Synthesis, analysis of single crystal structure and computational studies on a novel picrate derivative: 2-(Pyridine-2-ylthio)pyridine-1-ium picrate

Fatma Aydin; Asli Ozturk Kiraz

doi:10.5155/eurjchem.16.2.117-128.2673

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Published: Jun 30, 2025

DOI: https://doi.org/10.5155/eurjchem.16.2.117-128.2673

Keywords:

Thermal properties, 2-Mercaptopyridine, Density functional theory, X-ray structure determination, Molecular electrostatic potentials, 2-(Pyridine-2-ylthio)pyridine-1-ium picrate

Section

Research Article

Issue

Vol. 16 No. 2 (2025): June 2025

Dates

Received 2025-02-12
Accepted 2025-05-01
Published 2025-06-30

Fatma Aydin

Department of Chemistry, Faculty of Science, Çanakkale Onsekiz Mart University, 17100, Çanakkale, Turkey

https://orcid.org/0000-0002-7219-6407

Asli Ozturk Kiraz

Department of Physics, Computational Physics Laboratory, Faculty of Science, Pamukkale University, 20070, Denizli, Turkey

https://orcid.org/0000-0001-9837-0779

Abstract

A new organic salt, 2-(pyridine-2-ylthio)pyridine-1-ium picrate (C₁₆H₁₁N₅O₇S: 2-PyrTPPc), has been synthesized and characterized using various spectroscopic methods such as ¹H NMR, ¹³C NMR, and FT-IR. The crystal structure of the title compound was analyzed using X-ray structure analysis, which revealed that it belongs to the monoclinic P2₁/c space group with a = 16.876(4) Å, b = 7.6675(18) Å, c = 13.846(3) Å, Z = 4, and V = 1766.9(7) Å³. The molecular packing of the compound showed the presence of several intermolecular hydrogen bonds between different atoms. The electronic properties of the crystal were investigated using density functional theory (DFT) with B3LYP/6-311G(d,p) level. Frontier molecular orbitals were drawn and related global quantities such as electronic chemical potential, chemical hardness-softness, electrophilicity, HOMO and LUMO energy eigenvalues, and the difference between HOMO and LUMO (∆E) were calculated and discussed. TG/DTG analysis revealed the thermal stability of the 2-PyrTPPc crystal. The single stage of decomposition and the sharpness of the peak in the temperature range of 157-224 °C illustrated the purity and good crystallinity of the grown crystal. The different vibration modes of the 2-PyrTPPc molecule were determined by analyzing the FT-IR and FT-Raman spectra. The detection of vibrations of the pyrNH⁺ and aromatic thioether moiety supports the confirmation of the di(pyridin-2-yl)sulfane structure through the intermediate formed by the transfer of the proton from picric acid to 2-mercaptopyridine.

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Aydin, F.; Kiraz, A. O. Synthesis, Analysis of Single Crystal Structure and Computational Studies on a Novel Picrate Derivative: 2-(Pyridine-2-ylthio)pyridine-1-Ium Picrate. Eur. J. Chem. 2025, 16, 117-128.

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