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Preparation, thermal behavior, luminescent properties, and crystal structures of aminoguanidinium 2,n-pyridine-dicarboxylate (n = 3, 4, 5, and 6) salts

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Abstract

The reaction of 2,n-pyridinedicarboxylic acids (H2pydc) (n = 3, 4, 5, and 6) with the base guanylhydrazine bicarbonate [(H2N)2C=N(H)NH2][HCO3] in different mole ratios has yielded three types of salts, viz. the 1:1 salt, [(H2N)2C=N(H)NH2][Hpydc] (1), the 2:1 salt [(H2N)2C=N(H)NH2]2[pydc] (2), and the 1:3 complex [(H2N)2C=N(H)NH2][Hpydc].2[H2pydc] (3) in which the 1:1 salt co-crystallizes with the acid. These salts have been characterized by IR, thermal analysis, and luminescence properties, and their antioxidant activity has been investigated. The structures of 1 (n = 3 and 6) have been determined by X-ray crystallography. The quinolinate salt [(H2N)2C=N(H)NH2][Hpydc] (n = 3) crystallizes as a monohydrate whereas the dipicolinate salt [(H2N)2C=N(H)NH2][Hpydc] (n = 6) crystallizes without lattice water. The structure of the quinolinate derivative reveals a conventional mono-deprotonated dicarboxylic acid, NC5H3(COOH)(COO−), whereas the dipicolinate derivative exhibits an unusual zwitterionic anion, HNC5H3(COO−)2. These structures are stabilized through extensive hydrogen bonding and π–π stacking. Both the parent acids and their salts display strong fluorescent emission at room temperature.

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Acknowledgements

The authors (S.P, A.P and S.G) thank the UGC-SAP-DRS II, New Delhi (India) for financial support. A.P. is also thankful for the award of Research Fellowship in Sciences for Meritorious Students (RFSMS) scheme by UGC, New Delhi, India, and J.M.R. would like to thank the CRC program for financial support.

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Authors and Affiliations

  1. Department of Chemistry, Bharathiar University, Coimbatore, 641 046, India

    S. Packiaraj, A. Pushpaveni, C. Senthil & S. Govindarajan

  2. Department of Chemistry and Biochemistry, The University of Windsor, Windsor, ON, N9B3P4, Canada

    J. M. Rawson

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  1. S. Packiaraj
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  2. A. Pushpaveni
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  3. C. Senthil
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Correspondence to S. Govindarajan.

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Packiaraj, S., Pushpaveni, A., Senthil, C. et al. Preparation, thermal behavior, luminescent properties, and crystal structures of aminoguanidinium 2,n-pyridine-dicarboxylate (n = 3, 4, 5, and 6) salts. J Therm Anal Calorim 119, 15–25 (2015). https://doi.org/10.1007/s10973-014-4098-3

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