Crystal structure, spectroscopy, DFT studies and thermal characterization of Cobalt(II) complex with 2-protonated aminopyridinium cation as ligand
Graphical abstract
Introduction
A great deal of interest has arisen in the synthesis of hybrid materials as a result of their special functional properties such as magnetic or ferroelectric transitions, conductivity, electroluminescence and photoluminescence [1], [2], [3], [4], [5], [6]. Furthermore, mixed organic-inorganic salts with the general formula A2MX4 (A: organic cation, M: transition metal and X: halogen = Cl, Br, I) have attracted considerable interest due to their multiple phase transitions related to the dynamics of the organic cations and inorganic anions. Interest in these compounds is rapidly increasing, as some of them exhibit interesting structural and physical properties like ferro-electricity, ferro-elasticity and low dimensional magnetism [7], [8], [9], [10], [11], [12], [13], [14], [15], [16]. The current attention, herein, is the incorporation of metal halide systems and organic cations as counter-ions in the extremely interesting hybrid materials and this strategy is expected to affect their appealing structural, optical and photoluminescence properties, which should lead to new interesting functional compounds. The present work deals with the synthesis and the characterizations of a novel hybrid compound, (2-HAMP)2[CoBr4], with an organic layer of 2-aminopyridine (C5H6N2), single X-ray diffraction study and detailed vibrational spectral analysis aided by Density Functional Theory (DFT) calculations. In the light of the theoretical calculations, correlation between FT-IR and FT-Raman spectra and computed results help unambiguous identification of vibrational modes and provide deeper insight into the bonding and structural features of the title compound. An optical absorption measurement and thermal studies were also performed.
Section snippets
Materials
All materials used in this work were of reagent grade purity and were used as commercially obtained: CoBr2·xH2O (99%, SIGMA ALDRICH), 2-aminopyridine (C5H6N2) (98%, SIGMA ALDRICH) and Hydrobromic Acid HBr (48%, SIGMA ALDRICH). Distilled water was used in this synthesis.
Synthesis of (2-HAMP)2[CoBr4]
A mixture of CoBr2·xH2O (0.218 g), 2-aminopyridine (C5H6N2) (0.094 g) and HBr (0.080 g) in the mole ratio 1:1:1 was heated for 34 h at 120 °C. The reaction was conducted in 23 ml poly(fluoroethylene-propylene) lined pressure
Crystal structure of (2-HAMP)2[CoBr4]
The present compound crystallizes in the monoclinic C2/c space group with four formula units in unit cell (Z = 4) with the following lattice parameters: a = 8.339(4) Å, b = 14.913(4) Å, c = 13.637(5) Å and β = 95.964(3)°. A summary of the key crystallographic informations for the title compound was quoted in Table 1. Selected experimental and calculated bond distances and angles, with a relative error for each one, are illustrated in Table 2. We find an average relative error of almost 3.4% for
Conclusion
The present work is devoted to the synthesis, X-ray characterization, spectroscopic properties and thermal analysis of (C5H7N2)2[CoBr4]. The structural and vibrational spectra calculated by DFT/B3LYP/LanL2DZ level of theory agree satisfactory with the experimental results. On the basis of agreement between experimental and theoretical results, assignments of all observed bands were examined and proposed in this investigation. The optical properties were conducted by absorption measurements
Conflicts of interest
The authors declare no competing financial interest.
Acknowledgements
The authors are grateful to Pr. Abdelmottaleb OUEDERNI for his assistance in TGA/DTA measurements of this study (The Unit of Joint Service of Research–National School of Engineers of Gabes, University of Gabes, Tunisia).
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