Australian Journal of Basic and Applied Sciences, 4(10): 5178-5183, 2010 ISSN 1991-8178 2010, INSInet Publication

Preparation, Physico-Chemical and Spectroscopic Investigation of Thiacetazone and Quinalizarin Complexes with Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II)
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Shayma A. Shaker, 2H.A. Mohammed and 3Abbas Ali Salih

Department of Engineering Sciences and Mathematics, College of Engineering, Universiti Tenaga Nasional, Jalan Kajang-Puchong, 43009 Kajang, Selangor, Malaysia, 2 Department of Mechanical Engineering, College of Engineering, University Tenaga Nasional, Jalan Kajang-Puchong, 43009 Kajang, Selangor, Malaysia, 3 Department of Chemistry, College of Science for women, University of Baghdad, Iraq
Abstract: Some new complexes of thiacetazone (Thz) and quinalizarin (Qz) with Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) were prepared. The ligands and their metal complexes were characterized by phisco-chemical spectroscopic techniques. The spectral data suggested that the thiacetazone as a neutral bidentate ligand is coordinated with the metal ions through the N and S atoms. The quinalizarin is negatively charged as a bidentate ligand and it is coordinated with the metal ions through the two O atoms. It is concluded that all the complexes of divalent metal ions have tetrahedral geometry except Pb(II) complex which has irregular tetrahedral geometry. Key words: Thiacetazone complexes, Quinalizarin complexes, Mixed ligand complexes, 4Formylacetanilidethiosemicarbazone complexes, Spectral studies. INTRODUCTION

Thioseemicarbazone derivatives are well known for their pharmacological activities and have received considerable attention over the past few years (Akbar and Tarafdar, 1977; Balwan and Harihar, 1986). Furthermore, the thiacetazone (4-formylacetanilidthiosemicarbazone) has been found to be useful as anticonvulsants, possess antiphtyviral activities and it is also used to treat mycobacterial infections as it is resistant to ionized, as well as known as anti-tuberculosis drug (Kanagaraj and Rao, 1993; Papia et al., 1989). Moreover, the metal complexes of the thiacetazone were used in chemotherapy of tuberculosis, and it is also shows wide spectrum of bioactivity against leprosy, bacterial, tuberculosis and viral infections (Kanagaraj and Rao, 1993; Papia et al., 1989). The bioactivity of these compounds is come from the nature of the heteroaromatic ring and the position of attachment to the ring which was formed of the thiosemicarbazone derivatives (Neto et al., 2006). However, these derivatives have received more attention because the interaction of those donors compounds with the metal ions which gives biologically active complexes and gives complexes with different geometries and properties (Harlai and Varshney, 2006). Thus, these complexes have remarkable carcinostatic activities (Akbar and Bose, 1984; Karbeng et al., 2004). Therefore, as part of our general study of metal complexes of thiacetazone and quinalizarine which is containing oxygen, nitrogen and sulfur as the donor atoms. We report herein the coordination chemistry and spectral studies of some metal complexes containing two different ligands. Experimental: Material and Measurements: All chemicals were obtained from commercial sources and were used without further purifications (MnCl2.2H2O, FeCl2.4H2O, CoCl2.6H2O, NiCl2.6H2O, CuCl2.2H2O, ZnCl2, CdCl2. H2O, Pb(NO3)2 and KOH) from Merck. Thiacetazone and quinalizarin were obtained from Sigma. Methanol, ethanol, DMSO and DMSOd6 from BDH. UV-Visible spectra were measured in dimethylsulfoxide (DMSO) using a Shimadzu UV-2450 Uv-Vis spectrophotometer. The I.R spectra in the range of 4000-200 cm-1 were recorded as CsI disc on a Shimadzu
Corresponding Author: Shayma A. Shaker, Department of Engineering Sciences and Mathematics, College of Engineering, Universiti Tenaga Nasional, Jalan Kajang-Puchong, 43009 Kajang, Malaysia. E-mail: drshaimaa611@yahoo.com

