Synthesis and Characterization of Zn(II) Complexes of 2-Amino-6-substituepyridine Derivatives and 5-Sulfosalicylic Acid

Abstract

This study, four new Zn(II) complexes {(HX)2[Zn(Hssal)2(H2O)2], (H3ssal: 5-sulfosalicylic acid, X = 2-amino-6-methylpyridine (1) for 5, 2-amino-3-ethyl-6-methylpyridine (2) for 6, 2-amino-3-nitro-6-methylpyridine (3) for 7, and [Zn(Hssal)(X)2(H2O)2], X = 2-amino-3-nitro-6-chloropyridine (4) for 8} were synthesized. The structures of Zn(II) complexes (5-8) were characterized by elemental analysis, AAS, FT-IR, molar conductivity and magnetic susceptibility analyses. The results of IR and conductivity analyses, it was observed that 5-7 metal complexes were ionic, while 8 metal complexes were non-ionic. AAS and elemental analysis tests also support these results. In magnetic susceptibility studies, it was observed that Zn(II) (d10) metal complexes did not carry unpaired electrons as expected. The results of the spectroscopic analysis of complexes 5-8 have an octahedral structure.

Keywords

• 5-Sulfosalicylic acid
• 2-Aminopyridine
• Zn(II) complex
• Octahedral structure

2-Amino-6-sübstitüepiridin Türevleri ile 5-Sülfosalisilik Asitin Zn(II) Komplekslerinin Sentezi ve Karakterizasyonu

Abstract

Bu çalışmada, dört yeni Zn(II) kompleksleri {(HX)2[Zn(Hssal)2(H2O)2], H3ssal: 5-sülfosalisilik asit, X = 5 için 2-amino-6-metilpiridin (1), 6 için 2-amino-3-etil-6-metilpiridin (2) ve 7 için 2-amino-3-nitro-6-metilpiridin (3)} ve {[Zn(Hssal)(X)2(H2O)2] {X = 8 için 2-amino-3-nitro-6-kloropiridin (4)} elde edildi. Zn(II) komplekslerinin yapıları element analizi, AAS, FT-IR, molar iletkenlik ve manyetik duyarlılık analizleri ile karakterize edildi. IR ve iletkenlik analizleri sonucunda 5-7 metal komplekslerinin iyonik olduğu ve 8 metal kompleksinin ise iyonik olmadığı gözlenmiştir. Bu sonuçları AAS ve elementel analiz testleri de desteklemektedir. Manyetik duyarlılık çalışmalarında Zn(II) (d10) metal komplekslerinin beklendiği gibi eşleşmemiş elektron taşımadıkları gözlenmiştir. Yapılan spektroskopik analiz sonuçlarında tüm komplekslerin (5-8) oktahedral yapıya sahip oldukları önerilmiştir.

