(μ-Diphenyl­phosphanido-κ2 P:P′)bis­[2,2′-(pyridine-2,6-diyl)diphenyl-κ3 C 1,N,C 1′)gold(III)] perchlorate acetonitrile solvate

Xin-Sheng Li; Juan Mo; Su-Mei Zhang; Li Yuan; Jian-Hua Liu

doi:10.1107/S1600536808024537

. 2008 Aug 6;64(Pt 9):m1126–m1127. doi: 10.1107/S1600536808024537

(μ-Diphenylphosphanido-κ² P:P′)bis[2,2′-(pyridine-2,6-diyl)diphenyl-κ³ C ¹,N,C ^1′)gold(III)] perchlorate acetonitrile solvate

Xin-Sheng Li ^a, Juan Mo ^a,^*, Su-Mei Zhang ^a, Li Yuan ^a, Jian-Hua Liu ^a

PMCID: PMC2960555 PMID: 21201586

Abstract

The title complex, [Au₂(C₁₇H₁₁N)₂(C₁₂H₁₀P)]ClO₄·C₂H₃N, contains two Au^III atoms bridged by a diphenylphosphanide ligand. Each Au atom is in a square-planar environment coordinated by diphenylphosphanide and 2,6-diphenylpyridine ligands. There are weak π–π stacking interactions between neighbouring molecules (the interplanar separations between two neighbouring dpp units are 3.40 and 3.57 Å). The intramolecular Au⋯Au separation is 3.788 (5) Å. The crystal structure shows weak intermolecular C—H⋯O and C—H⋯N hydrogen bonds involving an O atom of the perchlorate counter-ion and the N atom of the acetonitrile solvent molecule, respectively.

Related literature

For related literature, see: Goshe et al. (2003 ▶); Kui et al. (2006 ▶); Li et al. (2006 ▶); Lu et al. (2004 ▶); Wong et al. (1998 ▶); Yam et al. (2002 ▶).

Experimental

Crystal data

[Au₂(C₁₇H₁₁N)₂(C₁₂H₁₀P)]ClO₄·C₂H₃N
M _r = 1178.14
Monoclinic,
a = 10.0612 (16) Å
b = 13.526 (2) Å
c = 29.640 (5) Å
β = 98.828 (4)°
V = 3985.9 (11) Å³
Z = 4
Mo Kα radiation
μ = 7.51 mm⁻¹
T = 113 (2) K
0.32 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.147, T _max = 0.221
38570 measured reflections
10221 independent reflections
8923 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.057
S = 1.04
10221 reflections
534 parameters
H-atom parameters constrained
Δρ_max = 1.52 e Å⁻³
Δρ_min = −1.55 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: XP in SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024537/bx2152sup1.cif

e-64-m1126-sup1.cif^{(35KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808024537/bx2152Isup2.hkl

e-64-m1126-Isup2.hkl^{(489.8KB, hkl)}

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

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

Au1—N1	2.027 (3)
Au1—C17	2.105 (3)
Au1—C1	2.111 (3)
Au1—P1	2.3121 (9)
Au2—N2	2.041 (3)
Au2—C18	2.091 (3)
Au2—C34	2.113 (3)
Au2—P1	2.3180 (8)

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N1—Au1—C17	79.97 (12)
N1—Au1—C1	80.18 (12)
C17—Au1—C1	160.10 (13)
N1—Au1—P1	172.84 (8)
C17—Au1—P1	95.15 (9)
C1—Au1—P1	104.75 (10)
N2—Au2—C18	80.19 (12)
N2—Au2—C34	80.02 (12)
C18—Au2—C34	160.15 (13)
N2—Au2—P1	173.99 (8)
C18—Au2—P1	93.98 (9)
C34—Au2—P1	105.84 (9)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21⋯O3ⁱ	0.95	2.46	3.311 (7)	149
C36—H36⋯O2	0.95	2.57	3.372 (8)	143
C38—H38⋯O2ⁱⁱ	0.95	2.59	3.540 (5)	175
C43—H43⋯O1ⁱⁱⁱ	0.95	2.59	3.517 (3)	165
C46—H46⋯N3^iv	0.95	2.62	3.417 (4)	142
C48—H48C⋯O1^v	0.98	2.54	3.423 (8)	150

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

We thank Henan Agricultural University for the generous support of this study.

supplementary crystallographic information

Comment

Recently, extensive investigations on the biological properties of gold(III) have been reported (Kui et al., 2006; Wong et al., 1998). The stability of metal compounds is usually enhanced by multidentate chelating ligands. Li and his co-workers have reported multinuclear gold complex of 2,6-diphenyl-Pyridine ligand (dpp) to generate a planar gold(III) moiety (Li et al., 2006). In this context, the title complex, (I), has been prepared and its crystal structure is reported here.

The title compound show gold(III) atoms bridged by diphenylphosphanide. Each Au atom is surrounded by one P atom from diphenylphosphanide ligand and two C atoms, one N atom from dpp in a square-planar geometry, the least-squares plane through Au^III and dpp has a mean deviation of 0.04 (3) Å. The intramolecular Au···Au contact of 3.788Å is beyond a normal range of metal-metal interactions for d⁸ metal ions (3.09–3.50 Å) (Yam et al., 2002; Goshe et al., 2003; Lu et al., 2004). The Au–N(pyridyl) distances (2.027 (3), 2.041 (3) Å) are comparable to the related distances found in [Au(dpp)L]ⁿ⁺ analogues (1.94–2.06 Å), The Au–C(phenyl) distances (2.091 (3)–2.113 (3) Å) are comparable to the related distances found in [Au(dpp)L]ⁿ⁺ analogues (2.06–2.13 Å) (Li et al., 2006). The interplanar separation between two neighbouring dpp molecules are 3.40 and 3.57Å (Fig. 2). The crystal packing shows weak intermolecular C-H..O and C-H···N hydrogen bonds with O atoms of perchlorate counter-ion and N atom of acetonitrile molecule respectively. (Fig. 3, Table 2).

Experimental

A mixture of Au(dpp)Cl (0.092 g, 0.2 mmol) and diphenylphosphine (0.018 g, 0.1 mmol) in acetonitrile (30 ml) was stirred for 2 h. Excess LiClO₄ was then added to yield a yellow precipitate, which was filtered, washed with diethyl ether. The precipitate was redissolve in acetonitrile. Yellow crystals suitable for X-ray diffraction were formed by vapour diffusion of diethyl ethyl ether into acetonitrile solution.