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FTIR8300 Fourier Transform infrared spectrophotometer. Determinations for metals were carried out using Atomic absorption spectrometer A-Analysis 800 Perkin Elmer. Elemental analysis (C, H, N, S) was performed on a Perkin Elmer B-240 Elemental Analyzer. 1H NMR spectra were recorded using the JEOL JNM-ECP 400 Spectrometer in DMSO-d6, relative to the internal standard tetramethylsilane (TMS). Conductivity measurements were carried out at 25oC in DMSO using a Philips Pw-9526 digital conductivity meter. Melting points were determined using a Digital Melting Point apparatus. The magnetic susceptibility measurements were eventually obtained using a Magnetic Susceptibility Balance, Model MsB-MK1. Preparation of Metal Complexes: An KOH ethanolic solution 12 ml of quinalizarin (Qz) (0.205-0.499 g) and an ethanolic solution 15 ml of thiacetazone (Thz) (0.178-0.433 g) were added respectively to an aqueous solution of metal salts. The mixture was heated in water bath for 30 minutes with constant stirring and then formed the products were filtered off, washed and recrystallized with mixture of (1:3) water: ethanol and dried at 60 oC. RESULTS AND DISCUSSION The prepared complexes were found to be solid, insoluble in water but they were soluble in dimethylsulfoxide. Moreover, the metal complexes were found to be non-conducting in DMSO because the molar conductance values of these complexes are very low (Burger, 1973; Kettel, 1975; Shayma et al., 2010; Shayma et al., 2009). However, the analytical data for the metal complexes in Table 1 were found to be in agreement with the proposed molecular formula. The Magnetic Susceptibility: The moments for the complexes of Mn(II) d5, Fe(II) d6 and Co(II)d7 were found to be 4.723, 4.067 and 3.271 BM within the expected spin-only values (David, 1984; Ehssan, 1988; Shayma and Yang, 2009). Moreover, the higher value of the magnetic momentum for Ni(II) d8 complex was 3.01 BM which is attributed to the orbital contribution. Furthermore, the eff of the Cu(II) d9 complex was found to be 1.901 BM within the expected value for one electron. Finally, the complexes of Zn(II), Cd(II) and Pb(II) are diamagnetic as expected from their electron configuration (Cotton and Wilkinson, 1998). All the data and remarks are listed in Table 2. The Electronic Spectral Studies: The electronic spectrum of the Thz and Qz have shown 6* and n6* at 273, 278 nm and 315, 360 nm respectively. The Mn(II) complex is violet in solution and shows absorption bands at 418 and 568 nm due to 6 A164T2(G) and 6A164T1(G) respectively. So, it also shows a strong charge transfer band at 270 nm. The observed electronic spectrum suggested a tetrahedral geometry (Lutfullah, et al., 2007). The dark violet complex of Fe(II) shows band in the visible region due to the electronic transition 5E(D) 65T2(D) at 659 nm. This indicates that the Fe(II) complex is a tetrahedral complex (Lever, 1968; Shayma et al., 2009). For the Co(II) complex, there are three absorption bands, two in the visible region at 431 and 604 nm which are attributed to the 4A2(F) 64T1(F) and 4A2(F) 64T2(F) respectively. In addition the third band was observed in the UV at 310 nm assigned to 4A2(F) 64T1(P) which corresponds to the charge transfer band. All this spectral data support the high spin tetrahedral structure for Co(II) complex. The dark violet tetrahedral complex of Ni(II) show bands at 300, 488 and 867, 873 nm which are due to 3T1(F) 63A2(F), 3T1(F) 63T1(P) and 3T1(F) 63T2(F) respectively. The dark brown of the Cu(II) complex in DMSO shows only band in the visible region of the lower energy was attributed to 2T2(D) 62E(D). In fact, it is difficult to recognize between a square planer and tetrahedral Cu(II) complex because it occurs in the same region for both geometries (Lutfullah et al., 2007). In this case the magnetic moment for Cu(II) complex is 1.901 BM which confirmed the tetrahedral geometry for the [Cu(Thz)(Qz)] complex. Finally, the absorption bands of the Zn(II), Cd(II) and Pb(II) complexes exhibited charge transfer M6L at 287, 270 and 299 nm respectively. This is because of the electronic configuration and the diamagnetic of these complexes which confirmed the absence of any d-d electronic transition (Aljanabi, 1983; Lever, 1968). All the absorption bands were fully assigned in Table 2.

