Tetra­phenyl­phospho­nium bis­(2-thioxo-1,3-dithiole-4,5-dithiol­ato)aurate(III) acetone solvate and ethyl­triphenyl­phospho­nium bis­(2-thioxo-1,3-dithiole-4,5-dithiol­ato)aurate(III)

In the two title complexes, (C₂₄H₂₀P)[Au(C₃S₅)₂]·C₃H₆O, (I), and (C₂₀H₂₀P)[Au(C₃S₅)₂], (II), the Au^III atoms exhibit square-planar coordinations involving four S atoms from two 2-thioxo-1,3-dithiole-4,5-dithiol­ate (dmit) ligands. The Au-S bond lengths, ranging from 2.3057 (8) to 2.3233 (7) Å in (I) and from 2.3119 (8) to 2.3291 (10) Å in (II), are slightly smaller than the sum of the single-bond covalent radii. In (I), there are two halves of independent Ph₄P⁺ cations, in which the two P atoms lie on twofold rotation axis sites. The Ph₄P⁺ cations and [Au(C₃S₅)₂]^- anions are inter­spersed as columns in the packing. Layers composed of Ph₄P⁺ and [Au(C₃S₅)₂]^- are separated by layers of acetone molecules. In (II), the [Au(C₃S₅)₂]^- anions and EtPh₃P⁺ counter-cations form a layered arrangement, and the [Au(C₃S₅)₂]^- anions form discrete pairs with a long inter­molecular Au...S inter­action for each Au atom in the crystal structure.

S1. Comment

The third-order nonlinear optical (TONLO) response is very important in all-optical switching, signal processing and ultrafast optical communications (Sutherland, 1996). For the realisation of all-optical switching devices, the material requirements which have to be met are W >> 1 and T << 1. These two figures of merit are defined as W = n₂I/(αλ) and T = βλ/n₂, where n₂ is the nonlinear refractive index, α is the linear absorption coefficient, β is the nonlinear absorption coefficient, λ is the wavelength and I is the light irradiance. Furthermore, ultrafast response times are required for the nonlinear processes involved. Therefore, to be practically useful for all-optical switching, materials should have a large n₂ at the operating wavelength, small α and β and an ultrafast response time, together with good physicochemical properties, such as environmental stability and processability (Kuang et al., 2003).

For nearly three decades, the synthesis and characterization of 2-thioxo-1,3-dithiole-4,5-dithiolate (dmit) complexes and related analogues have been paid great attention (Steimeck & Kirmse, 1979). As special π-electron conjugated systems, dmit and related ligands have been used as building units for electrical conductors and superconductors (Svenstrup & Becher, 1995; Cassoux, 1999; Pullen & Olk, 1999; Robertson & Cronin, 2002). The π-electron delocalization in conjugated systems can also contribute to an ultrafast optical response capability and large TONLO effects (Coe, 2004). Recently, many dmit complexes have been reported as possessing good TONLO properties (Wang et al., 1999; Liu et al., 2002). In our previous studies, the TONLO properties of a series of such complexes were reported. The results showed that they possess large TONLO properties with sub-picosecond response times (Yang et al., 2005; Sun et al., 2006). Along with this research, Au–dmit complexes (Li et al., 2005, 2006) have been found to possess large n₂ and nearly zero absorption with good figures of merit, W and T, for all-optical switching applications at 1064 nm. Therefore, they are potential candidates for all-optical switching device applications. To continue this work, the preparation and structural characterization of the two title compounds, (C₂₄H₂₀P)[Au(C₃S₅)₂]·C₃H₆O, (I), and (C₂₀H₂₀P)[Au(C₃S₅)₂], (II), are reported here.

The two structures show similarities with and differences from each other and the previously reported crystal structures of 18 related Au–dmit complexes in the Cambridge Structural Database (CSD; Version 5.38 of May 2007; Allen, 2002). The similarities are that in all these crystal structures, dmit exhibits its typical behaviour as a bidentate ligand and the Au³⁺ ion is coordinated by four S atoms from two dmit molecules in an almost square-planar geometry. The four S atoms are planar, with a slight deviation of the Au atom therefrom, and all of them have a slight T_d distortion. The anion is generally planar. [Original text was not clear - please check rephrasing] Like the previously reported complexes, the Au—S bond lengths [2.3057 (8)–2.3233 (7) Å for (I), and 2.3119 (8)–2.3291 (10) Å for (II)] are slightly smaller than the sum of the single-bond covalent radii (1.36 Å; Pauling, 1960). The S—Au—S bite angles [87.20 (3)–91.76 (3)° for (I) and 86.97 (3)–91.49 (3)° for (II)] are almost nominal right angles and the trans S—Au—S angles [176.97 (3) and 177.20 (3)° for (I), and 178.22 (3) and 178.40 (3)° for (II)] are very close to 180°. The C═S double bond is much longer than the typical C═S bond length (1.599 Å; Allen et al., 1987). The other C—S bonds [1.723 (4)–1.747 (3) Å for (I) and 1.728 (3)–1.751 (3) for (II)] are shorter than the typical C—S single bond (1.819 Å; Allen et al., 1987) and are essentially single bonds with some double-bond character. The two C═C bond lengths of the dmit ion [1.345 (4) and 1.340 (4) Å for (I), and 1.336 (5) and 1.340 (5) Å for (II)] are very close to the corresponding double-bond value of 1.34 Å (Allen et al., 1987 ?).

An obvious difference between these 20 compounds lies in the [Au(C₃S₅)₂]^- anion. There is one type of [Au(C₃S₅)₂]^- anion in some of these complexes, with large counter-cations (Miura et al., 2004; Li et al., 2006), and compounds (I) and (II) belong to this class. On the other hand, there are two kinds of crystallographically independent [Au(C₃S₅)₂]^- anions in another type of [Au(C₃S₅)₂]^- anion (Matsubayashi & Yokozawa, 1990; Li et al., 2005), with small counter-cations. The counter-cations and their orientations with respect to the [Au(C₃S₅)₂]^- anions are different in these crystal structures. In (I), there are two halves of independent (C₂₄H₂₀P)⁺ cations, in which the two P atoms lie on twofold rotation axis sites. The (C₂₄H₂₀P)⁺ cations and [Au(C₃S₅)₂]^- anions are interspersed as columns in the packing. Layers composed of (C₂₄H₂₀P)⁺ and [Au(C₃S₅)₂]^- are separated by layers of acetone. In (II), there are layers of (C₂₁H₂₂P)⁺ cations and of [Au(C₃S₅)₂]^- anions, and the [Au(C₃S₅)₂]^- anions form discrete pairs with a long intermolecular Au···S interaction for each Au atom in the crystal structure.

All the data show that the two [Au(C₃S₅)₂]^- ring systems in the title compounds have a high degree of electron delocalization. The most striking physical characteristic of these two crystal structures is the extended electronically delocalized core, comprising the central Au³⁺ ion, four S atoms and the adjacent C═C units in the quasi-square plane. It has been shown that when Au³⁺ takes the place of group 12 metal ions (Zn²⁺, Cd²⁺ and Hg²⁺), electron delocalization is enhanced (Li et al., 2003). This is due to the unfilled d electron shell of Au³⁺, which allows the possibility of low-energy charge-transfer transitions and is an important contribution to optical nonlinearity. In particular, the 3p orbitals of S and 3d orbitals of Au³⁺ can overlap to form a highly delocalized system. This delocalization will greatly enhance hyperpolarizability and nonlinear susceptibility, and lead to large TONLO properties. The TONLO properties of these two compounds were measured by the Z-scan technique (Sheik-Bahae et al., 1989, 1990), in mM solutions of both acetone and acetonitrile at 1064 nm. These revealed that their nonlinear refractive indices were superior to that of CS₂ [Quantify this statement?].

