Bis[μ-bis­(diphenyl­phosphino)methane-κ2P:P′]digold(I)(Au—Au) dinitrate perdeuteromethanol solvate

Jongh, L.-A. de; Strasser, C.E.; Cronje, S.; Raubenheimer, H.G.

doi:10.1107/S1600536807030887

Bis[μ-bis(diphenylphosphino)methane-κ²P:P′]digold(I)(Au—Au) dinitrate perdeuteromethanol solvate

L.-A. de Jongh, C. E. Strasser, S. Cronje and H. G. Raubenheimer

In the centrosymmetric dicationic cyclic title compound [Au₂(C₂₅H₂₂P₂)₂](NO₃)₂·2CD₃OD, an aurophilic interaction with a distance of 3.0245 (3) Å is found between the linear-dicoordinated Au^I centres. The perdeuteromethanol solvent molecules are linked to the nitrate anions via hydrogen bonds.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030887/hg2244sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030887/hg2244Isup2.hkl Contains datablock I

CCDC reference: 657576

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.005 Å
R factor = 0.022
wR factor = 0.052
Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.52
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            P2  -AU1 -P1  -C21   136.70  0.70   3.665   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          4
            P2  -AU1 -P1  -C11    12.60  0.70   3.665   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          7
            P2  -AU1 -P1  -C1   -103.60  0.70   3.665   1.555   1.555   1.555
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.11 Ratio

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Au1         (9)       1.25

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Binuclear gold complexes with bridging bidentate ligands and various counter-ions have been the subject of several studies due to their rich luminescence and bonding properties (King et al., 1989) and have been structurally characterized (Jaw et al., 1989; Khan et al., 1989; Porter et al., 1989; Liou et al., 1994; Wang & Liu, 1994; Bauer & Schmidbaur, 1997). The bridging methylene carbon can be exploited as a coordination and reactive centre. Neutral homo- or heterometallic tetranuclear derivatives have been reported (Uson et al., 1986). It is assumed that Au···Au distances are determined by electronic effects of the substituents L and X at gold but it has become more obvious that steric effects play a decisive role. The weak forces associated with Au···Au contacts can be overruled by steric repulsion and other factors like packing forces (Angermaier & Schmidbaur, 1995). Here we report another crystal and molecular structure containing this dication. Each nitrate counter anion engages in a hydrogen bond to one perdeuteromethanol lattice solvent.

The asymmetric unit of (A) consists of one half of the dication, [(µ-dppm)₂Au₂]²⁺, containing one nitrate anion and one deuterated methanol molecule. The rest of the molecule is related by a centre of symmetry between the gold atoms of each dimer. The Au···Au separation is 3.0245 (3) Å. This agrees with a weak Au···Au interaction (Schmidbaur et al., 2005). In this instance the steric constraints of the dppm ligand assist the aurophillic interaction in the Au₂P₄C₂ ring which has a chair conformation (Perreault et al., 1992; Bauer & Schmidbaur, 1997). The Au centres adopt a normal linear two-coordinate geometry of 177.76 (3) Å, slightly distorted from ideality by the aurophilic bonding. Channels of anions are observed running parallel to the a axis. Two oxygen atoms of the nitrate are aligned towards the gold atom in the cation with distances of 3.470 (2) Å for O2–Au1ⁱ [symmetry code: (i) = -x + 1, -y + 1,-z] and 3.357 (2) Å for O1—Au1.

Related literature top

For related literature, see: Angermaier & Schmidbaur (1995); Bauer & Schmidbaur (1997); Cooper et al. (1984); Jaw et al. (1989); Khan et al. (1989); King et al. (1989); Liou et al. (1994); Malatesa et al. (1966); Perreault et al. (1992); Porter et al. (1989); Schmidbaur et al. (2005); Uson et al. (1986); Wang & Liu (1994).

Experimental top

The title compound was prepared using (µ-dppm)₂AuCl₂ (Cooper et al., 1984) and literature methods (Malatesa et al., 1966). Colourless crystals that were suitable for X-Ray diffraction were obtained at 251 K in deuterated methanol.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED.