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Table 1: Elemental analysis and some physical properties of the prepared complexes. Elemental Analysis Calc (found %) Compound Color Yield % M.P. oC ----------------------------------------------------------------------------------------------------------------------C H N S M [Mn(Thz)(Qz)] Violet 70 >300 51.339 (50.116) 3.228 (2.943) 9.978 (9.013) 5.711 (5.065) 9.785 (9.01) [Fe(Thz)(Qz)] Dark violet 50 >300 51.256 (50) 3.223 (2.669) 9.962 (8.910) 5.701(5.135) 9.930 (8.56) [Co(Thz)(Qz)] Dark Blue 64 287-288 50.976 (49.871) 3.205 (3.012) 9.908 (9.011) 5.670 (4.321) 10.422 (9.91) [Ni(Thz)(Qz)] Dark Violet 60 259-261 50.997 (50.017) 3.207 (2.130) 9.912 (9.210) 5.673 (4.931) 10.384 (10.09) [Cu(Thz)(Qz)] Dark brown 77 >300 50.563 (51.826) 3.179 (3.006) 9.827 (9.20) 5.624 (4.001) 11.147 (9.99) [Zn(Thz)(Qz)] White 73 244-246 50.401 (50.987) 3.169 (3.345) 9.796 (8.32) 5.606 (4.312) 11.432 (11.01) [Cd(Thz)(Qz)] White 55 280-281 46.571 (45.311) 2.928 (2.676) 9.051 (8.542) 5.180 (5.917) 18.162 (17.98) [Pb(Thz)(Qz)] White 63 >300 40.386 (39.91) 2.539 (1.23) 7.849 (7.13) 4.492 (4.781) 29.031 (28.1) Molar conductivity Ohm-1 cm2 mol-1 4.4 4.8 5.6 4.6 12.6 4 9.2 3.4

Table 2: The Uv-Vis spectra and magnetic moment values of the free ligand and their complexes Compound max n.m Wave numbercm-1 gmaxLmol-1cm-1 Assignment Thz 273 36630 746 6* 315 31746 4027 n6* Qz 278 35971 330 6* 360 27777 103 n6* [Mn(Thz)(Qz)] 270 37037 419 Charge transfer (C.T) 6 A164T2(G) 418 23923 581 6 A164T1(G) 568 17605 202 [Fe(Thz)(Qz)] 323 30959 109 C.T 5 E(D) 65T2(D) 659 15174 93 4 A2(F) 64T1(P) [Co(Thz)(Qz)] 310 32258 218 4 A2(F) 64T1(F) 431 23201 58 4 A2(F) 64T2(F) 604 16556 93 3 [Ni(Thz)(Qz)] 300 33333 207 T1(F) 63A2(F) 3 T1(F) 63T1(P) 488 20491 67 3 T1(F) 63T2(F) 867 11534 39 873 11454 41 [Cu(Thz)(Qz)] 295 33898 282 C.T 2 T2(D) 62E(D) 464 21551 47 [Zn(Thz)(Qz)] 287 34843 145 CT M6L 335 29850 377 CT M6L [Cd(Thz)(Qz)] 270 37037 114 CT M6L [Pb(Thz)(Qz)] 299 33444 160 CT M6L

effCalc.(found) BM 5.916 (4.723) 4.898 (4.067) 3.872 (3.001) 2.828 (3.12) 1.73 (1.901) diamagnetic diamagnetic diamagnetic

