Synthesis and crystal structure of copper(II) complexes with pyridoxal S-methylisothiosemicarbazone bearing a new coordination mode

Marko V. Rodić, Mirjana M. Radanović, Ljiljana S. Vojinović-Ješić, Svetlana K. Belošević, Željko K. Jaćimović, Vukadin M. Leovac


The reaction of copper(II) nitrate and pyridoxal S-methylisothiosemicarbazone (PLITSC) in the presence of ammonium thiocyanate resulted in the formation of two types of complexes. Dimeric complex of the formula [{Cu(m-PLITSC)NCS}2](NCS)2×2MeOH was obtained in the presence of excess of ammonium thiocyanate, while in the presence of its nearly equimolar amount crystals of polymeric complex {[Cu(m-PLITSC)NCS]NO3∙MeOH}n were formed. Complexes are characterized by elemental analysis, conductometry, IR spectroscopy, and their structures are unequivocally determined by single crystal X-ray crystallography. In both complexes, the copper atom is five-coordinated, situated in a deformed square-pyramidal environment. The basal plane of the square pyramid is defined by oxygen atom of the deprotonated phenol group and terminal nitrogen atoms of the isothiosemicarbazide moiety of the Schiff base, as well as the nitrogen atom of the coordinated thiocyanate ion, while the apical site is occupied by the oxygen atom of the hydroxymethyl group of the neighboring asymmetric unit. This coordination mode of the PLITSC was hitherto unknown. Survey of the Cambridge Structural Database showed that the coordination of the hydroxymethyl group is rare within pyridoxal-based Schiff base metal complexes.


dimeric and polymeric Cu(II) complexes; Schiff bases; tetradentate coordination mode; X-ray crystallography

Full Text:

PDF (1,102 kB)



S. Padhyé, G. B. Kauffman, Coord. Chem. Rev. 63 (1985) 127 (

J. S. Casas, M. S. Garcı́a-Tasende, J. Sordo, Coord. Chem. Rev. 209 (2000) 197 (

T. S. Lobana, R. Sharma, G. Bawa, S. Khanna, Coord. Chem. Rev. 253 (2009) 977 (

H. Beraldo, D. Gambino, Mini-Reviews Med. Chem. 4 (2004) 31 (

C. B. Scarim, D. H. Jornada, M. G. M. Machado, C. M. R. Ferreira, J. L. dos Santos, M. C. Chung, Eur. J. Med. Chem. 162 (2019) 378 (

B. Atasever, B. Ülküseven, T. Bal-Demirci, S. Erdem-Kuruca, Z. Solakoğlu, Invest. New Drugs 28 (2010) 421 (

D. X. West, S. B. Padhye, P. B. Sonawane, Structural and physical correlations in the biological properties of transition metal heterocyclic thiosemicarbazone and S-alkyldithiocarbazate complexes, in Complex Chem. Struct. Bond. Vol 76., Springer, Berlin, Heidelberg, 1991, pp. 1–50 (

C. Santini, M. Pellei, V. Gandin, M. Porchia, F. Tisato, C. Marzano, Chem. Rev. 114 (2014) 815 (

V. M. Leovac, V. S. Jevtović, L. S. Jovanović, G. A. Bogdanović, J. Serb. Chem. Soc. 70 (2005) 393 (

M. Revenco, P. Bulmaga, E. Jora, O. Palamarciuc, V. Kravtsov, P. Bourosh, Polyhedron 80 (2014) 250 (

V. M. Leovac, G. A. Bogdanović, V. I. Češljević, V. Divjaković, Acta Crystallogr. Sect. C Cryst. Struct. Commun. 56 (2000) 936 (

V. M. Leovac, V. I. Češljević, J. Serb. Chem. Soc. 59 (1994) 13

G. A. Bogdanović, A. Spasojević-de Biré, B. V. Prelesnik, V. M. Leovac, Acta Crystallogr. Sect. C Cryst. Struct. Commun. 54 (1998) 766 (

V. M. Leovac, R. Herak, B. Prelesnik, S. R. Niketic, J. Chem. Soc., Dalt. Trans. (1991) 2295 (

N. V. Gerbeleu, Y. A. Simonov, V. B. Arion, V. M. Leovac, K. I. Turta, K. M. Indrichan, D. I. Gradinaru, V. E. Zavodnik, T. I. Malinovskii, Inorg. Chem. 31 (1992) 3264 (

