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Acta Cryst. (2008). E64, m1189-m1190    [ doi:10.1107/S1600536808025646 ]

Dichlorido(4,4'-di-tert-butyl-2,2'-bipyridine-[kappa]2N,N')gold(III) tetrachloridoaurate(III) acetonitrile solvate

S. Ö. Yildirim, M. Akkurt, N. Safari, V. Amani, V. McKee, A. Abedi and H. R. Khavasi

Abstract top

In the title compound, [AuCl2(C9H12N)2][AuCl4]·C2H3N, there is a mirror plane passing through Au and the central C-C bond of the bipyridyl ligand in the cation, and through Au and two Cl atoms of the anion. A cis-AuCl2N2 square-planar geometry for the cation and a square-planar AuCl4 geometry for the anion result. The two C atoms and the N atom of the acetonitrile molecule all have m site symmetries. In the crystal structure, weak C-H...Cl interactions may help to establish the packing.

Comment top

Several AuIII complexes, with formula, [AuCl2(N—N)], such as [AuCl2(bipy)][BF4], (II), (McInnes et al., 1995), [AuCl2(bipy)](NO3), (III), (Bjernemose et al., 2004), [AuCl2(bipy)][AuBr4], (IV), (Hayoun et al., 2006) and [AuCl2(phen)]Cl.H2O, (V), (Abbate et al., 2000) [where bipy is 2,2'-bipyridine and phen is 1,10-phenanthroline] have been synthesized and characterized by single-crystal X-ray diffraction methods.

Other AuIII complexes, with formula, [AuCl2L2], such as [AuCl2(py)2][AuCl4], (VI) and [AuCl2(py)2]Cl.H2O, (VII), (Adams & Strähle 1982) [where py is pyridine] have also bee prepared and characterized. We report herein the synthesis and crystal structure of the title compound, (I).

The asymmetric unit of (I) (Fig. 1) contains one half-cation, one half-anion and one half-acetonitrile molecule; the whole assemblage is symmetric according to a mirror plane. Both Au ions have square-planar coordination (Table 1) and the individual bond lengths and angles are in good agreement with the corresponding values in (II), (III), (IV), (V), (VI) and (VII).

In the crystal of (I), weak intermolecular C—H···Cl hydrogen bonds (Table 2) link the molecules to form a supramolecular structure (Fig. 2 and Fig. 3).

Related literature top

For related structures, see: Abbate et al. (2000); Adams & Strähle (1982); Bjernemose et al. (2004); Hayoun et al. (2006); McInnes et al. (1995).

Experimental top

A solution of 4,4'-di-tert-butyl-2,2'-bipyridine (0.15 g, 0.56 mmol) in acetonitrile (40 ml) was added to a solution of HAuCl4.3H2O, (0.22 g, 0.56 mmol) in EtOH (50 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 laths and prisms of (I) were isolated (yield 0.38 g; 74.0%).

