μ-1,1′-Bis(diphenyl­phosphino)ferrocene-κ2P:P′-bis­{[(Z)-O-isopropyl N-(4-nitro­phen­yl)thio­carbamato-κS]gold(I)} chloro­form disolvate

Ho, S.Y.; Tiekink, E.R.T.

doi:10.1107/S1600536809043864

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages m1466-m1467

https://doi.org/10.1107/S1600536809043864

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μ-1,1′-Bis(diphenylphosphino)ferrocene-κ²P:P′-bis{[(Z)-O-isopropyl N-(4-nitrophenyl)thiocarbamato-κS]gold(I)} chloroform disolvate

Soo Yei Ho ^a and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, National University of Singapore, Singapore 117543, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 22 October 2009; accepted 23 October 2009; online 31 October 2009)

The dinuclear title molecule, [Au₂Fe(C₁₀H₁₁N₂O₃S)₂(C₁₇H₁₄P)₂]·2CHCl₃, has crystallographic twofold symmetry with the Fe atom (bonded to two η⁵-cyclopentadienyl rings) situated on the rotation axis. The Au atom exists within a linear geometry defined by an S,P-donor set with a deviation from linearity [S—Au—P = 176.86 (6)°] due to the close approach of the thiocarbamate O atom [Au⋯O = 3.108 (5) Å]. The molecule has a U-shaped geometry which facilitates the formation of an intramolecular Au⋯Au interaction [3.0231 (5) Å]. In the crystal, the presence of C—H⋯O_nitro contacts leads to the formation of layers with substantial voids; these are occupied by the solvent molecules of crystallization, which are held in place by C—H⋯S contacts.

Related literature

For structural systematics and luminescence properties of phosphinegold(I) carbonimidothioates, see: Ho et al. (2006 ); Ho & Tiekink (2007 ); Kuan et al. (2008 ). For the synthesis, see: Hall et al. (1993 ).

Experimental

Crystal data

[Au₂Fe(C₁₀H₁₁N₂O₃S)₂(C₁₇H₁₄P)₂]·2CHCl₃
M_r = 1665.56
Monoclinic, C 2/c
a = 25.9661 (13) Å
b = 11.5544 (6) Å
c = 23.3615 (13) Å
β = 117.293 (1)°
V = 6228.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 5.36 mm⁻¹
T = 223 K
0.36 × 0.07 × 0.04 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.572, T_max = 1
21839 measured reflections
7148 independent reflections
4988 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.104
S = 0.97
7148 reflections
357 parameters
H-atom parameters constrained
Δρ_max = 2.08 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Au—S1	2.3127 (16)
Au—P1	2.2594 (15)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21⋯O2ⁱ	0.94	2.54	3.403 (9)	154
C25—H25⋯O3ⁱⁱ	0.94	2.46	3.254 (12)	142
C28—H28⋯S1ⁱⁱⁱ	0.99	2.61	3.527 (8)	154
Symmetry codes: (i) $[-x, y+1, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y, z-{\script{1\over 2}}]$ ; (iii) $[x, -y, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809043864/hb5168sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043864/hb5168Isup2.hkl

checkCIF report

Comment top

The dinuclear title compound, dppf{Au[SC(O-ⁱPr)NC₆H₄NO₂-p]}₂, was investigated as a part of systematic studies of phosphinegold(I) thiocarbamides (Ho et al. 2006; Ho & Tiekink, 2007; Kuan et al., 2008). Crystals were isolated as the di-chloroform solvate, (I), and are isomorphous with the methoxy analogue (Ho et al., 2006). The dinuclear molecule has crystallographic twofold symmetry with the Fe atom lying on the axis; the asymmetric unit comprises half a dinuclear molecule and one chloroform molecule. The gold atom exists in the expected linear geometry defined by a SP donor set, Table 1, and the deviation from linearity is ascribed to the close approach of the O1 atom, Au···O = 3.108 (5) Å. The anion, with a Z configuration about the C1═N1 bond, shows the expected characteristics. Overall, the molecule has a U-shaped configuration which allows for the formation of an aurophilic interaction, Au···Auⁱ = 3.0231 (5) Å; (i): -x, y, 1/2 - z.

In the crystal structure of (I), supramolecular layers are formed in the bc plane that are mediated by C—H···O interactions, Table 2 and Fig. 2. The resulting framework has solvent accessible voids and these are occupied by the chloroform molecules which are connected via C—H···S contacts, Table 2. Layer thus formed stack along the a direction.

Related literature top

For structural systematics and luminescence properties of phosphinegold(I) carbonimidothioates, see: Ho et al. (2006); Ho & Tiekink (2007); Kuan et al. (2008). For the synthesis, see: Hall et al. (1993).

