Comparative Studies of Some Novel Cu(II) Polymeric Complexes Derived from Cyanoacetylhydrazine (CAH; L). The Role of Solvents Used on the Structure and Geometry of the Isolated Cu2+ Complexes
Novel polymeric Cu2+ complexes derived from the reaction of cyanoacetylhydrazine (CAH; L) with CuCl2?2H2O in different solvents were synthesized and characterized. The isolated solid polymeric complexes were investigated using modern conventional physicochemical and spectral (IR, 1H-NMR, UV-Vis. ESR, Raman), magnetic and thermal studies. The results revealed that CAH behaves in different ways towards the coordination of the Cu2+ ion. The promotion of solvents to the cyano group was discussed on the basis of the solvent and the Cu2+ ion used. Magnetic and spectral studies suggest octahedral geometry is proposed for the Cu2+ complexes. EPR studies indicate the existence of polymeric complexes depending on the results of g-values. The results suggest that the number of copper atoms ranges from three to twelve atoms. The molecular modeling is drawn and some chemical characteristics are calculated such as chemical reactivity and energy components are investigated between the different types of the ligands.
References
[1]
Rahman, V.P.M., Mukhtar, S., Ansari, W.H. and Lemiere, G. (2005) Synthesis, Stereochemistry and Biological Activity of Some Novel Long Alkyl Chain Substituted Thiazolidin-4-Ones and Thiazan-4-One from 10-Undecenoic Acid Hydrazide. European Journal of Medicinal Chemistry, 40, 173-184. https://doi.org/10.1016/j.ejmech.2004.10.003
[2]
Ajani, O.O., Obafemi, C.A., Nwinyi, O.C. and Akinpelu, D.A. (2010) Microwave Assisted Synthesis and Antimicrobial Activity of 2-Quinoxalinone-3-Hydrazone Derivatives. Bioorganic & Medicinal Chemistry, 18, 214-221. https://doi.org/10.1016/j.bmc.2009.10.064
[3]
Bondock, S., Tarhoni, A.E. and Fadda, A.A. (2006) Utility of Cyanoacetic Acid Hydrazide in Heterocyclic Synthesis. Arkivoc, 9, 113-156. https://doi.org/10.3998/ark.5550190.0007.905
[4]
Donald, P.R., Seifart, H.I., Parkin, D.P. and van Jaarsveld, P.P. (1994) Hydrazine Production in Children Receiving Isoniazid for the Treatment of Tuberculous Meningitis. Annals of Pharmacotherapy, 28, 1340-1343. https://doi.org/10.1177/106002809402801202
[5]
Zheng, L.W., Wu, L.W., Zhao, B.X., Dong, W.L. and Miao, Y.J. (2009) Synthesis of Novel Substituted Pyrazole-5-Carbohydrazide Hydrazone Derivatives and Discovery of a Potent Apoptosis Inducer in A549 Lung Cancer Cells. Bioorganic & Medicinal Chemistry, 17, 1957. https://doi.org/10.1016/j.bmc.2009.01.037
[6]
Elnagdi, M.H., Elmoghayar, M.R.H. and Elgemeie, G.E.H. (1984) Activated Nitriles in Heterocyclic Synthesis: A New Approach for the Synthesis of Pyridine and Pyridinopyrimidine Derivatives. Synthesis, 11, 970-972. https://doi.org/10.1055/s-1984-31042
[7]
Gaber, A.M., El-Gaby, M.S.A., El-Dean, A.M.K., Eyada, H.A. and Al-Kamali, A.S.N. (2004) Synthesis of Novel Polyfunctionally Substituted Thieno[2,3-cPyridazines]. Journal of the Chinese Chemical Society, 51, 1325-1331. https://doi.org/10.1002/jccs.200400192
[8]
Elagamey, A.G.A., El-Taweel, F.M., Khodeir, M.N.M. and Elnagdi, M.H. (1993) Nitriles in Heterocyclic Synthesis. Teh Reaction of Polyhydric Naphthalenes, 4-Methylcoumarin-3-Carbonitrile, and Akylidenemalononitrile with Methylene Malononitrile. Bulletin of the Chemical Society of Japan, 66, 464-468. https://doi.org/10.1246/bcsj.66.464
[9]
Hussein, A.H.M. (1998) Utility of Cyano Acid Hydrazide in Heterocyclic Chemistry: A New Route for the Synthesis of New 1,2,4-Triazolo[l,5-a]Pyridines and l,2,4-Triazolo[l,5-a]Isoquinolines. Verlag der Zeitschrift für Naturforschung, 53b, 488-494. https://doi.org/10.1515/znb-1998-0417
[10]
Elnagdi, M.H. and Erian, A.W. (1991) New Routes to Polyfunctionally Substituted Pyridine, Pyridopyridine, Quinoline, and Pyridazine Derivatives. Archiv der Pharmazie, 324, 853-858. https://doi.org/10.1002/ardp.2503241106
[11]
Gilman, A.G. and Goodman, L.M.S. (1985) The Pharmaceutical Basis of Therapeutics. Macmillan, New York.
