Synthesis and Characterization of 3-Aminomethylpyridine and the Salt of 2,6-Pyridinedicarboxylic Acid and Fe(III), Co(II) and Cu(II) Complexes of the Salt

Abstract

In this study, proton transfer salt {(H3amp)+(Hdipic)-, 1)} between 3-aminomethylpyridine (3amp) and 2,6-pyridinedicarboxylic acid (H2dipic) and it Fe(III) {(H3amp)[Fe(dipic)2].2H2O, 2}, Co(II) {(H3amp)2[Co(dipic)2].3H2O, 3} and Cu(II) {(H3amp)2[Cu(dipic)2].5H2O, 4} were synthesized. Novel compounds were characterized by FT-IR, AAS, NMR (1H and 13C), UV, magnetic, and molar conductivity tests. According to the spectroscopic analysis results, the acid:base ratio is 1:1 for salt, while the metal:acid:base ratio is 1:2:1 for 2 and 1:2:2 for 3 and 4. The structures of all complexes are proposed to be octahedral.

Keywords

• 3-Aminomethylpyridine
• Dipicolinic acid
• Proton transfer salt
• Fe(III) complex
• Co(II) complex
• Cu(II) complex

3-Aminometilpiridin ile 2,6-Piridindikarboksilik Asitin Tuzu ve Tuzun Fe(III), Co(II) ve Cu(II) Komplekslerinin Sentezi ve Karakterizasyonu

Öz

Bu çalışmada, 3-aminometilpiridin (3amp) ile dipikolinik asit’in (H2dipic) proton transfer tuzu {(H3amp)+(Hdipic)-, 1)} ve tuzun Fe(III) {(H3amp)[Fe(dipic)2].2H2O, 2}, Co(II) {(H3amp)2[Co(dipic)2].3H2O, 3} ve Cu(II) {(H3amp)2[Cu(dipic)2].5H2O, 4} kompleksleri sentezlenmiştir. Yeni sentezlenen bileşiklerin karakterizasyonu için FT-IR, AAS, NMR (1H ve 13C), UV, manyetik ve molar iletkenlik ölçümleri kullanılmıştır. Spektroskopik analiz sonuçlarına göre asit:baz oranı tuz için 1:1 iken, metal:asit:baz oranı 2 için 1:2:1 ve 3 ve 4 için 1:2:2 ‘dir. Tüm komplekslerin yapıları oktahedral olarak önerilmiştir.

Anahtar Kelimeler

• 3-Aminometilpiridin
• Dipikolinik asit
• Proton transfer tuzu
• Fe(III) kompleks
• Co(II) kompleks
• Cu(II) kompleks

Kaynakça

1. M. Marinescu, “2-Aminopyridine – a classic and trendy pharmacophore,” Inter. J. Pharm. Bio Sci., vol. 8(2), pp. 338-355, 2017.
2. B.M.P. Beebeejaun-Boodoo, M. Rademeyer, “Coordination polymers and metallocycles of metal halides with n-(aminomethyl)pyridine, n = 3 or 4: Structures and solid-state fluorescence,” Polyhedron, vol. 179, pp. 114364, 2020.
3. P. Rodney, F. Cody, E. Carson, K.K. Klausmeyer, “Silver(I) 3-aminomethylpyridine complexes, part 1:  effect of ligand ratio, π-stacking, and temperature with a noninteracting anion,” Inorg. Chem., vol. 45(6), pp. 2627-2634, 2006.
4. X.H. Ding, L.F. Cui, Y.H. Li, S. Wang, W. Huang, “Proton-transfer supramolecular salts resulting from 3,5-dinitrobenzoic acid and aminomethyl pyridine,” New J. Chem., vol. 36(9), pp. 1884-1890, 2012.
5. J.G. Camarasa, M. Lluch, E. Serra-Baldrich, M. Zamorano, A. Malet, P.A. “García-Calderón, Allergic contact dermatitis from 3-(aminomethyl)-pyridyl salicylate,” Contact derm., vol. 20(5), pp. 347-51, 1989.
6. R.J. Schmidt, L.F. de Corres, “Allergic contact dermatitis from proprietary topical analgesic sprays 3-(aminomethyl)-pyridyl salicylate”, Dermatolog., vol. 174(6), pp. 272-279, 1987.
7. P. Tang, D. Xiao, B. Wang, “Synthesis of 3-(aminomethyl)pyridine by traceless C3-selective umpolung of 1-amidopyridin-1-ium salts,” Chem. Commun., vol. 12, pp. 1993-1996, 2017.
8. D. Karaagac, “Vibrational spectroscopic and thermal investigations of the cyanobridged polymeric complexes with 3-aminomethylpyridine,” Eskişehir Tech. Univ. J. Sci. Tech. A- Appl. Sci. Eng., vol. 20(3), pp. 216-226, 2019.

