Conseguences of soil crude oil pollution on some wood properties of olive trees Chemistry |69 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Synthesis, Spectroscopic and Theoretical Studies of Some New Transition Metal Complexes with Mixed ligands Schiff Base and Bipyridyl Abbas Ali Salih Al-Hamdani Dept. of Chemistry/College of Science for Women/University of Baghdad Maher Abdulrazk Mohammad Alta'yy Nawres Khalid Gabraael Al-dulyme Dept. of Chemistry/ College of Education for Women/ University of Mousl Received in:23/March/2016،Accepted in:9/October/2016 Abstract The complexes Shiff base and mixed ligands complexes of bipyridyl and Schiff base 1,5- dimethyl-4-(5-oxohexan-2-ylideneamino)-2-phenyl-1H-pyrazol-3(2H)-one (L) with Cr(III), Mn(II), Fe(II) and Co(II) were prepared. The compounds have been characterized by FT-IR, UV-Vis, mass and 1 H and 13 C-NMR spectra, magnetic moment, elemental microanalyses (C.H.N.), chloride containing, atomic absorption and molar conductance. The studies made are indicating towards octahedral geometry for these complexes. Hyper Chem-8 program has been used to prediction structural geometries of compounds in gas state, the heat of formation, binding energy, total energy and electronic energy and dipole moment at 298 o K. The compounds were also screened for their bioactive to antibacterial and antifungal. Key words: Complexes, Mixed ligands, Bipyrdayl, Bioactive. Chemistry |70 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Introduction Schiff bases are a class of important compounds in medical and pharmaceutical field. They show biological activities including antibacterial, antifungal[1,2], anticancer and herbicidal activities[3]. The notion of mixed ligands complexes is always fascinating to the chemistry interest in synthesis because of their easiness of synthesis and generally less time requirement for using synthesized ligand and metal salt these reactions to happen than normal complex formation reaction. These formation have prompted many researchers to publish their research work in this wonderful and interesting area of study[4-6]. mixed ligand complexes play an important role in numerous biological and chemical systems such as water softening, ion exchange resin, drying, electroplating, photosynthesis in plants, antioxidant, removal of undesirable and harmful metals from living organisms. Much of these metal complexes exhibit good biological activity against pathogenic microorganisms[7-13]. bipyridyl and its derivatives are betwen the most more utilized class of ligands [14-51]. In report herein the synthesis and spectroscopic studies as well as the thermal realization of a new mixed ligands bipyridyl and Schiff base with some transition metals to Cr(III), Mn(II), Fe(II) and Co(II). The complexes were characterized by FT.IR, UV-Vis, mass spectra, magnetic moment, elemental microanalyses (C.H.N.), chloride containt, atomic absorption and molar conductance, were obtained to determine the structure of the complexes, theoretical and also studies of biological activeties. Materials and Methods The following chemicals were commercially available and were used without further purification: (2,5-hexanedione, 4-aminoantpyrene, FeCl2.H2O, Aldrich)( diethyl ether, CaCl2, bipyridyl, CrCl3.6H2O, BDH) (DMSO, pure ethanol, methanol, Fluka)(MnCl2.4H2O CoCl2.6H2O, Reedel). FT-IR spectra were recorded in the range (4000-400) cm-1 on a Shimadzu 3800, spectrometer. Electronic absorption spectra were recorded in the range (200-900)nm for solution in Dimethyl sulfoxide (DMSO) (103-) on a Shimadzu 160 Spectrophotometer. 