[12]
Writer, S. and Shaffer, L. (2020) RNA-Based Pesticides Aim to Get around Resistance Problems. Inner Workings, 117, 32823-32826. https://doi.org/10.1073/pnas.2024033117
[13]
De Marinis, R.M., Hoover, J.R.E., Dunn, G.L., Actor, P., Uri, J.V. and Weisbach, J.A. (1975) A New Parenteral Cephalosporin. Sk & f 59962: 7-Trifluoromethyl Thioacetamido-3-(1-Methyl-1H-Tetrazol-5-Ylthylthiomethyl)-3-Cephem-4-Carboxylic Acid. Chemistry and Structure Activity Relationship. The Journal of Antibiotics, 28, 463-470. https://doi.org/10.7164/antibiotics.28.463
[14]
Fahmy, S.M., Badran, A.H. and Elnagdi, M.H.J. (1980) Synthesis of Some New Zopyrazole Dyes. Journal of Chemical Technology & Biotechnology, 30, 390-395. https://doi.org/10.1002/jctb.503300147
[15]
Fahmy, S.M., El-Hosami, M., Elgamal, S. and Elnagdi, M.H. (1982) Dimerised Ethyl Cyanoacetate in Heterocyclic Dye Synthesis. Journal of Chemical Technology & Biotechnology, 32, 1042-1048. https://doi.org/10.1002/jctb.5030320748
[16]
Premkumars, T. and Govindarajan, S. (2002) The Chemistry of Hydrazine Derivatives—Thermal Behavior and Characterisation of Hydrazinium Salts and Metal Hydrazine Complexes of 4,5-Imidazoledicarboxylic Acid. Thermochimica Acta, 386, 35-42. https://doi.org/10.1016/S0040-6031(01)00756-0
[17]
Shallaby, A.M., Soliman, M.S., El-Shazely, R.M. and Mostafa, M.M. (1988) Metal Complexes and Metal Promoted Reactions of Cyanoacetyl-Hydrazine (CAH). Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 18, 807-821. https://doi.org/10.1080/00945718808060823
[18]
El-Shazely, R.M., Shallaby, A.M. and Mostafa, M.M. (1990) Metal Complexes and Metal Promoted Reactions of Salicylaldehyde Cyanoacetyl-Hydrazone in Ethanol. Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, Part III, 20, 283-299. https://doi.org/10.1080/00945719008048135
[19]
El-Shazely, R.M., Soliman, M.S., Shallaby, A.M. and Mostafa, M.M. (1990) Synthesis of New Metal Complexes Derived From Cyanocetyl Hydrazone (SCH) and Its Derivatives with Some Transition Metal Ions in Isopropanol and Tert-Butanol(IV). Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 20, 301-318. https://doi.org/10.1080/00945719008048136
[20]
Bain, G.A. and Berry, J.F. (2008) Diamagnetic Corrections and Pascal’s Constants. Journal of Chemical Education, 85, 532-536. https://doi.org/10.1021/ed085p532
[21]
Geary, W.J. (1971) The Use of Conductivity Measurements in Organic Solvents for the Characterisation of Coordination Compounds. Coordination Chemistry Reviews, 7, 81-122. https://doi.org/10.1016/S0010-8545(00)80009-0
[22]
Mlahi, M.R., Azhari, S.J., El-Asmy, A.A. and Mostafa, M.M. (2015) Comparative Spectroscopic and DFT Calculations of Binary and Ternary Complexes Derived From 4-Allyl-1-(2-Tydroxybenzoyl) Thiosemicarbazide (L1) and 2,2’-Dipyridyl. Spectrochimica Acta, 134, 465-472. https://doi.org/10.1016/j.saa.2014.06.098
[23]
