Di-μ-chlorido-bis­[chlorido(η⁶-toluene)­ruthenium(II)]

In the centrosymmetric dinuclear title complex, [Ru₂Cl₄(η⁶-C₆H₅CH₃)₂], accessible from RuCl₃·nH₂O and 1-methyl­cyclo­hexa-1,4-diene, the toluene ligand is planar with a ruthenium–centroid distance of 1.646 Å.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.039
• wR factor = 0.082
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level B
RINTA01_ALERT_3_B  The value of Rint is greater than 0.15
            Rint given   0.165
PLAT020_ALERT_3_B The value of Rint is greater than 0.10 .........       0.17

Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ru     -   Cl2_a   ..       5.56 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         Ru

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound, which is known for more then 30 years (Bennett & Smith, 1974), and regularly used as building block in organometallic chemistry, has never been characterized by X-ray structure analysis. The two halves of the dinuclear complex are related by a crystallographic inversion centre. The bond distances and angles are similar to other [RuCl₂(η⁶-arene)]₂ complexes; arene = hexamethylbenzene (McCormick & Gleason, 1988), arene = trindane (Gupta et al., 1997), arene = ethylbenzoate (Therrien et al., 1998), arene = 1,2,3,4-tetrahydronaphthalene (Bown & Bennett, 1999), arene = 1,2-C₆H₄(Me)COOMe (Braga et al., 2001), arene = hexaethylbenzene (Baldwin et al., 2002), arene = indane (Vieille-Petit et al., 2002), arene = para-cymene (Allardyce et al., 2003; Dinçer et al., 2006), arene = benzene (Canivet et al., 2005).

The aromatic ring of the toluene is planar and the Ru-toluene (centroid) distance is 1.648 Å. The metal possesses two bridging and one terminal chlorines, the Ru—Cl (bridged) distances are 2.4426 (10) and 2.4378 (10) Å, when the Ru—Cl (terminal) distance is 2.4037 (10) Å, see Fig. 1. No meaningful interactions between the dinuclear ruthenium complexes are observed in the crystal packing.

Related literature

For similar dinuclear chloro-bridged arene ruthenium complexes, see: McCormick & Gleason (1988); Gupta et al. (1997); Therrien et al. (1998); Bown & Bennett (1999); Braga et al. (2001); Baldwin et al. (2002); Vieille-Petit et al. (2002); Allardyce et al. (2003); Canivet et al. (2005); Dinçer et al. (2006). For the synthesis of [RuCl₂(η⁶-toluene)]₂, see: Bennett & Smith (1974).

S2. Experimental

[RuCl₂(η⁶-toluene)]₂ is disolved in hot chloroform, and crystals suitable for X-ray diffraction analysis are obtained, after weeks, by slow evaporation of the diluted chloroform solution.

S3. Refinement

The high R_int value is not a consequence of weak high-angle diffraction, but more probably a consequence of a high ratio of collected reflections to unique reflections. The H atoms were included in calculated positions and refined using a riding model, with C—H = 0.93–0.96 Å and with U_iso(H) = 1.2 (1.5 for methyl groups) times U_eq(C).

Computing details

Data collection: EXPOSE in IPDS Software (Stoe & Cie, 2000); cell refinement: CELL in IPDS Software (Stoe & Cie, 2000); data reduction: INTEGRATE in IPDS Software (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. The molecular structure of [RuCl2(η^6-toluene)]2 with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.[Symmetry code:(i) 2 - x, -y, 2 - z]

Di-µ-chlorido-bis[chlorido(η⁶-toluene)ruthenium(II)]

Crystal data

[Ru2Cl4(C7H8)2]	F(000) = 512
Mr = 528.21	Dx = 2.192 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5559 reflections
a = 7.5144 (10) Å	θ = 2.2–26.1°
b = 9.135 (1) Å	µ = 2.54 mm^−1
c = 11.6595 (13) Å	T = 173 K
β = 90.691 (15)°	Block, orange
V = 800.30 (16) Å^3	0.22 × 0.19 × 0.18 mm
Z = 2

Data collection

Stoe IPDS diffractometer	1332 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.165
Graphite monochromator	θmax = 26.0°, θmin = 2.7°
Detector resolution: 0.81Å pixels mm^-1	h = −9→9
φ oscillation scans	k = −11→11
6143 measured reflections	l = −14→14
1567 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0382P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
1567 reflections	Δρmax = 0.91 e Å^−3
93 parameters	Δρmin = −0.86 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0116 (14)

Special details

Experimental. A crystal was mounted at 173 K on a Stoe Image Plate Diffraction System (Stoe & Cie, 2000) using Mo Kα graphite monochromated radiation. Image plate distance 70 mm, φ oscillation scans 0 - 200°, step Δφ = 1.5°, 3 minutes per frame.