The Infrared Spectra Studies: The infrared spectrum of the Qz shows very strong bands at 1608 and 1580 cm-1 which are assigned to (C=O) and (C=C) respectively. Furthermore, the spectrum of the ligand shows a strong band at 3339 which is attributed to the (OH), this band was disappeared in the complexes. Moreover, the band at 1234 cm-1 which is due to the (C-O) was shifted to the lower frequencies by 8-4 in cm-1 complexation. Moreover, the spectrum of the complexes exhibited weak bands between 522-591 cm-1 which are belonging to the (M-O). This indicates that the quinalizarin is bidentate ligand and it is coordinated with the metal ions through the two O atoms (Ayari et al., 2007; Dallali and Agrawal, 2004). The spectrum of the Thz shows very strong bands due to the NH acetamide, NH2 carbothioamide and NH hydrazine at 3323, 3256 and 3160 cm-1. Thus, the spectrum of the complexes shows bands at 3161-3325 cm-1 which indicate the non involvement of the NH for coordination (Kanagaraj and Rao, 1993). Furthermore, the Thz compound may be exhibited as thion-thiol tautomerism as shown in Fig 1. Actually, the absence of (S-H) band in their IR spectra proved that the Thz remains as the thioketo tautomerism (Hossain et al., 1996). Moreover, the spectrum of the ligand exhibits a strong band at 1583 cm-1 which is attributed to the (C=N). This band is shifted to the lower frequencies by 74-3 cm-1 in the spectra of its complexes. However, this lowering of the (C=N) on complexes may be due to M-N bond formation (Akbar and Bose, 1977; Shayma, 2010). Thus, the (CS) band of the ligand is observed at 830 cm-1 and this band is also shifted to lower frequencies by 30-10 cm-1 in the spectra of the complexes. So, the spectrum of the complexes shows weak bands due to (M-N) and (M-S) in the region of 418-524 cm-1 and 394-466 cm-1 respectively. This indicates that the Thz as bidentate is coordinated with the metal ions through the N and S atoms (Cross and Alan, 1969; Socrates, 1980). All the infrared data of the free ligands and their complexes are presented in Table 3.
1

H NMR Spectra Studies: The 1H NMR spectrum of the Qz in DMSO-d6 shows signal protons at 7.87, 7.40 and 7.34 ppm which are due to the two group of OH. These signal protons were disappeared in Zn(II), Cd(II) and Pb(II) complexes which may indicate that the Qz is negative charge and is coordinated with the metal ions through the two O atoms (Farnet, et al., 1998). 5180

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Fig. 1: Thione and thiole Tautomerism

Table 3: Fundemental infrared Compound (OH) Thz Qz 3339 [Mn(Thz)(Qz)] [Fe(Thz)(Qz)] [Co(Thz)(Qz)] [Ni(Thz)(Qz)] [Cu(Thz)(Qz)] [Zn(Thz)(Qz)] [Cd(Thz)(Qz)] [Pb(Thz)(Qz)] bands of the ligands and their complexes (NH) (C=O) (C=N) (C-O) 3160 1668 1583 1608 3165 1579 1509 1231 3325 1660 1509 1230 3161 1582 1509 1232 3162 1666 1580 1230 3162 1582 1510 1226 3165 1660 1580 1228 3157 1670 1570 1230 3150 1583 1512 1229 (CS) 830 1234 804 807 806 800 806 807 800 820 (M-O) 588 589 587 586 587 523 522 591 (M-N) 493 466 525 524 466 418 495 463 (M-S) 466 397 466 430 419 397 394 420

The 1H NMR spectrum of the Thz shows signal proton and it is splitted to the 7.93 and 7.90 ppm which is attributed to the NH2 group of carbothiamide. This signal exhibits in the Zn(II), Cd(II) and Pb(II) complexes at 7.98, 7.95 and 7.90 ppm respectively. Moreover, the spectrum of the ligand shows signal protons which belong to the NH hydrazine and NH acetamide at 11.28 and 10 ppm respectively. The chemical shifts due to those signal protons remain unchanged in the spectra of the complexes. This indicates that both of the nitrogen of the NH hydrazine and NH acetamide are not involved to coordinate with the metal ions. Thus, the spectrum of the Thz also shows signal protons due to CH methylene group and CH3 of acetamide group at 8.09 and 2.01 ppm respectively. Nevertheless, the chemical shifts of the CH aromatic were observed at 7.70, 7.66, 7.60 and 7.52 ppm. Thus, the absence of the signal proton of SH group at 12.10 ppm is further supported the presence of the thione form of the Thz in the complexes instead of thiole form (Kanagaraj and Rao, 1993; Neto et al., 2006). All the 1H NMR data of the free ligand Thz and its complexes are listed in Table 4. Conclusion: From the present investigation it has been observed that there is a possibility of preparation a new mixed ligand complexes from thiacetazone and quinalizarine with some metal ions such as Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II). The molar conductivity for the complexes in DMSO was nonelectrolyte. Moreover, the structure for these complexes based on spectral studies and magnetic moments were proposed. The results indicate that the Thz is bidentate ligand and it is coordinated with the metal ions through the N and S atoms. While, the Qz is also bidentate and it can be coordinated with the metal ions through the two O atoms. Therefore, it can be suggested that the tetrahedral geometry for the Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes as can be seen in Fig 2. Nevertheless, the Pb(II) complex has irregular tetrahedral geometry can be seen in Fig 3.