Figures top

Fig. 1. The molecular structure of (A), showing atom labels and 50% probability displacement ellipsoids for non-H atoms.

Bis[µ-bis(diphenylphosphino)methane-κ²P:P']digold(I)(Au—Au) dinitrate perdeuteromethanol solvate top

Crystal data top

[Au₂(C₂₅H₂₂P₂)₂](NO₃)₂·2CD₄O	F(000) = 1320
M_r = 1358.71	D_x = 1.834 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 414.8 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.6214 (8) Å	Cell parameters from 6683 reflections
b = 13.6313 (9) Å	θ = 2.4–26.4°
c = 16.4319 (12) Å	µ = 6.14 mm⁻¹
β = 109.048 (1)°	T = 100 K
V = 2460.5 (3) Å³	Prism, colourless
Z = 2	0.27 × 0.19 × 0.13 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	5019 independent reflections
Radiation source: fine-focus sealed tube	4626 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 26.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→14
T_min = 0.256, T_max = 0.450	k = −17→12
14182 measured reflections	l = −20→18

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.052	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0256P)² + 0.7357P] where P = (F_o² + 2F_c²)/3
5019 reflections	(Δ/σ)_max = 0.001
309 parameters	Δρ_max = 1.64 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Au₂(C₂₅H₂₂P₂)₂](NO₃)₂·2CD₄O	V = 2460.5 (3) Å³
M_r = 1358.71	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.6214 (8) Å	µ = 6.14 mm⁻¹
b = 13.6313 (9) Å	T = 100 K
c = 16.4319 (12) Å	0.27 × 0.19 × 0.13 mm
β = 109.048 (1)°

Data collection top

Bruker APEX CCD area-detector diffractometer	5019 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	4626 reflections with I > 2σ(I)
T_min = 0.256, T_max = 0.450	R_int = 0.025
14182 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.052	H-atom parameters constrained
S = 1.06	Δρ_max = 1.64 e Å⁻³
5019 reflections	Δρ_min = −0.47 e Å⁻³
309 parameters

