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Acta Cryst. (2008). E64, m1237    [ doi:10.1107/S1600536808027876 ]

Bis(2,6-dimethylpyridine-[kappa]N)gold(I) tetrachloridoaurate(III)

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

Abstract top

In the cation of the title compound, [Au(C7H9N)2][AuCl4], the AuI atom is two-coordinated in a linear arrangement by two N atoms from two 2,6-dimethylpyridine ligands. In the anion, the AuIII 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.

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 AuIII 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 AuIII 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 AuI–AuIII 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 AuI atom is two-coordinated in a linear arrangement by two N atoms from two 2,6-dimethylpyridine ligands. In the anion, the AuIII 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).

Refinement top

All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) and 0.96 (methyl) Å and with Uiso(H) = 1.2Ueq(C). The highest residual electron density was found 0.90 Å from atom Au2 and the deepest hole 0.81 Å from atom Au2.

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
[Figure 1] 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
Mr = 750.04Dx = 2.62 Mg m−3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 971 reflections
a = 17.773 (3) Åθ = 2.6–29.2°
b = 6.8395 (8) ŵ = 15.97 mm−1
c = 8.3728 (14) ÅT = 298 K
β = 110.929 (12)°Block, yellow
V = 950.6 (3) Å30.20 × 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 scansRint = 0.092
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		θmax = 29.2°, θmin = 2.6°
Tmin = 0.112, Tmax = 0.275h = −23→24
5473 measured reflectionsk = −9→8
1384 independent reflectionsl = −11→11
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.044 w = 1/[σ2(Fo2) + (0.0468P)2 + 5.4887P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.115(Δ/σ)max = 0.004
S = 1.20Δρmax = 1.76 e Å−3
1384 reflectionsΔρmin = −2.1 e Å−3
69 parameters
Crystal data top
[Au(C7H9N)2][AuCl4]V = 950.6 (3) Å3
Mr = 750.04Z = 2
Monoclinic, C2/mMo Kα radiation
a = 17.773 (3) ŵ = 15.97 mm−1
b = 6.8395 (8) ÅT = 298 K
c = 8.3728 (14) Å0.20 × 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)
Tmin = 0.112, Tmax = 0.275Rint = 0.092
5473 measured reflectionsθmax = 29.2°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.115Δρmax = 1.76 e Å−3
S = 1.20Δρmin = −2.1 e Å−3
1384 reflectionsAbsolute structure: ?
69 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Au100.50.50.04157 (18)
Au2000.50.0484 (2)
Cl10.13598 (17)00.6416 (5)0.0656 (9)
Cl20.0196 (2)00.2445 (5)0.0726 (10)
N10.1180 (5)0.50.6531 (12)0.044 (2)
C10.0754 (8)0.50.8993 (16)0.068 (4)
H1A0.08030.61460.96840.081*
H1B0.02380.50.80840.081*
C20.1398 (7)0.50.8262 (15)0.054 (3)
C30.2206 (8)0.50.9317 (17)0.071 (4)
H30.23530.51.050.085*
C40.2774 (8)0.50.859 (2)0.079 (5)
H40.33150.50.92880.095*
C50.2568 (8)0.50.684 (2)0.065 (3)
H50.29650.50.63610.078*
C60.1763 (6)0.50.5816 (15)0.047 (2)
C70.1497 (8)0.50.3949 (19)0.069 (4)
H7A0.17020.3860.35740.083*
H7B0.09190.50.34730.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Au10.0319 (3)0.0531 (4)0.0374 (3)00.00961 (19)0
Au20.0327 (3)0.0502 (4)0.0538 (3)00.0053 (2)0
Cl10.0327 (12)0.071 (2)0.077 (2)0−0.0006 (12)0
Cl20.0641 (19)0.090 (3)0.0611 (18)00.0195 (15)0
N10.024 (3)0.050 (5)0.050 (5)00.002 (3)0
C10.060 (7)0.097 (12)0.045 (6)00.017 (5)0
C20.038 (5)0.065 (8)0.042 (5)0−0.006 (4)0
C30.047 (6)0.098 (12)0.047 (6)0−0.008 (5)0
C40.036 (6)0.098 (13)0.086 (10)00.002 (6)0
C50.045 (6)0.075 (10)0.078 (9)00.026 (6)0
C60.040 (5)0.050 (6)0.053 (6)00.020 (4)0
C70.057 (7)0.088 (11)0.074 (9)00.037 (7)0
Geometric parameters (Å, °) top
Au1—N12.030 (8)C2—C31.392 (15)
Au1—N1i2.030 (8)C3—C41.35 (2)
Au2—Cl1i2.280 (3)C3—H30.93
Au2—Cl12.280 (3)C4—C51.38 (2)
Au2—Cl22.286 (4)C4—H40.93
Au2—Cl2i2.286 (4)C5—C61.381 (17)
N1—C21.360 (15)C5—H50.93
N1—C61.370 (14)C6—C71.463 (18)
C1—C21.479 (18)C7—H7A0.96
C1—H1A0.96C7—H7B0.96
C1—H1B0.96
N1—Au1—N1i180.0 (3)C4—C3—C2118.8 (12)
Cl1i—Au2—Cl1180.00 (8)C4—C3—H3120.6
Cl1i—Au2—Cl290.05 (14)C2—C3—H3120.6
Cl1—Au2—Cl289.95 (14)C3—C4—C5121.4 (12)
Cl1i—Au2—Cl2i89.95 (14)C3—C4—H4119.3
Cl1—Au2—Cl2i90.05 (14)C5—C4—H4119.3
Cl2—Au2—Cl2i180.00 (17)C4—C5—C6119.0 (12)
C2—N1—C6119.6 (9)C4—C5—H5120.5
C2—N1—Au1120.7 (8)C6—C5—H5120.5
C6—N1—Au1119.7 (7)N1—C6—C5120.3 (11)
C2—C1—H1A109.5N1—C6—C7117.4 (10)
C2—C1—H1B109.5C5—C6—C7122.3 (11)
H1A—C1—H1B109.5C6—C7—H7A109.5
N1—C2—C3120.9 (12)C6—C7—H7B109.5
N1—C2—C1118.2 (10)H7A—C7—H7B109.5
C3—C2—C1120.9 (11)
C6—N1—C2—C30.000 (4)C3—C4—C5—C60.000 (5)
Au1—N1—C2—C3180.000 (4)C2—N1—C6—C50.000 (4)
C6—N1—C2—C1180.000 (4)Au1—N1—C6—C5180.000 (3)
Au1—N1—C2—C10.000 (3)C2—N1—C6—C7180.000 (3)
N1—C2—C3—C40.000 (6)Au1—N1—C6—C70.000 (3)
C1—C2—C3—C4180.000 (5)C4—C5—C6—N10.000 (4)
C2—C3—C4—C50.000 (6)C4—C5—C6—C7180.000 (4)
Symmetry codes: (i) −x, y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···Cl1ii0.932.773.572 (14)145
Symmetry codes: (ii) −x+1/2, y+1/2, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Au1—N12.030 (8)Au2—Cl22.286 (4)
Au2—Cl12.280 (3)
Cl1i—Au2—Cl290.05 (14)Cl1—Au2—Cl289.95 (14)
Symmetry codes: (i) −x, y, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···Cl1ii0.932.773.572 (14)145
Symmetry codes: (ii) −x+1/2, y+1/2, −z+2.
Acknowledgements top

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

references
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