Experimental top

The unsolvated compound was prepared following the standard literature procedure from the reaction of dppf(AuCl)₂ and i-PrOC(═S)N(H)C₆H₄NO₂-4 in the presence of base (Hall et al., 1993); m. pt. 409–410 K. Analysis for C₅₄H₅₀Au₂FeN₄O₆P₂S₂: found (calculated): C: 45.64 (45.45); H: 3.49 (3.53). IR (cm^-1): ν(C—S) 1100 s, 899m; ν(C—N) 1585 s; ν(C—O) 1153 s. ³¹P{¹H} NMR: δ 32.0 p.p.m. Orange crystals of the di-chloroform solvate (I) were obtained from the layering of ethanol on a chloroform solution of the characterized product.

Structure description top

For structural systematics and luminescence properties of phosphinegold(I) carbonimidothioates, see: Ho et al. (2006); Ho & Tiekink (2007); Kuan et al. (2008). For the synthesis, see: Hall et al. (1993).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the dinuclear complex in (I) showing displacement ellipsoids at the 35% probability level. The molecule has twofold symmetry and unlabelled atoms are generated by the symmetry operation -x, y, 1/2 - z.
	Fig. 2. Supramolecular layer formation in (I) mediated by C—H···O contacts (blue dashed lines). The chloroform molecules are connected via C—H···S contacts (orange dashed lines). Colour code: Au, orange; Cl, cyan; S, yellow; P, pink; O, red; N, blue; C, grey; and H, green.

µ-1,1'-Bis(diphenylphosphino)ferrocene-κ²P:P'- bis{[(Z)-O-isopropyl N-(4-nitrophenyl)thiocarbamato-κS]gold(I)} chloroform disolvate top

Crystal data top

[Au₂Fe(C₁₀H₁₁N₂O₃S)₂(C₁₇H₁₄P)₂]·2CHCl₃	F(000) = 3248
M_r = 1665.56	D_x = 1.776 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 3297 reflections
a = 25.9661 (13) Å	θ = 4.4–23.2°
b = 11.5544 (6) Å	µ = 5.36 mm⁻¹
c = 23.3615 (13) Å	T = 223 K
β = 117.293 (1)°	Needle, orange
V = 6228.7 (6) Å³	0.36 × 0.07 × 0.04 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	7148 independent reflections
Radiation source: fine-focus sealed tube	4988 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −31→33
T_min = 0.572, T_max = 1	k = −15→15
21839 measured reflections	l = −30→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0493P)²] where P = (F_o² + 2F_c²)/3
7148 reflections	(Δ/σ)_max = 0.001
357 parameters	Δρ_max = 2.08 e Å⁻³
0 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

[Au₂Fe(C₁₀H₁₁N₂O₃S)₂(C₁₇H₁₄P)₂]·2CHCl₃	V = 6228.7 (6) Å³
M_r = 1665.56	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 25.9661 (13) Å	µ = 5.36 mm⁻¹
b = 11.5544 (6) Å	T = 223 K
c = 23.3615 (13) Å	0.36 × 0.07 × 0.04 mm
β = 117.293 (1)°

Data collection top

Bruker SMART CCD diffractometer	7148 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	4988 reflections with I > 2σ(I)
T_min = 0.572, T_max = 1	R_int = 0.056
21839 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 0.97	Δρ_max = 2.08 e Å⁻³
7148 reflections	Δρ_min = −0.74 e Å⁻³
357 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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) top