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
Au1	0.408600 (9)	0.485644 (8)	0.046685 (7)	0.01107 (5)
P1	0.26529 (6)	0.57042 (6)	−0.06166 (5)	0.01064 (16)
P2	0.45307 (7)	0.60437 (6)	−0.15453 (5)	0.01081 (16)
O1	0.6025 (2)	0.78397 (16)	0.18981 (15)	0.0216 (5)
O2	0.6738 (2)	0.66210 (17)	0.13524 (14)	0.0230 (5)
O3	0.5548 (2)	0.63412 (17)	0.21084 (15)	0.0248 (5)
O4	0.3636 (2)	0.7250 (2)	0.26312 (16)	0.0338 (6)
D4	0.4274	0.6978	0.2610	0.051*
N1	0.6106 (2)	0.6935 (2)	0.17854 (17)	0.0182 (6)
C1	0.2969 (3)	0.5708 (2)	−0.16312 (19)	0.0122 (6)
H1A	0.2404	0.6173	−0.2029	0.015*
H1B	0.2796	0.5046	−0.1891	0.015*
C4	0.3516 (4)	0.7089 (3)	0.3450 (3)	0.0389 (10)
D4A	0.4209	0.7384	0.3894	0.058*
D4B	0.3496	0.6383	0.3554	0.058*
D4C	0.2759	0.7390	0.3468	0.058*
C11	0.1141 (3)	0.5171 (2)	−0.0928 (2)	0.0132 (6)
C12	0.0970 (3)	0.4237 (3)	−0.0638 (2)	0.0220 (7)
H12	0.1636	0.3896	−0.0247	0.026*
C13	−0.0175 (3)	0.3809 (2)	−0.0922 (2)	0.0264 (8)
H13	−0.0291	0.3173	−0.0727	0.032*
C14	−0.1141 (3)	0.4298 (3)	−0.1485 (2)	0.0224 (7)
H14	−0.1922	0.3999	−0.1678	0.027*
C15	−0.0980 (3)	0.5223 (3)	−0.1770 (2)	0.0226 (8)
H15	−0.1654	0.5562	−0.2155	0.027*
C16	0.0151 (3)	0.5660 (2)	−0.1499 (2)	0.0187 (7)
H16	0.0257	0.6296	−0.1701	0.022*
C21	0.2552 (2)	0.6982 (2)	−0.03458 (19)	0.0115 (6)
C22	0.3051 (3)	0.7273 (2)	0.0513 (2)	0.0150 (6)
H22	0.3408	0.6798	0.0945	0.018*
C23	0.3027 (3)	0.8244 (2)	0.0735 (2)	0.0171 (7)
H23	0.3366	0.8438	0.1320	0.021*
C24	0.2508 (3)	0.8942 (2)	0.0104 (2)	0.0170 (7)
H24	0.2498	0.9613	0.0259	0.020*
C25	0.2008 (3)	0.8660 (2)	−0.0748 (2)	0.0154 (6)
H25	0.1648	0.9137	−0.1177	0.019*
C26	0.2031 (3)	0.7684 (2)	−0.0975 (2)	0.0154 (6)
H26	0.1692	0.7493	−0.1561	0.018*
C31	0.4599 (3)	0.5910 (2)	−0.2622 (2)	0.0132 (6)
C32	0.3662 (3)	0.6220 (2)	−0.3352 (2)	0.0150 (6)
H32	0.2903	0.6422	−0.3306	0.018*
C33	0.3844 (3)	0.6232 (2)	−0.4144 (2)	0.0160 (7)
H33	0.3211	0.6454	−0.4638	0.019*
C34	0.4930 (3)	0.5925 (2)	−0.4223 (2)	0.0199 (7)
H34	0.5052	0.5946	−0.4767	0.024*
C35	0.5846 (3)	0.5587 (3)	−0.3505 (2)	0.0214 (7)
H35	0.6590	0.5363	−0.3562	0.026*
C36	0.5691 (3)	0.5571 (2)	−0.2710 (2)	0.0187 (7)
H36	0.6322	0.5331	−0.2223	0.022*
C41	0.4729 (3)	0.7353 (2)	−0.1336 (2)	0.0128 (6)
C42	0.5348 (3)	0.7659 (2)	−0.0495 (2)	0.0163 (7)
H42	0.5652	0.7187	−0.0052	0.020*
C43	0.5520 (3)	0.8650 (3)	−0.0308 (2)	0.0216 (7)
H43	0.5931	0.8856	0.0266	0.026*
C44	0.5096 (3)	0.9340 (2)	−0.0954 (2)	0.0208 (7)
H44	0.5222	1.0019	−0.0827	0.025*
C45	0.4485 (3)	0.9034 (2)	−0.1791 (2)	0.0207 (7)
H45	0.4191	0.9508	−0.2234	0.025*
C46	0.4301 (3)	0.8047 (2)	−0.1984 (2)	0.0176 (7)
