Synthesis and Characterization of Zn(II) Complexes Containing 5-Sulfosalicylic Acid and 2--Amino-4-substituepyridine Derivatives

Abstract

Four new Zn(II) complexes {[Zn(Hssal)(X)2(H2O)2] (H3ssal: 5-sulfosalicylic acid, X = 2-amino-4-methylpyridine (1) for 5, 2-amino-3-nitro-4-methylpyridine (2) for 6 and (HX)2[Zn(Hssal)2(H2O)2], X = 2-amino-4,6-dimethylpyridine (3) for 7, 2-amino 4-chloropyridine (4) for 8} were synthesized and its structures were proposed by elemental analysis, AAS, IR, molar conductivity and magnetic susceptibility. The results of IR and conductivity analyses, it was observed that 5 and 6 metal complexes were non-ionic, while 7 and 8 metal complexes were 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.

5-Sülfosalisilik asit ve 2-amino-4-Sübstitüepiridin içeren Zn(II) komplekslerinin sentezi ve karakterizasyonu

Abstract

Dört yeni Zn(II) kompleksleri {[Zn(Hssal)(X)2(H2O)2] {H3ssal: 5-sülfosalisilik asit, X = 5 için 2-amino-4-metilpiridin (1), 6 için 2-amino-3-nitro-4-metilpiridin (2) ve (HX)2[Zn(Hssal)2(H2O)2] X = 7 için 2-amino-4,6-dimetilpiridin (3), 8 için 2-amino-4-kloropiridin (4)} sentezlendi ve yapıları element analiz, AAS, IR, molar iletkenlik ve manyetik duyarlılık ile önerildi. IR ve iletkenlik analizleri sonucunda 5 ve 6 nolu metal komplekslerinin iyonik olmadığı, 7 ve 8 nolu metal komplekslerinin ise iyonik olduğu gözlenmiştir. Bu sonuçları AAS ve elementel analiz 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. [1] W. A. Zordok, S. A. Sadeek and A. F. El-Farargy, “Synthesis, characterization, DFT modeling and biological studies of new Co(II, pp. Ni(II) and Cu(II) 4,6-bis(4-chlorophenyl)-2-amino-1,2-dihydropyridine-3-carbinitrile complexes”. J. Iran. Chem. Soc., vol. 14, no. 12, pp. 2529-2547, 2017, doi: 10.1007/s13738-017-1188-8
2. [2] N. Büyükkıdan, C. Yenikaya, H. İlkimen, C. Karahan, C. Darcan and E. Şahin, 2013, “Synthesis, characterization and antimicrobial activity of a novel proton salt and its Cu(II) complex”. Russ. J. Coord. Chem., vol. 39, no. 1, pp. 96-103, doi: 10.1134/S1070328412100028.
3. [3] Marinescu, M, “2-Aminopyridine – a classic and trendy pharmacophore”. Inter. J. Pharm. Bio Sci., vol. 8, no. 2, pp. 338-355, 2017, doi: 10.22376/ijpbs.2017.8.2.p338-355.
4. [4] C. Yenikaya, M. Poyraz, M. Sarı, F. Demirci, H. İlkimen and Büyükgüngör O, “Synthesis, characterization and biological evaluation of a novel Cu(II) complex with the mixed ligands 2,6-pyridinedicarboxylicacid and 2-aminopyridine”. Polyhedron, vol. 28, no. 16, pp. 3526-3532, 2009, doi: 10.1016/j.poly.2009.05.079.
5. [5] S. A. Heleno, A. Martins, M. J. R. P. Queiroz and I. C. F. R. Ferreira, “Bioactivity of phenolic acids: metabolites versus parent compounds: a review”. Food Chem., vol. 173, 501-513, 2015, doi: 10.1016/j.foodchem.2014.10.057
6. [6] P. Randjelović, S. Veljković, N. Stojiljković, D. Sokolović, I. Ilić and D. Laketić, et al. “The beneficial biological properties of salicylic acid”. Acta Facul. Med. Nais., vol. 32, 259-265, 2015, doi: 10.1515/afmnai-2015-0026.
7. [7] H. İlkimen, B. İlkimen and C. Yenikaya, “Metal complexes of 5-sulfosalicylic acid”. New developments in science and mathematics, pp. 221-234, Hiperyayın Evi, 2022.
8. [8] K. V. Rajagopalan, R. Kalyanaraman and M. Sundaresan, “Thermal decompositions of sulfosalicylates of magnesium(II), calcium(II) and zinc(II)”. J. Therm. Anal. Cal., vol. 34, no. 1, pp. 329-334, 1988, doi: 10.1007/BF01913400.