1H- 13C NMR spectra were recorded using Bruker 400 MHz spectrometer Elemental (C.H.N) analyses were carried out on a Perkin-Elmer automatic equipment model 240.B. Mass spectra were obtained by using LC-Mass 100P Shimadzu. Melting points obtained on a Buchi SMP - 20 capillary melting point apparatus and are uncorrected. Metal ratio were identified using a Shimadzu (A.A) 680G Atomic Absorption Spectrometer. Conductivity measurements were measured for solution in DMSO(103-) using a Jenway 4071 digital conductivity meter in room temperature, Chloride ion content is specified by using potentiometric titration method at a 686-Titro processor – 665 Dosimat Metrohm Swiss. Magnetic properties were measured using (Magnetic susceptibility balance model MSR- MKI). Study of Bioactivity: All the metal complexes,ligands and metal salts were screened against staphylococcus aureus (gram positive ) and Pseudomonas aeruginosa (gram negative) bacteria as well fungi like Penicillium expansum, Fusarium graminearum, Macrophomina phasealina, and Candida albicans, by using the wall agar diffusion method. using solvent (DMSO), the concentration of the compounds by this exposure was (10-3 M) by using disc sensitivity inspection. This method involves the exposure of the zone inhibition toward the diffusion from micro-organism on agar plate. The plates were incubated for 24 and 48 hurs of bacteria and fungi respectively at 37 OC. Chemistry |71 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Synthesis of Schiff base Ligand: 1,5-Dimethyl-4-(5-oxohexan-2- ylideneamino)-2-phenyl-1H-pyrazol-3 (2H) -one. (16) A solution of 4-aminoantpyrene (1 g, 4.92 mmol) in methanol (25 ml) was mixed with a solution of 2,5-hexanedione (0.56g, 4.92mmol). The reaction was stirred and heated at (40- 50)°C for four hrs. A colorless precipitated formed which was washed with diethyl ether and recrystallized from ethanol: water (1:1) mixture. The product was dried via anhydrous CaCl2 in vacuum as shown in Scheme (1). The yield is (1.38g), 93.66%, mp.179°C. N N H3C H3C O NH2 CH3 C CH2 H2C C H3C O O N N H3C H3C O N CH3 C H2C CH2 C CH3 O H2O 1,5-Dimethyl-4-(5-oxohexan-2-ylideneamino) -2-phenyl-1H -pyrazol-3(2H )-one 2,5-hexanedione MeOH / Ref luxe 4- aminoantipyrene Scheme (1) Synthesis of Schiff base Complexes A solution of Schiff base ligand (0.25g, 0.836 mmole) in methanol was added gradually with stirring to 0.105g, 0.222g, 0.165g 0.198g respectively, of FeCl2.H2O, CrCl3.6H2O, MnCl2.4H2O and CoCl2.6H2O, respectively. The reaction mixture was allowed to reflux and the solid wase collected by filtration recrystallized from ethanol and dried in labortory temperature. Microelemental analysis data, yiled and color at the compounds are given in Table(1). Synthesis of Mixed Ligands Complexes A solution of the Schiff base ligand (0.25g, 0.836 mmole)in methanol was added gradually with stirring to the 0.105g, 0.222g, 0.165g 0.198g respectively, of FeCl2.H2O, CrCl3.6H2O, MnCl2.4H2O and CoCl2.6H2O, respectively.It was added to the mixture gradually while stirring (0.13g,0.836mmol)of bipyrdayl dissolved in (10)cm 3 methanol, The reaction mixture was allowed to reflux and the solids were collected by filtration recrystallized from ethanol and dried in room temperature. Microelemental analysis data, color and yield for the compounds are given in Table (1). Programs used in theoretical calculation Hyper Chem-8 program is a sophisticated molecular modeler, editor and powerful computational pack that are known for its type, flexibility and ease of use. It is also uniting 3D