μ3-Oxido-tris­{dichlorido[1,3-bis­(1,3,5-trimethyl­phen­yl)imidazol-2-yl­idene]gold(III)} bis­(trifluoro­methane­sulfon­yl)imide–[bis­(trifluoro­methane­sulfon­yl)imide]­silver(I) (1/2)

Pažický, M.; Rominger, F.; Limbach, M.

doi:10.1107/S160053681001994X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages m724-m725

doi:10.1107/S160053681001994X

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μ₃-Oxido-tris{dichlorido[1,3-bis(1,3,5-trimethylphenyl)imidazol-2-ylidene]gold(III)} bis(trifluoromethanesulfonyl)imide–[bis(trifluoromethanesulfonyl)imide]silver(I) (1/2)

Marek Pažický,^a Frank Rominger ^b and Michael Limbach ^a ^*

^aCaRLa – Catalysis Research Laboratory, Universität Heidelberg, Im Neuenheimer Feld 584, D-69120 Heidelberg, Germany, and ^bOrganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
^*Correspondence e-mail: michael.limbach@basf.com

(Received 20 May 2010; accepted 26 May 2010; online 5 June 2010)

The unusual trinuclear Au^III oxide title complex, [Au₃Cl₆O(C₂₁H₂₄N₂)₃](C₂F₆NO₄S₂)·2[Ag(C₂F₆NO₄S₂)], is the side product of the reaction of [1,3-bis(1,3,5-trimethylphenyl)imidazol-2-ylidene]dichloridophenylgold(III) with silver bis(trifluoromethanesulfonyl)imide in the presence of traces of water. In contrast to corresponding Au^I complexes, the core structure of the title compound is planar. Two silver(I) bis(trifluoromethanesulfonyl)imide units are loosely bound to the complex cation. Here the silver atoms, disordered over two positions in a 0.870 (2):0.130 (2) ratio, interact either with the lone pairs of three chlorine ligands or two chlorine ligands and one edge of the mesityl π-system. The crystal under investigation was a partial racemic twin.

Related literature

Tris[(phosphane)gold(I)]oxonium ions are a convenient source for (phosphane)gold cations see: Nesmeyanov et al. (1980 ). For the trigonal-pyramidal structure of these trinuclear complexes, see, for example: Yang et al. (1993 ); Schmidbaur et al. (1993 ); Angermaier & Schmidbaur (1994 , 1995 ). For the silver coordination of the bis(trifluoromethanesulfonyl)imide anion via oxygen, see: Nockemann et al. (2008 ). For details of the preparation, see: Pažický et al. (2010 ).

Experimental

Crystal data

[Au₃Cl₆O(C₂₁H₂₄N₂)₃](C₂F₆NO₄S₂)·2[Ag(C₂F₆NO₄S₂)]
M_r = 2789.06
Tetragonal, P 4₃ 2₁ 2
a = 13.9472 (9) Å
c = 45.724 (3) Å
V = 8894.5 (10) Å³
Z = 4
Mo Kα radiation
μ = 5.79 mm⁻¹
T = 200 K
0.25 × 0.17 × 0.11 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.326, T_max = 0.569
93947 measured reflections
11087 independent reflections
10564 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.094
S = 1.27
11087 reflections
581 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 1.65 e Å⁻³
Δρ_min = −1.45 e Å⁻³
Absolute structure: Flack (1983 ), 4737 Friedel pairs
Flack parameter: 0.396 (7)

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008b ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681001994X/hg2690sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681001994X/hg2690Isup2.hkl

checkCIF report

Comment top

The structure of the title compound consists of a trinuclear complex cation around a central oxygen atom with a trigonal planar Au^III environment. Loosley bound to this cation are two silver bis(trifluoromethanesulfonyl)imide moieties with a twofold disordered silver position. Finally there is another free bis(trifluoromethanesulfonyl)imide anion to compensate the charge of the cation. Although tris[(phosphane)gold(I)]oxonium ions are a well known source for LAu+ as shown by Nesmeyanov et al. (1980), to the best of our knowledge there have been no reports on trimeric [Au₃O]⁺ complexes with N-heterocyclic carbenes or generally [Au^IIIO]⁺ complexes in the literature before.

Both, the trinuclear cation and the free imide anion reside at a special position on a crystallographic twofold axis. The non-crystallographic symmetry of the cation is D₃. Thus, in contrast to corresponding [(LAu^I)₃O]⁺ complexes with pyramidal geometry (e.g. Yang et al., 1993; Schmidbaur et al., 1993; Angermaier & Schmidbaur, 1994, 1995), the structure of the Au^III₃O core of the title compound is flat. Therefore the Au···Au distances are with 3.4655 (5) and 3.5688 (6) Å necessarily much longer than in the Au^I complexes and we assume no aurophilic interactions. The Au—O distances amount to 2.046 (7) and 2.010 (3) Å, the Au—C_NHC distances to 2.018 (12) and 1.982 (7) Å. The Cl—Au—Cl axes are inclined with respect to the Au₃O plane by about 37.0° and 42.0°, which leads to a octahedral chlorine environment for the central oxygen atom with Cl···O distances between 2.986 (5) and 2.996 (5) Å, which is clearly below the van der Waals distance (3.27 Å). As already mentioned two Ag[N(SO₂CF₃)₂] units are loosley bound to this cation. Remarkably there are two alternative positions for the silver center which are occupied by 87% and 13% resp. At the main position the silver is in contact with three chlorine atoms of the cation (Ag···Cl between 2.644 (2) and 2.769 (3) Å), at the alternative position among two chlorine atoms (Ag···Cl 2.302 (8) and 2.754 (8) Å) the silver contacts one edge of the mesityl π-system (Ag···C 2.544 (12) and 2.587 (13) Å). The distorted tetrahedral environment of the silver centers is completed in both cases remarkably with an oxygen atom of the bis(trifluoromethanesulfonyl)imide anion (Ag···O 2.340 (7) and 2.342 (10) Å) rather than the nitrogen. This unexpected coordination mode of the bis(trifluoromethanesulfonyl)imide anion has been observed before by Nockemann et al. (2008).

Related literature top

Tris[(phosphane)gold(I)]oxonium ions are a convenient source for LAu⁺ [define L], see: as Nesmeyanov et al. (1980). For the trigonal pyramidal structure of these trinuclear complexes, see, for example: Yang et al. (1993); Schmidbaur et al. (1993); Angermaier & Schmidbaur (1994, 1995). For the silver coordination of the bis(trifluoromethanesulfonyl)imide anion via oxygen, see: Nockemann et al. (2008). For details of the preparation, see: Pažický et al. (2010).

Experimental top

To a solution of phenyldichloro-1,3-bis(1,3,5-trimethylphenyl)imidazol-2-ylidene gold(III) (20 mg, 30.8 µmol) in dry d2-dichloromethane, as described by Pažický et al. (2010), silver bis(trifluoromethanesulfonyl)imide (12 mg, 30.8 µmol) was added at room temperature. The solution was stirred for five minutes and filtered over celite. Yellow crystals of the title compound besides white crystals of dichloro-1,3-bis(1,3,5-trimethylphenyl)imidazol-2-ylidene gold(III) bis(trifluoromethanesulfonyl)imide were obtained by slow diffusion of the concentrated filtrate of the crude product into pentane at 8 °C.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008b); program(s) used to refine structure: SHELXTL (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top

Fig. 1. Thermal ellipsoid representation of the trinuclear oxo cation of the title compound. Displacement ellipsoids were plotted at 50% probability level. Hydrogen atoms, the anion and the silver moiety are omitted for the sake of clarity.

