PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): m1026.
Published online 2010 July 31. doi:  10.1107/S1600536810029326
PMCID: PMC3007517

Bis(1,1,2,2-tetramethyldiphosphane-1,2-dithione-κ2 S,S′)gold(I) trifluoro­methane­sulfonate

Abstract

In the title compound, [Au(C4H12P2S2)2](CF3SO3), the gold(I) atom is tightly bonded to two S atoms belonging to different ligand mol­ecules and forms two weaker contacts to the remaining S atoms. The coordination geometry around gold is inter­mediate between linear-dicoordinate and tetra­hedral with an S—Au—S angle of 161.49 (3)°.

Related literature

For related structure, see: Gimeno et al. (2000 [triangle]); LeBlanc et al. (1997 [triangle]). For complexes of group 11 metals with bidentate diphosphine disulfides, see: Liu et al. (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1026-scheme1.jpg

Experimental

Crystal data

  • [Au(C4H12P2S2)2](CF3O3S)
  • M r = 718.43
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1026-efi1.jpg
  • a = 13.0115 (10) Å
  • b = 12.6797 (10) Å
  • c = 14.2892 (11) Å
  • β = 90.800 (1)°
  • V = 2357.2 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 6.99 mm−1
  • T = 100 K
  • 0.22 × 0.17 × 0.10 mm

Data collection

  • Bruker APEX CCD area detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.331, T max = 0.542
  • 13530 measured reflections
  • 4790 independent reflections
  • 4513 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.021
  • wR(F 2) = 0.052
  • S = 1.05
  • 4790 reflections
  • 234 parameters
  • H-atom parameters constrained
  • Δρmax = 1.10 e Å−3
  • Δρmin = −0.63 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2003 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]; Atwood & Barbour, 2003 [triangle]); software used to prepare material for publication: X-SEED.

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks I, Global. DOI: 10.1107/S1600536810029326/dn2589sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029326/dn2589Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We would like to thank the National Research Foundation (NRF) of South Africa for financial support.

supplementary crystallographic information

Comment

Complexes of the group 11 metals with bidentate diphosphine disulfides (2L) have so far only encompassed the lighter elements Cu and Ag (Liu et al., 2003) which readily yield [M(2L)2]+ cations. Gold complexes have not been investigated, despite the interesting results the combination of these bidentate ligands with the propensity for AuI to form linear-dicoordinate complexes could produce.

The title compound shown in Figure 1 exhibits a structure that is intermediate between classic linear-dicoordinate and tetrahedral coordination. AuI thus forms a complex of the same stoichiometry as its lighter group elements, but with a significantly different geometry. It can be envisaged as a tetrahedron formed by the sulfur donor atoms in which the gold is displaced from the centre towards an edge. The metal is coordinated by two sulfur atoms of different ligands yielding short Au—S bonds [2.3099 (7) and 2.3044 (7) Å] and is further associated with the other sulfur atoms through Au···S contacts [3.3939 (8) and 3.2472 (8) Å]. The attractive nature of these contacts is demonstrated by the S—Au—S angle of 161.49 (3)° which significantly deviates from linearity.

In the molecular structure of the complex [Ag(C4H12P2S2)2]BF4 (Liu et al., 2003) the four Ag—S bonds are more uniform in length with distances between 2.534 (2) and 2.676 (2) Å. The replacement of silver by gold thus causes two of the four bonds to become significantly stronger while the other bonds are reduced to non-classical contacts. Au—S bonds in other phosphine sulfide complexes are significantly shorter than in the present structure, 2.277 (2) Å in [Au(SPPh3)2]PF2O2 (LeBlanc et al., 1997) and 2.281 (5) and 2.299 (5) Å in [1,1'-bis(diphenylthiophosphoryl)ferrocene]gold(I) tetrachloroaurate(III) (Gimeno et al., 2000), which can be attributed to the absence of additional stabilizing contacts in these structures.

The [Au(C4H12P2S2)2]+ cations in the crystal structure of the title compound are isolated and no intermolecular Au···Au or Au···S interactions are observed. The packing shown in Figure 2 is characterized by alternating layers of cations and anions parallel to the bc plane. The trifluoromethanesulfonate anion shows no disorder and exhibits low thermal movement.

