Bis[dichlorido(5,5′-dimethyl-2,2′-bi­pyridine-κ2 N,N′)gold(III)] tetra­chlorido­aurate(III) dichloridooaurate(I)

Selvi Karaca; Mehmet Akkurt; Nasser Safari; Vahid Amani; Orhan Büyükgüngör; Anita Abedi

doi:10.1107/S1600536809006436

. 2009 Feb 28;65(Pt 3):m335–m336. doi: 10.1107/S1600536809006436

Bis[dichlorido(5,5′-dimethyl-2,2′-bipyridine-κ² N,N′)gold(III)] tetrachloridoaurate(III) dichloridooaurate(I)

Selvi Karaca ^a, Mehmet Akkurt ^a,^*, Nasser Safari ^b, Vahid Amani ^b, Orhan Büyükgüngör ^c, Anita Abedi ^d

PMCID: PMC2968657 PMID: 21582104

Abstract

The title compound, [Au^IIICl₂(C₁₂H₁₂N₂)]₂[Au^IIICl₄][Au^ICl₂], contains three distinct types of Au atom. In the cation, the Au^III atom is four-coordinated in a distorted square-planar arrangement by an N,N′-bidentate 5,5′-dimethyl-2,2′-bipyridine ligand and two terminal Cl atoms. In the [AuCl₄]⁻ anion, the centrosymmetric Au^III atom has a square-planar coordination. The centrosymmetric [AuCl₂]⁻ anion is linear. Intra- and intermolecular C—H⋯Cl hydrogen bonds help to establish the conformation and packing.

Related literature

For related stuctures, see: Abbate et al. (2000 ▶); Adams & Strähle (1982 ▶); Ahmadi, Amani & Khavasi (2008 ▶); Ahmadi, Dehghan, Amani & Khavasi (2008 ▶); Bjernemose et al. (2004 ▶); Hayoun et al. (2006 ▶); Hollis & Lippard (1983 ▶); McInnes et al. (1995 ▶); Yıldırım et al. (2008 ▶).

Experimental

Crystal data

[AuCl₂(C₁₂H₁₂N₂)]₂[AuCl₄][AuCl₂]
M _r = 1510.86
Triclinic,
a = 9.0698 (4) Å
b = 10.0886 (4) Å
c = 11.1678 (5) Å
α = 91.155 (4)°
β = 108.148 (4)°
γ = 111.344 (3)°
V = 894.09 (7) Å³
Z = 1
Mo Kα radiation
μ = 17.13 mm⁻¹
T = 295 K
0.41 × 0.28 × 0.08 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.054, T _max = 0.341
9898 measured reflections
3651 independent reflections
3193 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.112
S = 1.05
3651 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 1.64 e Å⁻³
Δρ_min = −1.91 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006436/hb2902sup1.cif

e-65-0m335-sup1.cif^{(22KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006436/hb2902Isup2.hkl

e-65-0m335-Isup2.hkl^{(175.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Au1—N1	2.028 (9)
Au1—N2	2.027 (7)
Au1—Cl1	2.252 (3)
Au1—Cl2	2.262 (3)
Au2—Cl3	2.246 (5)
Au2—Cl4	2.261 (3)
Au3—Cl5	2.248 (3)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl1	0.93	2.59	3.203 (11)	124
C8—H8⋯Cl2ⁱ	0.93	2.75	3.666 (12)	169
C11—H11⋯Cl2	0.93	2.64	3.233 (11)	122

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS-2 diffractometer (purchased under grant F.279 of the University Research Fund). NS, VA and AA are grateful to Shahid Beheshti University for financial support.

supplementary crystallographic information

Comment

Recently, we reported the synthesis and crystal structure of the [Au(dtbpy)Cl₂][AuCl₄].CH₃CN, (II), (Yıldırım et al., 2008) [where dtbpy is 4,4'-di-tert-butyl-2,2'-bipyridine]. There are several Au^III complexes, with formula, [AuCl₂ (N—N)]X, such as [AuCl₂(bipy)][BF₄], (III), (McInnes et al., 1995), [AuCl₂(bipy)](NO₃), (IV), (Bjernemose et al., 2004), [AuCl₂(bipy)][AuBr₄], (V), (Hayoun et al., 2006), [AuCl₂(dmphen)][AuCl₄], (VI), (Ahmadi, Amani et al., 2008) and [AuCl₂ (phen)]Cl.H₂O, (VII), (Abbate et al., 2000) [where bipy is 2,2'-bipyridine, dmphen is 4,7-diphenyl-1,10-phenanthroline and phen is 1,10-phenanthroline] have been synthesized and characterized by single-crystal X-ray diffraction methods. Two Au^III complexes with formula, [AuCl₂L₂]X, [AuCl₂(py)₂][AuCl₄], (VIII), and [AuCl₂(py)₂]Cl.H₂O, (IX), (Adams & Strähle 1982) [py is pyridine] and two mixed-valence Au^I—Au^III complexes, [Au(terpy)Cl]₂[AuCl₂]₃[AuCl₄], (X), (Hollis & Lippard, 1983) and [Au(dmpy)₂][AuCl₄], (XI), (Ahmadi, Dehghan et al., 2008) [where terpy is 2,2',2''-terpyridine and dmpy is 2,6-dimethylpyridine] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound (I).

In the asymmetric unit of the title compound (I), (Fig. 1), there are one cation and two half-anions. In the cation, the Au^III atom is four-coordinated in a distorted square-planar configuration by two N atoms from the ligand and two terminal Cl atoms. In the anion AuCl₄, the Au^III atom has a square-planar coordination. The anion AuCl₂ is linear. In the cation, the Au—Cl and Au—N bond lengths and angles (Table 1) are in good agreement with the corresponding values in (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and, (XI). In the anion, the Au—Cl bond lengths and angles (Table 1) are normal.

Intra and intermolecular C—H···Cl hydrogen bonding interactions (Table 2) stabilize the molecular conformation and the packing arrangement (Fig. 2).

Experimental

A solution of 5,5'-dimethyl-2,2'-bipyridine (0.20 g, 1.09 mmol) in ethanol (20 ml) was added to a solution of HAuCl₃.3H₂O, (0.37 g, 1.09 mmol) in acetonitrile (20 ml) and the resulting yellow solution was stirred for 10 min at 313 K. Then, it was left to evaporate slowly at room temperature. After one week, yellow prismatic crystals of (I) were isolated (yield 0.28 g, 72.8%; m.p. 553 K).