visualization and animation with quantum chemical calculations, molecular mechanics and dynamics. at the present work, parameterization method (PM3) was used for the calculation of heat of binding energy and formation for all metal complexes. PM3 is more popular than last semi empirical method due to the availability of algorithms and it is more accurate than last method .PM3 / TM is an extension of the PM3 method to include orbital’s with transition metals[17]. Chemistry |72 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Results and Discussion The LC-Mass for ligand (Schiff base) (299.3m/ z) with (C17H21N3O2), (244.2 m/ z) with (C14H18N3O), (243.3m/ z) with (C14H17N3O) and (144.2m/ z) with (C6H14N3O). 1 H-NMR (DMSO-d6, ppm): δ 2.044 (s‚3H, N=C-CH3), 2.147 (s‚3H, O=C-CH3), 3.11 (s, 3H, C=C- CH3), 3.31 (s‚3H, N-CH3), 5.88 (tri, 4H, CH2-CH2), 7.282-7.513 (m, 5H, Ar-H). 13 C-NMR (100.622 MHz, DMSO-d6): δ 162.22 (C16), 153.25 (C12), 134.67 (C4), 129 (C2, 6), 127 (C8, 10), 124.31 (C9), 109.83 (C11), 105.95(C7), 77.25(C5, 15), 76.93(C3), 50.41(C17), 36.09 (C4), 12.5 (C13), 10.62 (C1), shown the Figure (1). Molar conductance values in (DMSO) solution (10-3M) were found in the range (12-23) S. cm2 mol-1for all complexes Cr(III), Mn(II), Fe(II) and Co(II) which indicates that they are non-electrolytes, except that of Cr(III) mixed ligand complex with bipyrdyl (43) S. cm 2 . mol - 1 which refers to electrolyte nature (1:1) [18,19]. Physical properties and elemental microanalysis in are listed in Table(1). Mass spectra for complexes High resolution mass spectra of the [Mn(L)Cl2(H2O)2], [Co(L)Cl2(H2O)2] and mixed ligands [Cr(L)(bipy)Cl2]Cl , [MnL(bipy)Cl2] and [FeL(bipy)Cl2] complexes, Shous parent ion peak m/z=461.3(M), 465.2(M), 614.3(M), 581.3(M), 571.4(M) respectively[19]. Further details for the fragmentation and their relative abunduance for each compound are given in Table(2). IR spectra 1.Infrared Spectra from Free Ligands The spectrum of ligands(L) and bipy exhibited weak bands at 3035 and 3055 cm-1, this could be attributed to ν(C-H) aromatic respectively. Other strong bands belong to the ν(C=N) were found at 1640 and 1617 cm -1 respectively. The spectrum of ligand L, was noticed band at exhibited two bands 1740 and 1696 cm -1 which lwere attributed to ν(C=O)ring of pyrazol and ν(C=O) respectively. 2.Infrared Spectra Complexes The infrared spectra from the prepared complexes exhibited ν(C=N) at the range from 1616-1626cm -1 which exhibited a shifting to the lower frequencies 16-18 cm -1 comparison with ligand (L), also appeared shifting to the higher frequencies among 9-7 cm -1 comparison with ligand (bipy), whose indicated the coordination from ligands with metal ions through the nitrogen atoms by their structures. The spectra of complexes showed bands in the range of 1670-1678cm-1 were differentiate for the carbonyl group which suffer a shift. So, it is suggested that the oxygen atom of the carbonyl group is coordinated with the metal ion [11]. the spectra of complexes showed bands at (487-548) cm -1 referred to the ν(M-N) and in the range of (412-490)cm -1 which was attributed to the of ν(M-O) [20-22]. This indicates that the ligand was coordinated with the metal ions through O carbonyl groups and N azomethine group. The IR-spectral data for the ligands and prepared complexes were listed in Table(3) UV–Vis Spectra, Magnetic Moments The electronic spectrum from the ligands of Schiff base and bipy exhibit intense absorption in (282,280)nm attributed to π→π* respectively. Cr(III) Complexes [Cr(L)Cl3 (H2O)] and [Cr(L)Cl2(bipy)]Cl