Experimental

A Schlenk vessel was charged with tetramethyldiphosphine disulfide (129 mg, 0.69 mmol), [AuCl(tht)] (tht = tetrahydrothiophene) (150 mg, 0.47 mmol) and sodium trifluoromethanesulfonate (86 mg, 0.50 mmol). Acetonitrile (20 ml) was added and the suspension stirred for 1 h and evaporated to dryness in vacuo. The residue was suspended in acetonitrile (20 ml), filtered, concentrated to ca 7 ml and layered with diethyl ether. Crystals grown at 258 K were washed with toluene to remove co-precipitated amorphous solids.

Refinement

All H atoms were positioned geometrically (C—H = 0.98 Å) and constrained to ride on their parent atoms; Uiso(H) values were set at 1.5 times Ueq(C).

The largest residual electron density peak of 1.10 e Å-3 is located 0.83 Å from Au1.

Figures

Fig. 1.
Asymmetric unit of the title compound, ellipsoids are drawn at the 50% probability level.
Fig. 2.
Perspective view of the packing of the title compound along the crystallographic b axis. Ellipsoids are drawn at the 50% probability level, element colours correspond to those used in Figure 1.

Crystal data

[Au(C4H12P2S2)2](CF3O3S)F(000) = 1392
Mr = 718.43Dx = 2.024 Mg m3
Monoclinic, P21/cMelting point: 458 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 13.0115 (10) ÅCell parameters from 7735 reflections
b = 12.6797 (10) Åθ = 2.7–26.4°
c = 14.2892 (11) ŵ = 6.99 mm1
β = 90.800 (1)°T = 100 K
V = 2357.2 (3) Å3Plate, colourless
Z = 40.22 × 0.17 × 0.10 mm

Data collection

Bruker APEX CCD area detector diffractometer4790 independent reflections
Radiation source: fine-focus sealed tube4513 reflections with I > 2σ(I)
graphiteRint = 0.025
ω–scansθmax = 26.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)h = −15→16
Tmin = 0.331, Tmax = 0.542k = −15→15
13530 measured reflectionsl = −16→17