Refinement top

All H atoms were positioned geometrically (C—H = 0.93-0.96Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I) with displacement ellipsoids for non-H atoms drawn at the 30% probability level and H atoms omitted for clarity. The symmetry codes a and b both refer to (x, 1/2 - y, z).
[Figure 2] Fig. 2. A view of the packing and the hydrogen bonding (dashed lines) of (I) down the a axis in the unit cell.
[Figure 3] Fig. 3. View of the unit-cell packing of (I) down the c axis.
Dichlorido(4,4'-di-tert-butyl-2,2'-bipyridine- κ2N,N')gold(III) tetrachloroaurate(III) acetonitrile solvate top
Crystal data top
[AuCl2(C9H12N1)2][AuCl4]·C2H3NF000 = 856
Mr = 916.09Dx = 2.247 Mg m−3
Monoclinic, P21/mMo Kα radiation
λ = 0.71069 Å
Hall symbol: -P 2ybCell parameters from 2450 reflections
a = 6.7880 (9) Åθ = 2.9–24.8º
b = 14.2270 (19) ŵ = 11.43 mm−1
c = 14.1330 (19) ÅT = 150 (2) K
β = 97.151 (2)ºLath, yellow
V = 1354.3 (3) Å30.14 × 0.10 × 0.01 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer		3888 independent reflections
Radiation source: sealed tube2860 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.060
T = 150(2) Kθmax = 29.5º
φ and ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −9→9
Tmin = 0.298, Tmax = 0.894k = −19→19
14949 measured reflectionsl = −19→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.079  w = 1/[σ2(Fo2) + (0.0318P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
3888 reflectionsΔρmax = 1.60 e Å−3
155 parametersΔρmin = −1.24 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[AuCl2(C9H12N1)2][AuCl4]·C2H3NV = 1354.3 (3) Å3
Mr = 916.09Z = 2
Monoclinic, P21/mMo Kα
a = 6.7880 (9) ŵ = 11.43 mm−1
b = 14.2270 (19) ÅT = 150 (2) K
c = 14.1330 (19) Å0.14 × 0.10 × 0.01 mm
β = 97.151 (2)º
Data collection top
Bruker APEXII CCD
diffractometer		3888 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2860 reflections with I > 2σ(I)
Tmin = 0.298, Tmax = 0.894Rint = 0.060
14949 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036155 parameters
wR(F2) = 0.079H-atom parameters constrained
S = 1.01Δρmax = 1.60 e Å−3
3888 reflectionsΔρmin = −1.24 e Å−3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
xyzUiso*/UeqOcc. (<1)
Au10.23789 (4)0.25000−0.04727 (2)0.0241 (1)
Cl10.2075 (2)0.13933 (12)−0.16278 (11)0.0366 (5)
N10.2670 (6)0.3421 (3)0.0624 (3)0.0238 (14)
C10.3143 (8)0.3571 (4)0.2320 (4)0.0258 (17)
C20.2920 (7)0.3000 (4)0.1509 (4)0.0222 (16)
C30.2636 (8)0.4365 (4)0.0544 (4)0.0286 (17)
C40.2861 (8)0.4940 (4)0.1338 (4)0.0303 (17)
C50.3113 (8)0.4559 (4)0.2252 (4)0.0277 (17)
C60.3361 (8)0.5158 (4)0.3150 (4)0.0287 (17)
C70.5416 (9)0.4930 (4)0.3701 (4)0.0345 (19)
C80.1694 (9)0.4913 (4)0.3758 (4)0.0333 (19)