	x	y	z	U_iso*/U_eq
Au	0.038384 (9)	0.040380 (18)	0.217132 (11)	0.03822 (9)
Fe	0.0000	0.36727 (10)	0.2500	0.0348 (3)
Cl1	0.09462 (11)	0.1755 (2)	0.62226 (16)	0.1115 (10)
Cl2	0.09451 (11)	0.4042 (2)	0.66861 (19)	0.1263 (13)
Cl3	−0.00491 (9)	0.2607 (2)	0.63203 (13)	0.0870 (7)
S1	0.08961 (7)	−0.09108 (14)	0.29813 (8)	0.0475 (4)
P1	−0.00697 (6)	0.17293 (13)	0.13880 (7)	0.0354 (3)
O1	0.17098 (19)	0.0531 (4)	0.3072 (2)	0.0568 (13)
O2	0.1974 (2)	−0.6234 (5)	0.4520 (3)	0.0835 (19)
O3	0.1523 (4)	−0.5385 (5)	0.4984 (3)	0.097 (2)
N1	0.2054 (2)	−0.1139 (5)	0.3638 (3)	0.0548 (15)
N2	0.1784 (3)	−0.5363 (5)	0.4654 (3)	0.0637 (18)
C1	0.1632 (3)	−0.0518 (5)	0.3277 (3)	0.0458 (16)
C2	0.1963 (2)	−0.2195 (6)	0.3880 (3)	0.0480 (17)
C3	0.2107 (3)	−0.3236 (6)	0.3689 (4)	0.0560 (18)
H3	0.2246	−0.3233	0.3381	0.067*
C4	0.2049 (3)	−0.4253 (6)	0.3942 (4)	0.0542 (19)
H4	0.2147	−0.4951	0.3810	0.065*
C5	0.1849 (3)	−0.4263 (6)	0.4384 (3)	0.0509 (17)
C6	0.1698 (3)	−0.3254 (6)	0.4587 (3)	0.0588 (19)
H6	0.1557	−0.3275	0.4893	0.071*
C7	0.1757 (3)	−0.2224 (6)	0.4334 (3)	0.0556 (19)
H7	0.1658	−0.1530	0.4468	0.067*
C8	0.2304 (3)	0.0878 (8)	0.3263 (5)	0.075 (3)
H8	0.2569	0.0509	0.3678	0.089*
C9	0.2330 (4)	0.2145 (8)	0.3331 (6)	0.113 (4)
H9A	0.2254	0.2364	0.3686	0.170*
H9B	0.2042	0.2493	0.2936	0.170*
H9C	0.2713	0.2414	0.3415	0.170*
C10	0.2436 (4)	0.0462 (9)	0.2737 (6)	0.107 (4)
H10A	0.2424	−0.0377	0.2723	0.160*
H10B	0.2819	0.0724	0.2820	0.160*
H10C	0.2150	0.0769	0.2327	0.160*
C11	−0.0392 (2)	0.2915 (5)	0.1610 (3)	0.0340 (13)
C12	−0.0298 (2)	0.4126 (5)	0.1557 (3)	0.0378 (14)
H12	−0.0075	0.4446	0.1373	0.045*
C13	−0.0598 (3)	0.4751 (5)	0.1828 (3)	0.0445 (16)
H13	−0.0610	0.5561	0.1855	0.053*
C14	−0.0877 (3)	0.3958 (5)	0.2052 (3)	0.0445 (15)
H14	−0.1104	0.4149	0.2256	0.053*
C15	−0.0756 (2)	0.2828 (5)	0.1919 (3)	0.0354 (13)
H15	−0.0891	0.2137	0.2016	0.042*
C16	−0.0634 (2)	0.1105 (5)	0.0653 (3)	0.0342 (13)
C17	−0.0487 (3)	0.0138 (5)	0.0404 (3)	0.0483 (17)
H17	−0.0105	−0.0142	0.0606	0.058*
C18	−0.0892 (3)	−0.0405 (6)	−0.0132 (4)	0.0547 (18)
H18	−0.0791	−0.1059	−0.0298	0.066*
C19	−0.1452 (3)	0.0012 (6)	−0.0428 (3)	0.0529 (18)
H19	−0.1732	−0.0353	−0.0800	0.063*
C20	−0.1603 (3)	0.0951 (6)	−0.0183 (3)	0.0569 (19)
H20	−0.1987	0.1221	−0.0383	0.068*
C21	−0.1191 (3)	0.1504 (5)	0.0357 (3)	0.0499 (17)
H21	−0.1294	0.2156	0.0522	0.060*
C22	0.0426 (3)	0.2447 (5)	0.1154 (3)	0.0423 (15)
C23	0.1015 (3)	0.2386 (6)	0.1572 (3)	0.0490 (16)
H23	0.1150	0.1944	0.1951	0.059*
C24	0.1405 (3)	0.2984 (7)	0.1426 (4)	0.068 (2)
H24	0.1804	0.2935	0.1705	0.081*
C25	0.1213 (4)	0.3646 (6)	0.0878 (4)	0.070 (2)
H25	0.1477	0.4071	0.0790	0.084*
C26	0.0623 (4)	0.3680 (6)	0.0455 (4)	0.064 (2)
H26	0.0489	0.4108	0.0071	0.077*
C27	0.0234 (3)	0.3085 (5)	0.0599 (3)	0.0525 (17)
H27	−0.0165	0.3119	0.0314	0.063*
