Bacillus powerful and potent bacterostaticagent, subtilis. In case of antifungal activity thus, inhibiting the growth of bacteria Schiff base and its complexes were and fungi more than the parent Schiff found to be active, table (4). It is base.
Table -4 : Antimicrobial results of Schiff base and its metal complexes Conc (mg.ml- P. Comp. No. E. coli B. subtilis A. niger 1) crysogenum 100 8 11 10 7 (L) 200 9 14 10 8 500 11 18 12 10 100 5 14 7 5 [A1] 200 10 10 10 8 500 13 8 10 10 100 8 12 9 8 [A2] 200 8 9 7 8 500 7 10 10 8 100 10 14 7 9 [A3] 200 12 12 8 10 500 11 10 10 8 100 8 10 9 7 [A4] 200 10 12 10 5 500 8 10 10 9 100 9 16 8 6 [A5] 200 12 11 5 8 500 12 14 7 6 100 5 14 7 7 [A6] 200 12 16 7 6 500 14 18 6 9
Suggested stereo chemistry structure analysis as well as magnetic moment of Schiff base (L) and its metal and conductivity measurements, the complexes [A1-A6] suggested structure of the above According to the results mentioned compounds can be obtained from elemental and spectral illustrated as follows :
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C N N
(L) C N O O N H H
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H
O N
C N N
[A1] C N O Cl OHC2H5 Cr H OHC H Cl 2 5 Cl
H O N
C N N
[A2] C N O OH2 H Mn
H2O Cl Cl
H O N
C N N [A3] C N O OH2 H Co
H2O Cl Cl
C N N
C O N O N Cl2 H Ni H [A4] H H N N O O C
C N N C
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H O N
C N N
[A5] C N O OHC2H5 H Cu H5C2HO Cl Cl
H O N C
N N C
[A6] O N Cl H Zn 2 OH2
OH2
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