Novel boron compounds of 2,3- and 2,5-pyridinedicarboxylic acids

doi:10.1016/j.ica.2011.11.006

Inorganica Chimica Acta

Volume 383, 30 March 2012, Pages 169-177

https://doi.org/10.1016/j.ica.2011.11.006 Get rights and content

Abstract

The (Hea)[B(ph)₂(2,3-pydc)] (1) and (Hea)[B(ph)₂(2,5-pydc)] (2) boron compounds (2,3-H₂pydc = 2,3-pyridinedicarboxylic acid, 2,5-H₂pydc = 2,5-pyridinedicarboxylic acid, Hea = ethanolammonium) were synthesized and characterized by elemental analysis, spectroscopic measurements (UV–Vis, ¹¹B NMR, ¹³C NMR, ¹H NMR and IR spectra) and single crystal X-ray diffraction technique. Compound 1 and 2 crystallize in the monoclinic space group P2₁/c. The crystal packing of compound 1 is stabilized through strong intermolecular hydrogen bonding and C–H⋯π interactions, resulting in a 3D framework. The individual molecules of 2 are connected by the N–H⋯O and O–H⋯O hydrogen bonds leading to two-dimensional hydrogen bonded layer. The in vitro antibacterial and anticandidal activities of (1) and (2) were evaluated by disc diffusion method and MIC tests. Both new complexes showed antimicrobial activity against MRSA and clinical and standard yeast isolates.

Graphical abstract

The (Hea)[B(ph)₂(2,3-pydc)] (1) and (Hea)[B(ph)₂(2,5-pydc)] (2) boron compounds were synthesized and characterized by elemental analysis, spectroscopic measurements and single crystal X-ray diffraction technique. The in vitro antibacterial and anticandidal activities of (1) and (2) were evaluated by the disc diffusion method and MIC tests. Two complexes were effective against MRSA and Candida sp.

Highlights

► The strong intermolecular hydrogen bonding and C–H···π interactions is observed. ► The biological activities of compounds were evaluated method various. ► The compounds exhibited antimicrobial activity against MRSA.

Introduction

The chemistry of elemental boron, its compounds and crystalline phases based on them is currently a vast and quite complicated scientific field at the boundary of inorganic and organo-element chemistry. Boron compounds are successfully used in various areas of materials science, in catalysis, surface chemistry, inorganic and organic synthesis, biochemistry, agriculture, medicine, forestry and OLEDs [1], [2], [3], [4], [5], [6], [7]. The synthesis of boron derivatives of biomolecules such as amino acids, peptides, nucleosides, porphyrins and sugars is a major area of research [8]. For the past decade chemists have been interested in the synthesis and characterization of five- and six-membered boron compounds with a coordinative N → B bond. Also such boron compounds have been prepared from pyridinedicarboxylic acids [9], [10], [11], [12], [13]. These acids can act as both a multiple proton donor and an acceptor while also using their carboxylate oxygen and nitrogen atoms, which are highly accessible to metal ions, to form interesting network structures [14], [15]. Pyridinedicarboxylic acids have widely been used as organic ligands for the construction of organic–inorganic hybrid materials, which have been of great interest in recent years [16], [17], [18], [19], [20], [21], [22]. These types of ligands combine the advantages of both organic multi-carboxylic acid and aromatic compounds. 2,3- and 2,5-pyridinedicarboxylic acids with divergent function groups, which possibly form bridging hydrogen bonds, are interesting and have potential for self-assembly. In addition, the carboxylic groups in position 5 of the pyridine ring may be prone to involvement in hydrogen bonds [23], [24]. Organic boron compounds can be studied by multinuclear NMR techniques. Particularly, ¹¹B NMR provides valuable structural information due to its sensitivity to electronic and steric effects as well as to the boron coordination number. The structures of several new compounds have been determined by X-ray diffraction analyses [25].

Herein, we report the synthesis, characterization and antimicrobial activity of two novel boron compounds, using 2,3- and 2,5-pyridinedicarboxylic acids involving coordinative N → B bonds.

Section snippets

Materials and measurements

All chemicals and solvents used for the syntheses were of reagent grade. The synthesis of diphenylborinic acid was carried out under an atmosphere of dry argon by using standard Schlenk techniques. ¹H and ¹³C NMR spectra were recorded with Varian AS 400. ¹¹B NMR spectra were recorded with a Varian AS 600 spectrometer. NMR references were (CH₃)₄Si and BF₃·Et₂O. 2,3-Pyridinedicarboxylic acid and 2,5-pyridinedicarboxylic acid (Aldrich) were used as received. Elemental analysis (C, H, and N) was

NMR spectra

The treatment of 2-aminoethyl diphenylborinate whit methanol at −78 °C probably led to the formation of methyl diphenylborinate and ethanolamine, causing a transesterification reaction of a carboxylic acid group (2,3-pyridinedicarboxylic acid) with boron (methyl diphenylborinate) to take place [10], resulting in the formation of a boron compound. During formation of the boron compound and ethanolamine an acid–base reaction occurred between the other carboxylic acid group of the boron compound

Acknowledgments

This work was supported by Dumlupınar University, project No. 2007/14 and by Adnan Menderes University project No. FEF-08002.

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Novel boron compounds of 2,3- and 2,5-pyridinedicarboxylic acids

Abstract

Graphical abstract

Highlights

Introduction

Section snippets

Materials and measurements

NMR spectra

Acknowledgments

J. Organomet. Chem.

Biores. Tech.

J. Organomet. Chem.

Bioorg. Med. Chem. Lett.

J. Organomet. Chem

J. Mol. Struct.

J. Mol. Struct.

Polyhedron

J. Mol. Struct.

Inorg. Chem. Commun.

Inorg. Chim. Acta

Polyhedron

Inorg. Chem. Commun.

Coord. Chem. Rev.

J. Organomet. Chem.

J. Alloys. Comp.

J. Mol. Struct.

J. Europ. Ceram. Soc.

Russ. Chem. Rev.

Chem. Commun.