Fig. 2. Both alternative silver positions (87% Ag3:13% Ag3B) and their coordination modes to the trinuclear oxo cation in a simple ball and stick representation. From the bis(trifluoromethanesulfonyl)imide anion coordinated to the silver only the coordinating oxygen atom (O11) is shown for clarity. Due to the 2-fold symmetry the same pattern is found at the reverse side of the cation, which is omitted for the sake of clarity as well.

µ₃-Oxido-tris{dichlorido[1,3-bis(1,3,5-trimethylphenyl)imidazol-2-ylidene]gold(III)} bis(trifluoromethanesulfonyl)imide–[bis(trifluoromethanesulfonyl)imide]silver(I) (1/2) top

Crystal data top

[Au₃Cl₆O(C₂₁H₂₄N₂)₃](C₂F₆NO₄S₂)·[Ag(C₂F₆NO₄S₂)]₂	D_x = 2.083 Mg m⁻³
M_r = 2789.06	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₃2₁2	Cell parameters from 7947 reflections
Hall symbol: P 4nw 2abw	θ = 2.3–26.5°
a = 13.9472 (9) Å	µ = 5.79 mm⁻¹
c = 45.724 (3) Å	T = 200 K
V = 8894.5 (10) Å³	Polyhedron, orange
Z = 4	0.25 × 0.17 × 0.11 mm
F(000) = 5376

Data collection top

Bruker SMART APEX diffractometer	11087 independent reflections
Radiation source: fine-focus sealed tube	10564 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
ω scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −18→18
T_min = 0.326, T_max = 0.569	k = −18→18
93947 measured reflections	l = −61→59

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0179P)² + 57.4255P] where P = (F_o² + 2F_c²)/3
S = 1.27	(Δ/σ)_max = 0.001
11087 reflections	Δρ_max = 1.65 e Å⁻³
581 parameters	Δρ_min = −1.45 e Å⁻³
12 restraints	Absolute structure: Flack (1983), 4737 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.396 (7)

Crystal data top

[Au₃Cl₆O(C₂₁H₂₄N₂)₃](C₂F₆NO₄S₂)·[Ag(C₂F₆NO₄S₂)]₂	Z = 4
M_r = 2789.06	Mo Kα radiation
Tetragonal, P4₃2₁2	µ = 5.79 mm⁻¹
a = 13.9472 (9) Å	T = 200 K
c = 45.724 (3) Å	0.25 × 0.17 × 0.11 mm
V = 8894.5 (10) Å³

