Synthesis and Characterization of N-((6-methylpyridin-2- yl)carbamothioyl)thiophene-2-carboxamide and its Co(II), Ni(II) and Cu(II) Complexes: Calculation of the Molecular Orbitals and Antioxidant and Antitumor Activities

Year 2016, Volume: 3 Issue: 3, 1 - 14, 08.01.2017

Tuncay Yeşilkaynak

https://doi.org/10.18596/jotcsa.80465

Cited By: 3

Abstract

N-((6-methylpyridin-2-yl)carbamothioyl)thiophene-2-carboxamide, C₁₂H₁₁N₃OS₂ (HL)and its Co(II), Ni(II) and Cu(II) complexes (ML₂ type) have been synthesized and characterized by elemental analysis, FT-IR ,¹H-NMR and HR-MS methods. In addition, HL was characterized by single crystal X-ray difraction method. The HL crystallizes in the monoclinic crystal system with P 1 2₁/c 1 space group, Z=4, a=7.2326(8) Å, b=18.3492(16) Å, c=9.7724(9) Å. The [ML₂] complex structures were optimized using B97D/TZVP level. Molecular orbitals of HL ligand was calculated at the same level. Antioxidant activity of the complexes were measured by using the DPPH and ABTS assays. Anticancer activity of the complex were studied MTT assay in MCF-7 breast cancer cells.

 

