77 American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) ISSN (Print) 2313-4410, ISSN (Online) 2313-4402 © Global Society of Scientific Research and Researchers http://asrjetsjournal.org/ Preparation, Characterization of Mixed-Ligand Complexes for Some Divalent Transition Metal Ions Involving Biologically Important Bidentate Ligands Kamal Rashid Hsejan Al- Jorani* Wasit University, College of Science, Department of Chemistry, Al-Sadea, Baghdad, 00964, Iraq Email: Kjorany@yahoo.com Abstract This paper describes the synthesis, characterization of mixed ligand complexes. The reaction of benzene-1,2- diamine(o-phenylenediamine) derivatives with anthranilic acid (Ant) yield 2-(1H-benzimidazol-2-yl)aniline derivatives (BIAD) as (primary ligands) in Effective and appropriate solvent, which confirmed by FT-IR, Elemental analyses (C. H. N, O) and 1H NMR spectral. These ligands coordinated with some transition metal ions (CoII ,NiII, CuII, ZnII ) and anthranilic acid as (secondary ligand) at the (1 : 1 : 1) ratio of the components to yielded a mixed-ligand complexes. All complexes have been studied by IR spectra, 1H NMR, Elemental analyses (C. H. N. O), atomic absorption, molar conductivity and magnetic moment. Ligands produce chelates with (1;1;1) (metal; ligands; ligand) interactive elements. From all results was suggested that octahedral geometry to complexes and have the formulae [M(BIAD)(Ant)(H2O)2]2- where M = Co(II), Ni(II), Cu(II) and Zn(II). Keywords: Mixed-Ligand; anthranilic acid; BIAD; Benzimidazole. 1. Introduction Benzimidazole is a moiety which contains benzene ring and a heterocyclic imidazole ring. Benzimidazole derivative are an important category of bioactive molecules in the domain of drugs and pharmaceuticals [1]. 2- Substituted analogs of benzimidazoles have very wide range of biologically active compounds, Anti- inflammatory activity [2,3], anti fungi and bacteria[4], antiviral[5], anti-hypertensive[6], human glucagon receptor antagonistic[7], and anti-infective [8] activities. 4-nitro-o- phenylenediamine ligand have a wide used in the synthesis of compounds with biological activities, like Quinoxaline [9], one of the other uses of 4-nitro-o- phenylenediamine ligand is in the Determination of Diacetyl in Beer [10]. ------------------------------------------------------------------------ * Corresponding author. http://asrjetsjournal.org/ American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 78 Anthranilic acid is one of important compounds that have widely biological activity, as an important precursor of tryptophan. Anthranilic acid is used with some mono oxidation metals to studies the demeanor of potassium in the biological systems [11]. Complexes that anthranilic acid contain ligand have extensive biological activity, anti-inflammatory activities[12], antibacterial[13]. The synthesis of a new mix-ligand complexes was a probably the most significant