Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 3(12), 50-53, December (2013) Res. J. Chem. Sci. International Science Congress Association 50 Transition Metal Complexes of Bidentate Ligand N-aminoquinolino-2- one and Anthranilic HydrazideIsraa A. Hassan Department of chemistry, College of Science University of Mosul, IRAQAvailable online at: www.isca.in, www.isca.me Received 24th November 2013, revised 3rd December 2013, accepted 18th December 2013Abstract This research involves the preparation of some transition metal complexes of Ni(II), Cu(II), Zn(II) and Hg(II) with the ligand N-aminoquinolino-2-one(L) andmixed ligands such as anthranilic hydrazide as abidentate ligand. Complexes of the general formula [M(L)Cl], [M(LCl] and[M(L(L)]Cl were prepared through direct reaction of the above ligand with the metal respectively (1:1), (1:2) and (1:2:1)ligand with anthranilic acid. These complexes characterized by means of Microanalysis (M) molar conductance measurements, Magnetic measurements, Infrared and electronic spectral techniques. Keywords: Metal complexes, N-amino quinolino-2-one, spectral study. Introduction Interest in coordination chemistry is increasing continuously with the preparation of organic ligands containing a variety of donor groups1-2 and it is multiplied many fold when the ligand have biological importance3-4. Coumarins have stimulated extensive research in biology, organic chemistry and medicine, due to their antibiotic, anti–coagulan6-7, anticancer, anti-inflammatory, Coumarins are now a day an important group of organic compounds that are used as additives to food and cosmetic10, the derivatives of coumarin usually occur as secondary metabolites present in seeds, roots and leaves of many species. Transition metal has varying utility and interesting chemistry Coordination compounds are important due to their role in biological and chemical system in various ways. Al-Amery reported the synthesis and antimicrobial studies of Co(II), Ni(II), Cu(II)) complexes with Schiff bases derivative from N-amino Quinolone11. The present research reports the preparations and characterization of some new complexes formed by the reaction of Ni(II), Cu(II), Zn(II) and Hg(II) with two different donor atoms12. Experimental: The ligands (L) have been synthesized according to the reported procedure13. Material and Methods All chemical were of reagent grade, were used as supplied (Fluka) or (B.D.H.) metal estimation were done on PYE UNICAM SPg atomic absorption spectro-photometer.the chloride was determined using the method in Vogel14. Conductivity measurements for 10-3M solution of the complexes in (DMF) were carried out with on Jenway 4070 conductivity meter and a dip cell with platinalized electrode. Infrared spectra were recorded on a FTIR Burcker Tensor 27co spectrophotometer in 400-4000 cm-1 range using KBr discs. The UV/Vis spectra were recorded on Shimadzu UV-160 spectrophotometer for 10-3 M solution of complexes in DMF using 1cm quartz cell. Melting points were measured using anelectro thermal 9300 digital melting point apparatus. Magnetic susceptibility was measured on the solid state by Faradays' method using Burcker BM6 instrument at 25C. All magnetic susceptibility values were corrected for diamagnetic using Pascal's constant. Synthesis of the ligand: Treatment