Physico-chemical Characterization of Some Metal Complexes Formed by Substituted Thiourea

G. Swarnabala *

Swaram Biochem, Hyderabad, India.

S. B. Khatavkar

Research Laboratory, Chemistry Department, G. N. Khalsa College, Mumbai– 400019, India.

G. S. Sadana

Research Laboratory, Chemistry Department, G. N. Khalsa College, Mumbai– 400019, India.

Anahita Bharadwaj

Department of Agricultural & Biological Engineering, Penn State College, Pennsylvania, USA.

*Author to whom correspondence should be addressed.


Abstract

In view of unique physico-chemical observations affecting the geometry and various properties of the substituted thiourea complexes in literature along with several biological activities, N-(hydroxy)-N,N-diphenyl thiourea was taken up for study.  Complexes with geometries of high spin octahedral for iron(II), cobalt(II); tetrahedral & square planar for nickel(II); and dimeric square planar for copper chloride, copper perchlorate, copper acetate and distorted octahedral for copper nitrate were synthesized and characterized based on magnetic moments, visible spectra, diffuse reflectance spectra, electron spin resonance, infrared spectral studies, and thermal analysis.

Interestingly, the nature of anion influenced the geometry, the complex from copper nitrate salt resulted in a distorted octahedral structure and complexes formed from copper chloride, copper perchlorate, copper acetate exhibited sub-normal magnetic moments, highly insoluble in the most common organic solvents and water. Based on these and spectral data, polymeric or square-planar dimeric geometry with sulfur bridging between copper atoms is proposed.  It was confirmed by the application of Bleaney-Bower’s equation for magnetic susceptibility, applicable to dimeric copper complexes.

The overall thermal behavior of the ligand and complexes were observed and the detailed calculations interestingly lead to confirmation of the above proposed geometrical structures.

Keywords: Bleaney-bowers equation, polymeric complexes, thermal analysis, freeman and carroll equation, vosburgh and cooper method, job’s continuous variation method


How to Cite

Swarnabala, G., Khatavkar, S. B., Sadana, G. S., & Bharadwaj, A. (2022). Physico-chemical Characterization of Some Metal Complexes Formed by Substituted Thiourea. Asian Journal of Chemical Sciences, 12(2), 50–89. https://doi.org/10.9734/ajocs/2022/v12i2218

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References

Shadab Mohd, Aslam M. Synthesis and Characterization of Some Transition Metal complexes with N-phenyl-N’-[substituted phenyl] Thiourea. Mat Sci Res India. 2014;11(1):83-9.

Available:https://doi.org/10.13005/msri/110111

K.MW. Chem Sci J. 2020;11.

Available:https://doi.org/10.37421/csj.2020.11.208

Chayah M, Camacho ME, Carrión MD, Gallo MA, Romero M, Duarte J. N , N ′-Disubstituted thiourea and urea derivatives: design, synthesis, docking studies and biological evaluation against nitric oxide synthase. MedChemComm. 2016;7(4):667-78.

Available:https://doi.org/10.1039/c5md00477b

Ozturk II, Yarar S, Banti CN, Kourkoumelis N, Chrysouli MP, Manoli M et al.. QSAR studies on antimony(III) halide complexes with N-substituted thiourea derivatives. Polyhedron. 2017;123:152-61.

Available:https://doi.org/10.1016/j.poly.2016.11.008

Journal I, Hassan AM, Elbialy ZI, Wahdan KM. Organic & medicinal chem IJ9; 2020.

Available:https://doi.org/10.19080/OMCIJ.2020.09.555767

Ajibade PA, Zulu NH Zulu. Metal complexes of diisopropylthiourea: synthesis, characterization and antibacterial studies. Int J Mol Sci. 2011;12(10):7186-98.

Available: https://doi.org/10.3390/ijms12107186

Rakhshani S, Rezvani AR, Dušek M, Eigner V. Design and fabrication of novel thiourea coordination compounds as potent inhibitors of bacterial growth. J Antibiot (Tokyo). 2019;72(5):260-70. doi: 10.1038/s41429-019-0147-2, PMID 30755737.

Mansour AM, Shehab OR. Spectroscopic and TDDFT studies of N-phenyl-N′-(3-triazolyl)thiourea) compounds with transition metal ions. Arab J Chem. 2021;14(2).

