Abstract
In general, molecules with certain functional groups such as amine (-NH2) and carboxyl (-COOH) can promote the growth of co-crystals leading to the formation of supramolecular networks. However, if the differences in the pKa values of the two molecules are large [pKa (base)—pKa (acid)], salts can result instead of ‘real’ co-crystals. Here, we report the formation of such salt by letting pyrazine-2-carboxylic acid (pKa = 2.9) crystallize together with aminoguanidine (pKa = 11.5; high Δpka = 8.6) a nitrogen-rich organic base. The title salt has been prepared by slow evaporation of an equimolar ratio of guanylhydrazine bicarbonate (i.e., aminoguanidine bicarbonate (AgunH.HCO3)) and pyrazine-2-carboxylic acid (Pymca) in aqueous medium. The salt was characterized by IR spectroscopy, powder and single-crystal X-ray diffraction techniques. This material shows enhanced antioxidant activity and this is due to the crucial role of hydrazinic moiety in the aminoguanidinium salt.
Similar content being viewed by others
References
A.N. Manin, A.P. Voronin, K.V. Drozd, A.V. Churakov, G.L. Perlovich, Pharmaceutical salts of emoxypine with dicarboxylic acids, Acta Cryst., C74 (2018) 797–806.
A. Dalpiaz, B. Pavan, V. Ferretti, Can pharmaceutical co-crystals provide an opportunity to modify the biological properties of drugs? Drug Discov. Today 22, 1134–1138 (2017)
N. Schultheiss, A. Newman, Pharmaceutical cocrystals and their physico- chemical properties. Cryst. Growth Des. 9(6), 2950–2967 (2009)
K.V. Drozd, S.G. Arkhipov, E.V. Boldyreva, G.L. Perlovich, Crystal structure of a 1:1 salt of 4-aminobenzoic acid (vitamin B10) with pyrazinoic acid, Acta Cryst., E74 (2018) 1923–1927.
S. Packiaraj, A. Pushpaveni, S. Govindarajan, J.M. Rawson, Structural and anti-oxidant properties of guanidinium pyrazole-3,5-dicarboxylates. Cryst. Eng. Commun. 18(41), 7978–7993 (2016)
S. Packiaraj, A. Pushpaveni, C. Senthil, S. Govindarajan, J.M. Rawson, 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)
P.P. Deyn (ed.), Guanidino Compounds in Biology and Medicine (London, England, J. Libbey, 1992)
V. Sivashankar, R. Siddheswaran, P. Murugakoothan, Synthesis, growth, structural, optical and thermal properties of a new semiorganic nonlinear optical guanidinium perchlorate single crystal. Mater. Chem. Phys. 130, 323–326 (2011)
R.E. Khomaa, V.O. Gelmboldta, V.N. Baumerd, O.V. Shishkind, L.V. Koroevaa, Synthesis and structure of aminoguanidinium sulfite monohydrate. Russ. J. Inorg. Chem. 58, 843–847 (2013)
J.H. Bryd, The crystal structure of aminoguanidine hydrochloride. Acta Cryst. 10, 677–720 (1957)
A. Akella, D.A. Keszler, Aminoguanidinium nitrate, Acta Cryst., C50 (1994) 1974–1976.
E.R. Khomaa, O.V. Gelmboldta, N.V. Baumerd, V.O. Shishkind, V.L. Koroevaa, Synthesis and Structure of Aminoguanidinium Sulfite Monohydrate. Russ. J. Inorg. Chem. 58(7), 843–847 (2013)
I. Nemec, Z. Machackova, K. Teubner, I. Cisarova, P. Vanek, Z. Micka, The structural phase transitions of aminoguanidinium(1+) dihydrogen phosphate – study of crystal structures, vibrational spectra and thermal behavior. J. Solid State Chem. 177(12), 4655–4664 (2004)
J.N. Adams, The crystal structure of aminoguanidinium dihydrogen orthophosphate. Acta Cryst., B33 (1997) 1513–1515.
