Sains Malaysiana 47(8)(2018): 1775–1785

http://dx.doi.org/10.17576/jsm-2018-4708-16

 

Synthesis, Structure and Spectroscopic Properties of Oxovanadium Tris(3,5-dimethylpyrazolyl)borate Aroylthiourea Complexes

(Sintesis, Struktur dan Sifat Spektroskopi Kompleks Oksovanadium Tris(3,5-dwimetilpirazolil)borat Aroiltiourea)

 

SYAHIDAH MOHD TAHIR1, AISHA AL-ABBASI1, QURNISHA GHAZALI1, KHUZAIMAH ARIFIN2 & MOHAMMAD B. KASSIM1,2*

 

1School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

 

2Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

 

Received: 21 September 2017/Accepted: 4 March 2018

 

 

ABSTRACT

Aroylthiourea ligands, 1-aroyl-3-cyclohexyl-3-methylthiourea (HL1), 1-(2-chloroaroyl)-3-cyclohexyl-3-methylthiourea (HL2), 1-(3-chloroaroyl)-3-cyclohexyl-3-methylthiourea (HL3) and 1-(4-chloroaroyl)-3-cyclohexyl-3-methylthiourea (HL4) were synthesized through a condensation reaction of methylcyclohexylamine and aroylisothiocyanate with a general formula (X-Ph)(CO)NH(CS)N(C6H5)(CH3) where X = H, o-Cl, m-Cl and p-Cl, fully characterized by CHNS micro elemental analysis, infrared spectroscopy, UV-visible, nuclear magnetic resonance (1H, 13C) and X-ray crystallography. 1-(3-chloroaroyl)-3-cyclohexyl-3-methylthiourea (HL3) crystallized in the monoclinic system, a=14.504(3), b=4.9599(11), c=22.325(5) Å, β=98.461(7)°, Z= 4 and V=1588.5(6) Å with space group P21/c. The IR spectra of the ligands exhibits the characteristic v(CO) and v(N-H) at range 1701-1640 cm-1and 3317-3144 cm-1, respectively. Whereas the 1H and 13C NMR spectra shows the resonances for N-H and -CO groups at range 8.3-8.5 and 160-163 ppm, respectively. A one-pot reaction involving the aroylthiourea ligand, oxovanadium(IV) ion and potassium hydrotris(3,5-dimethylpyrazolyl)borate (KTp*) complex gave the desired [oxovanadium(IV)(tris(pyrazolyl)borate)(aroylthiourea)] complexes namely Tp*VOL1, Tp*VOL2, Tp*VOL3 and Tp*VOL4 and all complexes were characterized accordingly. X-ray study showed that Tp*VOL1 adopted a monoclinic crystal, a=3.415(2), b=19.463(3), c=14.22(3) Å, β=107.411(4)°, Z= 4 and V=3542.7(11) Å with P21/c space group. The VO2+ center adopted a pseudo-octahedral geometry O2N3S, with the oxovanadium(IV) coordinated to the bidentate ligand (X-Ph)(CO)NH(CS)N(C6H5)(CH3) and tridentate Tp* ligands. The results showed that aroylthiourea ligands behave as bidentate chelate through O and S atom and the Tp* C3v symmetry adds stabilization to the VO2+ through its protective tripodal geometry.

 

Keywords: Aroylthiourea; chelate; oxovanadium(IV); tris(pyrazolyl)borate; vanadyl

 