Related literature

For related literature, see: Allen (2002); Allen et al. (1987); Cassoux (1999); Coe (2004); Kuang et al. (2003); Li et al. (2003, 2005, 2006); Liu et al. (2002); Matsubayashi & Yokozawa (1990); Miura et al. (2004); Pauling (1960); Pullen & Olk (1999); Robertson & Cronin (2002); Sheik-Bahae, Said & Van Stryland (1989); Sheik-Bahae, Said, Wei, Hagan & Van Stryland (1990); Steimeck & Kirmse (1979); Sun et al. (2006); Sutherland (1996); Svenstrup & Becher (1995); Wang et al. (1999, 2005); Yang et al. (2005).

S2. Experimental

For the preparation of (I), 4,5-bis(furoylsulfanyl)-1,3-dithiole-2-thione (1.211 g) (Wang et al., 2005) was suspended in methanol (15 ml). Under a nitrogen atmosphere, a sodium methoxide solution obtained from Na (0.145 g) in methanol (15 ml) was added to the above-mentioned mixture at room temperature to give a dark-red solution. To this solution, separate solutions of NaAuCl₄·2H₂O (0.597 g) dissolved in methanol (5 ml), and C₂₄H₂₀PBr (0.659 g) in methanol (5 ml), were added consecutively with stirring at room temperature. The reaction mixture was stirred for about 30 min. The product was collected by filtration and washed with methanol to afford a dark-brown precipitate of (C₂₄H₂₀P)[Au(C₃S₅)₂]. An acetone solution of the product was left standing at room temperature, and brown crystals of the solvate, (I), suitable for structure determination were obtained. Electronic absorption (Hitachi model U-3500 recording spectrophotometer; nm):339 and 347 (π–π* transition of the dmit ligand), 466 (Au←S charge-transfer transition).

For the preparation of (II), 4,5-bis(furoylsulfanyl)-1,3-dithiole-2-thione (1.211 g) was suspended in methanol (15 ml). Under a nitrogen atmosphere, a sodium methoxide solution obtained from Na (0.145 g) in methanol (15 ml) was added to the above-mentioned mixture at room temperature to give a dark-red solution. To this solution, separate solutions of NaAuCl₄·2H₂O (0.597 g) dissolved in methanol (5 ml), and C₂₄H₂₀PBr (0.584 g) in methanol (5 ml), were added consecutively with stirring at room temperature. The reaction mixture was stirred for about 30 min. The product was collected by filtration and washed with methanol to afford a dark-brown precipitate of (II). An acetone solution of (II) was left standing at room temperature, and brown crystals of (II) suitable for structure determination were obtained. Electronic absorption (Hitachi model U-3500 recording spectrophotometer; nm): 316 and 367 (π–π* transition of the dmit ligand), 446 (Au←S charge-transfer transition).

S3. Refinement

For compound (I), all H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H = 0.93 Å (for CH groups) or 0.96 Å (for CH₃ groups), and with U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for CH₃ groups. Although atoms S1 and S10 had large anisotropic parameters, no suitable disorder model could be found. Their U^ij components were restrained to isotropic behaviour. The three atoms of the acetone molecule were also disordered and no treatment could be applied. The C32—C33 and C31—C32 distances were restrained to reasonable values. Since the reflections 100 and 302 were obscured by the beam stop, F_o² is much less than F_c² in these reflections. They were omitted in the final refinement.

For compound (II), all H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H = 0.93 Å (for CH groups) or 0.96 Å (for CH₃ groups), and with U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for CH₃ groups.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. There are two halves of independent (C24H20P)^+ cations where the two P atoms lie on twofold rotation axis sites. Fig. 2. The crystal packing in (I), viewed along the b axis. H atoms have been omitted. Fig. 3. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Fig. 4. The crystal packing in (II), viewed along the b axis. H atoms have been omitted.

(I) Tetraphenylphosphonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)aurate(III) acetone solvate

Crystal data

(C24H20P)[Au(C3S5)2]·C3H6O	F(000) = 1944
Mr = 987.07	Dx = 1.727 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 6858 reflections
a = 24.4198 (7) Å	θ = 2.5–27.5°
b = 7.4511 (2) Å	µ = 4.50 mm^−1
c = 23.1654 (6) Å	T = 296 K
β = 115.772 (1)°	Prism, brown
V = 3795.78 (18) Å^3	0.24 × 0.23 × 0.15 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	8724 independent reflections
Radiation source: fine-focus sealed tube	7545 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ and ω scans	θmax = 27.5°, θmin = 0.9°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −31→27
Tmin = 0.379, Tmax = 0.508	k = −9→8
33785 measured reflections	l = −30→30

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0246P)^2 + 1.8915P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.004
8724 reflections	Δρmax = 0.62 e Å^−3
419 parameters	Δρmin = −0.44 e Å^−3
14 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00015 (3)

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.