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7146 (6)	−0.2107 (4)	0.8576 (4)	0.0344 (9)
C2	0.5746 (5)	−0.1062 (4)	0.8626 (4)	0.0337 (9)
H2	0.4809	−0.1215	0.9126	0.040*
C3	0.5750 (6)	0.0186 (5)	0.7941 (4)	0.0375 (10)
H3	0.4818	0.0853	0.7987	0.045*
C4	0.7162 (6)	0.0448 (6)	0.7172 (4)	0.0441 (11)
H4	0.7171	0.1279	0.6712	0.053*
C5	0.8533 (6)	−0.0569 (6)	0.7126 (4)	0.0460 (12)
H5	0.9464	−0.0412	0.6623	0.055*
C6	0.8551 (6)	−0.1834 (5)	0.7822 (4)	0.0416 (10)
H6	0.9496	−0.2488	0.7781	0.050*
C7	0.7188 (8)	−0.3395 (5)	0.9370 (5)	0.0579 (13)
H7A	0.6257	−0.3301	0.9922	0.087*
H7B	0.8319	−0.3433	0.9760	0.087*
H7C	0.7014	−0.4278	0.8936	0.087*
Cl1	0.78551 (15)	0.26134 (10)	0.94473 (10)	0.0429 (3)
Cl2	1.14333 (12)	0.04611 (11)	0.90842 (8)	0.0299 (2)
Ru	0.82237 (4)	0.01024 (3)	0.88814 (2)	0.02185 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.039 (2)	0.0254 (16)	0.038 (2)	−0.0065 (16)	−0.0093 (17)	−0.0074 (17)
C2	0.028 (2)	0.042 (2)	0.031 (2)	−0.0087 (16)	−0.0015 (16)	−0.0012 (18)
C3	0.028 (2)	0.044 (2)	0.040 (3)	0.0026 (16)	−0.0095 (19)	0.0028 (19)
C4	0.051 (3)	0.054 (2)	0.028 (2)	−0.013 (2)	−0.0102 (19)	0.010 (2)
C5	0.046 (3)	0.071 (3)	0.021 (2)	−0.016 (2)	0.0109 (19)	−0.018 (2)
C6	0.041 (2)	0.040 (2)	0.044 (2)	0.0051 (18)	0.0007 (19)	−0.028 (2)
C7	0.077 (3)	0.027 (2)	0.069 (3)	−0.006 (2)	−0.021 (3)	0.009 (2)
Cl1	0.0576 (7)	0.0247 (5)	0.0467 (6)	0.0059 (4)	0.0130 (5)	−0.0036 (4)
Cl2	0.0270 (5)	0.0408 (5)	0.0218 (5)	−0.0052 (4)	0.0017 (3)	0.0048 (4)
Ru	0.0244 (2)	0.0235 (2)	0.0176 (2)	0.00096 (10)	0.00095 (13)	−0.00096 (10)

Geometric parameters (Å, º)