9. J. Wu, H. Liu, Z. Lin, M. Cao, Z. Yu, H. Hao, L. Guo, “Synthesis, structure, and electrochemical properties of nano-layered organic-inorganic perovskites containing Fe(CN) layers and its application for detection of DNA hybridization,” Proc. SPIE, vol. 381, pp. 73810N/1-73810N/10, 2009.
10. C. Krebs, I. Jess, C. Näther, “Synthesis, crystal structure and thermal properties of poly[bis­[μ-3-(aminomethyl)pyridine-κ2N:N′]bis(thiocyanatoκN)manganese(II)],” Acta Cryst. vol. E77, pp. 765-769, 2021.
11. D. Kowalkowska-Zedler, A. Dolega, N. Nedelko, R. Lyszczek, P. Aleshkevych, I. Demchenko, J. Luczak, A. Slawska-Waniewska, A. Pladzyk, “Structural, magnetic and spectral properties of tetrahedral cobalt(II) silanethiolates: a variety of structures and manifestation of field-induced slow magnetic relaxation,” Dalton Trans., vol. 49(3), pp. 697-710, 2020.
12. M. Shukla, “Raman spectroscopic study of water tetramer in [Cu(3-aminomethyl)pyridine OH2oxalate·2H2O]n,” Polyhedron, vol. 105, pp. 200-204, 2016.
13. M. Shukla, B. Kharediya, N. Srivastava, S. Saha, S. Sunkari, “Water square (uudd) in novel Cu framework structures built from isomeric (aminomethyl)pyridines and oxalate: Synthesis, structure, spectral and DFT studies,” Polyhedron, vol. 54, pp. 164-172, 2013.
14. S.S. Sunkari, B. Kharediya, S. Saha, B. Elrez, J.P. Sutter, “Chain of dimers to assembly of trimers: temperature and ligand influenced formation of novel supramolecular assemblies of Cu(II) with isomeric (aminomethyl) pyridines and azide,” New J. Chem., vol. 38(8), pp. 3529-3539, 2014.
15. M. Barquin, M.J. Gonzalez Garmendia, S. Pacheco, E. Pinilla, S. Quintela, J.M. Seco, M.R. Torres, “Synthesis, crystal structure, magnetic properties and EPR spectra of copper(II) acetate derivatives: tetra-(μ-acetato)bis(2-methylaminopyridine)copper(II) and catena-poly(aquadiacetato-μ-3-aminomethylpyridine)copper(II). Sheets formed by chains connected through hydrogen-bonds,” Inorg. Chim. Acta, vol. 357(11), pp. 3230-3236, 2004.
16. J.H. Li, L. Wei, Z.Z. Bao, G.M. Wang, Z.H. Wang, “Assembly of two novel inorganic-organic hybrid solids based on 3-(aminomethyl)pyridine ligand,” Solid State Sci., vol. 51, pp. 13-17, 2016.
17. H. Aghabozorg, F. Manteghi, S. Sheshmani, “A brief review on structural concepts of novel supramolecular proton transfer compounds and their metal complexes,” J. Iran. Chem. Soc., vol. 5(2), pp. 184-227, 2008.
18. L. Yang, D.C. Crans, S.M. Miller, A. La Cour, O.P. Anderson, P.M. Kaszynski, M.E. Godzala, L.D. Austin, G.R. Willsky, “Cobalt(II) and cobalt(III) dipicolinate complexes:  solid state, solution, and in vivo insulin-like properties,” Inorg. Chem., vol. 41, pp. 4859-4871, 2002.
19. P. Buglyo´, D.C. Crans, E.M. Nagy, R.L. Lindo, L. Yang, J.J. Smee, W. Jin, L.H. Chi, M.E. Godzala, G.R. Willsky, “Aqueous chemistry of the vanadiumIII (VIII) and the VIII−dipicolinate systems and a comparison of the effect of three oxidation states of vanadium compounds on diabetic hyperglycemia in rats,” Inorg. Chem. vol. 44, pp. 5416-5427, 2005.
20. N. Büyükkıdan, C. Yenikaya, H. İlkimen, C. Karahan, C. Darcan, E. Şahin, “Synthesis, characterization and antimicrobial activity of a novel proton salt and its Cu(II) complex,” Russian J. Coord. Chem., vol. 39(1), pp. 96-103, 2013.
21. N. Büyükkıdan, C. Yenikaya, H. İlkimen, C. Karahan, C. Darcan, T. Korkmaz, Y. Süzen, “Synthesis, characterization and biological activities of metal(II) dipicolinate complexes derived from pyridine-2,6-dicarboxylic acid and 2-(piperazin-1-yl)ethanol,” J. Mol. Struct., vol. 1101, pp. 139-146, 2015.
22. N. Büyükkıdan, H. İlkimen, S. Bozyel, M. Sarı, A. Gülbandılar, “The syntheses, structural and biological studies of Co(II) complexes of 1,2-bis(pyridin-4-yl)ethane with 2-aminobenzene-1,4-disulfonic acid and 2,6-pyridinedicarboxylic acid,” J. Mol. Struct., vol. 1275, 134586, 2023.