Fig. 2: Sugessted structure of [M(Thz)(Qz)] complexes

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Fig. 3: Suggested structure of [Pb(Thz)(Qz)] complex

Table 4: 1H NMR chemical shifts (d,ppm) of the free ligand and its complexs NHace NH2 car CHme CHaro Compound NHhyd Thz 11.28 10 7.90, 7.93 8.09 7.70,7.66,7.60,7.52 [Zn(Thz)(Caf)] 11.25 10.17 7.98 8 7.72, 7.60, 7.59, 7.50 [Cd(Thz)(Caf)] 11.24 10.17 7.95 8 7.70, 7.64, 7.62, 7.54 [Pb(Thz)(Caf)] 11.25 10.11 7.90 8.03 7.74, 7.62, 7.60, 7.51 hyd=hydrazine, ace=acetamide, car=carbothioamide, me=methylene and aro=aromatic CH3 ace 2.01 2.02 2.02 2

ACKNOWLEDGMENTS The author would sincerely like to thank the staff of the library in Universiti Kebangsaan Malaysia for their kind help. REFERENCES Akbar, M.A. and M.T.H. Tarafdar, 1977. Metal Complexes of Sulfur and Nitrogen-Containing Ligands Complexes of S-Benzyldithiocarbazate and a Schiff Base Formed by Its Condensation with Pyridine-2Carboxaldehyde, J. Inorg. Nucl. Chem., 39: 1785. Akbar, A.M. and R.N. Bose, 1984. Transition Metal Complexes of Furfural and Benzyl Schiff Bases Derived from S-benzyldithiocarbazate, Polyhedron, 3: 517. Akbar, M.A. and R. Bose, 1977. Metal complexes of Schiff bases formed by condensation of 2methoxybenzaldehyde and 2-hydroxybenzaldehyde with S-benzyldithiocarbazate, J. Inorg. Nucl. Chem., 39: 265. Aljanabi, M.Y., 1983. The Physical Methods in Inorganic Chemistry. University of Baghdad, Iraq. Ayari, F., E. Srasra and M.A. Trabelsi, 2007. Retention of Organic Molecule Quinalizarin by Bentonitic Clay Saturated with Different Cations, Desalination, 206: 499. Balwan, S. and M. Harihar, 1986. Cobalt(II), Nickel(II), Copper(II), Zinc(II), Cdmium(II) and Dioxouranium(II) complexes of thiophene-2-aldehyde-4-phenyl-thiosemicarbazone, Indian Chem. Soc., LXIII, 1069. Burger, K., 1973. Coordination Chemistry Experimental Methods. Bult worths and Co publisher Ltd, London. Cotton, F.A. and G. Wilkinson, 1998. Advanced Inorganic Chemistry. Wiely inter science, New York. Cross, A.D. and J. Alan, 1969. An Introduction to Practical Infrared Spectroscopy. Butterworths, London, 3ed edn. Dallali, N. and Y.K. Agrawal, 2004. Solvent Extraction and Spectrophotometric Determination of Magnesium by Paratoly 1-2-thenohydroxamic acid and Quinalizarin, Iran J. Chem. And Chem. Eng., 23: 65. David, N., 1984. Complexes and First Row Transition Elements. American Elsevier. Ehssan, A., 1988. Inorganic and Coordination Chemistry. Mousel University, Iraq. Farnet, C.M., B. Wang, M. Hansen, J.R. Lipford, L. Zalkow, W.E. Robinson, J.R. Siegel and F. Bushman, 1998. Human Immunodeficiency virus type 1 cDNA integration, new aromatic hydroxylated inhibitors and studies of the inhibition mechanism, Antimicrobial Agents and Chemotherapy, 2245. Harlai, S. and A.K. Varshney, Synthesis, 2006. Structural and Biochemical Studies of Organotin(IV) with Schiff Bases Having Nitrogen and Sulfur Donor Ligands, Bioinorganic Chem Appl, 2006: 1.

