The Crystal Structure of Tetrakis(N-methylthiourea)copper(I) chloride with an Elaborate Network of Hydrogen Bonding

Abstract

The complexation of thiones toward copper(I) has received considerable attention in view of their variable bonding modes, structural diversity and promising biological implications. 1 In view of this, the solid-state structures of several copper(I) complexes with thiourea and its derivatives have been reported. 2 In these complexes, a high variety of stoichiometries and different structure types are observed with copper-to-sulfur ratios ranging from 1:4, as in monomeric [Cu(tu)4(SiF6)0.5], 3 up to 1:1.5, as in tetrameric [Cu4(tu)6(NO3)4]•4H2O (tu = thiourea). 4 The present report describes the synthesis and an x-ray structure analysis of tetrakis(N-methylthiourea)copper(I) chloride, which shows a three-dimensional supramolecular structure due to extensive hydrogen bonding in the solid state. The white crystalline compound 1, cf. Fig. 1, was prepared by treating copper(I) chloride (1.0 mmol) dissolved in 15 of mL acetonitrile (by adding 3 drops of conc. HCl) with one or two equivalents of N-methylthiourea (2.0 mmol) in acetonitrile. The white precipitates formed were dissolved in methanol, and the resulting colorless solution when allowed to stand for 24 h yielded crystals suitable for X-ray structure analysis.

Synthesis and characterization of palladium(II) complexes of thioureas. X-ray structures of [Pd(N,N′-dimethylthiourea)4]Cl2 · 2H2O and [Pd(tetramethylthiourea)4]Cl2

“…3. Such an involvement of Cl -counter ion in hydrogen bonding with the coordinated ligands was also observed in [Cu(Metu) 4 ]Cl [2]. It is proposed that the disordered water molecules connect between Cl(1) and Cl (2) with OHÁÁÁCl and between Cl(1) and Cl(1) with OHÁÁÁCl and OHÁÁÁO bonds.…”

“…It may be caused by NHÁÁÁCl hydrogen bonds just above palladium atom from N2, N4, N6, and N8 to Cl(1) ( Table 6). The other N atoms hydrogen-bond to the other independent Cl atoms, Cl (2). This regular pattern of hydrogen bonds makes the complex a two-dimensional sheet, a top view of a part of which is illustrated in Fig.…”

“…The interaction of thioureas with metal ions has been the subject of several recent investigations because of their variable binding modes and because of the relevance of their binding sites to those in living systems [1][2][3][4][5][6][7][8][9][10]. The complexes of palladium(II) and platinum(II) in this regard are particularly important because some of them are known to exhibit antibacterial and antitumor activity [7][8][9][10][11].…”

“…Consequently, in this study we have prepared a number of palladium(II) complexes with thiourea and its derivatives and characterized them by IR and NMR spectroscopic methods. We also present the crystal structures of two of these compounds, [Pd(Dmtu) 4 ]Cl 2 Á 2H 2 O (1) and [Pd(Tmtu) 4 ]Cl 2 (2). The structures of ligands used in this study are shown in Scheme 1.…”

Synthesis, characterization, and antibacterial activities of copper(I) bromide complexes of thioureas: X-ray structure of [Cu(Metu)4]Br

“…The interaction of thiourea and substituted thioureas with metal ions has been the subject of several recent investigations because of their variable binding modes and because of the relevance of their binding sites to those in living systems [1][2][3][4][5][6][7][8][9][10][11][12]. A large number of spectral and structural studies on copper(I) complexes containing thioamides reveal that these ligands are coordinated via the sulfur atom either in a triplanar or in tetrahedral environment .…”