C28	0.0705 (3)	0.2630 (6)	0.6651 (4)	0.062 (2)
H28	0.0867	0.2328	0.7096	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au	0.03377 (13)	0.03382 (12)	0.04130 (14)	0.00501 (10)	0.01225 (10)	0.00307 (11)
Fe	0.0327 (6)	0.0341 (6)	0.0337 (6)	0.000	0.0118 (5)	0.000
Cl1	0.0976 (18)	0.1016 (18)	0.161 (3)	−0.0139 (15)	0.0819 (19)	−0.0543 (19)
Cl2	0.0878 (17)	0.0519 (12)	0.239 (4)	−0.0138 (12)	0.074 (2)	−0.0203 (18)
Cl3	0.0653 (13)	0.0782 (14)	0.121 (2)	−0.0069 (11)	0.0461 (14)	−0.0200 (14)
S1	0.0364 (8)	0.0424 (8)	0.0557 (10)	0.0049 (7)	0.0142 (8)	0.0126 (8)
P1	0.0335 (8)	0.0328 (7)	0.0369 (8)	0.0014 (6)	0.0135 (7)	−0.0007 (6)
O1	0.037 (2)	0.048 (3)	0.072 (3)	−0.003 (2)	0.014 (2)	0.017 (2)
O2	0.073 (4)	0.041 (3)	0.136 (6)	−0.006 (3)	0.047 (4)	0.004 (3)
O3	0.152 (7)	0.061 (4)	0.103 (5)	−0.014 (4)	0.079 (5)	−0.004 (3)
N1	0.030 (3)	0.058 (3)	0.068 (4)	0.007 (3)	0.015 (3)	0.019 (3)
N2	0.060 (4)	0.046 (4)	0.075 (5)	−0.010 (3)	0.022 (4)	0.001 (3)
C1	0.044 (4)	0.045 (4)	0.046 (4)	0.000 (3)	0.019 (3)	0.005 (3)
C2	0.029 (3)	0.055 (4)	0.051 (4)	0.005 (3)	0.011 (3)	0.008 (3)
C3	0.044 (4)	0.061 (4)	0.066 (5)	0.008 (3)	0.028 (4)	0.006 (4)
C4	0.039 (4)	0.046 (4)	0.076 (5)	0.005 (3)	0.024 (4)	−0.001 (4)
C5	0.043 (4)	0.050 (4)	0.053 (4)	−0.003 (3)	0.015 (3)	0.003 (3)
C6	0.077 (5)	0.052 (4)	0.051 (4)	−0.006 (4)	0.032 (4)	0.002 (3)
C7	0.064 (5)	0.042 (4)	0.055 (4)	0.011 (3)	0.023 (4)	0.002 (3)
C8	0.035 (4)	0.079 (6)	0.091 (6)	0.000 (4)	0.013 (4)	0.030 (5)
C9	0.065 (6)	0.091 (7)	0.146 (10)	−0.037 (5)	0.016 (6)	−0.003 (7)
C10	0.066 (6)	0.108 (8)	0.159 (11)	0.005 (5)	0.063 (7)	0.021 (8)
C11	0.035 (3)	0.031 (3)	0.028 (3)	0.003 (2)	0.008 (3)	0.001 (2)
C12	0.038 (3)	0.034 (3)	0.035 (3)	−0.001 (2)	0.011 (3)	0.003 (3)
C13	0.044 (3)	0.037 (3)	0.041 (3)	0.007 (3)	0.010 (3)	0.003 (3)
C14	0.035 (3)	0.051 (4)	0.042 (4)	0.007 (3)	0.013 (3)	−0.002 (3)
C15	0.023 (3)	0.043 (3)	0.035 (3)	−0.002 (2)	0.010 (2)	0.003 (3)
C16	0.035 (3)	0.032 (3)	0.030 (3)	0.002 (2)	0.011 (2)	0.005 (2)
C17	0.043 (4)	0.046 (4)	0.050 (4)	0.009 (3)	0.017 (3)	−0.004 (3)
C18	0.060 (4)	0.045 (4)	0.062 (4)	−0.001 (3)	0.031 (4)	−0.013 (3)
C19	0.043 (4)	0.061 (4)	0.047 (4)	−0.014 (3)	0.015 (3)	−0.015 (3)
C20	0.036 (3)	0.062 (4)	0.056 (4)	0.005 (3)	0.006 (3)	−0.009 (4)
C21	0.048 (4)	0.039 (3)	0.057 (4)	0.007 (3)	0.019 (3)	−0.008 (3)
C22	0.052 (4)	0.034 (3)	0.051 (4)	0.000 (3)	0.033 (3)	−0.006 (3)
C23	0.044 (4)	0.048 (4)	0.057 (4)	−0.007 (3)	0.026 (3)	−0.009 (3)
C24	0.055 (4)	0.082 (6)	0.075 (6)	−0.013 (4)	0.037 (4)	−0.016 (5)
C25	0.097 (6)	0.052 (4)	0.097 (7)	−0.032 (4)	0.076 (6)	−0.029 (5)
C26	0.103 (7)	0.046 (4)	0.068 (5)	−0.005 (4)	0.060 (5)	−0.003 (4)
C27	0.076 (5)	0.042 (4)	0.053 (4)	−0.001 (3)	0.041 (4)	−0.006 (3)
C28	0.054 (4)	0.047 (4)	0.084 (6)	0.005 (3)	0.030 (4)	0.000 (4)