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Hossain, M.E., M.N. Alam, J. Begum, A.M. Akbar, M. Nazimuddin, F.E. Smith and R.C. Hynes, 1996. The Preparation, Characterization, Crystal Structure and Biological Activity of Some Copper(II) Complexes of the 2-Benzoylpyridine Schiff Bases of S-methyl and S-benzyldithiocarbazate, Inorganic Chimica Acta, 249: 207. Kanagaraj, G. and G.N. Rao, 1993. Synthesis and Characterization of Complexes of cobalt(II), nickel(II), zinc(II), cadmium(II) and mercury(II) with r-acetamidobenzaldehydethiosemicarbazone, polyhedron, 12: 383. Karbeng, C., M.T.H. Tarafder, A.C. Karen, A.M. Ali, B.M. Yamin, H.K. Fun, 2004. Synthesis, Characterization and Bioactivity of Metal Complexes of Bidentate N-S Isomeric Schiff Bases Derived from s-methyldithiocarbazate (SMDTC) and the X-ray Structure of the bis[S-methyl--N-(2-furylmethylketone)dithiocarbazato]cadmium(II) complex, Polyhedron, 23: 1385. Kettel, S.F.A., 1975. Coordination Compounds. Thomas Nelson and sons, London. Lever, A.B.P., 1968. Inorganic Electronic Spectroscopy. Elsevier publishing. Co. Ltd., New York. Lutfullah, Ahmed, U., M.R. Mohammed, M.K. Mohammed and B.H. Yoon, 2007. Synthesis and PhysicChemical and Spectroscopic Investigation of Sodium Dihydro bis(1,2,3-benzotriazolyl)borate Ligand and Its Transition Metal Complexes, Turk J Chem., 31: 179. Neto, J.L., G.M. Delima and H. Beraldo, 2006. Platinum and Palladium Complexes of Thiosemicarbazones Derived of 2-acetylthiophene, Synthesis and Spectral Studies, Spectrochimica Acta part A., 63: 669. Papia, C., T.K.D. Harji, B.V. Agarwala and K.D. Arun, 1989. Bipositive metal complexes of novel Schiff bases derived from carbazides and 2-aminopyridine, J. Indian Chem. Soc., 66: 550. Shayma, A.S., F. Yang, M. Sadia and E. Mohean, 2010. Synthesis and Characterization of Mixed Ligand Complexes of Caffeine, Adenine and Thiocyanate with Some Transition Metal ions, Sains Malaysiana, 39(6): 957-962. Shayma, A.S., F. Yang and A.S. Abbas, 2009. Synthesis and Characterization of Mixed Ligand Complexes of 8-Hydroxyquinoline and o-hydroxybenzylidene-1-phenyl-2,3-dimethyl-4-amino-3-pyrazolin-5-on with Fe(II), Co(II), Ni(II) and Cu(II) ions, European Journal of Scientific Research, 33: 702. Shayma, A.S. and F. Yang, 2009. Preparing and Characterization of Some Mixed Ligand Complexes of 1,3,7-Trimethylxanthin, -Picoline and Thiocyanate with Some Metal Ions, American Journal of Scientific Research, 5: 20. Shayma, A.S., Synthesis, 2010. Spectral and Magnetic Studies of Newly Mixed Ligand Complexes of 4Formylacetanilidethiosemicarbazone and 3, 4-dihydroxycinna- mic acid with Some Metal ions, Accepted in EJournal of Chemistry, (in press), 7(5). Socrates, G., 1980. Infrared Characteristic Group Frequencies. Wiely-Interscience publication, New York.

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