step in the evolution of metal complexes which offer unique properties and new reactivity. Mixed-ligand complexes (anthranilic acid) can inhibit the DNA interactions, and cytotoxicities[14]. Previously study show that the complexes of Rh with anthranilic acid and N-phenyl anthranilic acid can act as catalysts for hydrogenation [15], Terbium(III) complexes of anthranilic acid can appear the photoluminescence properties[16], a model into a peroxidase inhibitor complex[17].The complexes of metals ion with tow differences kinds of bioligands, as a heteroaromatic nitrogen bases may be present the importing biochemical interactions in different ways[18].However, the ligand of anthranilic acid have no anti-inflammatory activity, but it have ability to exhibit activity because of certain binding of Cu(II) ions at inflammatory locations [19]. Anthranilic acid ligand bidentate and bonding to the metals through the ionized carboxyl group and N amine atom [20]. In this work a several of mixed-ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) containing anthranilic acid (Ant) as secondary ligand and 2-(1H-benzimidazol-2-yl)aniline derivatives as primary ligands was synthesized and characterization. 2. Experimental 2.1. Materials and measurements Metals, anthranilic acid (Ant) and all o-phenylenediamine derivatives are provide from BDH and Sigma Aldrich companies were used without purification. Melting points was registered by using digital Stuart scientific SMP30. Infrared Spectra Measurements was registered by FT-IR-8400S – SHIADZU by using KBr discs. 1H- NMR spectra was registered on Burker 500MHz device by employing dimethyl solfoxide-d6 and TMS. TLC were implemented all over ligand reactions by (Gelman sciences LTD. U.K.). (C, H, N, O) analysis data was gained by employing a EA 3000 analysis instrument, (CoII ,NiII, CuII, ZnII ) were determined by atomic absorption technique using Shimadzu AA-6300. The complexes diagnoses by using Magnetic susceptibilities was specified by Sherwood Scientific's Magnetic Susceptibility Balances. Molar conductance of the Mixed-Ligand Complexes was detected in DMF using conductivity meter Alpha-800 in (25 °C, 10−3 mol L−1). 2.2. General methods to prepare the 2-(1H-benzimidazol-2-yl)aniline derivatives (BIAD) ligands Mixture of (0.03 mole, 6.27g) anthranilic acid, (0.03 mole) o-phenylenediamine derivatives, 50 ml dioxane were reflex for 1 hour in water bath. The concentration ammonia solution was graduated addition to mixture. The precipitate collected and recrystallized with C2H5OH to produce crystals. The Physical features of ligands are recorded in (table 1). American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 79 Table 1: Physiochemical properties of ligands (BIAD) ( 1a-g). Comp. o-ph.diam. derivatives Mol. formula Mol. Wt. M.P. % yield colour 1a NH2 NH2 C13H11N3 209.24 85–87 72.68 gray 1b NH2 NH2 Cl C13H10ClN3 243.69 106- 108 76.30 Pale