C90.3254 (9)0.6207 (4)0.2926 (5)0.035 (2)
N20.3784 (17)0.250000.4696 (8)0.066 (4)
C100.104 (2)0.250000.5775 (11)0.087 (6)
C110.2608 (17)0.250000.5153 (9)0.049 (4)
Au20.79109 (4)0.250000.14539 (2)0.0258 (1)
Cl20.8353 (4)0.250000.30734 (16)0.0402 (8)
Cl30.7908 (2)0.40938 (11)0.14566 (12)0.0363 (5)
Cl40.7455 (3)0.25000−0.01937 (17)0.0364 (7)
H10.331400.329200.292000.0310*
H30.245700.46360−0.006000.0340*
H40.284300.558900.126100.0360*
H7A0.642200.501100.328700.0520*
H7B0.542900.429200.392200.0520*
H7C0.567400.534600.423700.0520*
H8A0.183000.529500.432200.0500*
H8B0.178900.426100.393600.0500*
H8C0.042600.502900.339500.0500*
H9A0.431800.637500.257100.0520*
H9B0.337200.655700.351100.0520*
H9C0.200600.634800.255600.0520*
H10A0.073200.186400.593200.1300*0.500
H10B−0.012700.279700.545300.1300*0.500
H10C0.148200.283900.635000.1300*0.500
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Au10.0226 (2)0.0279 (2)0.0216 (2)0.00000.0016 (1)0.0000
Cl10.0483 (9)0.0351 (8)0.0257 (8)0.0000 (7)0.0023 (7)−0.0050 (7)
N10.023 (2)0.024 (2)0.024 (3)−0.0009 (19)0.0014 (19)−0.003 (2)
C10.023 (3)0.025 (3)0.029 (3)0.002 (2)0.002 (2)0.004 (2)
C20.014 (2)0.038 (3)0.015 (3)0.000 (2)0.003 (2)0.001 (2)
C30.033 (3)0.029 (3)0.024 (3)−0.001 (3)0.004 (2)0.002 (3)
C40.032 (3)0.025 (3)0.033 (3)−0.001 (2)0.000 (3)0.000 (3)
C50.021 (3)0.032 (3)0.031 (3)−0.001 (2)0.007 (2)−0.001 (3)
C60.029 (3)0.024 (3)0.032 (3)0.005 (2)0.000 (3)−0.002 (3)
C70.036 (3)0.036 (4)0.030 (3)0.002 (3)−0.002 (3)−0.006 (3)
C80.034 (3)0.035 (4)0.031 (3)−0.002 (3)0.004 (3)−0.007 (3)
C90.036 (3)0.035 (4)0.032 (4)−0.001 (3)−0.001 (3)−0.003 (3)
N20.081 (8)0.053 (6)0.068 (7)0.00000.020 (6)0.0000
C100.109 (12)0.079 (10)0.080 (10)0.00000.043 (9)0.0000
C110.061 (7)0.035 (6)0.051 (7)0.00000.012 (6)0.0000
Au20.0194 (2)0.0261 (2)0.0318 (2)0.00000.0033 (1)0.0000
Cl20.0509 (14)0.0399 (13)0.0290 (12)0.00000.0018 (10)0.0000
Cl30.0365 (8)0.0275 (8)0.0448 (10)−0.0009 (6)0.0046 (7)0.0040 (7)
Cl40.0272 (10)0.0439 (13)0.0377 (12)0.00000.0022 (9)0.0000
Geometric parameters (Å, °) top
Au1—Cl12.2590 (17)C1—H10.9300
Au1—N12.020 (4)C3—H30.9300
Au1—Cl1i2.2590 (17)C4—H40.9300
Au1—N1i2.020 (4)C7—H7B0.9600
Au2—Cl22.271 (2)C7—H7A0.9600
Au2—Cl32.2675 (16)C7—H7C0.9600
Au2—Cl42.311 (2)C8—H8A0.9600
Au2—Cl3i2.2675 (16)C8—H8C0.9600
N1—C31.348 (7)C8—H8B0.9600
N1—C21.378 (7)C9—H9B0.9600
N2—C111.088 (17)C9—H9C0.9600
C1—C51.409 (8)C9—H9A0.9600
C1—C21.398 (8)C10—C111.462 (19)
C2—C2i1.423 (8)C10—H10Bi0.9600
C3—C41.382 (8)C10—H10Ci0.9600
C4—C51.392 (8)C10—H10Ai0.9600
C5—C61.521 (8)C10—H10A0.9600
C6—C81.544 (8)C10—H10B0.9600
C6—C91.526 (8)C10—H10C0.9600
C6—C71.545 (8)
Cl1—Au1—N1176.24 (13)H7A—C7—H7C109.00
