مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Synthesis, Characterisation and biological activity for binuclear complexes with Co(II), Cu(II) and Zn(II) with new ligand m-phenylendi(azo-2-naphthol) ligand type N2O2. W. A. J. Al-Saedi Departme nt of Chemistry, College of Education, I bn Al-Haitham, Unive rsity of Baghdad Received in : 23 November 2011 Accepte d in :11 January 2012 Abstract In this work, t he(m-p heny lenediamine) and (2-nap hthol) have been used in the sy nthesis of tetradentate ligand [m-phenylenedi(azo-2-nap hthol)][H2L] type (N2O2). The ligand was reflu xed in the ethanol with the metal ions [Co(II), Cu(II) and Zn(II)] salts, using triethy leamine as a base in (2:2) molar ratio to give the binuclear comp lexes. These comp lexes were characterised by (A.A), F.T .I.R, (U.V-Vis) sp ectroscop ies, along with conductivity , chloride content and melting p oint measurement. These studies revealed an octahedral geometries for Co(II), Cu(II) and Zn(II) complexes with the general st ructure [M 2(L)2(H2O)4]. The ligand and its comp lexes exhibited biolo gical activity against the Bacillus(G+) strain and the Pseudomonase(G-)strains. Keywor d: m-ph eny lene, azo, 2-n aphtho l Introduction The naphthols are naphthalene homolo gues of p henol, with the hy droxy l group being more reactive than the p henols, they can be used in p roduction of dy es and in organic sy nthesis[1], p igments, fluorescent whiteners, t anning agents, antioxidants and antisep tics[2]. 2-naphthol comp ounds had medical uses as a counterirritant in alop ecia, also as an anthelmintic and as an antisep tic in treatment of scabies[3]. Az o comp ounds are among the most p op ular sy nthetic dy es, esp ecially in the clothing and fashion industry . Typically, azo dy es are also used in a variety of cosmetics[4] and as a food colorin g[5], and its biolo gical activity along with oxidation cataly sis and electro chemical analysis[6,7]. In the recent p ast, number of st udies have high lighted the use of azo comp ounds in various si gnificant applications[8,9]. The aim of the present study is sy nthesis, characterisation and evaluate the metal complexes as antibacterial agent as p romisin g addition of new class of comp lexes as metal based drugs. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Materials and Methods All chemicals used supp lied from Fluka and M erck comp anies and used without any further p urification. Infrared sp ectra were p erformed using a Shimadzu (FT –IR)–8400S sp ectrop hotometer in the range (4000 – 400 cm –1 ). Sp ectra were r ecoded as p otassium bromide discs at Ibn-sina comp any. The electronic sp ectra of the comp ounds were obtained using a (U. V.–Visible) sp ectrop hotometer type Shimadzu 160, in the range (200–900 n m) using quartz cell of (1.0)cm len gth with concentration (10 -3 ) mole L -1 of samples in DM F at 25 ° C, and electrical conductivity measurements of the co mplexes were record ed at (25 ºC) for (10 -3 –10 -5 )M solutions of the samples in DMF using a PW 9526 digital conductivity meter. The chloride content determined using p otentiometric titration method on 686–Titro Processor–665 Dosim A–M etrohm/Swiss, and meltin g p oint obt ained using an electrot hermal apparatus Stuart, and metals were determined with a Shimadzu (A.A.) 680G atomic absorption sp ectrop hotometer, all measurements were obtained in Ibn Sina comp any. Ant ibacterial screening was done at central laboratory in biological d epartment, college of science, university of Baghdad, usin g agar d iffusion technique. The comp ounds were screened for their in vitro antibacterial activity against Gram-negative of p sedomonase and Gram-positive of Bacillus bacterial strains. 