Linert, W. and Taha, A. (1994) Coordination of Solvent Molecules to Square-Planar Mixed-Ligand Nickel(II) Complexes: A Thermodynamic and Quantum-Mechanical Study. Journal of the Chemical Society, Dalton Transactions, 7, 1091-1095. https://doi.org/10.1039/dt9940001091
[24]
Ramachandran, R., Rani, R.M. and Kabilan, S. (2010) Synthesis, Structure and Conformation Alanalysis of 2,4-Diaryl-3-Azabicyclo[3.3.1]Nonan-9-One Thiosemicarbazones and Semicarbazones. Journal of Molecular Structure, 970, 42-50. https://doi.org/10.1016/j.molstruc.2010.02.005
[25]
Govindarajan, M., Periandy, S. and Carthigayen, K. (2012) FT-IR and FT-Raman Spectra, Thermodynamical Behavior, HOMO and LUMO, UV, NLO Properties, Computed Frequency Estimation Analysis and Electronic Structure Calculations on α-Bromotoluene. Spectrochimica Acta, 97, 411-422. https://doi.org/10.1016/j.saa.2012.06.028
[26]
Pearson, R.G. (1989) Absolute Electronegativity and Hardness: Applications to Organic Chemistry. The Journal of Organic Chemistry, 54, 1423-1430. https://doi.org/10.1021/jo00267a034
[27]
Padmanabhan, J., Parthasarathi, R., Subramanian, V. and Chattaraj, P. (2007) Electrophilicity-Basbed Charge Transfer Descriptor. The Journal of Physical Chemistry, 111, 1358-1361. https://doi.org/10.1021/jp0649549
[28]
Parthasarathi, R., Padmanabhan, J., Sarkar, U., Maiti, B., Subramanian, V. and Chattaraj, P.K. (2003) Toxicity Analysis of Benzidine through Chemical Reactivity and Selectivity Profiles: A DFT Approach. Internet Electronic Journal of Molecular Design, 2, 798-813.
[29]
Kivelson, D. and Neiman, R. (1961) ESR Studies on the Bonding in Copper Complexes. The Journal of Chemical Physics, 35, 149-155. https://doi.org/10.1063/1.1731880
[30]
Hathway, B.J. and Billing, D.E. (1970) The Electronic Properties and Stereochemistry of Mono-Nuclear Complexes of the Copper(II) Ion. Coordination Chemistry Reviews, 5, 143-207. https://doi.org/10.1016/S0010-8545(00)80135-6
Zink, J.I. and Drago, R.S. (1972) Interpretation of Electron Spin Resonance Parameters for Transition Metal Complexes. Journal of the American Chemical Society, 4, 4550-4554. https://doi.org/10.1021/ja00768a023
[33]
June, V.S.X., Anantharam, R. and Murugesan, R. (1999) The Temperature Dependence of EPR Spectra of Cu(II)-Doped Hexakis(imidazole)Cadmium(II) Perchlorate. Spectrochimica Acta A, 55, 135-142. https://doi.org/10.1016/S1386-1425(98)00174-7
[34]
Rao, C.N.R. (1975) Ultraviolet and Visible Spectroscopy. Plenum Press, New York.
Kato, M., Jonassen, KB and Fanning, GC, (1964) Copper(II) Complexes with Subnormal Magnetic Moments. Chemical Reviews, 64, 99-128. https://doi.org/10.1021/cr60228a003
[37]
Mlahi, M.R., Afsah, E.M., Negm, A. and Mostafa, M.M. (2015) Synthesis of 8-Hydroxyquinolium Chloroacetate and Synthesis of Complexes Derived from 8-Hydroxyquinoline and Characterization, Density Functional Theory and Biological Studies. Applied Organometallic Chemistry, 29, 200-208. https://doi.org/10.1002/aoc.3265