Keywords

• 5-Sülfosalisilik asit
• 2-Aminopiridin
• Zn(II) kompleksi
• Oktahedral yapı

References

1. Banowski, B., Kropf, C., (2015), Cosmetic antiperspirants with aromatic sulphonic acids. Germany, DE102013220789 A1 2015-04-16a.
2. Banowski, B., Kropf, C., (2015), Cosmetic antiperspirants with aromatic sulphonic acids. World Intellectual Property Organization, WO2015055198 A1 2015-04-23b.
3. Buyukkidan, N., Yenikaya, C., Ilkimen, H., Karahan, C., Darcan, C., Şahin, E., (2013), Synthesis, characterization and antimicrobial activity of a novel proton salt and its Cu(II) complex. Russian Journal of Coordination Chemistry, 39(1), 96-103.
4. Chen, Z. F., Shi, S. M., Hu, R. X., Zhang, M., Liang, H., Zhou, Z. Y., (2003), Synthesis, crystal structure, fluorescence property and antibacterial activity of two unprecedented one-dimensional chain metalorganic coordination polymers: Zn(H-SSA)(Phen)(H2O)2 and Cu(H-SSA)(Phen)(H2O)2. Chinese Journal of Chemistry, 21(8), 1059-1065.
5. Cook, D., (1961), Vibrational spectra of pyridinium salts. Canadian Journal of Chemistry, 39(10), 2009-2024.
6. Du, Z. X., Li, J. X., Wang, L. Y., (2009), Syntheses, crystal structures and fluorescent properties of two 4,4'-dipyridylsulfide based zinc(II) and cadmium(II) helical complexes. Journal of Coordination Chemistry, 62(15), 2411-2420.
7. Duan, X., Li, D., Lin, Y., Zhang, L., Tuo, Z., (2006), Method for preparing layered double hydroxides-sulfosalicylic acid having supramol İntercalating structure and its application. China, CN1861702 A 2006-11-15.
8. Fan, S. R., Zhu, L. G., Xiao, H. P., (2005), catena-Poly[[cis-diaqua(2,2'-bipyridine)zinc(II)]-μ-5-sulfonatosalicylato]. Acta Crystallographica, E61(5), m804-m806.