Data collection top

Bruker SMART APEX diffractometer	11087 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	10564 reflections with I > 2σ(I)
T_min = 0.326, T_max = 0.569	R_int = 0.068
93947 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0179P)² + 57.4255P] where P = (F_o² + 2F_c²)/3
S = 1.27	Δρ_max = 1.65 e Å⁻³
11087 reflections	Δρ_min = −1.45 e Å⁻³
581 parameters	Absolute structure: Flack (1983), 4737 Friedel pairs
12 restraints	Absolute structure parameter: 0.396 (7)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Au1	0.47994 (2)	0.47994 (2)	0.0000	0.01855 (9)
Cl1	0.49234 (17)	0.47738 (18)	0.04966 (4)	0.0362 (5)
Au2	0.56741 (2)	0.69371 (2)	0.027945 (7)	0.01900 (7)
Cl2	0.41769 (15)	0.71618 (17)	0.00937 (5)	0.0337 (5)
Cl3	0.71719 (17)	0.6628 (2)	0.04497 (7)	0.0477 (7)
O1	0.5837 (3)	0.5837 (3)	0.0000	0.0284 (19)
Ag3	0.46707 (8)	0.68405 (8)	−0.04559 (2)	0.0536 (3)	0.870 (2)
Ag3B	0.5271 (5)	0.8028 (6)	−0.03324 (15)	0.058 (2)	0.130 (2)
C1	0.3776 (6)	0.3776 (6)	0.0000	0.037 (3)
N2	0.3920 (5)	0.2874 (5)	0.00768 (19)	0.037 (2)
C3	0.3046 (7)	0.2407 (7)	0.0040 (3)	0.062 (4)
H3	0.2933	0.1741	0.0067	0.074*
C6	0.5503 (6)	0.8017 (6)	0.05561 (17)	0.0222 (16)
N7	0.5764 (6)	0.8943 (5)	0.05029 (17)	0.0308 (17)
C8	0.5536 (8)	0.9498 (7)	0.0742 (2)	0.044 (3)
H8	0.5645	1.0166	0.0763	0.053*
C9	0.5128 (9)	0.8909 (7)	0.0937 (2)	0.047 (3)
H9	0.4893	0.9089	0.1124	0.056*
N10	0.5109 (6)	0.8000 (5)	0.08202 (15)	0.0286 (16)
C11	0.4835 (7)	0.2484 (6)	0.0171 (2)	0.0332 (19)
C12	0.4957 (11)	0.2391 (7)	0.0473 (2)	0.058 (4)
C13	0.5888 (12)	0.2127 (7)	0.0558 (2)	0.062 (4)
H13	0.6021	0.2046	0.0760	0.075*
C14	0.6622 (9)	0.1978 (7)	0.0358 (2)	0.045 (3)
C15	0.6394 (8)	0.1980 (7)	0.0071 (2)	0.037 (2)
H15	0.6862	0.1773	−0.0066	0.045*
C16	0.5505 (7)	0.2271 (6)	−0.0033 (2)	0.033 (2)
C17	0.4194 (14)	0.2516 (10)	0.0696 (3)	0.101 (7)
H17A	0.3590	0.2686	0.0599	0.152*
H17B	0.4377	0.3029	0.0832	0.152*
H17C	0.4110	0.1917	0.0805	0.152*
C18	0.7632 (11)	0.1742 (9)	0.0464 (3)	0.074 (5)
H18A	0.8061	0.1674	0.0296	0.112*
H18B	0.7620	0.1140	0.0575	0.112*
H18C	0.7864	0.2260	0.0591	0.112*
C19	0.5314 (7)	0.2320 (7)	−0.0354 (2)	0.037 (2)
H19A	0.5889	0.2121	−0.0461	0.056*
H19B	0.5147	0.2978	−0.0409	0.056*
H19C	0.4781	0.1891	−0.0404	0.056*
C21	0.6180 (6)	0.9258 (6)	0.02272 (19)	0.0237 (17)
C22	0.7164 (7)	0.9273 (6)	0.0204 (2)	0.032 (2)
C23	0.7551 (6)	0.9507 (7)	−0.0071 (2)	0.035 (2)
H23	0.8228	0.9537	−0.0094	0.042*
C24	0.6973 (7)	0.9695 (7)	−0.0308 (2)	0.036 (2)
C25	0.5982 (7)	0.9694 (6)	−0.0267 (2)	0.037 (2)
H25	0.5579	0.9835	−0.0429	0.044*
C26	0.5560 (6)	0.9495 (6)	0.0003 (2)	0.0314 (19)
C27	0.7821 (7)	0.9102 (8)	0.0458 (2)	0.043 (2)
H27A	0.8488	0.9161	0.0394	0.064*
H27B	0.7712	0.8456	0.0536	0.064*
H27C	0.7691	0.9577	0.0611	0.064*
C28	0.7370 (8)	0.9888 (8)	−0.0611 (2)	0.049 (3)
H28A	0.6840	1.0019	−0.0746	0.073*
H28B	0.7727	0.9325	−0.0679	0.073*
H28C	0.7799	1.0444	−0.0604	0.073*
C29	0.4533 (8)	0.9624 (8)	0.0046 (3)	0.052 (3)
H29A	0.4227	0.9762	−0.0143	0.078*
H29B	0.4423	1.0160	0.0180	0.078*
H29C	0.4258	0.9037	0.0129	0.078*
C31	0.4692 (7)	0.7163 (6)	0.09582 (18)	0.0275 (18)
C32	0.3718 (7)	0.6983 (8)	0.0923 (2)	0.036 (2)
C33	0.3346 (8)	0.6165 (8)	0.1046 (2)	0.044 (3)
H33	0.2683	0.6029	0.1023	0.053*
C34	0.3913 (8)	0.5534 (8)	0.1202 (2)	0.044 (3)
C35	0.4871 (8)	0.5756 (7)	0.1245 (2)	0.040 (2)
H35	0.5254	0.5342	0.1362	0.049*
C36	0.5283 (8)	0.6565 (7)	0.11232 (18)	0.037 (2)
C37	0.3100 (8)	0.7712 (9)	0.0770 (3)	0.054 (3)
H37A	0.3500	0.8245	0.0702	0.082*
H37B	0.2615	0.7954	0.0906	0.082*
H37C	0.2783	0.7412	0.0602	0.082*
C38	0.3493 (11)	0.4622 (9)	0.1320 (3)	0.064 (4)
H38A	0.3986	0.4271	0.1429	0.096*
H38B	0.3264	0.4226	0.1157	0.096*
H38C	0.2956	0.4773	0.1450	0.096*
C39	0.6317 (8)	0.6810 (10)	0.1185 (2)	0.058 (3)
H39A	0.6606	0.6304	0.1305	0.087*
H39B	0.6350	0.7421	0.1290	0.087*
H39C	0.6668	0.6865	0.1000	0.087*
N11	0.3867 (6)	0.9291 (7)	−0.11355 (19)	0.041 (2)
S1	0.44103 (18)	0.84305 (18)	−0.09968 (5)	0.0356 (5)
O11	0.4141 (6)	0.8202 (6)	−0.07076 (16)	0.054 (2)
O12	0.5421 (5)	0.8391 (6)	−0.10565 (19)	0.056 (2)
C41	0.3857 (10)	0.7501 (9)	−0.1216 (3)	0.050 (3)
F1	0.4146 (7)	0.6650 (5)	−0.11142 (19)	0.086 (3)
F2	0.2925 (6)	0.7518 (5)	−0.12012 (18)	0.070 (2)
F3	0.4097 (7)	0.7548 (6)	−0.14891 (17)	0.085 (3)
S2	0.40339 (16)	1.03734 (17)	−0.10456 (5)	0.0305 (5)
O21	0.4876 (5)	1.0540 (6)	−0.08791 (16)	0.0469 (18)
O22	0.3869 (6)	1.0968 (5)	−0.12919 (14)	0.0466 (19)
C42	0.3037 (8)	1.0632 (9)	−0.0801 (2)	0.046 (3)
F4	0.3092 (6)	1.0118 (6)	−0.05641 (14)	0.085 (3)
F5	0.2218 (5)	1.0482 (6)	−0.09288 (16)	0.067 (2)
F6	0.3077 (6)	1.1556 (6)	−0.07284 (16)	0.072 (2)
N31	0.0200 (6)	0.0200 (6)	0.0000	0.036 (2)
S3	0.07670 (17)	0.04173 (16)	0.02944 (5)	0.0366 (5)
O31	0.1221 (6)	0.1333 (5)	0.03190 (16)	0.0480 (18)