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

	x	y	z	Uiso*/Ueq
Au1	0.743045 (4)	0.072091 (14)	0.744125 (4)	0.03323 (4)
C1	0.61106 (18)	0.5443 (5)	0.54607 (16)	0.0647 (10)
C2	0.67440 (12)	0.3955 (4)	0.65743 (13)	0.0381 (6)
C3	0.67318 (12)	0.2724 (4)	0.61440 (12)	0.0408 (6)
C4	0.81844 (13)	−0.1314 (4)	0.87232 (13)	0.0436 (7)
C5	0.81351 (13)	−0.2546 (4)	0.82822 (13)	0.0420 (7)
C6	0.8809 (2)	−0.4073 (5)	0.93658 (17)	0.0773 (13)
C7	0.50051 (12)	0.1656 (4)	0.68865 (12)	0.0371 (6)
C8	0.45587 (15)	0.0332 (4)	0.66528 (15)	0.0501 (8)
H8	0.4262	0.0264	0.6802	0.060*
C9	0.45560 (16)	−0.0872 (4)	0.62025 (15)	0.0557 (8)
H9	0.4256	−0.1749	0.6046	0.067*
C10	0.49958 (16)	−0.0784 (4)	0.59830 (15)	0.0531 (8)
H10	0.4991	−0.1597	0.5676	0.064*
C11	0.54409 (15)	0.0500 (5)	0.62151 (16)	0.0545 (8)
H11	0.5740	0.0545	0.6068	0.065*
C12	0.54496 (13)	0.1734 (4)	0.66678 (14)	0.0453 (7)
H12	0.5752	0.2606	0.6823	0.054*
C13	0.56529 (12)	0.4570 (4)	0.78121 (13)	0.0377 (6)
C14	0.60901 (14)	0.4460 (4)	0.84412 (14)	0.0519 (8)
H14	0.6069	0.3566	0.8711	0.062*
C15	0.65604 (16)	0.5705 (5)	0.86636 (17)	0.0647 (10)
H15	0.6853	0.5649	0.9087	0.078*
C16	0.65990 (15)	0.7007 (5)	0.82693 (17)	0.0580 (9)
H16	0.6921	0.7818	0.8423	0.070*
C17	0.61632 (14)	0.7126 (4)	0.76451 (16)	0.0513 (8)
H17	0.6190	0.8020	0.7378	0.062*
C18	0.56901 (14)	0.5928 (4)	0.74156 (14)	0.0457 (7)
H18	0.5394	0.6020	0.6995	0.055*
C19	0.93779 (12)	0.5504 (4)	0.70427 (13)	0.0393 (6)
C20	0.88291 (14)	0.5617 (5)	0.70767 (17)	0.0561 (9)
H20	0.8765	0.6514	0.7320	0.067*
C21	0.83756 (17)	0.4391 (6)	0.6748 (2)	0.0745 (12)
H21	0.8006	0.4461	0.6772	0.089*
C22	0.84676 (17)	0.3076 (5)	0.63892 (18)	0.0700 (11)
H22	0.8160	0.2254	0.6171	0.084*
C23	0.90077 (16)	0.2956 (5)	0.63477 (16)	0.0587 (9)
H23	0.9065	0.2067	0.6097	0.070*
C24	0.94674 (15)	0.4154 (4)	0.66771 (15)	0.0510 (8)
H24	0.9838	0.4062	0.6656	0.061*
C25	0.98150 (12)	0.8390 (4)	0.80145 (12)	0.0384 (6)
C26	0.93880 (14)	0.9737 (4)	0.77422 (15)	0.0513 (8)
H26	0.9198	0.9876	0.7299	0.062*
C27	0.92444 (16)	1.0866 (5)	0.81239 (18)	0.0595 (9)
H27	0.8955	1.1762	0.7938	0.071*
C28	0.95230 (19)	1.0684 (5)	0.87763 (19)	0.0657 (10)
H28	0.9421	1.1448	0.9032	0.079*
C29	0.9952 (2)	0.9371 (6)	0.90531 (18)	0.0738 (12)
H29	1.0145	0.9256	0.9497	0.089*
C30	1.00990 (16)	0.8216 (5)	0.86709 (15)	0.0572 (9)
H30	1.0389	0.7325	0.8859	0.069*
P1	0.5000	0.31188 (14)	0.7500	0.0353 (2)
P2	1.0000	0.69624 (14)	0.7500	0.0360 (2)
S1	0.56884 (7)	0.6801 (2)	0.48764 (5)	0.1163 (6)
S2	0.63706 (4)	0.59766 (11)	0.62603 (4)	0.0564 (2)
S3	0.63422 (4)	0.33387 (14)	0.53405 (4)	0.0623 (2)
S4	0.70838 (4)	0.36335 (10)	0.74012 (3)	0.04252 (17)
S5	0.70504 (4)	0.05928 (10)	0.63341 (3)	0.04545 (17)
S6	0.78624 (4)	0.08266 (10)	0.85538 (3)	0.04876 (19)
S7	0.77268 (4)	−0.22242 (10)	0.74579 (3)	0.04580 (17)
S8	0.86143 (5)	−0.19546 (14)	0.95187 (4)	0.0709 (3)
S9	0.84996 (5)	−0.45844 (12)	0.85599 (4)	0.0633 (3)
S10	0.92384 (9)	−0.5475 (2)	0.99244 (6)	0.1455 (8)
O1	0.8261 (3)	0.0873 (8)	1.0601 (4)	0.218 (3)
C31	0.7672 (6)	0.3303 (12)	1.0190 (5)	0.369 (11)
H31A	0.7706	0.3740	1.0594	0.553*
H31B	0.7271	0.3549	0.9862	0.553*
H31C	0.7968	0.3892	1.0086	0.553*
C32	0.7782 (4)	0.1340 (11)	1.0232 (3)	0.160 (4)
C33	0.7244 (4)	0.0304 (16)	0.9827 (4)	0.274 (8)
H33A	0.7335	−0.0954	0.9892	0.410*
H33B	0.7126	0.0599	0.9385	0.410*