Yellow 1c NH2 NH2 Cl Cl C13H9Cl2N3 278.13 218- 220 84.00 yellow 1d NH2 NH2 Br C13H10BrN3 288.14 225- 227 76.84 Dark brown 1e NH2 NH2 O CH3 C14H13N3O 239.27 231- 233 55.5 gray 1f NH2 NH2 CH3 C14H13N3 223.27 166- 169 53.76 Orang 1g NH2 NH2 OCH3 C15H15N3O 253.29 204- 206 52.12 Colorless 2.3. preparing of 2-(1H-benzimidazol-2-yl)aniline (1a) Were prepared from anthranilic acid and o- phenylenediamine; (1H-NMR) : 12.49 (s, 1H, H-N), 5.0 (s, 2H, NH2), 6.49–6.50 (dd, Phen-H), 6.34–6.38 (dd, Phen-H), 7.84–7.83 (d 1H, Phen-H), 7.12– 7.14 (d, 1H, Phen-H), 7.39–7.41 (m, 2H, Phen-H), 7.59–7.63 (d, 1H, Phen-H). IR (υ, cm-1): 3420-3427 ( -NH2), 3358 (-NH), 1618 (C=N). (Calcd.). Found, to C13H11N3 (209.25): C ( 73.61) H ( 6.29) N ( 21.10)%. Found: C 73.79; H 6.44; N 21.89%. 2.4. Synthesis of 2-(6-chloro-1H-benzimidazol-2-yl)aniline (1b) Was Synthesis from anthranilic acid and 4-chlorobenzene-1,2-diamine; (1H-NMR): 11.97 (s, 1H, H-N), 5.82 (s, American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 80 2H, NH2), 7.36 (s, 1H, Phen-H), 8.51 (d, 1H, Phen-H), 7.14 (d, 1H, Phen-H), 6.99 (d, 1H, Phen-H), 7.62 (d, 1H, Phen-H), 7.28 (t, 1H, Phen-H), 6.96 (d, 1H, Phen-H). IR (υ, cm-1): 3420 - 3418 (- NH2), 3410 (-NH), 1630 (C=N) 1046 (Ar-Cl). (Calcd.). Found, to C13H10ClN3 (243.69): C (65.10) H (5.14) N (18.25) Found: C 65.11; H 5.18; N 18.23 %. 2.5. Synthesis of 2-(4,6-dichloro-1H-benzimidazol-2-yl)aniline (1c) Was prepared from anthranilic acid and 3,5-dichlorobenzene-1,2-diamine; (1H-NMR ): 11.97(s, 1H, H-N), 5.78 (s, 2H, NH2), 8.24 (s, 1H, Benzi-H), 8.28 (s, 1H, Benzi-H), 7.01 (d, 1H, Phen-H), 7.62 (d, 1H, Phen-H), 7.28 (t, 1H, Phen-H), 6.96 (t, 1H, Phen-H). IR (υ, cm-1): 3420 - 3418 (-NH2), 3412 (-NH), 1630 (C=N) 1110 (Ar-Cl). (Calcd.). Found, to C13H9Cl2N3 (278.13) : C(57.15) H(4.26) N(14.12) % Found: C, 57.12 ; H, 4.26; N, 14.13%. 2.6. Synthesis of 2-(6-bromo-1H-benzimidazol-2-yl)aniline (1d) Was synthesis from anthranilic acid and 4-bromobenzene-1,2-diamine; (1H-NMR): 12.10 (s, 1H, -HN), 5.79 (s, 2H, NH2), 7.87 (s, 1H, Benzi-H), 8.46 (d, 1H, Benzi-H), 8.10 (d, 1H, Benzi-H), 6.99 (m, 1H, Phen-H), 7.62 (d, 1H, Phen-H), 7.28 (m, 1H, Phen-H), 6.96 (m,1H, Phen-H). IR (υ, cm-1): 3419 - 3417 (- NH2), 3410 (-NH), 1631 (C=N), 1030 (Ar-Br). (Calcd.). Found, to C13H10BrN3 (288.14) : C(55.20) H(4.50) N(13.51) % Found: C, 55.21 ; H, 4.52; N, 13.59 %. 2.7. Synthesis of 2-(6-methoxy-1H-benzimidazol-2-yl)aniline (1e) Was prepared from anthranilic acid and 4-methoxybenzene-1,2-diamine ; ( 1H-NMR ): 12.55 (s, 1H, H-N), 5.78 (s, 2H, NH2), 7.12 (s, 1H, Benz-H), 8.56 (d, 1H, Benz-H), 6.93 (d, 1H, Benz-H), 6.99 (m, 1H, Phen-H), 7.62 (d, 1H, Phen-H), 7.28 (m, 1H, Phen-H), 6.96 (m,1H, Phen-H), 3.87(s, 3H, methyl). IR (υ, cm-1): 3420 - 3417 (- NH2), 3408 (-NH), 1635 (C=N), 2844-2926 (C-H aliphatic). (Calcd.). Found, to C14H13N3O (239.27) : C(71.28) H(4.98) N(16.56) O(6.69) % Found: C, 71.30 ; H, 4.94; N, 16.60 ; O, 6.67%. 