O32	0.0217 (6)	0.0065 (6)	0.05325 (16)	0.059 (2)
C43	0.1783 (9)	−0.0397 (9)	0.0274 (3)	0.060 (3)
F7	0.2316 (7)	−0.0298 (7)	0.0511 (2)	0.107 (3)
F8	0.2302 (5)	−0.0250 (6)	0.00419 (18)	0.078 (2)
F9	0.1494 (6)	−0.1304 (5)	0.0266 (2)	0.078 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.01652 (12)	0.01652 (12)	0.02262 (19)	−0.00444 (16)	0.00103 (12)	−0.00103 (12)
Cl1	0.0411 (13)	0.0417 (12)	0.0257 (9)	−0.0049 (10)	0.0032 (9)	0.0017 (9)
Au2	0.01676 (14)	0.01689 (14)	0.02334 (13)	−0.00161 (11)	0.00300 (12)	−0.00450 (12)
Cl2	0.0203 (10)	0.0392 (13)	0.0416 (12)	0.0038 (8)	−0.0038 (9)	−0.0035 (9)
Cl3	0.0249 (12)	0.0474 (15)	0.0707 (18)	0.0065 (10)	−0.0177 (12)	−0.0156 (13)
O1	0.022 (3)	0.022 (3)	0.042 (5)	−0.015 (3)	0.019 (3)	−0.019 (3)
Ag3	0.0658 (7)	0.0547 (6)	0.0404 (5)	0.0226 (5)	−0.0012 (5)	0.0145 (5)
Ag3B	0.045 (4)	0.078 (5)	0.051 (4)	0.016 (4)	0.004 (3)	0.012 (4)
C1	0.023 (3)	0.023 (3)	0.064 (9)	−0.009 (4)	0.007 (4)	−0.007 (4)
N2	0.026 (3)	0.022 (4)	0.065 (5)	−0.021 (3)	0.014 (3)	0.002 (3)
C3	0.013 (4)	0.032 (5)	0.141 (12)	−0.013 (4)	0.020 (6)	−0.013 (7)
C6	0.026 (4)	0.015 (4)	0.026 (4)	0.004 (3)	−0.001 (3)	−0.010 (3)
N7	0.044 (5)	0.012 (3)	0.036 (4)	−0.008 (3)	0.008 (4)	−0.006 (3)
C8	0.058 (7)	0.023 (5)	0.052 (6)	−0.002 (4)	0.018 (5)	−0.016 (4)
C9	0.070 (8)	0.027 (5)	0.044 (6)	−0.005 (5)	0.023 (6)	−0.024 (4)
N10	0.040 (4)	0.019 (3)	0.027 (3)	0.004 (3)	0.006 (3)	−0.008 (3)
C11	0.045 (5)	0.012 (4)	0.042 (5)	−0.003 (3)	0.024 (4)	0.000 (3)
C12	0.112 (11)	0.021 (5)	0.043 (6)	0.019 (6)	0.044 (7)	0.012 (4)
C13	0.137 (13)	0.014 (5)	0.036 (6)	0.018 (6)	0.005 (7)	0.011 (4)
C14	0.072 (8)	0.015 (4)	0.048 (6)	0.011 (5)	−0.009 (5)	0.001 (4)
C15	0.053 (6)	0.025 (5)	0.033 (5)	−0.010 (5)	0.003 (4)	0.007 (4)
C16	0.047 (6)	0.015 (4)	0.037 (5)	−0.007 (4)	0.010 (4)	−0.001 (4)
C17	0.167 (17)	0.055 (9)	0.081 (10)	0.026 (10)	0.090 (11)	0.022 (7)
C18	0.108 (12)	0.050 (8)	0.065 (8)	0.033 (8)	−0.039 (8)	−0.005 (6)
C19	0.035 (5)	0.027 (5)	0.050 (6)	0.001 (4)	−0.007 (4)	−0.009 (4)
C21	0.018 (4)	0.018 (4)	0.035 (5)	0.005 (3)	0.002 (3)	0.001 (4)
C22	0.039 (5)	0.016 (4)	0.042 (5)	−0.001 (4)	−0.003 (4)	−0.006 (4)
C23	0.019 (4)	0.036 (5)	0.050 (6)	−0.003 (4)	0.003 (4)	0.008 (4)
C24	0.040 (5)	0.029 (5)	0.039 (5)	−0.005 (4)	−0.002 (4)	0.007 (4)
C25	0.044 (6)	0.020 (4)	0.045 (5)	−0.004 (4)	−0.009 (5)	−0.002 (4)
C26	0.026 (4)	0.021 (4)	0.047 (5)	−0.006 (3)	−0.010 (4)	0.001 (4)
C27	0.034 (6)	0.048 (7)	0.046 (6)	−0.012 (4)	−0.010 (5)	0.001 (5)
C28	0.052 (7)	0.046 (7)	0.048 (6)	−0.001 (5)	0.005 (5)	0.019 (5)
C29	0.043 (6)	0.052 (7)	0.062 (7)	0.019 (5)	0.004 (5)	0.014 (6)
C31	0.036 (5)	0.025 (4)	0.022 (4)	0.003 (4)	0.007 (4)	−0.004 (3)
C32	0.030 (5)	0.048 (6)	0.029 (5)	0.014 (4)	0.002 (4)	−0.006 (4)
C33	0.035 (6)	0.066 (8)	0.030 (5)	0.004 (5)	0.014 (4)	0.004 (5)
C34	0.052 (7)	0.051 (7)	0.029 (5)	−0.001 (5)	0.006 (4)	0.000 (4)
C35	0.054 (6)	0.040 (5)	0.027 (5)	0.015 (5)	−0.006 (4)	0.002 (4)
C36	0.049 (6)	0.046 (6)	0.017 (4)	0.002 (5)	−0.001 (4)	−0.003 (4)
C37	0.042 (6)	0.062 (8)	0.060 (7)	0.022 (6)	0.017 (6)	0.007 (6)
C38	0.102 (11)	0.042 (7)	0.047 (7)	−0.006 (7)	0.019 (7)	0.006 (5)
C39	0.053 (7)	0.083 (10)	0.039 (6)	−0.012 (7)	−0.018 (5)	0.004 (6)
N11	0.045 (5)	0.035 (5)	0.044 (5)	0.008 (4)	−0.012 (4)	0.000 (4)
S1	0.0315 (12)	0.0343 (12)	0.0409 (13)	0.0072 (10)	−0.0020 (10)	0.0067 (10)
O11	0.061 (5)	0.056 (5)	0.045 (4)	0.016 (4)	0.000 (4)	0.016 (4)
O12	0.033 (4)	0.058 (5)	0.077 (6)	0.018 (4)	0.009 (4)	0.019 (4)
C41	0.059 (8)	0.043 (7)	0.048 (7)	0.008 (6)	−0.012 (6)	−0.001 (5)
F1	0.116 (7)	0.032 (4)	0.109 (6)	0.016 (4)	−0.023 (6)	0.002 (4)
F2	0.062 (5)	0.058 (5)	0.091 (6)	−0.010 (4)	−0.016 (4)	−0.006 (4)
F3	0.115 (8)	0.086 (6)	0.055 (5)	0.019 (5)	0.004 (5)	−0.017 (4)
S2	0.0290 (11)	0.0361 (13)	0.0264 (11)	0.0080 (9)	0.0001 (9)	0.0017 (9)
O21	0.034 (4)	0.055 (5)	0.052 (4)	0.007 (4)	−0.014 (3)	−0.002 (4)
O22	0.064 (5)	0.049 (5)	0.027 (4)	0.007 (4)	0.003 (3)	0.005 (3)
C42	0.042 (6)	0.064 (7)	0.031 (5)	0.014 (6)	0.004 (5)	0.001 (5)
F4	0.096 (6)	0.115 (7)	0.044 (4)	0.052 (5)	0.033 (4)	0.033 (4)
F5	0.033 (4)	0.086 (6)	0.083 (5)	0.008 (3)	0.008 (3)	0.003 (4)
F6	0.071 (5)	0.069 (5)	0.075 (5)	0.017 (4)	0.012 (4)	−0.025 (4)
N31	0.027 (3)	0.027 (3)	0.055 (7)	0.001 (5)	−0.006 (4)	0.006 (4)
S3	0.0335 (12)	0.0326 (12)	0.0437 (12)	−0.0024 (9)	0.0002 (11)	0.0019 (10)
O31	0.058 (5)	0.033 (4)	0.054 (4)	−0.012 (3)	0.001 (4)	−0.012 (3)
O32	0.064 (5)	0.063 (6)	0.050 (4)	−0.011 (4)	0.021 (4)	0.005 (4)
C43	0.056 (8)	0.053 (8)	0.070 (8)	0.004 (6)	−0.017 (7)	−0.005 (7)
F7	0.101 (7)	0.098 (7)	0.121 (7)	0.028 (6)	−0.078 (6)	−0.002 (6)
F8	0.037 (4)	0.105 (6)	0.091 (6)	0.025 (4)	0.019 (4)	0.019 (5)
F9	0.072 (5)	0.036 (4)	0.124 (7)	0.016 (3)	−0.017 (5)	−0.002 (4)