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.052H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0282P)2] where P = (Fo2 + 2Fc2)/3
4790 reflections(Δ/σ)max = 0.002
234 parametersΔρmax = 1.10 e Å3
0 restraintsΔρmin = −0.63 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Au10.440979 (8)0.844393 (8)0.524100 (8)0.01389 (5)
S10.52186 (5)0.92223 (5)0.65138 (5)0.01472 (15)
S20.63626 (6)0.67687 (6)0.47459 (5)0.01673 (15)
S30.35744 (6)0.82264 (6)0.38215 (5)0.01501 (15)
S40.32851 (6)0.64875 (6)0.62763 (6)0.01872 (17)
P10.64439 (6)0.82795 (6)0.67067 (5)0.01163 (15)
P20.71405 (5)0.79124 (6)0.53285 (5)0.01190 (15)
P30.29943 (6)0.67616 (6)0.39245 (5)0.01318 (15)
P40.22373 (6)0.65658 (5)0.52912 (6)0.01294 (16)
C110.7375 (2)0.8935 (2)0.7437 (2)0.0171 (6)
H11A0.70550.91440.80260.026*
H11B0.76290.95640.71150.026*
H11C0.79500.84560.75710.026*
C120.6124 (2)0.7039 (2)0.7218 (2)0.0164 (6)
H12A0.67460.66090.72840.025*
H12B0.56240.66730.68140.025*
H12C0.58260.71550.78350.025*
C210.7118 (2)0.9145 (2)0.4715 (2)0.0186 (6)
H21A0.74650.96840.50950.028*
H21B0.64040.93570.45960.028*
H21C0.74720.90670.41180.028*
C220.8470 (2)0.7616 (2)0.5572 (2)0.0186 (6)
H22A0.88270.74930.49830.028*
H22B0.85160.69830.59640.028*
H22C0.87900.82110.59030.028*
C310.3938 (2)0.5739 (2)0.3907 (2)0.0195 (6)
H31A0.35980.50510.39520.029*
H31B0.44150.58280.44380.029*
H31C0.43190.57760.33210.029*
C320.2097 (3)0.6538 (2)0.2981 (2)0.0213 (7)
H32A0.24200.67140.23860.032*
H32B0.14900.69830.30660.032*
H32C0.18900.57950.29760.032*
C410.1386 (2)0.7673 (2)0.5343 (2)0.0198 (6)
H41A0.09430.76830.47830.030*
H41B0.17890.83260.53730.030*
H41C0.09610.76170.59010.030*
C420.1452 (2)0.5404 (2)0.5155 (2)0.0219 (7)
H42A0.10060.53310.56990.033*
H42B0.18940.47810.51080.033*
H42C0.10280.54680.45860.033*
F11.09451 (13)0.54274 (14)0.87757 (13)0.0238 (4)
F20.93924 (14)0.50519 (17)0.91581 (15)0.0390 (5)
F31.00332 (15)0.43955 (15)0.79097 (16)0.0387 (5)
C10.9995 (2)0.5259 (2)0.8438 (2)0.0202 (6)
S50.95244 (6)0.63932 (6)0.77742 (6)0.01722 (16)
O11.02253 (19)0.64635 (19)0.70158 (18)0.0325 (6)
O20.95933 (18)0.72418 (18)0.84446 (16)0.0319 (6)
O30.84886 (15)0.60862 (18)0.75253 (16)0.0268 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Au10.01265 (7)0.01445 (7)0.01452 (7)0.00035 (4)−0.00187 (5)−0.00070 (4)
S10.0147 (3)0.0143 (3)0.0151 (4)0.0019 (3)−0.0008 (3)−0.0025 (3)
S20.0184 (4)0.0175 (3)0.0142 (4)−0.0030 (3)−0.0009 (3)−0.0036 (3)
S30.0163 (4)0.0145 (3)0.0142 (4)−0.0032 (3)−0.0027 (3)0.0017 (3)
S40.0183 (4)0.0235 (4)0.0142 (4)−0.0013 (3)−0.0033 (3)0.0026 (3)
P10.0115 (3)0.0131 (3)0.0103 (4)−0.0004 (3)−0.0005 (3)−0.0008 (3)
P20.0123 (3)0.0125 (3)0.0110 (4)0.0006 (3)0.0008 (3)0.0003 (3)
P30.0140 (4)0.0139 (3)0.0117 (4)−0.0026 (3)−0.0002 (3)−0.0004 (3)
P40.0131 (4)0.0129 (4)0.0129 (4)−0.0014 (3)0.0009 (3)0.0009 (3)
C110.0150 (14)0.0216 (15)0.0146 (15)−0.0046 (12)−0.0016 (12)−0.0025 (12)
C120.0189 (15)0.0147 (14)0.0155 (15)0.0012 (12)−0.0007 (12)0.0027 (11)
C210.0233 (15)0.0163 (15)0.0163 (16)−0.0004 (12)0.0040 (13)0.0026 (12)
C220.0131 (14)0.0243 (16)0.0184 (16)0.0014 (12)−0.0024 (12)−0.0010 (13)
C310.0221 (15)0.0149 (15)0.0217 (16)−0.0003 (12)0.0065 (13)0.0006 (12)
C320.0255 (18)0.0246 (18)0.0138 (16)−0.0068 (12)−0.0049 (14)−0.0019 (12)
C410.0213 (15)0.0192 (16)0.0189 (16)0.0045 (12)0.0036 (13)0.0019 (12)
C420.0205 (16)0.0228 (16)0.0225 (17)−0.0074 (13)0.0000 (13)0.0009 (13)
F10.0159 (9)0.0270 (10)0.0282 (10)0.0025 (7)−0.0078 (8)−0.0023 (8)
F20.0261 (11)0.0484 (13)0.0425 (13)0.0023 (9)0.0034 (9)0.0292 (11)
F30.0340 (11)0.0209 (10)0.0605 (15)0.0079 (8)−0.0227 (10)−0.0133 (10)
C10.0150 (14)0.0191 (15)0.0263 (17)0.0015 (12)−0.0048 (13)0.0015 (13)
S50.0147 (4)0.0196 (4)0.0174 (4)0.0021 (3)0.0008 (3)0.0052 (3)
O10.0239 (13)0.0513 (17)0.0226 (14)0.0040 (10)0.0080 (11)0.0127 (11)
O20.0419 (15)0.0237 (13)0.0302 (14)0.0075 (11)−0.0031 (11)−0.0039 (10)
O30.0164 (11)0.0299 (13)0.0339 (14)0.0012 (9)−0.0052 (10)0.0097 (11)