Geometric parameters (Å, º) top

Au—S1	2.3127 (16)	C8—H8	0.9900
Au—P1	2.2594 (15)	C9—H9A	0.9700
Au—Auⁱ	3.0231 (5)	C9—H9B	0.9700
Fe—C12ⁱ	2.041 (6)	C9—H9C	0.9700
Fe—C12	2.041 (6)	C10—H10A	0.9700
Fe—C11	2.045 (5)	C10—H10B	0.9700
Fe—C11ⁱ	2.045 (5)	C10—H10C	0.9700
Fe—C13ⁱ	2.047 (6)	C11—C15	1.431 (8)
Fe—C13	2.047 (6)	C11—C12	1.436 (8)
Fe—C14ⁱ	2.050 (6)	C12—C13	1.407 (9)
Fe—C14	2.050 (6)	C12—H12	0.9400
Fe—C15	2.051 (5)	C13—C14	1.409 (9)
Fe—C15ⁱ	2.051 (5)	C13—H13	0.9400
Cl1—C28	1.729 (8)	C14—C15	1.411 (8)
Cl2—C28	1.736 (7)	C14—H14	0.9400
Cl3—C28	1.744 (7)	C15—H15	0.9400
S1—C1	1.767 (6)	C16—C21	1.365 (8)
P1—C11	1.802 (6)	C16—C17	1.392 (8)
P1—C22	1.812 (6)	C17—C18	1.363 (9)
P1—C16	1.818 (5)	C17—H17	0.9400
O1—C1	1.353 (7)	C18—C19	1.380 (9)
O1—C8	1.453 (8)	C18—H18	0.9400
O2—N2	1.223 (8)	C19—C20	1.363 (10)
O3—N2	1.239 (9)	C19—H19	0.9400
N1—C1	1.257 (7)	C20—C21	1.382 (8)
N1—C2	1.410 (8)	C20—H20	0.9400
N2—C5	1.463 (9)	C21—H21	0.9400
C2—C7	1.390 (10)	C22—C27	1.372 (9)
C2—C3	1.392 (9)	C22—C23	1.389 (8)
C3—C4	1.355 (9)	C23—C24	1.390 (10)
C3—H3	0.9400	C23—H23	0.9400
C4—C5	1.353 (10)	C24—C25	1.373 (11)
C4—H4	0.9400	C24—H24	0.9400
C5—C6	1.381 (10)	C25—C26	1.391 (11)
C6—C7	1.369 (9)	C25—H25	0.9400
C6—H6	0.9400	C26—C27	1.386 (9)
C7—H7	0.9400	C26—H26	0.9400
C8—C9	1.470 (12)	C27—H27	0.9400
C8—C10	1.498 (14)	C28—H28	0.9900