gave two absorptions at (287, 299nm) assigned to ligand field respectively. The electronic spectrum of [Cr(L)Cl3(H2O)] complex showed three broad peaks at 493, 601 and 668 nm assigned to(d-d) transition type 4 A2g → 4 T1g (p), 4 A2g → 4 T1g (F), 4 A2g → 4 T2g (f) respectively and the given peak at 361 nm due for charge transfer (C.T). The electronic spectrum of [Cr(L)Cl2(bipy)]Cl complex showed three broad peaks at 487,640 and 752nm Chemistry |73 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 assigned to(d-d) transition type 4 A2g→ 4 T1g(P), 4 A2g→ 4 T1g(F), 4 A2g→ 4 T2g(F) respectively and a peak at 414 nm due to charge transfer (C.T). Mn(II) Complexes [Mn(L)Cl2(H2O)2] and[MnL(bipy)Cl2] gave absorptions at (293, 293nm) assigned to ligand field respectively. The electronic spectrum of [MnLCl2(H2O)2] complex showed two broad peaks at 429 and 488 nm assigned to (d-d) transition type 6 A1g → 4 A1g, 4 Eg(4G), 6 A1g → 4 T2g(4G) respectively. The electronic spectrum of [MnL(bipy)Cl2] complex showed two broad peaks at 498 and 632nm assigned to(d-d) transition type 6 A1g→ 4 A1g, 4 Eg(4G), 6 A1g→ 4 T2g(4G) respectively and apeak at 428 nm due to charge transfer(C.T). Fe(II) Complexes [Fe(L) Cl2(H2O)2] and [Fe(L)Cl2(bipy)] gave absorptions at (279, 282,348nm) assigned to ligand field respectively. the electronic spectrum of [Fe(L)Cl2(H2O)2] complex showed one broad peak at 481 nm assigned to(d-d) transition type 5 T2g(D) → 5 E1g(D) and two peaks at (359, 438nm ) due to charge transfer (C.T). [Fe(L)Cl2(bipy)] complexes showed one broad peak at 489nm assigned to 5 T2g(D) → 5 E1g(D) and one peak at 436nm due to charge transfer (C.T). Co(II) complexes [Co( L)Cl2(H2O)2] and [Co(L)Cl2(bipy)] gave two absorptions at (280, 298nm) assigned to ligand field respectively. the spectrum of [Co( L)Cl2(H2O)2] complex showed three broad peaks at 611, 652 and 664 nm assigned to(d-d) transition type 4 T1g(F)→ 4 T1g(p), 4 T1g(F)→ 4 A2g(F) to 4 T1g(F)→ 4 T2g(f),transition respectively and two peaks at 414 and 488nm due to charge transfer (C.T). The spectrum of [Co(L)Cl2(bipy)] complex showed three broad peaks at 621,669 and 760nm assigned to(d-d) transition type 4 T1g(F)→ 4 T1g(p), 4 T1g(F)→ 4 A2g(F), 4 T1g(F)→ 4 T2g(f) transition respectively. The (d-d) electronic transition for all prepared complexes were in a good agreement for octahedral geometry around Cr(III), Mn(II), Fe(II) and Co(II) central ion. The magnetic moment value (3.78, 3.79), (5.93, 5.81), (4.91, 5.00) and (3.70, 3.65) B.M. of Cr(III) (d 3 ) Mn(II) (d 5 ), Fe(II) (d 6 ) and Co(II) (d 7 ) complexes respectively are typical for octahedral geometry [22-24]. All these electronic spectra data can be shown in Table (4). Electrostatic Potentials Electron distribution governs the electrostatic potential of the molecules. The electrostatic potential (E.P) term the interaction of energy from the molecular system with a positive point charge. (E.P) is helpful at finding sites of reaction in a molecule; positively charged species tend to attack a molecule where the electro static potential is strongly negative (electrophonic attack) [17]. The (E.P) of the free ligand was calculated and shape as 2D contour to investigate the reactive sites from the molecules show in Figure (3). Also one can interpret the stereo chemistry and rates of many reactions involving “soft” electrophiles and nucleophiles on terms from the properties of frontier orbital HOMO and LUMO. The results of calculations show that the LUMO of transition metal ions prefer to reaction with the HOMO of two-donor atoms of oxygen carbonyl and