Australian Journal of Basic and Applied Sciences. Preparation and Spectral Characterization of Isonazide Ligand with Some Transition Metal Complexes

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1 ISS: Australian Journal of Basic and Applied Sciences Journal home page: Preparation and Spectral haracterization of Isonazide Ligand with Some Transition Metal omplexes Ahmed Ahmed, Dalia M. and Fatmaa. Department of hemistry, ollege of Science, Al- ahrain University, Baghdad, Iraq. A R T I L E I F Article history: Received 28 August 2015 Accepted 15 September 2015 Available online 15 ctober 2015 Keywords: Isoniazid, Schiff bases, Derivative spectroscopy, ydrazide hydrazone, Metal complexses. A B S T R A T The isonazide drug Schiff bases derivatives with (salicyldehyde, 2- hydroxynaphthaldehyde) as a ligands and the Mn(II), i(ii), o(ii), d(ii) complexes were synthesized. The complexes were characterized using solubility, melting point, UV measurement and infrared spectroscopy. Isonazide complexes of coordination of the metal to the ligands is through the oxygen of carbonyl group, the nitrogen of the imine group and coordination through the oxygen of the hydroxyl group. Schiff bases derived from isonazide have been synthesized. The UV-Visible spectra of the compounds have been investigated. For some derivatives showed that all Schiff bases studied the derived between the omplex L1 and omplex L2(o(II), Mn(II) AESI Publisher All rights reserved. To ite This Article: Ahmed Ahmed, Dalia M. and Fatmaa., Preparation and Spectral haracterization of Isonazide Ligand with Some Transition Metal omplexses. Aust. J. Basic & Appl. Sci., 9(31): 42-46, 2015 ITRDUTI Isonicotinic acid hydrazide (isoniazid, I) is a known tuberculostatic agent, it forms metal chelates with many bivalent ions (Bharti, Meena and Suman, 2014). Bactericide and fungicide properties of various mixed ligand complexes of metal ions with isoniazid and hydrazone derivatives (Angela, Lucica, icoleta, Ileana and icolae, 2010). Imine compounds play an important role in inorganic chemistry as they easily form stable complexes with most transition metal ions in the periodic table (Ram, Lakshman, Deepak and Ritu, 2005). The Schiff bases have pronounced biological activities and form a class of important compounds in medicine and pharmaceutical field. Most of the common biological active compounds have structure quite suitable for chelation with metal ions and studies on the chelation tendency of various organic compounds have supported the hypothesis that formation of strain free chelate rings enhance the biological activity. In recent years imines interest has been developed in metal with ligand containing -S- and -- moieties (Shashi and Shamim, 2009). ne of the simplest method for an increasing a selectivity is derivatisation of spectra. This operation allows to remove spectral interferences and as a consequence leads to increase selectivity of assay. Derivatisation of sets of digital data is well known method of separation useful signals from noised data (Talsky, 1994). istorically, the beginning of derivative spectrophotometry is dated on 1953 when the first analogue spectrophotometer was build by Singleton and ooler (Talsky, 1994). But the fast development of this technique started in 70-s of twentieth century, when new generation of spectrophotometers controlled by computers were constructed. An apogee of its popularity occurred in 80-s of last century. owadays, it is only additional technique, rarely used, though it is fully available as a build-in function in software of modern spectrophotometers. I hope that this work gives some light on derivative spectrophotometry and restores it in some way (Joanna, 2012). A number of complexes of transition metals with isonicotinoyl hydrazone ligands were obtained and characterized. ere in this paper, we are describing synthesis and characterization of Mn(II), i(ii), o(ii), d(ii) complexes with Schiff base of Isonicotinic acid, and study the derivative spectroscopy of the complexes. MATERIALS AD METDS hemicals and instruments: All chemicals were reagent grade. ommon organic solvent available were used. The FTIR spectra of the prepared compounds were recorded. The electronic spectra of the complexes were obtained Shimadzu- UV-Visible-160A, Ultraviolet spectrophotometer at room temperature. The magnetic susceptibility values for the prepared complexes were obtained at room temperature using orresponding Author: Ahmed Ahmed, Department of hemistry, ollege of Science, Al- ahrain University, Baghdad, Iraq.

