cis-Bis(2,2′-bipyridine-κ2 N,N′)carbonyl­chloridoruthenium(II) hexa­fluorido­phosphate

Tsugiko Takase; Bisa Mun; Dai Oyama

doi:10.1107/S1600536812048246

. 2012 Dec 5;69(Pt 1):m1–m2. doi: 10.1107/S1600536812048246

cis-Bis(2,2′-bipyridine-κ² N,N′)carbonylchloridoruthenium(II) hexafluoridophosphate

Tsugiko Takase ^a, Bisa Mun ^b, Dai Oyama ^c,^*

PMCID: PMC3588243 PMID: 23476313

Abstract

In the title compound, [RuCl(C₁₀H₈N₂)₂(CO)]PF₆, the Ru^II atom is coordinated in a distorted octahedral geometry by four N atoms of the bipyridine ligands, a carbonyl C atom and a chloride ion. The carbonyl and chloride ligands in the cation adopt a mutually cis arrangement and these are disordered over two sets of sites with site occupancies of 0.721 (6) and 0.279 (6). The Ru—N bond length [2.117 (2) Å] trans to the carbonyl ligand is slightly longer than the average of the other Ru—N bond lengths (2.08 Å), which can be explained by the expected trans influence of the carbonyl group. In the crystal, weak C—H⋯F interactions are observed between the complex cation and the PF₆ ⁻ anion, leading to the formation of a three-dimensional supramolecular structure. The crystal studied was an inversion twin with twin fractions of 0.78 (4) and 0.22 (4).

Related literature

For details of the synthesis, see: Oyama et al. (2012 ▶). For a related structure, see: Clear et al. (1980 ▶). For general background to catalytic reactions using [Ru(bpy)₂(CO)Cl]⁺, see: Ishida et al. (1986 ▶); Lehn & Ziessel (1990 ▶).

Experimental

Crystal data

[RuCl(C₁₀H₈N₂)₂(CO)]·PF₆
M _r = 621.87
Orthorhombic,
a = 10.882 (5) Å
b = 12.063 (5) Å
c = 17.410 (7) Å
V = 2285.2 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.95 mm⁻¹
T = 93 K
0.20 × 0.10 × 0.02 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T _min = 0.897, T _max = 0.981
22875 measured reflections
5177 independent reflections
4689 reflections with F ² > 2σ(F ²)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.062
S = 1.08
5177 reflections
330 parameters
H-atom parameters constrained
Δρ_max = 1.37 e Å⁻³
Δρ_min = −1.28 e Å⁻³
Absolute structure: Flack (1983 ▶), 2249 Friedel pairs
Flack parameter: 0.22 (4)

Data collection: CrystalClear-SM (Rigaku, 2009 ▶); cell refinement: CrystalClear-SM; data reduction: CrystalClear-SM; 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, 2012 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2006 ▶).

Supplementary Material

Click here for additional data file.^{(33.1KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812048246/is5220sup1.cif

e-69-000m1-sup1.cif^{(33.1KB, cif)}

Click here for additional data file.^{(253.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812048246/is5220Isup2.hkl

e-69-000m1-Isup2.hkl^{(253.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ru1—Cl1	2.3521 (17)
Ru1—N1	2.086 (2)
Ru1—N2	2.070 (2)
Ru1—N3	2.070 (2)
Ru1—N4	2.117 (2)
Ru1—C21	1.890 (8)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯F2ⁱ	0.95	2.46	3.166 (4)	131
C4—H4⋯F1ⁱⁱ	0.95	2.41	3.257 (4)	148
C7—H5⋯F1ⁱⁱ	0.95	2.54	3.431 (4)	156
C8—H6⋯F2ⁱⁱⁱ	0.95	2.50	3.265 (4)	138
C13—H11⋯F5^iv	0.95	2.39	3.331 (4)	168

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

supplementary crystallographic information

Comment

Ruthenium(II) complexes containing both carbonyl and polypyridyl-based supporting ligands have been studied as catalysts for the reduction of carbon dioxide and in the water-gas shift reaction (Ishida et al., 1986; Lehn & Ziessel, 1990). Of the series complexes, [Ru(bpy)₂(CO)Cl]⁺ (bpy = 2,2'-bipyridine) has been used not only as catalysts but also as a precursor to a family of [Ru(bpy)₂(CO)L]ⁿ⁺-type complexes (L = monodentate ligand). We have used the complex as the starting point for the preparation of more complex functional systems, and we report here the crystal structure of its hexafluoridophosphate salt.

The Ru^II atom has a distorted octahedral geometry, with four N atoms of the bidentate bipyridine ligands, a carbonyl carbon, and a chloride ion completing the first coordination sphere. The CO and Cl ligands in the cation are mutually cis arrangement (Fig. 1) and these are disordered over two sets of sites with site occupancies of 0.721 (6) and 0.279 (6). The Ru—N length trans to the CO ligand [2.117 (2) Å] is slightly longer than the average of other Ru—N lengths (2.08 Å) (Table 1). This can be explained by the expected trans influence of the CO group. In the crystal, the complex cation and the PF₆^- anion are linked via a number of weak C—H···F interactions, leading to the formation of a three-dimensional supramolecular structure. The crystal studied was an inversion twin with twin fractions of 0.78 (4) and 0.22 (4). The bond parameters of the complex are closely comparable to those of the reported ClO₄^- salt, although the corresponding ClO₄^- salt was refined using anisotropic temperature factors for Ru and Cl only (Clear et al., 1980).

Experimental

The title compound was prepared according to a literature procedure (Oyama et al., 2012). X-ray quality crystals were grown by the diffusion of diethyl ether into an acetone solution of the complex over a week.