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

Yıl 2019, Cilt: 6 Sayı: 2, 124 - 136, 27.12.2019

Füreya Elif Özbek

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

Destekleyen Kurum

TÜBİTAK

Proje Numarası

106T472

Teşekkür

Çalışma 106T472 numaralı TÜBİTAK projesi ile desteklenmiştir. Desteklerinden dolayı TÜBİTAK’a teşekkür ederim.

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

Proje Numarası

106T472

Kaynakça

• 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.
• 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).
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• Lakowicz J. R. (2010). Principles of fluorescence spectroscopy (Third edition, corrected at 4. printing.). New York, NY: Springer.
• Lever A. B. P. (1986). Inorganic electronic spectroscopy (2. ed.), 2. impression (with corr.). Amsterdam: Elsevier.
• 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.
• M. Qadir A. (2017). Copper(II) Carboxylate Containing Paddle Wheel Structure: Synthesis and Crystal Structure. Oriental Journal of Chemistry, 33(2), 968–970.
• Mahata P., Ramya, K. V., Natarajan S. (2007). Synthesis, structure and optical properties of rare-earth benzene carboxylates. Dalton Transactions, (36), 4017.
• 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.
• 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.
• 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.
• Nakamoto K. (1986). Infrared and Raman spectra of inorganic and coordination compounds (4. ed.). New York: Wiley.
• 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.
• 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.
• 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.
• 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
• 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.
• 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.
• 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.
• 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.
• Silverstein R.M., Webster F.X., Kiemle D.J., Bryce, D.L. (Eds.). (2015). Spectrometric identification of organic compounds (8. ed.). Hoboken, NJ: Wiley.
• 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.
• Sorenson J. R. J. (1976). Copper chelates as possible active forms of the antiarthritic agents. Journal of Medicinal Chemistry, 19(1), 135–148.
• 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.
• 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.
• 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.
• 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.
• 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.