Synthesis, vibrational spectra and X-ray structures of copper(I) thiourea complexes

Bombicz, Petra and Mutikainen, I. and Krunks, M. and Leskela, T. and Madarász, János (2004) Synthesis, vibrational spectra and X-ray structures of copper(I) thiourea complexes. INORGANICA CHIMICA ACTA, 357 (2). pp. 513-525. ISSN 0020-1693

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Complex formation of thiourea with copper takes place as an intermediate step in the preparation of copper sulfide thin films by spray pyrolysis starting from aqueous solutions of copper(II) chloride and thiourea. The stoichiometry of the complex and that of the resulting thin film primarily depends on the molecular ratio of the starting materials. For comparison, the structures of all copper(I) thiourea complexes found in the Cambridge Structural Database are classified in this paper. In addition, syntheses, structural (single crystal XRD also at low temperature 193 K) and spectroscopic studies (FTIR and Raman) of six copper-thiourea complexes are now reported. The copper to thiourea stoichiometric ratio is 1:3 in four of these complexes, but their structures are basically different as dimerization or polymer formation takes place depending on whether the water of crystallisation is present or absent. The structure of bis(mu-thiourea)tetrakis(thiourea)dicopper(I) dichloride dihydrate, [Cu-2(tu)(6)]Cl-2 . 2H(2)O (1) was determined at room and also at low temperature. Bis(mu-thiourea)tetrakis(thiourea)dicopper(I) dibromide dihydrate, [Cu-2(tu)(6)]Br-2 . 2H(2)O (2) is isomorphous with 1, like the anhydrous compounds chlorotris(thiourea)copper(I), [Cu(tu)(3)]Cl (3) and bromotris(thiourea)copper(I), [Cu(tu)(3)]Br (4) are isomorphous. In the third isomorphous pair of complexes the copper to thiourea stoichiometric ratio is 1:1, viz. chloro(thiourea)copper(I) hemihydrate, [Cu(tu)]Cl . 0.5H(2)O (5) and bromo(thiourea)copper(I) hemihydrate, [Cu(tu)]Br . 0.5H(2)O (6). During the preparation of chloro(thiourea)copper(I) hemihydrate (5) a reaction by product alpha,alpha'-dithiobisformamidinium dichloride, [SC(NH2)(2)](2)Cl-2 (7) was identified and structurally characterized which made it possible to suggest a reaction path leading to complex formation. (C) 2003 Elsevier B.V. All rights reserved.

Item Type: Article
Additional Information: ISI:000188715300022
Uncontrolled Keywords: Copper–thiourea complexes; Role of water of crystallisation; Vibrational spectra; Synthesis; Crystal structure; Isomorphous crystals
Subjects: Q Science / természettudomány > QD Chemistry / kémia > QD01 Analytical chemistry / analitikai kémia
Depositing User: MTMT SWORD
Date Deposited: 23 Jun 2014 13:51
Last Modified: 24 Jun 2014 11:51

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