Marina Tašner, Draginja Mrvoš-Sermek, Emina Hajdarpašić, Dubravka Matković-Čalogović


A new dinuclear paddle-wheel copper(II) complex with caffeine was synthesized by the solvent-based and mechanochemical methods from copper(II) acetate and caffeine in a 1:1 molar ratio. Mechanochemical synthesis was found to be the fastest and easiest way to prepare the complex. The reaction proceeds with addition of small amounts of methanol or ethanol. The complex was characterized by FT-IR spectroscopy, elemental and thermoanalytical methods (TG and DSC) and X-ray diffraction methods. The molecular and crystal structure was determined by the single crystal X-ray diffraction method. The complex molecule consists of a centrosymmetric dinuclear unit, Cu2(-Ac)4(caf)2, with two copper(II) atoms bridged by four acetato groups, and N-coordinated caffeine (caf) molecules in the apical posi-tions.


copper(II); paddle-wheel structure; caffeine; crystal structure; mechanochemical synthesis

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M. Melnik, O. Sprusansky, P. Musil, Bio-medical aspects of purine alkaloids, Adv. Biol. Chem., 4 (2014), pp. 274–280.

S. V. Paston, A. M. Polyanichko, O. V. Shulenina, Study of DNA interactions with Cu2+ and Mg2+ ions in the presence of caffeine, J. Struct. Chem., 58 (2017), pp. 399–405.

M. B. Cingi, A. Ch. Villa, A. G. Manfredotti, C. Guastini, Crystal structure of triaquanitratocaf-feinecopper(II) nitrite monohydrate, Cryst. Struct. Commun., 1 (1972), pp. 363–365.

G. Bandoli, M. B. Cingi, D. A. Rizzardi, Preparation, crystal and molecular structure of aqua-dichlorocaffeinecopper(II), Inorg. Chim. Acta, 20 (1976), pp.71–76.

T. Kawata, H. Uekusa, S. Ohba, T. Furukawa, T. Tokii, Y. Muto, M. Kato, Magneto-structural corre-lation in dimeric copper(II) benzoates, Acta Cryst., B48 (1992), pp. 253–261.

M. Koman, M. Melnik, J. Moncol, T. Glowiak, Caffeine in copper(II) complexes: crystal and mo-lecular structure of di(caffeine)tetrakis(na-proxenato)dicopper(II), Inorg. Chem. Commun., 3 (2000), pp. 489–492.

F. Valach, M. Tokarčik, M. Melnik, Distortion isomerism and plasticity of the coordination sphere of binuclear Cu(II) complexes: Crystal structure of the monoclinic isomer of [Cu2(2-bromopropio-nato)4(caffeine)2], Journal of Coord. Chem. 62 (2009), pp. 225–233.

Z. Ma, B. Moulton, Supramolecular medicinal chemistry: mixed-ligand coordination complexes, Mol. Pharmaceutics, 4 (2007), pp. 373–385.

F. Valach, M. Melnik, G. Bernardinelli, K. K. Fromm, A structural study of copper(II) carbox-ylates: crystal structure and physical characteriza-tion of [Cu2(2-bromo-propionato)4(caffeine)2], J. Chem. Crystallogr., 36 (2006), pp. 571–579.

F. Valach, M. Tokarčik, T. Maris, D. J. Watkin, C. K. Prout, Bond-valence approach to the copper-copper and copper-nitrogen bonding in binuclear copper(II) complexes: Structure of tetrakis(2-iodobenzoato)bis(caffeine)dicopper(II) at 210 K, J. Organomet. Chem., 622 (2001), pp. 166–171.

B. Koreň, F. Valach, P. Sivý, M. Melnik, Structures of binuclear copper(II) chloroacetate complexes: tetrakis(μ-monochloroacetato-O,O)-bis3,7-dihyd-ro-1,3,7-trimethyl-1H-purine-2,6-dione)cop¬per(II), [Cu2(C2H2ClO2)4(C8H10N4O2)2], Acta Cryst., C41 (1985), pp. 1160–1162.

A. Harada, M. Tsuchimoto, S. Ohba, K. Iwasawa, T. Tokii, Structures and magnetic properties of di-meric copper(II) benzoylformates, Acta Cryst., B53 (1997), pp. 654–661.

H. Horie, S. Husebye, M. Kato, E. A. Meyers, Y. Muto, I. Suzuki, T. Tokii, R. A. Zingaro, The mag-netic properties of three copper(II) trichloroacetate; Adducts with caffeine and the crystal structure of dicaffeinetetrakis(μ-trichloroacetato)dicopper(II)di¬benzene solvate, [Cu(CCl3COO)2(C8H10N4O2)2]2 • 2C6H6, Acta. Chem. Scand. A, 40 (1986), pp. 579–589.

H. Uekusa, S. Ohba, T. Tokii, Y. Muto, M. Kato, S. Husebye, O.W. Steward, S.-C. Chang, J. P. Rose, F. Pletcher, I. Suzuki, Magneto-structural correlations of dimeric copper(II) trichloroacetates, Acta Cryst., B48 (1992), pp. 650–667.

M. Melnik, M. Koman, T Glowiak, Structure, spec-tral and magnetic behaviours of tetrakis(flufena-mato)(caffeine)(aqua)dicopper(II). The firs exam-ple of two nonequivalent ligands at the apex, Poly-hedron, 17 (1998), pp.1767–1771.

