Bis(2,6-dimethyl­pyridine-κN)gold(I) tetra­chloridoaurate(III)

Ahmadi, R.; Dehghan, L.; Amani, V.; Khavasi, H.R.

doi:10.1107/S1600536808027876

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1237

doi:10.1107/S1600536808027876

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Bis(2,6-dimethylpyridine-κN)gold(I) tetrachloridoaurate(III)

Roya Ahmadi,^a Leila Dehghan,^a Vahid Amani ^a ^* and Hamid Reza Khavasi ^b

^aIslamic Azad University, Shahr-e-Rey Branch, Tehran, Iran, and ^bDepartment of Chemistry, Shahid Beheshti University, Tehran 1983963113, Iran
^*Correspondence e-mail: v_amani2002@yahoo.com

(Received 15 August 2008; accepted 31 August 2008; online 6 September 2008)

In the cation of the title compound, [Au(C₇H₉N)₂][AuCl₄], the Au^I atom is two-coordinated in a linear arrangement by two N atoms from two 2,6-dimethylpyridine ligands. In the anion, the Au^III atom has a virtually square-planar coordination geometry. The Au atoms both are located on centers of inversion. The crystal structure involves intermolecular C—H⋯Cl hydrogen bonds.

Related literature

For related literature, see: Abbate et al. (2000 ); Adams & Strähle (1982 ); Ahmadi et al. (2008 ); Amani et al. (2008 ); Bjernemose et al. (2004 ); Hayoun et al. (2006 ); Hojjat Kashani et al. (2008 ); Hollis & Lippard (1983 ); McInnes et al. (1995 ); Yildirim et al. (2008 ).

Experimental

Crystal data

[Au(C₇H₉N)₂][AuCl₄]
M_r = 750.04
Monoclinic, C 2/m
a = 17.773 (3) Å
b = 6.8395 (8) Å
c = 8.3728 (14) Å
β = 110.929 (12)°
V = 950.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 15.97 mm⁻¹
T = 298 (2) K
0.20 × 0.12 × 0.08 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.112, T_max = 0.275
5473 measured reflections
1384 independent reflections
1123 reflections with I > 2σ(I)
R_int = 0.092

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.115
S = 1.20
1384 reflections
69 parameters
H-atom parameters constrained
Δρ_max = 1.76 e Å⁻³
Δρ_min = −2.1 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Au1—N1	2.030 (8)
Au2—Cl1	2.280 (3)
Au2—Cl2	2.286 (4)

Cl1ⁱ—Au2—Cl2	90.05 (14)
Cl1—Au2—Cl2	89.95 (14)
Symmetry code: (i) -x, y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl1ⁱⁱ	0.93	2.77	3.572 (14)	145
Symmetry code: (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+2]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027876/hy2150sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027876/hy2150Isup2.hkl

checkCIF report

Comment top

Recently, we reported the syntheses and crystal structures of [Au(dmphen)Cl₂][AuCl₄], (II), (Ahmadi et al., 2008), [dmpyH][PtCl₆], (III), (Amani et al., 2008) and [H₂DA18C6][AuCl₄].2H₂O, (IV), (Hojjat Kashani et al., 2008) (dmphen = 4,7-diphenyl-1,10-phenanthroline; dmpyH = 2,6-dimethylpyridinium and H₂DA18C6 = 1,10-diazonia-18-crown-6). Several Au^III complexes with formula [AuCl₂L]X, such as [AuCl₂(bipy)](BF₄), (V), (McInnes et al., 1995), [AuCl₂(bipy)](NO₃), (VI), (Bjernemose et al., 2004), [AuCl₂(bipy)][AuBr₄], (VII), (Hayoun et al., 2006), [AuCl₂(dtbpy)][AuCl₄].CH₃CN, (VIII), (Yildirim et al., 2008) and [AuCl₂(phen)]Cl.H₂O, (IX), (Abbate et al., 2000) (bipy = 2,2'-bipyridine; dtbpy = 4,4'-ditertbutyl-2,2'-bipyridine; phen = 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], (X), and [AuCl₂(py)₂]Cl.H₂O, (XI), (Adams & Strahle, 1982) (py = pyridine) and only one mixed-valence Au^I–Au^III complex, [Au(terpy)Cl]₂[AuCl₂]₃[AuCl₄], (XII), (Hollis & Lippard, 1983) (terpy = 2,2',2''-terpyridine) 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 cation of the title compound (Fig. 1), the Au^I atom is two-coordinated in a linear arrangement by two N atoms from two 2,6-dimethylpyridine ligands. In the anion, the Au^III atom has a square-planar coordination geometry. The Au atoms each are located on an inversion center. In the cation, the Au—N bond length (Table 1) is in good agreement with the corresponding values in (X) and (XI) and in the anion, the Au—Cl bond lengths and angles (Table 1) are within a normal range, comparable with those in (II), (VIII) and (XII). In the crystal structure, intermolecular C—H···Cl hydrogen bonds are observed.

