cis-Dichloridotetra­kis­(trimethyl­phosphane-κP)ruthenium(II) benzene disolvate

Chen Fu; Ting Bin Wen

doi:10.1107/S1600536810049706

. 2010 Dec 4;67(Pt 1):m14. doi: 10.1107/S1600536810049706

cis-Dichloridotetrakis(trimethylphosphane-κP)ruthenium(II) benzene disolvate

Chen Fu ^a, Ting Bin Wen ^a,^*

PMCID: PMC3050259 PMID: 21522541

Abstract

The title compound, cis-[RuCl₂(C₃H₉P)₄]·2C₆H₆, contains a complex molecule with a crystallographic mirror plane passing through the Ru^II atom, the two cis-disposed Cl ligands and two P atoms of the two cis-disposed P(CH₃)₃ ligands. The Ru^II atom adopts a distorted octahedral RuCl₂P₄ coordination geometry with the two trans-disposed P atoms occupying the axial positions. The packing of the structure is accomplished through non-classical C—H⋯Cl hydrogen bonds between the benzene solvent molecule and one of the Cl ligands.

Related literature

For general background to trans-[RuCl₂(P(CH₃)₃)₄], see: Csok et al. (2007 ▶); Gotzig et al. (1985 ▶); Hartwig et al. (1991 ▶); Hirano et al. (2010 ▶); Kohlmann & Werner (1993 ▶). For a related structure, see: Joo et al. (1994 ▶).

Experimental

Crystal data

[RuCl₂(C₃H₉P)₄]·2C₆H₆
M _r = 632.47
Orthorhombic,
a = 17.6243 (15) Å
b = 18.1889 (19) Å
c = 9.4610 (11) Å
V = 3032.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 173 K
0.18 × 0.12 × 0.06 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.949, T _max = 1.000
14352 measured reflections
3550 independent reflections
1653 reflections with I > 2σ(I)
R _int = 0.148

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.081
S = 0.82
3550 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810049706/wm2431sup1.cif

e-67-00m14-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049706/wm2431Isup2.hkl

e-67-00m14-Isup2.hkl^{(174.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ru1—P1	2.2690 (19)
Ru1—P2	2.297 (2)
Ru1—P3	2.3819 (14)
Ru1—Cl1	2.479 (2)
Ru1—Cl2	2.5038 (19)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4S—H4SA⋯Cl2	0.93	2.83	3.710 (5)	159

Open in a new tab

Acknowledgments

The authors acknowledge financial support from the Young Talent Project of Department of Science & Technology of Fujian Province (grant No. 2007 F3095).

supplementary crystallographic information

Comment

The ruthenium(II) complex trans-[RuCl₂(PMe₃)₄], which can be readily prepared from the reaction of RuCl₂(PPh₃)₃ with PMe₃ in hexane at room temperature (Gotzig et al., 1985), has proved to be a useful precursor for a wide variety of ruthenium compounds (Hartwig et al., 1991; Kohlmann & Werner, 1993; Csok et al., 2007; Hirano et al., 2010). However, its geometrical isomer, cis-[RuCl₂(PMe₃)₄], has not been reported yet. During our preparation of ruthenium compounds with phosphine ligands using trans-[RuCl₂(PMe₃)₄] as the starting material, we found that the trans-isomer slowly isomerizes to the cis-isomer, the structure of which we report here as the benzene disolvate.

As shown in Fig.1, the structure of the title complex possesses a crystallographic mirror plane passing through the Ru^II atom, the two cis-disposed Cl ligands and the two P atoms as well as two C atoms of the two cis-disposed PMe₃ ligands. Thus the asymmetric unit of the structure contains half of a molecule. The Ru^II atom adopts a distorted octahedral geometry with the two trans-disposed P atoms occupying the axial positions. The bond lengths of the two axial Ru—P bonds (2.3819 (14) Å), which are actually image-related, are slightly longer than those of the two equatorial Ru—P bonds which are trans to the Cl ligands (2.2690 (19) and 2.297 (2) Å, respectively). The two Ru—Cl bond lengths are 2.479 (2) and 2.5038 (19) Å, respectively, while the Cl(1)—Ru(1)—Cl(2) bond angle is 86.20 (7)°. These geometric values are similar to those reported for the only example of a sructurally characterized monodentate tetrakis(phosphine)-cis-dichlorido-ruthenium(II) complex, viz. [cis-RuCl₂(PTA)₄] (PTA = 1,3,5-triaza-7-phospha-adamantane-κP); 2.488 (2) and 2.503 (2) Å, 84.2 (1) °; Joo et al., 1994).

The packing of the structure (Fig. 2) is accomplished through non-classical C—H···Cl hydrogen bonds between the benzene solvent molecule and one of the Cl ligands (Table 2).

Experimental

Route A: To a solution of RuCl₂(PPh₃)₃ (0.25 g, 0.24 mmol) in toluene (8 ml) under nitrogen atmosphere was added PMe₃ (0.27 ml, 2.5 mmol) and the resulting yellow solution was refluxed for 20 h. The solvent was removed under vacuum, and the solid residue was washed with n-hexane, and dried under vacuum to afford a white solid. Yield: 90 mg, 80%. Route B: A solution of trans-[RuCl₂(PMe₃)₄] (100 mg, 0.21 mmol) in benzene (5 ml) was refluxed for 12 h under nitrogen atmosphere. After the solution was cooled to ambient temperature, a white solid was precipitated, which was collected by filtration, washed with n-hexane, and dried under vacuum. Yield: 72 mg, 72%. Crystals suitable for X-ray analysis were obtained from standing a solution of trans-[RuCl₂(PMe₃)₄] in benzene at room temperature for 2 weeks.