cis-Dichlorido(1,3-dimesitylimidazolidin-2-yl­idene)(2-formyl­benzyl­idene-κ2C,O)ruthenium diethyl ether solvate

Slugovc, C.; Perner, B.; Stelzer, F.; Mereiter, K.

doi:10.1107/S1600536810000826

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages m154-m155

https://doi.org/10.1107/S1600536810000826

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cis-Dichlorido(1,3-dimesitylimidazolidin-2-ylidene)(2-formylbenzylidene-κ²C,O)ruthenium diethyl ether solvate

Christian Slugovc,^a Bernhard Perner,^a Franz Stelzer ^a and Kurt Mereiter ^b ^*

^aInstitute for Chemistry and Technology of Materials (ICTM), Graz University of Technology, Stremayrgasse 16, A-8010 Graz, Austria, and ^bInstitute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna, Austria
^*Correspondence e-mail: kurt.mereiter@tuwien.ac.at

(Received 4 January 2010; accepted 7 January 2010; online 13 January 2010)

The title compound, [RuCl₂(C₈H₆O)(C₂₁H₂₆N₂)]·C₄H₁₀O, contains a catalytically active ruthenium carbene complex of the `second-generation Grubbs/Hoveyda' type with Ru in a square-pyramidal coordination, the apex of which is formed by the benzylidene carbene atom with Ru=C 1.827 (2) Å. The complex shows the uncommon cis, rather than the usual trans, arrangement of the two chloride ligands, with Ru—Cl bond lengths of 2.3548 (6) and 2.3600 (6) Å, and a Cl—Ru—Cl angle of 89.76 (2)°. This cis configuration is desirable for certain applications of ring-opening metathesis polymerization (ROMP) of strained cyclic olefins. The crystalline solid is a diethyl ether solvate, which is built up from a porous framework of Ru complexes held together by π–π stacking and C—H⋯Cl and C—H⋯O interactions. The disordered diethyl ether solvent molecules are contained in two independent infinite channels, which extend parallel to the c axis at x,y = 0,0 and x,y = $[{1\over 2}]$ , $[{1\over 2}]$ and have solvent-accessible void volumes of 695 and 464 Å³ per unit cell.

Related literature

For the synthesis and application of the title compound in ring-opening metathesis polymerization (ROMP), see: Slugovc et al. (2004 ); Burtscher et al. (2006 ). For thermally switchable initiators for olefin metathesis polymerization, see: Gstrein et al. (2007 ); Szadkowska & Grela (2008 ). For a recent authoritative review on ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts, see: Vougioukalakis & Grubbs (2010 ).

Experimental

Crystal data

[RuCl₂(C₈H₆O)(C₂₁H₂₆N₂)]·C₄H₁₀O
M_r = 670.66
Tetragonal, $[P \overline 4c 2]$
a = 19.8603 (4) Å
c = 15.6582 (7) Å
V = 6176.1 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.71 mm⁻¹
T = 100 K
0.43 × 0.25 × 0.22 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.78, T_max = 0.86
90504 measured reflections
8992 independent reflections
7306 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.067
S = 1.01
8992 reflections
322 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 ), 4175 Friedel pairs
Flack parameter: −0.02 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C29—H29C⋯Cl1	0.98	2.67	3.634 (3)	166
C39—H39C⋯Cl1	0.98	2.76	3.371 (3)	121
C37—H37A⋯O49	0.98	2.39	3.268 (3)	150
C13—H13B⋯Cl1ⁱ	0.99	2.94	3.395 (2)	109
C14—H14A⋯Cl1ⁱ	0.99	2.90	3.324 (3)	107
C27—H27A⋯Cl2ⁱ	0.98	2.85	3.724 (3)	149
C37—H37C⋯Cl2ⁱ	0.98	2.88	3.736 (3)	146
C25—H25⋯Cl1ⁱⁱ	0.95	2.98	3.831 (3)	150
C29—H29A⋯Cl1ⁱⁱ	0.98	2.71	3.673 (3)	169
C46—H46⋯Cl2ⁱⁱⁱ	0.95	3.04	3.553 (2)	115
C48—H48⋯O49ⁱⁱⁱ	0.95	2.50	3.014 (3)	114
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) -y+1, x, -z; (iii) -x, -y+1, z.