H46	0.3884	0.7844	−0.2558	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.00955 (7)	0.01244 (7)	0.01065 (7)	0.00124 (4)	0.00248 (5)	0.00256 (4)
P1	0.0095 (3)	0.0108 (4)	0.0113 (4)	0.0002 (3)	0.0029 (3)	0.0006 (3)
P2	0.0099 (4)	0.0119 (4)	0.0102 (4)	0.0001 (3)	0.0027 (3)	0.0013 (3)
O1	0.0273 (13)	0.0147 (12)	0.0199 (13)	−0.0031 (10)	0.0036 (10)	−0.0014 (9)
O2	0.0262 (12)	0.0255 (13)	0.0175 (13)	0.0054 (10)	0.0075 (10)	0.0000 (10)
O3	0.0308 (13)	0.0208 (13)	0.0224 (14)	−0.0106 (10)	0.0083 (11)	0.0022 (10)
O4	0.0357 (15)	0.0440 (17)	0.0221 (14)	−0.0021 (13)	0.0098 (12)	0.0010 (12)
N1	0.0187 (14)	0.0206 (15)	0.0105 (14)	−0.0001 (12)	−0.0018 (11)	−0.0004 (11)
C1	0.0114 (14)	0.0128 (15)	0.0114 (15)	0.0015 (12)	0.0025 (12)	0.0015 (12)
C4	0.055 (3)	0.037 (2)	0.032 (2)	−0.012 (2)	0.022 (2)	−0.0014 (18)
C11	0.0118 (15)	0.0148 (16)	0.0138 (16)	−0.0007 (12)	0.0052 (13)	−0.0006 (12)
C12	0.0181 (16)	0.0187 (18)	0.029 (2)	0.0009 (13)	0.0073 (15)	0.0064 (14)
C13	0.0214 (17)	0.0187 (18)	0.040 (2)	−0.0025 (14)	0.0110 (16)	0.0043 (15)
C14	0.0141 (16)	0.0269 (19)	0.026 (2)	−0.0064 (14)	0.0065 (14)	−0.0047 (15)
C15	0.0140 (16)	0.033 (2)	0.0194 (19)	0.0003 (14)	0.0033 (14)	0.0046 (14)
C16	0.0156 (15)	0.0171 (17)	0.0229 (18)	−0.0003 (13)	0.0056 (14)	0.0034 (13)
C21	0.0098 (14)	0.0117 (15)	0.0143 (16)	0.0001 (11)	0.0057 (12)	−0.0002 (12)
C22	0.0134 (15)	0.0178 (17)	0.0131 (16)	0.0005 (12)	0.0035 (13)	0.0026 (12)
C23	0.0187 (16)	0.0208 (17)	0.0121 (16)	0.0006 (13)	0.0054 (13)	−0.0043 (13)
C24	0.0171 (16)	0.0135 (16)	0.0227 (18)	−0.0001 (12)	0.0098 (14)	−0.0024 (13)
C25	0.0170 (15)	0.0129 (16)	0.0178 (17)	0.0049 (12)	0.0076 (13)	0.0049 (12)
C26	0.0157 (15)	0.0173 (16)	0.0124 (16)	0.0005 (13)	0.0036 (13)	0.0007 (12)
C31	0.0138 (14)	0.0118 (15)	0.0155 (16)	−0.0019 (12)	0.0068 (13)	−0.0010 (12)
C32	0.0123 (15)	0.0135 (16)	0.0173 (17)	−0.0010 (12)	0.0023 (13)	−0.0023 (12)
C33	0.0201 (16)	0.0145 (16)	0.0111 (16)	−0.0012 (13)	0.0022 (13)	0.0001 (12)
C34	0.0246 (17)	0.0228 (18)	0.0144 (17)	−0.0033 (14)	0.0091 (14)	−0.0004 (13)
C35	0.0161 (16)	0.029 (2)	0.0218 (18)	0.0018 (14)	0.0101 (14)	0.0017 (15)
C36	0.0155 (15)	0.0219 (18)	0.0195 (18)	0.0026 (13)	0.0069 (13)	0.0032 (14)
C41	0.0111 (14)	0.0130 (15)	0.0153 (16)	−0.0007 (12)	0.0058 (13)	−0.0008 (12)
C42	0.0143 (15)	0.0191 (17)	0.0140 (17)	0.0040 (13)	0.0028 (13)	0.0023 (13)
C43	0.0162 (16)	0.0253 (19)	0.0199 (18)	−0.0008 (14)	0.0013 (14)	−0.0087 (14)
C44	0.0197 (16)	0.0141 (17)	0.029 (2)	0.0004 (13)	0.0080 (15)	−0.0046 (14)
C45	0.0248 (17)	0.0139 (17)	0.0243 (19)	0.0015 (14)	0.0092 (15)	0.0055 (13)
C46	0.0184 (16)	0.0195 (17)	0.0134 (17)	−0.0012 (13)	0.0033 (13)	0.0007 (13)