P1—Au—S1	176.86 (6)	C10—C8—H8	110.3
P1—Au—Auⁱ	101.03 (4)	C8—C9—H9A	109.5
S1—Au—Auⁱ	81.38 (5)	C8—C9—H9B	109.5
C12ⁱ—Fe—C12	150.2 (3)	H9A—C9—H9B	109.5
C12ⁱ—Fe—C11	166.6 (2)	C8—C9—H9C	109.5
C12—Fe—C11	41.1 (2)	H9A—C9—H9C	109.5
C12ⁱ—Fe—C11ⁱ	41.1 (2)	H9B—C9—H9C	109.5
C12—Fe—C11ⁱ	166.6 (2)	C8—C10—H10A	109.5
C11—Fe—C11ⁱ	129.3 (3)	C8—C10—H10B	109.5
C12ⁱ—Fe—C13ⁱ	40.3 (3)	H10A—C10—H10B	109.5
C12—Fe—C13ⁱ	116.8 (2)	C8—C10—H10C	109.5
C11—Fe—C13ⁱ	152.7 (3)	H10A—C10—H10C	109.5
C11ⁱ—Fe—C13ⁱ	68.4 (2)	H10B—C10—H10C	109.5
C12ⁱ—Fe—C13	116.8 (2)	C15—C11—C12	106.9 (5)
C12—Fe—C13	40.3 (2)	C15—C11—P1	126.4 (4)
C11—Fe—C13	68.4 (2)	C12—C11—P1	126.6 (5)
C11ⁱ—Fe—C13	152.7 (3)	C15—C11—Fe	69.8 (3)
C13ⁱ—Fe—C13	105.0 (3)	C12—C11—Fe	69.3 (3)
C12ⁱ—Fe—C14ⁱ	68.0 (3)	P1—C11—Fe	122.5 (3)
C12—Fe—C14ⁱ	107.0 (3)	C13—C12—C11	108.0 (6)
C11—Fe—C14ⁱ	120.4 (2)	C13—C12—Fe	70.1 (4)
C11ⁱ—Fe—C14ⁱ	68.4 (2)	C11—C12—Fe	69.6 (3)
C13ⁱ—Fe—C14ⁱ	40.2 (3)	C13—C12—H12	126.0
C13—Fe—C14ⁱ	124.6 (3)	C11—C12—H12	126.0
C12ⁱ—Fe—C14	107.0 (3)	Fe—C12—H12	125.9
C12—Fe—C14	68.0 (3)	C12—C13—C14	108.6 (5)
C11—Fe—C14	68.4 (2)	C12—C13—Fe	69.6 (3)
C11ⁱ—Fe—C14	120.4 (2)	C14—C13—Fe	70.0 (3)
C13ⁱ—Fe—C14	124.6 (3)	C12—C13—H13	125.7
C13—Fe—C14	40.2 (3)	C14—C13—H13	125.7
C14ⁱ—Fe—C14	161.5 (4)	Fe—C13—H13	126.3
C12ⁱ—Fe—C15	127.7 (2)	C13—C14—C15	108.4 (6)
C12—Fe—C15	68.5 (2)	C13—C14—Fe	69.8 (3)
C11—Fe—C15	40.9 (2)	C15—C14—Fe	69.9 (3)
C11ⁱ—Fe—C15	110.4 (2)	C13—C14—H14	125.8
C13ⁱ—Fe—C15	163.0 (3)	C15—C14—H14	125.8
C13—Fe—C15	67.8 (2)	Fe—C14—H14	126.1
C14ⁱ—Fe—C15	156.4 (3)	C14—C15—C11	108.1 (5)
C14—Fe—C15	40.2 (2)	C14—C15—Fe	69.8 (3)
C12ⁱ—Fe—C15ⁱ	68.5 (2)	C11—C15—Fe	69.4 (3)
C12—Fe—C15ⁱ	127.7 (2)	C14—C15—H15	125.9
C11—Fe—C15ⁱ	110.4 (2)	C11—C15—H15	125.9
C11ⁱ—Fe—C15ⁱ	40.9 (2)	Fe—C15—H15	126.4
C13ⁱ—Fe—C15ⁱ	67.8 (2)	C21—C16—C17	119.2 (5)
C13—Fe—C15ⁱ	163.0 (3)	C21—C16—P1	123.5 (5)
C14ⁱ—Fe—C15ⁱ	40.2 (2)	C17—C16—P1	117.2 (4)
C14—Fe—C15ⁱ	156.4 (3)	C18—C17—C16	120.6 (6)
C15—Fe—C15ⁱ	123.1 (3)	C18—C17—H17	119.7
C1—S1—Au	105.3 (2)	C16—C17—H17	119.7
C11—P1—C22	103.1 (3)	C17—C18—C19	119.4 (6)
C11—P1—C16	107.1 (3)	C17—C18—H18	120.3
C22—P1—C16	105.8 (3)	C19—C18—H18	120.3
C11—P1—Au	114.88 (19)	C20—C19—C18	120.4 (6)
C22—P1—Au	112.1 (2)	C20—C19—H19	119.8
C16—P1—Au	113.01 (18)	C18—C19—H19	119.8
C1—O1—C8	116.6 (5)	C19—C20—C21	120.0 (6)
C1—N1—C2	120.5 (5)	C19—C20—H20	120.0
O2—N2—O3	122.9 (7)	C21—C20—H20	120.0
O2—N2—C5	117.7 (8)	C16—C21—C20	120.2 (6)
O3—N2—C5	119.3 (7)	C16—C21—H21	119.9
N1—C1—O1	121.5 (6)	C20—C21—H21	119.9
N1—C1—S1	124.8 (5)	C27—C22—C23	119.8 (6)
O1—C1—S1	113.7 (4)	C27—C22—P1	122.0 (5)
C7—C2—C3	118.6 (6)	C23—C22—P1	118.1 (5)
C7—C2—N1	121.4 (6)	C22—C23—C24	119.6 (7)
C3—C2—N1	120.0 (7)	C22—C23—H23	120.2
C4—C3—C2	120.5 (7)	C24—C23—H23	120.2
C4—C3—H3	119.7	C25—C24—C23	120.7 (7)
C2—C3—H3	119.7	C25—C24—H24	119.6
C5—C4—C3	120.0 (7)	C23—C24—H24	119.6
C5—C4—H4	120.0	C24—C25—C26	119.3 (7)
C3—C4—H4	120.0	C24—C25—H25	120.3
C4—C5—C6	121.6 (7)	C26—C25—H25	120.3
C4—C5—N2	119.8 (7)	C27—C26—C25	120.0 (7)
C6—C5—N2	118.6 (7)	C27—C26—H26	120.0
C7—C6—C5	118.7 (7)	C25—C26—H26	120.0
C7—C6—H6	120.7	C22—C27—C26	120.5 (7)
C5—C6—H6	120.7	C22—C27—H27	119.8
C6—C7—C2	120.6 (7)	C26—C27—H27	119.8
C6—C7—H7	119.7	Cl1—C28—Cl2	111.1 (5)
C2—C7—H7	119.7	Cl1—C28—Cl3	111.5 (4)
O1—C8—C9	107.3 (7)	Cl2—C28—Cl3	109.9 (4)
O1—C8—C10	105.6 (7)	Cl1—C28—H28	108.1
C9—C8—C10	113.0 (9)	Cl2—C28—H28	108.1
O1—C8—H8	110.3	Cl3—C28—H28	108.1
C9—C8—H8	110.3