9. [9] Hecht, E. “catena-Poly[[tetraaquazinc(II)]-μ-5-sulfosalicylato-κ2O:O']”. Acta Cryst., vol. E60, no. 9, pp. m1286-m1288, 2004, doi: 10.1107/S1600536804020070.
10. [10] J. F. Ma, J. Yang and J. F. Liu, “Hexaaquazinc(II) 3-carboxy-4-hydroxybenzenesulfonate tetrahydrate”. Acta Cryst., vol. E59, no. 7, pp. m487-m488, 2003, doi: 10.1107/S1600536803013096.
11. [11] P. V. Khadikar, S. Joshi, S. G. Kashkhedikar and B. D. Heda, “Metal-complexes of 5-sulfosalicylic acid and their antimicrobial activity”. Indian J. Pharm. Sci., vol. 46, no. 6, pp. 209-211, 1984.
12. [12] J. H. Song, D. W. Kim, D. W. Kang, W. R. Lee and C.S. Hong, “Humidity-triggered single-crystal-to-single-crystal structural transformations in a Zn(II) coordination polymer displaying unusual activation energy change in proton conductivity. Chem. Commun., vol. 55, no. 65, pp. 9713-9716, 2019, doi: 10.1039/C9CC04474D.
13. [13] X. Duan, D. Li, Y. Lin, L. Zhang and Z. Tuo, “Method for preparing layered double hydroxides-sulfosalicylic acid having supramol intercalating structure and its application”. China, CN1861702 A 2006-11-15.
14. [14] M. Lamshoeft, J. Storp, B. Ivanova and M. Spiteller, “Gas-phase CT-stabilized Ag(I) and Zn(II) metal-organic complexes - Experimental versus theoretical study”. Polyhedron, vol. 30, no. 15, pp. 2564-2573, 2011, doi: 10.1016/j.poly.2011.07.003.
15. [15] B. Ivanova and M. Spiteller, “On the nature of the coordination bonding of metal-organics for ions with the d10 electronic configuration - Experimental and theoretical analyses”. Polyhedron, vol. 137, 256-264, 2017, doi: 10.1016/j.poly.2017.08.011.
16. [16] B. Banowski and C. Kropf, “Cosmetic antiperspirants with aromatic sulphonic acids”. Germany, DE102013220789 A1 2015-04-16.
17. [17] B. Banowski and C. Kropf, “Cosmetic antiperspirants with aromatic sulphonic acids”. World Intellectual Property Organization, WO2015055198 A1 2015-04-23.
18. [18] T. Y. Xu, H. J. Nie, J. M. Li and Z. F. Shi, “Highly selective sensing of Fe3+/Hg2+ and proton conduction using two fluorescent Zn(II) coordination polymers”. Dalton Trans., vol. 49, no. 32, pp. 11129-11141, 2020, doi: 10.1039/D0DT02327B.
19. [19] T. Y. Xu, H. Wang, J. M. Li, Y. L. Zhao, Y. H. Han and X. L. Wang, et al. “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”. Inorg. Chim. Acta, vol. 493, 72-80, 2019, doi: 10.1016/j.ica.2019.05.002.
20. [20] T. Koksharova, Y. Slyvka, O. Savchenko, T. Mandzii and S. Smola, “5-Sulfosalicylato Cu(II), Zn(II) and Ni(II) coordination compounds with benzohydrazide: Synthesis, structure and luminescent properties”. J. Mol. Struct., vol. 1271, 133980, 2023, doi: 10.1016/j.molstruc.2022.133980.
21. [21] Y. Yang, P. Du, J. F. Ma, W. Q. Kan, B. Liu and Yang, J. “Series of metal-organic frameworks based on different salicylic derivatives and 1,1'-(1,4-butanediyl)bis(imidazole) ligand: syntheses, structures, and luminescent properties”. Cryst. Grow. Des., vol. 11, no. 12, pp. 5540-5553, 2011, doi: 10.1134/S0022476615050297.