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT, SADABS and XPREP (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009 ); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ), PLATON and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810000826/bt5164sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000826/bt5164Isup2.hkl

checkCIF report

Comment top

The ruthenium complex RuCl₂(C₈H₆O)(C₂₁H₂₆N₂), which is the main constituent of the title compound, (I), was prepared by a carbene exchange reaction of (H₂IMes)(pyridine)₂(Cl)₂RuCHPh (1eq.; H₂IMes = 1,3-bismesityl-4,5-dihydroimidazol-2-ylidene) with 2-vinylbenzaldehyde (2 eq.) in CH₂Cl₂ at room temperature (Slugovc et al., 2004). In sharp contrast to most of the ruthenium carbene complexes bearing two halides and neutral donor co-ligands (phosphines or N-heterocyclic carbenes), which exhibit a trans stereochemistry of the two halide ligands, the ruthenium complex of the title compound bears them in a cis-disposition of a square pyramidal coordination about Ru, the apex of which is formed by the benzylidene carbon C41 with a characteristically short Ru—C bond of 1.827 (2) Å whereas the bond to the N-heterocyclic carbene carbon C11 is longer by 0.077 Å (Fig. 1 and Table 1). It has been shown, that cis-isomer is thermodynamically favoured over its trans-dichlorido counterpart (Slugovc et al., 2004). Ruthenium carbene complexes bearing a cis-dichlorido arrangement are particularly interesting, because they exhibit distinctly lower initiation rates in ring opening metathesis polymerization (ROMP) of strained cyclic olefins when compared to their trans-dichlorido counterparts (Gstrein et al., 2007). This feature is used to design latent ROMP initiators and catalysts for e.g. ring closing metathesis at elevated temperatures (Szadkowska & Grela, 2008; Burtscher et al., 2006; Vougioukalakis & Grubbs, 2010).

A view of the Ru complex in the title compound is presented in Fig. 1. Bond lengths and angles about Ru (Table 1) are in good agreement with the bis-dichloromethane solvate of the same complex, RuCl₂(C₈H₆O)(C₂₁H₂₆N₂).2CH₂Cl₂, which crystallizes in a moclinic lattice, space group P2₁/c, a = 12.1933 (6), b = 15.4520 (7), c = 19.3799 (9) Å, β = 108.181 (1)°, V = 3469.1 (3) Å³, Z = 4 (Slugovc et al., 2004). Both complexes, in (I) and in the dichloromethane solvate, show similar conformations and are stabilized by significant intramolecular π-π stacking interactions between the 2-formylbenzylidene and the adjacent mesityl moiety with the shortest intramolecular π-π contacts of C41···C21 = 3.00 Å, C42···C22 = 3.40 Å, and C43···C24 = 3.45 Å in (I) and 2.99, 3.42, and 3.43 Å in the dichloromethane solvate. Moreover, both complexes show intramolecular C—H···O,Cl interactions, e.g. in (I) between C37 and Cl1 and and C29 and Cl1 (Fig. 1 and Table 2). In contrast to the dichloromethane solvate, where the Ru complexes do not show any intermolecular π-π-stacking but are held together mainly by C—H···π and C—H···Cl intercations, intermolecular π-π-stacking is an important factor in the crystal structure of (I). Fig. 2 demonstrates that the structure of (I) contains columnar stacks of molecules extending along the c-axis and showing intermolecular π-π-stacking between the formylbenzylidene and one of the two mesityl groups [corresponding π-π-contacts are C44···C33(x,1 - y,-1/2 + z) = 3.59 Å and C43···C32(x,1 - y,-1/2 + z) = 3.81 Å]. Further π-π-stacking interactions arise from the mutual indentation of these stacks [corresponding π-π-contacts are C22···C24(y,x,1/2 - z) = 3.82 Å, C23···C23(y,x,1/2 - z) = 3.64 Å and C24···C22(y,x,1/2 - z) = 3.82 Å]. Finally, the Ru-complexes are also held together by a larger number of weak intermolecular C—H···Cl,O interactions (Table 2). The result of all these interactions between the Ru complexes in (I) is a framework-like structure of tetragonal symmetry containing continuous channels which extend along the c-axis and contain the diethyl ether solvent molecules. As shown in Fig. 3, there are two different kinds of continuous channels in the this framework, both coinciding with the two crystallographically different sets of 4 axes of the lattice. The larger channel in this framework is centered at x,y = 0,0 and has a minimal net-diameter in the (001)-projection of 5.6 Å and a solvent-accessible volume per unit cell of 695 Å³ (program PLATON; Spek, 2009). The smaller channel is centered at x,y = 1/2,1/2, has in the projection a minimal net-diameter of 4.2 Å and a solvent-accessible volume per unit cell of 464 Å³. As described in the experimental section, the diethyl ether solvent molecules inside these channels are disordered with about 5 molecules per unit cell in the large and about 3 molecules per unit cell in the small channel.

