A six-membered Cu3S3 ring in decakis(thiourea)tetracopper(I) hexafluorosilicate monohydrate: X-ray crystallographic structure determination

Crystal Structures and Vibrational Spectroscopy of Copper(I) Thiourea Complexes

“…There are corresponding bands in the Raman spectrum at 202, 234 cm −1 . This compound consists of six-membered rings of alternating Cu and S atoms connected by sulfur bridges to form chains, which are in turn interconnected via a Cu 2 S 2 four-membered ring to form a three-dimensional polymer with d (CuS) in the range 2.27−2.43 Å (av 2.34 Å) . According to a previously established relationship between d (CuS) and ν(CuS), this corresponds to a ν(CuS) range of 160−239 cm −1 (av 201 cm −1 ).…”

“…This compound consists of sixmembered rings of alternating Cu and S atoms connected by sulfur bridges to form chains, which are in turn interconnected via a Cu 2 S 2 four-membered ring to form a threedimensional polymer with d(CuS) in the range 2.27-2.43 Å (av 2.34 Å). 55 According to a previously established relationship between d(CuS) and ν(CuS), 50 this corresponds to a ν(CuS) range of 160-239 cm -1 (av 201 cm -1 ). While the average d(CuS) in both of the above compounds are very similar, the range is considerably wider in [Cu 4 (tu) 10 ](SiF 6 ) 2 , leading to a greater spread of vibrational frequencies and to a splitting of the ν(CuS) band.…”

“…A considerable number of complexes of simple copper(I) salts, formed with thiourea and its derivatives, relevant in many biological and pharmaceutical areas, , and involving a wide variety of compositions and structures, have been reported in the past; − in these, thiourea behaves as a “soft” ligand, capable of unidentate or diverse bridging modes in its complexes with copper(I) salts, associated “hard” anions usually being excluded from the coordination sphere while “soft” anions such as the heavier halide ions (i.e., not F) may be competitive. In the context of crystallization from diverse solvents, the strong hydrogen-bonding characteristics, capable of modification by substitution, may be relevant.…”

Hydrogen‐Bonded Network and Layered Supramolecular Structures Assembled from ClO4− Counterions with Unprecedented Monomeric [AgL2]+ and Chain Polymeric [AgL2]nn+ Complex Cations (L = Thioamide or Thiourea‐Like Ligands)

“…[61] These bridging ligand molecular orbitals (HOMOs), each accommodating one electron pair, are able to interact with two vacant tetrahedral sp 3 or other hybrid orbitals, one for each silver atom of the AgϪSϪAg bridge. Considerations of this kind, aimed at proposing an MϪS bonding model from an analysis of the stereochemistry, have previously been performed for dinuclear [1,32] and some polymeric [22,23,27,55,56] sulfur-bridged complexes of thioamide or thiourea ligands. All these earlier examples, however, contain both bridging and terminal ligands, which is not the case here.…”

Four Different Crystalline Products from One Reaction: Unexpected Diversity of Products of the CuCl2 Reaction with N-(2-Pyridyl)thiourea

“…1 The reaction of thiourea and its derivatives with copper(II) salts in solution results in a reduction of Cu(II) ions into Cu(I) and the formation of many different stabile polynuclear products. [2][3][4][5][6][7][8][9][10][11][12] The chemistry of thioureas in copper-ion containing solutions is complex due to a variable and frequently uncertain nature of the redox processes involved. A number of copper(I) and even copper(II) complexes have been obtained with different molecular structures.…”