Geometric parameters (Å, º) top

Au1—C1	2.018 (12)	C22—C27	1.500 (13)
Au1—O1	2.046 (7)	C23—C24	1.376 (13)
Au1—Cl1ⁱ	2.277 (2)	C23—H23	0.9500
Au1—Cl1	2.278 (2)	C24—C25	1.394 (14)
Cl1—Ag3ⁱ	2.684 (3)	C24—C28	1.516 (13)
Au2—C6	1.982 (7)	C25—C26	1.394 (14)
Au2—O1	2.010 (3)	C25—H25	0.9500
Au2—Cl3	2.271 (2)	C26—C29	1.457 (14)
Au2—Cl2	2.276 (2)	C27—H27A	0.9800
Au2—Ag3B	3.234 (7)	C27—H27B	0.9800
Cl2—Ag3	2.644 (2)	C27—H27C	0.9800
Cl2—Ag3B	2.754 (8)	C28—H28A	0.9800
Cl3—Ag3Bⁱ	2.302 (8)	C28—H28B	0.9800
Cl3—Ag3ⁱ	2.769 (3)	C28—H28C	0.9800
O1—Au2ⁱ	2.010 (3)	C29—H29A	0.9800
Ag3—O11	2.340 (7)	C29—H29B	0.9800
Ag3—Cl1ⁱ	2.684 (3)	C29—H29C	0.9800
Ag3—Cl3ⁱ	2.769 (3)	C31—C32	1.390 (13)
Ag3B—Cl3ⁱ	2.302 (8)	C31—C36	1.395 (13)
Ag3B—O11	2.342 (10)	C32—C33	1.374 (15)
Ag3B—C25	2.544 (12)	C32—C37	1.504 (14)
Ag3B—C26	2.587 (13)	C33—C34	1.382 (15)
C1—N2	1.322 (10)	C33—H33	0.9500
C1—N2ⁱ	1.322 (10)	C34—C35	1.385 (15)
N2—C3	1.392 (11)	C34—C38	1.500 (15)
N2—C11	1.452 (13)	C35—C36	1.385 (14)
C3—C3ⁱ	1.31 (2)	C35—H35	0.9500
C3—H3	0.9500	C36—C39	1.508 (15)
C6—N10	1.327 (10)	C37—H37A	0.9800
C6—N7	1.364 (10)	C37—H37B	0.9800
N7—C8	1.375 (11)	C37—H37C	0.9800
N7—C21	1.455 (11)	C38—H38A	0.9800
C8—C9	1.340 (14)	C38—H38B	0.9800
C8—H8	0.9500	C38—H38C	0.9800
C9—N10	1.376 (11)	C39—H39A	0.9800
C9—H9	0.9500	C39—H39B	0.9800
N10—C31	1.450 (11)	C39—H39C	0.9800
C11—C16	1.352 (12)	N11—S1	1.555 (9)
C11—C12	1.400 (14)	N11—S2	1.582 (9)
C12—C13	1.40 (2)	S1—O11	1.411 (8)
C12—C17	1.484 (16)	S1—O12	1.437 (8)
C13—C14	1.390 (17)	S1—C41	1.812 (13)
C13—H13	0.9500	C41—F3	1.294 (14)
C14—C15	1.349 (14)	C41—F2	1.303 (14)
C14—C18	1.526 (17)	C41—F1	1.338 (13)
C15—C16	1.389 (14)	S2—O22	1.418 (7)
C15—H15	0.9500	S2—O21	1.419 (7)
C16—C19	1.495 (13)	S2—C42	1.821 (10)
C17—H17A	0.9800	C42—F4	1.301 (12)
C17—H17B	0.9800	C42—F5	1.301 (13)
C17—H17C	0.9800	C42—F6	1.332 (14)
C18—H18A	0.9800	N31—S3ⁱ	1.590 (6)
C18—H18B	0.9800	N31—S3	1.590 (6)
C18—H18C	0.9800	S3—O32	1.420 (7)
C19—H19A	0.9800	S3—O31	1.431 (7)
C19—H19B	0.9800	S3—C43	1.818 (12)
C19—H19C	0.9800	C43—F8	1.302 (15)
C21—C22	1.376 (12)	C43—F7	1.318 (14)
C21—C26	1.383 (12)	C43—F9	1.328 (14)
C22—C23	1.406 (13)

C1—Au1—O1	180.0 (3)	C24—C23—C22	121.5 (9)
C1—Au1—Cl1ⁱ	92.44 (6)	C24—C23—H23	119.2
O1—Au1—Cl1ⁱ	87.56 (6)	C22—C23—H23	119.2
C1—Au1—Cl1	92.44 (6)	C23—C24—C25	118.3 (9)
O1—Au1—Cl1	87.56 (6)	C23—C24—C28	122.6 (9)
Cl1ⁱ—Au1—Cl1	175.12 (12)	C25—C24—C28	119.0 (9)
Au1—Cl1—Ag3ⁱ	90.42 (7)	C24—C25—C26	122.5 (9)
C6—Au2—O1	179.5 (3)	C24—C25—Ag3B	111.8 (6)
C6—Au2—Cl3	92.1 (2)	C26—C25—Ag3B	76.0 (5)
O1—Au2—Cl3	88.25 (13)	C24—C25—H25	118.7
C6—Au2—Cl2	91.3 (2)	C26—C25—H25	118.7
O1—Au2—Cl2	88.36 (12)	Ag3B—C25—H25	82.3
Cl3—Au2—Cl2	176.55 (9)	C21—C26—C25	116.1 (8)
C6—Au2—Ag3B	100.0 (3)	C21—C26—C29	122.9 (10)
O1—Au2—Ag3B	80.16 (16)	C25—C26—C29	120.7 (9)
Cl3—Au2—Ag3B	123.08 (16)	C21—C26—Ag3B	110.3 (6)
Cl2—Au2—Ag3B	56.83 (15)	C25—C26—Ag3B	72.5 (5)
Au2—Cl2—Ag3	95.30 (8)	C29—C26—Ag3B	91.4 (7)
Au2—Cl2—Ag3B	79.40 (16)	C22—C27—H27A	109.5
Ag3—Cl2—Ag3B	42.07 (18)	C22—C27—H27B	109.5
Au2—Cl3—Ag3Bⁱ	123.6 (2)	H27A—C27—H27B	109.5
Au2—Cl3—Ag3ⁱ	92.12 (9)	C22—C27—H27C	109.5
Ag3Bⁱ—Cl3—Ag3ⁱ	43.8 (2)	H27A—C27—H27C	109.5
Au2—O1—Au2ⁱ	125.2 (3)	H27B—C27—H27C	109.5
Au2—O1—Au1	117.41 (17)	C24—C28—H28A	109.5
Au2ⁱ—O1—Au1	117.41 (17)	C24—C28—H28B	109.5
O11—Ag3—Cl2	104.3 (2)	H28A—C28—H28B	109.5
O11—Ag3—Cl1ⁱ	142.3 (2)	C24—C28—H28C	109.5
Cl2—Ag3—Cl1ⁱ	104.40 (8)	H28A—C28—H28C	109.5
O11—Ag3—Cl3ⁱ	100.4 (2)	H28B—C28—H28C	109.5
Cl2—Ag3—Cl3ⁱ	102.64 (9)	C26—C29—H29A	109.5
Cl1ⁱ—Ag3—Cl3ⁱ	96.55 (8)	C26—C29—H29B	109.5
Cl3ⁱ—Ag3B—O11	115.9 (4)	H29A—C29—H29B	109.5
Cl3ⁱ—Ag3B—C25	100.4 (4)	C26—C29—H29C	109.5
O11—Ag3B—C25	104.7 (4)	H29A—C29—H29C	109.5
Cl3ⁱ—Ag3B—C26	114.8 (4)	H29B—C29—H29C	109.5
O11—Ag3B—C26	117.2 (4)	C32—C31—C36	122.2 (9)
C25—Ag3B—C26	31.5 (3)	C32—C31—N10	119.1 (8)
Cl3ⁱ—Ag3B—Cl2	113.1 (3)	C36—C31—N10	118.7 (8)
O11—Ag3B—Cl2	101.0 (3)	C33—C32—C31	118.1 (9)
C25—Ag3B—Cl2	122.3 (4)	C33—C32—C37	122.3 (10)
C26—Ag3B—Cl2	90.8 (3)	C31—C32—C37	119.5 (10)
Cl3ⁱ—Ag3B—Au2	79.3 (2)	C32—C33—C34	121.6 (10)
O11—Ag3B—Au2	143.1 (4)	C32—C33—H33	119.2
C25—Ag3B—Au2	105.1 (3)	C34—C33—H33	119.2
C26—Ag3B—Au2	80.4 (3)	C33—C34—C35	118.9 (10)
Cl2—Ag3B—Au2	43.77 (11)	C33—C34—C38	120.2 (11)
N2—C1—N2ⁱ	111.0 (11)	C35—C34—C38	120.9 (11)
N2—C1—Au1	124.5 (5)	C36—C35—C34	121.7 (9)
N2ⁱ—C1—Au1	124.5 (5)	C36—C35—H35	119.2
C1—N2—C3	106.3 (9)	C34—C35—H35	119.2
C1—N2—C11	124.7 (7)	C35—C36—C31	117.4 (10)
C3—N2—C11	129.0 (8)	C35—C36—C39	120.5 (10)
C3ⁱ—C3—N2	108.1 (6)	C31—C36—C39	122.1 (10)
C3ⁱ—C3—H3	126.0	C32—C37—H37A	109.5
N2—C3—H3	126.0	C32—C37—H37B	109.5
N10—C6—N7	106.8 (7)	H37A—C37—H37B	109.5
N10—C6—Au2	128.1 (6)	C32—C37—H37C	109.5
N7—C6—Au2	125.0 (6)	H37A—C37—H37C	109.5
C6—N7—C8	109.2 (7)	H37B—C37—H37C	109.5
C6—N7—C21	123.1 (7)	C34—C38—H38A	109.5
C8—N7—C21	127.6 (7)	C34—C38—H38B	109.5
C9—C8—N7	106.5 (8)	H38A—C38—H38B	109.5
C9—C8—H8	126.8	C34—C38—H38C	109.5
N7—C8—H8	126.8	H38A—C38—H38C	109.5
C8—C9—N10	108.3 (8)	H38B—C38—H38C	109.5
C8—C9—H9	125.9	C36—C39—H39A	109.5
N10—C9—H9	125.9	C36—C39—H39B	109.5
C6—N10—C9	109.2 (8)	H39A—C39—H39B	109.5
C6—N10—C31	125.2 (7)	C36—C39—H39C	109.5
C9—N10—C31	125.5 (7)	H39A—C39—H39C	109.5
C16—C11—C12	125.2 (11)	H39B—C39—H39C	109.5
C16—C11—N2	119.0 (9)	S1—N11—S2	124.0 (6)
C12—C11—N2	115.7 (9)	O11—S1—O12	115.5 (5)
C11—C12—C13	114.1 (10)	O11—S1—N11	115.3 (5)
C11—C12—C17	125.5 (14)	O12—S1—N11	115.5 (5)
C13—C12—C17	120.3 (12)	O11—S1—C41	104.1 (6)
C14—C13—C12	122.6 (10)	O12—S1—C41	106.5 (6)
C14—C13—H13	118.7	N11—S1—C41	96.8 (5)
C12—C13—H13	118.7	S1—O11—Ag3	124.1 (5)
C15—C14—C13	117.8 (11)	S1—O11—Ag3B	122.1 (5)
C15—C14—C18	121.9 (11)	Ag3—O11—Ag3B	49.0 (3)
C13—C14—C18	120.1 (11)	F3—C41—F2	108.0 (10)
C14—C15—C16	123.0 (10)	F3—C41—F1	107.7 (10)
C14—C15—H15	118.5	F2—C41—F1	107.4 (11)
C16—C15—H15	118.5	F3—C41—S1	112.8 (10)
C11—C16—C15	116.4 (9)	F2—C41—S1	112.5 (8)
C11—C16—C19	123.0 (10)	F1—C41—S1	108.3 (8)
C15—C16—C19	120.6 (9)	O22—S2—O21	117.7 (5)
C12—C17—H17A	109.5	O22—S2—N11	109.2 (5)
C12—C17—H17B	109.5	O21—S2—N11	114.7 (5)
H17A—C17—H17B	109.5	O22—S2—C42	104.4 (5)
C12—C17—H17C	109.5	O21—S2—C42	105.7 (5)
H17A—C17—H17C	109.5	N11—S2—C42	103.7 (5)
H17B—C17—H17C	109.5	F4—C42—F5	109.7 (11)
C14—C18—H18A	109.5	F4—C42—F6	108.9 (9)
C14—C18—H18B	109.5	F5—C42—F6	107.7 (10)
H18A—C18—H18B	109.5	F4—C42—S2	111.0 (8)
C14—C18—H18C	109.5	F5—C42—S2	111.3 (7)
H18A—C18—H18C	109.5	F6—C42—S2	108.2 (8)
H18B—C18—H18C	109.5	S3ⁱ—N31—S3	121.8 (7)
C16—C19—H19A	109.5	O32—S3—O31	119.2 (5)
C16—C19—H19B	109.5	O32—S3—N31	108.3 (5)
H19A—C19—H19B	109.5	O31—S3—N31	117.2 (5)
C16—C19—H19C	109.5	O32—S3—C43	104.1 (6)
H19A—C19—H19C	109.5	O31—S3—C43	102.5 (6)
H19B—C19—H19C	109.5	N31—S3—C43	103.0 (4)
C22—C21—C26	124.1 (8)	F8—C43—F7	109.8 (11)
C22—C21—N7	118.1 (8)	F8—C43—F9	107.2 (11)
C26—C21—N7	117.8 (8)	F7—C43—F9	107.1 (11)
C21—C22—C23	117.2 (8)	F8—C43—S3	112.1 (9)
C21—C22—C27	123.0 (9)	F7—C43—S3	109.4 (9)
C23—C22—C27	119.7 (9)	F9—C43—S3	111.1 (9)