Related literature top

For the synthesis and application of the title compound in ring-opening metathesis polymerization (ROMP), see: Slugovc et al. (2004); Burtscher et al. (2006). For thermally switchable initiators for olefin metathesis polymerization, see: Gstrein et al. (2007); Szadkowska & Grela (2008). For a recent authoritative review on ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts, see: Vougioukalakis & Grubbs (2010).

Experimental top

The title compound was synthesized as described by Slugovc et al. (2004). It was then dissolved in a small amount of CHCl₃ and crystallized at room temperature by the vapour diffusion method using diethyl ether as the anti-solvent. Small green prismatic crystals were obtained, which remained stable at room temperature under oil for at least one hour. They were accompanied by some larger green crystals of different morphology, which after removal from the mother liquor crumbled by solvent loss within minutes and were probably a CHCl₃ containing solvate.

Structure description top

For the synthesis and application of the title compound in ring-opening metathesis polymerization (ROMP), see: Slugovc et al. (2004); Burtscher et al. (2006). For thermally switchable initiators for olefin metathesis polymerization, see: Gstrein et al. (2007); Szadkowska & Grela (2008). For a recent authoritative review on ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts, see: Vougioukalakis & Grubbs (2010).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT, SADABS and XPREP (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level.
	Fig. 2. Packing diagram of (I) viewed along the b-axis. The Ru complexes in the center are shown in space-filling representation in order to emphasize their column-like stacking along the c-axis and part of their π-π stacking interactions.
	Fig. 3. Packing diagram of (I) viewed down the c-axis showing the two different kinds of channels which are occupied by disordered diethyl ether molecules.

cis-Dichlorido(1,3-dimesitylimidazolidin-2-ylidene)(2- formylbenzylidene-κ²C,O)ruthenium top

Crystal data top

[RuCl₂(C₈H₆O)(C₂₁H₂₆N₂)]·C₄H₁₀O	D_x = 1.443 Mg m⁻³
M_r = 670.66	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4c2	Cell parameters from 8875 reflections
a = 19.8603 (4) Å	θ = 2.3–29.6°
c = 15.6582 (7) Å	µ = 0.71 mm⁻¹
V = 6176.1 (3) Å³	T = 100 K
Z = 8	Prism, green
F(000) = 2784	0.43 × 0.25 × 0.22 mm

Data collection top

Bruker SMART APEX CCD diffractometer	8992 independent reflections
Radiation source: normal-focus sealed tube	7306 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
φ and ω scans	θ_max = 30.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −27→27
T_min = 0.78, T_max = 0.86	k = −27→27
90504 measured reflections	l = −21→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0309P)² + 1.9302P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
8992 reflections	Δρ_max = 0.42 e Å⁻³
322 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 4175 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (2)