C1—C6	1.404 (6)	C5—C6	1.412 (7)
C1—C2	1.422 (5)	C5—Ru	2.152 (4)
C1—C7	1.497 (6)	C5—H5	0.9300
C1—Ru	2.202 (4)	C6—Ru	2.173 (4)
C2—C3	1.392 (6)	C6—H6	0.9300
C2—Ru	2.162 (4)	C7—H7A	0.9600
C2—H2	0.9300	C7—H7B	0.9600
C3—C4	1.418 (6)	C7—H7C	0.9600
C3—Ru	2.149 (5)	Cl1—Ru	2.4037 (10)
C3—H3	0.9300	Cl2—Ru^i	2.4378 (10)
C4—C5	1.388 (7)	Cl2—Ru	2.4426 (10)
C4—Ru	2.161 (5)	Ru—Cl2^i	2.4378 (10)
C4—H4	0.9300
C6—C1—C2	117.9 (4)	H7A—C7—H7C	109.5
C6—C1—C7	121.1 (4)	H7B—C7—H7C	109.5
C2—C1—C7	120.9 (4)	Ru^i—Cl2—Ru	99.12 (3)
C6—C1—Ru	70.1 (2)	C3—Ru—C5	68.10 (19)
C2—C1—Ru	69.5 (2)	C3—Ru—C4	38.42 (17)
C7—C1—Ru	128.0 (3)	C5—Ru—C4	37.5 (2)
C3—C2—C1	121.3 (4)	C3—Ru—C2	37.67 (16)
C3—C2—Ru	70.7 (2)	C5—Ru—C2	80.28 (17)
C1—C2—Ru	72.5 (2)	C4—Ru—C2	68.71 (17)
C3—C2—H2	119.3	C3—Ru—C6	80.89 (18)
C1—C2—H2	119.3	C5—Ru—C6	38.12 (19)
Ru—C2—H2	130.1	C4—Ru—C6	68.8 (2)
C2—C3—C4	120.5 (4)	C2—Ru—C6	67.93 (16)
C2—C3—Ru	71.7 (3)	C3—Ru—C1	68.63 (16)
C4—C3—Ru	71.2 (3)	C5—Ru—C1	68.22 (18)
C2—C3—H3	119.8	C4—Ru—C1	81.60 (18)
C4—C3—H3	119.8	C2—Ru—C1	38.02 (15)
Ru—C3—H3	129.8	C6—Ru—C1	37.44 (16)
C5—C4—C3	118.2 (4)	C3—Ru—Cl1	90.25 (12)
C5—C4—Ru	70.9 (3)	C5—Ru—Cl1	123.16 (15)
C3—C4—Ru	70.3 (3)	C4—Ru—Cl1	94.09 (15)
C5—C4—H4	120.9	C2—Ru—Cl1	113.92 (11)
C3—C4—H4	120.9	C6—Ru—Cl1	161.26 (14)
Ru—C4—H4	130.3	C1—Ru—Cl1	151.11 (12)
C4—C5—C6	121.8 (4)	C3—Ru—Cl2^i	125.80 (13)
C4—C5—Ru	71.6 (2)	C5—Ru—Cl2^i	148.65 (16)
C6—C5—Ru	71.7 (2)	C4—Ru—Cl2^i	164.10 (13)
C4—C5—H5	119.1	C2—Ru—Cl2^i	96.38 (11)
C6—C5—H5	119.1	C6—Ru—Cl2^i	111.70 (14)
Ru—C5—H5	130.3	C1—Ru—Cl2^i	89.89 (12)
C1—C6—C5	120.2 (4)	Cl1—Ru—Cl2^i	86.88 (4)
C1—C6—Ru	72.4 (2)	C3—Ru—Cl2	153.12 (13)
C5—C6—Ru	70.1 (2)	C5—Ru—Cl2	90.72 (13)
C1—C6—H6	119.9	C4—Ru—Cl2	115.01 (13)
C5—C6—H6	119.9	C2—Ru—Cl2	157.99 (11)
Ru—C6—H6	130.1	C6—Ru—Cl2	92.63 (12)
C1—C7—H7A	109.5	C1—Ru—Cl2	119.97 (11)
C1—C7—H7B	109.5	Cl1—Ru—Cl2	87.84 (4)
H7A—C7—H7B	109.5	Cl2^i—Ru—Cl2	80.88 (4)
C1—C7—H7C	109.5
C6—C1—C2—C3	0.8 (6)	C3—C4—Ru—Cl2^i	7.8 (7)
C7—C1—C2—C3	176.1 (4)	C5—C4—Ru—Cl2	54.3 (3)
Ru—C1—C2—C3	53.3 (4)	C3—C4—Ru—Cl2	−174.8 (2)
C6—C1—C2—Ru	−52.5 (3)	C1—C2—Ru—C3	133.5 (4)
C7—C1—C2—Ru	122.8 (4)	C3—C2—Ru—C5	−66.6 (3)
C1—C2—C3—C4	−0.1 (7)	C1—C2—Ru—C5	66.9 (3)
Ru—C2—C3—C4	54.0 (4)	C3—C2—Ru—C4	−29.4 (3)
C1—C2—C3—Ru	−54.1 (4)	C1—C2—Ru—C4	104.1 (3)
C2—C3—C4—C5	−0.1 (7)	C3—C2—Ru—C6	−104.2 (3)
Ru—C3—C4—C5	54.1 (4)	C1—C2—Ru—C6	29.3 (3)
