Malaysian Journal of Analytical Sciences Vol 21 No 5 (2017): 1036 - 1044

DOI: https://doi.org/10.17576/mjas-2017-2105-05

 

 

 

SYNTHESIS, CRYSTAL STRUCTURE AND COORDINATION CHEMISTRY OF DI-2-PYRIDYLMETHANEAMINE-BASED CHELATING LIGANDS WITH CADMIUM SALTS

 

(Sintesis, Struktur Hablur dan Kimia Koordinatan Ligan Pengkelat Berasaskan Di-2-Piridilmetanaamina dengan Garam Kadmium)

 

Maisara Abdul Kadir¹* and Christopher James Sumby²

 

¹School of Fundamental Science,

Universiti Malaysia Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia

²School of Physical Sciences, Centre for Advanced Nanomaterials,

The University of Adelaide, Adelaide, South Australia 5005, Australia

 

*Corresponding author:  maisara@umt.edu.my

 

 

Received: 16 August 2016; Accepted: 17 July 2017

 

 

Abstract

Chelating ligands play a prominent role as organic linker in the construction of multinuclear complexes due to their strong binding to metal ions. Thus, in this study, two new bridging ligands with chelating arms, namely 1,3-N,N’-[bis(di(pyridin-2-yl)methyl)]isophthalamide (L1) and 1,4-N,N’-bis[(di(pyridin-2-yl)methyl)]terephthalamide (L2) were successfully synthesized and characterized using Fourier Transform Infrared (FTIR), ¹H and ¹³C Nuclear Magnetic Resonances (¹H and ¹³C NMR) and X-ray crystallography. Reaction of L1 and L2 with metal salts gave two multinuclear cadmium complexes, with formula molecules [{CdCl₂(CH₃OH)(L1)CdCl₂}₂] and [(CdBr₂)₂(L₂)(CH₃OH)₂], respectively. X-ray crystallography reveals that ligands L1 and L2 used all four nitrogen donors from di-2-pyridylmethaneamine units to chelate with cadmium ions in forming stable multinuclear complexes. The complexes are also stabilized by supramolecular interactions such as hydrogen bonding and pi-pi stacking, as observed in the crystal packing.

 

Keywords:  crystal, chelating ligands, synthesis, pi stacking, supramolecular

 

Abstrak

Ligan pengkelat memainkan peranan penting sebagai penghubung organik dalam pembentukan kompleks multinuklear kerana ikatan yang kuat terhadap ion logam. Oleh itu, dalam kajian  ini, dua ligan penghubung baharu yang mempunyai kumpulan pengkelat, iaitu 1,3-N,N’-[bis(di(piyridin-2-il)metil)]isoptalamida (L1) dan 1,4-N,N’-bis[(di(piridin-2-il)metil)]tereptalamida (L2) telah berjaya disintesis dan dicirikan menggunakan analisis Inframerah Transformasi Fourier (FTIR), ¹H dan ¹³C Resonan Magnetik Nuklear  (¹H dan ¹³C RMN) dan kristalografi sinar-X. Kajian kimia koordinatan ligan L1 dan L2 dengan garam logam menghasilkan dua kompleks multinuklear kadmium dengan formula molekul masing-masing adalah [{CdCl₂(CH₃OH)(L1)CdCl₂}₂] dan [(CdBr₂)₂(L₂)(CH₃OH)₂]. Kajian hablur kristalografi sinar-X menunjukkan bahawa ligan L1 dan L2 menggunakan empat atom penderma nitrogen dari di-2-piridilmetanaamina unit untuk berikatan pada ion kadmium dalam menghasilkan kompleks multinuklear yang lebih stabil. Kompleks ini turut distabilkan oleh interaksi supramolekul seperti ikatan hidrogen dan interaksi pertindihan pi-pi sebagaimana yang dilihat dalam padatan hablur.

 

Kata kunci:  hablur, ligan pengkelat, sintesis, pertindihan pi, supramolekular

 

References

1.       Sumby C. J. (2011). Bridging ligands comprising two or more di-2-pyridylmethyl or amine arms:   alternatives to 2,2’- bipyridyl-containing bridging ligands. Coordination Chemistry Review, 255: 1937 – 1967.

2.       Antonioli B., Clegg J. K., Bray D. J., Gloe K., Gloe K., Kataeva O. N., Lindoy L. F., McMurtrie J. C., Steel P. J., Sumby C. J. and Wenzela M. (2006).  Silver(I) complexation of linked 2,2’-dipyridylamine derivatives. Synthetic, solvent extraction, membrane transport and X-ray structural studies. Dalton Transaction, 40:  4783 – 4794.

3.       Sumby C. J. and Steel P. J. (2007). Steel Mono- and dinuclear ruthenium complexes of bridging ligands incorporating two di-2-pyridylamine motifs: Synthesis, spectroscopy and electrochemistry. Polyhedron,  26: 5370 – 5381.

