Synthesis, Characterization and Crystal Structure of Caffeine Complex of Mn(II) p-Hydroxybenzoate

Document Type: Research Article


1 Kafkas University, Department of Chemical Engineering, Faculty of Engineering and Architecture, 36300 Kars, TURKEY

2 Kafkas University, Department of Chemistry, Faculty of Sciences and Arts, 36300 Kars, TURKEY

3 Department of Physics, Hacettepe University, 06800 Beytepe, Ankara, TURKEY

4 Scientific and Technological Application and Research Center, Aksaray University, 68100 Aksaray, TURKEY


A new manganese(II) complex containing p-hydroxybenzoate and caffeine ligands, namely [Mn(OH-C6H4COO)2(H2O)4].2(C8H10N4O2).8H2O has been prepared. The synthesized complex has been characterized by elemental analyses, FT-IR spectroscopy, X-ray crystallography, and molar conductance measurements. The thermal properties of the complex were analyzed by TGA/DTA. The complex crystallizes in the monoclinic space group P21/c having cell dimensions a=11.1311(2), b=14.3579(3), c=13.5383(3) Å, β=101.879(2)º, V=2117.34(8) Å3, Z=2. In the mononuclear complex, Mn atom is coordinated by two p-hydroxybenzoate anions and four water molecules. Moreover, the asymmetric unit of the complex also contains four uncoordinated water molecules and one caffeine ligand. Crystal structure of the complex has 3D supramolecular networks formed via O-HOH···Ocaf, O-Hw···Ow, O-Hw···Ncaf, O-Hw···Ocaf, and O-Hw···Ocar hydrogen bonds.


Main Subjects

[1] Salem N.M.H., Rashad A.R., El Sayed L., Foro S., Haase W., Iskander M.F., Synthesis, Characterization, Molecular Structure and Supramolecular Architectures of Some Copper(II) Complexes Derived from Salicylaldehyde Semicarbazone, Inorganica Chim. Acta, 432: 231–242 (2015).


[2] Chakrabarty R., Mukherjee P.S., Stang P.J., Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles, Chem. Rev., 111: 6810–6918 (2011).


[3] Gale P.A., Supramolecular Chemistry Anniversary, Chem. Soc. Rev., 36: 141 (2007).


[4] Xin-Jian, W., Yi-Ping, C., Ze-Min, X., Su-Zhi, G., Feng, C., Ling-Yan, Z., Jian-Zhong, C., Synthesis, crystal structures and intermolecular interactions of two Mn(II) complexes with 4,4′-bipy and methyl Benzoates, J. Mol. Struct., 1035:318–325 (2013).


[5] Baran E.J., Yilmaz V.T., Metal Complexes of Saccharin, Coord. Chem. Rev., 250:1980–1999 (2006).



[7] Dorkov P., Pantcheva I.N., Sheldrick W.S., Mayer-Figge H., Petrova R., Mitewa M., Synthesis, Structure and Antimicrobial Activity of Manganese(II) and Cobalt(II) Complexes of the Polyether Ionophore Antibiotic Sodium Monensin A., J. Inorg. Biochem., 102:26–32 (2008).


[8] Mandal S., Rout A.K., Ghosh A., Pilet G., Bandyopadhyay D., Synthesis, Structure and Antibacterial Activity of Manganese(III) Complexes of a Schiff Base Derived from Furfurylamine, Polyhedron., 28:3858–3862 (2009).



[10] Qiu-Yun C., Dong-Fang Z., Juan H., Wen-Jie G., Jing G., Synthesis, Anticancer Activities, Interaction with DNA and Mitochondria of Manganese Complexes, J. Inorg. Biochem., 104:1141–1147 (2010).


[11] Singh D.P., Kumar K., Sharma C., New 14-Membered Octaazamacrocyclic Complexes: Synthesis, Spectral, Antibacterial and Antifungal Studies, Eur. J. Med. Chem., 45:1230–1236 (2010).


[12] Hua Q., Su Z., Zhao Y., Okamura T., Xu G.-C., Sun W.-Y., Ueyama N., Synthesis, Structure and Property of Manganese(II) Complexes with Mixed Tetradentate Imidazole-Containing Ligand and Benzenedicarboxylate, Inorganica Chim. Acta., 363:3550–3557 (2010).


[13] Lindsay Smith J.R., Gilbert B.C., Mairata i Payeras A., Murray J., Lowdon T.R., Oakes J., Pons i Prats R., Walton P.H., Manganese 1,4,7-trimethyl-1,4,7-Triazacyclononane Complexes: Versatile Catalysts for the Oxidation of Organic Compounds with Hydrogen Peroxide, J. Mol. Catal. Chem., 251:114–122 (2006).


[14] Rajabi M., Gholivand K., Salami R., Molaei F., Thibonnet J., Zare K., Tirani F.F., Schenk K.J., Synthesis, Structural Determination, Theoretical Studies and Catalytic Activity of Mn(II) Complex of N-isonicotinyl Phosphoric Triamide Ligand, Inorganica Chim. Acta.., 432:149–157 (2015).


[15] Shnulin A.N., Nadzhafov G.N., Mamedov K.S., Crystal Structures of Manganese(II) p-Hydroxybenzoate Octahydrate and Trihydrate, J. Struct. Chem., 25:421–429 (1984).


[16] Su J.-R., Zhang L., Xu D.-J., Aqua(4-hydroxybenzoato-κO)bis(1,10-phenanthroline-κ2N,N ′)manganese(II) 4-hydroxybenzoate monohydrate, Acta Crystallogr. Sect. E Struct. Rep. Online, 61:m939–m941 (2005).


[17] Hu Z.-Q., Wu L.-B., Lai G.-Q., Bis(2,2′-bipyridine-κ2N,N′)bis(4-hydroxybenzoato-κO) manganese(II), Acta Crystallogr. Sect. E Struct. Rep. Online, 62:m712–m713 (2006).


[18] Liu F.-C., Xue M., Wang H.-C., Ou-Yang J., New Divalent Manganese Complex with Pyridine Carboxylate N-oxide Ligand: Synthesis, Structure and Magnetic Properties, J. Solid State Chem., 183:1949–1954 (2010).


[19] Che, S.-C., Hu M., Zhang Z.-H., Sun F.-A., Wang L., Zhou W.-Y., He M.-Y., Chen Q., Syntheses, Structures, and Properties of Zinc(II), Cadmium(II), Cobalt(II), and Manganese(II) Coordination Polymers with Tetraiodoterephthalate, Transit. Met. Chem., 37:619–627 (2012).


[20] Esteves D., Tedesco J.C.D., Pedro S.S., Cruz C., Reis M.S., Brandão, P., New Manganese (II) Structures Derived from 2,6-dichlorobenzoic Acid: Syntheses, Crystal Structures and Magnetism, Mater. Chem. Phys., 147:611–616 (2014).


[21]Čechová D., Martišková A., Padělková Z., Gal’a L., Dlháň L., Valigura D., Valko M., Boča R., Moncol J., Manganese(II) One-dimensional Coordination Polymers with Nitrobenzoato or Nitrosalicylato bridges: Syntheses, Crystal Structures, and Magnetic Properties, Polyhedron., 79:129–137 (2014).


[22] Zhao Q.-H., Zhao L., Wang K.-M., Zhou H., catena -Poly[[[bis(μ-4-hydroxybenzoato)bis[(4-hydroxybenzoato)manganese(II)]]-di-μ-4,4′-bipyridine] 4,4′-bipyridine disolvate tetrahydrate], Acta Crystallogr. Sect. E Struct. Rep. Online., 66:m358–m358 (2010).


[23] Taşdemir E., Özbek F.E., Sertçelik M., Hökelek T., Çelik R.Ç., Necefoğlu H., Supramolecular Complexes of Co(II), Ni(II) and Zn(II) p-Hydroxybenzoates with Caffeine: Synthesis, Spectral Characterization and Crystal Structure, J. Mol. Struct., 1119:472–478 (2016).


[24] Sheldrick G.M., A Short History of SHELX, Acta Crystallogr. A., 64:112–122 (2008).


[25] Farrugia L.J., WinGX and ORTEP for Windows:  An Update, J. Appl. Crystallogr., 45:849–854 (2012)



[27] Icbudak H., Heren Z., Kose D.A., Necefoglu H., Bis(nicotinamide) and bis(N,N-diethyl nicotinamide) p-hydroxybenzoate Complexes of Ni(II), Cu(II) and Zn(II), J. Therm. Anal. Calorim., 76: 837–851 (2004).


[28] Homzová K., Győryová K., Bujdošová Z., Hudecová D., Ganajová M., Vargová Z., Kovářová J., Synthesis, Thermal, Spectral and Biological Properties of Zinc(II) 4-hydroxybenzoate Complexes, J. Therm. Anal. Calorim., 116: 77–91 (2014).


[29] Zhang H.-J., Gou R.-H., Yan L., Yang R.-D., Synthesis, Characterization and Luminescence Property of N,N′-di(pyridine N-oxide-2-yl)pyridine-2,6-dicarboxamide and Corresponding lanthanide (III) Complexes, Spectrochim. Acta. A. Mol. Biomol. Spectrosc., 66: 289–294 (2007).


[30] Bellamy L.J., The Infrared Spectra of Complex Molecules, second ed., Halsted Press, a division of John Wiley & Sons, Inc., Methuen, London (1958).

[31] Nikolaev V.A., Logvinenko L.T., Myachina, Thermal Analysis. Vol. 2, Academic Press, New York (1969)