of coumarin (1.46gm, 0.01mol) with excess hydrazine hydrate (99%) (3.2 gm, 0.1 mol) in absolute ethanol (25ml) was refluxed for 12h , it was then cooled and the formed solid was collected and recrystallized from chloroform (m.p131-133C). O O + NHNH N O NH Preparation of the metal complexes Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 3(12), 50-53, December (2013) Res. J. Chem. Sci. International Science Congress Association 51 A-1 [M (L) Cl2] or [M (LCl]: A hot ethanolic (20ml) solution of the ligand (L)(1.34 gm. 0.01mol) or(2.68gm 0.02mol) was added hot ethanolic (20ml) solution of the metal salts (0.01 mol) with stirring the mixture was reflexes for hr-cooling gave complexes with different color. They were filtered off washed with cold Etoh and dried in vacuum. B-2[M (L(L)]Cl: The same above procedure besides the addition of the ligand (L) Results and Discussion The new bidentate (L) was prepared by the reaction of coumarin with excess of hydrazide hydrate to give N-amino quinoline -2- one in high yield. The complexes were prepared through direct reaction of the metal chlorides NiCl.6HO, CuCl. 6HO, ZnCl2 and HgCl with the above ligand in different molar ratio, gave the complexes of the general formula [M(L)Cl], [M(LCl],and some mixed ligand like anthranilic hydrazide as bidentate ligand. The analytical date of the ligand and its complexes are given in table-1. These data were in a good agreement with the proposed formula. All the complexes in the air are stable at room temperature and in insoluble in common organic solvents but they are soluble in dimethyl forma amide (DMF) or dimethyl sulfoxide (DMSO). The electrical molar conductance of the complexes no. (1-8) were (14–31) ohm-1 mol-1 cm indicating non–conductive. Where the complexes no. (9–12) gives (151–192) which are corresponding conductivity complexes indicating a 1:2 ohm-1mol-1 cm electrolytic nature of the complexes15 (table-1) Table-1 Physical properties of ligand and its complexes No Complex Color M.P Yield Molar Conductivity cm -1, mol-1 Elemental analysis L 1 Orange 131-133 91% 1. [Ni(L 1 )Cl 2 ] Light blue 246 80% 22 20.41 (18.92) 2. [Cu(L 1 )Cl 2 ] Brown 270 81% 29 21.61 (23.26) 3. [Zn(L 1 )Cl 2 ] Yellow 198.8 73% 15 22.26 (18.99) 4. [Hg(L 1 )Cl 2 ] Light yellow 218.4 60% 21 50.90 (47.14) 5. [Ni(L 1 ) 2 Cl 2 ] Grey 153 86% 26 13.16 (11.50) 6. [Cu(L 1 ) 2 Cl 2 ] Brown 182 84% 24 14.01 (14.33) 7. [Zn(L 1 ) 2 Cl 2 ] Dark yellow 144 67% 31 14.46 (12.69) 8. [Hg(L 1 ) 2 Cl 2 ] White 139 69% 14 36.33 (34.10) 9. [Ni(L 1 )(L 2 )]Cl 2 Grey 118.9 70% 151 10.93 (9.99) 10. [Cu(L 1 )(L 2 )]Cl 2 Dark green 143.0 64% 155 11.66 (10.02) 11. [Zn(L 1 )(L 2 )]Cl 2 Light yellow 124.3 72% 192 12.04 (11.20) 12. [Hg(L 1 )(L 2 )]Cl 2 Light orange 133.2 57% 159 29.78 (27.15) Table-2 Infrared spectral data of ligand and their complexes No. Compound N-H N-N C=O N-H M-N M-O L 1683 930 1198 3060 1. [Ni(L 1 )Cl 2 ] 1640 987 1167 3244 490 450 2. [Cu(L 1 )Cl 2 ] 1645 976 1157 3236 471 461 3. [Zn(L 1 )Cl 2 ] 1625 975 1163 3282 525 462 4. [Hg(L 1 )Cl 2 ] 1641 977 1184 3246 513 423 5. [Ni(L 1 ) 2 Cl 2 ] 1634 985 1240 3445 471 439 6. [Cu(L 1 ) 2 Cl 2 ] 1636 969 1157 3381 485 453 7. [Zn(L 1 ) 2 Cl 2 ] 1628 978 1125 3234 495 441 8. [Hg(L 1 ) 2 Cl 2 ] 1640 980 1163 3373 503 465 9. [Ni(L 1 ) 2 (L 2 )]Cl 2 1630 957 1161 3373 492 427 10. [Cu(L 