M. Koskinen, I. Mutikainen, H.A. Elo, Aminoguanidinium(+2)-sulpahte. Z. Naturforsch., 49b (1994) 556.
I. Mutikainen, M. Koskinen, H.A. Elo, Crystallographic study on aminoguanidine dinitrate. Pharmazie. 49C, 739 (1994)
T. Kolev, R. Petrova, Zwitterionic 2-guanidinium-1-aminocarboxylate monohydrate. Acta Cryst., E59 (2003) 447–449.
J.T. Koskinen, M. Koskinen, I. Mutikainen, P. Tilus, B. Mannfors, H.A. Elo, Experimental and Computational Studies on Aminoguanidine Free Base, Monocation and Dication, Z. Naturforsch., 52b (1997) 1259.
M. Koskinen, I. Mutikainen, P. Tilus, E. Petittari, M. Korvela, H.A. Elo, Structure of aminoguanidine hemioxalate. Implications for the synthesis of amidinohydrazones. Monatsh. Chem. 128, 767–775 (1997)
Z. Machackova, I. Nemec, K. Teubner, P. Nemec, P. Vanek, Z. Micka, The crystal structure, vibrational spectra, thermal behavior and second harmonic generation of aminoguanidinium (1+) hydrogen (L)-tartrate monohydrate. J. Mol. Struc. 832, 101–107 (2007)
T. Kolev, Z. Glavcheva, R. Stahl, H. Preut, P. Bleckmann, V. Radomirska, Aminoguanidinium Squarate. Acta Cryst., C53 (1997).
S. Murugavel, P.S. Kannan, A. Subbiah Pandi, S. Govindarajan, R. Selvakumar, Aminoguanidinium hydrogen succinate. Acta Cryst., E65 (2009) o454.
S. Murugavel, G. Ganesh, A. Pandi, S. Govindarajan, R. Selvakumar, Aminoguanidinium hydrogen fumarate. Acta Cryst. E65, o548 (2009)
M. Göbel, T.M. Klapötke, Potassium-, ammonium-, hydrazinium-, guanidinium-, aminoguanidinium-, diaminoguanidinium-, triaminoguanidinium- and melaminium nitroformate-synthesis, characterization and energetic properties. Z. Anorg. Allg. Chem. 633, 1006–1017 (2007)
T. Premkumar, R. Selvakumar, N.P. Rath, S. Govindarajan, Synthesis and spectroscopic, thermal and crystal structure studies of hydrazinium hydrogensuccinate. S. Afr. J. Chem. 67, 85–90 (2014)
S. Vairam, S. Govindarajan, New hydrazinium salts of benzene tricarboxylic and tetracarboxylic acids - Preparation and their thermal studies. Thermochim. Acta 414(2), 263–270 (2004)
T. Premkumar, S. Govindarajan, The chemistry of hydrazine derivatives - Thermal behavior and characterisation of hydrazinium salts and metal hydrazine complexes of 4,5-imidazoledicarboxylic acid. Thermochim. Acta 386(1), 35–42 (2002)
T. Premkumar, S. Govindarajan, W.-P. Pan, Preparation, spectral and thermal studies of pyrazinecarboxylic acids and their hydrazinium salts. J Chem Sci. 115(2), 103–111 (2003)
K. Saravanan, S. Govindarajan, Preparation and Thermal Reactivity Of Hydrazinium 2, n-pyridinedicarboxylates (n=3, 4, 5 and 6). J. Therm. Anal. Calorim. 73, 951–959 (2000)
A. Pushpaveni, S. Packiaraj, S. Govindarajan, G.T. McCandless, C.F. Fronczek, F.R. Fronczek, Structural resemblance and variation in transition metal complexes derived from dipicolinic acid and guanylhydrazine. Inorganica Chimica Acta 471(24), 537–549 (2018)
K.D. Prasad, S. Cherukuvada, R. Ganduri, L.D. Stephen, S. Perumalla, T.N. Guru Row, Differential Cocrystallization behavior of isomeric pyridine carboxamides toward anti-tubercular drug Pyrazinoic acid. Cryst. Growth Des. 15, 858 (2015). https://doi.org/10.1021/cg501642m
W. Xu, K. Hu, Y. Lu, H. Ye, S. Jin, M. Li, M. Guo, D. Wang, The crystal structures of ten supramolecular salts of benzylamine and organic acids. J. Mol. Struct. 1219, 128554–128578 (2020)
W. Fang, B. Chen, D. Chen, S. Wang, Y. Yan, S. Jin, W. Xu, D. Wang, Seven supramolecular adducts of 4-dimethylaminopyridine and carboxylic acids constructed by classical H-Bonds and some non covalent interactions. J. Mol. Struct. 1203, 127353 (2020). https://doi.org/10.1016/j.molstruc.2019.127353
J.A. Fernandes, B. Liu, J.P.C. Tomé, L. Cunha-Silva, F.A. Almeida Paz, Crystal structure of 5-amino-4H-1,2,4-triazol-1-ium pyrazine-2-carboxylate: an unexpected salt arising from the decarboxylation of both precursor, Acta Cryst., E71 (2015) 840–843.