Cl1—Au1—Cl1i88.38 (6)C6—C7—H7C109.00
Cl1—Au1—N1i95.38 (13)H7A—C7—H7B109.00
Cl1i—Au1—N195.38 (13)H7B—C7—H7C109.00
N1—Au1—N1i80.86 (17)C6—C8—H8C110.00
Cl1i—Au1—N1i176.24 (13)C6—C8—H8A109.00
Cl2—Au2—Cl3i89.91 (4)C6—C8—H8B109.00
Cl2—Au2—Cl389.91 (4)H8A—C8—H8B109.00
Cl2—Au2—Cl4179.90 (8)H8A—C8—H8C109.00
Cl3i—Au2—Cl490.10 (4)H8B—C8—H8C109.00
Cl3—Au2—Cl490.10 (4)H9A—C9—H9B109.00
Cl3—Au2—Cl3i179.77 (6)H9A—C9—H9C110.00
Au1—N1—C2113.8 (3)H9B—C9—H9C110.00
Au1—N1—C3125.7 (4)C6—C9—H9A109.00
C2—N1—C3120.5 (5)C6—C9—H9B109.00
C2—C1—C5121.7 (5)C6—C9—H9C109.00
C1—C2—C2i125.5 (5)N2—C11—C10179.5 (14)
N1—C2—C2i115.8 (5)C11—C10—H10Ci110.00
N1—C2—C1118.7 (5)C11—C10—H10A110.00
N1—C3—C4121.5 (5)C11—C10—H10B110.00
C3—C4—C5120.8 (5)C11—C10—H10C110.00
C1—C5—C6120.2 (5)C11—C10—H10Ai110.00
C1—C5—C4116.8 (5)C11—C10—H10Bi110.00
C4—C5—C6123.0 (5)H10Ai—C10—H10B60.00
C8—C6—C9108.5 (5)H10B—C10—H10Bi52.00
C5—C6—C7107.6 (4)H10B—C10—H10Ci141.00
C5—C6—C8109.0 (5)H10Ai—C10—H10C52.00
C5—C6—C9112.2 (5)H10Bi—C10—H10C141.00
C7—C6—C8110.5 (5)H10C—C10—H10Ci60.00
C7—C6—C9109.1 (5)H10Ai—C10—H10Bi109.00
C5—C1—H1119.00H10Ai—C10—H10Ci109.00
C2—C1—H1119.00H10Bi—C10—H10Ci109.00
N1—C3—H3119.00H10A—C10—H10B109.00
C4—C3—H3119.00H10A—C10—H10C109.00
C5—C4—H4120.00H10A—C10—H10Ai141.00
C3—C4—H4120.00H10A—C10—H10Bi60.00
C6—C7—H7B109.00H10A—C10—H10Ci52.00
C6—C7—H7A109.00H10B—C10—H10C109.00
Cl1i—Au1—N1—C2−179.5 (3)N1—C2—C2i—N1i0.0 (6)
Cl1i—Au1—N1—C30.5 (4)N1—C2—C2i—C1i−179.8 (5)
N1i—Au1—N1—C20.5 (3)C1—C2—C2i—N1i179.8 (5)
N1i—Au1—N1—C3−179.6 (4)C1—C2—C2i—C1i0.0 (8)
Au1—N1—C2—C1179.8 (4)N1—C3—C4—C5−0.6 (8)
Au1—N1—C2—C2i−0.4 (5)C3—C4—C5—C10.6 (8)
C3—N1—C2—C1−0.2 (7)C3—C4—C5—C6−179.8 (5)
C3—N1—C2—C2i179.6 (5)C1—C5—C6—C760.9 (6)
Au1—N1—C3—C4−179.6 (4)C1—C5—C6—C8−58.9 (7)
C2—N1—C3—C40.4 (8)C1—C5—C6—C9−179.1 (5)
C5—C1—C2—N10.2 (8)C4—C5—C6—C7−118.7 (6)
C5—C1—C2—C2i−179.6 (5)C4—C5—C6—C8121.4 (6)
C2—C1—C5—C4−0.3 (8)C4—C5—C6—C91.3 (8)
C2—C1—C5—C6−180.0 (5)
Symmetry codes: (i) x, −y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···Cl3ii0.932.663.561 (6)162
C3—H3···Cl1i0.932.643.231 (6)122
Symmetry codes: (ii) −x+1, −y+1, −z; (i) x, −y+1/2, z.
Table 1
Selected geometric parameters (Å, °) top
Au1—Cl12.2590 (17)Au2—Cl32.2675 (16)
Au1—N12.020 (4)Au2—Cl42.311 (2)
Au2—Cl22.271 (2)
N2—C11—C10179.5 (14)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···Cl3i0.932.663.561 (6)162
C3—H3···Cl1ii0.932.643.231 (6)122
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, −y+1/2, z.
Acknowledgements top

We are grateful to the Shahid Beheshti University and Islamic Azad University, North Tehran Branch, for financial support.

references
References top

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