1 ) 2 (L 2 )]Cl 2 1641 966 1161 3341 503 435 11. [Zn(L 1 ) 2 (L 2 )]Cl 2 1625 977 1238 3218 512 427 12. [Hg(L 1 ) 2 (L 2 )]Cl 2 1639 945 1230 3415 528 427 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 3(12), 50-53, December (2013) Res. J. Chem. Sci. International Science Congress Association 52 Infrared spectral studies of the free ligand shows strong band at 1683 cm-1which is assignable(C=0) of coumarin and other band at 3060, 1198 cm-1 belong to NH, NH. The spectra bands of complexes at (1625–1645) cm-1 were characterized for the carbonyl group which indicates that the oxygen atom of the carbonyl group was coordinated to the metal ion and the prepared complexes exhibited NH in the range of (3236–3445) cm-1, which shows a shifting to the higher frequencies, A medium band at (1230-1271)cm-1 maybe assigned to NHstretching vibration. Weak band located at (930-987) cm-1 can be assigned (N-N) group. negative and positive shift in (N-N) hydrazide groups16. The absorption band in the range (471–535) and (423–465)cm-1 were assigned to (M–N) and (M–O) bands (table 3) Table-3 Magnetic moment and electronic spectral data of the complexes No. Complexes µ eff(B.M) max cm - 1 1. [Ni(L 1 )Cl 2 ] 3.29 13173,15889,30860 2. [Cu(L 1 )Cl 2 ] 1.34 15330,15514,26042 3. [Zn(L 1 )Cl 2 ] ____ 27933,30120 4. [Hg(L 1 )Cl 2 ] ____ 25000,34101 5. [Ni(L 1 ) 2 Cl 2 ] 2.91 10419,16534,25509 6. [Cu(L 1 ) 2 Cl 2 ] 1.99 13290,17250,25011 7. [Zn(L 1 ) 2 Cl 2 ] ____ 26040,34021 8. [Hg(L 1 ) 2 Cl 2 ] ____ 30131,32000 9. [Ni(L 1 )(L 2 )]Cl 2 2.71 10101,18559,26737 10. [Cu(L 1 )(L 2 )]Cl 2 1.73 12871,19424,31002 11. [Zn(L 1 )(L 2 )]Cl 2 ____ 30822,32011 12. [Hg(L 1 )(L 2 )]Cl 2 ____ 28212,34120 The magnetic moment of Ni (II) complexes no.1 was 3.29 B.M. The electronic spectra showed broad band in the range at (13173–15889) cm-1 assigned to 1(F)1(p)transition17 and another band at 30860 cm-1was absorbed due to charge transfer these values suggested a tetrahedral geometry18, but another Ni(II) complexes no.(5,9) the magnetic moment were(2.91,2.88) B.M and the electronic spectra of these complexes shows three bands at (10126–10149) (16534–18559) (25509–25899)cm-1 correspond to three spin allowed transition (F))(F)(1), (F) (2) and (F) (p) (3) 19. The magnetic moment of Cu(II) complexes (2, 6, and 10)has been found to be (1.34, 1.99, and 1.73) B.M the lower value suggested the presence one unpaired electron. The electronic spectra of this complex showed a band at (15330–15514)cm-1 were assigned to g Eg transition in tetrahedral environment20, where the electronic spectra of two copper (II) complexes display bands at (13290-17250) and (12871- 19424) cm-1 assigned to the Gg transition in distorted octahedral structure around the Cu(II) ions21-22. N N O M Cl Cl Fig.-1- N N O M Cl Cl Fig.-2- N O N N O M Fig.-3- O N N N N C O H Suggested structure of complex , where M = Ni+2, Cu+2, Zn+2, Hg+2 Figure-1 Figure-2 Figure-3 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 3(12), 50-53, December (2013) Res. J. Chem. Sci. International Science Congress Association 53 Conclusion The electronic spectra of Zn(II), Hg(II) complexes gives only charge transfer in the range(25000–34211)cm-1 and the magnetic susceptibility showed that all these complexes were diamagnetic23. 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