Auⁱ—Au—S1—C1	−136.1 (2)	C11—Fe—C13—C12	−38.2 (3)
Auⁱ—Au—P1—C11	35.1 (2)	C11ⁱ—Fe—C13—C12	−174.3 (4)
Auⁱ—Au—P1—C22	152.3 (2)	C13ⁱ—Fe—C13—C12	113.9 (4)
Auⁱ—Au—P1—C16	−88.2 (2)	C14ⁱ—Fe—C13—C12	74.6 (4)
C2—N1—C1—O1	175.8 (6)	C14—Fe—C13—C12	−119.8 (5)
C2—N1—C1—S1	−5.1 (10)	C15—Fe—C13—C12	−82.4 (4)
C8—O1—C1—N1	2.9 (10)	C15ⁱ—Fe—C13—C12	51.0 (9)
C8—O1—C1—S1	−176.2 (6)	C12ⁱ—Fe—C13—C14	−84.9 (4)
Au—S1—C1—N1	−166.5 (6)	C12—Fe—C13—C14	119.8 (5)
Au—S1—C1—O1	12.6 (5)	C11—Fe—C13—C14	81.6 (4)
C1—N1—C2—C7	−69.1 (9)	C11ⁱ—Fe—C13—C14	−54.4 (6)
C1—N1—C2—C3	114.0 (8)	C13ⁱ—Fe—C13—C14	−126.3 (4)
C7—C2—C3—C4	−0.2 (10)	C14ⁱ—Fe—C13—C14	−165.5 (3)
N1—C2—C3—C4	176.8 (6)	C15—Fe—C13—C14	37.4 (4)
C2—C3—C4—C5	0.0 (10)	C15ⁱ—Fe—C13—C14	170.9 (7)
C3—C4—C5—C6	0.3 (11)	C12—C13—C14—C15	−0.4 (7)
C3—C4—C5—N2	179.7 (6)	Fe—C13—C14—C15	−59.5 (4)
O2—N2—C5—C4	7.8 (10)	C12—C13—C14—Fe	59.1 (4)
O3—N2—C5—C4	−169.4 (7)	C12ⁱ—Fe—C14—C13	111.6 (4)
O2—N2—C5—C6	−172.8 (7)	C12—Fe—C14—C13	−37.2 (4)
O3—N2—C5—C6	10.0 (10)	C11—Fe—C14—C13	−81.7 (4)
C4—C5—C6—C7	−0.4 (11)	C11ⁱ—Fe—C14—C13	154.4 (4)
N2—C5—C6—C7	−179.8 (6)	C13ⁱ—Fe—C14—C13	70.9 (6)
C5—C6—C7—C2	0.2 (11)	C14ⁱ—Fe—C14—C13	40.4 (3)
C3—C2—C7—C6	0.1 (10)	C15—Fe—C14—C13	−119.5 (5)
N1—C2—C7—C6	−176.8 (6)	C15ⁱ—Fe—C14—C13	−173.3 (5)
C1—O1—C8—C9	−148.5 (8)	C12ⁱ—Fe—C14—C15	−128.9 (4)
C1—O1—C8—C10	90.7 (8)	C12—Fe—C14—C15	82.3 (4)
C22—P1—C11—C15	−170.5 (5)	C11—Fe—C14—C15	37.8 (4)
C16—P1—C11—C15	78.1 (5)	C11ⁱ—Fe—C14—C15	−86.1 (4)
Au—P1—C11—C15	−48.3 (5)	C13ⁱ—Fe—C14—C15	−169.6 (4)
C22—P1—C11—C12	4.3 (6)	C13—Fe—C14—C15	119.5 (5)
C16—P1—C11—C12	−107.1 (5)	C14ⁱ—Fe—C14—C15	159.9 (4)
Au—P1—C11—C12	126.6 (4)	C15ⁱ—Fe—C14—C15	−53.8 (9)
C22—P1—C11—Fe	−82.8 (4)	C13—C14—C15—C11	0.4 (6)
C16—P1—C11—Fe	165.8 (3)	Fe—C14—C15—C11	−59.0 (4)
Au—P1—C11—Fe	39.4 (4)	C13—C14—C15—Fe	59.4 (4)
C12ⁱ—Fe—C11—C15	34.7 (11)	C12—C11—C15—C14	−0.3 (6)
C12—Fe—C11—C15	−118.1 (5)	P1—C11—C15—C14	175.4 (4)
C11ⁱ—Fe—C11—C15	75.1 (3)	Fe—C11—C15—C14	59.3 (4)
C13ⁱ—Fe—C11—C15	−161.5 (5)	C12—C11—C15—Fe	−59.6 (4)
C13—Fe—C11—C15	−80.7 (4)	P1—C11—C15—Fe	116.1 (4)
C14ⁱ—Fe—C11—C15	160.9 (3)	C12ⁱ—Fe—C15—C14	70.1 (5)
C14—Fe—C11—C15	−37.2 (3)	C12—Fe—C15—C14	−80.9 (4)
C15ⁱ—Fe—C11—C15	117.5 (4)	C11—Fe—C15—C14	−119.5 (5)
C12ⁱ—Fe—C11—C12	152.8 (8)	C11ⁱ—Fe—C15—C14	113.4 (4)
C11ⁱ—Fe—C11—C12	−166.8 (4)	C13ⁱ—Fe—C15—C14	30.7 (10)
C13ⁱ—Fe—C11—C12	−43.4 (6)	C13—Fe—C15—C14	−37.4 (4)
C13—Fe—C11—C12	37.4 (4)	C14ⁱ—Fe—C15—C14	−164.2 (4)
C14ⁱ—Fe—C11—C12	−81.0 (4)	C15ⁱ—Fe—C15—C14	157.3 (4)
C14—Fe—C11—C12	80.9 (4)	C12ⁱ—Fe—C15—C11	−170.4 (3)
C15—Fe—C11—C12	118.1 (5)	C12—Fe—C15—C11	38.6 (3)
C15ⁱ—Fe—C11—C12	−124.4 (4)	C11ⁱ—Fe—C15—C11	−127.1 (4)
C12ⁱ—Fe—C11—P1	−86.2 (11)	C13ⁱ—Fe—C15—C11	150.2 (8)
C12—Fe—C11—P1	120.9 (5)	C13—Fe—C15—C11	82.1 (4)
C11ⁱ—Fe—C11—P1	−45.9 (3)	C14ⁱ—Fe—C15—C11	−44.7 (7)
C13ⁱ—Fe—C11—P1	77.5 (6)	C14—Fe—C15—C11	119.5 (5)
C13—Fe—C11—P1	158.4 (4)	C15ⁱ—Fe—C15—C11	−83.2 (3)
C14ⁱ—Fe—C11—P1	40.0 (5)	C11—P1—C16—C21	−0.6 (6)
