Soo Yei Ho

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.

Prevalence of the thioamide {⋯H–N–CS}2 synthon—solid-state (X-ray crystallography), solution (NMR) and gas-phase (theoretical) structures of O-methyl-N-aryl-thiocarbamides

Structural investigations, i.e. solid-state (X-ray), solution (1H NMR) and gas-phase (theoretical), on molecules with the general formula MeOC(S)N(H)C6H4-4-Y: Y = H (1), NO2 (2), C(O)Me (3), Cl (4) have shown a general preference for the adoption of an E-conformation about the central C–N bond. Such a conformation allows for the formation of a dimeric hydrogen-bonded {⋯H–N–CS}2 synthon as the building block. In the cases of 1–3, additional C–H⋯O interactions give rise to the formation of tapes of varying topology. A theoretical analysis shows that the preference for the E-conformation is about the same as the crystal packing stabilisation energy and consistent with this, the compound with Y = C(O)OMe, (5), adopts a Z-conformation in the solid-state that facilitates the formation of N–H⋯O, C–H⋯O and C–H⋯S interactions, leading to a layer structure. Global crystal packing considerations are shown to be imperative in dictating the conformational form of molecules 1–5.

Supramolecular aggregation patterns in the crystal structures of the dinuclear phosphinegold(I) thiolates, [(Ph2P(CH2)4PPh2){AuSC(OR)NC6H4Y-4}2] for R = Me, Et or iPr and Y = H, NO2 or Me: the influence on intermolecular interactions exerted by R and Y

The molecular structures of all but the R = Et/Y = NO2 derivative of the series of structures [(Ph2P(CH2)4PPh2){AuSC(OR)NC6H4Y-4}2] for R = Me, Et or iPr and Y = H, NO2 or Me, display anti-conformations with the carbonimidothioate ligands external to the dppb (Ph2P(CH2)4PPh2) bridge. In the exceptional structure, the thiolate ligands occupy positions proximate to the dppb bridge, an observation rationalized in terms of the dictates of crystal packing. Aurophilic (Au⋯Au) interactions are not observed in their molecular or in their crystal structures. In the Y = NO2 structures, C–H⋯O interactions dominate the crystal packing leading to chain (R = Me or iPr) and layer (R = Et) motifs. Synthons of the type {Au⋯S}2 dominate the crystal packing, leading to a chain, in one example, i.e. R = Me and Y = H. Similar {Au⋯S}2 synthons potentially appear in all the remaining structures except for R = Et and Y = H, but the Au⋯S distances are too long to be considered significant so that C–H⋯S interactions clearly dominate the crystal packing. With the exception of the layer motif found for the R = Et and Y = NO2 derivative, chain motifs, mediated by {Au⋯S}2, C–H⋯O or C–H⋯S interactions persist in the crystal structures.

Chloro­[tris(p‐methoxy­phenyl)­phosphine]­gold(I)

The Au atom in the title compound, (p-MeOC6H4)3PAuCl or [AuCl(C7H7O3P)], exhibits a linear geometry so that the Au—Cl bond length is 2.2885 (9) A, Au—P is 2.2333 (8) A and the angle at gold is 175.94 (3)°.

(N,N-Diethyl­di­thio­carbamato)(tri­cyclo­hexyl­phosphine)­gold(I)

The Au atom in the title compound, (c-C6H11)3PAu(S2CNEt2) or [Au(C18H33P)(C5H10NS2)], exists in a linear geometry so that Au—S is 2.3340 (11), Au—P is 2.2599 (10) A and the angle at gold is 171.61 (4)°. The distortion from linearity may be traced to the close approach of the non-coordinating S atom which is separated from the Au atom by 3.0859 (13) A.

Crystal and molecular structures of two triorganophosphinegold(I) 2-amino-cyclopent-1-ene-1-carbodithioates

Abstract The molecular structures of Ph3PAu · (S2CC5H6NH2-2) and (4-MeOC6H4)3PAu(S2CC5H6NH2-2) · CH2Cl2 display the expected linear S-Au-P coordination geometries. The hydrogen-bonding functionality in the 1,1-dithiolate ligands, i.e., —NH2 groups, allows for the formation of hydrogen-bonded, i.e., N—H…S, mediated chains in the respective crystal structures.

μ-1,1'-Bis(diphenyl-phosphino)ferrocene-κP:P'-bis-{[(Z)-O-isopropyl N-(4-nitro-phen-yl)thio-carbamato-κS]gold(I)} chloro-form disolvate.

The dinuclear title molecule, [Au2Fe(C10H11N2O3S)2(C17H14P)2]·2CHCl3, has crystallographic twofold symmetry with the Fe atom (bonded to two η5-cyclopentadienyl rings) situated on the rotation axis. The Au atom exists within a linear geometry defined by an S,P-donor set with a deviation from linearity [S—Au—P = 176.86 (6)°] due to the close approach of the thiocarbamate O atom [Au⋯O = 3.108 (5) Å]. The molecule has a U-shaped geometry which facilitates the formation of an intramolecular Au⋯Au interaction [3.0231 (5) Å]. In the crystal, the presence of C—H⋯Onitro contacts leads to the formation of layers with substantial voids; these are occupied by the solvent molecules of crystallization, which are held in place by C—H⋯S contacts.

[(Z)-O-Ethyl N-(4-nitro­phen­yl)thio­carbamato-κS](triethyl­phosphine-κP)gold(I)

In the title compound, [Au(C9H9N2O3S)(C6H15P)], two virtually identical molecules comprise the asymmetric unit. These are connected by Au⋯Au [3.6796 (4) Å] and Au⋯S [3.6325 (18) and 3.5471 (18) Å] contacts, forming a dimeric aggregate. The presence of intramolecular Au⋯O contacts [2.993 (5) and 2.957 (5) Å] is responsible for the slight deviations from the ideal linear coordination environments about the AuI ions. The conformation about the central C=N double bond is Z. Supramolecular chains sustained by π–π [3.573 (4) Å] and C—H⋯π interactions are evident in the crystal structure. These are connected into layers via weak intermolecular C—H⋯O interactions involving the nitro-group O atoms.

(O-Ethyl­di­thio­carbonato)[tris(p-methoxy­phenyl)­phosphine]­gold(I)

The Au atom in the title compound, (p-MeOC6H4)3PAu(S2COEt) or [Au(C3H5OS2)(C21H21O3P)], exists in a linear geometry, such that the Au—S bond length is 2.3004 (8) A and Au—P is 2.2505 (7) A, and the angle at gold is 175.87 (3)°.

[μ-1,1′-Bis(diphenyl­phosphino)ferrocene]bis­{[(Z)-O-ethyl N-phenyl­thio­carbamato-κS]gold(I)} dichloro­methane solvate

The binuclear title compound, [Au2Fe(C9H10NOS)2(C17H14P)2]·CH2Cl2, which has the Fe atom located on a crystallographic centre of inversion, crystallizes as a 1:1 dichloromethane solvate, which is disordered about a centre of inversion. There is a small deviation from linearity defined by the SP donor set [S1—Au—P1 angle is 175.35 (5) °] which is due to an intramolecular Au⋯O contact [3.080 (5) Å]. The primary intermolecular contacts between binuclear molecules are of the type C—H⋯π, and are arranged so as to form columns in the a-axis direction in which the disordered solvent molecules reside.