H33C	0.6917	0.0586	0.9936	0.410*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.03741 (6)	0.02613 (6)	0.03684 (6)	0.00169 (4)	0.01677 (4)	0.00220 (4)
C1	0.074 (2)	0.077 (3)	0.0472 (17)	0.028 (2)	0.0295 (17)	0.0220 (17)
C2	0.0420 (15)	0.0327 (16)	0.0403 (14)	0.0040 (12)	0.0186 (12)	0.0066 (11)
C3	0.0425 (15)	0.0407 (17)	0.0374 (13)	0.0031 (13)	0.0156 (12)	0.0071 (12)
C4	0.0494 (17)	0.0389 (17)	0.0409 (14)	0.0064 (13)	0.0181 (13)	0.0067 (12)
C5	0.0484 (16)	0.0319 (17)	0.0433 (14)	0.0063 (13)	0.0177 (13)	0.0086 (12)
C6	0.104 (3)	0.075 (3)	0.0485 (19)	0.039 (2)	0.030 (2)	0.0207 (18)
C7	0.0418 (15)	0.0349 (16)	0.0345 (13)	0.0017 (12)	0.0164 (12)	0.0009 (11)
C8	0.0565 (19)	0.050 (2)	0.0531 (17)	−0.0114 (15)	0.0326 (15)	−0.0079 (14)
C9	0.067 (2)	0.047 (2)	0.0545 (18)	−0.0144 (16)	0.0279 (16)	−0.0118 (15)
C10	0.063 (2)	0.050 (2)	0.0439 (16)	0.0076 (16)	0.0211 (15)	−0.0080 (14)
C11	0.0509 (18)	0.065 (2)	0.0552 (18)	0.0056 (16)	0.0297 (15)	−0.0057 (16)
C12	0.0417 (15)	0.048 (2)	0.0474 (15)	−0.0020 (13)	0.0204 (13)	−0.0036 (14)
C13	0.0395 (14)	0.0336 (17)	0.0416 (14)	0.0000 (12)	0.0192 (12)	−0.0034 (11)
C14	0.0506 (18)	0.054 (2)	0.0446 (16)	−0.0060 (15)	0.0148 (14)	0.0038 (14)
C15	0.053 (2)	0.074 (3)	0.0533 (19)	−0.0146 (19)	0.0099 (16)	−0.0058 (18)
C16	0.0466 (18)	0.052 (2)	0.079 (2)	−0.0125 (15)	0.0312 (17)	−0.0189 (18)
C17	0.0555 (18)	0.0386 (18)	0.069 (2)	−0.0047 (15)	0.0355 (17)	−0.0022 (15)
C18	0.0485 (17)	0.0410 (19)	0.0476 (15)	0.0016 (14)	0.0208 (14)	0.0028 (13)
C19	0.0399 (14)	0.0374 (17)	0.0411 (14)	−0.0014 (12)	0.0179 (12)	0.0014 (12)
C20	0.0453 (17)	0.060 (2)	0.068 (2)	−0.0080 (16)	0.0291 (16)	−0.0178 (17)
C21	0.051 (2)	0.082 (3)	0.099 (3)	−0.021 (2)	0.040 (2)	−0.028 (2)
C22	0.063 (2)	0.066 (3)	0.079 (2)	−0.0253 (19)	0.029 (2)	−0.022 (2)
C23	0.066 (2)	0.048 (2)	0.062 (2)	−0.0096 (17)	0.0284 (17)	−0.0155 (16)
C24	0.0500 (17)	0.049 (2)	0.0573 (18)	−0.0023 (15)	0.0269 (15)	−0.0079 (15)
C25	0.0411 (15)	0.0371 (17)	0.0388 (13)	−0.0010 (12)	0.0189 (12)	−0.0012 (12)
C26	0.0535 (18)	0.051 (2)	0.0485 (16)	0.0083 (15)	0.0212 (15)	0.0012 (14)
C27	0.061 (2)	0.045 (2)	0.077 (2)	0.0090 (16)	0.0341 (19)	−0.0015 (17)
C28	0.081 (3)	0.057 (2)	0.074 (2)	0.000 (2)	0.048 (2)	−0.0170 (19)
C29	0.094 (3)	0.080 (3)	0.0492 (19)	0.016 (2)	0.033 (2)	−0.0071 (19)
C30	0.067 (2)	0.057 (2)	0.0456 (16)	0.0149 (17)	0.0230 (16)	0.0016 (15)
P1	0.0373 (5)	0.0340 (6)	0.0344 (5)	0.000	0.0154 (4)	0.000
P2	0.0363 (5)	0.0360 (6)	0.0371 (5)	0.000	0.0171 (4)	0.000
S1	0.1541 (12)	0.1358 (12)	0.0627 (6)	0.0918 (10)	0.0506 (7)	0.0565 (7)
S2	0.0747 (6)	0.0461 (5)	0.0492 (4)	0.0232 (4)	0.0275 (4)	0.0160 (4)
S3	0.0767 (6)	0.0712 (7)	0.0354 (4)	0.0186 (5)	0.0210 (4)	0.0086 (4)
S4	0.0572 (4)	0.0295 (4)	0.0365 (3)	0.0088 (3)	0.0163 (3)	0.0014 (3)
S5	0.0601 (5)	0.0366 (4)	0.0393 (3)	0.0054 (3)	0.0212 (3)	−0.0013 (3)
S6	0.0680 (5)	0.0368 (4)	0.0391 (3)	0.0103 (4)	0.0211 (3)	0.0006 (3)
S7	0.0591 (4)	0.0314 (4)	0.0410 (4)	0.0104 (3)	0.0163 (3)	0.0003 (3)
S8	0.0957 (7)	0.0706 (7)	0.0383 (4)	0.0295 (6)	0.0215 (4)	0.0105 (4)
S9	0.0852 (6)	0.0460 (5)	0.0523 (4)	0.0276 (5)	0.0239 (4)	0.0124 (4)
S10	0.2187 (18)	0.1316 (13)	0.0624 (7)	0.1149 (13)	0.0389 (9)	0.0432 (8)
O1	0.155 (5)	0.187 (6)	0.270 (8)	0.030 (4)	0.053 (5)	0.076 (5)
C31	0.50 (2)	0.166 (10)	0.273 (14)	0.123 (13)	0.014 (14)	−0.009 (10)
C32	0.223 (9)	0.174 (7)	0.122 (5)	0.117 (7)	0.111 (6)	0.070 (5)
C33	0.268 (11)	0.463 (19)	0.148 (7)	−0.239 (13)	0.145 (8)	−0.135 (10)

