Malaysian Journal of Analytical Sciences Vol 26 No 1 (2022): 70 - 83

 

 

 

 

SUPRAMOLECULAR ASSEMBLIES OF 1,2-DISUBSTITUTED CYCLOHEXANE AMIDE LIGANDS AND THEIR COORDINATION POLYMER: SYNTHESIS, CHARACTERISATION, AND CRYSTAL STRUCTURE

 

(Himpunan Supramolekul Ligan Amida Sikloheksana 1,2-Tertukar Ganti dan Polimer Koordinatannya: Sintesis, Pencirian, dan Struktur Hablur)

 

Nur Shuhaila Haryani Haris1, Nafisah Mansor1, Maisara Abdul Kadir1,2*

 

1Faculty of Science and Marine Environment,

2Advanced Nano Materials Research Group, Faculty of Science and Marine Environment,

Universiti Malaysia Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia

 

*Corresponding author: maisara@umt.edu.my

 

 

Received: 13 September 2021; Accepted: 18 December 2021; Published: 25 February 2022

 

 

Abstract

Supramolecular interactions such as hydrogen bonding, - stacking, Van der Waals interactions, and metal-ligand are important in stabilising the structure of molecules. In order to determine the presence of supramolecular interactions in two novel compounds, 1,2-disubstituted cyclohexane amide ligands, namely 1,2-bis[N, N'--6-(3-pyridylmethylamido)pyridyl-2-carboxyamido]cyclohexane (L1) and 1,2-bis[N,N'-6-(4-pyridylmethylamido)pyridyl-2-carboxyamido]cyclohexane (L2) were successfully synthesised and fully characterised by FTIR, 1H and 13C NMR and mass spectrometry, while the molecular formula was determined by elemental analysis. X-ray crystallography revealed that the folded conformations of both ligands were stabilised by intramolecular N-H...O=C and N-H...N hydrogen bonds at the pre-organised amide moieties. The crystal's structure was stabilised by weak face-to-face p-stacking interaction or centroid-centroid p-stacking interaction involving the two pendant pyridine rings. In the crystal structure of one-dimensional coordination polymer, there are two intermolecular hydrogen bonding interactions ( N-H...O=C, d = 2.094 Å, D = 2.946 Å and d = 2.090 Å, D = 2.938 Å, N-H...O angle = 161.52 o ) formed between the pre-organised NH amide donors of a molecule of L1 in one coordination polymer and the amide carbonyl group of a molecule of L1 in an adjacent polymer that leads to the formation of 2-D hydrogen-bonded sheets extend in the ac diagonal.

 

Keywords: supramolecular, coordination polymer, cyclohexane, hydrogen bonding, racemic

 

Abstrak

Interaksi supramolekul seperti ikatan hidrogen, susunan - , interaksi Van der Waals dan logam-ligan adalah penting dalam menstabilkan struktur molekul. Dalam usaha mengenalpasti kehadiran interaksi supramolekul dalam dua sebatian baharu, ligan amida sikloheksana 1,2-tertukar ganti, iaitu 1,2-bis[N,N'-6-(3-piridilmetilamino)piridil-2-karboksiamido]sikloheksana (L1) and 1,2-bis[N,N'--6-(4-piridilmetilamido)piridil-2-karboksiamido]sikloheksana (L2) telah disintesis dan dicirikan sepenuhnya dengan FTIR, 1H dan 13C NMR serta spektrometri jisim, manakala formula molekul ditentukan melalui analisis unsur. Kristalografi sinar-X menunjukkan bahawa konformasi bagi kedua-dua ligan distabilkan oleh ikatan hidrogen intramolekul N-H...O=C dan N-H...N pada kawasan amida separa tersusun. Struktur hablur juga distabilkan oleh interaksi lemah susunan muka ke muka atau titik pusat ke titik pusat di antara gelang aromatik piridina. Dalam struktur hablur polimer koordinatan satu dimensi, terdapat dua ikatan hidrogen intermolekul ( N-H...O=C, d = 2.094 Å, D = 2.946 Å dan d = 2.090 Å, D = 2.938 Å, N-H...O sudut = 161.52 o ) yang terbentuk di antara NH amida dari molekul L1 dalam polimer koordinatan dan karbonil amida dari molekul L1 dalam polimer bersebelahannya dan menghasilkan lapisan 2-D ikatan hidrogen yang bersambung ke diagonal ac.

 

Kata kunci: supramolekul, polimer koordinatan, sikloheksana, ikatan hidrogen, rasemik

 

 

 


Graphical Abstract

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