Synthesis, Spectroscopic Studies and Biological Activities of Mixed Metal (III) Complexes of Uracil with 1, 10- Phenanthroline

New complexes of the [M(Ura)(Phen)(OH2)Cl2]Cl.2H2O type, where (Ura) uracil ; (Phen) 1,10-phenanthroline hydrate; M (Cr +3 , Fe +3 and La +3 ) were synthesized from mix ligand and characterized . These complexes have been characterized by the elemental micro analysis, spectral (FT-IR., UV-Vis, 1 HNMR, 13 CNMR and Mass) and magnetic susceptibility as well the molar conductive mensuration. Cr +3 , Fe +3 and La +3 complexes of six–coordinated were proposed for the insulated for three metal(III) complexes for molecular formulas following into uracil property and 1,10phenanthroline hydrate present . The proposed molecular structure for all metal (III) complexes is octahedral geometries .The biological activity was tested of metal(III) salts, ligands as well as metal(III) complexes to the pathogenic bacteria as well as the antifungal activity has been studied .


Introduction:
Uracil (Ura) a colorless, a planar, and crystalline organic compound of the pyrimidine family .The Ura is one of four nitrogenous bases back to RNA molecule: Ura is cytosine (derivative to pyrimidine), adenine and guanine (derivative to urine). Ura is also a component of coenzymes that act in conjunction with enzymes in operation of carbohydrate metabolism [1-2]. Primarily posted discovery in 1900, secluded from before hydrolysis of leaven nuclei which is located in cows thymus and spleen, herring sperm [3]. Ura can be used for drug receipt and as a pharmaceutical as materials [4][5], such as 5-fluorouracil is an anticancer drug used to masquerade as Ura during the nucleic acid replication process [6], as well as orotic acid (vitamin B 13 ) is the basic intermediate in synthesis of nucleic acids. The being only precursor at the way to form all pryimidine nucleotides in living creatures. Vitamin "B 13 " plays as a primary role at metabolism of vitamin " V 6 " (folic acid) Open Access and vitamin B 12 (cobalamine), as well as orotic acid has attracted increasing interest in the field medicine [7]. Considerable interest is being evinced in the phenomenon of metal chelation in biological systems. Many of metal ions transition metal complexes with Ura such as the interaction of Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with Ura [8] and its derivatives complexes [9] . In lanthanide complexes at different kinds from multi ligand, the metal may be investigated altitude coordination number allowing structural formula the variation responsibility them significant characteristics and their uses in diagnostic medicinal and laser technology [10] . 1,10-phenanthroline (Phen) is a wellknown complexing agent which forms a multitude of coordination with various metal ions [11] . Complexes of Phen at metal ions(III) are pointed out their high composition constants in aqueous solution and sometimes to high molar absorbance . It is worth mentioning the tris-phen iron (II) complex that finds interest as an indicator at oxidimetry result to its high molar absorbance, its high stability in strongly acid solutions and its reverse high oxidation potential. So Phen use in analytical chemistry as an oxidation-reduction indicator is extensive [12]. Phen ligand and its derivatives have resulted in many interesting structures and applications in biological activities [13][14] .Metal complexes which contain diimine ligands like bipyridine and Phen have acquired significant results of their many-sided roles accordingly constructing blocks into installation of metallo-dendrimers and molecular scaffolding into supramolecular collecting and in analytical chemistry, catalysis, electrochemistry, ring-opening qualified change the situation polymerized as well biochemistry [15][16].
In the present paper, the synthesis, physical spectroscopic properties of the Cr +3 , Fe +3 and La +3 complexes of mixed ligands (Ura and Phen) and the present work deals with the study of the antibacterial and antifungal of these reported compounds.

