Synthesis and Spectroscopic and Thermal Properties of N,N'-Diethylnicotinamide Complexes of Cu(II) p-Fluoro-, p-Chloro- and p-Bromobenzoates

Öz

In this study, three new mixed ligand metal complexes containing N,N'-diethylnicotinamide ligand of copper (II) p-fluoro-, p-chloro- and p-bromobenzoates were synthesized and their structures were investigated. Elemental analysis, FT-IR and UV-Vis spectroscopy, thermal analysis (TGA-DTA) methods were used to evaluate the structures of the complexes. The general formulas of the complexes were determined as [Cu(p-F-C₆H₄COO)₂(C₁₀H₁₄N₂O)₂(H₂O)] (I), [Cu(p-Cl-C₆H₄COO)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (II) ve [Cu(p-Br-C₆H₄COO)₂(H₂O)₂] (III). In all complexes, p-halogenobenzoates and N,N'-diethylnicotinamide behave as monodentate ligand. In the complexes, each metal ion possesses an octahedral geometry with two oxygen atoms of two p-halogenobenzoate anions, two nitrogen atoms from two N,N'-diethylnicotinamide ligands and two oxygen atoms of two water molecules. Copper: p-halogenobenzoate: N, N'-diethylnicotinamide ratios were determined to be 1: 2: 2. The thermal stability of the complexes is III≥II> I. The thermal decomposition product of the complexes was determined as copper (II) oxide.

Anahtar Kelimeler

• Cu Complexes
• p-Fluorobenzoic Acid
• p-Chlorobenzoic Acid
• p-Bromobenzoic Acid
• NN-diethylnicotinamide

Cu(II) p-Floro-, p-Kloro- ve p-Bromobenzoatların N,N'-Dietilnikotinamid Komplekslerinin Sentezi, Spektroskopik ve Termik Özellikleri

Öz

Bu çalışmada bakır(II) p-floro-, p-kloro- ve p-bromobenzoatların N,N'-dietilnikotinamid ligandı içeren üç yeni karışık ligandlı metal kompleksi sentezlendi ve yapıları incelendi. Komplekslerin yapılarının tartışılmasında elemental analiz, FT-IR ve UV-Vis spektroskopisi, termik analiz (TGA-DTA), yöntemlerinden faydalanıldı. Komplekslerin kapalı formülleri [Cu(p-F-C₆H₄COO)₂(C₁₀H₁₄N₂O)₂(H₂O)] (I), [Cu(p-Cl-C₆H₄COO)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (II) ve [Cu(p-Br-C₆H₄COO)₂(H₂O)₂] (III) olarak belirlendi. Yapıda p-halojenobenzoatlar ve N,N'-dietilnikotinamid monodentat olarak koordine olmuştur. Komplekslerin yapısında, metal atomu çevresinde iki p-halojenobenzoat anyonundan gelen iki oksijen atomu, iki N,N'-dietilnikotinamid ligandından gelen iki azot atomu ve iki su molekülünden gelen iki oksijen atomu ile oktahedral geometri meydana gelmiştir. Bakır: p-halojenobenzoat:N,N'-dietilnikotinamid oranlarının 1:2:2 olduğu belirlenmiştir. Komplekslerin termal kararlılık sıralaması ise III≥II>I şeklindedir. Komplekslerin termal bozunma ürünleri ise bakır (II) oksittir.

Anahtar Kelimeler

• Bakır kompleksleri
• p-Florobenzoik Asit
• p-Klorobenzoik Asit
• p-Bromobenzoik Asit
• NN-dietilnikotinamid