ABSTRAK

Ligan aroiltiourea, 1-aroil-3-sikloheksil-3-metiltiourea (HL1), 1-(2-kloroaroil)-3- sikloheksil-3-metiltiourea (HL2), 1-(3-kloroaroil)-3- sikloheksil-3-metiltiourea (HL3) dan 1-(4-kloroaroil)-3-sikloheksil-3-metiltiourea (HL4) telah disintesis melalui tindak balas kondensasi antara metilsikloheksilamina dan aroilisotiosianat dengan formula asas, (X-Ph)(CO)NH(CS)N(C6H5)(CH3 dengan X=H, o-Cl, m-Cl dan p-Cl. Pencirian penuh telah dilakukan dengan mikroanalisis unsur CHNS, spektroskopi inframerah, ultralembayung boleh nampak, resonans magnet nukleus (1H, 13C) serta kristalografi sinar-X. Ligan, 1-(3-kloroaroil)-3-sikloheksil-3-metiltiourea (HL3) menghablur dalam sistem monoklinik, a=14.504(3), b=4.9599(11), c=22.325(5) Å, β=98.461(7)°, Z= 4 dan V=1588.5(6) dengan kumpulan ruang P21/c. Spektrum IR bagi kesemua ligan mempamerkan sifat v(CO) dan v(N-H) masing-masing dalam lingkungan 1680-1690 cm-1 dan 3120-3144 cm-1. RMN 1H dan 13C menunjukkan resonans bagi kumpulan (N-H) dan –CO masing-masing dalam lingkungan 8.3-8.5 dan 160-163 ppm. Tindak balas serentak melibatkan ligan aroiltiourea, ion oksovanadium(IV) dan kompleks kalium hidrotris(3,5-dimethilpirazolil)borat (KTp*) untuk membentuk kompleks yang diinginkan [oksovanadium(IV)(tris(pirazolil)borat)(aroiltiourea)] dinamakan Tp*VOL1, Tp*VOL2, Tp*VOL3 dan Tp*VOL4 telah berjaya disintesis dan dicirikan. Kristalografi sinar-X menunjukkan Tp*VOL1 mempunyai sistem hablur monoklinik, a=3.415(2), b=19.463(3), c=14.22(3) Å, β=107.411(4)°, Z= 4 dan V=3542.7(11) Å dengan kumpulan ruang P21/c. Pusat VO2+ menyarankan geometri kompleks yang terbentuk adalah pseudo-oktahedral O2N3S dengan pusat oksovanadium(IV) berkoordinat dengan ligan bidentate (X-Ph)(CO)NH(CS)N(C6H5)(CH3) dan ligan tridentat Tp*. Ligan aroiltiourea bertindak sebagai pengkelat bidentat melalui atom O dan S dan ligan Tp* yang bersimetri C3v memberikan kestabilan kepada pusat VO2+ dengan geometri tripodal.

 

Kata kunci: Aroiltiourea; kelat; oksovanadium(IV); tris(pirazolil)borat; vanadil

REFERENCES

Al-Abbasi, A.A., Yamin, B.M. & Kassim, M.B. 2011. 1-(4-Chlorobenzoyl)-3-cyclohexyl-3-methylthiourea. Acta Crystallographica Section E Structure Reports Online 67(8): 1891.

Alfallous, K.A. & Aburzeza, M.M. 2015. Synthesis, characterization, biological activity and use of thiourea derivative (PhTTU) studies of Cd(II) ion complex. International Journal of Science and Research 4(6): 350-352.

Arslan, H., Duran, N., Borekci, G., Ozer, C.K. & Kabay, C. 2009. Antimicrobial activity of some thiourea derivatives and their nickel and copper complexes. Molecules 14(1): 519-527.

Bai, F.Y., Li, X.T., Zhu, G.S. & Xing, Y.H. 2010. Synthesis and structure of a new scorpionate-dithio carboxyl oxovanadium complex and an organic dithio carboxyl compound. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 75(5): 1388-1393.

Beddoes, R.L., Collison, D., Mabbs, F.E. & Passand, M.A. 1990. Synthesis and charatcterization of some -diketonate derivatives of hydrotris(3,5-dimethylpyrazolyl)borato oxovanadium(IV). The crystal and molecular structure of hydrotris(3,5-dimethylpyrazolyl)borato pentane-2,4-dionato oxovanadium(IV). Polyhedron 9(20): 2483-2489.

Collison, D., Eardley, D.R., Mabbs, F.E., Powell, A.K. & Scott, S. 1993. Synthesis, crystallographic and spectroscopic characterization, and magnetic properties of mixed-ligand oxovanadium(IV) hydrotris(3,5-dimethylpyrazolyl)borate complexes. Inorganic Chemistry 32(5): 664-671.

Cotton, F.A. & Wilkinson, G. 1966. Advanced Inorganic Chemistry. New York: John Wiley and Sons. pp. 409-412.

Etienne, M. 1996. Hydridotris (pyrazolyl) borato complexes of the group 5 metals: Inorganic and organometallic chemistry. Coordination Chemistry Reviews 156: 201-236.

Gunasekaran, N. & Karvembu, R. 2010. Synthesis, characterization, and catalytic applications of Ru(III) complexes containing N- [di(alkyl/aryl)carbamothioyl]benzamide derivatives and triphenylphosphine/triphenylarsine. Inorganic Chemistry Communications 13(8): 952-955.

Gunasekaran, N., Remya, N., Radhakrishnan, S. & Karvembu, R. 2011. Ruthenium(II) carbonyl complexes with N -[di(alkyl/aryl)carbamothioyl]benzamide derivatives and triphenylphosphine as effective catalysts for oxidation of alcohols. Journal of Coordination Chemistry 64(3): 491-501.

Hernández, W., Spodine, E., Beyer, L., Schröder, U., Richter, R., Ferreira, J. & Pavani, M. 2005. Synthesis, characterization and antitumor activity of copper(II) complexes, [CuL2] [HL1-3] =N,N-Diethyl-N'-(R-Benzoyl)Thiourea (R=H, o-Cl and p-NO2)]. Bioinorganic Chemistry and Applications 3(3-4): 299-316.

