Primjira P. Tadbuppa

Electronic and steric control over Au⋯Au, C–H⋯O and C–H⋯π interactions in the crystal structures of mononuclear triarylphosphinegold(I) carbonimidothioates: R3PAu[SC(OMe)=NR′] for R = Ph, o-tol, m-tol or p-tol, and R′ = Ph, o-tol, m-tol, p-tol or C6H4NO2-4

The structures of R3PAu[SC(OMe)=NR′], for R = Ph, o-tol, m-tol or p-tol, and R′ = Ph, o-tol, m-tol, p-tol or C6H4NO2-4, feature linear P-Au-S coordination geometries with intramolecular Au⋯O or Au⋯π interactions depending on the substitution patterns of the R and/or R′ groups. For R = Ph, intramolecular Au⋯O interactions are observed exclusively but when R = p-tol, intramolecular Au⋯π interactions are found unless precluded by steric crowding, i.e. in the case when R′ = m-tol, or by electronic reasons such as the presence of an electron withdrawing nitro group, i.e. when R′ = C6H4NO2-4. In the latter case, aurophilic interactions (Au⋯Au = 3.0872(4) A) are formed, uniquely amongst the series. The mode of coordination of the thiolate ligands in these complexes, arising from either steric or electronic factors or both, has a profound influence on the supramolecular aggregation patterns operating in their crystal structures. In the solvent-free systems that feature intramolecular Au⋯O interactions, columns of molecules stack so that the thiolate residues interdigitate to a greater or lesser extent leaving the aryl groups of the phosphine ligands facing each other, forming phenyl embraces in the Ph3P species or being connected by C–H⋯π contacts involving methyl-H atoms in the isomeric tolyl3P structures. In structures featuring intramolecular Au⋯π interactions, the methoxy-O atom is more accessible for the formation of C–H⋯O contacts. Finally, in the cases where the nitro substituent is present, at least one of the nitro-O atoms is involved in C–H⋯O intercations. In summary, subtle changes in electronic character and/or steric profile of the phosphine and thiolate ligands are seen to influence, systematically, the crystal packing.

Principles of crystal packing in O-isopropyl-N-aryl-thiocarbamides: iPrOC(S)N(H)C6H4-4-Y: Y = H, Cl, and Me

Crystallographic analysis shows no significant influence is exerted by the nature of Y upon the molecular parameters of the central O–C(S)–N(H) chromophore in the structures of iPrOC(S)N(H)C6H4-4-Y, for Y = H (1), Cl (2), and Me (3); this is verified by a theoretical study. The crystal structures each feature dimeric aggregates as a result of the uniform formation of the {⋯H–N–CS}2, thioamide, synthon. An analysis of the crystal structures shows that the substitution of the chloride atom in (2) by a methyl group, leading to (3), has a profound influence on the crystal packing owing to the participation of the chloride atom in structure directing C–H⋯Cl interactions that link the dimeric aggregates into a double layer structure. In the structures of (1) and (3), C–H⋯S interactions serve to connect molecules into columnar and layer structures, respectively, with weak C–H⋯O (and π⋯π interactions in (3)) further reinforcing the crystal packing.

[(Z)-O-Methyl N-(3-chloro­phen­yl)thio­carbamato-κS](triphenyl­phosphine-κP)gold(I)

The Au atom in the title compound, [Au(C8H7ClNOS)(C18H15P)], exists within a slightly distorted linear geometry defined by an S,P-donor set [S—Au—P angle = 174.61 (4)°], with the distortion related to a short intramolecular Au⋯O contact [2.988 (3) Å]. In the crystal structure, molecules are arranged into supramolecular chains along the b axis by C—H⋯π interactions.

[(Z)-O-Ethyl-N-(p-tol-yl)thio-carbamato-κS](triphenyl-phosphine)-κP]gold(I).

The title compound, [Au(C10H12NOS)(C18H15P)], features a linear S,P-donor set about the central Au atom. The thiocarbamate ligand is orientated to place the aryl ring in close proximity to Au [the closest Au⋯C distance is 3.238 (4) Å], which results in a small deviation from the ideal linear P—Au—S geometry.

[(Z)-O-Ethyl-N-propylthiocarbamato-κS](triphenylphosphine-κP)gold(I)

In the title compound, [Au(C5H10NOS)(C18H15P)], the AuI atom is linearly coordinated within an S,P-donor set with distortion from an ideal linear geometry [S—Au—P = 176.71 (6)°] due to an intramolecular Au⋯O contact [2.943 (4) Å]. In the crystal structure, centrosymmetrically related molecules associate via C—H⋯O interactions.

[(Z)-O-Methyl N-(3-chloro-phen-yl)thio-carbamato-κS](tricyclo-hexyl-phosphine-κP)gold(I).

Two independent molecules comprise the asymmetric unit of the title compound, [Au(C8H7ClNOS)(C18H33P)], which differ in the relative orientations of each of the cyclohexyl groups as well as the benzene ring. In each molecule, the Au atom is coordinated within a S,P-donor set that defines a slightly distorted linear geometry [S—Au—P = 175.10 (5) and 177.26 (5)° for the two molecules], with the distortion due in part to the close intramolecular approach of the O atom [Au⋯O contacts = 3.054 (4) and 3.013 (4) Å, respectively, for the two molecules].

[(Z)-EthylN-isopropylthiocarbamato-κS](tricyclohexylphosphine-κP)gold(I)

The AuI atom in the title compound, [Au(C6H12NOS)(C18H33P)], is coordinated within a S,P-donor set that defines a slightly distorted linear geometry [S—Au—P angle = 173.44 (5)°], with the distortion due in part to a close intramolecular Au⋯O contact [3.023 (4) Å]. The N-bound isopropyl group is disordered over two orientations in a 0.618 (15):0.382 (15) ratio.

[μ-1,1′-Bis(diphenyl­phosphino)ferrocene-κ2P:P′]bis­{[(Z)-O-isopropyl-N-(4-methyl­phen­yl)thio­carbamato-κS]gold(I)}

In the title compound, [Au2Fe(C11H14NOS)2(C17H14P)2], the FeII atom is located on a crystallographic centre of inversion. For the AuI atom, the deviation from linearity defined by its S,P-donor set [S—Au—P = 178.17 (8) Å] is due to an intramolecular Au⋯O contact [3.079 (4) Å]. In the crystal, supramolecular chains mediated by C—H⋯N interactions are formed, which run parallel to [001].

[(Z)-N-(2-Chloro­phen­yl)-O-methyl­thio­carbamato-κS](triphenyl­phosphine-κP)gold(I)

In the title compound, [Au(C8H7ClNOS)(C18H15P)], the AuI atom has a near-linear geometry, defined by an S,P-donor set [S—Au—P = 175.09 (5)°]. The proximity of the methoxy O atom to Au may be responsible for the deviation from linearity [Au⋯O = 2.959 (4) Å].

[(Z)-N-Isopropyl-O-methyl­thio­carbamato-κS](tri-p-tolyl­phosphine-κP)gold(I)

In the title compound, [Au(C5H10NOS)(C21H21P)], two independent molecules comprise the asymmetric unit, and these are connected by an aurophilic interaction [Au⋯Au = 3.1351 (3) Å]. Each AuI atom is linearly coordinated within a S,P-donor set with the distortion from ideal linear geometry [S—Au—P = 175.31 (5) and 176.45 (5)°] ascribed to an intramolecular Au⋯O contact in each case [2.974 (4) and 3.027 (4) Å].