2.8. Synthesis of 2-(6-methyl-1H-benzimidazol-2-yl)aniline (1f) Was synthesis from anthranilic acid and 4-methylbenzene-1,2-diamine ; ( 1H-NMR ): 12.56 (s, 1H, H-N), 5.79 (s, 2H, NH2), 7.43 (s, 1H, Benz-H), 8.12 (d, 1H, Benz-H), 7.00 (d, 1H, Benz-H), 7.62 (m, 1H, Phen-H), 7.54 (d, 1H, Benz-H), 7.28 (m, 1H, Phen-H), 6.96 (m,1H, Phen-H), 2.42(s, 3H, methyl). IR (υ, cm-1): 3421 - 3418 (- NH2), 3411 (-NH), 1633 (C=N) 2840-2931 (C-H aliphatic). (Calcd). Found, to C14H13N3 (239.27) : C(74.33) H(5.87) N(17.82) % Found: C, 74.36 ; H, 5.89; N, 17.80 %. 2.9. Synthesis of 2-(6-ethoxy-1H-benzimidazol-2-yl)aniline (1g) Was synthesis from anthranilic acid and 4-ethoxybenzene-1,2-diamine ; ( 1H-NMR ): 12.11 (s, 1H, -HN), 5.79 (s, 2H, NH2), 8.08 (d, 1H, Benz-H), 6.99 (d, 1H, Phen-H), 8.62 (d, 1H, Phen-H), 8.28 (m, 1H, Phen-H), 6.96 (m, 1H, Phen-H), 4.04 (s, 2H, methylene), 1.34 (s,3H, methyl). IR (υ, cm-1): 3421 - 3415 (- NH2), 3404 (-NH), 1622 (C=N), 2835-2939 (C-H aliphatic). (Calcd). Found, for C14H13N3O (253.29) : C(72.13) H(6.91%) N(15.19) American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 81 O(7.32) % Found: C 72.14 ; H 6.96 ; N 15.58 ; O 7.33%. 2.10. Preparation of the complexes An absolute EtOH solution (10 ml) containing 5 mmol of anthranilic acid plus 5 mmol of suitable metal ions, CoCl2.6H2O, NiCl2.6H2O, CuCl2.2H2O and ZnCl2. Was added slowly to another absolute EtOH solution (10 ml) containing 5mmol 2-(1H-benzimidazol-2-yl)aniline derivatives. The acidity of the mixture was regulating to (PH~ 8) by addition of a little drops of KOH. Mixture of reaction refluxed for 3h, the solvent vaporized by heating to half of volume and Keep it cooled. The precipitate were filtered and washed with cooled distilled water and re-crystallization with EtOH, isolated complexes was dried at 50 0C overnight. 3. Results and Discussion The synthesis of the ligands is illustrative in (Figure 2). The prepared ligands offer satisfactory analysis for the suggested structures, which was specified depends on spectral and elemental analysis [ FT-IR , 1H NMR and (C, H, N, O)] data. Several complexes ions Cobalt, Nickel, Copper, Zinc with mix ligands, was prepared by the reaction of 1:1:1 ratio of Metal with primary, secondary ligands in ethanol are represented in (Figure 4). Figure 2: Preparation of ligands. The suggested mechanism for formation of 2-(1H-benzimidazol-2-yl)aniline derivatives (BIAD) showing in (Figure 3). NH2 NH2 X Y NH2 C OH O NH2 NH X Y NH2 C OH O H P.T. NH2 NH X Y NH2 C O+ O H H NH2 NH X Y NH2 C O -H2O N N H X Y NH2 C O HH N N H NH2X Y - H2O Figure 3: The suggested mechanism for formation of (BIAD). American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 82 N H N NH2 X Y KOH ref. 3 h MCl2.XH 2O EthOH + O OH NH2 O O NH OH2 NH N NH M OH2 X Y Figure 4: Reaction of (Cu-, Ni-, Zn- and Co- ) with primary, secondary ligands. Complexes are colored solids, non-hygroscopic, stable, excellent