nitrogen from azomethen group at free ligands [25], Figure (2). All theoretically probable structures of free ligand and their complexes have been calculated through (PM3) and (ZINDO/1) methods in gas state to search for the most probable model building stable structure. Calculation from parameters has been optimized bond lengths of the free ligand and metal complexes which to give excellent agreement with the experimental data as shown in Table (5). Antimicrobial activity of ligands and all complexes Bipyridyl, schiff base, metal salts and their complexes of transition metals were screened for antibacterial and antifungal activity. The entire tested compound exhibited variable activity antifungal and antibacterial as shown in figures (4 and 5). Schiff base activity exhibited antibacterial against S. aureus and P.aeruginosa but activity was to be lower than the metal complexes and salts metals. bipy also exhibited activity antibacterial against S. aureus and P.aeruginosa but activity high in complexes and metal Chemistry |74 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 salts as shown in, Figure (4). schiff base which did not exhibit have antifungal activity but exhibited activity was in some metal complexes and salts metals as shown in, Figure (4). Where exhibited CrL and CoL Complex activity lower compared with salts of Cr and Co against P.expansum and F. graminearum. While the bipy and some salts metals exhibiting antifungal strong activity against P.expansum and C. albicans, by not exhibited antifungal activity against F.graminearum and M. phaseolina as compared with the antimicrobial activity with some mixed ligand metal complexes which exhibited antifungal activity top than ligands as shown in(5). exhibited some complexes Prepared antifungal activity strong against F.graminearum and M. phaseolina as compared with the ligands which did not exhibite antimicrobial activity. from the data shown in the Table (6) and Figures (6,7,8,9 and 10) alot of compounds exhibited bio activety againts 2 kinds of bacteria and 4 kinds of fungal. 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Yield% Sample Formula Cl M N H C - - 14.04 7.07 68.20 - Colorless 179 299.37 89 L C17H21N3O2 - - 14.44 6.68 68.95 - - - - - - White 70 156.18 bipy C10H8N2 - - - - - (22.05) (11.04) (9.13) (5.13) (43.16) 19 reddish brown 122 475.74 82 CrL C17H23N3O3CrCl3 22.36 10.93 8.83 4.87 42.92 (16.03) (12.03) (10.01) (4.86) (44.72) 12 Yellow 145 461.24 87 MnL C17H25N3O4MnCl2 15.37 11.91 9.11 5.46 44.27 (16.04) (12.87) (9.13) (4.87) (43.92) 20 reddish brown 228 462.15 75 FeL C17H25N3O4FeCl2 15.34 12.08 9.09 5.45 44.18 (15.24) (13.13) (9.16) (4.98) (44.05) 13 Green 185d 465.24 77 CoL C17H25N3O4CoCl2 15.54 12.67 9.03 5.42 43.89 (16.18) (9.13) (11.44) (5.11) (53.13) 43 Orange 165 613.91 79 CrL+bipy C27H29N5O2CrCl3 17.32 8.47 11.14 4.76 52.82 (11.76) (10.01) (12.78) (4.85) (55.10) 23 Yellow 161d 581.4 78 MnL+bipy C27H29N5O2MnCl2 12.20 9.45 12.05 5.03 55.78 (12.88) (10.18) (11.75) (4.93) (56.03) 21 Red 159 582.30 79 FeL+bipy C27H29N5O2FeCl2 12.18 9.59 12.03 5.02 55.69 (11.95) (10.28) (12.24) (5.15) (55.11) 18 Green 163 585.39 76 CoL+bipy C27H29N5O2CoCl2 12.11 10.07 11.96 5.03 55.87 Chemistry |77 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Table (2) :The Fragmentation pattern data for complexes complexes Assignment Peak m/z Relative abundance% [MnL Cl2 (H2O)2] M= (C17H25N3O4MnCl2) 461.3 81% M- C6H10O Mn = M1 308.2 24% M1- CH10= M2 287.2 17% M2-H = M3 286.2 57% M3- C2H4N 244.2 16% [CoLCl2(H2O)2] M= (C17H25N3O4CoCl2) 465.2 83% M- C5H6O2 Co = M1 308.2 