P. Stachová, J. Moncol, D. Valigura, T. Lis, Unusual O-coordination of caffeine in tetrakis(μ-3,5-dinitrobenzoato-2O:O)bis(caffeine-O)copper(II)], Acta Cryst., C62 (2006), pp. m375–m377.

C. R. Groom, I. J. Bruno, M. P. Lightfoot and S. C. Ward, Acta Cryst., B72 (2016), pp. 171–179.

T. Friščić, I. Halasz, V.Štrukil, M. Eckert-Maksić, R. E. Dinnebier, Clean and efficient synthesis using mechanochemistry: coordination polymers, metal-organic frameworks and metallodrugs, Croat. Chem. Acta, 85(3) (2012), pp. 367–378.

F. C. Strobridge, N. Judaš, T. Friščić, A stepwise mechanism and the role of water in the liquid-assisted grinding synthesis of metal–organic mate-rials, CrystEngComm 12 (2010), pp. 2409−2418.

A. Pichon, S. L. James, An array-based study of reactivity under solvent-free mechanochemical conditions — insights and trends, CrystEngComm, 10 (2008) pp. 1839–1847.

W. Yuan, A. L. Garay, A. Pichon, R. Clowes, C. D. Wood, A. I. Cooper, S. L. James, Study of mecha-nochemical formation and resulting properties of an archetypal MOF: Cu3(BTC)2 (BTC = 1,3,5-benzen¬etricarboxylate), CrystEngComm, 12 (2010) pp. 4063–4065.

J. Pejić, D. Vušak, G. Szalontai, B. Prugovečki, D. Mrvoš-Sermek, D. Matković-Čalogović, J. Sabo-lović, Disorder at the chiral Cα center and room-temperature solid-state cis–trans isomerization; synthesis and structural characterization of cop-per(II) complexes with D-allo, L-isoleucine, Cryst. Growth Des., 18 (2018), pp. 5138–5154.

D. Vušak, B. Prugovečki, D. Milić, M. Marković, I. Petković, M. Kralj, D. Matković-Čalogović, Syn-thesis and crystal structure of solvated complexes of copper(II) with serine and phenanthroline and their solid-state-to-solid-state transformation into one stable solvate. Cryst. Growth Des. 17 (2017), pp. 6049–6061.

STARe Software V.9.01., MettlerToledo GmbH, (2006).

CrysAlisPro Software System, Version; Rigaku Oxford Diffraction (2017).

L. J. Farrugia, J. Appl. Crystallogr., 45 (2012), pp. 849-854.

G. M. Sheldrick, A short history of SHELX, Acta Cryst., A64 (2008), pp. 112-122.

G. M. Sheldrick, Crystal structure refinement with SHELXL, Acta Cryst., C71 (2015), pp. 148-155.

A. Spek, Structure validation in chemical crystal-lography, Acta Cryst., D65 (2009), pp. 148−155.

C. F. Macrae, I. J. Bruno, J. A. Chisholm, P. R. Edg-ington, P. McCabe, E. Pidcock, L. Rodriguez-Monge, R. Taylor, J. van de Streek, P. A. Wood, Mercury CSD 2.0 – new features for the visualiza-tion and investigation of crystal structures, J. Appl. Crystallogr., 41 (2008), pp. 466−470.

L. J. Farrugia, ORTEP-3 for Windows – a version of ORTEP-III with a Graphical User Interface (GUI), J. Appl. Crystallogr., 30 (1997) pp. 565−566.

POV-Ray, version 3.6; Persistence of Vision Pty. Ltd., Persistence of Vision Raytracer, (2004), avail-able at http://www.povray.org/.

T. Degen, M. Sadki, E. Bron, U. König, G. Nénert, Powder Diffraction, Supplement S2, 29 (2014), pp. S13-S18.

A. C. Tella, J. A. Obaleye, U. B. Eke, A. Y. Isaac, O. M. Ameen, Solvent-free synthesis, X-ray studies and in vitro inhibitory activities of copper(II) com-plexes of non-steroidal anti-inflammatory drugs, Res. Chem. Intermed, 40 (2014), pp. 1441–1457.

H. EL Hamdani, M. EL. Amane, Y. Kennouche, M. Bouhdada, A. Ahmami, M. Hadad, Synthesis and characterization of the mixed ligand complexes [M(Ac)2(caf)2 M=Ni(II), Co(II), Zn(II), [Cu2(μ-Ac)4(caf)2], Ac=CH3COO–, caf=caffeine, J. Mar. Chim. Heterocycl., 15 (2016), pp. 41–49.

M. Melnik, Binuclear caffeine adducts of Cu(II) acetate and Cu(II) chloroacetates with unusually high antiferromagnetic interaction, Inorg. Nucl. Chem., 43 (1981), pp. 3035–3038.

S. J. Jenniefer, P. T. Muthiah, Synthesis, character-ization and X-ray structural studies of four cop-per(II) complexes containing dinuclear paddle wheel structures, Chem. Cent. J., 7 (2013), pp. 1–15.

K. Nakamoto, Infrared Spectra of Inorganic and Coordination Compounds, J. Wiley & Sons., Inc. New York, 2009.

F. Ucun, A. Sağlam, V. Güçlü, Molecular structures and vibrational frequencies of xanthine and me-thyl derivatives (caffeine and theobromine) by abinitio Hartree-Fock and density functional theo-ry calculations, Spectrochim. Acta Part A, 67 (2007), pp. 342–349.

DOI: http://dx.doi.org/10.20903/csnmbs.masa.2018.39.2.122


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