Geometric parameters (Å, º) top

Au1—P1	2.3116 (8)	C21—C26	1.393 (4)
Au1—P2ⁱ	2.3175 (8)	C21—C22	1.397 (4)
Au1—Au1ⁱ	3.0245 (3)	C22—C23	1.375 (4)
Au1—O3	3.357 (2)	C22—H22	0.9500
P1—C21	1.811 (3)	C23—C24	1.391 (4)
P1—C11	1.814 (3)	C23—H23	0.9500
P1—C1	1.821 (3)	C24—C25	1.384 (4)
P2—C31	1.805 (3)	C24—H24	0.9500
P2—C41	1.818 (3)	C25—C26	1.384 (4)
P2—C1	1.832 (3)	C25—H25	0.9500
P2—Au1ⁱ	2.3175 (8)	C26—H26	0.9500
O1—N1	1.256 (3)	C31—C32	1.397 (4)
O2—N1	1.253 (3)	C31—C36	1.402 (4)
O2—Au1ⁱ	3.470 (2)	C32—C33	1.385 (4)
O3—N1	1.257 (3)	C32—H32	0.9500
O4—C4	1.414 (4)	C33—C34	1.376 (4)
O4—D4	0.8400	C33—H33	0.9500
C1—H1A	0.9900	C34—C35	1.384 (5)
C1—H1B	0.9900	C34—H34	0.9500
C4—D4A	0.9800	C35—C36	1.376 (4)
C4—D4B	0.9800	C35—H35	0.9500
C4—D4C	0.9800	C36—H36	0.9500
C11—C16	1.394 (4)	C41—C46	1.389 (4)
C11—C12	1.396 (4)	C41—C42	1.397 (4)
C12—C13	1.387 (4)	C42—C43	1.385 (4)
C12—H12	0.9500	C42—H42	0.9500
C13—C14	1.372 (5)	C43—C44	1.384 (5)
C13—H13	0.9500	C43—H43	0.9500
C14—C15	1.378 (5)	C44—C45	1.389 (5)
C14—H14	0.9500	C44—H44	0.9500
C15—C16	1.379 (4)	C45—C46	1.383 (4)
C15—H15	0.9500	C45—H45	0.9500
C16—H16	0.9500	C46—H46	0.9500