C2—C3—C4—Ru	−54.2 (4)	C3—C2—Ru—C1	−133.5 (4)
C3—C4—C5—C6	−0.3 (7)	C3—C2—Ru—Cl1	55.5 (3)
Ru—C4—C5—C6	53.5 (4)	C1—C2—Ru—Cl1	−171.0 (2)
C3—C4—C5—Ru	−53.8 (4)	C3—C2—Ru—Cl2^i	144.9 (3)
C2—C1—C6—C5	−1.2 (6)	C1—C2—Ru—Cl2^i	−81.6 (2)
C7—C1—C6—C5	−176.5 (4)	C3—C2—Ru—Cl2	−133.7 (3)
Ru—C1—C6—C5	−53.4 (4)	C1—C2—Ru—Cl2	−0.2 (5)
C2—C1—C6—Ru	52.2 (3)	C1—C6—Ru—C3	−66.6 (3)
C7—C1—C6—Ru	−123.1 (4)	C5—C6—Ru—C3	65.9 (3)
C4—C5—C6—C1	1.0 (7)	C1—C6—Ru—C5	−132.5 (4)
Ru—C5—C6—C1	54.4 (4)	C1—C6—Ru—C4	−104.5 (3)
C4—C5—C6—Ru	−53.4 (4)	C5—C6—Ru—C4	28.0 (3)
C2—C3—Ru—C5	102.9 (3)	C1—C6—Ru—C2	−29.7 (2)
C4—C3—Ru—C5	−29.7 (3)	C5—C6—Ru—C2	102.8 (3)
C2—C3—Ru—C4	132.6 (4)	C5—C6—Ru—C1	132.5 (4)
C4—C3—Ru—C2	−132.6 (4)	C1—C6—Ru—Cl1	−129.3 (4)
C2—C3—Ru—C6	65.5 (3)	C5—C6—Ru—Cl1	3.2 (6)
C4—C3—Ru—C6	−67.1 (3)	C1—C6—Ru—Cl2^i	58.4 (3)
C2—C3—Ru—C1	28.7 (2)	C5—C6—Ru—Cl2^i	−169.0 (2)
C4—C3—Ru—C1	−103.9 (3)	C1—C6—Ru—Cl2	139.7 (2)
C2—C3—Ru—Cl1	−131.1 (2)	C5—C6—Ru—Cl2	−87.8 (3)
C4—C3—Ru—Cl1	96.3 (3)	C6—C1—Ru—C3	103.4 (3)
C2—C3—Ru—Cl2^i	−44.8 (3)	C2—C1—Ru—C3	−28.4 (3)
C4—C3—Ru—Cl2^i	−177.4 (2)	C7—C1—Ru—C3	−142.1 (5)
C2—C3—Ru—Cl2	143.2 (2)	C6—C1—Ru—C5	29.3 (3)
C4—C3—Ru—Cl2	10.5 (4)	C2—C1—Ru—C5	−102.5 (3)
C4—C5—Ru—C3	30.4 (3)	C7—C1—Ru—C5	143.8 (5)
C6—C5—Ru—C3	−103.6 (3)	C6—C1—Ru—C4	65.8 (3)
C6—C5—Ru—C4	−134.0 (4)	C2—C1—Ru—C4	−66.0 (3)
C4—C5—Ru—C2	67.6 (3)	C7—C1—Ru—C4	−179.7 (5)
C6—C5—Ru—C2	−66.5 (3)	C6—C1—Ru—C2	131.8 (4)
C4—C5—Ru—C6	134.0 (4)	C7—C1—Ru—C2	−113.7 (5)
C4—C5—Ru—C1	105.2 (3)	C2—C1—Ru—C6	−131.8 (4)
C6—C5—Ru—C1	−28.9 (3)	C7—C1—Ru—C6	114.5 (5)
C4—C5—Ru—Cl1	−44.7 (3)	C6—C1—Ru—Cl1	149.0 (3)
C6—C5—Ru—Cl1	−178.8 (2)	C2—C1—Ru—Cl1	17.2 (4)
C4—C5—Ru—Cl2^i	153.9 (2)	C7—C1—Ru—Cl1	−96.5 (5)
C6—C5—Ru—Cl2^i	19.9 (4)	C6—C1—Ru—Cl2^i	−127.7 (3)
C4—C5—Ru—Cl2	−132.6 (3)	C2—C1—Ru—Cl2^i	100.5 (2)
C6—C5—Ru—Cl2	93.3 (3)	C7—C1—Ru—Cl2^i	−13.2 (4)
C5—C4—Ru—C3	−131.0 (4)	C6—C1—Ru—Cl2	−48.3 (3)
C3—C4—Ru—C5	131.0 (4)	C2—C1—Ru—Cl2	179.9 (2)
C5—C4—Ru—C2	−102.1 (3)	C7—C1—Ru—Cl2	66.2 (5)
C3—C4—Ru—C2	28.9 (3)	Ru^i—Cl2—Ru—C3	173.5 (3)
C5—C4—Ru—C6	−28.4 (3)	Ru^i—Cl2—Ru—C5	−149.65 (15)
C3—C4—Ru—C6	102.5 (3)	Ru^i—Cl2—Ru—C4	−179.30 (16)
C5—C4—Ru—C1	−65.0 (3)	Ru^i—Cl2—Ru—C2	−84.4 (3)
C3—C4—Ru—C1	66.0 (3)	Ru^i—Cl2—Ru—C6	−111.56 (14)
C5—C4—Ru—Cl1	143.8 (3)	Ru^i—Cl2—Ru—C1	−84.55 (14)
C3—C4—Ru—Cl1	−85.2 (3)	Ru^i—Cl2—Ru—Cl1	87.19 (4)
C5—C4—Ru—Cl2^i	−123.2 (5)	Ru^i—Cl2—Ru—Cl2^i	0.0

Symmetry code: (i) −x+2, −y, −z+2.