1-Preparation of the precursor m-phe nylenediazo. M -p heny lenediamine (2.0 g, 18 mmol.) was dissolved in warm mixture of 15 ml. of concentrated hy drochloric acid and 15 ml. of water contained in 250 ml. b eaker, kept in ice- salt bath (0-5) o C whilst st irring vigorously , m-phenylenediamine hy drochloride will sep arate in a f inely divid ed cryst alline form. A cold solution of sodium nitrite (2.48 g, 36 mmo l.)in 16 ml. of water was added slowly and with stirring to an end-point with p otassium ioded-st arch p ap er. 2-Preparation of the ligand m-phe nylenedi(azo-2-naphthol)[H2L]. 2-naphthol (5.0 g, 36 mmol.) was dissolved in a solution of sodium hy droxide (7.0 g) in 25 ml. water, then cooled in ice bath and added to the diazotized solution with stirring. Concentrated hy drochloric acid was added slowly and with vi gorous stirring, and then filtered with gentle suction, washed with water until free acid and dried up on filter-pap er in the air, the yield percent (74%), m.p .(240 o C) dec. 3-Preparation of the [Co2(L)2(H2O)4] complex(1). A solution of (0.1 g, 0.4 mmo l.) of hexahydrated cobalt(II) chlor ide dissolved in 10ml. ethanol was added drop wise to a solution of [H2L] (0.2 g,0.4 mmol.) d issolved in 15 ml.hot ethanol, the PH of the reaction mixture was adjust ed by adding triethy leamine in equiv alent quantity, and the reaction mixture was allowed to reflux for 2 hours. A p recipitate was formed, which was filtered off, washed several times with absolute ethanol and dried, the y ield percent (86%), m.p .(over 300 o C) dec. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 4-Preparation of the [Cu2(L)2(H2O)4](2) and [Zn2( L)2(H2O)4](3) complexes. A similar method to that mentioned for the p reparation of [Co2(L)2(H2O)4](1) comp lex was used to p rep are the complexes of the [H2L] with Cu(II) and Zn(II) ions. Results and Discussion The ligand [H2L] was obtain ed in high y ield by the addition reaction usin g on e equivalent of m-phenylenediazonium and two equiv alent of 2-n aphthol, where a p otentially tetradentate new cyclic ligand typ e N2O2 donor atoms have been sy nthesised. The ligand contains two labile p roton [H2L] and by removing these p rotons an anionic(-2) tetradentate system is formed. The ligand was p repared accordin g to the route shown in the Scheme 1. S cheme 1 preparation of the ligand [H2L] All complexes were prepared wit h similar method by refluxing t he ligand [H2L] wit h t he corresponding met al chloride salt in ethanol, as a solv ent, and t riethy leamin e, as a base where the pure complexes were formed Scheme 2 N2 Cl N2 Cl + 2 OH N=N OH N=N OH KOH مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 +2MCl2.n( H2O) Co, n=6 Cu, n =2 Zn, n=0 Scheme 2 P reparat ion route of the metal complexes. N=N OH N=N OH N=N N=N N=N N=N O M OH2 OH2 H2 O H2 O O O O M مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Infrared spectral data I.R. sp ectral data for the ligand [H2L] and 1, 2 and 3 complexes are shown in Figs.(1,2,3 and 4) resp ectively . The important infrared bands for the ligand and the p roduced comp lexes with their assignments are listed in Table (1). The I.R. sp ectrum for [H2L] disp lay ed band at 3028cm -1 assigned to the aromatic ν(C- H) st retching while a broad band at 3464cm -1 can be att ributed to ν(OH) stretching and the absence of this band in all complexes indicates the deprotonation followed by comp lexation[10], while app earance of bands at (3444, 3429 and 3433) and at(991,995 and 991)cm -1 for comp lexes 1, 2 and 3 resp ectively assigned to coordinated aqua(H2O)ligands. The two bands at (1554 and 1496)cm -1 which can be att ributed to ν(N=N) stretching ortho and meta resp ectively in the sp ectrum of the