C1—Au1—Cl1—Ag3ⁱ	131.82 (6)	N7—C21—C22—C23	175.2 (8)
O1—Au1—Cl1—Ag3ⁱ	−48.18 (6)	C26—C21—C22—C27	174.1 (9)
Cl1ⁱ—Au1—Cl1—Ag3ⁱ	−48.18 (6)	N7—C21—C22—C27	−7.9 (13)
C6—Au2—Cl2—Ag3	140.2 (2)	C21—C22—C23—C24	−1.3 (14)
O1—Au2—Cl2—Ag3	−40.19 (15)	C27—C22—C23—C24	−178.3 (9)
Cl3—Au2—Cl2—Ag3	−50.6 (18)	C22—C23—C24—C25	3.1 (14)
Ag3B—Au2—Cl2—Ag3	39.12 (19)	C22—C23—C24—C28	−176.1 (9)
C6—Au2—Cl2—Ag3B	101.1 (3)	C23—C24—C25—C26	−1.2 (14)
O1—Au2—Cl2—Ag3B	−79.3 (2)	C28—C24—C25—C26	178.1 (9)
Cl3—Au2—Cl2—Ag3B	−89.7 (18)	C23—C24—C25—Ag3B	−88.0 (10)
C6—Au2—Cl3—Ag3Bⁱ	168.8 (4)	C28—C24—C25—Ag3B	91.2 (10)
O1—Au2—Cl3—Ag3Bⁱ	−10.8 (3)	Cl3ⁱ—Ag3B—C25—C24	−1.4 (8)
Cl2—Au2—Cl3—Ag3Bⁱ	−0.4 (19)	O11—Ag3B—C25—C24	−121.8 (7)
Ag3B—Au2—Cl3—Ag3Bⁱ	−87.8 (2)	C26—Ag3B—C25—C24	119.8 (10)
C6—Au2—Cl3—Ag3ⁱ	136.3 (2)	Cl2—Ag3B—C25—C24	124.7 (7)
O1—Au2—Cl3—Ag3ⁱ	−43.33 (16)	Au2—Ag3B—C25—C24	80.2 (8)
Cl2—Au2—Cl3—Ag3ⁱ	−32.9 (18)	Cl3ⁱ—Ag3B—C25—C26	−121.2 (6)
Ag3B—Au2—Cl3—Ag3ⁱ	−120.4 (2)	O11—Ag3B—C25—C26	118.4 (6)
C6—Au2—O1—Au2ⁱ	179 (100)	Cl2—Ag3B—C25—C26	4.9 (7)
Cl3—Au2—O1—Au2ⁱ	−53.29 (8)	Au2—Ag3B—C25—C26	−39.5 (6)
Cl2—Au2—O1—Au2ⁱ	127.34 (6)	C22—C21—C26—C25	4.6 (13)
Ag3B—Au2—O1—Au2ⁱ	70.74 (14)	N7—C21—C26—C25	−173.4 (7)
C6—Au2—O1—Au1	−1 (30)	C22—C21—C26—C29	−169.7 (9)
Cl3—Au2—O1—Au1	126.71 (8)	N7—C21—C26—C29	12.3 (13)
Cl2—Au2—O1—Au1	−52.66 (6)	C22—C21—C26—Ag3B	84.5 (10)
Ag3B—Au2—O1—Au1	−109.26 (14)	N7—C21—C26—Ag3B	−93.5 (8)
C1—Au1—O1—Au2	45.730 (10)	C24—C25—C26—C21	−2.5 (13)
Cl1ⁱ—Au1—O1—Au2	132.01 (6)	Ag3B—C25—C26—C21	104.6 (8)
Cl1—Au1—O1—Au2	−47.99 (6)	C24—C25—C26—C29	171.9 (9)
C1—Au1—O1—Au2ⁱ	−134.270 (10)	Ag3B—C25—C26—C29	−81.0 (9)
Cl1ⁱ—Au1—O1—Au2ⁱ	−47.99 (6)	C24—C25—C26—Ag3B	−107.1 (9)
Cl1—Au1—O1—Au2ⁱ	132.01 (6)	Cl3ⁱ—Ag3B—C26—C21	−44.0 (8)
Au2—Cl2—Ag3—O11	−125.6 (2)	O11—Ag3B—C26—C21	174.9 (6)
Ag3B—Cl2—Ag3—O11	−57.9 (3)	C25—Ag3B—C26—C21	−112.1 (9)
Au2—Cl2—Ag3—Cl1ⁱ	79.04 (10)	Cl2—Ag3B—C26—C21	72.0 (6)
Ag3B—Cl2—Ag3—Cl1ⁱ	146.8 (2)	Au2—Ag3B—C26—C21	29.4 (6)
Au2—Cl2—Ag3—Cl3ⁱ	−21.24 (9)	Cl3ⁱ—Ag3B—C26—C25	68.0 (6)
Ag3B—Cl2—Ag3—Cl3ⁱ	46.5 (2)	O11—Ag3B—C26—C25	−73.1 (7)
Au2—Cl2—Ag3B—Cl3ⁱ	42.5 (3)	Cl2—Ag3B—C26—C25	−175.9 (6)
Ag3—Cl2—Ag3B—Cl3ⁱ	−67.9 (3)	Au2—Ag3B—C26—C25	141.4 (6)
Au2—Cl2—Ag3B—O11	167.0 (3)	Cl3ⁱ—Ag3B—C26—C29	−170.1 (6)
Ag3—Cl2—Ag3B—O11	56.6 (3)	O11—Ag3B—C26—C29	48.8 (8)
Au2—Cl2—Ag3B—C25	−77.7 (4)	C25—Ag3B—C26—C29	121.8 (9)
Ag3—Cl2—Ag3B—C25	172.0 (5)	Cl2—Ag3B—C26—C29	−54.1 (6)
Au2—Cl2—Ag3B—C26	−75.1 (3)	Au2—Ag3B—C26—C29	−96.8 (6)
Ag3—Cl2—Ag3B—C26	174.5 (4)	C6—N10—C31—C32	−91.8 (11)
Ag3—Cl2—Ag3B—Au2	−110.34 (19)	C9—N10—C31—C32	85.8 (12)
C6—Au2—Ag3B—Cl3ⁱ	134.2 (3)	C6—N10—C31—C36	88.5 (11)
O1—Au2—Ag3B—Cl3ⁱ	−46.3 (3)	C9—N10—C31—C36	−94.0 (12)
Cl3—Au2—Ag3B—Cl3ⁱ	35.1 (3)	C36—C31—C32—C33	−2.8 (14)
Cl2—Au2—Ag3B—Cl3ⁱ	−140.8 (3)	N10—C31—C32—C33	177.5 (8)
C6—Au2—Ag3B—O11	−106.6 (7)	C36—C31—C32—C37	173.3 (9)
O1—Au2—Ag3B—O11	72.9 (6)	N10—C31—C32—C37	−6.5 (13)
Cl3—Au2—Ag3B—O11	154.3 (5)	C31—C32—C33—C34	0.4 (15)
Cl2—Au2—Ag3B—O11	−21.6 (5)	C37—C32—C33—C34	−175.6 (10)
C6—Au2—Ag3B—C25	36.2 (4)	C32—C33—C34—C35	2.6 (15)
O1—Au2—Ag3B—C25	−144.3 (4)	C32—C33—C34—C38	−176.7 (10)
Cl3—Au2—Ag3B—C25	−62.9 (4)	C33—C34—C35—C36	−3.4 (15)
Cl2—Au2—Ag3B—C25	121.2 (4)	C38—C34—C35—C36	175.9 (9)
C6—Au2—Ag3B—C26	16.4 (3)	C34—C35—C36—C31	1.1 (14)