24% M1- C1H9= M2 287.2 14% M2- H = M3 286.2 56% M3- C3H6 244.2 16% [CrL(bipy)Cl2]Cl M= (C27H29N5O2CrCl3) 614.3 82% M- C6H3N2= M1 511.3 9% M1-C9H11O2Cr = M2 308.2 24% M2-CH9 = M3 287.2 17% M3-H = M4 286.2 57% M4- C2H4N 244.2 16% [MnL(bipy)Cl2] M= (C27H29N5O2MnCl2) 581.3 82% M- C2H4N3= M1 511.3 9% M1-C8H6NO2Mn = M2 308.2 24% M2-CH9 = M3 287.2 17% M3-H = M4 286.2 57% M4-C2H4N = M5 244.2 16% M5-C3H3 = M6 205.2 13% M6-H 204.2 98% [FeL(bipy)Cl2] M-C = M1 571.4 14% M1-CH4N2O = M2 511.3 9% M2-C8H4OFeCl = M3 308.2 24% M3-CH9 = M4 287.2 7% M4-H = M5 286.2 87% M5-C2H4N = M6 244.2 16% M6-C3H3 = M7 205.2 14% M7- H 204.2 98% Table (3): The Infrared spectra data of the free ligand and its metal complexes in(cm 1 ) Comp. υC-H aliph. υC-H arom. υC=O ring υC=O υC=N υC=N rang υH2O υM-N υM-O L - 3035 1740 1696 1640 - - - - bipy - 3055 - - 1617 - - - - CrL 2916 3063 1736 1670 1623 - 3422-867 548 470 455 MnL 2916 3036 1736 1674 1624 - 3429-887 532 490 416 FeL 2916 3063 1730 1670 1616 - 3422-867 548 455 470 CoL 2916 3033 1734 1672 1622 - 3422-887 487 422 412 CrL+bipy 2915 3076 1741 1675 1626 1582 - 544 489 476 420 MnL+bipy 2915 3076 1743 1675 1626 1578 - 544 498 476 420 FeL+bipy 2912 3070 1741 1678 1624 1581 - 544 498 471 420 CoL+bipy 2915 3073 1746 1673 1623 1580 - 544 594 474 425 Chemistry |78 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Table (4): Electronic spectral data and magnetic moments of the prepared compounds. Compound Geometry µeff B.M ύ (cm -1 ) ABS λmax (nm) ε max L mol -1 cm -1 Assignments L - 35460.99 2.48 282 24800 π→π * bipy - 35714.2 - 280 - π→π* [Cr(L)Cl3(H2O)] Octahedral 3.78 34843.2 27700.8 20283.9 16638.9 14970.0 2.005 0.632 0.506 0.265 0.154 287 361 493 601 668 2005 632 506 265 154 L.F C.T 4 A2g → 4 T1g (P) 4 A2g → 4 T1g (F) 4 A2g → 4 T2g (F) [Mn (L)Cl2(H2O)2] Octahedral 5.93 34129.6 23310.0 20491.8 2.114 0.138 0,187 293 429 488 2114 138 187 L.F 6 A1g → 4 A1g, 4 Eg(4G) 6 A1g → 4 T2g(4G) [Fe(L)Cl2(H2O)2] Octahedral 4.91 35842.2 27855.1 228031. 20790.0 1.967 0.689 0.333 0.373 279 359 438 481 1967 689 333 373 L.F C.T C.T 5 T2g(D) → 5 E1g(D) [Co( L)Cl2(H2O)2] Octahedral 3.70 35714.2 24154.5 20491.8 16366.6 15337.4 15060.2 2.034 0.339 0.568 0.125 0.106 0.110 280 414 488 611 652 664 2034 339 568 125 106 110 L.F C.T C.T 4 T1g(F) → 4 T1g(p) 4 T1g(F) → 4 A2g(F) 4 T1g(F) → 4 T2g(F) [Cr(L)Cl2(bipy)]Cl Octahedral 3.79 33444.8 24154.4 20533.8 15625.0 13297.8 2.386 0.334 0.670 0.052 0.043 299 414 487 640 752 2386 334 670 52 43 L.F C.T 4 A2g → 4 T1g(p) 4 A2g→ 3 T1g(F) 4 A2g→ 3 T2g(F) [Mn(L)Cl2(bipy)] Octahedral 5.81 34129.6 23364.4 20080.3 15822.7 2.114 0.861 0.710 0.072 293 428 498 632 2114 861 710 72 L.F C.T 6 A1g → 4 A1g, 4 Eg(4G) 6 A1g → 4 T2g(4G) [Fe(L)Cl2(bipy)] Octahedral 5.00 34965.0 28735.6 22935.7 20449.8 2.051 0.521 0.201 0.291 282 348 201 489 2051 521 436 291 L.F L.F C.T 5 T2g(D) → 5 E1g(D) [Co(L)Cl2(bipy)] Octahedral 3.65 33557.0 16103.0 14947.6 13157.8 2.312 0.114 0.147 0.056 298 621 669 760 2312 114 147 56 L.F 4 T1g(F) → 4 T1g(p) 4 T1g(F) → 4 A2g(F) 4 T1g(F) → 4 T2g(F) Table (5): Conformation energetic in (K J.Mol -1 ) for the ligands and complexes Comp. Total energy Binding energy Heat of formation Electronic energy Dipole Debyes L -78659.2647 -4472.7426 -15.35266 -600793.517 3.160 bipy -37068.2314542 -1736.1966222 615.5193778 -201757.1026775 0.010 CrL -113536.5548061 -4632.6657591 170.4572409 -962898.8007352 7.548 MnL -116948.6270148 -4784.8350078 125.7609922 -1002483.2873625 9.225 FeL -119947.9356997 -4672.8458167 269.3501833 -1038227.9787860 5.503 CoL -126215.8958556 -5008.8710646 -63.5750646 -1059178.1703876 6.392 CrL+bipy -136611.2137034 -6919.4704874 42.6155126 -1496731.4119088 2.401 MnL+bipy -139955.0160289 -7010.1267259 -75.3407259 -1524685.6060488 2.163 FeL+bipy -142965.9951884 -6909.8080094 56.5779906 -1547982.6779546 2.534 CoL+bipy -148920.3131448 -6932.1910578 37.2949422 -1565519.7816116 3.661 Chemistry |79 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Figure (1): Structure of Schiff base Ligand Table (6): Antibacterial and antifungal activities for ligands, metal Salts and complexes. no Compound Staphylococcu s aureus G(+) Pseudomona s aeruginosa G(-) Penicillium expansum Fusarium graminearum Macrophomin a phaseolina Candida albicans A B A B A B A B A B A B 1 bipy 35 32 35 32 46 36 ـــــ ـــــ ــــــ ــــــ *** *** 3 CrCl3.6H2O 15 12 16 15 38 28 38 33 ـــــ ـــــ ـــــ ــــــ 4 CoCl2.6H2O 40 25 23 18 30 18 26 15 10 20 ــــــ ــــــ 5 MnCl2.4H2O 40 18 20 14 ـــــ ـــــ ــــــ ــــــ ــــــ ــــــ ـــــ ـــــ 6 FeCl2. H2O 30 12 15 ـــــ ـــــ ــــــ ــــــ ــــــ ــــــ ــــــ ـــــ ــــــ 7 L 12 ـــــ ـــــ ــــــ ــــــ ـــــ ــــــ ــــــ ــــــ ــــــ 12 ـــــ 8 MnL 20 ـــــ ـــــ ــــــ ــــــ ـــــ ــــــ ـــــ ــــــ ــــــ 12 ــــــ 9 CrL 16 ـــــ ـــــ 16 24 22 28 18 20 ــــــ 15 ــــــ 10 CoL 20 ـــــ ـــــ 16 25 ــــــ ــــــ ــــــ 13 ــــــ 15 ــــــ 11 FeL 12 ـــــ ـــــ ــــــ ــــــ ـــــ ــــــ ـــــ ـــــ ــــــ 10 ـــــ 12 FeL+bipy 24 ـــــ ـــــ 15 20 ـــــ ــــــ ـــــ ــــــ 10 14 ـــــ 13 CrL+bipy 18 ـــــ ـــــ 15 25 ـــــ ــــــ 20 23 18 20 ــــــ 14 CoL+bipy 20 12 14 12 ـــــ ـــــ 14 25 ـــــ ــــــ ـــــ ــــــ 15 MnL+bipy 24 8 12 20 24 ـــــ 12 ـــــ 12 15 20 ـــــ 20 Con. 0 0 0 0 0 0 0 0 0 0 0 0 ***= highly active, A=conc., B=dilu. Chemistry |80 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Figure (2): Electrostatic potential (HOMO and LUMO) contours for ligands Electrostatic potential -8.77736 Ev Electrostatic potential -18.68472 Ev Chemistry |81 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Schiff base and Bipy CrL Complex CrL+bipy Figure (3):Bond length and 3D-structure for ligands and complexes Chemistry |82 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Figure (4):The antibacterial activity of compounds against S. aureus and P.aeruginosa Figure (5):The antibacterial activity of compounds against P.expansum, F.graminearum, Figure (6):Effect of the ligands complexes towards the Staphylococcus aureus and Pseudomonas aeruginosa . 0 5 10 15 20 25 30 35 40 45 b ip y F e C l2 .4 H 2 O C rC l2 .6 H 2 O C o C l2 .6 H 2 O M n C l2 .4 H 2 O M n L C rL C o L F e L F e L + b ip y C rL + b ip y C o L + b ip y M n L + b ip y Z o n e o f in h ip it o n e ( m m ) Compounds A=Conce ,S.aureus A=Dilu,S.aureus A=Conce,P.aeruginosa B=Dilu,P.aeruginosa 0 10 20 30 40 50 60 70 b ip y F e C l2 .4 H 2 O C rC l2 .6 H 2 O C o C l2 .6 H 2 O M n C l2 .4 H 2 O L M n L C rL C o L F e L F e L+ b ip y C rL + b ip y C o L+ b ip y M n L+ b ip y Z o n e o f in h ip it o n e Compound A=Conce,Penicillium expansum B=Dilu.,Penicillium expansum A=Conce, Fusarium graminearum B=Dilu, Fusarium gusarium A=Conce,Marophomin phaseoline B=Dilu ,Macrophomina phaseoline A= Conce, Candida albicans B=Dilu,Candida albicans Chemistry |83 2017( عام 2العدد ) 30هجلة ابن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Figure (7): Effect of the ligands and complexes towards the Penicillium expansum Figure (8): Effect of the ligands and complexes towards the Fusarium graminearum Figure (9): Effect of the ligands and complexes towards the Macrophomina phaseolina Figure (10):Effect of the ligands and complexes towards the Candida albican.