V. Arion, K. Wieghardt, T. Weyhermueller, E. Bill, V. Leovac, A. Rufinska, Inorg. Chem. 36 (1997) 661 (

U. Knof, T. Weyhermüller, T. Wolter, K. Wieghardt, J. Chem. Soc., Chem. Commun. (1993) 726 (

J. S. Casas, M. D. Couce, J. Sordo, Coord. Chem. Rev. 256 (2012) 3036 (

V. M. Leovac, L. S. Vojinović-Ješić, S. A. Ivković, M. V. Rodić, L. S. Jovanović, B. Holló, K. M. Szécsényi, J. Serb. Chem. Soc. 79 (2014) (

V. M. Leovac, V. S. Jevtović, G. A. Bogdanović, Acta Crystallogr. Sect. C Cryst. Struct. Commun. 58 (2002) m514 (

Rigaku Oxford Diffraction, CrysAlisPro Software system, Rigaku Corporation, Oxford, UK, Oxford, UK, 2018

G. M. Sheldrick, Acta Crystallogr. Sect. A Found. Adv. 71 (2015) 3 (

G. M. Sheldrick, Acta Crystallogr. Sect. C Struct. Chem. 71 (2015) 3 (

C. B. Hübschle, G. M. Sheldrick, B. Dittrich, J. Appl. Crystallogr. 44 (2011) 1281 (

A. L. Spek, Acta Crystallogr. Sect. D Biol. Crystallogr. 65 (2009) 148. (

L. J. Farrugia, J. Appl. Crystallogr. 45 (2012) 849 (

W. J. Geary, Coord. Chem. Rev. 7 (1971) 81 (

K. Nakamoto, Infrared and Raman spectra of inorganic and coordination compounds. Part B, Applications in coordination, organometallic, and bioinorganic chemistry, Wiley, 2009.

C. R. Groom, I. J. Bruno, M. P. Lightfoot, S. C. Ward, Acta Crystallogr. Sect. B Struct. Sci. Cryst. Eng. Mater. 72 (2016) 171 (

M. B. Ferrari, F. Bisceglie, G. Pelosi, P. Tarasconi, R. Albertini, P. P. Dall’Aglio, S. Pinelli, A. Bergamo, G. Sava, J. Inorg. Biochem. 98 (2004) 301 (

P. Adak, B. Ghosh, A. Bauzá, A. Frontera, A. J. Blake, M. Corbella, C. Das Mukhopadhyay, S. K. Chattopadhyay, RSC Adv. 6 (2016) 86851 (

L. S. Vojinović-Ješić, M. V. Rodić, B. Barta Holló, S. A. Ivković, V. M. Leovac, K. Mészáros Szécsényi, J. Therm. Anal. Calorim. 123 (2016) 2069 (

M. M. Lalović, L. S. Vojinović-Ješić, L. S. Jovanović, V. M. Leovac, V. I. Češljević, V. Divjaković, Inorganica Chim. Acta 388 (2012) 157 (

M. Belicchi-Ferrari, F. Bisceglie, C. Casoli, S. Durot, I. Morgenstern-Badarau, G. Pelosi, E. Pilotti, S. Pinelli, P. Tarasconi, J. Med. Chem. 48 (2005) 1671 (

S. Mandal, Y. Sikdar, R. Sanyal, S. Goswami, J. Mol. Struct. 1128 (2017) 471 (

K. Aoki, H. Yamazaki, J. Chem. Soc., Chem. Commun. (1987) 1241 (

S. A. Ivković, L. S. Vojinović-Ješić, V. M. Leovac, M. V. Rodić, S. B. Novaković, G. A. Bogdanović, Struct. Chem. 26 (2015) 269 (

R. R. Holmes, Five-Coordinated Structures, in S. J. Lippard (Ed.), Prog. Inorg. Chem. Vol. 32, John Wiley & Sons, Ltd, New York, 1984, pp. 119–235 (

V. Chaurin, E. C. Constable, C. E. Housecroft, New J. Chem. 30 (2006) 1740 (

D. Vidovic, A. Radulovic, V. Jevtovic, Polyhedron 30 (2011) 16 (

J. C. A. Boeyens, J. Cryst. Mol. Struct. 8 (1978) 317 (

D. Cremer, J. A. Pople, J. Am. Chem. Soc. 97 (1975) 1354. (


Copyright (c) 2019 J. Serb. Chem. Soc.

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

IMPACT FACTOR 0.797 (139 of 171 journals)
5 Year Impact Factor 0.923 (134 of 171 journals)