yields, insoluble in water, ethanol, partially in methanol and soluble in DMF and DMSO. DMF solvent were applied after appropriate dilution for metal analysis. Elemental analyses (C, H, N, O) and atomic absorption technique were Elements and metal contents of the complexes was measured (Table 3). The elemental analysis (molar conductivity, magnetic moments) data of complexes (Table 2) indicate that all complexes are of the nature electrolyte (1 : 3 electrolyte type) in DMF (10-3 M) [21,22]. Table 2: Analytical data and some physical properties of complexes. number complexes Chemical Formula F.W(g·mol- 1) colour M. Point(°C) Yield (%) Μeff (B.M.) Conductivity Cohm-1. cm2.mol-1 1 [Co(1a)(Ant)(H2O)2] C13H12N3O2Co 438.3 Pale green 178-180 73 3.89 221 2 [Ni(1a)(Ant)(H2O)2] C13H12N3O2Ni 438.08 Gray >300 79 3.1 213 3 [Cu(1a)(Ant)(H2O)2] C13H12N3O2Cu 442.9 Deep orange 195-197 77 1.9 211 4 [Zn(1a)(Ant)(H2O)2] C13H12N3O2Zn 444.8 yellow 156-159 68 0 232 5 [Co(1b)(Ant)(H2O)2] C13H11ClN3O2Co 472.7 Dark brown 217-220 89 4.1 237 6 [Ni(1b)(Ant)(H2O)2] C13H11ClN3O2Ni 472.5 Pale green >300 83 3.1 203 7 [Cu(1b)(Ant)(H2O)2] C13H11ClN3O2Cu 477.3 blue >300 85 1.8 207 American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 83 8 [Zn(1b)(Ant)(H2O)2] C13H11ClN3O2Zn 479.2 yellow 220 de 73 0 240 9 [Co(1c)(Ant)(H2O)2] C13H10Cl2N3O2C o 507.2 pale brown 221-223 79 3.9 226 10 [Ni(1c)(Ant)(H2O)2] C13H10Cl2N3O2N i 506.9 green 177-180 69 2.88 218 11 [Cu(1c)(Ant)(H2O)2] C13H10Cl2N3O2C u 511.8 Violet 233-236 83 1.76 235 12 [Zn(1c)(Ant)(H2O)2] C13H10Cl2N3O2Z n 513.7 Gray >300 85 0 231 13 [Co(1d)(Ant)(H2O)2] C13H11BrN3O2Co 517.2 pale brown 187-200 66 4.3 234 14 [Ni(1d)(Ant)(H2O)2] C13H11BrN3O2Ni 517.0 green 213-216 91 3.4 203 15 [Cu(1d)(Ant)(H2O)2] C13H11BrN3O2Cu 521.8 Deep violet 230-233 74 1.9 223 16 [Zn(1d)(Ant)(H2O)2] C13H11BrN3O2Zn 523.7 Gray 214-217 79 0 214 17 [Co(1e)(Ant)(H2O)2] C14H14N3O3Co 468.3 pale brown >300 85 4.5 235 18 [Ni(1e)(Ant)(H2O)2] C14H14N3O3Ni 468.1 green >300 71 3.3 225 19 [Cu(1e)(Ant)(H2O)2] C14H14N3O3Cu 478.0 Deep brown >300 91 1.78 229 20 [Zn(1e)(Ant)(H2O)2] C14H14N3O3Zn 474.8 gray >300 80 0 231 21 [Co(1f)(Ant)(H2O)2] C14H14N3O2Co 452.3 pale brown 143-146 75 4.7 205 22 [Ni(1f)(Ant)(H2O)2] C14H14N3O2Ni 452.1 yellow 184-188 78 3.4 232 23 [Cu(1f)(Ant)(H2O)2] C14H14N3O2Cu 457.0 Deep violet 122-125 83 2.0 214 24 [Zn(1f)(Ant)(H2O)2] C14H14N3O2Zn 458.8 Gray 200-203 90 0 238 25 [Co(1g)(Ant)(H2O)2] C15H16N3O3Co 482.3 pale brown >300 82 4.8 236 26 [Ni(1g)(Ant)(H2O)2] C15H16N3O3Ni 482.1 blue 269-272 76 2.87 210 27 [Cu(1g)(Ant)(H2O)2] C15H16N3O3Cu 487.0 Violet 280-283 69 1.9 219 28 [Zn(1g)(Ant)(H2O)2] C15H16N3O3Zn 488.8 Gray 240-242 64 0 207 American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 84 Elemental analysis exhibit in the (table-3-) show that all mixed-ligand Complexes have (1:1:1) stoichiometry with estimate (Metal: BIAD : Ant.) , all of them have a dark colored amorphous substances. Table 3: Analytical data of complexes.