ISSN: 0973-4945; CODEN ECJHAO E-Journal of Chemistry http://www.e-journals.net 2010, 7(S1), S594-S600 Synthesis, Spectral and Magnetic Studies of Newly Mixed-Ligand Complexes of 4-Formyl-Acetanilide Thiosemicarbazone and 3,4-Dihydrocinnamic Acid with Some Metal Ions SHAYMA A. SHAKER Department of Engineering Sciences and Mathematics College of Engineering, Universiti Tenaga Nasional 43009 Kajang, Selangor, Malaysia [email protected]Received 30 March 2010; Accepted 25 May 2010 Abstract: New complexes with thiosemicarbazone derivative and 3, 4- dihydrocinnamic acid were prepared and characterized by elemental analysis, determination of metal, IR, 1 H NMR, electronic spectroscopy and magnetic measurements. The thiosemicarbazone derivative forms bidentate ligand complexes of the general formula, [M(Thz)(Caf)] where Thz = 4-formyl- acetanilide thiosemicarbazone, Caf = 3,4-dihydrocinnamic acid and M=Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Cd 2+ and Pb 2+ . The IR and 1 H NMR spectra indicates that the (Thz) was coordinated with the metal ions through the N and S atoms and the (Caf) was negatively charged bidentat ligand and was coordinated with the metal ions through the two O atoms. Electronic spectra and magnetic susceptibility measurements of the solid complexes indicates the tetrahedral geometry around the Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Zn 2+ , Cd 2+ and irregular tetrahedral geometry around Pb 2+ ion while the Cu 2+ complex has squar planer geometry. Keywords: 4-Formyl-acetanilide thiosemicarbazone complexes, Mixed-ligand complexes, 3,4-Dihydrocinnamic acid complexes, Caffeic acid complexes. Introduction Thiosemicarbazone is an important class of compound containing both hard (N) and soft (S) donors ligands 1,2 . The ligand and most of their complexes were found to remarkably exhibit activity against some plant pathogenic fungi 3 . Moreover, it shows marked and selective antitumor, antiviral, antimalarial activities 4,5 . Thus, thiosemicarbazone derivatives and their metal complexes have shown significant anticancer activity 2,6 .
8
Embed
Synthesis, Spectral and Magnetic Studies of Newly Mixed ...downloads.hindawi.com/journals/chem/2010/307842.pdfcombination with isoniazid 9. As part of ongoing study of thiosemicarbazone
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
http://www.e-journals.net 2010, 7(S1), S594-S600
Synthesis, Spectral and Magnetic
Studies of Newly Mixed-Ligand Complexes
of 4-Formyl-Acetanilide Thiosemicarbazone and
3,4-Dihydrocinnamic Acid with Some Metal Ions
SHAYMA A. SHAKER
Department of Engineering Sciences and Mathematics
College of Engineering, Universiti Tenaga Nasional
ace=acetamide, hyd=hydrazine, car=carbothioamide, me=methylene and aro=aromatic
The spectrum of the ligand Caf in DMSO-d6 shows five signal protons of hydrogen at: δ
6.93(H1), 6.87(H2), 6.60(H3), 7.12(H4) and 6.15(H5). When Caf was complexed with Zn2+
, Cd2+
and Pb2+
all these signal protons were desheilded downfield for aromatic protons H2, H3 and H4,
which are highly hydrophobic and corresponding to the benzene ring and portion of ethylene27
.
Synthesis, Spectral and Magnetic Studies S599
Furthermore, the spectrum of Caf exhibited two signal protons at 8.40 and 8.19 ppm which are
attributed to two groups of OH. These signal protons were disappeared in complexes which may
indicate that the Caf was coordinated with the Zn2+
, Cd2+
and Pb2+
through the two O atoms28
. The 1H NMR chemical shift values of free ligand Caf and their complexes are reported in Table 5.
Table 5. 1H NMR chemical shifts (δ, ppm) of the free ligand and its complexes
Compound H1 H2 H3 H4 H5
Caf 6.93 6.87 6.60 7.12 6.15
[Zn(Thz)(Caf)] 6.97 6.88 6.73 7.15 6.22
[Cd(Thz)(Caf)] 6.95 6.86 6.71 7.15 6.18
[Pb(Thz)(Caf)] 6.97 6.88 6.73 7.14 6.22
Conclusion
A newly synthesized mixed ligand complexes of 4-formyl-acetanilide thiosemicarbazone and
3,4-dihydrocinnamic acid with some metal ions is presented in this article. All the complexes
were non-electrolyte in DMSO except the Cu2+
complex was electrolyte because of its high
molar conductivity. The Thz and Caf behave as a bidentate ligand with the metal ions. The IR
spectra suggested that the Thz was coordinated with the metal ions through the N and S atoms
and the Caf ligand was coordinated with the metal ions through the two O atoms. The electronic
spectra and magnetic moments have suggested that the Mn2+
, Fe2+
, Co2+
, Ni2+
, Zn2+
and Cd2+
complexes have tetrahedral geometry as can be seen in Figure 1. The Cu2+
complex has square
planer geometry. The Pb2+
complex has irregular tetrahedral can be seen in Figure 2.