Geometric parameters (Å, º)

Au1—S7	2.3057 (8)	C17—C18	1.371 (4)
Au1—S4	2.3166 (7)	C17—H17	0.9300
Au1—S5	2.3191 (7)	C18—H18	0.9300
Au1—S6	2.3233 (7)	C19—C20	1.379 (4)
C1—S1	1.645 (3)	C19—C24	1.392 (4)
C1—S2	1.723 (4)	C19—P2	1.792 (3)
C1—S3	1.730 (4)	C20—C21	1.381 (5)
C2—C3	1.345 (4)	C20—H20	0.9300
C2—S4	1.742 (3)	C21—C22	1.366 (5)
C2—S2	1.747 (3)	C21—H21	0.9300
C3—S5	1.739 (3)	C22—C23	1.366 (5)
C3—S3	1.743 (3)	C22—H22	0.9300
C4—C5	1.340 (4)	C23—C24	1.376 (4)
C4—S8	1.745 (3)	C23—H23	0.9300
C4—S6	1.746 (3)	C24—H24	0.9300
C5—S9	1.736 (3)	C25—C30	1.376 (4)
C5—S7	1.744 (3)	C25—C26	1.386 (4)
C6—S10	1.639 (4)	C25—P2	1.796 (3)
C6—S9	1.725 (4)	C26—C27	1.372 (4)
C6—S8	1.729 (4)	C26—H26	0.9300
C7—C12	1.384 (4)	C27—C28	1.368 (5)
C7—C8	1.393 (4)	C27—H27	0.9300
C7—P1	1.795 (3)	C28—C29	1.372 (5)
C8—C9	1.374 (4)	C28—H28	0.9300
C8—H8	0.9300	C29—C30	1.389 (5)
C9—C10	1.375 (5)	C29—H29	0.9300
C9—H9	0.9300	C30—H30	0.9300
C10—C11	1.370 (5)	P1—C7^i	1.795 (3)
C10—H10	0.9300	P1—C13^i	1.797 (3)
C11—C12	1.388 (4)	P2—C19^ii	1.792 (3)
C11—H11	0.9300	P2—C25^ii	1.796 (3)
C12—H12	0.9300	O1—C32	1.162 (8)
C13—C14	1.385 (4)	C31—C32	1.483 (8)
C13—C18	1.396 (4)	C31—H31A	0.9600
C13—P1	1.797 (3)	C31—H31B	0.9600
C14—C15	1.389 (4)	C31—H31C	0.9600
C14—H14	0.9300	C32—C33	1.460 (8)
C15—C16	1.364 (5)	C33—H33A	0.9600
C15—H15	0.9300	C33—H33B	0.9600
C16—C17	1.376 (5)	C33—H33C	0.9600
C16—H16	0.9300
S7—Au1—S4	177.20 (3)	C22—C21—C20	120.3 (3)
S7—Au1—S5	87.20 (3)	C22—C21—H21	119.8
S4—Au1—S5	91.76 (3)	C20—C21—H21	119.8
S7—Au1—S6	91.48 (3)	C21—C22—C23	120.6 (3)
S4—Au1—S6	89.68 (3)	C21—C22—H22	119.7
S5—Au1—S6	176.97 (3)	C23—C22—H22	119.7
S1—C1—S2	123.3 (2)	C22—C23—C24	119.9 (3)
S1—C1—S3	123.8 (2)	C22—C23—H23	120.1
S2—C1—S3	112.88 (18)	C24—C23—H23	120.1
C3—C2—S4	124.6 (2)	C23—C24—C19	120.0 (3)
C3—C2—S2	116.1 (2)	C23—C24—H24	120.0
S4—C2—S2	119.30 (16)	C19—C24—H24	120.0
C2—C3—S5	124.9 (2)	C30—C25—C26	119.3 (3)
C2—C3—S3	116.0 (2)	C30—C25—P2	121.8 (2)
S5—C3—S3	119.13 (17)	C26—C25—P2	118.9 (2)
C5—C4—S8	115.5 (2)	C27—C26—C25	120.2 (3)
C5—C4—S6	124.9 (2)	C27—C26—H26	119.9
S8—C4—S6	119.53 (18)	C25—C26—H26	119.9
C4—C5—S9	117.1 (2)	C28—C27—C26	120.5 (3)
C4—C5—S7	124.0 (2)	C28—C27—H27	119.8
S9—C5—S7	118.88 (17)	C26—C27—H27	119.8
S10—C6—S9	122.9 (2)	C27—C28—C29	119.9 (3)
S10—C6—S8	124.0 (2)	C27—C28—H28	120.0
S9—C6—S8	113.16 (19)	C29—C28—H28	120.0
C12—C7—C8	119.5 (3)	C28—C29—C30	120.0 (3)
C12—C7—P1	122.7 (2)	C28—C29—H29	120.0
C8—C7—P1	117.6 (2)	C30—C29—H29	120.0
C9—C8—C7	120.1 (3)	C25—C30—C29	120.0 (3)
C9—C8—H8	119.9	C25—C30—H30	120.0
C7—C8—H8	119.9	C29—C30—H30	120.0
C8—C9—C10	120.2 (3)	C7—P1—C7^i	105.24 (18)
C8—C9—H9	119.9	C7—P1—C13	111.92 (12)
C10—C9—H9	119.9	C7^i—P1—C13	110.91 (12)
C11—C10—C9	120.1 (3)	C7—P1—C13^i	110.91 (12)
C11—C10—H10	119.9	C7^i—P1—C13^i	111.92 (12)
C9—C10—H10	119.9	C13—P1—C13^i	106.06 (18)
C10—C11—C12	120.5 (3)	C19—P2—C19^ii	105.36 (19)
C10—C11—H11	119.7	C19—P2—C25	110.98 (13)
C12—C11—H11	119.7	C19^ii—P2—C25	111.10 (12)
C7—C12—C11	119.5 (3)	C19—P2—C25^ii	111.10 (12)
C7—C12—H12	120.3	C19^ii—P2—C25^ii	110.98 (13)
C11—C12—H12	120.3	C25—P2—C25^ii	107.36 (19)
C14—C13—C18	119.6 (3)	C1—S2—C2	97.48 (15)
C14—C13—P1	122.1 (2)	C1—S3—C3	97.53 (15)
C18—C13—P1	118.1 (2)	C2—S4—Au1	99.44 (10)