(M = Co ,Ni, Cu, Zn ) Complexes % C (Calcd).Found % H (Calcd).Found % N (Calcd).Found %O (Calcd).Found %M (Calcd).Found [Co(1a)(Ant)(H2O)2] (54.80) 54.78 (4.37) 4.35 (12.78) 12.68 (14.60) 14.68 (13.45) 13.51 [Ni(1a)(Ant)(H2O)2] (54.83) 54.81 (4.37) 4.35 (12.79) 12.75 (14.61) 14.59 (13.40) 13.44 [Cu(1a)(Ant)(H2O)2] (54.23) 54.78 (4.32) 4.30 (12.65) 12.63 (14.45) 14.41 (14.35) 14.39 [Zn(1a)(Ant)(H2O)2] (54.01) 54.04 (4.31) 4.29 (12.60) 12.65 (14.39) 14.36 (14.71) 14.84 [Co(1b)(Ant)(H2O)2] (50.81) 50.83 (3.84) 3.81 (11.85) 11.82 (13.54) 13.52 (12.47) 12.32 [Ni(1b)(Ant)(H2O)2] (50.84) 50.82 (3.84) 3.84 (11.86) 11.84 (13.54) 13.51 (12.42) 12.37 [Cu(1b)(Ant)(H2O)2] (50.32) 50.35 (3.80) 3.78 (11.74) 11.71 (13.41) 13.38 (13.31) 13.43 [Zn(1b)(Ant)(H2O)2] (50.12) 50.09 (3.79) 3.76 (11.69) 11.65 (13.35)13.32 (13.65) 13.75 [Co(1c)(Ant)(H2O)2] (47.36) 47.34 (3.38) 3.36 (11.05) 11.11 (12.62) 12.58 (11.62) 11.58 [Ni(1c)(Ant)(H2O)2] (47.38) 47.36 (3.38) 3.35 (11.05) 11.12 (12.62)12.59 (11.58) 11.56 [Cu(1c)(Ant)(H2O)2] (46.93) 46.91 (3.35) 3.33 (10.95) 10.93 (12.50) 12.47 (12.42) 12.39 [Zn(1c)(Ant)(H2O)2] (46.76) 46.74 (3.34) 3.32 (10.91) 10.88 (12.46) 12.43 (12.73) 12.70 [Co(1d)(Ant)(H2O)2] (46.44) 46.41 (3.51) 3.49 (10.83) 10.80 (12.37) 12.35 (11.39) 11.36 [Ni(1d)(Ant)(H2O)2] (46.46) 46.44 (3.51) 3.47 (10.84) 10.87 (12.83) 12.80 (11.35) 11.32 [Cu(1d)(Ant)(H2O)2] (44.85) 44.89 (3.37) 3.34 (11.01) 11.05 (12.58) 12.56 (12.49) 12.47 [Zn(1d)(Ant)(H2O)2] (45.87) 45.93 (3.46) 3.44 (10.70) 10.68 (12.22) 12.20 (12.49) 12.47 [Co(1e)(Ant)(H2O)2] (53.85) 53.82 (4.52) 4.49 (11.96) 11.94 (17.08) 17.11 (12.58) 12.55 [Ni(1e)(Ant)(H2O)2] (53.88) 53.82 (4.52) 4.49 (11.97) 11.95 (17.09) 17.06 (12.54) 12.51 [Cu(1e)(Ant)(H2O)2] (53.33) 53.42 (4.48) 4.47 (11.85) 11.82 (16.91) 16.95 (13.44) 13.41 [Zn(1e)(Ant)(H2O)2] (53.12) 53.18 (4.46) 4.43 (11.80) 11.76 (16.85) 16.89 (13.78) 13.75 [Co(1f)(Ant)(H2O)2] (55.76) 55.83 (4.68) 4.66 (12.39) 12.36 (14.15) 14.12 (13.03) 13.01 [Ni(1f)(Ant)(H2O)2] (55.79) 55.85 (4.68) 4.63 (12.39) 12.37 (14.16) 14.13 (12.98) 12.95 [Cu(1f)(Ant)(H2O)2] (55.20) 55.24 (4.63) 4.60 (12.26) 12.24 (14.01) 14.06 (13.91) 13.88 [Zn(1f)(Ant)(H2O)2] (54.97) 54.93 (4.61) 4.57 (12.21) 12.18 (13.95) 13.91 (14.26) 14.23 [Co(1g)(Ant)(H2O)2] (54.78) 54.74 (4.81) 4.78 (11.61) 11.59 (16.58) 16.55 (12.22) 12.19 [Ni(1g)(Ant)(H2O)2] (54.81) 54.77 (4.81) 4.77 (11.62) 11.58 (16.59) 16.57 (12.17) 12.15 [Cu(1g)(Ant)(H2O)2] (54.26) 54.23 (4.76) 4.73 (11.50) 11.57 (16.43) 16.41 (13.05) 13.02 [Zn(1g)(Ant)(H2O)2] (54.05) 54.10 (4.74) 4.71 (11.46) 11.43 (16.36) 16.34 (13.38) 13.35 American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 85 3.1. Infrared spectra The FT-IR of ligands show perfect value of peaks which conform the structure, the spectra of complexes Showed disappear some of active group peaks and appear the new peaks (Table 4). In complexes spectra υ(- NH2) frequency