Geometric parameters (Å, °)

Au1—S12.3099 (7)C21—H21B0.9800
Au1—S23.3939 (8)C21—H21C0.9800
Au1—S32.3044 (7)C22—H22A0.9800
Au1—S43.2472 (8)C22—H22B0.9800
S1—P12.0086 (10)C22—H22C0.9800
S2—P21.9486 (10)C31—H31A0.9800
S3—P32.011 (1)C31—H31B0.9800
S4—P41.9483 (12)C31—H31C0.9800
P1—P22.2285 (10)C32—H32A0.9800
P1—C111.793 (3)C32—H32B0.9800
P1—C121.786 (3)C32—H32C0.9800
P2—C211.792 (3)C41—H41A0.9800
P2—C221.799 (3)C41—H41B0.9800
P3—P42.2135 (11)C41—H41C0.9800
P3—C311.787 (3)C42—H42A0.9800
P3—C321.793 (3)C42—H42B0.9800
P4—C411.791 (3)C42—H42C0.9800
P4—C421.802 (3)F1—C11.338 (3)
C11—H11A0.9800F2—C11.329 (4)
C11—H11B0.9800F3—C11.331 (4)
C11—H11C0.9800C1—S51.823 (3)
C12—H12A0.9800S5—O11.429 (2)
C12—H12B0.9800S5—O21.443 (2)
C12—H12C0.9800S5—O31.443 (2)
C21—H21A0.9800
S1—Au1—S295.59 (2)P2—C21—H21B109.5
S1—Au1—S3161.49 (3)H21A—C21—H21B109.5
S1—Au1—S499.84 (2)P2—C21—H21C109.5
S2—Au1—S394.99 (2)H21A—C21—H21C109.5
S2—Au1—S487.73 (2)H21B—C21—H21C109.5
S3—Au1—S495.71 (2)P2—C22—H22A109.5
P1—S1—Au1101.88 (4)P2—C22—H22B109.5
P2—S2—Au180.28 (3)H22A—C22—H22B109.5
P3—S3—Au1102.65 (4)P2—C22—H22C109.5
P4—S4—Au186.97 (3)H22A—C22—H22C109.5
S1—P1—P2109.57 (4)H22B—C22—H22C109.5
S2—P2—P1108.53 (4)P3—C31—H31A109.5
C11—P1—S1109.42 (10)P3—C31—H31B109.5
C11—P1—P2109.37 (10)H31A—C31—H31B109.5
C12—P1—S1113.03 (10)P3—C31—H31C109.5
C12—P1—C11109.26 (14)H31A—C31—H31C109.5
C12—P1—P2106.1 (1)H31B—C31—H31C109.5
C21—P2—C22106.63 (14)P3—C32—H32A109.5
C21—P2—S2115.78 (11)P3—C32—H32B109.5
C21—P2—P1104.25 (10)H32A—C32—H32B109.5
C22—P2—S2114.80 (11)P3—C32—H32C109.5
C22—P2—P1105.92 (10)H32A—C32—H32C109.5
S3—P3—P4109.89 (4)H32B—C32—H32C109.5
S4—P4—P3109.13 (5)P4—C41—H41A109.5
C31—P3—S3114.25 (10)P4—C41—H41B109.5
C31—P3—C32108.39 (15)H41A—C41—H41B109.5
C31—P3—P4104.2 (1)P4—C41—H41C109.5
C32—P3—S3109.38 (10)H41A—C41—H41C109.5
C32—P3—P4110.63 (11)H41B—C41—H41C109.5
C41—P4—S4115.93 (11)P4—C42—H42A109.5
C42—P4—S4115.23 (11)P4—C42—H42B109.5
C41—P4—P3103.38 (10)H42A—C42—H42B109.5
C41—P4—C42107.16 (16)P4—C42—H42C109.5
C42—P4—P3104.80 (11)H42A—C42—H42C109.5
P1—C11—H11A109.5H42B—C42—H42C109.5
P1—C11—H11B109.5F1—C1—F2107.7 (3)
H11A—C11—H11B109.5F1—C1—F3107.1 (2)
P1—C11—H11C109.5F2—C1—F3107.6 (3)
