The sulfonate derivate of chrysin coordinates with Ca2+ to form a novel tetra-nuclear calcium complex [(Ca(C15H8O7S)(H2O)(DMSO)3(Ca(C15H8O7S)(DMSO)2]·4DMSO. The structure of the complex is characterized by IR,1H NMR and X-ray single-crystal diffraction analysis. The results show that the complex crystallizes in triclinic, space group PĪ, cell parametera = 1.4725(6) nm,b = 1.6480(7) nm,c = 2.1006(8) nm, α = 83.928(7)°, β= 85.938(7)°, γ= 85.212(7)°,V = 5.041(3) nm3,Dc = 1.476 g/cm3,Z = 2, μ=0.568 nm−1,F(000) = 2324,R = 0.0778,wR = 0.1821. In the complex, four Ca2+ which are bridged by four 5-hydroxyanion-7-dihydro-xyfla-vone-6-sulfonate ligands with their carbonyl and 5-hydroxyanion group build an approximate square. The coordination number of Ca2+ is 7 and the coordinated atoms are all oxygen from the carbonyl, hydroxyl and suflo-group of 5-hydroxyanion-7-hydroxyflavone-6-sulfonate, H2O and DMSO. Four ligands locate on two sides of the square. Two of them on the same side are almost paralleled and aromatic п-п stacking exists between them. Ligands on the opposite side are nearly perpendicular to each other. Meanwhile, the solid of title compound has the photoluminescent phenomenon. The title compound emits green fluorescence (λem = 520 nm) when it is excited at the wavelength of 410 nm and its photoluminescent mechanism is discussed.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Ji, L. N., Huang, J. W., Mo, T. H., Bioinorganic Chemistry, An Introduction (2nd ed.) (in Chinese), Guangzhou: Zhongshan University Press, 2001, 167–170.
Nath, B. B., Chattopadhyay, S., Sarkar, S., Lanthanides as blood anticoaglants: mode of action, Indian J. Biochem. Biophys., 1982, 19(1): 32–40.
Lu, Y., Deng, G. C., Miao, F. M. et al., Sugar complexation with calcium ion. Crystal structure and FT-IR study of a hydrated calcium chloride complex of D-ribose, J. Inorg. Biochem., 2003, 96(4): 487–492.
Cao, W. K., He, S. Y., Zhao, J. S. et al., Synthesis, thermal decomposition and crystal structure of two-dimensional network binuclear complex [Ca2(C10H8N2O4)2(DMSO)2 (H2O)4] ·2DMSO, Acta Chimica Sinica (in Chinese), 2003, 61(10): 1612–1617.
Pusz, J., Nikta, B., Synthesis and physicochemical properties of the complexes of Co(II), Ni(II) and Cu(II) with chrysin, Microchem. J., 1997, 56(3): 373–381.
Pusz, J., Nikta, B., Synthesis and physicochemical properties of the complexes of Al(III), Ga(III) and In(III) with chrysin, Microchem. J., 2000, 65(3): 245–253.
Pusz, J., Nikta, B., Kapacz, S. et al., Synthesis and physico-chemical study of solid complexes of Ti(IV), Zr(IV) and Zn(II) with chrysin, Russian Journal of General Chemistry, 2003, 73(4): 634–637.
Pusz, J., Nitka, B., Wolowiec, S., The titanium(IV), iron(III) and manganese(II) complexes of chrysin-4-sulfonate, Polish J. Chem., 2001, 75(5): 795–801.
You, X. Z., Meng, Q. J., Han, W. S., Progress in Coordination Chemistry (in Chinese), Beijing: Higher Education Press, 2000, 170–190.
Hitchcock, P. B., Lappert, M. F., Lawless, G. et al., The synthesis and structure of the alkaline earth metal organic compounds M(THF)in3(OR)2(M=Ca, n = 0,3; M=Ba, n = 4) and [Ca(THF)[μ-N (SiMe3)2]]2 and the X-ray structure of bis[2,6-di-tert-butyl-4-methyl-phenoxy] tristetrahydrofuran calcium, J. Chem. Soc., Chem. Commun., 1990(17): 1141–1142.
Richard, P. J., Bruce, M. R. M., Patrick, S. B. et al., Formation of a metal-hydride bond and the insertion of carbon dioxide. Key steps in the electrocatalytic reduction of carbon dioxide to formate anion, Inorg. Chem., 1991, 30(1): 86–91.
Wojtczak, W. A., Fleig, P. F., Hampden-Smith, M. J., A review of group 2( II A)(Ca, Sr, Ba) metal-organic compounds as precursors for chemical vapor deposition, Adv. Organomet. Chem., 1996(40): 215–340.
Karipides, A., Miller, C., Crystal structure of calcium 2-fluoro-benzoate dihydrate: indirect calcium-fluorine binding through a water-bridged outer-sphere intermolecular hydrogen bond, J. Am. Chem. Soc., 1984, 106(5): 1494–1495.
Yuan, R. X., Xiong, R. G., Chen, Z. F. et al. Preparation, characterization and X-ray crystal structure of a one-dimensional calcium-based coordination polymer with strong blue fluorescent emission, Inorg. Chem. Commun., 2001, 4(10): 430–433.
Kazuo, N., Infrared and Roman Spectra of Inorganic and Coordination Compounds (Translated by Huang, D. R., Wang, R. Q.), Beijing: Chemical Industry Press, 1986, 360–365.
Ning, Y. C., Structural Identification of Organic Compounds and Organic Spectroscopy, Beijing: Science Press, 2000, 497–498.
Waller, M. P., Hibbs, D. E., Overgaard, J. et al., Flavone, Acta Cryst., 2003, E59: o767-o768.
Janiak, C., A critical account on pi-pi stacking in metal complexes with aromatic nitrogen-containing ligands, J. Chem. Soc., Dalton Trans., 2000, 3885–3886.
Chen, G. Z., Huang, X. Z., Zhen, Z. Z. et al., The Analytical Method of Fluorescence (2nd ed.) (in Chinese), Beijing: Science Press, 1990, 37–40.
About this article
Cite this article
Zhang, Z., Guo, Y. & Liu, Q. Synthesis, crystal structure and photoluminescence of a novel tetra-nuclear calcium complex [(Ca(C15H8O7S)-(H2O)(DMSO))3(Ca(C15H8O7S) (DMSO)2]·4DMSO. Sc. China Ser. B-Chem. 47, 396–406 (2004). https://doi.org/10.1007/BF02990900
- tetra-nuclear calcium complex
- crystal structure