Related literature top

For related literature, see: Abbate et al. (2000); Adams & Strahle (1982); Ahmadi et al. (2008); Amani et al. (2008); Bjernemose et al. (2004); Hayoun et al. (2006); Hojjat Kashani et al. (2008); Hollis & Lippard (1983); McInnes et al. (1995); Yildirim et al. (2008).

Experimental top

A solution of 2,6-dimethylpyridine (0.12 g, 1.09 mmol) in methanol (15 ml) was added to a solution of HAuCl₃.3H₂O, (0.37 g, 1.09 mmol) in acetonitrile (15 ml). The resulting yellow solution was stirred for 10 min at 313 K, and then it was left to evaporate slowly at room temperature. After one week, yellow block crystals of (I) were isolated (yield 75.8%, 0.31 g; m. p. 489 K).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 40% probability level. [Symmetry code: (i) -x, y, 1 - z.]

Bis(2,6-dimethylpyridine-κN)gold(I) tetrachloridoaurate(III) top

Crystal data top

[Au(C₇H₉N)₂][AuCl₄]	F(000) = 684
M_r = 750.04	D_x = 2.62 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 971 reflections
a = 17.773 (3) Å	θ = 2.6–29.2°
b = 6.8395 (8) Å	µ = 15.97 mm⁻¹
c = 8.3728 (14) Å	T = 298 K
β = 110.929 (12)°	Block, yellow
V = 950.6 (3) Å³	0.20 × 0.12 × 0.08 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1123 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.092
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θ_max = 29.2°, θ_min = 2.6°
T_min = 0.112, T_max = 0.275	h = −23→24
5473 measured reflections	k = −9→8
1384 independent reflections	l = −11→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.044	w = 1/[σ²(F_o²) + (0.0468P)² + 5.4887P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.115	(Δ/σ)_max = 0.004
S = 1.20	Δρ_max = 1.76 e Å⁻³
1384 reflections	Δρ_min = −2.1 e Å⁻³
69 parameters

Crystal data top

[Au(C₇H₉N)₂][AuCl₄]	V = 950.6 (3) Å³
M_r = 750.04	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 17.773 (3) Å	µ = 15.97 mm⁻¹
b = 6.8395 (8) Å	T = 298 K
c = 8.3728 (14) Å	0.20 × 0.12 × 0.08 mm
β = 110.929 (12)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1384 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1123 reflections with I > 2σ(I)
T_min = 0.112, T_max = 0.275	R_int = 0.092
5473 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.20	Δρ_max = 1.76 e Å⁻³
1384 reflections	Δρ_min = −2.1 e Å⁻³
69 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0	0.5	0.5	0.04157 (18)
Au2	0	0	0.5	0.0484 (2)
Cl1	0.13598 (17)	0	0.6416 (5)	0.0656 (9)
Cl2	0.0196 (2)	0	0.2445 (5)	0.0726 (10)
N1	0.1180 (5)	0.5	0.6531 (12)	0.044 (2)
C1	0.0754 (8)	0.5	0.8993 (16)	0.068 (4)
H1A	0.0803	0.6146	0.9684	0.081*
H1B	0.0238	0.5	0.8084	0.081*
C2	0.1398 (7)	0.5	0.8262 (15)	0.054 (3)
C3	0.2206 (8)	0.5	0.9317 (17)	0.071 (4)
H3	0.2353	0.5	1.05	0.085*
C4	0.2774 (8)	0.5	0.859 (2)	0.079 (5)
H4	0.3315	0.5	0.9288	0.095*
C5	0.2568 (8)	0.5	0.684 (2)	0.065 (3)
H5	0.2965	0.5	0.6361	0.078*
C6	0.1763 (6)	0.5	0.5816 (15)	0.047 (2)
C7	0.1497 (8)	0.5	0.3949 (19)	0.069 (4)
H7A	0.1702	0.386	0.3574	0.083*
H7B	0.0919	0.5	0.3473	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.0319 (3)	0.0531 (4)	0.0374 (3)	0	0.00961 (19)	0
Au2	0.0327 (3)	0.0502 (4)	0.0538 (3)	0	0.0053 (2)	0
Cl1	0.0327 (12)	0.071 (2)	0.077 (2)	0	−0.0006 (12)	0
Cl2	0.0641 (19)	0.090 (3)	0.0611 (18)	0	0.0195 (15)	0
N1	0.024 (3)	0.050 (5)	0.050 (5)	0	0.002 (3)	0
C1	0.060 (7)	0.097 (12)	0.045 (6)	0	0.017 (5)	0
C2	0.038 (5)	0.065 (8)	0.042 (5)	0	−0.006 (4)	0
C3	0.047 (6)	0.098 (12)	0.047 (6)	0	−0.008 (5)	0
C4	0.036 (6)	0.098 (13)	0.086 (10)	0	0.002 (6)	0
C5	0.045 (6)	0.075 (10)	0.078 (9)	0	0.026 (6)	0
C6	0.040 (5)	0.050 (6)	0.053 (6)	0	0.020 (4)	0
C7	0.057 (7)	0.088 (11)	0.074 (9)	0	0.037 (7)	0