9. Geary, W. J., (1971), The use of conductivity measurements in organic solvents for the characterisation of coordination compounds. Coordination Chemistry Reviews, 7, 81-122.
10. Han, Q., Wang, X. C., Li, X. Y., Yao, G. X., Yan, Y. S., (2009), Aqua(2-hydroxy-5-sulfonatobenzoato-κO1)bis(2-phenyl-1H-1,3,7,8-tetraazacyclopenta[l]phenanthrene-κ2N7,N8)zinc(II). Acta Crystallographica, E65(11), m1282-m1283.
11. Hecht, E., (2004), catena-Poly[[tetraaquazinc(II)]-μ-5-sulfosalicylato-κ2O:O'] Acta Crystallographica, E60(9), m1286-m1288.
12. Heleno, S. A., Martins, A., Queiroz, M. J. R. P, Ferreira, I. C. F. R., (2015), Bioactivity of phenolic acids: metabolites versus parent compounds: a review. Food Chemistry, 173, 501-513.
13. Ilkimen, H., İlkimen, B., Yenikaya, C., (2022), Metal complexes of 5-sulfosalicylic acid. New developments in science and mathematics, Bölüm 2.3, ss 221-234, Hiperyayın Evi.
14. Ivanova, B., Spiteller, M., (2017), On the nature of the coordination bonding of metal-organics for ions with the d10 electronic configuration - Experimental and theoretical analyses. Polyhedron, 137, 256-264.
15. Khadikar, P. V., Joshi, S., Kashkhedikar, S. G., Heda, B. D., (1984), Metal-complexes of 5-sulfosalicylic acid and their antimicrobial activity. Indian Journal of Pharmaceutical Sciences, 46(6), 209-211.
16. Koksharova, T., Slyvka, Y., Savchenko, O., Mandzii, T., Smola, S., (2023), 5-Sulfosalicylato Cu(II), Zn(II) and Ni(II) coordination compounds with benzohydrazide: Synthesis, structure and luminescent properties. Journal of Molecular Structure, 1271, 133980.
17. Lamshoeft, M., Storp, J., Ivanova, B., Spiteller, M., (2011), Gas-phase CT-stabilized Ag(I) and Zn(II) metal-organic complexes - Experimental versus theoretical study. Polyhedron, 30(15), 2564-2573.
18. Ma, J. F., Yang, J., Liu, J. F., (2003), Hexaaquazinc(II) 3-carboxy-4-hydroxybenzenesulfonate tetrahydrate. Acta Crystallographica, E59(7), m487-m488.
19. Ma, W. X., Qian, B. H., Gao, J., Xu, X. Y., Lu, L. D., Yang, X. J., Wang, X., Song, H. B., (2005), Synthesis, crystal structure and spectral characterization of the complex [Zn(tren)(SSA)]. Wuji Huaxue Xuebao, 21(4), 612-616.
20. Marinescu, M., (2017), 2-Aminopyridine – a classic and trendy pharmacophore. International Journal of Pharma and Bio Sciences, 8(2), 338-335.
21. Nakamoto, K., Infrared and raman spectra of inorganic and coordination compounds, 5th ed Wiley-Interscience, New York, 1997.
22. Rajagopalan, K. V., Kalyanaraman, R., Sundaresan, M., (1988), Thermal decompositions of sulfosalicylates of magnesium(II), calcium(II) and zinc(II). Journal of Thermal Analysis and Calorimetry, 34(1), 329-334.
23. Randjelović, P., Veljković, S., Stojiljković, N., Sokolović, D., Ilić, I., Laketić, D., Randjelović, D., Randjelović, N., (2015), The beneficial biological properties of salicylic acid. Acta Facultatis Medicae Naissensis, 32, 259-265.
24. Sharma, G., Tandon, J. P., (1970), Potentiometric studies on stepwise mixed ligand complex formation copper(II), nickel(II), or zinc(II)-nitrilotriacetic acid-hydroxy acid. Journal of Inorganic and Nuclear Chemistry, 32(4), 1273-1278.
25. Song, J. H., Kim, D. W., Kang, D. W., Lee, W. R., Hong, C.S., (2019), Humidity-triggered single-crystal-to-single-crystal structural transformations in a Zn(II) coordination polymer displaying unusual activation energy change in proton conductivity. Chemical Communications, 55(65), 9713-9716.
26. Tunca, E., Bülbül, M., İlkimen, H., Canlıdinç, R.S., Yenikaya, C., (2020), Investigation of the effects of the proton transfer salts of 2-aminopyridine derivatives with 5-sulfosalicylic acid and their Cu(II) complexes on cancer-related carbonic anhydrases: CA IX and CA XII. Chemical Papers, 74, 2365-2374.
27. Xu, T. Y., Wang, H., Li, J. M., Zhao, Y. L., Han, Y. H., Wang, X. L., He, K. H., Wang, A. R., Shi, Z. F., (2019), A water-stable luminescent Zn(II) coordination polymer based on 5-sulfosalicylic acid and 1,4-bis(1Himidazol-1-yl)benzene for highly sensitive and selective sensing of Fe ion. Inorganica Chimica Acta, 493, 72-80.
28. Xu, T. Y., Nie, H. J., Li, J. M., Shi, Z. F., (2020), Highly selective sensing of Fe3+/Hg2+ and proton conduction using two fluorescent Zn(II) coordination polymers. Dalton Transactions, 49(32), 11129-11141.
29. Yang, Y., Du, P., Ma, J. F., Kan, W. Q., Liu, B., Yang, J., (2011), Series of metal-organic frameworks based on different salicylic derivatives and 1,1'-(1,4-butanediyl)bis(imidazole) ligand: syntheses, structures, and luminescent properties. Crystal Growth Design, 11(12), 5540-5553.
30. Zhang, K. L., Yang, B., Ng, S. W., (2009), Diaquabis(1,10-phenanthroline-κ2N,N')zinc(II) 2-hydroxy-5-sulfonatobenzoate tetrahydrate. Acta Crystallographica, E65(2), m239-m240.
31. Zordok, W. A., Sadeek, S. A., El-Farargy, A. F., (2017), Synthesis, characterization, DFT modeling and biological studies of new Co(II), Ni(II) and Cu(II) 4,6-bis(4-chlorophenyl)-2-amino-1,2-dihydropyridine-3-carbinitrile complexes. Journal of the Iranian Chemical Society, 14(12), 2529-2547.
32. Zotkin, I. I., Kuznetsova, N. V., Kabanova, L., (2013), Zinc or copper(2+) salts used as biocides in polymer materials. Russian Federation, RU2497857 C1 2013-11-10.