Halim, N.I.M., Kassim, K., Fadzil, A.H. & Yamin, B.M. 2011. Synthesis, characterization and antibacterial studies of benzoylthiourea derivatives. 2nd International Conference on Chemistry and Chemical Engineering 14: 55-59.

Kavak, G., Ozbey, S., Binzet, G. & Nevzat, K. 2009. Synthesis and single crystal structure analysis of three novel benzoylthiourea derivatives. Turkish Journal of Chemistry 33: 857-868.

Khairul, W.M., Tukimin, N. & Rahamathullah, R. 2016. Synthesis, characterization and electrical properties of N-([4-(aminophenylethynyl)toluene]-N'-(cinnamoyl) thiourea (AECT) as single molecular conductive film. Sains Malaysiana 45(5): 825-831.

Khairul, W.M., Faisol, S.L.M., Jasman, S.M., Che Soh, S.K. & Shamsuddin, M. 2014. Catalytic studies featuring palladium(II) benzoylthiourea derivative as catalyst in sonogashira reaction. Bulletin of Chemical Reaction Engineering and Catalysis 9(3): 241-248.

Kime-Hunt, E., Spartalian, K., DeRusha, M., Nunn, C.M. & Carrano, C.J. 1989. Synthesis, characterization and molecular structures of a series of [(3,5-Dimethylpyrazolyl)borato] vanadium(III) and -(IV) complexes. Inorganic Chemistry 28: 4392-4399.

Kripal, R. & Shukla, S. 2009. 4 symmetry crystal field and ground state wavefunction of the VO2+ Ion. Chinese Physics Letter 26(8): 26-29.

Li, Z.P., Xing, Y.H., Cao, Y.Z., Zeng, X.Q., Ge, M.F. & Niu, S.Y. 2009. Synthesis, structure and properties of a series of scorpionate oxovanadium(IV)–carboxylate complexes. Polyhedron 28(4): 865-871.

Limban, C., Marutescu, L. & Chifiriuc, M.C. 2011. Synthesis, spectroscopic properties and antipathogenic activity of new thiourea derivatives. Molecules (Basel, Switzerland) 16(9): 7593-7607.

Mark Lee, W.F., Pui, L.K., Heng, L.Y. & Kassim, M. 2013. Molybdenum complex as potential photosensitiser for direct water splitting. Materials Science Forum 756: 231- 237.

Mark Lee, W.F., Ng, K.H., Lorna, J.M., Umar, A.A. & Kassim, M. 2012a. Penentuan aras jalur tenaga kompleks tungsten nitrosilditiolena. Sains Malaysiana 41(4): 439-444.

Mark Lee, W.F., Lorna, J.M. & Kassim, M. 2012b. Sifat foto-kimia kompleks molibdenum ditiolena. Sains Malaysiana 41(5): 597-601.

Maia, P.I.D.S., Pavan, F.R., Leite, C.Q.F., Lemos, S.S., de Sousa, G.F., Batista, A.A., Nascimento, O.R., Ellena, J., Castellano, E.E., Niquet, E. & Deflon V.M. 2009. Vanadium complexes with thiosemicarbazones: Synthesis, characterization, crystal structures and anti-mycobacterium tuberculosis activity. Polyhedron 28(2): 398-406.

Mangalam, N.A. & Kurup, M.R.P. 2009. Synthesis and spectral investigations of vanadium(IV/V) complexes derived from an ONS donor thiosemicarbazone ligand. Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy 71(5): 2040- 2044.

Maurya, M.R., Kumar, A., Abid, M. & Azam, A. 2006. Dioxovanadium(V) and μ-oxo bis[oxovanadium(V)] complexes containing thiosemicarbazone based ONS donor set and their antiamoebic activity. Inorganica Chimica Acta 359(8): 2439-2447.

McCleverty, J.A., Seddon, D., Bailey, N.A. & Joe” Walker, N.W. 1976. The chemistry of cyclopentadienyl and related nitrosyl complexes of molybdenum. Part V. dihalogenonitrosyl[tris(p yrazolyl)borato]molybdenum complexes, their alcoholysis, and the crystal structure of chloronitrosylisopropoxo[tris(4- chloro-3,5-dimethylpyraz. Dalton Transactions 10: 898-908.

Nguyen, H.H. & Abram, U. 2007. Rhenium and technetium complexes with N,N-dialkyl-N'-benzoylthioureas. Inorganic Chemistry 46(13): 5310-5319.