Materials and Methods:
Chemical: Uracil and 1,10-Phenanthroline hydrate were parchased, metals(III) chloride as well solvents solution of (Merck, B.D.H. and Riedel). The reagents have been utilized without moreover refining. . The mixtures were heated on a water bath to reflux for 12 hours except Cr +3 complex for 24 hour at 70 0 C.The metal complexes were crystal residues observed. The precipitated complexes then were refined off and washed with ether followed by drying at room temperature and analyzing employing standared methods . Study of biological activity: The activity of microbes from the metal(III) salts, ligands as well metal(III) complexes were examined by agar well spread method. The antibacterial action of the metal (III) salts, ligands and the identical complexes were checked with each other against Gram positive bacteria (G + ve), (Staphylococcus and Bacillus) and Gram negtive bacteria(Gve), (E.Coli and Pseudomonas) and the antifungal activity against the pathogenic Candida (Yeast) by means of nutritions agar well -diffusion method . The solvent utilized for working exam samples and level was DMSO, which was considered the best solvent in biological effects study [17] and sample of (1 -200 μg/ml) were utilized. antimicrobial activity of any compound were estimated by means of the welldiffusion method. 1cm3 at a 24h broth the culture including 106CFU/cm3 was placed in sterilized Petri-dishes.Molten nutritious agar (15cm 3 ) was kept in ca.45 o C and teeming in the Petri-dishes and pliable into stiffen. Other holes of 6mm diameter were punctured accurately employing a sterilized cork borer and these were perfectly stuffed for the exam solutions. The dishes were brood into 24h within 37 o C.

Results and Discussion:
The analytical informations and some of the physical characteristics are collected in Table (1) . La +3 -complex is colorless, while, the Cr +3 and Fe +3complexes are colored . The complexes dissolvable in water, DMF and DMSO, but slight dissolvable in CH 3 Cl, CCl 4 , CH 3 OH , C 2 H 5 OH and C 6 H 6 , while non soluble in ether. The elemental analysis information (