Available: https://doi.org/10.1038/s41429-019-0147-2

Mathur N, Jain N, Sharma AK. Synthesis, Characterization and Biological Analysis of Some Novel Complexes of Phenyl Thiourea Derivatives with Copper. CHEM. 2019;5(1):182-95.

Available:https://doi.org/10.2174/1874842201805010182

Al-Riyahee AAA, Horton PN, Coles SJ, Berry C, Horrocks PD, Pope SJA et al., BASRA JOURNAL OF SCIENCE39 (2021) 96–118. N,N’-Substituted thioureas and their metal complexes: syntheses, structures and electronic properties. Dalton Trans. 2022;51(9):3531-45.

Available:https://doi.org/10.29072/basjs.202117

Swarnabala G [MSc thesis] submitted to The University of Bombay; December 6, 1982, Structural Investigation of Metal Complexes, of N(hydroxyl)-N,N-diphenyl Thiourea, and references therein.

Mishra A, Sharma P, Soni N, Awate R. Synthesis and characterization of metal complexes of 3-( N -phenyl)-thiourea-pentanone-2. J Coord Chem. 2008;61(22):3687-92.

Available:https://doi.org/10.1080/00958970802123477

Dwarakanath K, Sathyanarayana DN, Current Science Association. 1978;47:706-8.

Available:https://www.jstor.org/stable/24082155.

Rathakrishnan S, Jameel A, Syed A, Padusha M. Int J Sci Res Publi. 2014;4:1-8.

Available: http://www.ijsrp.org/e-journal.html

Holt SL, Carlin RL, Chem M. LaB12. [doctoral thesis] submitted to Brown University, June 1965. p. 3017-24 and references therein; 1964.

Available: https://datapdf.com/some-transition-metal-complexes-of-substituted-thioureas-11-.html

Arora OP, Sankhla DS, Mishra SN. Proc Indian Natl Sci Acad. 1980;46A(4):378-80.

Askalani P, Bailey RA. Can J Chem. 1969;47:2275-82.

Available: chrome-extension://efaidnbmnnnibpcajpcglclefindmkaj.

Morgan GT, Burstall FH. XXI.—researches on residual affinity and co-ordination. Part XXX. Complex ethylenethiocarbamido-salts of univalent and bivalent metals. J Chem Soc. 1928;143:143-55.

Available:https://doi.org/10.1039/JR9280000143

Larkworthy LF, Nelson-Richardson MHO. Complexes of chromium(II) halides with thiourea and substituted thioureas. Inorganica Chimica Acta. 1980;40:217-21.

Available: https://doi.org/10.1016/S0020-1693(00)92008-5

Swarnabala G, Khatavkarand SB, Sadana GS, All India Science Congress, Tirupati. Structural investigations of metal complexes of N-(hydroxy)-N,N-diphenyl thiourea; January 1983.

Swarnabala G, Khatavkarand SB, Sadana GS. Thermal studies of some transition metal complexes of N-(hydroxy)-N,N-diphenyl thiourea, Annual Convention of Chemists held at Cuttack; December 26-30; 1983.

Guoy LG, ComptesRendus. 1889;935.

Available:https://www.biodiversitylibrary.org/item/23727#page/1043/mode/1up

Figgis BB. Modern coordination chemistry Lewis J, Wilkins RG, editors. New York: Interscience; 1960.

Dains FB, Brewster RQ, Olander CP. Organic synthesis. 1926;1:6 72.

Available:http://www.orgsyn.org/demo.aspx?prep=CV1P0447.

Jeffery GH, Bonnett J, Mendham J, Denney RC. A Text book of Quantitative Inorganic analysis. Vol. 497(479), 309. New York: Wiley and sons, 1975;3:529-628.

Hasan M, Mathur SP, Mehta VP, Bhandari CS. Indian J Technol. 1978;16:123.

Soni PL. Text book of Organic Chemistry, Sultanchand and sons, New Deihi. 1980;1:35-42.

Yoe JH, Jones AL. Ind. Eng. Chem. 1944;111-115:Anal16.

Available: https://doi.org/10.1021/i560126a015

Vosburgh WC, Cooper GR. Complex Ions. I. The Identification of Complex Ions in Solution by Spectrophotometric Measurements. J Am Chem Soc. 1941;63(2):437-42.