of sharp absorption bands (~3415-3422 cm-1) of 2-(1H-benzimidazol-2-yl)aniline derivatives (BIAD) disappearance , also disappear the band at (3592 cm−1 ),(3394-3542 cm-1 symmetric and asymmetric) corresponding to (O–H), (NH2) stretching respectively in anthranilic acid [23], that conclusive evidence of coordinate metal ions both by nitrogen of NH2 group (in BIAD, Ant.) and oxygen atoms of the carboxylic group. This was also confirmed by outcrop of a new band at ( ~420 , ~535 cm-1 ) due to the υ(M-O, M-N) respectively (Table 4). The clear, new interesting bands can be observed at (~3745 cm-1) which related to H2O molecules [24,25] , and that good evidence of Participate the H2O molecules in inner coordination sphere of complexes. The bands shifts of active group (C=O) in complexes can be observed in comparison with free anthranilic acid bands. Table 4: FT-IR spectral data in cm-1 to the complexes. complexes υ O- H υ N- H2 Ant. υ N-H2 BIAD υ N-H BIAD υ (C-H) Aliph υ Ar-Cl υ Ar- Br υ C=O Ant. υ H2O υ (M- N) υ (M- O) [Co(1a)(Ant)(H2O)2] ---- --- --- 3404 --- --- --- 1712 3732 521 437 [Ni(1a)(Ant)(H2O)2] --- --- --- 3411 --- --- --- 1710 3711 523 430 [Cu(1a)(Ant)(H2O)2] --- --- --- 3409 --- --- --- 1717 3749 521 452 [Zn(1a)(Ant)(H2O)2] --- --- --- 3403 --- --- --- 1724 3718 554 412 [Co(1b)(Ant)(H2O)2] --- --- --- 3389 --- 1045 --- 1694 3743 513 423 [Ni(1b)(Ant)(H2O)2] --- --- --- 3393 --- --- --- 1697 3708 523 411 [Cu(1b)(Ant)(H2O)2] --- --- --- 3378 --- --- --- 1685 3774 544 404 [Zn(1b)(Ant)(H2O)2] --- --- --- 3421 --- --- --- 1701 3714 560 409 [Co(1c)(Ant)(H2O)2] --- --- --- 3417 --- 109 4 --- 1705 3775 545 423 [Ni(1c)(Ant)(H2O)2] --- --- --- 3411 --- --- --- 1707 3753 543 452 [Cu(1c)(Ant)(H2O)2] --- --- --- 3407 --- --- --- 1715 3747 526 428 [Zn(1c)(Ant)(H2O)2] --- --- --- 3414 --- --- --- 1711 3742 513 416 [Co(1d)(Ant)(H2O)2] --- --- --- 3406 --- --- 105 1709 3735 527 411 American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 86 5 [Ni(1d)(Ant)(H2O)2] --- --- --- 3402 --- --- --- 1718 3738 543 458 [Cu(1d)(Ant)(H2O)2] --- --- --- 3397 --- --- --- 1712 3726 536 437 [Zn(1d)(Ant)(H2O)2] --- --- --- 3393 --- --- --- 1710 3731 524 417 [Co(1e)(Ant)(H2O)2] --- --- --- 3410 286 1- 298 7 --- --- 1713 3718 513 435 [Ni(1e)(Ant)(H2O)2] --- --- --- 3413 --- --- --- 1709 3720 540 418 [Cu(1e)(Ant)(H2O)2] --- --- --- 3396 --- --- --- 1707 3729 544 454 [Zn(1e)(Ant)(H2O)2] --- --- --- 3391 --- --- --- 1716 3737 550 436 [Co(1f)(Ant)(H2O)2] --- --- --- 3418 284 5- 298 9 --- --- 1712 3742 547 412 [Ni(1f)(Ant)(H2O)2] --- --- --- 3405 --- --- --- 1711 3740 551 445 [Cu(1f)(Ant)(H2O)2] --- -- --- 3412 --- --- --- 1709 3710 537 426 [Zn(1f)(Ant)(H2O)2] --- --- --- 3406 --- --- --- 1702 3716 548 415 [Co(1g)(Ant)(H2O)2] --- --- --- 3409 282 1- 297 6 --- --- 1716 3726 536 421 [Ni(1g)(Ant)(H2O)2] --- --- --- 3417 --- --- --- 1713 3729 529 431 [Cu(1g)(Ant)(H2O)2] --- --- --- 3399 --- --- --- 1709 3716 556 416 [Zn(1g)(Ant)(H2O)2] --- --- --- 3392 --- --- --- 1711 3715 531 440 3.2. 