Keywords

Thiourea, thiophene, anticancer activity, crystal structure, molecular orbita

References

• Burrows AD, Coleman MD, Mahon MF. Platinum thiosemicarbazide and thiourea complexes: the crystal structure of [PtCl(dppe){SC(NHMe)NHNMe2-S}](PF6) and the influence of intramolecular hydrogen bonding on ligand co-ordination mode. Polyhedron. 1999 Aug;18(20):2665–71.
• Domı́nguez M, Anticó E, Beyer L, Aguirre A, Garcı́a-Granda S, Salvadó V. Liquid–liquid extraction of palladium(II) and gold(III) with N-benzoyl-N′,N′-diethylthiourea and the synthesis of a palladium benzoylthiourea complex. Polyhedron. 2002 Jun;21(14–15):1429–37.
• König K-H, Schuster M, Schneeweis G, Steinbrech B. Zur Chromatographie von Metallchelaten: XIV. Dünnschicht-Chromatographie von N,N-Dialkyl-N?-benzoylthioharnstoff-Chelaten. Fresenius’ Zeitschrift für Analytische Chemie. 1984;319(1):66–9.
• König K-H, Schuster M, Steinbrech B, Schneeweis G, Schlodder R. N,N-Dialkyl-N?-benzoylthioharnstoffe als selektive Extraktionsmittel zur Abtrennung und Anreicherung von Platinmetallen. Fresenius’ Zeitschrift für Analytische Chemie. 1985;321(5):457–60.
• Ozpozan N, Ozpozan T, Arslan H, Karipçin F, Külcü N. Thermal behaviours of Co(II), Ni(II), Cu(II)), and Pb(II) complexes of N,N-dipropyl-N′-benzoylthiourea. Thermochimica Acta. 1999 Sep;336(1–2):97–103.
• Özpozan N, Arslan H, Özpozan T, Özdeş N, Külcü N. Thermal studies of Ni(II), Pd(II), Pt(II) and Ru(III) complexes of N,N-dihexyl-N′-benzoylthiourea. Thermochimica Acta. 2000 Jan;343(1–2):127–33.
• Özpozan N, Arslan H, Özpozan T, Merdivan M, Külcü N. Thermal Decomposition Kinetics of Some Metal Complexes of N,N-diethyl-n ’-benzoylthiourea. Journal of Thermal Analysis and Calorimetry. 2000;61(3):955–65.
• Madan V, Taneja A, Kudesia V. SYNTHESIS AN SPECTRAL STUDIES OF SOME PYRIMIDYL AND THIAZOLYL SUBSTITUTED THIOUREAS AS POTENTIAL FUNGICIDES AND NEMATICIDES. J Ind Chem Soc. 1991;68(8):471–2.
• Arslan H, Flörke U, Külcü N. Synthesis, characterization, and crystal structure of 1-(4-chloro-benzoyl)-3-naphthalen-1-yl-thiourea. J Chem Crystallog. 203AD;33(12):919–24.
• Gunasekaran N, Jerome P, Ng SW, Tiekink ERT, Karvembu R. Tris-chelate complexes of cobalt(III) with N-[di(alkyl/aryl)carbamothioyl] benzamide derivatives: Synthesis, crystallography and catalytic activity in TBHP oxidation of alcohols. Journal of Molecular Catalysis A: Chemical. 2012 Feb;353–354:156–62.
• Frisch M, Trucks G, Schlegel H, Scuseria G, Robb M, Cheeseman J, et al. Gaussian [Internet]. Gaussian, Inc.; 2009. Available from: http://www.gaussian.com/
• Grimme S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. Journal of Computational Chemistry. 2006 Nov 30;27(15):1787–99.
• Schäfer A, Huber C, Ahlrichs R. Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr. The Journal of Chemical Physics. 1994;100(8):5829.
• O’boyle NM, Tenderholt AL, Langner KM. cclib: A library for package-independent computational chemistry algorithms. Journal of Computational Chemistry. 2008 Apr 15;29(5):839–45.
• Legault C. CYLview, 1.0b [Internet]. Université de Sherbrooke; 2009. Available from: http://www.cylview.org
• Sheldrick GM. A short history of SHELX. Acta Crystallographica Section A Foundations of Crystallography. 2008 Jan 1;64(1):112–22.
• Macrae CF, Bruno IJ, Chisholm JA, Edgington PR, McCabe P, Pidcock E, et al. Mercury CSD 2.0 – new features for the visualization and investigation of crystal structures. Journal of Applied Crystallography. 2008 Apr 1;41(2):466–70.
• Arslan H, Külcü N, Flörke U. Synthesis and characterization of copper(II), nickel(II) and cobalt(II) complexes with novel thiourea derivatives. Trans Met Chem. 2003;28(7):816–9.
• Binzet G, Arslan H, Flörke U, Külcü N, Duran N. Synthesis, characterization and antimicrobial activities of transition metal complexes of N,N -dialkyl- N′ -(2-chlorobenzoyl)thiourea derivatives. Journal of Coordination Chemistry. 2006 Aug 5;59(12):1395–406.
• Arslan H, Flörke U, Külcü N, Emen MF. Crystal structure and thermal behaviour of copper(II) and zinc(II) complexes with N -pyrrolidine- N ′-(2-chloro-benzoyl)thiourea. Journal of Coordination Chemistry. 2006 Jan 20;59(2):223–8.
• Ugur D, Arslan H, Külcü N. Synthesis, characterization and thermal behavior of 1,1-dialkyl-3-(4-(3,3-dialkylthioureidocarbonyl)-benzoyl)thiourea and its Cu(II), Ni(II), and Co(II) complexes. Russian Journal of Coordination Chemistry. 2006 Sep;32(9):669–75.
• Emen M, Arslan H, Külcü N, Flörke U, Duran N. Synthesis, characterization and antimicrobial activities of some metal complexes with N’-(2-chloro-benzoyl)thiourea ligands : The crystal structure of fac-[CoL3] and cis-[PdL2]. Pol J Chem. 2005;79(10):1615–26.
• Binzet G, Emen FM, Flörke U, Yeşilkaynak T, Külcü N, Arslan H. 4-Chloro- N -[ N -(6-methyl-2-pyridyl)carbamothioyl]benzamide. Acta Crystallographica Section E Structure Reports Online. 2009 Jan 15;65(1):o81–2.
• Yesilkaynak T, Flörke U, Külcü N, Arslan H. 1-Benzoyl-3-(4-methylpyridin-2-yl)thiourea. Acta Crystallographica Section E Structure Reports Online. 2006 Sep 15;62(9):o3934–5.
• Emen FM, Flörke U, Külcü N, Arslan H. cis -Bis( N , N -dimethyl- N ′-2-chlorobenzoylthioureato)nickel(II). Acta Crystallographica Section E Structure Reports Online. 2003 Aug 15;59(8):m582–3.
• Ozer CK, Arslan H, Vanderveer D, Binzet G. Synthesis and characterization of N -(alky(aryl)carbamothioyl)cyclohexanecarboxamide derivatives and their Ni(II) and Cu(II) complexes. Journal of Coordination Chemistry. 2009 Jan;62(2):266–76.
• Hernández W, Spodine E, Vega A, Richter R, Griebel J, Kirmse R, et al. Cis-trans Isomerism in Copper(II) Complexes with N-acyl Thiourea Ligands. Zeitschrift für anorganische und allgemeine Chemie. 2004 Aug;630(10):1381–6.
• Binzet G, Arslan H, Külcü N. Synthesis and Thermal Behaviour of Co(II), Ni(II) and Cu(II) Complexes of N,N-di-n-propyl-N?- (2-chlorobenzoyl)thiourea. Asian Journal of Chemistry. 2007;19(7):5711–7.
• Dong Y, Venkatachalam T., Narla RK, Trieu VN, Sudbeck EA, Uckun FM. Antioxidant function of phenethyl-5-bromo-pyridyl thiourea compounds with potent anti-HIV activity. Bioorganic & Medicinal Chemistry Letters. 2000 Jan;10(1):87–90.
• Liu W, Zhou J, Zhang T, Zhu H, Qian H, Zhang H, et al. Design and synthesis of thiourea derivatives containing a benzo[5,6]cyclohepta[1,2-b]pyridine moiety as potential antitumor and anti-inflammatory agents. Bioorganic & Medicinal Chemistry Letters. 2012 Apr;22(8):2701–4.
• Kumar R, Obrai S, Jassal AK, Hundal MS, Mitra J, Sharma S. Synthesis, structure, computational, antimicrobial and in vitro anticancer studies of copper(II) complexes with N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine and tris(2-hydroxyethyl)amine. Journal of Coordination Chemistry. 2015 Jun 18;68(12):2130–46.
• Zhang X-T, Ma Z-Y, Zhao C, Zhou Q-J, Xie C-Z, Xu J-Y. Synthesis, crystal structures, DNA binding, and cytotoxicity activities of two copper(II) complexes based on unsymmetrical tripodal ligands. Journal of Coordination Chemistry. 2015 Jul 3;68(13):2307–23.
• Muslu H, Golcu A, Tumer M, Ozsoz M. Electrochemical investigation and DNA-binding studies of pefloxacin–metal(II/III) complexes. Journal of Coordination Chemistry. 2011 Oct 10;64(19):3393–407.