μ-Bis(diphenyl­arsino)methane-κ2 As:As′-bis­[chloridogold(I)]

Uwe Monkowius; Manfred Zabel; Hartmut Yersin

doi:10.1107/S1600536809004802

. 2009 Feb 18;65(Pt 3):m281. doi: 10.1107/S1600536809004802

μ-Bis(diphenylarsino)methane-κ² As:As′-bis[chloridogold(I)]

Uwe Monkowius ^a,^*, Manfred Zabel ^b, Hartmut Yersin ^c

PMCID: PMC2968680 PMID: 21582067

Abstract

The title structure, [Au₂Cl₂(C₂₅H₂₂As₂)], consists of discrete molecules disposed about a crystallographic twofold axis. The Au atom exhibits a nearly linear coordination by As and Cl atoms. Au⋯Au interactions [3.4285Å(4) Å] and a weak intermolecular C—H⋯Cl hydrogen bond are present.

Related literature

For related structures, see: Healy (2003 ▶); Schmidbaur et al. (1977a ▶,b ▶). For the synthesis of related complexes, see: Monkowius et al. (2003a ▶,b ▶).

Experimental

Crystal data

[Au₂Cl₂(C₂₅H₂₂As₂)]
M _r = 937.11
Monoclinic,
a = 22.7171 (18) Å
b = 7.3151 (6) Å
c = 18.2047 (15) Å
β = 120.342 (8)°
V = 2610.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 13.96 mm⁻¹
T = 173 K
0.24 × 0.20 × 0.18 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: analytical [from crystal shape; X-SHAPE and X-RED in IPDS Software (Stoe & Cie, 1998 ▶)] T _min = 0.051, T _max = 0.083
12353 measured reflections
2790 independent reflections
2431 reflections with I > 2σ(I)
R _int = 0.062

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.055
S = 0.96
2790 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 1.65 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Data collection: IPDS Software (Stoe & Cie, 1998 ▶); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004802/nc2133sup1.cif

e-65-0m281-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809004802/nc2133Isup2.hkl

e-65-0m281-Isup2.hkl^{(137.1KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Au1—As1	2.3426 (5)
Au1—Cl1	2.2887 (16)

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As1—Au1—Cl1

174.82 (4)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cl1ⁱⁱ	0.99	2.70	3.658 (4)	163

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Symmetry code: (ii) Inline graphic .

Acknowledgments

This work was supported by the Bundesministerium für Bildung und Forschung (BMBF).

supplementary crystallographic information

Comment

The title compound was prepared from dpam [dpam = bis(diphenylarsino)methane] and (tht)AuCl (tht = tetrahydrothiophene) in methylene chloride in nearly quantitative yields. It is isomorphous to the crystal structure of the phosphorus congener [dppm(AuCl)₂], which was determined by Schmidbaur et al. (1977b) [a = 22.31 (1) Å, b = 7.215 (7) Å, c = 18.12 (1) Å and β = 120.43 (8)°]. The structure consists of discrete molecules of [dpam(AuCl)₂] disposed about a crystallographic twofold axis, which passes through the C1 atom. The Au atom is in a standard linear coordination [As—Au—Cl 174.82 (4)°] with As—Au and Au—Cl bond lengths of 2.3426 (5) and 2.289 (2) Å, respectively. The Au—As···As—Au torsion angle is 66.78 (2)°, yielding a staggered conformation of both Ph₂AsAuCl moieties and an intramolecular Au···Au distance of 3.4285 (4) Å, indicative of attractive aurophilic interactions. The shortest intermolecular Au···Au distance is 5.863 Å. In its crystal, the complexes are linked to infinite chains via weak C—H···Cl intermolecular hydrogen bonds with C···Cl distance of 3.658 (4) Å and a C1—H1a···Cl1ⁱⁱ angle of 163° (symmetry code: (ii) -x, y + 1, -z + 1/2).

For comparison, the geometrical data of the phosphorus compound are: Au—P 2.238 (5), Au—Cl 2.288 (7), Au···Au 3.351 (2) Å, P—Au—Cl 175 (2), Au—P···P—Au 67 (1)°. It should be noted, that a second polymorph of the phosphorus complex exists: Unlike the herein presented structure, there are no aurophilic bonds between the gold(I) atoms (Healy, 2003).

All attempts to prepare the 1:1 complex [(dpamAuCl)₂] starting from the title compound analogous to the published synthesis of phosphorus complex [(dppmAuCl)₂] (Schmidbaur et al., 1977a) failed.

Experimental

The title compound was prepared analogously to a previously published procedure (Monkowius et al., 2003a,b): dpam (0.22 g, 0.47 mmol) and (tht)AuCl (0.30 g, 0.94 mmol, tht = tetrahydrothiophene) were stirred in methylene chloride (20 ml) at room temperature for 2 h. The product was precipitated with n-pentane and isolated by filtration. Recrystallization from methylene chloride/diethyl ether yields colourless crystals suitable for X-ray crystallography. Yield: 0.40 g (0.43 mmol, 91%); ¹H NMR (300 MHz, CDCl₃): 7.55–7.60 (m, Ph—H, 8 H), 7.37–7.51 (m, Ph—H, 12 H), 3.48 p.p.m. (s, CH₂, 2 H); ¹³C NMR (75.5 MHz, CDCl₃): 134.63, 132.93, 130.44, 129.23, 25.08 p.p.m.; MS (ESI): m/z (%) = 1605.3 [L₂Au₃Cl₂]⁺ (5), 1373.3 [L₂Au₃Cl]⁺ (47), 1141.3 [L₂Au]⁺ (76), 901.1 [M—Cl]⁺ (25), 669.2 [LAu]⁺ (100); EA (C₂₅H₂₂As₂Au₂Cl₂) calc.: C 32.04, H 2.37, found: C 32.01, H 2.37.