C14—Fe—C11—P1	−158.2 (4)	C22—P1—C16—C21	−110.1 (6)
C15—Fe—C11—P1	−121.0 (5)	Au—P1—C16—C21	126.9 (5)
C15ⁱ—Fe—C11—P1	−3.5 (4)	C11—P1—C16—C17	−177.7 (5)
C15—C11—C12—C13	0.1 (6)	C22—P1—C16—C17	72.8 (5)
P1—C11—C12—C13	−175.6 (4)	Au—P1—C16—C17	−50.2 (5)
Fe—C11—C12—C13	−59.8 (4)	C21—C16—C17—C18	0.2 (10)
C15—C11—C12—Fe	59.9 (4)	P1—C16—C17—C18	177.4 (6)
P1—C11—C12—Fe	−115.8 (4)	C16—C17—C18—C19	0.2 (11)
C12ⁱ—Fe—C12—C13	−48.7 (3)	C17—C18—C19—C20	−0.9 (12)
C11—Fe—C12—C13	119.0 (5)	C18—C19—C20—C21	1.2 (12)
C11ⁱ—Fe—C12—C13	168.6 (9)	C17—C16—C21—C20	0.1 (10)
C13ⁱ—Fe—C12—C13	−81.6 (5)	P1—C16—C21—C20	−176.9 (6)
C14ⁱ—Fe—C12—C13	−123.9 (4)	C19—C20—C21—C16	−0.8 (11)
C14—Fe—C12—C13	37.2 (4)	C11—P1—C22—C27	−70.8 (6)
C15—Fe—C12—C13	80.7 (4)	C16—P1—C22—C27	41.6 (6)
C15ⁱ—Fe—C12—C13	−163.3 (4)	Au—P1—C22—C27	165.1 (5)
C12ⁱ—Fe—C12—C11	−167.7 (4)	C11—P1—C22—C23	106.0 (5)
C11ⁱ—Fe—C12—C11	49.5 (13)	C16—P1—C22—C23	−141.7 (5)
C13ⁱ—Fe—C12—C11	159.4 (3)	Au—P1—C22—C23	−18.1 (5)
C13—Fe—C12—C11	−119.0 (5)	C27—C22—C23—C24	0.7 (10)
C14ⁱ—Fe—C12—C11	117.1 (4)	P1—C22—C23—C24	−176.2 (5)
C14—Fe—C12—C11	−81.8 (4)	C22—C23—C24—C25	0.9 (11)
C15—Fe—C12—C11	−38.4 (3)	C23—C24—C25—C26	−2.4 (11)
C15ⁱ—Fe—C12—C11	77.6 (4)	C24—C25—C26—C27	2.3 (11)
C11—C12—C13—C14	0.2 (6)	C23—C22—C27—C26	−0.7 (9)
Fe—C12—C13—C14	−59.3 (4)	P1—C22—C27—C26	176.0 (5)
C11—C12—C13—Fe	59.5 (4)	C25—C26—C27—C22	−0.8 (10)
C12ⁱ—Fe—C13—C12	155.3 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···O2ⁱⁱ	0.94	2.54	3.403 (9)	154
C25—H25···O3ⁱⁱⁱ	0.94	2.46	3.254 (12)	142
C28—H28···S1^iv	0.99	2.61	3.527 (8)	154

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

Experimental details

Crystal data
Chemical formula	[Au₂Fe(C₁₀H₁₁N₂O₃S)₂(C₁₇H₁₄P)₂]·2CHCl₃
M_r	1665.56
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	223
a, b, c (Å)	25.9661 (13), 11.5544 (6), 23.3615 (13)
β (°)	117.293 (1)
V (Å³)	6228.7 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.36
Crystal size (mm)	0.36 × 0.07 × 0.04

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.572, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	21839, 7148, 4988
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.104, 0.97
No. of reflections	7148
No. of parameters	357
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.08, −0.74

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), PATTY in DIRDIF92 (Beurskens et al., 1992), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

Selected geometric parameters (Å, º) top

Au—S1	2.3127 (16)	Au—P1	2.2594 (15)

P1—Au—S1	176.86 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···O2ⁱ	0.94	2.54	3.403 (9)	154
C25—H25···O3ⁱⁱ	0.94	2.46	3.254 (12)	142
C28—H28···S1ⁱⁱⁱ	0.99	2.61	3.527 (8)	154

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

Acknowledgements

The National University of Singapore (grant No. R-143–000–213–112) is thanked for support.

References

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