G.H. Jeffery, J. Bassett, J. Mendham, R.C. Denney, “Vogel’s Textbook of Quantitative Chemical Analysis”. 1986,5thEd.
O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H. Puschmann, Olex2: A complete structure solution, refinement and analysis program. J. Appl. Cryst. 42, 339–341 (2009)
L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard, H. Puschmann, The anatomy of a comprehensive constrained, restrained, refinement program for the modern computing environment - olex2 disected. Acta. Cryst. A A71, 59–71 (2015)
F. Kleemiss, O.V. Dolomanov, M. Bodensteiner, N. Peyerimhoff, L. Midgley, L.J. Bourhis A. Genoni, L.A. Malaspina, D. Jayatilaka, J.L. Spencer, F. White, B. GrundkStock, S. Steinhauer D. Lentz, H. Puschmann, S. Grabowsky, Accurate crystal structures and chemical properties from NoSpherA2, Chem. Sci., (2021).
P. Prieto, M. Pineda, M. Aguilar, Spectrophotometric quantization of antioxidant capacity through the formation of a phosphomolybdenum complex: specific application to the determination of vitamin E. Anal Biochem. 69, 337–341 (1992)
K. Nagendra Prasad, B. Yang, S. Yang, Y. Chen, M. Zhao, M. Ashraf, Identification of phenolic compounds and appraisal of antioxidant and antityrosinase activities from litchi (Litchi sinensis Sonn.) seeds. Food Chem. 116, 1–7 (2009)
S. Packiaraj, S. Govindarajan, Synthesis, thermal behaviour, XRD, and luminescent properties of lighter lanthanidethiodipropionate hydrates containing aminogunidine as neutral ligand, Open. J. Inorgan. Chem. 4(3), 41–49 (2014)
S. Packiaraj, P. Kanchana, A. Pushpaveni, H. Puschmann, S. Govindarajan, Different coordination geometries of lighter lanthanates driven by the symmetry of guanidines as charge compensators. New J. Chem. 43(2), 979–991 (2019)
T.L. Kumar, P. Vishweshwar, J.M. Babu, K. Vyas, Salts of hydrates of imiquimod, an immune response modifier. Cryst. Growth. Des. 9, 4822–4829 (2009)
U.P. Singh, S. Narang, A supramolecular approach towards the construction of molecular salts using phosphonic acid and pyrazole. Cryst. Eng. Comm. 16, 7777–7789 (2014)
Acknowledgements
S. P. and L. K wishes to thank URF for the award of a research fellowship in science for meritorious students under the University Research Fellowship. The author S. G. thanks the UGC-SAP-DRS II, New Delhi (India), for financial support. S. G. is also thankful for the award of UGC-Emeritus Fellowship by UGC, New Delhi, India.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Packiaraj, S., Kousalya, L., Pushpaveni, A. et al. Structural and antioxidant properties of guanylhydrazinium pyrazine-2-carboxylate. J Mater Sci: Mater Electron 32, 7704–7718 (2021). https://doi.org/10.1007/s10854-021-05489-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10854-021-05489-2