Crystal data top

[RuCl₂(C₈H₆O)(C₂₁H₂₆N₂)]·C₄H₁₀O	Z = 8
M_r = 670.66	Mo Kα radiation
Tetragonal, P4c2	µ = 0.71 mm⁻¹
a = 19.8603 (4) Å	T = 100 K
c = 15.6582 (7) Å	0.43 × 0.25 × 0.22 mm
V = 6176.1 (3) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	8992 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	7306 reflections with I > 2σ(I)
T_min = 0.78, T_max = 0.86	R_int = 0.058
90504 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.067	Δρ_max = 0.42 e Å⁻³
S = 1.01	Δρ_min = −0.31 e Å⁻³
8992 reflections	Absolute structure: Flack (1983), 4175 Friedel pairs
322 parameters	Absolute structure parameter: −0.02 (2)
0 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ru	0.163541 (9)	0.497964 (9)	0.046582 (10)	0.02129 (4)
Cl1	0.27041 (3)	0.53239 (3)	−0.00175 (4)	0.02852 (11)
Cl2	0.11254 (3)	0.57173 (3)	−0.05230 (4)	0.03066 (12)
C11	0.20523 (12)	0.48129 (11)	0.16118 (14)	0.0236 (5)
N12	0.23047 (10)	0.42655 (10)	0.19933 (12)	0.0262 (4)
C13	0.25911 (14)	0.44070 (13)	0.28464 (16)	0.0346 (6)
H13A	0.3083	0.4328	0.2854	0.042*
H13B	0.2376	0.4125	0.3291	0.042*
C14	0.24273 (15)	0.51526 (12)	0.29779 (18)	0.0345 (6)
H14A	0.2094	0.5216	0.3442	0.041*
H14B	0.2838	0.5415	0.3111	0.041*
N15	0.21431 (10)	0.53461 (9)	0.21391 (12)	0.0262 (4)
C21	0.23113 (12)	0.35894 (11)	0.16561 (14)	0.0253 (5)
C22	0.17748 (12)	0.31643 (12)	0.18503 (14)	0.0269 (5)
C23	0.17985 (12)	0.25113 (12)	0.15293 (15)	0.0288 (5)
H23	0.1435	0.2214	0.1646	0.035*
C24	0.23375 (13)	0.22794 (12)	0.10419 (16)	0.0302 (5)
C25	0.28701 (12)	0.27169 (12)	0.08777 (16)	0.0296 (5)
H25	0.3243	0.2562	0.0553	0.035*
C26	0.28676 (12)	0.33789 (12)	0.11807 (15)	0.0285 (5)
C27	0.11903 (14)	0.33958 (13)	0.23832 (17)	0.0348 (6)
H27A	0.1354	0.3547	0.2941	0.052*
H27B	0.0874	0.3022	0.2462	0.052*
H27C	0.0962	0.3769	0.2094	0.052*
C28	0.23392 (14)	0.15699 (12)	0.06930 (18)	0.0359 (6)
H28A	0.2786	0.1464	0.0464	0.054*
H28B	0.2004	0.1532	0.0237	0.054*
H28C	0.2229	0.1253	0.1152	0.054*
C29	0.34414 (13)	0.38489 (13)	0.09885 (18)	0.0350 (6)
H29A	0.3799	0.3602	0.0691	0.052*
H29B	0.3619	0.4033	0.1524	0.052*
H29C	0.3281	0.4218	0.0626	0.052*
C31	0.18137 (13)	0.59830 (11)	0.20283 (15)	0.0275 (5)
C32	0.11424 (13)	0.60492 (12)	0.22833 (15)	0.0303 (5)
C33	0.08306 (13)	0.66723 (13)	0.21854 (17)	0.0339 (6)
H33	0.0371	0.6719	0.2344	0.041*
C34	0.11702 (15)	0.72254 (13)	0.18645 (17)	0.0355 (6)
C35	0.18389 (14)	0.71537 (13)	0.16534 (17)	0.0361 (6)
H35	0.2076	0.7535	0.1447	0.043*
C36	0.21842 (14)	0.65417 (13)	0.17305 (16)	0.0317 (5)
C37	0.07556 (14)	0.54747 (13)	0.26922 (17)	0.0359 (6)
H37A	0.0719	0.5101	0.2286	0.054*
H37B	0.0304	0.5630	0.2849	0.054*
H37C	0.0994	0.5322	0.3205	0.054*
C38	0.08123 (17)	0.78913 (15)	0.1766 (2)	0.0498 (8)
H38A	0.1139	0.8259	0.1818	0.075*
H38B	0.0470	0.7936	0.2213	0.075*
H38C	0.0596	0.7911	0.1204	0.075*
C39	0.29151 (14)	0.64977 (14)	0.15142 (18)	0.0384 (6)
H39A	0.3106	0.6089	0.1767	0.058*
H39B	0.3150	0.6893	0.1741	0.058*
H39C	0.2969	0.6482	0.0892	0.058*