Available:https://doi.org/10.1021/ja01847a025

Job P. Ann Chim. 1928;9:113-203[CAS]. Google Scholar.

Gupta SL, Soni RN, Jaitly JN. [CAS]. J Indian Chem Soc. 1966;43:331. Google Scholar.

Bleaney B, Bowers KD. Proc R Soc Lond A. 1952;214:451,

Available: chrome-extension://efaidnbmnnnibpcajpcglclefindmkaj.

Dwarakanath K, Satyanarayana DN. Indi. J Chem. 1979;24:302.

Khatavkar SB, Haldar BC. Structural investigations of nickel(II) complexes of isonitrosoacetylacetone. J Inorg Nucl Chem. 1974;36(10):2239-45.

Available: https://doi.org/10.1016/0022-1902(74)80261-7

Suzuki I. Infrared Spectra and Normal Vibrations of Thioamides. III. N -Methylthioformamide and N -Methylthioacetamide. Boll Chem Soc. 1962;35(9):1456-64. Available: https://doi.org/10.1246/bcsj.35.1456

Rao CNR, Chaturvedi GC. Normal vibrations of N-methylthioacetamide. Spectrochim Acta A Mol Spectrosc A. 1971;27(3):520-2.

Available:http://old.jncasr.ac.in/cnrrao/1971.html

Geetharani K, Satyanarayana DN. Indian J Chem A. 1976;14(03):170-3.

Available: http://nopr.niscpr.res.in/handle/123456789/53638

Maki G. Ligand Field Theory of Ni(II) Complexes. III. Electronic Spectra and Solution Paramagnetism of Some Diamagnetic Ni(II) Complexes. J Chem Phys. 1958;29(5):1129-38.

Available: chrome-extension://efaidnbmnnnibpcajpcglclefindmkaj/ https://etd.ohiolink.edu/apexprod/rws_etd/send_file/send?accession=osu1486562013353342&disposition=inline

Manch W, Fernelius WC. J Chem Educ. 1963;40:260. Manch W, Fernelius WC. The structure and spectra of nickel(II) and copper(II) complexes. J Chem Educ. 1961;38(4):192.

Available: chrome-extension://efaidnbmnnnibpcajpcglclefindmkaj. doi: 10.1021/ed038p192.

Mecke RMR, Luthingham R. Chem Ber. 1957;90:975-86.

Available:https://doi.org/10.1002/cber.19570901117

Gosavi RK, Agarwala U, Rao CNR. Infrared Spectra and Configuration of Alkylthiourea Derivatives. Normal Vibrations of N,N′-Dimethyl- and Tetramethylthiourea. J Am Chem Soc. 1967;89(2):235-9.

Available:https://doi.org/10.1021/ja00978a009

Gosavi RK, Rao CNR. Infrared absorption spectra of metal complexes of alkylthioureas and some related ligands. J Inorg Nucl Chem. 1967;29(8):1937-45.

Available: https://doi.org/10.1016/0022-1902(67)80453-6

Tucker I, Singh RP, Zacharias PS. [CAS]. Indian J Chem. 1979;18A:60. Google Scholar.

Cotton FA, Wilkinson G. Wiley eastern Ltd. Adv Inorg Chem. 1980.

Klemn W, Schuth W, Anorg Z, Allgem. [Crossref]. Chem. 1931;203:104. Google Scholar.

Muto Y. Metal Complexes with Terdentate Ligands. II. Synthesis and Properties of Tri-coordinated Copper(II) Complexes. Bull Chem Soc Jpn. 1960;33(9):1242-7.

Available:https://doi.org/10.1039/JR961000312.

Walls AF. Structural Inorganic chemistry. 1962;463:591, 873.

Nickless G. Amsterdam, London: Inorganic Sulfur Chemistry, Elsevier Publishing company; 1968.

Chhatwal. Anand, Instrumental methods of Analysis. 1st ed. Himalayan Publishing House; 1979.

Freeman ES, Carroll B. The Application of Thermoanalytical Techniques to Reaction Kinetics: The Thermogravi- metric Evaluation of the Kinetics of the Decomposition of Calcium Oxalate Monohydrate. J Phys Chem. 1958;62(4):394-7.

Available:http://dx.doi.org/10.1021/j150562a003

Reiche L, Stivala SS. Elements of polymer degradation. Gracan Hill Limited; 1979.