O1—Au2—Ag3B—C26	−164.1 (3)	C34—C35—C36—C39	177.3 (10)
Cl3—Au2—Ag3B—C26	−82.7 (3)	C32—C31—C36—C35	2.0 (13)
Cl2—Au2—Ag3B—C26	101.4 (3)	N10—C31—C36—C35	−178.2 (8)
C6—Au2—Ag3B—Cl2	−85.0 (3)	C32—C31—C36—C39	−174.1 (9)
O1—Au2—Ag3B—Cl2	94.5 (2)	N10—C31—C36—C39	5.7 (13)
Cl3—Au2—Ag3B—Cl2	175.88 (11)	S2—N11—S1—O11	72.3 (8)
O1—Au1—C1—N2	−161.2 (4)	S2—N11—S1—O12	−66.5 (8)
Cl1ⁱ—Au1—C1—N2	112.5 (5)	S2—N11—S1—C41	−178.5 (7)
Cl1—Au1—C1—N2	−67.5 (5)	O12—S1—O11—Ag3	−49.2 (8)
O1—Au1—C1—N2ⁱ	18.8 (4)	N11—S1—O11—Ag3	172.0 (5)
Cl1ⁱ—Au1—C1—N2ⁱ	−67.5 (5)	C41—S1—O11—Ag3	67.2 (7)
Cl1—Au1—C1—N2ⁱ	112.5 (5)	O12—S1—O11—Ag3B	10.0 (8)
N2ⁱ—C1—N2—C3	1.4 (7)	N11—S1—O11—Ag3B	−128.8 (6)
Au1—C1—N2—C3	−178.7 (7)	C41—S1—O11—Ag3B	126.5 (6)
N2ⁱ—C1—N2—C11	179.6 (10)	Cl2—Ag3—O11—S1	167.3 (5)
Au1—C1—N2—C11	−0.4 (10)	Cl1ⁱ—Ag3—O11—S1	−54.0 (8)
C1—N2—C3—C3ⁱ	−3.7 (19)	Cl3ⁱ—Ag3—O11—S1	61.3 (6)
C11—N2—C3—C3ⁱ	178.1 (13)	Cl2—Ag3—O11—Ag3B	62.2 (3)
O1—Au2—C6—N10	35 (31)	Cl1ⁱ—Ag3—O11—Ag3B	−159.2 (3)
Cl3—Au2—C6—N10	−93.2 (8)	Cl3ⁱ—Ag3—O11—Ag3B	−43.9 (3)
Cl2—Au2—C6—N10	86.2 (8)	Cl3ⁱ—Ag3B—O11—S1	−43.7 (8)
Ag3B—Au2—C6—N10	142.7 (7)	C25—Ag3B—O11—S1	65.9 (7)
O1—Au2—C6—N7	−144 (30)	C26—Ag3B—O11—S1	97.0 (6)
Cl3—Au2—C6—N7	88.2 (7)	Cl2—Ag3B—O11—S1	−166.3 (5)
Cl2—Au2—C6—N7	−92.4 (7)	Au2—Ag3B—O11—S1	−151.2 (5)
Ag3B—Au2—C6—N7	−35.9 (8)	Cl3ⁱ—Ag3B—O11—Ag3	65.7 (4)
N10—C6—N7—C8	0.9 (11)	C25—Ag3B—O11—Ag3	175.2 (4)
Au2—C6—N7—C8	179.7 (7)	C26—Ag3B—O11—Ag3	−153.6 (5)
N10—C6—N7—C21	−176.8 (8)	Cl2—Ag3B—O11—Ag3	−56.9 (2)
Au2—C6—N7—C21	2.0 (12)	Au2—Ag3B—O11—Ag3	−41.9 (5)
C6—N7—C8—C9	−0.6 (13)	O11—S1—C41—F3	−174.4 (8)
C21—N7—C8—C9	176.9 (10)	O12—S1—C41—F3	−51.9 (10)
N7—C8—C9—N10	0.2 (14)	N11—S1—C41—F3	67.3 (9)
N7—C6—N10—C9	−0.8 (11)	O11—S1—C41—F2	63.2 (10)
Au2—C6—N10—C9	−179.6 (7)	O12—S1—C41—F2	−174.3 (8)
N7—C6—N10—C31	177.1 (8)	N11—S1—C41—F2	−55.1 (10)
Au2—C6—N10—C31	−1.7 (13)	O11—S1—C41—F1	−55.3 (10)
C8—C9—N10—C6	0.4 (13)	O12—S1—C41—F1	67.2 (10)
C8—C9—N10—C31	−177.5 (9)	N11—S1—C41—F1	−173.6 (9)
C1—N2—C11—C16	−78.3 (11)	S1—N11—S2—O22	149.0 (7)
C3—N2—C11—C16	99.6 (13)	S1—N11—S2—O21	14.5 (9)
C1—N2—C11—C12	99.5 (10)	S1—N11—S2—C42	−100.2 (7)
C3—N2—C11—C12	−82.6 (14)	O22—S2—C42—F4	179.2 (9)
C16—C11—C12—C13	5.3 (15)	O21—S2—C42—F4	−56.1 (10)
N2—C11—C12—C13	−172.4 (8)	N11—S2—C42—F4	64.9 (10)
C16—C11—C12—C17	−172.7 (11)	O22—S2—C42—F5	56.7 (10)
N2—C11—C12—C17	9.7 (16)	O21—S2—C42—F5	−178.6 (8)
C11—C12—C13—C14	0.4 (16)	N11—S2—C42—F5	−57.6 (9)
C17—C12—C13—C14	178.5 (11)	O22—S2—C42—F6	−61.5 (8)
C12—C13—C14—C15	−8.0 (16)	O21—S2—C42—F6	63.3 (8)
C12—C13—C14—C18	176.9 (10)	N11—S2—C42—F6	−175.7 (7)
C13—C14—C15—C16	10.6 (15)	S3ⁱ—N31—S3—O32	160.1 (4)
C18—C14—C15—C16	−174.3 (10)	S3ⁱ—N31—S3—O31	21.6 (4)
C12—C11—C16—C15	−3.0 (14)	S3ⁱ—N31—S3—C43	−90.0 (5)
N2—C11—C16—C15	174.5 (7)	O32—S3—C43—F8	171.7 (9)
C12—C11—C16—C19	175.6 (9)	O31—S3—C43—F8	−63.4 (10)
N2—C11—C16—C19	−6.8 (13)	N31—S3—C43—F8	58.7 (10)
C14—C15—C16—C11	−5.3 (14)	O32—S3—C43—F7	−66.3 (11)
C14—C15—C16—C19	175.9 (9)	O31—S3—C43—F7	58.6 (11)
C6—N7—C21—C22	−93.0 (11)	N31—S3—C43—F7	−179.3 (10)
C8—N7—C21—C22	89.8 (12)	O32—S3—C43—F9	51.8 (11)
C6—N7—C21—C26	85.2 (11)	O31—S3—C43—F9	176.6 (9)
C8—N7—C21—C26	−92.1 (12)	N31—S3—C43—F9	−61.2 (11)
C26—C21—C22—C23	−2.8 (14)

