Elsevier

Journal of Molecular Structure

Volume 1166, 15 August 2018, Pages 470-478
Journal of Molecular Structure

A novel coordination polymer of Cd(II) based on 2-mercaptopyrimidine: Sonochemical synthesis, characterization, and antibacterial properties

https://doi.org/10.1016/j.molstruc.2018.04.054Get rights and content

Highlights

  • The complex crystallizes in the tetragonal system, space group P42/nnm.

  • Nanoparticles was also synthetized by sonochemical process.

  • Synthesized nanoparticle has stronger antibacterial activity than the complex.

Abstract

A new complex of [Cd(2-mpym)4(H2O)2](NO3)2 (1) was obtained from the reaction of Cd(NO3)2.4H2O with 2-mercaptopyrimidine in methanol solution. This complex and its nano form were characterized by elemental analysis, UV–Vis absorption spectra, Fourier transform infrared spectroscopy (FT-IR), luminescence measurements, thermal analysis (TG-DTA), and single X-ray diffraction. X-ray structure determination revealed two types of cadmium metal ions: hexagonally coordinated cadmium with two oxygen atom of a water molecule, and four sulfur atom of 2-mpym ligand; and eight-coordinated cadmium with four sulfur atoms and four nitrogen atoms of the pyrimidine ring of 2-mpym ligand. The antibacterial properties of this compound were investigated in vitro against standard Gram-positive and Gram-negative bacterial strains. The results of antibacterial tests showed that the complex 1 was a stronger antibacterial agent than the free ligand.

In this study, 1 was also synthetized in a form of nanoparticles by sonochemical process. The nanoparticles of the size about 80 nm were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–Vis absorption spectra, and Fourier transform infrared spectroscopy (FT-IR). It was found that preparing the complex 1 as nanoparticles enhanced its antibacterial effect.

Introduction

Chelating ligands containing sulfur and nitrogen are important compounds in structural chemistry of metal complexes with a strong electron-donating property. The presence of nitrogen and sulfur decreases solubility of the complexes and allows the complex to be isolated from the solution [1]. Ambidentate aromatic ligands including sulfur and nitrogen take part in a variety of reactions [[2], [3], [4]]. Many important drugs are related to analogues of pyridine, pyrimidine and their sulfur-containing derivatives [[5], [6], [7]]. Thio derivatives of pyrimidine, mercaptopyrimidines, exhibit remarkable antiviral, antibacterial, antitumor and antithyroidal activities [[8], [9], [10], [11], [12]]. These heterocyclic compounds are involved in a tautomeric equilibrium of the thiol/thione (pym-SH/Pym-NH) kind, which has important biological consequences [[13], [14], [15], [16]].

In this work, we reported the synthesis, characterization and crystal structure of a new cadmium (II) complex with 2-mercaptopyrimidine ligand. As a representative of mercaptopyrimidines, this ligand exhibits a rich coordination chemistry [17], and its tautomerism influences the coordination ability and biological activities of the corresponding coordination compounds [[18], [19], [20]]. We tested antibacterial properties of the complex prepared in a form of single crystals as well as nanoparticles. For preparation of the nanomaterial, we used sonochemistry, which provides the targeted compounds at mild temperatures, without surfactants, and usually yields small particles [[21], [22], [23], [24], [25], [26]]. The ultrasonic irradiation may accelerate or initialize new reactions which cannot occur under normal conditions [[27], [28], [29]].

Section snippets

Materials and instruments

All purchased chemicals were of reagent grade and used without further purification. Elemental analyses were performed by using a Leco, CHNS-932 elemental analyzer. IR spectrum was recorded using FT-IR JASCO 460 spectrophotometer with KBr pellets in the 4000-400 cm−1 regions.

Simultaneous Thermal Analysis (STA) was recorded by using NETZSCH STA 409 PC/PG equipment. XRD data were collected on a Bruker D8 advance in the 2θ range from 3° to 50°, using Copper X-Ray tube and Bragg-Brentano

Results and discussion

The title complex, [Cd3(2-mpym)4(H2O)2](NO3)2, was prepared by the reaction of Cd(NO3)2.6H2O with 2-mercaptopyrimidine in methanol solution. Its molecule is shown in Fig. 1.

Conclusions

A new cadmium coordination polymer with 2-mercaptopyrimidine ligand was successfully synthesized under reflux conditions, and also by the sonochemical method as nanoparticles. Single crystal X-ray diffraction analysis revealed the expected the structure of the complex, while the X-ray analysis of the nanopowder confirmed the same composition of 1 prepared by two different methods. The results of antibacterial tests showed that nanoparticles of 1 is stronger antibacterial agent than the complex 1

Acknowledgements

The authors are thankful to University of Sistan and Bluchestan for the support of this work. The crystallographic part was supported by the project 18-10504S of the Czech Science Foundation using instruments of the ASTRA lab established within the Operation program Prague Competitiveness - project CZ.2.16/3.1.00/24510.

References (46)

  • M.A. Alavi et al.

    Syntheses and characterization of Mg(OH)2 and MgO nanostructures by ultrasonic method

    Ultrason. Sonochem.

    (2010)
  • K.-H. Kim et al.

    Ultrasound assisted synthesis of nano-sized lithium cobalt oxide

    Ultrason. Sonochem.

    (2008)
  • R. Moosavi et al.

    Ultrasound-assisted coating of polyester fiber with silver bromide nanoparticles

    Ultrason. Sonochem.

    (2012)
  • L.-Z. Cai et al.

    Syntheses, structures and luminescent properties of four new 1D lanthanide complexes with 2-thiopheneacetic acid ligand

    Inorg. Chem. Commun.

    (2004)
  • N. Chattopadhyay et al.

    Photophysical studies of 7-hydroxy-4-methyl-8-(4′-methylpiperazin-1′-yl) methylcoumarin: a new fluorescent chemosensor for zinc and nickel ions in water

    J. Photochem. Photobiol., A

    (2006)
  • M. Alias et al.

    Synthesis, spectral, thermal and antibacterial studies of Cd(II), Mn(II) and Fe(III) complexes containing trithiocarbonate 1,3,4-thiadiazole moiety

    J. King Saud Univ. Sci.

    (2013)
  • L.N. Suvarapu et al.

    Synthesis and characterization of 4-Benzyloxybenzaldehyde-4-methyl-3-thiosemicarbazone (containing sulphur and nitrogen donor atoms) and its Cd(II) complex

    Metals

    (2015)
  • P. Mura et al.

    Displacement of coordinated carbon monoxide as a result of an intramolecular nucleophilic attack. Crystal and molecular structure of the ‘intermediate’, cis-dicarbonyl bis(pyridine-2-thiolato)triphenylphosphineruthenium(II), and of the product, monocarbonyl bis(pyridine-2-thiolato)triphenylphosphine ruthenium(II)

    Inorg. Chim. Acta.

    (1985)
  • B.T. Khan et al.

    Metal complexes of substituted pyrimidines, lnorg

    Chim. Acta

    (1986)
  • D.T. Hust

    An Introduction to the Chemistry and Biochemistry of Pyrimidines, Purines and Pteridines

    (1980)
  • E. Shefter et al.

    The crystal and molecular structure of 2,4-dithiouracil

    J. Am. Chem. Soc.

    (1967)
  • G.F. de Sousa et al.

    Complexes with ambidentate ligands derived from pyridine and pyrimidine-Part 1. Cyclic nickel(II) complexes

    Transition Met. Chem.

    (1990)
  • P.K. Robins

    Antitumor activity and structural relationships of purine derivatives and related compounds against neoplasms in experimental animals

    J. Med. Chem.

    (1964)
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