Parihar, S., Pathan, S., Jadeja, R.N., Patel, A. & Gupta, V.K. 2012. Synthesis and crystal structure of an oxovanadium(IV) complex with a pyrazolone ligand and its use as a heterogeneous catalyst for the oxidation of styrene under mild conditions. Inorganic Chemistry 51: 1152-1161.

Pettinari, C. 2004. Scorpionates: Pinch and Sting the Metal. La Chimica e l'Industria 86(10): 94-100.

Prasad, K.S., Kumar, L.S., Shekar, S.C., Prasad, M. & Revanasiddappa, H.D. 2011. Oxovanadium complexes with bidentate N, O ligands: Synthesis, characterization, DNA binding, nuclease activity and antimicrobial studies. Chemical Sciences Journal 12: 1-10.

Rauf, M.K., Imtiaz-ud-Din, Badshah, A., Gielen, M., Ebihara, M., Vos, D.D. & Ahmed, S. 2009. Synthesis, structural characterization and in vitro cytotoxicity and anti-bacterial activity of some Copper(I) complexes with N,N'-disubstituted thioureas. Journal of Inorganic Biochemistry 103(8): 1135- 1144.

Saeed, A., Flörke, U. & Erben, M.F. 2014. A review on the chemistry, coordination, structure and biological properties of 1-(acyl/aroyl)-3-(substituted) thioureas. Journal of Sulfur Chemistry 35(3): 318-355.

Saeed, S., Rashid, N., Jones, P.G., Ali, M. & Hussain, R. 2010. Synthesis, characterization and biological evaluation of some thiourea derivatives bearing benzothiazole moiety as potential antimicrobial and anticancer agents. European Journal of Medicinal Chemistry 45(4): 1323-1331.

Shardin, R., Tan, S.S. & Kassim, M.B. 2017. Synthesis and structural characterization of N-bromobenzoyl-N'-(1,10- phenanthroline-5-yl)thiourea derivatives. Malaysian Journal of Analytical Sciences 21(1): 60-71.

Solinas, A., Faure, H., Roudaut, H., Traiffort, E., Schoenfelder, A., Mann, A., Manetti, F., Taddei, M. & Ruat M. 2012. Acylthiourea, acylurea, and acylguanidine derivatives with potent hedgehog inhibiting activity. Journal of Medicinal Chemistry 55(4): 1559-1571.

Tan, S.S., Al-Abbbasi, A.A., Tahir, M.I.M. & Kassim, M.B. 2014. Synthesis, structure and spectroscopic properties of cobalt(III) complexes with 1-benzoyl-(3,3-disubstituted) thiourea. Polyhedron 68: 287-294.

Wiberg, K.B. & Wang, Y. 2011. Transition metal-catalyzed formation of C–O and C–S bonds. Arkivoc 2011(5): 45-56.

Wlodarczyk, A., Richardson, R.M., Ward, M.D., Mccleverty, J.A., Hursthouse, M.H.B. & Coles, S.J. 1996. Complexes of tris (3, 5-Dimethylpyrazolyl)borates alkylated on the 4-position of the pyrazolyl rings. X-ray crystal structure of molybdenum dicarbonyl nitrosyl trus(3,5-dimethyl-4-n-butylpyrazolyl) borate. Polyhedron 15(1): 27-35.

Xing, Y., Zhang, Y., Sun, Z., Ye, L., Xu, Y., Ge, M., Zhang, B. & Niu, S. 2007a. Two new scorpionates vanadium haloperoxidases model complexes: Synthesis and structure of VO(O2)(pzH)(HB(pz)3) and VO(O2)(pzH)(B(pz)4) (pzH = pyrazole(C3H4N2)). Journal of Inorganic Biochemistry 101(1): 36-43.

Xing, Y., Bai, F.Y., Aoki, K., Sun, Z. & Ge, M.F. 2007b. Syntheses and structures of oxovanadium (IV) complexes, HB(pz)3VO(ph-acac)2H2O (pz, pyrazole) and HB(3,5- Me2pz)3VO(ph-acac)2H2O and V2O4[HB(pz)3]22CH3CN. Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry 37(3): 203-211.

Yadava, A.K., Yadav, H.S., Yadav, U.S. & Rao, D.P. 2012. Synthesis and structural characterization of novel square pyramidal oxovanadium (IV) complexes with ligands. Turkish Journal of Chemistry 36: 624-630.

Yang, W., Liu, H., Li, M., Wang, F., Zhou, W. & Fan, J. 2012. Synthesis, structures and antibacterial activities of benzoylthiourea derivatives and their complexes with cobalt. Journal of Inorganic Biochemistry 116: 97-105.

 

 

*Corresponding author, email: mb_kassim@ukm.edu.my

 

 

 

 

 

previous