Spectroscopy and structures of two complete families, one mononuclear, the other binuclear, of 1 : 2 CuX : dptu stoichiometry (X = Cl, Br, I; ‘dptu’ = N,N′-diphenylthiourea)

Abstract

Crystallization of the copper(i) halides (CuX; X = Cl, Br, I) with N,N'-diphenylthiourea ('dptu' = (PhNH)(2)CS) in 1 : 2 ratio from acetonitrile solution in ambient conditions yields a mononuclear isomorphous series of complexes of the form [XCu(dptu)(2)].H(2)O, an unusually complete array, with the central copper atoms in quasi-trigonal planar environments, as shown by single crystal X-ray studies, in turn providing a platform for comparative spectroscopic studies. Under anhydrous conditions, anhydrous compounds may be obtained, a full series again being accessible, but now of the binuclear form [(dptu)XCu(mu-S-dptu)(2)CuX(dptu)], the chloride being a bis(acetonitrile) solvate, the isomorphous bromide and iodide pair being unsolvated. A (solvated) sulfate salt is found to be of the form [Cu(dptu)(2)](2)(SO(4)), providing a novel example of a copper(i) atom being (quasi-)linearly coordinated by the pair of unidentate (dptu) sulfur ligands, Cu-S 2.1770(5), 2.1811(5) A, S-Cu-S 162.18(2) degrees . The nu(CuX) vibrational frequencies are assigned in the far-IR spectra of [XCu(dptu)(2)].H(2)O (X = Cl, Br, I) at 274, 207, and 190 cm(-1) respectively. The broadline static (65)Cu NMR spectra of [Cl(2)Cu(2)(dptu)(4)].2CH(3)CN and [X(2)Cu(2)(dptu)(4)] (X = Br, I) have been recorded at 9.4 and 7.05 T, and the spectra have been analysed to yield the (65)Cu nuclear quadrupole coupling and chemical shift parameters. The (63,65)Cu nuclear quadrupole resonance frequencies of [XCu(dptu)(2)].H(2)O (X = Cl, Br, I) have also been measured, and the resulting (65)Cu quadrupole coupling constants are ca. 4x those of the dimeric [X(2)Cu(2)(dptu)(4)] compounds.

Synthesis and Characterization of Copper(I) Halide Complexes with N‐(2, 6‐Diisopropylphenyl)‐N′‐benzoylthiourea: Monomeric, Dimeric, and Cage Structures

“…The Cu···Cu separation of 2Ј [2.6235(6) Å] is slightly longer than that of 3 but still shorter than those of other analogues. [13,29,30] No evident intermowww.zaac.wiley-vch.de lecular hydrogen bonding interaction is detected in 2Ј. The molecules are connected by intermolecular π-π stacking interactions between two neighboring 2,6-dimethylphenyl rings, face-to-face, in a direction parallel to each other, resulting in one type of 1D strand along the c axis ( Figure S11).…”

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

“…The crystal structures of several copper(I) complexes with thiourea and its derivatives demonstrate that copper(I) forms complexes with a wide variety of stoichiometries and structures having copper to sulfur ratios ranging from 1:4 as in monomeric [Cu(tu) 4 (SiF 6 ) 0.5 ] [25] up to 1:1.5 as in tetrameric [Cu 4 (tu) 6 (NO 3 ) 4 ]Á4H 2 O [32]. In some cases, extensive hydrogen bonding in the structure leads to 2-or 3-D networks [4,13,14]. Some reports are also available on the antimicrobial activities of copper(I)-thione complexes [11,12].…”

Synthesis, characterization and crystal structure of platinum(II) complexes with thiourea derivative ligands

“…For example N-(alkyl/aryl)-N'-acylthiourea and N-di(alkyl/aryl)-N'-acylthiourea derivatives which have oxygen, nitrogen and sulphur donor atoms, exhibit prevalent coordination modes. Organic ligands that have thiourea moiety are able to bind metal ions in several ways, like: (i) acting as monodentate ligands through sulphur atom in mononuclear complexes [1-4] (ii) binding to metal ions forming S-bridges in dinuclear complexes [4][5][6][7][8] or (iii) chelating sulphur and nitrogen atoms [4][5][6][8][9][10][11][12][13][14][15][16] Thiourea derivatives as a ligand have a large dipole moment and these ligands can also form extensive network of hydrogen bonds due to their unique structures. For example in 3-monosubstituted arylthioureas [17][18][19], the carbonyl group and the proton on the nitrogen attach in a strong hydrogen bond interaction which unite into a planar six-membered ring structure forming an "S" shaped conformation of the C=O and C=S groups [20,21].…”