CH3 N
H
C
N
H
N
C
H
NH2
SO
M
O
O
O
HO
M=Mn+2, Fe+2, Co+2, Ni+2, Zn+2 and Cd+2
3
4
12
4
5
1
32
Figure 1. Suggested structure of [M(Thz)(Caf)] complexes
CH3 N
H
C
N
H
N
C
H
NH2
SO
O
O
O
OH
Pb
1
4
5
23
2
4
3
1
Figure 2. Suggested structure of [Pb(Thz)(Caf)] complex
M = Mn2+, Fe2+, Co2+, Ni2+, Zn2+ and Cd2+
S600 SHAYMA A. SHAKER
Acknowledgment
The author would sincerely like to thank the Chemistry Department of College of Science, Al-Mousel University, Iraq for their technical assistance. Additional thanks are also due to Dr. Hussein A. Mohammed for his kind assistance.
References
1. Ram K. A, Lakshman S and Deepak K S, Bioinorg Chem Appl., 2006, 1-10. 2. Asok K. N, Siddhartha C and Sunil K. M, J Chem Soc Perkin Trans II, 1984, 1729-1733. 3. Mohammad A A, Aminul H M, Ray J B, Tarafder M T H and Manaf A. A, Inorg
Chimica Acta, 2001, 320, 1-6. 4. Paul V. B, Philip C. S, Mohammad I, David B. L, Danuta S. K and Des R R, J Med
Chem., 2009, 52(2), 407–415. 5. Subhash P, Coord Chem Rev., 1985, 63, 127-160. 6. Thahira B S A, Karen A C, Mohammed I M T, Andrew R. C. and Akbar M A,
Polyhedron, 2004, 23(16), 2491-2498. 7. Alfonso C and Dougls X W, J Mol Struct., 2002, 604, 113-118. 8. Chan S C, Koh L L, Leung P H, Ranford J D and Sim K Y, Inorganica Chimica Acta,
1995, 236(1), 101-108. 9. Luiz E B, Robert R, Peter K, Pricilla A, Clark B, Inderlied and Lowell S Y,
Antimicrob Agents Chemother., 2003, 47(8), 2685-2687. 10. Douglas X W, Heloisa B and Amal A N, Fathy A E and Mohammed I. A, Transition
Met Chem., 1999, 24, 421-424. 11. Akbar M. A and Livingstone S E, Coordination Chemistry Reviews, Elsevier
scientific Publishing Company, Amsterdam, 1974, 13(2-3), 101-132. 12. Patricia A M, Gonzalez A C and Evelina G F, Polyhedron, 2002, 21(20), 1979-1984. 13. Giorgio G B, Valerio B D M, Daniele M, Stefano M, Aikebaier R, Andrea T and Lisa V,
Polyhedron, 2007, 26(13), 3419-3427. 14. Cross A.D and Alan J, An Introduction to Practical Infrared Spectroscopy, 3
New York. 1980. 16. Lever A B P, Inorganic electronic spectroscopy, Elsevier publishing,Co.Ltd., New York, 1968. 17. Duward F S and Atkins P W, Inorganic Chemistry, Oxford University Press, 1990. 18. Shayma A. S, Yang F and Abbas A. S, European J Sci Res., 2009, 33(4), 702-709. 19. Shayma A. S and Yang F, Am J Sci Res., 2009, 5, 20-26. 20. Mun H E C, Karen A. C, Mohammed I. M T, Rozita R, Nasir U T and Andrew R C,
Polyhedron, 2008, 27(4), 1141-1149. 21. Cotton F A and Wilkinson G, Advanced Inorganic Chemistry, Wiely inter science,
New York, 1998. 22. Selbin J, Marion C and Day M C, Theoretical Inorganic Chemistry Transition
Elements, Reinhold, New York, 1983. 23. Aljanabi M Y, The Physical Methods in Inorganic Chemistry, University of Baghdad,
Iraq, 1983. 24. Dunn T M, The Visible and Ultraviolet Spectra of Complex Compounds in Modern
Coordination Chemistry, Inter science, New York, 1960. 25. Kanagaraj G and Rao G N, Polyhedron, 1993, 12(4), 383-387. 26. Neto J L, De Lima G M and Beraldo H, Spectrochimica Acta part A, 2006, 63(5), 669-672. 27. Min Z, Jinxia L, Liwei Z and Jianbin C, Spectrochimica Acta part A, 2009, 71, 1891-1895. 28. Sudina G F, Mirzoeva O K, Pushkareva M A, Korshunova G A, Sumbatyan N V and
Varfolomeev S D, FEBS Letters, 1993, 329(1-2), 21-24.