Crystal structures of triorganophosphinegold(I) O-cy clohexyldithiocarbonates: R₃PAu(S₂CO-c-C₆H₁₁), R = Et, Ph and c-hexyl

Abstract

The crystal structures of the title compounds R 3 PAu(S 2 CO-c-C 6 H n ), R = Et, Ph and c-hexyl, have been determined at room temperature. Monoclinic crystals of the R = Et compound have space group C2/c with unit cell dimensions a = 26.754(4) A, b = 7.264(1) Â, c = 18.928(3) A, β = 102.04(1)°, Z= 8 and D x = 1.811 Mg_m" 3 . Crystals of the R = Ph structure are triclinic with space group Pi and unit cell dimensions a = 11.372(2) À, ¿> = 13.053(6) A, c = 9.488(3)Â; α = 109.45(3)°, β = 99.19(2)°, y = 106.28(3)°, Ζ = 2 and D x = 1.722 Mg m -3 . The R = c-hexyl compound crystallizes in the orthorhombic space group Ρ1χ2 χ 2 χ with unit cell dimensions a = 8.121(1) A, b = 11.108(4) A, c = 30.212(5) A, Ζ = 4 and D x = 1.591 Mgm" 3 . The structures were refined by a full-matrix leastsquares procedure on 1908 reflections to final Λ = 0.039 for the R = Et compound, 3664 reflections and R = 0.055 for R = Ph and 1501 reflections and R = 0.040 for R = c-hexyl. The Au atom in each of the structures is linearly coordinated by the S atom, derived from a monodentate xanthate ligand, and the Ρ atom. Different orientations of the xanthate ligands results in two structural forms. For the R = Et and Ph compounds the O atom is in close proximity of the Au atom whereas for the R = c-hexyl compound the S atom is orientated towards the Au atom. The different structures are rationalized in terms of the steric demands of the phosphine ligands. A close Au...Au interaction of 3.120(1) A is found in the R =

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

“…3.140(5) A ˚; such intramolecular Au/O interactions are now well documented in gold(I) chemistry. 77,78,148 Allowing for differences in chemistry, the molecular structure of Ph 3 PAu[SC (OMe)¼NPh].0.5CHCl 3 is consistent with previous reports. 108,144 Substituting the nitrogen-bound aryl group in Ph 3 PAu[SC (OMe)¼N(H)Ph] for o-tol, characterised as a 1/8 methanol solvate (2), m-tol (3), or p-tol (4) does not have a profound influence on molecular geometry.…”

“…94 At the other end of the spectrum, smaller phosphorous-bound R groups might be expected to allow the formation of aurophilic interactions. For example, of the 16 77,[94][95][96][97][98][99][100][101][102][103][104][105][106][107][108] structures with the general formula Et 3 PAuX, in only six examples 77,98,99,103,104,108 are aurophilic interactions featured. In the Me 3 PAuX complexes, 20,71,[109][110][111][112][113][114][115][116][117][118][119][120][121][122][123][124] aurophilic interactions are more pervasive, being observed in the majority, i.e.…”

“…As highlighted recently, consideration of the size of the ''X'' anion in such complexes can be equally important. 65 The role of steric profiles of organic residues in metal complexes in moderating supramolecular aggregation patterns in their crystal structures has been a continuing theme in our work in gold chemistry 12,17,77,78,85,94 as well as in main group element systems, [134][135][136][137][138][139][140][141] and such considerations motivate the present study.…”

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, NO2or Me: the influence on intermolecular interactions exerted by R and Y

“…Such Au … O interactions, which are shorter than the sum of the van der Waals radii of gold and oxygen of 3.20 A ˚,19 have precedents in gold chemistry. [20][21][22] An examination of the geometric parameters, Table 1, in particular the C1-S1 and C1-N1 bond distances, and comparing these to those values found in the structure of the free ligand, i.e. 1.671(1) and 1.329(2) A ˚, respectively, 23 indicates that the ligand is functioning as a thiolate ligand, as concluded previously.…”

Relief of steric strain by intramolecular C–H · · · O interactions: structural evidence for the 1,4-disubstituted cyclohexanes

“…It must be stated, however, that all occur in organometallic compounds, where oxocyclohexane groups are frequently used as ligands. A typical example 20 is shown in Fig. 7.…”