free ligand, were shifted to a lower frequencies and appeared at (1500,1446), (1500,1473) and (1500,1481) cm -1 for complexes 1, 2 and 3 resp ectively, the shift to lower frequency may be du e to delocalisation of metal electron density into the ligand π-sy stem(HOM O→LUMO), indicating the coordination of nitrogen atom to the metal ions[11,12]. On the other hand, the band at 1315cm -1 which att ributed to the ν(C-O) st retching vibration in the sp ectrum of the free ligand, was shifted to a lower frequencies and observed at 1253, 1300 and 1300cm -1 for the comp lexes 1, 2 and 3 resp ectively, this shift in the ν(C-O)vibration confirms the coordination of nitrogen of the ligand throu gh the o xy gen atom to the metal ion[13,14]. Finally the comp lexes exh ibited bands at the ranges 462-497 and 524-555cm -1 which could be assign ed to the ν(M -O) and ν(M -N) st retching vibration modes resp ectively. (U.V.- Vis.) spectra (U.V.-Vis.) sp ectra and molar conductivity measurement for the ligand and its comp lexes 1, 2 and 3 were shown in Table (2), and the U.V.-Vis. sp ectra were shown in Figs.(5,6,7 and 8) resp ectively. The U.V.-Vis. sp ectrum of [H2L] exhibited intense absorp tion p eak at 305nm due to the (π → π*) transition, and p eak at 486nm related to(n→ π*) transition[15], The U.V.-Vis. sp ectrum of comp lex 1, exhibited a high intense p eak at 240n m due to t he (π → π*) transition and peak at 312nm which refer to the(n→ π*) transition, while a peak at 495nm which refer to the (C.T.)t ransition. Finally the peak at 687nm may be due to ( 4 T1g (F) → 4 A2g (F) ) transition[16], corresp onding to an octahedral geometry around the cobalt(II) ion. The U.V.-Vis. sp ectrum of comp lex 2, exhibited a p eak at 212nm due to t he(π → π*) transition, a peak at 242nm due to (n→ π*) t ransition, and a p eak at 368nm which refer to the (C.T.) transition, while a p eak at 507nm due to ( 2 B1g→ 2 B2 g) transition[16], corresp onding to an octahedral geometry around the cupper(II) ion. The U.V.-Vis. sp ectrum of comp lex 3 exhibited a p eak at 207nm due to t he (π → π*) transition, a peak at 242nm due to (n→ π*)transition, and a p eak at 287nm which refer to (C.T.) transitions[16], t he metal ion Zn(II) of this comp lex belong to d 10 system and this metal do not show (d-d)transition[16], suggesting to an octahedr al geometry around the zinc(II) ion[17]. The molar conductance of the complexes in DM F lie in the 3.01-5.45 S.cm 2 . mole -1 range, indicating their non-electroly tic behavior[18]. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Biological screening : The antibacterial activity test In our study the sy nthesised comp ounds have been screened for their antibacterial activity against the Bacillus(G+) and Pseudomonase(G-) strains by the Nutrient agar diffusion technique[19]. Each of the co mpounds was dissolved in DM F t o give a f inal concentration of 0.001mg/ml, and from the data shown in Table 3, and Fi gs.9 and 10 , all comp ounds exh ibited a biolo gical activity against the Bacillus(G+) st rain [inhibition zone = 20, 21, 22 and 30mm] for the ligand [H2L], Co(II), Cu(II) and Zn(II) comp lexes resp ectively, also the compounds exh ibited a b iolo gical activity against the Pseudomonase(G-) strain [inhibition zone = 20, 5, 5 and 25mm] for the ligand [H2L], Co(II), Cu(II) and Zn(II) comp lexes resp ectively. Table (4) represented below shows the chlor ide content, meltin g p oint, atomic absorption and some other p hy sical prop erties for the ligand and the sy nthesised complexes. Re ferences 1- Ikeda, T.; M isawa, N.; Ichihashi, Y. ; Nishiy ama, S. and Tsuruy a, S., (2005), " Coup ling of 2-naphthol by vanadium cataly st supp orted liqud-phase oxidative on mcm-41", Journal of M olecular Cataly sis A: Chemical, 231: 1381-1169. 