23. N. Büyükkıdan, H. İlkimen, S. Bozyel, M. Sarı, A. Gülbandılar, “Two new Cu(II) coordination complexes with 1,2-bis(pyridin-4-yl)ethane bridge-ligand: synthesis, characterization and antimicrobial activity,” Polyhedron, vol. 223, 115951, 2022.
24. C. Yenikaya, M. Poyraz, M. Sarı, F. Demirci, H. İlkimen, O. Büyükgüngör, Synthesis, characterization and biological evaluation of a novel Cu(II) complex with the mixed ligands 2,6-pyridinedicarboxylicacid and 2-aminopyridine,” Polyhedron, vol. 28(16), pp. 3526-3532, 2009.
25. C. Yenikaya, N. Büyükkıdan, M. Sarı, R. Keşli, H. İlkimen, M. Bülbül, O. Büyükgüngör, “Synthesis, characterization and biological evaluation of novel Cu(II) complexes with proton transfer salt of 2,6-pyridinedicarboxylic acid and 2-amino-4-methylpyridine,” J. Coord. Chem. vol. 64(19), pp. 3353-3365, 2011.
26. H. İlkimen, S.G. Salün, A, Gülbandılar, M. Sarı, “The new salt of 2-amino-3-methylpyridine with dipicolinic acid and its metal complexes: Synthesis, characterization and antimicrobial activity studies,” J. Mol. Struct., vol. 1270, 133961, 2022.
27. H. İlkimen, C. Yenikaya, M. Sarı, M. Bülbül, E. Tunca, Y. Süzen, “Synthesis and characterization of a proton transfer salt between dipicolinic acid and 2-amino-6-methylbenzothiazole and its complexes, and their inhibition studies on carbonic anhydrase isoenzymes,” Polyhedron, vol. 61, pp. 56-64, 2013.
28. H. İlkimen, C. Yenikaya, M. Sarı, M. Bülbül, E. Tunca, H. Dal, “Synthesis and characterization of a proton transfer salt between 2,6-pyridinedicarboxylic acid and 2-aminobenzothiazole, and its complexes and their inhibition studies on carbonic anhydrase isoenzymes,” J. Enzy. Inhib. Med. Chem., vol. 29(3), pp. 353-361, 2014.
29. H. İlkimen, C. Yenikaya, M. Sarı, M. Bülbül, M. Aslan, Y. Süzen, Synthesis and characterization of some metal complexes of a proton transfer salt, and their inhibition studies on carbonic anhydrase isoenzymes and the evaluation of the results by statistical analysis,” J. Enzy. Inhib. Med. Chem., vol. 29(5), pp. 695-701, 2014.
30. H. İlkimen, C. Yenikaya, M. Sarı, M. Bülbül, E. Tunca, H. Dal, M. Baş, “Synthesis and characterization of complexes of a novel proton transfer salt and their inhibition studies on carbonic anhydrase isoenzymes,” J. Enzy. Inhib. Med. Chem., vol. 30(2), pp. 195-203, 2015.
31. H. İlkimen, C. Yenikaya, A. Gülbandılar, M. Sarı, “Synthesis and characterization of a novel proton salt of 2-amino-6-nitrobenzothiazole with 2,6-pyridinedicarboxylic acid and its metal complexes and their antimicrobial and antifungal activity studies,” J. Mol. Struct., vol. 1120, pp. 25-33, 2016.
32. Z.A. Alkaya, H. İlkimen, C. Yenikaya, Y. Kaygısız, M. Bülbül, T. Tunç, M. Sarı, “A novel proton transfer salt of 2-amino-6-sulfamoylbenzothiazole and its metal complexes: the evaluation of inhibition effects on human cytosolic carbonic anhydrases,” J. Enzy. Inhib. Med. Chem., vol. 32(1), pp. 231-239, 2017.
33. Z.A. Alkaya, H. İlkimen, C. Yenikaya, E. Tunca, M. Bülbül. T. Tunç. M. Sarı. “Synthesis and characterization of Cu(II) complexes of 2-amino-6-sulfamoylbenzothiazole and their inhibition studies on carbonic anhydrase isoenzymes,” Polyhedron, vol. 151, pp. 199-205, 2018.
34. D. Cook. “Vibrational spectra of pyridinium salts” Canadian J. Chem., vol. 39, no. 10, pp. 2009-2024, 1961.
35. K. Nakamoto, “Infrared and raman spectra of inorganic and coordination compounds” 5th ed NewYork: Wiley-Interscience, pp 232, 1997.
36. W.J. Geary, “The use of conductivity measurements in organic solvents for the characterisation of coordination compounds,” Coord. Chem. Rev., vol. 7(1), pp. 81-122, 1971.