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Synthesis, structure, Hirshfeld surface analysis, and computational studies of 2-amino-5-nitropyridine-2,4-dinitrophenol cocrystal

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Abstract

A supramolecular cocrystal of 2-ammino-5-nitropyridine (ANP) with 2,4-dinitrophenol (DNP) has been successfully grown by the slow evaporation solution growth technique. The crystal structure of 2-amino-5-nitropyridine-2,4-dinitrophenol (ANDP) was elucidated by the single-crystal X-ray diffraction analysis, and it belongs to a monoclinic system with centrosymmetric space group P21/n. The bulk phase purity and homogeneity of the material were confirmed by powder X-ray diffraction analysis. The functional groups present in the molecule are identified by FT-IR analysis, and the band gap energy was estimated using diffuse reflectance data by the application of the Kubelka–Munk algorithm. The thermal stability of the compound was investigated by carrying out TG–DTA analysis. Theoretical calculations were performed using the density functional theory method to derive the dipole moment and hyperpolarizability. The high value of first-order molecular hyperpolarizability (β) suggests that it is a potential microlevel NLO candidate.

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Abbreviations

ANDP:

2-Amino-5-nitropyridine-2,4-dinitrophenol

ANP:

2-Ammino-5-nitropyridine

DNP:

2,4-Dinitrophenol

FT-IR :

Fourier transform infrared spectroscopy

TG-DTA:

Thermogravimetric and differential thermal analysis

NLO:

Nonlinear optical

SHG:

Second harmonic generation

MEP :

Molecular electrostatic potential

DFT :

Density functional theory

FMO :

Frontier molecular orbitals

HOMO :

Highest occupied molecular orbital

LUMO :

Lowest unoccupied molecular orbital

UV–Vis DRS:

Ultraviolet visible near-infrared diffuse reflectance spectroscopy

XRD:

X-ray diffraction

CCDC :

Cambridge Crystallographic Data Centre

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Funding

The authors thank the Council of Scientific and Industrial Research, New Delhi, for financial support through research grant No. 21 (1024)/16/EMR-II. SS and CB are grateful to the CSIR Emeritus Scientist Scheme for the award of the SRF/RA-ship.

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Authors and Affiliations

  1. Department of Chemistry, Annamalai University, Annamalainagar, -608002, Tamil Nadu, India

    Shanmugam Sivaraman, Chellakarungu Balakrishnan & Subbiah Meenakshisundaram

  2. Department of Chemistry, Indra Ganesan College of Engineering, Manikandam, Tiruchirapalli - 620012, Tamil Nadu, India

    Shanmugam Sivaraman

  3. Department of Chemistry, Erode Sengunthar Engineering College, Erode, - 638057, Tamil Nadu, India

    Chellakarungu Balakrishnan & Palusamy Suppuraj

Authors
  1. Shanmugam Sivaraman
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  2. Chellakarungu Balakrishnan
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  3. Palusamy Suppuraj
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  4. Subbiah Meenakshisundaram
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Contributions

S S: data curation, investigation, visualization, validation, writing, original draft. C B: data curation, investigation, visualization, validation. P S: investigation. SP M: review, editing, and supervision. The final version of the manuscript submitted was approved by all the authors.

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Correspondence to Subbiah Meenakshisundaram.

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Sivaraman, S., Balakrishnan, C., Suppuraj, P. et al. Synthesis, structure, Hirshfeld surface analysis, and computational studies of 2-amino-5-nitropyridine-2,4-dinitrophenol cocrystal. Struct Chem 34, 239–249 (2023). https://doi.org/10.1007/s11224-022-02087-8

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