2 43 Ahmed et al, 2015 (Faraday Method, by placing the sample in a small Pyrex container suspended from a balance through a fine, ylon thread to the center of electronic magnet. For this purpose, Bruker Magnet B.M.6 had been employed. The diamagnetic correction factor D was calculated using Pascal constant. Electric molar conductivity measurements were carried out at room temperature at the concentration (10-3 ) using digital conduct meter type LF521 (WTW). Gallenckamp M.F.B F melting point apparatus were used to measure the melting point apparatus was used to measure the melting point of the prepared compounds. Experimental: Preparation of the Ligand {(Schiff base) L1, L2} (Muhammed, Sayudevi and Krishnankutty, 2009). '-(2-hydroxybenzylidene)isonicotinohydrazide L1: '-((2-hydroxynaphthalen-1- yl)methylene)isonicotinohydrazide L2: An ethanolic solution of the isonazide drug (0.01 mol in 20 ml) was added to an ethanolic solution of salicyldehyde, 2- hydroxyl naphthaldehyde (0.01 mol) respectively and stirred in reflex conditions for (5 hours). Evaporated at reduced pressure and the crystalline compound formed was filtered. The solid was recrystallized from hot methanol to get pure compound. Preparation of omplexes (Raman, Ravichandran and Thangaraja, 2004). Preparation of (L1) omplexes: An ethanolic (20 ml) solution of L1 was mixed with metal in ethanol (10 ml) solution keeping ligand-metal ratio 2 :1. 1. Take (0.04 g) of ol with (0.1 g) from ligand and reflex (2 hours) the complex is blue 2. Take (0.04 g) of il with (0.1 g) from 3. Take 0.039g of MnL with (0.1 g) from 4. Take (0.037 g) of dl with (0.1 g) from Preparation of (L2) omplexes: An ethanolic (20 ml) solution of L2 was mixed with metal in ethanol (10 ml) solution keeping ligand-metal ratio 2 :1. 1. Take (0.07 g) of ol with (0.1 g) from ligand and reflex (2 hours) the complex is redorange 2. Take (0.07 g) of il with 0.1 g from ligand and reflex (2 hours) the complex is red 3. Take (0.07 g) of MnL with 0.1 g from ligand and reflex (2 hours) the complex is orange 4. Take (0.065 g) of dl with (0.1 g) from RESULT AD DISUSSI The two complexes (L1,L2) measured by UV- Vis spectrophotometry and show the absorbance for (dl1= 290, MnL1= 289, il1= 250, ol1=235)nm; we notice the interaction between the dl1 and MnL1 therefore can separation between them by derivative spectroscopy by using (1 st, 2 nd, 3 rd ) derivative shown in figure 1 to figure 3. And another ligand can use the same procedure because the same interaction between the (dl2 and MnL2) and separation by derivative, shown in figure-4 to figure-6. Measured the conductivity of these complex(l1,l2) and show the two complex are nonionic compound. The complexes were synthesized by the reaction of Isoniazid Schiff bases with metals in the ratio 2:1. The melting point obtained for each of the complexes is higher than the melting point of the ligands ranging from o. This shows that there is co-ordination between the ligands and their metal salts, thereby resulting to complexation from the results obtained in conductivity measurements, it was observed that the complexes are non-electrolyte (Siddappa and Sunilkumar, 2013). The molar conductance values were measured in DMS solutions. Electronic spectral analysis and magnetic measurements: The electronic spectra of Zn(II) and d(ii) complexes in the visible region are little help as because these ions have a d 10 onfiguration and their complexes d o not exhibit any d-d transition. The i, d complexes were found to be diamagnetic. The Melting Point for the drug, L1, L2, ol1, il1, MnL1, dl1, ol2, il2, MnL2, dl2 are (170, , , , , large 320, large 320, , , large 300, large 300). Table 1: Magnetic moment, conductivity and the suggested structure for complexes. complex Magnetic moment m eff(b.m.) onductivity Ms.cm -1 Suggested structure i(ii) dimagnetic 35 tetrahedral d(ii) dimagnetic 37 tetrahydral o(ii) tetrahydral Mn(II) octahydral

3 44 Ahmed et al, 2015 salicyldehyde L1 2 2-hydroxynaphthaldehyde L2 M metal(ii) chloride M metal(ii) chloride where: Mn(II), i(ii), o(ii), d(ii) Scheme 1: Synthesis route of ligand1, ligand 2 and there complexes.

4 45 Ahmed et al, 2015 Fig. 1: 1 st derivative for L1+(o, d, Mn, i). Fig. 2: 2 nd derivative L1+(o, d, Mn, i). Fig. 3: 3 rd derivative L1+(o, d, Mn, i). Fig. 4: 1 st derivative for L2+(o, d, Mn, i).

5 46 Ahmed et al, 2015 Fig. 5: 2 nd derivative L2+(o, d, Mn, i). Fig. 6: 3 rd derivative L2+(o, d, Mn, i). REFEREES Bharti, J., V. Meena and M. Suman, Synthesis, haracterization and Antibacterial Studies of Mixed Ligand omplexes of Zn (II) and Mn (II) With SalicylaldehydeIsonicotinic Acid ydrazone and etercyclic Base. Journal of hemical, Biological and Physical Sciences, 4(2): Angela, K., V.A. Lucica,. icoleta, R. Ileana and S. icolae, Synthesis and structural studies of complexes of u, o, i and Zn with isonicotinic acid hydrazide and isonicotinic acid (1- naphthylmethylene)hydrazide. Journal of the Serbian hemical Society. 75(2): Ram, K.A., S. Lakshman, K.S. Deepak and S. Ritu, Synthesis, Spectral and Thermal Investigations of Some xovanadium(iv) omplexes of ydrazones of Isonicotinic Acid ydrazide. Turkish Journal of hemistry, 29: Shashi, P.R. and A. Shamim, Synthesis, characterisation and biological activities of multidentate schiff bases and their metal complexes. riental Journal of hemistry, 25(3): Talsky, G., Derivative Spectrophotometry. 1st ed., V, Weinheim. Joanna, K., Basic Principles and Analytical Application of Derivative Spectrophotometry. ITE pen Access Publisher. Muhammed, B.U., P. Sayudevi and K. Krishnankutty, Schiff Bases of 3-[2-(1,3- Benzothiazol-2-Yl)ydrazinylidene] Pentane-2,4- Dione with Aliphatic Diamines and Their Metal omplexes. The Journal of the Argentine hemical Society, 97(2): Raman,., S. Ravichandran and. Thangaraja, opper(ii), cobalt(ii), nickel(ii) and zinc(ii) complexes of Schiff base derived from benzil-2,4- dinitrophenylhydrazone with aniline. Journal of hemical Science, 116(4): Siddappa, K. and B.M. Sunilkumar, Pharmacological Activity of (E) 3-2-(1-(1- ydroxynaphthalen-2-yl)methyleneamino)phenyl)- 2-Methylquinazoline-4(3h)-one Schiff Base and its Transition Metal omplexes. International Journal of Pharmacy and Pharmaceutical Sciences, 5(3):