2- Charles, C. (1986) W.M . Toxicology of the Ey e. 3rd ed. Sp ringfield, IL, 656. 3-Van der zee, F. P.; Lettinga ,G. and Field, J. A. (2000) The role of ( auto)catalysis in the mechan ism of an anaerobic azo reduction", Water Scien ce & Technology 42: 301-308. 4- Peter Vollhardt and Neil Schore (2010) Organic Chemist ry, Structure and Function, 6th Edition, W. H. Freeman. 5- Fennema, O.R. (1996) Food Chemist ry, 3rd edition, CRC Press. 6- Djebbar, S.; Benali, B.; and Deloume, J. (1998) Sy nthesis, characterization, electrochemical b ehaviour and catalytic activity of manganese(II) complexes with linear and trip odal tetradentate ligands derived fro m Schiff bases Trans.M et. 23: 443-447. 7- Sakakibara, Y.; Okut su , S.; Enokida, T. and Tani T. (1999) Red or ganic electroluminescen ce d evices with a r educed p orp hy rin comp ound, tetrap heny lchlorin, App lied Phy sics Letters 74: 2587. 8- M aury a, RC.; Verma, R. and Singh, H. (2003) Synthesis and Phy sico‐Chemical Studies of Some M ixed‐Ligand Complexes of bis(Benzoy lacetonato)copp er(II) with Some Biolo gically Active Heterocy clic Chelatin g Donors, sy nthesis and Reactivity in Inorganic and M etal- organic Chemist ry, 33: 1063-1080. 9- M aury a, RC.; Rajp ut, S., (2003), "Vanadium Co mplexes of Bioinor ganic Relevance: Sy nthesis, M agnetic, and Sp ectral Studies of Some M ixed‐Ligand Oxov anadium(IV) Complexes Having an N, O‐Donor Environm", sy nthesis and Reactivity in Inorganic and M etal-organic Chemist ry, 33: 1877-1894. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 10- Sarav anakumar, D.; Sengottuvelan, N.; Priyadarshni, G.; Kandaswamy, M . and Okawa, H. (2004) Sy nthesis of unsy mmetrical ‘end-off ’ p henoxo and oximinato di bridged cop p er(II) and nickel(II) comp lexes: sp ectral, electrochemical and magnetic p rop erties. Poly hedron, 23: 665-672. 11- Socrates, G. (1980) Infrared Characterst ic Group Frequencies, Wiley, Newy ork, 32-37. 12- El-Sonbati, A.Z .; El-bindary, A.A. and Al-Sarawy, A.A. (2002) Stereochemist ry of new nitrogen containin g heterocyclic aldehyde. IX. Sp ectroscop ic st udies on novel mixed- ligand co mplexes of Rh(III)", Sp ectrochim Acta Part A 58: 2771-2778. 13- Sreed aran, S.; Bhar athi, K.S.; Rahiman, A.K.; Rajesh, K.; Nirmala, G.; Jagadish, L. ; Kaviyarasan, V. and Narayanan, V. (2008) Sy nthesis, electrochemical, catalytic and antimicrobial activities of novel unsy mmetrical macrocyclic dicomp artmental binuclear nickel(II) comp lexes", Poly hedron, 27: 1867. 14 – Sreed aran, S.; Bhar athi, K.S.; Rahiman, A.K.; Jagadish, L.; Kav iyarasan, V. and Narayanan, V. (2008) Novel unsy mmetrical macrocyclic dicomp artmental binuclear copper(II) complexes bearin g 4- and 6-coordination sites: Electrochemical, magn etic, cataly tic and antimicrobial st udies", Polyhedron, 27: 2931. 15- Samir, A.H.; Hasan, A. and Aziz, M .R. (2010)sy nthesis of some metal comp lexes of azo type ligand and ev aluation of their antibacterial activity ”, Journal of Colle ge of Education al-mustansirya university, 1: 392-406. 16- Lever, A.B.P. (1984) Inorganic electronic sp ectroscopy, 2nd edn. Elesvier, New York. 17- Tajmir-Riahi, H.A. (1991) Coordination chemist ry of vitamin C. p art II. Interaction of L- Ascorbic acid with ZnII, CdII, HgII and M nII ions in the solid st ate and in aqueous solution'', Journal of Inorganic Biochemistry, 42: 47-55. 18- Geary, W.J. (1971) The use of conductivity measurements in organic solv ents for the characterisation of coord ination compounds”, Coord.Rev., 7: 81-122. 19- Shank, R.C.; Duguid, J.P.; M armion, B.P. and Swain, R.A. (1975) M edical M icrobiolo gy the Practical of M edical M icrobiolo gy ” 12th ed. Long M an Group Lted London, 2. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Table (1): I.R. spectral data of the synthesised compounds compo und υ (O- H) υ(N=N)ort ho υ(N=N)met a υ(C=C)n aph. υ(C=C)p hen. υ(C- C)naph. υ(C- C)ph en. υ(C- O) υ(C-H) aro mat ic υ(M- N) υ(M- O) [H2L] 34 64 1554 1496 1610 1600 1450 1404 13 15 3028 - - [Co2(L)2(H2O)4] 34 44 991 aqua 1500 1446 1597 1550 1357 1303 12 53 3059 55 5 497 [Cu2(L)2(H2O)4] 34 29 995 aqua 1500 1473 1593 1549 1400 1346 13 00 2974 52 4 462 [Zn2(L)2(H2O)4] 34 33 991 aqua 1500 1481 1600 1546 1400 1342 13 00 3062 55 0 466 مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Table (2): (U.V.-Vis.) spectral data and molar conducti vity in DMF solution. compo und  Assignment s mS.cm 2 mo l -1 Ratio Suggested struct ure [H2L] 30 5 48 6 π → π* n →π* - [Co2(L)2(H2O)4] 24 0 31 2 49 5 68 7 π → π* n →π* C.T . 4 T 1g (F) → 4 A2g (F) 5.45 Non- electrolyte oct ahedral [Cu2(L)2(H2O)4] 21 2 24 2 36 5 50 7 π → π* n →π* C.T . 2 B1g→ 2 B2g 3.01 Non- electrolyte oct ahedral [Zn2(L)2(H2O)4] 20 7 24 2 28 7 π → π* n →π* C.T . 4.23 Non- electrolyte oct ahedral C.T. :Charge T ransfer Table (3): The biological activity of the compounds compound Bacillus (G+) P seudomonase (G-) [H2L] 20 20 [Co2(L)2(H2O)4] 21 5 [Cu2(L)2(H2O)4] 22 5 [Zn2(L)2(H2O)4] 30 25 control 2 2 مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Table (4): Results of ele mental analysis and physical propertie s for the ligand and the synthesised complexes compound M.wt Yield % Color m.p. Met al Found, (calculat e) Cl - content [C26 H18N4O2] 41 8 74 Red- brown 24 0 Dec. - - [Co2 II C52 H32 N8O4(H2O)4] 1021.8 86 brown Over 30 0 Dec. 11.9 (1 2.4) Nil [Cu2 II C52H32 N8O4(H2O)4] 1031 45 Dark brown Over 30 0 Dec. 13.0 (1 3.2) Nil [Zn2 II C52 H32N8O4(H2O)4] 1034.8 86 brown Over 30 0 Dec. 13.2 (1 3.5) Nil مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Fig. (1): The I.R S pectrum of Ligand [H2L] Fig. (2): The I.R S pectrum of complex (1) Fig. (3): The I.R S pectrum of complex (2) Fig.(4): The I.R S pectrum of complex (3) مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Fig. (5): The U.V.-Vis. S pectrum of ligend (H2L) Fig.(6): The U.V.-Vis. S pectrum of complex (1) Fig.(7): The U.V.-Vis. S pectrum of complex (2) Fig.(8): The U.V.-Vis. S pectrum of complex (3) مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Fig.( 9): Effect of the compounds towards the Bacillus Subtilis Fig. (10): Effect of the compounds towards the Pseudomonas مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 تحضیر وتشخیص و دراسة الفعالیة البیولوجیة لمعقدات ثنائیة النواة بZn(II)، Cu(II)، Co(II)مع اللیكاند الجدید m-phenylendi(azo-2-naphthol) type N2O2. ورود علي جعفر الساعدي قسم الكیمیاء كلیة التربیة ابن الهیثم جامعة بغداد 2012 كانون الثاني 11: قبل البحث في 2011 تشرین الثاني 23:استلم البحث في الخالصة -m] لتحـضیر اللیكانــد الربــاعي الــسن (naphthol-2)و (m-phenylenediamine) البحــث تــم إسـتعمال هــذافـي p henylenedi(azo-2-nap hthol)][H2L] من نوع (N2O2). 2:2بنسبة ] Zn(II) مع Cu(II) و Co(II) [نات تم تصعید اللیكاند بإستعمال االیثانول مذیبا مع امالح االیو االشـعة تحـت الحمــراء (شخـصت المعقـدات بـالطرائق الطیفیـة. الثنائیـه النـواة بوجـود تـراي اثیـل امـین قاعـدة لتكـوین المعقـدات وقیاسـات محتــوى الكلوریــد، و التوصـیلیة الكهربائیــة مــع درجــة ،) المرئیـة مــع االمتــصاص الــذري-البنفــسجیة واالشـعة فــوق ] Zn(II) مــع Cu(II) و Co(II) [ هـذه الدراسـات بینـت ان الــشكل الهندسـي هـو ثمـاني الــسطوح لمعقـدات. االنـصهار M] بالصیغة العامة 2(L)2(H2O)4]البكتریا نوعین من ان المعقدات فعالة تجاه أما قیاسات الفعالیة البیولوجیة فأظهرت Bacillus(G+) and Pseudomonase(G-)strains. , m-phenylenediamine azo, 2-naphthol : الكلمات المفتاحیة مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012