Geometric parameters (Å, º) top

Au1—N1	2.030 (8)	C2—C3	1.392 (15)
Au1—N1ⁱ	2.030 (8)	C3—C4	1.35 (2)
Au2—Cl1ⁱ	2.280 (3)	C3—H3	0.93
Au2—Cl1	2.280 (3)	C4—C5	1.38 (2)
Au2—Cl2	2.286 (4)	C4—H4	0.93
Au2—Cl2ⁱ	2.286 (4)	C5—C6	1.381 (17)
N1—C2	1.360 (15)	C5—H5	0.93
N1—C6	1.370 (14)	C6—C7	1.463 (18)
C1—C2	1.479 (18)	C7—H7A	0.96
C1—H1A	0.96	C7—H7B	0.96
C1—H1B	0.96

N1—Au1—N1ⁱ	180.0 (3)	C4—C3—C2	118.8 (12)
Cl1ⁱ—Au2—Cl1	180.00 (8)	C4—C3—H3	120.6
Cl1ⁱ—Au2—Cl2	90.05 (14)	C2—C3—H3	120.6
Cl1—Au2—Cl2	89.95 (14)	C3—C4—C5	121.4 (12)
Cl1ⁱ—Au2—Cl2ⁱ	89.95 (14)	C3—C4—H4	119.3
Cl1—Au2—Cl2ⁱ	90.05 (14)	C5—C4—H4	119.3
Cl2—Au2—Cl2ⁱ	180.00 (17)	C4—C5—C6	119.0 (12)
C2—N1—C6	119.6 (9)	C4—C5—H5	120.5
C2—N1—Au1	120.7 (8)	C6—C5—H5	120.5
C6—N1—Au1	119.7 (7)	N1—C6—C5	120.3 (11)
C2—C1—H1A	109.5	N1—C6—C7	117.4 (10)
C2—C1—H1B	109.5	C5—C6—C7	122.3 (11)
H1A—C1—H1B	109.5	C6—C7—H7A	109.5
N1—C2—C3	120.9 (12)	C6—C7—H7B	109.5
N1—C2—C1	118.2 (10)	H7A—C7—H7B	109.5
C3—C2—C1	120.9 (11)

C6—N1—C2—C3	0.000 (4)	C3—C4—C5—C6	0.000 (5)
Au1—N1—C2—C3	180.000 (4)	C2—N1—C6—C5	0.000 (4)
C6—N1—C2—C1	180.000 (4)	Au1—N1—C6—C5	180.000 (3)
Au1—N1—C2—C1	0.000 (3)	C2—N1—C6—C7	180.000 (3)
N1—C2—C3—C4	0.000 (6)	Au1—N1—C6—C7	0.000 (3)
C1—C2—C3—C4	180.000 (5)	C4—C5—C6—N1	0.000 (4)
C2—C3—C4—C5	0.000 (6)	C4—C5—C6—C7	180.000 (4)

Symmetry code: (i) −x, y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ⁱⁱ	0.93	2.77	3.572 (14)	145

Symmetry code: (ii) −x+1/2, y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	[Au(C₇H₉N)₂][AuCl₄]
M_r	750.04
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	298
a, b, c (Å)	17.773 (3), 6.8395 (8), 8.3728 (14)
β (°)	110.929 (12)
V (Å³)	950.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	15.97
Crystal size (mm)	0.20 × 0.12 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.112, 0.275
No. of measured, independent and observed [I > 2σ(I)] reflections	5473, 1384, 1123
R_int	0.092
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.115, 1.20
No. of reflections	1384
No. of parameters	69
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.76, −2.1

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Au1—N1	2.030 (8)	Au2—Cl2	2.286 (4)
Au2—Cl1	2.280 (3)

Cl1ⁱ—Au2—Cl2	90.05 (14)	Cl1—Au2—Cl2	89.95 (14)

Symmetry code: (i) −x, y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ⁱⁱ	0.93	2.77	3.572 (14)	145

Symmetry code: (ii) −x+1/2, y+1/2, −z+2.

Acknowledgements

We are grateful to Islamic Azad University, Shahr-e-Rey Branch, for financial support.

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