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Molecular salts of pipemedic acid and crystal structure, spectral properties, and Hirshfeld surface analysis

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Abstract

The research involves synthesizing 1:1 salts of Pipemedic acid (PMA) with oxalic acid (OA), salicylic acid (SA), and p-Toluene sulfonic monohydrate (BS) using a slow evaporation method. Many characterization techniques, including FT-IR, DSC, Single XRD, and DFT calculations, were employed to analyze the salts’ structural and physicochemical properties. The proton is transferred from oxalic, salicylic acid, and p-toluene sulfonic monohydrate to pyridine nitrogen of PMA. The salt 1OA, crystallizes in the monoclinic space group P 21/c, with a = 9.923(3) Å a = 90°, b = 9.443(3) Å b = 92.470(10)°and c = 18.248(5) Å g = 90° and volume = 1708.3(9) Å3and Z = 4. The salt 2SA crystallizes in the monoclinic space group P 21/c, with a = 6.8877(3) Å a = 90°.b = 13.9149(6) Å b = 98.092(2)° and c = 21.5313(10) Å g = 90° with volume = 2043.05(16) Å3 and Z = 4.The salt 3BS crystallizes in the monoclinic space group P 21/c, with, a = 9.3352(4) Å a = 90°, b = 12.7754(5) Å b = 97.722(2)°, c = 19.5462(8) Å g = 90°,with volume = 2309.96(16) Å3 and Z = 4. Supramolecular centrosymmetric ring motifs are formed by N–H···O hydrogen bonds between protonated nitrogen of the pyridone ring and the carboxylic O atom of the oxalate ion, in both 1OA and 2SA. The dihedral angles of 1OA, 2SA, and 3BS are found to be 43.63°, 88.19°, and 53.89° respectively. The Hirshfeld surfaces and the related 2D fingerprint plots were explored which uncovered that more than two-thirds of close contacts were related to H⋯H, C–H, N–H, and C–C bonding interactions whereas in 3BS, the structure is stabilized by N–H···O and N–H···S hydrogen bonding interactions. These weak associations assume a significant role in crystal packing as revealed by the Hirshfeld surfaces and the related 2D fingerprint plots.

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Acknowledgements

SJC, thanks Sri Sathya Sai University for Human Excellence for all the support and encouragement. The authors acknowledge SAIF, IIT Madras for single-crystal X-ray data collection.

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  1. Sri Sathya Sai University for Human Excellence, Nallakadirenahalli, 561211, Chikkaballapura, India

    J. C. Shwetha

  2. Department of Chemistry, Prayoga Institute of Education Research, Bengaluru, 560082, India

    Anamika Sharma

  3. Department of Chemistry, Dayananda Sagar University, Bengaluru, 560068, India

    K. Anand Solomon

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Shwetha, J.C., Sharma, A. & Solomon, K.A. Molecular salts of pipemedic acid and crystal structure, spectral properties, and Hirshfeld surface analysis. J IRAN CHEM SOC 20, 3161–3176 (2023). https://doi.org/10.1007/s13738-023-02905-8

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