Symmetry code: (i) y, x, −z.

Experimental details

Crystal data
Chemical formula	[Au₃Cl₆O(C₂₁H₂₄N₂)₃](C₂F₆NO₄S₂)·[Ag(C₂F₆NO₄S₂)]₂
M_r	2789.06
Crystal system, space group	Tetragonal, P4₃2₁2
Temperature (K)	200
a, c (Å)	13.9472 (9), 45.724 (3)
V (Å³)	8894.5 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.79
Crystal size (mm)	0.25 × 0.17 × 0.11

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.326, 0.569
No. of measured, independent and observed [I > 2σ(I)] reflections	93947, 11087, 10564
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.094, 1.27
No. of reflections	11087
No. of parameters	581
No. of restraints	12
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0179P)² + 57.4255P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.65, −1.45
Absolute structure	Flack (1983), 4737 Friedel pairs
Absolute structure parameter	0.396 (7)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008b).

Acknowledgements

MP and ML work at CaRLa of Heidelberg University, being co-financed by the University of Heidelberg, the state of Baden-Württemberg and the BASF SE. Support of these institutions is greatly acknowledged. The authors are indebted to Kenneth G. Caulton, Indiana University, Bloomington, for careful proofreading of the final manuscript.

References

Angermaier, K. & Schmidbaur, H. (1994). Inorg. Chem. 33, 2069–2070. CSD CrossRef CAS Web of Science Google Scholar
Angermaier, K. & Schmidbaur, H. (1995). Acta Cryst. C51, 1793–1795. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Nesmeyanov, A. N., Perevalova, E. G., Struchkov, Y. T., Antipin, M. Y., Grandberg, K. I. & Dyadchenko, V. P. (1980). J. Organomet. Chem. 201, 343–351. CSD CrossRef CAS Web of Science Google Scholar
Nockemann, P., Thijs, B., Van Hecke, K., Van Meervelt, L. & Binnemans, K. (2008). Cryst. Growth Des. 8, 1353–1363. Web of Science CSD CrossRef CAS Google Scholar
Pažický, M., Loos, A., Ferreira, M. J., Rominger, F., Jäkel, C., Hashmi, A. S. K. & Limbach, M. (2010). Personal communication. Google Scholar
Schmidbaur, H., Kolb, A., Zeller, E., Schier, A. & Beruda, H. (1993). Z. Anorg. Allg. Chem. 619, 1575–1581. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, Y., Ramamoorthy, V. & Sharp, P. R. (1993). Inorg. Chem. 32, 1946–1951. CSD CrossRef CAS Web of Science Google Scholar

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