The new 1-(4-chloro phenyl )-3-(pyrimidin -2-yl) thiourea was synthesized from the condensation reaction of 2- amino pyrimidin with p-chlorophenyl isothiocyanate. The complexes were prepared from the reaction of the metal chloride with the ligand. The ligand  and its metal complexes were characterized by spectroscopic methods (FTIR , UV-Vis , 1H-NMR , A.A) , magnetic measurements , conductance and melting point. These studies revealed square planar geometries for the Co(II), Ni(II) and Cu(II) complexes. Keywords: 2- amino pyrimidin; p-chlorophenyl isothiocyanate and thiourea complexes. 

Resin Ali, Nawal Daami

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Chemistry and Materials Research                                                                                                                                                    www.iiste.org ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online) Vol.7 No.5, 2015  37 Synthesis and Characterization of 1-(4-Choro Phenyl )-3-(Pyrimidin -2-yl) Thiourea and its Complexes with Cobalt(II) , Nickel(II), and Copper(II)  Nawal Daami Resin Ali Department of chemistry. , Al-Mustansiriya University, Baghdad-Iraq Nawal_daamy@yahoo.com  Abstract  The new 1-(4-chloro phenyl )-3-(pyrimidin -2-yl) thiourea was synthesized from the condensation reaction of 2- amino pyrimidin with p-chlorophenyl isothiocyanate. The complexes were prepared from the reaction of the metal chloride with the ligand. The ligand  and its metal complexes were characterized by spectroscopic methods (FTIR , UV-Vis , 1H-NMR , A.A) , magnetic measurements , conductance and melting point. These studies revealed square planar geometries for the Co(II), Ni(II) and Cu(II) complexes.                                                                                    Keywords: 2- amino pyrimidin; p-chlorophenyl isothiocyanate and thiourea complexes.  Introduction  Thiourea are important sulfur and nitrogen containing compounds that have proved to be useful substances in drug research in recent years [1-6].  Thioureas can be used in the control of plant pathogens like penicillum expansum and fusarium oxysporum[7]. diaryl thioureas exhibited significant antifungal activity against pyriculari a okyzae and drechslera  oxyzae.. The biological activity   of new thiourea derivatives is scanty. Considering the biological activities of these compound [8]. The copper and cobalt complexes derived from 3-(N- phenyl) thiourea-pentanone-2 as the ligand have been synthesized . their complexation with copper and cobalt metals are crystalline in nature[9]. Thiourea (Tu) derivatives have a long history as a ligand in coordination chemistry and coordinate to a metal via both sulfur and oxygen[10] .   These hard and soft donor atoms provide a multitude of bonding possibilities [11].  Hydrogen bonding behaviours of some thioureas have been investigated and it is found that the intermolecular hydrogen bond between the sulphur and a hydrogen atom on N is common[12].    Thiourea derivatives and their transition metal complexes have been known for over a century and are easily  synthesized in good yields. Recently metal complexes of thiourea and thiourea  analogs  have  been  investigated[13].    Metal  complex  of  thiourea,  commonly  called  semi organics, include the advantages of both organic and inorganic part of the complex. A number of thiourea derivatives has been reported to form complexes with copper and cobalt. These 3-(N- phenyl) thiourea- pentanone-2 have been noticed to possess a remarkable capacity to coordinate with the transition metals  giving rise to highly colored cheated structure [14-16].  Experimental  Materials All reagents were commercially available and used without further purification. Solvents were distilled from appropriate drying agents immediately prior to use.  Physical measurements Melting point was obtained on aBuchi SMP-20 capillary melting point apparatus and is uncorrected. Infrared spectra were recorded as (KBr) disc using (8400) (FTIR) shimadzu spectrophotometer in the range (4000-400) cm-1. Uv-vis spectra for the compounds were measured in the region (200-900)nm for (10-3 M) solutions in EtOH at (RT) by using (Uv-vis) spectrophotometer type Shimadzu ,100. 1H-NMR spectrum was recorded in DMSO-d6 using aBruker 300 MHZ with tetra methyl silane(TMS) as an internal standard. Metals were determined using ashimadzu (A.A) 680 G atomic absorption spectrophotometer . Conductivity measurements were made with EtOH solutions using a pw 9526 digital conductivity meter, and room temperature magnetic moment were measured with a magnetic susceptibility balance (Jonson Mattey Catalytic System Division).  Synthetic procedures Preparation of 1-(4-choro phenyl )-3-(pyrimidin -2-yl) thiourea. A solution of 2-aminopyrimidin (9.5g , 0. 1mole) in ethanol (25mL) was added to a stirred solution of p-chlorophenyl isothiocyanate (16.6g ,0. 1mole ) in ethanol (3omL). The mixture was heated under reflux for 12h. The white precipitate was removed by filtration ,washed with hot ethanol and dried at room temperature. Yield= 71% , m.p=180-183   . 