Binuclear Nickel(II) Complex Containing 6-Methyl-2,2'-bipyridine and Chloride Ligands: Synthesis, Characterization, Thermal Analyses, and Crystal Structure Determination

Document Type : Research Article


1 Department of Chemistry, Farhangian University, Tehran, I.R. IRAN

2 Department of Chemistry, Yadegar-e-Imam Khomeini (RAH) Shahre Rey Branch, Islamic Azad University, Tehran, I.R. IRAN


A new binuclear complex of [{NiCl(6-mbipy)}2(μ-Cl)2] (1) was prepared from the reaction of NiCl2.6H2O and 6-methyl-2,2'-bipyridine (6-mbipy)  in a mixture of methanol and acetonitrile. Suitable crystals of 1 for X-ray diffraction measurement were obtained by slow evaporation of the resulted green solution at room temperature. Complex 1 was characterized by spectral methods (IR, UV–Vis, and luminescence), elemental analysis (CHN), and single-crystal X-ray diffraction. The structure of 1 is centrosymmetric binuclear complex and each Ni(II) cation is five-coordinated in a slightly distorted square-pyramidal configuration. In this binuclear complex, the Ni…Ni distance is 3.533(1)Å. Furthermore, the luminescence emission of the title complex was blue-shifted and is stronger than that of free 6-methyl-2,2'-bipyridine ligand. Thermal stabilities of this complex was also studied by thermogravimetric analysis.


Main Subjects

[3] Huang C., Zeng Y., Flisak Z., Zhao Z., Liang T., Sun W.H., Tailoring Polymers Through Interplay
of Ligands within Precatalysts: 8-(Nitro/benzhydryl-arylimino)-7,7- dimethyl -5,6- dihydroquinolylnickel Halides in Ethylene Polymerization,
J. Polym. Sci. Part A:Polym. Chem., 55(12): 2071-2083 (2017).
[4] Omoregie H. O., Ojattah P., Adeleke O. E., Woods J.A.O., Capitelli F., Synthesis, Spectral, and Antimicrobial Studies of Nickel(II) Complexes with Nitrogen-Containing Ligands, Synt.React. Inorg. Met. Org. Nano-Met. Chem., 45(4): 469-476 (2015).
[5] Le F., Sun D., Liu D., Zheng C., Liu Y., Liu J., Stabilization of G-Quadruplex DNA and Antitumor Activity by Different Structures of Nickel(II) Complexes, Inorg. Chem.Commun., 38(1): 20-27 (2013).
[6] Gao C.Y., Ma Z.Y., Zhang Y.P., Li S.T., Gu W., Liu X.,  Tian J.L., Xu J.Y., Zhao J.Z., Yan S.P.,  Four Related Mixed-ligand Nickel(II) Complexes: Effect of Steric Encumbrance on the Structure, DNA/BSA Binding, DNA Cleavage and Cytotoxicity,RSC Adv., 5(39): 30768-30779 (2015).
[9] Yakhvarov D., Trofimova E., Sinyashin O., Kataeva O., Budnikova Y., Lönnecke P., Hawkins E. H., Petr A., Krupskaya Y., Kataev V., Klingeler R.,  Büchner B., New Dinuclear Nickel(II) Complexes: Synthesis, Structure, Electrochemical, and Magnetic Properties,  Inorg.Chem., 50(10): 4553-4558 (2011).
[10] Abedi A., Saemian E., Amani V., Nickel(II) Complex Containing 5,5′-dimethyl-2,2′-bipyridine: Crystal Structure and Luminescent Properties, J. Struct. Chem., 56(8): 1545-1549 (2015).
[11] Guan L., Sheng H. F., Wang Y., Synthesis, Crystal Structures, and Luminescent Properties of Mononuclear Cu(II)/Ni(II) Complexes Containing N-Donor Ligands, Synt. React. Inorg. Met. Org. Nano-Met. Chem., 46(8): 1142-1148 (2016). 
[12] Zhu Y.L., Shao S., Ma K.R., Tang X.L., Cao L.,  Zhao H.C., Syntheses, Structures and luminescent Properties of Two Novel M(II)-Phen-SIP Supramolecular Compounds (M = Co, Ni), Bull. Korean Chem., 33(4): 1259-1263 (2012).
[15] Weber B.B., Constable E.C., Housecroft C.E., Kopecky P., Neuburger M., Zampese J.A., The Intramolecular Aryl Embrace: from Light Emission to Light Absorption, Dalton Trans.,40(46): 12584-12594 (2011).
[16] Ghiasi Z., Amani V., Mirzaei P., Safari N., Abedi A., Trichloridothallium(III) Complexes  with Bipyridine Derivatives: from Structure to Luminescence Properties, Aust.J. Chem., 66(6): 676-684 (2013).
[17] Sun Q., Vazquez S. M., Daku L. M. L., Guenee L., Goodwin H. A., Vauthey E., Hauser A., Experimental Evidence of Ultrafast Quenching of the 3MLCT Luminescence in Ruthenium(II) Tris-Bipyridyl Complexes via a 3dd State, J. Am. Chem. Soc., 135(37): 13660-13663 (2013).  
[19] Ostad S.N., Abedi A., Amani V., Karimi P.,  Heydarnezhad S., Influence of Methyl Group Position in Bipyridine Ligand on Structure and Luminescence of Related Zinc(II) Nitrate Complexes, J. Iran. Chem. Soc., 13(8): 1417-1427 (2016).
[21] Gaspar A.B., Ksenofontov V., Martinez V., Muñoz M.C., Real J. A., Gütlich P., A Novel dinuclear FeII spin-crossover complex based on a 2,2'-bipyrimidine bridge Ligand: [Fe(CH3bipy)(NCS)2]2bpym.Eur. J. Inorg. Chem., 2004(24):4770-4773 (2004). 
[22] Onggo D., Craig D. C., Rae A. D., Goodwin H. A., Coordination of 6-methyl-2,2'- bipyridine. structure of bivalent copper and palladium complexes. Aust. J. Chem., 44(2): 219-231 (1991).
 [23] Onggo D., Hook J. M., Rae A. D., Goodwin H. A., The influence of steric effects in substituted 2,2′-bipyridine on the spin state of iron(II) in [FeN6]2+ systems.  Inorg. Chim. Acta, 173(1): 19-30 (1990). 
[24] Houton E., Kelly B., Sanz S., McInnes E. J. L., Collison D., Brechin E. K., Barra A. L., Ryder A. G.,  Jones L. F., A facile synthetic route to a family of MnIII monomers and their  structural, magnetic and spectroscopic studies. Eur. J. Inorg. Chem., 2016(32): 5123-5131 (2016).
[25] Tominaga M., Kusukawa T., Sakamoto S., Yamaguchi K., Fujita M., Complementary Multicomplexation of Desymmetrized 2,2′-bipyridine Ligands on Square Planar Pd(II) Centers, Chem. Lett., 33(7): 794-795 (2004).
[27] Ahmadi R., Kalateh K., Ebadi A., Amani V.,  Khavasi H. R., Dichlorido(6-methyl-2,2'- bipyridine-κ2N,N')zinc(II). Acta Crystallogr., E64(10): m1266 (2008).
[28] Ahmadi R., Ebadi A., Kalateh K., Norozi A., Amani V., Dichlorido(6-methyl-2,2'-bipyridine-κ2N,N') mercury(II). Acta Crystallogr., E64(11),m1407 (2008).
[29] Kalateh K., Ahmadi R., Amani V., Dibromido(6-methyl-2,2'-bipyridine-κ2N,N')zinc(II), Acta Crystallogr., E66(10), m1241 (2010).
[31] Shirvan S. A., Haydari Dezfuli S., Khazali F., Borsalani A., Dibromido(6-methyl-2,2′-bipyridine-κ2 N,N′)cobalt(II), Acta Crystallogr.,E68(12), m1460 (2012).
[32] Shirvan S.A., Haydari Dezfuli S., Dibromido(dimethyl Sulfoxide-κO)(6-methyl-2,2′-bipyridine-κ2 N,N′)cadmium, Acta Crystallogr.,E68(8): m1124 (2012). 
[33] Gabbiani C., Casini A., Messori L., Guerri A., Cinellu M. A., Minghetti G., Corsini M., Rosani  C., Zanello P.,  Arca M., Structural Characterization, Solution Studies, and DFT Calculations on a Series of Binuclear Gold(III) oxo Complexes: Relationships to Biological Properties, Inorg. Chem., 47(7), 2368-2379 (2008).
[34] Abedi A., Safari N., Amani V., Tavajohi S.,  Ostad S.N., Synthesis, Characterization and Cytotoxicity
of a Series of Tetrachloridoplatinum(IV) Complexes
, Inorg. Chim. Acta, 376(1): 679-686 (2011).
[35] Sheldrick G. M., SADABS, Bruker AXS, Madison, WI, USA (1998).
[36] Bruker SMART and SAINT, Bruker AXS Inc., Madison,WI, USA (1998).
[37] Sheldrick G. M., The SHELX Programs for Crystal Structure Determination are Reviewed by Their Author, Acta Crystallogr., A64(1): 112-122 (2008).
[38] Mercury 2.4, Copyright Cambridge Crystallographic Data Center, Cambridge, UK (2001-2005).
[40] Li D., Zhong  G. Q., Zang, Q., Solid–Solid Synthesis, Crystal Structure and Thermal Decomposition of Copper(II) Complex of 2-Picolinic Acid. Iran. J.Chem. Chem. Eng. (IJCCE), 35(4), 21-29 (2016).
[41] Clark R. J., Williams C. S., The Far-Infrared Spectra of Metal-Halide Complexes of Pyridine  and Related ligands. Inorg. Chem., 4(3): 350-357 (1965). 
[43] Reedijk J., Verbiest J., A Dimeric High-Spin Nickei(II) Compound with a Transition to Monomeric Tetrahedral Nickel(II), Trans. Met. Chem., 3(1): 51-52 (1978).
[44] Warad I., Hammouti B., Hadda T.B., Boshaala A., Haddad S.F., X-Ray Single-Crystal Structure
of a Novel di-μ-chlorobis [chloro(2,9-dimethyl-1,10-phenanthroline) nickel(II)] Complex: Synthesis,
and Spectral and Thermal Studies,
Res. Chem. Intermed., 39(9): 4011-4020 (2013).
[46] Shamaei S., Heidari A., Amani V., Characterization, Luminescent Properties, and Crystal Structure Determination of [Pt(Ph2bipy)Cl2], J. Struct. Chem., 57(8): 1675-1679 (2016).
[50] Parveen N., Nazir R., Mazhar M., Thermal Degradation Pathways of nickel(II) Bipyridine Complexes to Size-Controlled Nickel Nanoparticles, J. Therm. Anal. Calorim., 111(1): 93–99 (2013).
[52] Shao C., Sun W. H., Chen Y., Wang R., Xi C., Self-Assembly of Dinuclear M2Cl4(C13H9N3)2: Stepwise Supramolecular Array by π–π Stacking: Inorg. Chem. Commun., 5(9): 667-670 (2002).
[53] Xia D. S., Chen W., Tang X. L., Zeng Q. F., Di-μ-chlorido-bis­{chlorido[2-(2-furyl­methyl­imino­ meth­yl)pyridine-κ2N,N′]nickel(II)},Acta Crystalloger, E64(6), m836 (2008).