P1—Au1—P2ⁱ	177.76 (3)	C26—C21—C22	119.4 (3)
P1—Au1—Au1ⁱ	89.62 (2)	C26—C21—P1	121.7 (2)
P2ⁱ—Au1—Au1ⁱ	91.70 (2)	C22—C21—P1	118.8 (2)
P1—Au1—O3	111.47 (4)	C23—C22—C21	120.2 (3)
P2ⁱ—Au1—O3	70.24 (4)	C23—C22—H22	119.9
Au1ⁱ—Au1—O3	94.27 (4)	C21—C22—H22	119.9
C21—P1—C11	108.68 (13)	C22—C23—C24	120.1 (3)
C21—P1—C1	105.71 (14)	C22—C23—H23	119.9
C11—P1—C1	102.07 (14)	C24—C23—H23	119.9
C21—P1—Au1	112.32 (10)	C25—C24—C23	120.1 (3)
C11—P1—Au1	113.89 (10)	C25—C24—H24	120.0
C1—P1—Au1	113.37 (10)	C23—C24—H24	120.0
C31—P2—C41	103.94 (14)	C24—C25—C26	120.1 (3)
C31—P2—C1	104.97 (14)	C24—C25—H25	120.0
C41—P2—C1	108.72 (13)	C26—C25—H25	120.0
C31—P2—Au1ⁱ	117.03 (10)	C25—C26—C21	120.1 (3)
C41—P2—Au1ⁱ	111.21 (10)	C25—C26—H26	120.0
C1—P2—Au1ⁱ	110.44 (10)	C21—C26—H26	120.0
N1—O2—Au1ⁱ	129.75 (18)	C32—C31—C36	119.3 (3)
N1—O3—Au1	104.14 (18)	C32—C31—P2	122.7 (2)
C4—O4—D4	109.5	C36—C31—P2	117.7 (2)
O2—N1—O1	120.3 (3)	C33—C32—C31	119.7 (3)
O2—N1—O3	119.9 (3)	C33—C32—H32	120.2
O1—N1—O3	119.7 (3)	C31—C32—H32	120.2
P1—C1—P2	114.91 (16)	C34—C33—C32	120.8 (3)
P1—C1—H1A	108.5	C34—C33—H33	119.6
P2—C1—H1A	108.5	C32—C33—H33	119.6
P1—C1—H1B	108.5	C33—C34—C35	119.6 (3)
P2—C1—H1B	108.5	C33—C34—H34	120.2
H1A—C1—H1B	107.5	C35—C34—H34	120.2
O4—C4—D4A	109.5	C36—C35—C34	120.8 (3)
O4—C4—D4B	109.5	C36—C35—H35	119.6
D4A—C4—D4B	109.5	C34—C35—H35	119.6
O4—C4—D4C	109.5	C35—C36—C31	119.8 (3)
D4A—C4—D4C	109.5	C35—C36—H36	120.1
D4B—C4—D4C	109.5	C31—C36—H36	120.1
C16—C11—C12	119.2 (3)	C46—C41—C42	119.7 (3)
C16—C11—P1	120.6 (2)	C46—C41—P2	122.1 (2)
C12—C11—P1	120.1 (2)	C42—C41—P2	118.2 (2)
C13—C12—C11	119.8 (3)	C43—C42—C41	120.1 (3)
C13—C12—H12	120.1	C43—C42—H42	119.9
C11—C12—H12	120.1	C41—C42—H42	119.9
C14—C13—C12	120.4 (3)	C44—C43—C42	120.2 (3)
C14—C13—H13	119.8	C44—C43—H43	119.9
C12—C13—H13	119.8	C42—C43—H43	119.9
C13—C14—C15	120.1 (3)	C43—C44—C45	119.6 (3)
C13—C14—H14	119.9	C43—C44—H44	120.2
C15—C14—H14	119.9	C45—C44—H44	120.2
C14—C15—C16	120.4 (3)	C46—C45—C44	120.7 (3)
C14—C15—H15	119.8	C46—C45—H45	119.7
C16—C15—H15	119.8	C44—C45—H45	119.7
C15—C16—C11	120.1 (3)	C45—C46—C41	119.8 (3)
C15—C16—H16	120.0	C45—C46—H46	120.1
C11—C16—H16	120.0	C41—C46—H46	120.1