Kaynakça

1. Abuhijleh A.L., Khalaf J. (2010). Copper (II) complexes of the anti-inflammatory drug naproxen and 3-pyridylmethanol as auxiliary ligand. Characterization, superoxide dismutase and catecholase – mimetic activities. European Journal of Medicinal Chemistry, 45(9), 3811–3817.
2. Agwara M.O., Ndifon P.T., Ndosiri N. B., Paboudam A. G., Yufanyi D.M., Mohamadou A. (2010). Synthesis, characterisation and antimicrobial activities of cobalt(II), copper(II) and zinc(II) mixed-ligand complexes containing 1,10-phenanthroline and 2,2’-bipyridine. Bulletin of the Chemical Society of Ethiopia, 24(3).
3. Amombo Noa F.M., Jacobs A. (2017). Phenylacetic acid co-crystals with acridine, caffeine, isonicotinamide and nicotinamide: Crystal structures, thermal analysis, FTIR spectroscopy and Hirshfeld surface analysis. Journal of Molecular Structure, 1139, 60–66.
4. Batool S.S., Gilani S.R., Tahir M.N., Rüffer T. (2017). Synthesis, and structural characterization of mixed ligand copper(II) complexes of N,N,N′,N’-tetramethylethylenediamine incorporating carboxylates. Journal of Molecular Structure, 1148, 7–14.
5. Bozkurt N., Tunç T., Çaylak Delibaş N., Necefoğlu H., Hökelek T. (2013). Aquabis(3-chlorobenzoato-κ O )bis( N , N -diethylnicotinamide-κ N )copper(II). Acta Crystallographica Section E Structure Reports Online, 69(8), m458–m459.
6. Bushma M. I., Zavodnik L.B., Lukienko P.I. (1989). [Effect of the diethylamide of nicotinic acid (cordiamine) on the hydroxylating function of the liver]. Farmakologiia I Toksikologiia, 52(4), 56–59.
7. Findoráková L., Győryová K., Melník M., Koman M., Nour El-Dien F.A. (2010). Preparation, thermal decomposition, and crystal structure of Zn(II) 2-chlorobenzoate complex with nicotinamide. Journal of Coordination Chemistry, 63(19), 3348–3355.
8. Fountoulaki S., Perdih F., Turel I., Kessissoglou D. P., Psomas G. (2011). Non-steroidal anti-inflammatory drug diflunisal interacting with Cu(II). Structure and biological features. Journal of Inorganic Biochemistry, 105(12), 1645–1655.