22. [22] I. I. Zotkin, N. V. Kuznetsova and L. Kabanova, “Zinc or copper(2+) salts used as biocides in polymer materials”. Russian Federation, RU2497857 C1 2013-11-10.
23. [23] Z. X. Du, J. X. Li and L. Y. Wang, “Syntheses, crystal structures and fluorescent properties of two 4,4'-dipyridylsulfide based zinc(II) and cadmium(II) helical complexes”. J. Coord. Chem., 62, no. 15, pp. 2411-2420, 2009, doi: 10.1080/00958970902838776.
24. [24] Q. Han, X. C. Wang, X. Y. Li, G. X. Yao and Y. S. Yan, “Aqua(2-hydroxy-5-sulfonatobenzoato-κO1)bis(2-phenyl-1H-1,3,7,8-tetraazacyclopenta [l]phenanthrene-κ2N7,N8)zinc(II)”. Acta Cryst. vol. E65, no. 11, pp. m1282-m1283, 2009, doi: 10.1107/S1600536809039154.
25. [25] S. R. Fan, L. G. Zhu and H. P. Xiao, “catena-Poly[[cis-diaqua(2,2'-bipyridine)zinc(II)]-μ-5-sulfonatosalicylato]”. Acta Cryst. vol. E61, no. 5, pp. m804-m806, 2005, doi: 10.1107/S1600536805009645.
26. [26] G. Sharma and J. P. Tandon, “Potentiometric studies on stepwise mixed ligand complex formation copper(II, pp. nickel(II) or zinc(II)-nitrilotriacetic acid-hydroxy acid”. J. Inorg. Nucl. Chem. vol. 32, no. 4, pp. 1273-1278, 1970, doi: 10.1016/0022-1902(70)80125-7.
27. [27] Z. F. Chen, S. M. Shi, R. X. Hu, M. Zhang, H. Liang and Z. Y. Zhou, “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 J. Chem. vol. 21, no. 8, pp. 1059-1065, 2003, doi: 10.1002/cjoc.20030210817.
28. [28] K. L. Zhang, B. Yang and S. W. Ng, “Diaquabis(1,10-phenanthroline-κ2N,N')zinc(II) 2-hydroxy-5-sulfonatobenzoate tetrahydrate”. Acta Cryst. vol. E65, no. 2, pp. m239-m240, 2009, doi: 10.1107/S1600536809003055.
29. [29] J. F. Song, Y. Chen, Z. G. Li, R. S. Zhou, X. Y. Xu, J. Q. Xu et al, “Syntheses, supramolecular structures and properties of six coordination complexes based on 5-sulfosalicylic acid and bipyridyl-like chelates”. Polyhedron, vol. 26, no. 15, pp. 4397-4410, 2007, doi: 10.1016/j.poly.2007.05.037.
30. [30] E. Tunca, M. Bülbül, H.·İlkimen, R. S. Canlıdinç and C. Yenikaya, “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”. Chem. Paper., vol. 74, pp. 2365-2374, 2020, doi: 10.1007/s11696-020-01078-5.
31. [31] K. Nakamoto, “Infrared and raman spectra of inorganic and coordination compounds”. 5th ed. NewYork: Wiley-Interscience, pp. 232 (1997).
32. [32] H. İlkimen, C. Yenikaya and A. Gülbandılar, “Antimicrobial activity of proton salts of 3-(sulfamoylphenylcarbamoyl) acrylic acid derivatives with aminopyridine derivatives. Journal of Scientific Reports-A, vol. 54, no. 2, pp. 264-272, 2023, doi: 10.59313/jsr-a.1311495.
33. [33] W. J. Geary, “The use of conductivity measurements in organic solvents for the characterisation of coordination compounds”. Coord. Chem. Rev. vol. 7, no. 1, pp. 81-122, 1971, doi: 10.1016/S0010-8545(00)80009-0.