1H-NMR spectrum of the ligand: (s,1H,NH)ð 4.6 ppm , (m,7H,Ar-H) ð (6.4-8.5)ppm, (S, 1H, SH) (13.1)ppm. Chemistry and Materials Research                                                                                                                                                    www.iiste.org ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online) Vol.7 No.5, 2015  38 Synthesis of the complexes General method To a hot solution of the ligand (2mmole) in ethanol(25ml) was added (1mmole) of the metal salt (metal(II) salt are hydrated chloride; MCl2.XH2O; where M= Co(II), Ni(II) and Cu(II) : X =6,6 and 2, respectively). The solution was stirred under reflex around 2h. A colored precipitate formed which was collected by filtration, washed with cold methanol (5ml), and dried at room temperature. Physical data for the complexes are given in Table (1). Table (1) Color, yield , elemental analysis and molar conductance values         ᴧ cm2Ω-1mole-1 Found (Calcu.)%  M.P Yield% color Compound N H C M  - 21.50 (21.21) 3.64 (3.41) 50.4 (50)  - 180-183 70 white L 67.7 17.98 (17.5) 2.95 (2.74) 40.72 (40.18) 8.31 (8.97) 270-272 52 Dark brown [Co(L)2]Cl2 76.5 17.20 (17.06) 2.88 (2.74) 40.45 (40.20) 9.2 (8.97) 250-252 72 Green [Ni(L)2]Cl2 65.8 17.02 (16.93) 2.76 (2.72) 40.1 (39.91) 9.23 (9.61) 282-284 58 Dark green [Cu(L)2]Cl2  Results and discussion Chemistry: The condensation reaction of 2-amino pyrimidin and p-chlorophenyl isothiocyanate  in mole ratios of 1:1 resulted in the formation of the ligand L in good yield (Scheme(1)).  The ligand was characterized by elemental analysis (Table(1)), IR(Table( 2 )), UV-Vis(Table( 3 )) spectroscopy and 1H NMR spectrum . The di-electrolyte metal complexes were synthesized by mixing at reflux 2 mmole of the ligand with 1 mmole of appropriate metal chloride. Monomeric complexes of general formula [M(L)2]+2 (where M= COII , NiII , CuII ) was obtained (sachem(1)). The coordination geometries of the complexes were deduced form their spectra. The analytical data (Table(1)) agree well with the suggested formulas. Conductivity measurements of the complexes in EtOH solution. Lie in 65-76 cm2 Ω-1 mole-1 range, indicating their 2:1 electrolytic behavior (Table (1))[17] .                                                        NNNH2NCSCl NNNHNHSClNNNH NHSClNNNHNHSClMCl2+EthanolReflux for 12hMCl2.XH2O Scheme(1) synthesis diagram of the ligand and complexes  IR spectra                                                                                                                                          The important infrared bands for the ligand and its metal complexes together with their assignments are listed in  (Table(2)) . The IR spectra of the ligand shows bands in the region (3524-3396 cm-1), which is assigned to the ʋ(N-H) vibration . The bands due to ʋ(C=N) and  ʋ (C=S) vibrations are located in the regions 1552 and 1330 Chemistry and Materials Research                                                                                                                                                    www.iiste.org ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online) Vol.7 No.5, 2015  39 Chemistry and Materials Research                                                                                                                                                    www.iiste.org ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online) Vol.7 No.5, 2015  40 Chemistry and Materials Research                                                                                                                                                    www.iiste.org ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online) Vol.7 No.5, 2015  41 References [1]. 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Kumar L, Chandra S Trans Met Chem 31:368(2006). [27].  Maany. H, Abdel-Hamid S, EL- Shafi O, EI-Asmy A .Trans Met Chem 31:522(2006)           The IISTE is a pioneer in the Open-Access hosting service and academic event management.  The aim of the firm is Accelerating Global Knowledge Sharing.  More information about the firm can be found on the homepage:  http://www.iiste.org  CALL FOR JOURNAL PAPERS There are more than 30 peer-reviewed academic journals hosted under the hosting platform.   Prospective authors of journals can find the submission instruction on the following page: http://www.iiste.org/journals/  All the journals articles are available online to the readers all over the world without financial, legal, or technical barriers other than those inseparable from gaining access to the internet itself.  Paper version of the journals is also available upon request of readers and authors.   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Synthesis and Characterization of 1-(4-Choro Phenyl )-3-(Pyrimidin -2-yl) Thiourea and its Complexes with Cobalt(II) , Nickel(II), and Copper(II)

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Synthesis and Characterization of 1-(4-Choro Phenyl )-3-(Pyrimidin -2-yl) Thiourea and its Complexes with Cobalt(II) , Nickel(II), and Copper(II)

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