9. Halaška J., Pevec A., Strauch P., Kozlevčar B., Koman M., Moncol J. (2013). Supramolecular hydrogen-bonding networks constructed from copper(II) chlorobenzoates with nicotinamide: Structure and EPR. Polyhedron, 61, 20–26.
10. Kuchtanin V., Moncol J., Mroziński J., Kalińska B., Padělková Z., Švorec J., Seglá P., Melník M. (2013). Study of copper(II) thiophenecarboxylate complexes with N-methylnicotinamide. Polyhedron, 50(1), 546–555.
11. Lakowicz J. R. (2010). Principles of fluorescence spectroscopy (Third edition, corrected at 4. printing.). New York, NY: Springer.
12. Lever A. B. P. (1986). Inorganic electronic spectroscopy (2. ed.), 2. impression (with corr.). Amsterdam: Elsevier.
13. Lewandowski W., Kalinowska M., Lewandowska H. (2005). The influence of halogens on the electronic system of biologically important ligands: spectroscopic study of halogenobenzoic acids, halogenobenzoates and 5-halogenouracils. Inorganica Chimica Acta, 358(7), 2155–2166.
14. M. Qadir A. (2017). Copper(II) Carboxylate Containing Paddle Wheel Structure: Synthesis and Crystal Structure. Oriental Journal of Chemistry, 33(2), 968–970.
15. Mahata P., Ramya, K. V., Natarajan S. (2007). Synthesis, structure and optical properties of rare-earth benzene carboxylates. Dalton Transactions, (36), 4017.
16. Mandal A., Patel B.K. (2017). Molecular structures and fluorescence property of Zn(II), Cd(II) complexes of 3-pyridyl-5-aryl-(1 H )-1,2,4-triazoles. Polyhedron, 132, 112–122.
17. Ming C.L., Hao Z.C., Yu B.Y., Van Hecke K., Cui G.H. (2015). Synthesis, Structures, and Catalytic Properties of Three New Metal–Organic Coordination Polymers Constructed from Flexible Benzimidazole-Based and cis-1,2-Cyclohexanedicarboxylate Synthons. Journal of Inorganic and Organometallic Polymers and Materials, 25(3), 559–568.
18. Mitra A., Clark R. J., Hubley C. T., Saha S. (2014). Anion–π and CH···anion interactions in naphthalenediimide-based coordination complexes. Supramolecular Chemistry, 26(3–4), 296–301.
19. Nakamoto K. (1986). Infrared and Raman spectra of inorganic and coordination compounds (4. ed.). New York: Wiley.
20. Özbek F. E., Sertçelik M., Yüksek M., Küçüköz B., Elmali A., Şahin E. (2019). Two new potential optical materials: Co(II) and Ni(II) 3-fluorobenzoate complexes with pyridine-3-carboxamide. Journal of Coordination Chemistry, 72(5–7), 786–795.
21. Özbek F. E., Sertçelik M., Yüksek M., Necefoğlu H., Çelik R. Ç., Nayir G. Y., Hökelek T. (2017). Cu(II) and Ni(II) 4-cyanobenzoate complexes with nicotinamide: Synthesis, spectral, structural and optical characterization and thermal behavior. Journal of Molecular Structure, 1150, 112–117.
22. Pavia D. L., Lampman G. M., Kriz G. S. (2001). Introduction to spectroscopy: a guide for students of organic chemistry (3. ed.). South Melbourne: Brooks/Cole.
23. Perec M., Baggio R. F., Peña O., Sartoris R. P., Calvo R. (2011). Synthesis and structures of four new compounds of the copper(II)–carboxylate–pyridinecarboxamide system. Inorganica Chimica Acta, 373(1), 117–123. https://doi.org/10.1016/j.ica.2011.03.065
24. Puchoňová M., Repická Z., Moncol J., Růžičková Z., Mazúr M., Valigura D. (2015). Supramolecular structure formation of molecular copper(II)methylsalicylate complexes with nicotinamide or methylnicotinamide – Crystal structure and spectral properties. Journal of Molecular Structure, 1092, 1–8.
25. Sertçelik M., Çaylak Delibaş N., Necefoğlu H., Hökelek T. (2012). Diaquabis(4-formylbenzoato-κO1)bis(nicotinamide-κN1)copper(II). Acta Crystallographica Section E Structure Reports Online, 68(7), m1010–m1011.
26. Sertçelik M., Çaylak Delibaş N., Necefoğlu H., Hökelek T. (2013). Bis( -4-formylbenzoato- 2O:O')bis[(4-formylbenzoato- 2O,O')bis(isonicotinamide- N1)copper(II)]. Acta Crystallographica Section E Structure Reports Online, 69, m290–m291.
27. Sertçelik M., Özbek F.E., Sugeçti S., Necefoğlu H. (2018). Synthesis of Izonicotınamide Complexes Of 4-Formilbenzoate with Co (II), Cu (II) And Zn (II); Investigation of Spectroscopic, Thermal Properties and Antibacterial Activıties. Journal of the Institute of Science and Technology, 189–195.
28. Silverstein R.M., Webster F.X., Kiemle D.J., Bryce, D.L. (Eds.). (2015). Spectrometric identification of organic compounds (8. ed.). Hoboken, NJ: Wiley.
29. Solomons, T.W.G., Fryhle C.B., Snyder S.A. (2016). Solomons´ organic chemistry ([12th edition], global edition.). Hoboken, New Jersey: John Wiley & Sons, Inc.
30. Sorenson J. R. J. (1976). Copper chelates as possible active forms of the antiarthritic agents. Journal of Medicinal Chemistry, 19(1), 135–148.
31. Stachová P., Melník M., Korabik M., Mrozinski J., Koman M., Glowiak T., Valigura D. (2007). Synthesis, spectral and magnetical characterization of monomeric [Cu(2-NO2bz)2(nia)2(H2O)2] and structural analysis of similar [Cu(RCOO)2(L–N)2(H2O)2] complexes. Inorganica Chimica Acta, 360(5), 1517–1522.
32. Tarushi A., Perontsis S., Hatzidimitriou A. G., Papadopoulos A. N., Kessissoglou D. P., Psomas G. (2015). Copper(II) complexes with the non-steroidal anti-inflammatory drug tolfenamic acid: Structure and biological features. Journal of Inorganic Biochemistry, 149, 68–79.
33. Wang D.W., Wang T., Du L., Zhou J., Yan T., Zhao, Q.H. (2018). Four supramolecular transition metal(II) complexes based on triazole-benzoic acid derivatives: crystal structure, Hirshfeld surface analysis, and spectroscopic and thermal properties. Structural Chemistry.
34. Xia C.K., Wu F., Yang K., Sun W., Min Y.Y., Wu Y.L., Lu, X.J. (2016). Zn(II) and Cd(II) complexes assembled from versatile 1,2,3,5-benzenetetracarboxylic acid and chelating N-donor auxiliary coligands. Polyhedron, 117, 637–643.
35. Zhang Q., Yue C., Zhang Y., Lü Y., Hao Y., Miao Y., Li J., Liu Z. (2018). Six metal-organic frameworks assembled from asymmetric triazole carboxylate ligands: Synthesis, crystal structures, photoluminescence properties and antibacterial activities. Inorganica Chimica Acta, 473, 112–120.