C13—C14—C15	119.1 (3)	C3—S5—Au1	99.35 (9)
C13—C14—H14	120.5	C4—S6—Au1	99.27 (10)
C15—C14—H14	120.5	C5—S7—Au1	100.09 (10)
C16—C15—C14	120.9 (3)	C6—S8—C4	97.25 (16)
C16—C15—H15	119.6	C6—S9—C5	96.93 (16)
C14—C15—H15	119.6	C32—C31—H31A	109.5
C15—C16—C17	120.2 (3)	C32—C31—H31B	109.5
C15—C16—H16	119.9	H31A—C31—H31B	109.5
C17—C16—H16	119.9	C32—C31—H31C	109.5
C18—C17—C16	120.1 (3)	H31A—C31—H31C	109.5
C18—C17—H17	119.9	H31B—C31—H31C	109.5
C16—C17—H17	119.9	O1—C32—C33	130.7 (9)
C17—C18—C13	120.1 (3)	O1—C32—C31	116.1 (10)
C17—C18—H18	119.9	C33—C32—C31	113.1 (9)
C13—C18—H18	119.9	C32—C33—H33A	109.5
C20—C19—C24	119.5 (3)	C32—C33—H33B	109.5
C20—C19—P2	121.6 (2)	H33A—C33—H33B	109.5
C24—C19—P2	118.7 (2)	C32—C33—H33C	109.5
C19—C20—C21	119.7 (3)	H33A—C33—H33C	109.5
C19—C20—H20	120.2	H33B—C33—H33C	109.5
C21—C20—H20	120.2
S4—C2—C3—S5	0.2 (4)	C14—C13—P1—C7^i	2.3 (3)
S2—C2—C3—S5	−178.12 (17)	C18—C13—P1—C7^i	−172.9 (2)
S4—C2—C3—S3	178.02 (16)	C14—C13—P1—C13^i	124.0 (3)
S2—C2—C3—S3	−0.3 (3)	C18—C13—P1—C13^i	−51.2 (2)
S8—C4—C5—S9	0.1 (4)	C20—C19—P2—C19^ii	124.0 (3)
S6—C4—C5—S9	179.40 (18)	C24—C19—P2—C19^ii	−51.8 (2)
S8—C4—C5—S7	179.68 (17)	C20—C19—P2—C25	3.7 (3)
S6—C4—C5—S7	−1.0 (4)	C24—C19—P2—C25	−172.2 (2)
C12—C7—C8—C9	−0.8 (5)	C20—C19—P2—C25^ii	−115.7 (3)
P1—C7—C8—C9	−177.3 (3)	C24—C19—P2—C25^ii	68.5 (3)
C7—C8—C9—C10	0.4 (5)	C30—C25—P2—C19	112.1 (3)
C8—C9—C10—C11	0.4 (5)	C26—C25—P2—C19	−70.0 (3)
C9—C10—C11—C12	−0.7 (5)	C30—C25—P2—C19^ii	−4.8 (3)
C8—C7—C12—C11	0.5 (4)	C26—C25—P2—C19^ii	173.1 (2)
P1—C7—C12—C11	176.8 (2)	C30—C25—P2—C25^ii	−126.3 (3)
C10—C11—C12—C7	0.2 (5)	C26—C25—P2—C25^ii	51.6 (2)
C18—C13—C14—C15	−0.4 (5)	S1—C1—S2—C2	178.1 (3)
P1—C13—C14—C15	−175.5 (3)	S3—C1—S2—C2	−2.0 (3)
C13—C14—C15—C16	−0.8 (5)	C3—C2—S2—C1	1.4 (3)
C14—C15—C16—C17	1.2 (5)	S4—C2—S2—C1	−177.0 (2)
C15—C16—C17—C18	−0.4 (5)	S1—C1—S3—C3	−178.2 (3)
C16—C17—C18—C13	−0.8 (5)	S2—C1—S3—C3	1.9 (3)
C14—C13—C18—C17	1.2 (4)	C2—C3—S3—C1	−1.0 (3)
P1—C13—C18—C17	176.5 (2)	S5—C3—S3—C1	177.0 (2)
C24—C19—C20—C21	0.0 (5)	C3—C2—S4—Au1	−0.6 (3)
P2—C19—C20—C21	−175.8 (3)	S2—C2—S4—Au1	177.61 (15)
C19—C20—C21—C22	−0.3 (6)	S5—Au1—S4—C2	0.63 (10)
C20—C21—C22—C23	−0.2 (7)	S6—Au1—S4—C2	177.97 (10)
C21—C22—C23—C24	0.9 (6)	C2—C3—S5—Au1	0.4 (3)
C22—C23—C24—C19	−1.1 (5)	S3—C3—S5—Au1	−177.39 (15)
C20—C19—C24—C23	0.7 (5)	S7—Au1—S5—C3	176.82 (10)
P2—C19—C24—C23	176.6 (3)	S4—Au1—S5—C3	−0.58 (10)
C30—C25—C26—C27	−1.0 (5)	C5—C4—S6—Au1	−2.3 (3)
P2—C25—C26—C27	−179.0 (3)	S8—C4—S6—Au1	176.91 (16)
C25—C26—C27—C28	0.4 (5)	S7—Au1—S6—C4	3.42 (11)
C26—C27—C28—C29	0.4 (6)	S4—Au1—S6—C4	−179.13 (11)
C27—C28—C29—C30	−0.7 (6)	C4—C5—S7—Au1	3.8 (3)
C26—C25—C30—C29	0.7 (5)	S9—C5—S7—Au1	−176.69 (15)
P2—C25—C30—C29	178.6 (3)	S5—Au1—S7—C5	173.48 (11)
C28—C29—C30—C25	0.2 (6)	S6—Au1—S7—C5	−3.80 (11)
C12—C7—P1—C7^i	−123.6 (3)	S10—C6—S8—C4	179.1 (3)
C8—C7—P1—C7^i	52.7 (2)	S9—C6—S8—C4	−1.5 (3)
C12—C7—P1—C13	−3.1 (3)	C5—C4—S8—C6	0.8 (3)
C8—C7—P1—C13	173.3 (2)	S6—C4—S8—C6	−178.5 (2)
C12—C7—P1—C13^i	115.2 (2)	S10—C6—S9—C5	−179.1 (3)
C8—C7—P1—C13^i	−68.5 (3)	S8—C6—S9—C5	1.5 (3)
C14—C13—P1—C7	−115.0 (3)	C4—C5—S9—C6	−1.0 (3)
C18—C13—P1—C7	69.9 (3)	S7—C5—S9—C6	179.4 (2)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+2, y, −z+3/2.

(II) ethyltriphenylphosphonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)aurate(III)

Crystal data

(C20H20P)[Au(C3S5)2]	F(000) = 1720
Mr = 880.96	Dx = 1.840 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7323 reflections
a = 17.3058 (2) Å	θ = 2.2–25.1°
b = 9.9306 (1) Å	µ = 5.35 mm^−1
c = 19.0668 (2) Å	T = 296 K
β = 103.959 (1)°	Prism, brown
V = 3179.99 (6) Å^3	0.24 × 0.17 × 0.13 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	7292 independent reflections
Radiation source: fine-focus sealed tube	5381 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ϕ and ω scans	θmax = 27.5°, θmin = 1.4°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −22→22
Tmin = 0.361, Tmax = 0.536	k = −12→12
22548 measured reflections	l = −24→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.057	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0231P)^2 + 0.4583P] where P = (Fo^2 + 2Fc^2)/3
7292 reflections	(Δ/σ)max = 0.004
344 parameters	Δρmax = 0.80 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

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 > σ(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 (Ų)

	x	y	z	Uiso*/Ueq
Au1	0.516859 (7)	0.169589 (14)	0.569909 (7)	0.05201 (5)
C1	0.23676 (19)	0.3873 (4)	0.61700 (18)	0.0583 (9)
C2	0.35561 (18)	0.2309 (4)	0.60940 (18)	0.0547 (8)
C3	0.36701 (18)	0.3427 (3)	0.57426 (18)	0.0515 (8)
C4	0.66656 (18)	−0.0074 (4)	0.57120 (18)	0.0569 (8)
C5	0.68057 (18)	0.1036 (4)	0.53625 (17)	0.0541 (8)
C6	0.80389 (19)	−0.0540 (4)	0.54034 (18)	0.0613 (9)
C7	0.4048 (2)	0.5503 (4)	0.8277 (2)	0.0688 (10)
H7	0.3937	0.6375	0.8401	0.083*
C8	0.3622 (3)	0.4440 (5)	0.8459 (2)	0.0871 (13)
H8	0.3221	0.4599	0.8697	0.104*
C9	0.3786 (3)	0.3175 (5)	0.8290 (3)	0.0901 (14)
H9	0.3502	0.2461	0.8421	0.108*
C10	0.4361 (3)	0.2923 (4)	0.7932 (3)	0.0865 (13)
H10	0.4466	0.2041	0.7819	0.104*
C11	0.4796 (2)	0.3982 (4)	0.7733 (2)	0.0733 (11)
H11	0.5185	0.3813	0.7483	0.088*
C12	0.46378 (18)	0.5292 (3)	0.79147 (17)	0.0516 (8)
C13	0.6044 (2)	0.5624 (5)	0.6776 (2)	0.0933 (15)
H13	0.5569	0.5377	0.6457	0.112*
C14	0.6763 (3)	0.5319 (5)	0.6614 (3)	0.1048 (16)
H14	0.6767	0.4853	0.6192	0.126*
C15	0.7455 (3)	0.5691 (5)	0.7062 (3)	0.0973 (16)
H15	0.7934	0.5466	0.6953	0.117*
C16	0.7458 (2)	0.6404 (5)	0.7686 (2)	0.0889 (14)
H16	0.7937	0.6687	0.7986	0.107*
C17	0.6746 (2)	0.6695 (4)	0.7859 (2)	0.0690 (11)
H17	0.6745	0.7163	0.8281	0.083*
C18	0.60295 (19)	0.6286 (4)	0.74024 (19)	0.0594 (9)
C19	0.54222 (19)	0.9288 (4)	0.8148 (2)	0.0635 (10)
H19	0.5340	0.9546	0.7667	0.076*
C20	0.5651 (2)	1.0231 (4)	0.8687 (3)	0.0740 (11)
H20	0.5731	1.1121	0.8571	0.089*
C21	0.5759 (2)	0.9858 (5)	0.9391 (3)	0.0785 (12)
H21	0.5910	1.0500	0.9753	0.094*
C22	0.5650 (2)	0.8558 (5)	0.9574 (2)	0.0789 (12)
H22	0.5721	0.8317	1.0057	0.095*
C23	0.5431 (2)	0.7593 (4)	0.9034 (2)	0.0638 (9)
H23	0.5365	0.6701	0.9155	0.077*
C24	0.53134 (17)	0.7957 (3)	0.83187 (18)	0.0516 (8)
C25	0.44500 (18)	0.7354 (4)	0.68109 (17)	0.0571 (9)
H25A	0.4691	0.8148	0.6657	0.068*
H25B	0.4404	0.6682	0.6434	0.068*
C26	0.36185 (19)	0.7719 (4)	0.6877 (2)	0.0678 (10)
H26A	0.3357	0.6927	0.6994	0.102*
H26B	0.3319	0.8082	0.6426	0.102*
H26C	0.3653	0.8378	0.7251	0.102*
P1	0.51085 (5)	0.67177 (9)	0.76198 (5)	0.0494 (2)
S1	0.15650 (6)	0.45163 (12)	0.63482 (6)	0.0814 (3)
S2	0.27188 (5)	0.22832 (10)	0.64467 (5)	0.0638 (2)
S3	0.29482 (5)	0.46755 (10)	0.56763 (5)	0.0659 (3)
S4	0.41871 (5)	0.09184 (10)	0.62318 (6)	0.0659 (3)
S5	0.44766 (5)	0.36954 (10)	0.53575 (6)	0.0660 (3)
S6	0.58309 (5)	−0.03155 (10)	0.60555 (5)	0.0669 (3)
S7	0.61831 (5)	0.24389 (10)	0.51903 (5)	0.0610 (2)
S8	0.73882 (6)	−0.13432 (11)	0.58270 (6)	0.0723 (3)
S9	0.76890 (5)	0.10384 (11)	0.50763 (5)	0.0627 (2)
S10	0.88848 (6)	−0.11736 (13)	0.53239 (7)	0.0858 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.05089 (8)	0.05820 (10)	0.04816 (8)	−0.00804 (6)	0.01430 (5)	−0.00256 (7)
C1	0.0574 (19)	0.063 (2)	0.053 (2)	−0.0057 (17)	0.0110 (16)	0.0054 (19)
C2	0.0487 (18)	0.060 (2)	0.056 (2)	−0.0077 (16)	0.0138 (15)	0.0003 (19)
C3	0.0514 (18)	0.051 (2)	0.053 (2)	−0.0054 (15)	0.0137 (15)	0.0002 (17)
C4	0.0537 (18)	0.061 (2)	0.053 (2)	−0.0022 (17)	0.0086 (15)	−0.001 (2)
C5	0.0512 (18)	0.067 (2)	0.0437 (19)	−0.0043 (16)	0.0114 (15)	−0.0050 (18)
C6	0.061 (2)	0.070 (2)	0.050 (2)	0.0018 (17)	0.0081 (16)	−0.0041 (19)
C7	0.086 (3)	0.051 (2)	0.078 (3)	0.0000 (19)	0.035 (2)	0.006 (2)
C8	0.107 (3)	0.069 (3)	0.095 (3)	−0.014 (3)	0.045 (3)	0.004 (3)
C9	0.108 (4)	0.067 (3)	0.091 (3)	−0.013 (3)	0.016 (3)	0.011 (3)
C10	0.100 (3)	0.045 (2)	0.101 (4)	0.003 (2)	−0.002 (3)	−0.002 (2)
C11	0.069 (2)	0.071 (3)	0.075 (3)	0.011 (2)	0.007 (2)	−0.013 (2)
C12	0.0575 (19)	0.048 (2)	0.0463 (19)	0.0056 (15)	0.0058 (15)	0.0018 (17)
C13	0.069 (2)	0.134 (4)	0.078 (3)	0.005 (3)	0.021 (2)	−0.042 (3)
C14	0.096 (3)	0.132 (5)	0.097 (4)	0.008 (3)	0.044 (3)	−0.043 (3)
C15	0.078 (3)	0.124 (4)	0.100 (4)	0.035 (3)	0.043 (3)	0.013 (3)
C16	0.057 (2)	0.132 (4)	0.077 (3)	0.019 (2)	0.015 (2)	0.021 (3)
C17	0.057 (2)	0.103 (3)	0.048 (2)	0.018 (2)	0.0134 (16)	0.009 (2)
C18	0.0536 (19)	0.069 (2)	0.057 (2)	0.0065 (17)	0.0162 (17)	−0.001 (2)
C19	0.059 (2)	0.065 (3)	0.065 (2)	−0.0011 (18)	0.0129 (18)	0.000 (2)
C20	0.071 (2)	0.055 (2)	0.095 (3)	−0.0036 (19)	0.016 (2)	−0.008 (3)
C21	0.070 (2)	0.078 (3)	0.081 (3)	0.007 (2)	0.006 (2)	−0.030 (3)
C22	0.084 (3)	0.091 (4)	0.056 (2)	0.014 (2)	0.005 (2)	−0.012 (3)
C23	0.073 (2)	0.059 (2)	0.055 (2)	0.0109 (18)	0.0069 (18)	−0.003 (2)
C24	0.0419 (16)	0.059 (2)	0.052 (2)	0.0050 (15)	0.0088 (14)	−0.0045 (18)
C25	0.059 (2)	0.066 (2)	0.045 (2)	−0.0056 (17)	0.0094 (15)	0.0055 (19)
C26	0.056 (2)	0.084 (3)	0.060 (2)	0.0087 (19)	0.0068 (17)	0.008 (2)
P1	0.0472 (4)	0.0557 (5)	0.0454 (5)	0.0040 (4)	0.0110 (4)	−0.0013 (4)
S1	0.0747 (6)	0.0850 (8)	0.0931 (8)	0.0171 (5)	0.0372 (6)	0.0155 (7)
S2	0.0552 (5)	0.0650 (6)	0.0764 (6)	0.0000 (4)	0.0261 (4)	0.0161 (5)
S3	0.0661 (5)	0.0566 (6)	0.0793 (7)	0.0004 (4)	0.0258 (5)	0.0131 (5)
S4	0.0664 (5)	0.0563 (6)	0.0832 (7)	0.0015 (5)	0.0341 (5)	0.0131 (5)
S5	0.0624 (5)	0.0642 (6)	0.0783 (7)	−0.0047 (4)	0.0305 (5)	0.0157 (5)
S6	0.0604 (5)	0.0659 (6)	0.0786 (7)	−0.0058 (4)	0.0248 (5)	0.0112 (5)
S7	0.0589 (5)	0.0636 (6)	0.0659 (6)	−0.0007 (4)	0.0256 (4)	0.0095 (5)
S8	0.0710 (6)	0.0658 (6)	0.0814 (7)	0.0044 (5)	0.0207 (5)	0.0068 (6)
S9	0.0552 (5)	0.0774 (7)	0.0583 (6)	0.0029 (5)	0.0189 (4)	0.0060 (5)
S10	0.0679 (6)	0.0973 (8)	0.0922 (8)	0.0212 (6)	0.0193 (6)	0.0041 (7)