H11A—C11—H11C109.5F1—C1—S5111.4 (2)
H11B—C11—H11C109.5F2—C1—S5111.2 (2)
P1—C12—H12A109.5F3—C1—S5111.6 (2)
P1—C12—H12B109.5O1—S5—O2115.00 (16)
H12A—C12—H12B109.5O1—S5—O3115.71 (15)
P1—C12—H12C109.5O2—S5—O3114.47 (15)
H12A—C12—H12C109.5O1—S5—C1103.30 (14)
H12B—C12—H12C109.5O2—S5—C1103.04 (15)
P2—C21—H21A109.5O3—S5—C1102.80 (14)
S3—Au1—S1—P1−134.62 (7)S1—P1—P2—S2−81.71 (5)
S4—Au1—S1—P178.61 (4)Au1—S3—P3—C31−69.84 (12)
S2—Au1—S1—P1−10.05 (4)Au1—S3—P3—C32168.48 (12)
S3—Au1—S2—P2136.79 (3)Au1—S3—P3—P446.85 (5)
S1—Au1—S2—P2−28.00 (4)Au1—S4—P4—C41−72.22 (12)
S4—Au1—S2—P2−127.67 (3)Au1—S4—P4—C42161.49 (12)
S1—Au1—S3—P3−163.26 (7)Au1—S4—P4—P343.95 (4)
S4—Au1—S3—P3−16.12 (4)C31—P3—P4—C41174.52 (15)
S2—Au1—S3—P372.08 (4)C32—P3—P4—C41−69.19 (15)
S3—Au1—S4—P4−18.69 (4)S3—P3—P4—C4151.70 (12)
S1—Au1—S4—P4151.24 (3)C31—P3—P4—C42−73.35 (15)
S2—Au1—S4—P4−113.48 (3)C32—P3—P4—C4242.94 (15)
Au1—S1—P1—C12−74.47 (11)S3—P3—P4—C42163.82 (11)
Au1—S1—P1—C11163.53 (10)C31—P3—P4—S450.59 (11)
Au1—S1—P1—P243.62 (5)C32—P3—P4—S4166.88 (11)
Au1—S2—P2—C21−64.82 (11)S3—P3—P4—S4−72.24 (6)
Au1—S2—P2—C22170.20 (11)F2—C1—S5—O1−177.2 (2)
Au1—S2—P2—P151.93 (4)F3—C1—S5—O1−57.0 (2)
C12—P1—P2—C21164.56 (14)F1—C1—S5—O162.7 (2)
C11—P1—P2—C21−77.71 (15)F2—C1—S5—O3−56.5 (3)
S1—P1—P2—C2142.23 (11)F3—C1—S5—O363.7 (2)
C12—P1—P2—C22−83.14 (15)F1—C1—S5—O3−176.6 (2)
C11—P1—P2—C2234.60 (15)F2—C1—S5—O262.7 (3)
S1—P1—P2—C22154.53 (11)F3—C1—S5—O2−177.1 (2)
C12—P1—P2—S240.61 (11)F1—C1—S5—O2−57.4 (2)
C11—P1—P2—S2158.35 (11)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2589).

References

  • Atwood, J. L. & Barbour, L. J. (2003). Cryst. Growth Des.3, 3–8.
  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2002). SADABS and SMART Bruker AXS Inc., Madison Wisconsin, USA.
  • Bruker (2003). SAINT Bruker AXS Inc., Madison Wisconsin, USA.
  • Gimeno, M. C., Jones, P. G., Laguna, A. & Sarroca, C. (2000). J. Organomet. Chem.596, 10–15.
  • LeBlanc, D. J., Britten, J. F. & Lock, C. J. L. (1997). Acta Cryst. C53, 1204–1206.
  • Liu, H., Calhorda, M. J., Drew, M. G. B. & Félix, V. (2003). Inorg. Chim. Acta, 347, 175–180.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography