[(Z)-N-(3-Fluorophenyl)-O-methylthiocarbamato-κS](triphenylphosphane-κP)gold(I): crystal structure, Hirshfeld surface analysis and computational study

Abstract

The title phosphanegold(I) thiolate, C26H22AuFNOPS or [Au(C8H7FNOS)(C18H15P)], has the AuI centre coordinated by phosphane-P [2.2494 (8) Å] and thiolate-S [2.3007 (8) Å] atoms to define a close to linear geometry [P—Au—S = 176.10 (3)°]. The thiolate ligand is orientated so that the methoxy-O atom is directed towards the Au atom, forming an Au...O close contact of 2.986 (2) Å. In the crystal, a variety of intermolecular contacts are discerned with fluorobenzene-C—H...O(methoxy) and phenyl-C—H...F interactions leading to dimeric aggregates. These are assembled into a three-dimensional architecture by phenyl-C—H...S(thiolate) and phenyl-C—H...π(fluorobenzene, phenyl) interactions. Accordingly, the analysis of the calculated Hirshfeld surface shows 30.8% of all contacts are of the type C...H/H...C but this is less than the H...H contacts, at 44.9%. Other significant contributions to the surface come from H...F/F...H [8.1%], H...S/S...H [6.9%] and H...O/O...H [3.2%] contacts. Two major stabilization energies have contributions from the phenyl-C—H...π(fluorobenzene) and fluorobenzene-C—H...C(imine) interactions (−37.2 kcal mol−1), and from the fluorobenzene-C—H...F and phenyl-C—H...O interactions (−34.9 kcal mol−1), the latter leading to the dimeric aggregate.

Crystal structure of (μ2-1,1′-bis(diphenylphosphino)butane-κ2 P,P′)-bis[(Z)-N-(3-fluorophenyl)-O-methylthiocarbamato-κS]-di-gold(I), C44H42Au2F2N2O2P2S2

“…The equivalent parameters for the Au2 atom are Au2-S2 = 2.3097(11) Å, Au2-P2 = 2.2505(10) Å and P2-Au2-S2 = 174.67(3)°, indicating a close similarity. The mode of coordination of the thiolate ligand and the gold atom coordination geometry in (I) is as found in all previous studies [5][6][7]10]. The most notable feature of the molecular structure is the relative orientation of the thiolate ligands.…”

“…The specific motivation for the preparation of the title binuclear dppb molecule, i.e. (dppb){Au[SC(OMe)=N(C 6 H4F-3)]} 2 (I), with a fluorinated phenyl ring in the thiolate ligand arose from investigations into biological activity [5]. Herein, the crystal and molecular structures of (I) are described.…”

Crystal structure of (μ2-1,1′-bis(diphenylphosphino)ferrocene-κ2 P,P′)-bis[(Z)N-(3-fluorophenyl)-O-methylthiocarbamato-S]digold(I) chloroform solvate, C50H42Au2F2FeN2O2P2S2, CHCl3

“…The 3-fluorophenyl ring was disordered over two co-planar orientations so the C atoms were exactly coincident but, two positions were apparent for the F atoms; the latter were refined independently. At the conclusion of the refinement, the major component of the ring had a site occupancy factor of 0.592 (5). The solvent chloroform molecule was statistically disordered about a centre of inversion.…”

Crystal structure of (tricyclohexylphosphane-κP)-[(Z)-N-(3-fluorophenyl)-O-methylthiocarbamato-k1 S]gold(I), C26H40AuFNOPS

“…NaOH (Merck; 0.020 g, 0.50 mmol) in water (5 mL) was added to a suspension of (cyclohexyl) 3 PAuCl (0.256 g, 0.50 mmol) in acetonitrile (20 mL), followed by the addition of MeOC(=S)N(H)C 6 H 4 F-3 [5] (0.093 g, 0.50 mmol) in acetonitrile (20 mL) and stirred for 3 h. The resulting mixture was left for slow evaporation at room temperature, yielding crystals after 2 weeks. Yield: 0.261 g (79%).…”