1H NMR spectra of the compounds 1H NMR spectra data of the complexes was gained at d6 - DMSO in (R.T.) utilize TMS as an internal standard (Table 5). Chemical shift of the NH2 protons in the ligands (~5.7 ppm for BIAD),(8.4 ppm for Ant.) was not noted in all the complexes. This conforms the bind of nitrogen and oxygen to the metal ions (N-M, O-M). The similarly result was proven by the FT-IR spectra. The singlet signal at δ 4.2–4.1 ppm appear due to the H2O atoms from the coordinated water molecule. All other absorption bands for the aromatic, aliphatic and (NH benzimidazole) protons in the ligands are in the same chemical shift and not affected by coordination. American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 87 Table 5: 1H NMR spectra of the complexes in d6-DMSO (δ ppm). complexes OH NH2 New NH OH2 [Co(1a)(Ant)(H2O)2] --- --- 4.3 4.2 [Ni(1a)(Ant)(H2O)2] --- --- 4.3 4.2 [Cu(1a)(Ant)(H2O)2] --- --- 4.3 4.1 [Zn(1a)(Ant)(H2O)2] --- --- 4.3 4.2 [Co(1b)(Ant)(H2O)2] --- --- 4.3 4.1 [Ni(1b)(Ant)(H2O)2] --- --- 4.3 4.1 [Cu(1b)(Ant)(H2O)2] --- --- 4.3 4.2 [Zn(1b)(Ant)(H2O)2] --- --- 4.3 4.2 [Co(1c)(Ant)(H2O)2] --- --- 4.4 4.1 [Ni(1c)(Ant)(H2O)2] --- --- 4.4 4.2 [Cu(1c)(Ant)(H2O)2] --- --- 4.4 4.2 [Zn(1c)(Ant)(H2O)2] --- --- 4.4 4.1 [Co(1d)(Ant)(H2O)2] --- --- 4.4 4.2 [Ni(1d)(Ant)(H2O)2] --- --- 4.4 4.2 [Cu(1d)(Ant)(H2O)2] --- --- 4.4 4.2 [Zn(1d)(Ant)(H2O)2] --- --- 4.4 4.2 [Co(1e)(Ant)(H2O)2] --- --- 4.4 4.1 [Ni(1e)(Ant)(H2O)2] --- --- 4.4 4.1 [Cu(1e)(Ant)(H2O)2] --- --- 4.4 4.2 [Zn(1e)(Ant)(H2O)2] --- --- 4.4 4.2 [Co(1f)(Ant)(H2O)2] --- --- 4.4 4.2 [Ni(1f)(Ant)(H2O)2] --- --- 4.4 41 [Cu(1f)(Ant)(H2O)2] --- --- 4.4 41 [Zn(1f)(Ant)(H2O)2] --- --- 4.4 4.1 [Co(1g)(Ant)(H2O)2] --- --- 4.4 4.2 [Ni(1g)(Ant)(H2O)2] --- --- 4.4 4.1 [Cu(1g)(Ant)(H2O)2] --- --- 4.4 4.2 [Zn(1g)(Ant)(H2O)2] --- --- 4.4 4.2 4. Conclusion In summary, we have synthesized and characterized ligands of (BIAD), prepared in this work through condensation of anthranilic acid and o-phenylenediamine derivatives in suitable solvent (dioxin). Twenty-eight complexes of mixed ligand with (CoII ,NiII, CuII, ZnII ) ions were prepared and characterized through {FT-IR, American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) (2017) Volume 38, No 2, pp 77-89 88 1H NMR, (C, H, N, O) analysis, atomic absorption, Magnetic susceptibilities, Molar conductance}. Data of all Previous Techniques support octahedral geometry for all metal complexes. Depends on the spectral and physical data of ligands and complexes which discussed previously, one can suppose that the metal ions are bind to the ligands through the carboxylic oxygen and amino nitrogen as clarify in Figure 1. O H H O H H NHO O N H N NH M X Y Figure 1: The suggested geometry of complexes. M = CoII, NiII, CuII, ZnII. Reference [1]. 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