Geometric parameters (Å, º)

Au1—S4	2.3119 (8)	C13—C18	1.369 (5)
Au1—S6	2.3215 (10)	C13—C14	1.386 (5)
Au1—S7	2.3215 (8)	C13—H13	0.9300
Au1—S5	2.3291 (10)	C14—C15	1.343 (6)
C1—S1	1.637 (3)	C14—H14	0.9300
C1—S3	1.728 (3)	C15—C16	1.383 (6)
C1—S2	1.728 (4)	C15—H15	0.9300
C2—C3	1.336 (5)	C16—C17	1.380 (5)
C2—S2	1.739 (3)	C16—H16	0.9300
C2—S4	1.740 (4)	C17—C18	1.393 (5)
C3—S3	1.743 (3)	C17—H17	0.9300
C3—S5	1.747 (3)	C18—P1	1.793 (3)
C4—C5	1.340 (5)	C19—C20	1.376 (5)
C4—S6	1.741 (3)	C19—C24	1.385 (5)
C4—S8	1.751 (3)	C19—H19	0.9300
C5—S9	1.743 (3)	C20—C21	1.362 (6)
C5—S7	1.743 (4)	C20—H20	0.9300
C6—S10	1.634 (3)	C21—C22	1.362 (6)
C6—S8	1.731 (4)	C21—H21	0.9300
C6—S9	1.741 (4)	C22—C23	1.391 (5)
C7—C8	1.379 (5)	C22—H22	0.9300
C7—C12	1.379 (4)	C23—C24	1.377 (5)
C7—H7	0.9300	C23—H23	0.9300
C8—C9	1.344 (6)	C24—P1	1.785 (3)
C8—H8	0.9300	C25—C26	1.518 (4)
C9—C10	1.359 (6)	C25—P1	1.797 (3)
C9—H9	0.9300	C25—H25A	0.9700
C10—C11	1.398 (6)	C25—H25B	0.9700
C10—H10	0.9300	C26—H26A	0.9600
C11—C12	1.390 (5)	C26—H26B	0.9600
C11—H11	0.9300	C26—H26C	0.9600
C12—P1	1.791 (3)
S4—Au1—S6	86.97 (3)	C17—C16—H16	120.2
S4—Au1—S7	178.22 (3)	C15—C16—H16	120.2
S6—Au1—S7	91.49 (3)	C16—C17—C18	120.0 (4)
S4—Au1—S5	91.43 (3)	C16—C17—H17	120.0
S6—Au1—S5	178.40 (3)	C18—C17—H17	120.0
S7—Au1—S5	90.11 (3)	C13—C18—C17	119.0 (3)
S1—C1—S3	124.6 (2)	C13—C18—P1	121.4 (3)
S1—C1—S2	123.1 (2)	C17—C18—P1	119.5 (3)
S3—C1—S2	112.30 (19)	C20—C19—C24	120.3 (4)
C3—C2—S2	116.3 (3)	C20—C19—H19	119.8
C3—C2—S4	124.9 (2)	C24—C19—H19	119.8
S2—C2—S4	118.8 (2)	C21—C20—C19	119.9 (4)
C2—C3—S3	116.0 (2)	C21—C20—H20	120.1
C2—C3—S5	124.5 (3)	C19—C20—H20	120.1
S3—C3—S5	119.51 (19)	C22—C21—C20	121.1 (4)
C5—C4—S6	124.5 (3)	C22—C21—H21	119.5
C5—C4—S8	116.4 (2)	C20—C21—H21	119.5
S6—C4—S8	119.1 (2)	C21—C22—C23	119.5 (4)
C4—C5—S9	115.8 (3)	C21—C22—H22	120.2
C4—C5—S7	125.0 (2)	C23—C22—H22	120.2
S9—C5—S7	119.3 (2)	C24—C23—C22	120.1 (4)
S10—C6—S8	124.3 (2)	C24—C23—H23	119.9
S10—C6—S9	123.8 (2)	C22—C23—H23	119.9
S8—C6—S9	111.89 (19)	C23—C24—C19	119.1 (3)
C8—C7—C12	121.0 (4)	C23—C24—P1	120.9 (3)
C8—C7—H7	119.5	C19—C24—P1	119.8 (3)
C12—C7—H7	119.5	C26—C25—P1	115.5 (2)
C9—C8—C7	119.9 (4)	C26—C25—H25A	108.4
C9—C8—H8	120.0	P1—C25—H25A	108.4
C7—C8—H8	120.0	C26—C25—H25B	108.4
C8—C9—C10	121.0 (4)	P1—C25—H25B	108.4
C8—C9—H9	119.5	H25A—C25—H25B	107.5
C10—C9—H9	119.5	C25—C26—H26A	109.5
C9—C10—C11	120.3 (4)	C25—C26—H26B	109.5
C9—C10—H10	119.8	H26A—C26—H26B	109.5
C11—C10—H10	119.8	C25—C26—H26C	109.5
C12—C11—C10	119.0 (4)	H26A—C26—H26C	109.5
C12—C11—H11	120.5	H26B—C26—H26C	109.5
C10—C11—H11	120.5	C24—P1—C12	109.53 (16)
C7—C12—C11	118.7 (3)	C24—P1—C18	108.04 (16)
C7—C12—P1	119.0 (3)	C12—P1—C18	112.37 (16)
C11—C12—P1	122.0 (3)	C24—P1—C25	111.65 (17)
C18—C13—C14	120.4 (4)	C12—P1—C25	107.78 (15)
C18—C13—H13	119.8	C18—P1—C25	107.51 (16)
C14—C13—H13	119.8	C1—S2—C2	97.65 (17)
C15—C14—C13	120.5 (4)	C1—S3—C3	97.67 (17)
C15—C14—H14	119.7	C2—S4—Au1	99.75 (11)
C13—C14—H14	119.7	C3—S5—Au1	99.30 (12)
C14—C15—C16	120.4 (4)	C4—S6—Au1	99.63 (13)
C14—C15—H15	119.8	C5—S7—Au1	99.36 (11)
C16—C15—H15	119.8	C6—S8—C4	97.78 (17)
C17—C16—C15	119.6 (4)	C6—S9—C5	98.17 (17)
S2—C2—C3—S3	−1.3 (4)	C11—C12—P1—C25	95.4 (3)
S4—C2—C3—S3	179.9 (2)	C13—C18—P1—C24	−163.6 (4)
S2—C2—C3—S5	178.82 (19)	C17—C18—P1—C24	12.8 (4)
S4—C2—C3—S5	0.0 (5)	C13—C18—P1—C12	75.4 (4)
S6—C4—C5—S9	179.55 (19)	C17—C18—P1—C12	−108.1 (3)
S8—C4—C5—S9	0.0 (4)	C13—C18—P1—C25	−43.0 (4)
S6—C4—C5—S7	0.2 (5)	C17—C18—P1—C25	133.4 (3)
S8—C4—C5—S7	−179.30 (19)	C26—C25—P1—C24	−64.3 (3)
C12—C7—C8—C9	0.9 (7)	C26—C25—P1—C12	56.0 (3)
C7—C8—C9—C10	−1.0 (8)	C26—C25—P1—C18	177.3 (3)
C8—C9—C10—C11	0.1 (7)	S1—C1—S2—C2	−179.0 (2)
C9—C10—C11—C12	0.8 (6)	S3—C1—S2—C2	2.1 (2)
C8—C7—C12—C11	0.1 (6)	C3—C2—S2—C1	−0.5 (3)
C8—C7—C12—P1	174.3 (3)	S4—C2—S2—C1	178.4 (2)
C10—C11—C12—C7	−0.9 (5)	S1—C1—S3—C3	178.4 (2)
C10—C11—C12—P1	−174.9 (3)	S2—C1—S3—C3	−2.7 (2)
C18—C13—C14—C15	−1.3 (8)	C2—C3—S3—C1	2.4 (3)
C13—C14—C15—C16	−1.1 (9)	S5—C3—S3—C1	−177.7 (2)
C14—C15—C16—C17	2.2 (8)	C3—C2—S4—Au1	2.2 (3)
C15—C16—C17—C18	−0.9 (6)	S2—C2—S4—Au1	−176.63 (17)
C14—C13—C18—C17	2.5 (7)	S6—Au1—S4—C2	177.37 (12)
C14—C13—C18—P1	179.0 (4)	S5—Au1—S4—C2	−2.56 (12)
C16—C17—C18—C13	−1.4 (6)	C2—C3—S5—Au1	−2.1 (3)
C16—C17—C18—P1	−178.0 (3)	S3—C3—S5—Au1	177.98 (17)
C24—C19—C20—C21	−1.0 (5)	S4—Au1—S5—C3	2.54 (12)
C19—C20—C21—C22	0.4 (6)	S7—Au1—S5—C3	−176.55 (12)
C20—C21—C22—C23	0.6 (6)	C5—C4—S6—Au1	1.0 (3)
C21—C22—C23—C24	−1.1 (6)	S8—C4—S6—Au1	−179.47 (17)
C22—C23—C24—C19	0.6 (5)	S4—Au1—S6—C4	179.56 (12)
C22—C23—C24—P1	175.1 (3)	S7—Au1—S6—C4	−1.35 (12)
C20—C19—C24—C23	0.5 (5)	C4—C5—S7—Au1	−1.3 (3)
C20—C19—C24—P1	−174.1 (3)	S9—C5—S7—Au1	179.37 (17)
C23—C24—P1—C12	27.1 (3)	S6—Au1—S7—C5	1.41 (12)
C19—C24—P1—C12	−158.4 (2)	S5—Au1—S7—C5	−178.68 (12)
C23—C24—P1—C18	−95.6 (3)	S10—C6—S8—C4	179.0 (2)
C19—C24—P1—C18	78.9 (3)	S9—C6—S8—C4	−0.6 (2)
C23—C24—P1—C25	146.4 (3)	C5—C4—S8—C6	0.3 (3)
C19—C24—P1—C25	−39.1 (3)	S6—C4—S8—C6	−179.2 (2)
C7—C12—P1—C24	43.0 (3)	S10—C6—S9—C5	−178.9 (2)
C11—C12—P1—C24	−143.0 (3)	S8—C6—S9—C5	0.6 (2)
C7—C12—P1—C18	163.1 (3)	C4—C5—S9—C6	−0.4 (3)
C11—C12—P1—C18	−22.9 (3)	S7—C5—S9—C6	179.0 (2)
C7—C12—P1—C25	−78.7 (3)