4.       Antonioli B., Bray D. J., Clegg J. K., Gloe K., Gloe K., Jager A., Jolliffe K. A., Kataeva O. N, Lindoy L. F., Steel P. J., Sumby C. J. and Wenzel M. (2008). Interaction of copper(II) and palladium(II) with linked 2,2-dipyridylamine derivatives: Synthetic and structural studies. Polyhedron, 27: 2889 – 2898.

5.       Sumby C. J. and Steel P. J. (2007). Coordination chemistry of di-2-pyridylamine-based bridging heterocyclic ligands: A structural study of coordination polymers and discrete dinuclear complexes.  Inorganic Chimica Acta, 360: 2100 – 2114.

6.       Philip, V., Suni, V., Kurup., P. R. M. and Nethai, M. (2005). Novel binuclear copper(II) complexes of di-2-pyridine ketone N(4)-methyl, N(4)-phenylthiosemicarbazone: Structural and spectral investigation, Polyhedron, 24: 1133 – 1142.

7.       Suni, V., Kurup, P. R. M. and Nethaji, M. (2007). Structural and spectral investigation on some new Ni(II) complexes of-di-2-pyridyl ketone N(4)-phenylthiosemicarbazone. Polyhedron, 26: 3097 – 3102

8.       Wu, S. H., Zhong, Y. W. and Yao J. (2013). 2,3-di(2-pyridyl)-5-phenylpyrazine: ANN-CNN-type bridging ligand for dinuclear transition-metal complexes. Chemistry Asian Journal, 8: 1504 – 1513

9.       Zhong, Y. W, Wu, S. H., Burkhardt, S. E. and Abruna H. D. (2011). Mononuclear and dinuclear ruthenium complexes of 2,3-di-2-pyridyl-5,6-diphenylpyrazine: Synthesis and spectroscopic and electrochemical studies. Inorganic Chemistry, 50: 517 – 524.

10.    Trilla, M., Pleixats, R., Man, M. W. C., Bied, C. and Moreau, J. J. E. (2006). Hybrid organic–inorganic silica materials containing di(2-pyridyl)methylamine–palladium dichloride complex as recyclable catalysts for Suzuki cross-coupling reactions. Tetrahedron, 47: 2399 – 2403.

11.    Chang, J., Plummer, S., Berman, E. S. F., Striplin, D. and Blauch, D. (2004). Synthesis and characterization of bis(di-2-pyridylmethanamine)ruthenium(II). Inorganic Chemistry, 43: 1735 – 1742.

12.    Kadir, M. A, Ramli, R., Kassim, N., Mansor, N., Sumby, C. J. (2015). Synthesis, structural and spectroscopic studies of palladium(II) metallo-macrocyles containing ancillary blocking ligands and N,N’-2,6-bis(3-pyridylmethyl)pyridine dicarboxamide. Malaysian Journal of Analytical Sciences, 19(3): 520 – 530.

13.    Idris, N. S. B., Kadir, M. A. and Khandaker, M. M. (2017), Synthesis, characterization and coordination chemistry of N,N’-bis(3-pyridylmethyl)benzene-1,4-dicarboxamide with palladium and ruthenium salts. Asian Journal of Chemistry, 29(7): 1459 – 1462.

14.    Renz, M., Hemmert, C. and Meunier, B. (1998). Synthesis of bis(di-2-pyridylmethyl)amine (BDPMA) by a novel one-pot multi-step reductive amination with molecular sieves and Zn/i-PrOH. European Journal of Inorganic Chemistry, 30: 1271 – 1273.

15.    Kitagawa, S., Kitaura, R. and Noro, S. I. (2004). Functional porous coordination polymers. Angewante Chemistry International Edition, 43: 2334 – 2375.

16.    Liu, T. F., Lu, J. and Cao R. (2010). Coordination polymers based on flexible ditopic carboxylate or nitrogen-donor ligands. Crystal Engineering Communication, 12: 660 – 670.

17.    Abdul-Kadir, M., Clements, P. R., Hanton, L. R., Hollis, C. A. and Sumby C. J. (2012). Pre-organisation or a hydrogen bonding mismatch: Silver(I) diamide ligand coordination polymers versus discrete metallo-macrocyclic assemblies. Supramolecular Chemistry, 24: 627 – 640.

18.    Abdul-Kadir, M., Hanton, L. R. and Sumby, C. J. (2011). Self-assembled metallo-macrocycle based coordination polymers with unsymmetrical amide ligands. Dalton Transaction, 40: 12374 – 12380.

19.    Abdul-Kadir, M., Hanton, L. R. and Sumby, C. J. (2012). Building blocks for coordination polymers: self-assembled cleft like and planar discrete metallo macrocyclic complexes. Dalton Transaction, 41: 4497 – 4505.

20.    Kadir, M. A., Mansor, N., Yusof, M. S. M. and Sumby, C. J. (2014). Synthesis and crystal structure of N-6-[(4-pyridylamino) carbonyl]-pyridine-2-carboxylic acid methyl ester zinc complex. Complex Metals, 1: 32  – 37.