Infrared Spectra:
The features frequencies of the ligands and complexes of the metals (III) are set in Table (2) for each of ligands and metal(III) -complexes and the Cr(III)complex in Figure 1. For each of ligands and Cr +3 -complex. The broad band appearing in the (3390-3414) cm -1 and (3109-3113) cm -1 areas in each of the complexes are refered into the -OH streching vibration at hydrated as well coordinated H 2 O molecules [19] and hydrogen bonds of the type N -H ---O [20] . Furthermore, The occurrence of a strong band in the rang (848-852) cm -1 in the IR spectra of the complexes, whom is assignable to the OH rocking vibration, confirms the presence of coordinated water [21]. The absorption frequencies of the metal (III)-compounds with Ura were contrasted to that of the free Ura in the area between (1800 -1300) cm -1 where the CO and NH frequency of Ura are existing [22] . The bending vibrations of δNH (1) and δNH (3) in 1508 cm -1 and 1419 cm -1 of free Ura and in the complexes stick about constant both in intensity and placement in (1508-1519) cm -1 and (1419-1423) cm -1 respectively . The υ(C (2) =O) band at 1735 cm -1 and 1716 cm -1 in Ura, which two bands evidenced, but in the complexes evidenced one band with complexes in (1712-1720) cm -1 with disappearance of the second band . The υ(C (4) =O) band at 1670 cm -1 and 1643 cm -1 in free Ura, the small vairation in the band situation of the 4-keto group of Ura in the complexes may be due to the hydrogen bonding [23] . It can be concluded that in metal (III)complexes Ura acts as chelating ligand, the coordination that occurs with the oxygen to the 2-keto group of the Ura with metals (III) . The υ(C=N) and (C=C) mode were observed at 1558 cm -1 to the spectra of free Phen ligand are showed to be shifted to lower wave number around (1454-1496) cm -1 to the spectrum from complexes . A negative shift into that vibrational mode at complexes referenced the coordination out of nitrogen donar from Phen with M (III) ions [24] . The presence of characteristic bands to the coordinated of the metaloxygen with 2-keto group of the Ura in the (450-480)cm -1 to metal (III)-complexes, which that Ura is monodentate in all the complexes, while the Phen ligand acts as a bidentate ligand all the complexes by coordinating through the metal -nitrogen with nitrogen group to the Phen in the (490-500) cm -1 to metal (III)complexes [25]. The Ʋ(M-Cl) bands are tentatively assigned in the lower region in the ( 351-366) cm-1 [26] .
The electronic spectra of six coordinated Cr +3 -complex exhibited two absorption bands 654nm (15290cm -1 ) and 443nm (22573 cm -1 ) due to 4 A 2g → 4 T 1g (F) and 4 A 2g → 4 T 2g (F) recpectively and the two band expected 322nm (31055 cm -1 ) and 269 nm (37174cm -1 ), overlaps with the ligand bands or charge transfer (LMCT) [29]. The chromium (III)-complex shows µ eff values 3.87 B.M. comforming to three unpaired electrons, which suggests a high spin to octahedral stereochemistry [30]. The electric spectrum of the Fe +3 complex shows three absorption bands at 450nm (22222.0cm -1 ) due to 6 A 1g → 4 T 2g (G) and the four absorption bands at 364 nm (274723 cm-1) due to the presence of a charge transfer (LMCT), which obscures the low indensity dd absorption bands and 345nm, 328nm and 270nm(28985, 30487.o and 37037.0cm -1 ) which assigned to ligand field (L.F). The magnetic moment amount of this complex was got 6.31 B.M., which was very near the value of octahedral spatial structure of high spin state [31] .
In the spectrum of the La +3 -complex of six coordinated exhibited one absorption band at 403nm (24813.o cm -1 ) in the UV-Vis region caused by charge transfer (LMCT) at 269 nm (37174.0 cm-1) and 322nm (31055.0cm -1 ) and 325nm (30769cm -1 ) in the UV-Vis region overlaps with the ligand bands [32] . Figure 3. suggests the framework and 3D-geometrical structure of the metal (III) -Complexes .   Table 4. and Figure 4. For Cr +3complex. Shows multiplet signal at δ(5.275-9.211ppm) refers to aromatic protons (10H). On the other hand, the signals at δ(10.784-11.136 ppm) (2H) are due to proton of (NH) of Ura group of the metal(III) complexes [33][34]. The signal characteristic to the NH of Ura ring appeared in the same position indicating that the NH group of Ura ring did not participate in coordination . Thus the 1 HNMR results further supports the IR inferences. Whereas, the signal at δ2.5 ppm referred to DMSO-d 6 . The presence of water molecules in the complexes is confirmed by the appearance of a new signal around δ(3.3-3.5ppm), attributed to H 2 O protons [35]. The 13 CNMR spectra data of the metal(III) complexes. and Figure 5. For Cr +3 -complex. The two peaks at δ(150.00 and 162.791) ppm were assigned to the (C 2 and C 4 ) of carbonyl group of the Ura ring [33]. There is a simple change in carbonyl group of the Ura ring in all of the complexes, where the two carbonyl groups remained unchanged at the complexs formation, also support the authenticity of the proposed structures of the three complexes .The signals to the carbon of Ura ring and Phen ring are shifted from δ(99.109-149.823)ppm and the signal at δ 40.296 ppm referred to DMSO-d 6 [36].  The mass spectra of Table 5. and Figure (6-8) are for each of Cr +3 , Fe +3 and La +3 complexes, respectively. Displayed peaks refered in the molecular ions m/z at 505, 508 and 592 M + into Cr +3 , Fe +3 and La +3 complexes, Consecutively. That datum is at good convention for the suggest molecular formulation into the complexes. The mass spectral data backing the structures of transition metal complexes. The fragmentation type to the complexes does not display the loss of one for chlorine and two water molecules, It is exist outside the coordination field one for chlorine and two water molecules [28]. The fragmentation patterns of the studies for Cr +3 , Fe +3 and La +3 complexes, respectively, obtained from the mass spectra are given in Table 5. The suggested molecular formula of these complexes was provened through resembling their molecular formula weights with m/z values.  The conclusion gained into antibacterial and antifungal experience models studies through agar gooddiffusion bioassay detect biological activity to the metal salts, ligands and metal complexes after 24h in Table 6 and Figure 9. In situation of Ura the antibacterial activity at E.Coli is higher activity like contrast to metal (III) salts, but Phen has a higher activity with E.Coli as compared to Ura, metal ions and metal complexes. In case of the metals complexes, Fe +3 and Cr +3 -complexes shows higher inhibtion area of 18 mm with Staphylococcus and E.Coli respectively, as compared to the metal salts, free ligands and other complexes . Phen and La +3 -complex that increased the value of inhibition of growth than were during the 24 hours. In the case of Candida that represent a class of fungi type of yeast that has a clear impact with Phen and less effect with each of FeCl 3 , LaCl 3 and La +3complex , with no effect with the rest. The consequences of biological checking reference that in several complexes are more effective than free ligands, increased activity of the complexes can exist, illustrated at the fundamental in chelation theory [37] .