P2ⁱ—Au1—P1—C21	136.7 (7)	C11—P1—C21—C22	110.4 (2)
Au1ⁱ—Au1—P1—C21	−97.16 (10)	C1—P1—C21—C22	−140.7 (2)
O3—Au1—P1—C21	−2.72 (11)	Au1—P1—C21—C22	−16.6 (3)
P2ⁱ—Au1—P1—C11	12.6 (7)	C26—C21—C22—C23	0.1 (4)
Au1ⁱ—Au1—P1—C11	138.74 (11)	P1—C21—C22—C23	177.7 (2)
O3—Au1—P1—C11	−126.82 (12)	C21—C22—C23—C24	−0.2 (5)
P2ⁱ—Au1—P1—C1	−103.6 (7)	C22—C23—C24—C25	0.4 (5)
Au1ⁱ—Au1—P1—C1	22.60 (11)	C23—C24—C25—C26	−0.5 (5)
O3—Au1—P1—C1	117.04 (11)	C24—C25—C26—C21	0.4 (5)
P1—Au1—O3—N1	−64.04 (18)	C22—C21—C26—C25	−0.2 (4)
P2ⁱ—Au1—O3—N1	117.50 (18)	P1—C21—C26—C25	−177.7 (2)
Au1ⁱ—Au1—O3—N1	27.23 (18)	C41—P2—C31—C32	−72.2 (3)
Au1ⁱ—O2—N1—O1	−123.0 (2)	C1—P2—C31—C32	41.9 (3)
Au1ⁱ—O2—N1—O3	56.9 (3)	Au1ⁱ—P2—C31—C32	164.8 (2)
Au1—O3—N1—O2	−49.4 (3)	C41—P2—C31—C36	101.2 (3)
Au1—O3—N1—O1	130.5 (2)	C1—P2—C31—C36	−144.6 (2)
C21—P1—C1—P2	74.66 (18)	Au1ⁱ—P2—C31—C36	−21.8 (3)
C11—P1—C1—P2	−171.74 (16)	C36—C31—C32—C33	−3.0 (4)
Au1—P1—C1—P2	−48.81 (18)	P2—C31—C32—C33	170.4 (2)
C31—P2—C1—P1	176.49 (16)	C31—C32—C33—C34	1.1 (5)
C41—P2—C1—P1	−72.8 (2)	C32—C33—C34—C35	1.0 (5)
Au1ⁱ—P2—C1—P1	49.50 (18)	C33—C34—C35—C36	−1.3 (5)
C21—P1—C11—C16	46.3 (3)	C34—C35—C36—C31	−0.6 (5)
C1—P1—C11—C16	−65.1 (3)	C32—C31—C36—C35	2.7 (5)
Au1—P1—C11—C16	172.3 (2)	P2—C31—C36—C35	−171.0 (3)
C21—P1—C11—C12	−137.5 (3)	C31—P2—C41—C46	32.8 (3)
C1—P1—C11—C12	111.1 (3)	C1—P2—C41—C46	−78.7 (3)
Au1—P1—C11—C12	−11.5 (3)	Au1ⁱ—P2—C41—C46	159.5 (2)
C16—C11—C12—C13	0.3 (5)	C31—P2—C41—C42	−146.4 (2)
P1—C11—C12—C13	−175.9 (3)	C1—P2—C41—C42	102.2 (3)
C11—C12—C13—C14	−0.2 (5)	Au1ⁱ—P2—C41—C42	−19.6 (3)
C12—C13—C14—C15	−0.2 (6)	C46—C41—C42—C43	0.8 (5)
C13—C14—C15—C16	0.6 (6)	P2—C41—C42—C43	180.0 (2)
C14—C15—C16—C11	−0.5 (5)	C41—C42—C43—C44	−1.0 (5)
C12—C11—C16—C15	0.1 (5)	C42—C43—C44—C45	0.7 (5)
P1—C11—C16—C15	176.3 (3)	C43—C44—C45—C46	−0.3 (5)
C11—P1—C21—C26	−72.1 (3)	C44—C45—C46—C41	0.1 (5)
C1—P1—C21—C26	36.9 (3)	C42—C41—C46—C45	−0.4 (5)
Au1—P1—C21—C26	161.0 (2)	P2—C41—C46—C45	−179.5 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—D4···O3	0.84	2.10	2.908 (4)	161

Experimental details

Crystal data
Chemical formula	[Au₂(C₂₅H₂₂P₂)₂](NO₃)₂·2CD₄O
M_r	1358.71
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	11.6214 (8), 13.6313 (9), 16.4319 (12)
β (°)	109.048 (1)
V (Å³)	2460.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.14
Crystal size (mm)	0.27 × 0.19 × 0.13

Data collection
Diffractometer	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.256, 0.450
No. of measured, independent and observed [I > 2σ(I)] reflections	14182, 5019, 4626
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.052, 1.06
No. of reflections	5019
No. of parameters	309
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.64, −0.47

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2003), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), X-SEED.

Selected geometric parameters (Å, º) top

Au1—P1	2.3116 (8)	P1—C1	1.821 (3)
Au1—P2ⁱ	2.3175 (8)	P2—C31	1.805 (3)
Au1—Au1ⁱ	3.0245 (3)	P2—C41	1.818 (3)
P1—C21	1.811 (3)	P2—C1	1.832 (3)
P1—C11	1.814 (3)

P1—Au1—P2ⁱ	177.76 (3)	P2ⁱ—Au1—Au1ⁱ	91.70 (2)
P1—Au1—Au1ⁱ	89.62 (2)