C41	0.17781 (11)	0.41460 (11)	0.00063 (15)	0.0247 (4)
H41	0.2229	0.4046	−0.0152	0.030*
C42	0.12846 (11)	0.36162 (11)	−0.01471 (14)	0.0237 (4)
C43	0.14811 (12)	0.30477 (12)	−0.06108 (16)	0.0291 (5)
H43	0.1929	0.3017	−0.0820	0.035*
C44	0.10326 (13)	0.25294 (13)	−0.07703 (17)	0.0349 (6)
H44	0.1178	0.2150	−0.1091	0.042*
C45	0.03799 (13)	0.25513 (12)	−0.0475 (2)	0.0382 (6)
H45	0.0079	0.2189	−0.0584	0.046*
C46	0.01669 (12)	0.31127 (12)	−0.00132 (19)	0.0329 (5)
H46	−0.0283	0.3135	0.0191	0.039*
C47	0.06097 (12)	0.36413 (11)	0.01500 (15)	0.0254 (5)
C48	0.03578 (12)	0.42013 (11)	0.06446 (14)	0.0256 (5)
H48	−0.0097	0.4179	0.0830	0.031*
O49	0.06864 (8)	0.47089 (8)	0.08469 (10)	0.0247 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru	0.02463 (9)	0.01835 (8)	0.02089 (6)	0.00016 (7)	−0.00329 (7)	0.00037 (7)
Cl1	0.0282 (3)	0.0274 (3)	0.0299 (3)	−0.0055 (2)	−0.0025 (2)	0.0014 (2)
Cl2	0.0356 (3)	0.0285 (3)	0.0279 (2)	0.0077 (2)	−0.0004 (2)	0.0049 (2)
C11	0.0246 (11)	0.0228 (10)	0.0234 (11)	−0.0010 (8)	−0.0020 (8)	0.0002 (8)
N12	0.0320 (10)	0.0237 (10)	0.0230 (8)	0.0054 (8)	−0.0083 (8)	−0.0013 (8)
C13	0.0451 (15)	0.0300 (13)	0.0288 (13)	0.0075 (11)	−0.0136 (11)	−0.0045 (10)
C14	0.0486 (16)	0.0283 (14)	0.0265 (11)	0.0037 (10)	−0.0150 (12)	−0.0027 (11)
N15	0.0354 (11)	0.0215 (10)	0.0218 (9)	−0.0018 (8)	−0.0085 (8)	−0.0018 (7)
C21	0.0306 (12)	0.0206 (11)	0.0248 (11)	0.0079 (9)	−0.0075 (9)	−0.0015 (9)
C22	0.0309 (12)	0.0255 (11)	0.0243 (11)	0.0063 (10)	−0.0056 (9)	0.0027 (9)
C23	0.0302 (12)	0.0252 (12)	0.0309 (12)	0.0012 (10)	−0.0049 (10)	0.0026 (9)
C24	0.0339 (13)	0.0264 (12)	0.0301 (12)	0.0075 (10)	−0.0114 (10)	−0.0025 (10)
C25	0.0271 (12)	0.0280 (12)	0.0336 (13)	0.0081 (10)	−0.0057 (10)	−0.0046 (10)
C26	0.0256 (12)	0.0297 (12)	0.0304 (12)	0.0064 (9)	−0.0070 (9)	0.0008 (10)
C27	0.0401 (15)	0.0304 (14)	0.0341 (13)	0.0037 (11)	0.0033 (11)	0.0010 (10)
C28	0.0401 (15)	0.0213 (12)	0.0463 (15)	0.0069 (10)	−0.0076 (12)	−0.0069 (10)
C29	0.0273 (13)	0.0310 (13)	0.0466 (15)	0.0039 (10)	−0.0056 (11)	−0.0010 (12)
C31	0.0368 (13)	0.0207 (10)	0.0251 (10)	−0.0017 (9)	−0.0081 (10)	−0.0005 (9)
C32	0.0367 (14)	0.0260 (12)	0.0282 (12)	−0.0048 (10)	−0.0084 (10)	−0.0026 (9)
C33	0.0305 (13)	0.0312 (13)	0.0400 (15)	0.0000 (10)	−0.0047 (11)	−0.0042 (11)
C34	0.0450 (16)	0.0234 (12)	0.0381 (14)	0.0018 (11)	−0.0060 (12)	−0.0022 (10)
C35	0.0461 (16)	0.0215 (12)	0.0406 (14)	−0.0065 (11)	−0.0035 (12)	0.0008 (10)
C36	0.0393 (14)	0.0267 (12)	0.0290 (12)	−0.0050 (11)	−0.0072 (11)	−0.0034 (10)
C37	0.0401 (15)	0.0320 (14)	0.0356 (13)	−0.0036 (12)	0.0013 (11)	−0.0002 (11)
C38	0.0548 (19)	0.0303 (15)	0.064 (2)	0.0097 (13)	0.0022 (16)	0.0049 (14)
C39	0.0403 (15)	0.0334 (14)	0.0416 (14)	−0.0077 (11)	−0.0017 (12)	−0.0058 (11)
C41	0.0244 (10)	0.0235 (10)	0.0261 (11)	0.0015 (8)	−0.0037 (9)	0.0015 (9)
C42	0.0253 (11)	0.0220 (10)	0.0238 (10)	−0.0001 (9)	−0.0036 (8)	0.0035 (8)
C43	0.0281 (11)	0.0271 (12)	0.0320 (12)	0.0035 (9)	−0.0020 (10)	−0.0044 (10)
C44	0.0342 (14)	0.0253 (12)	0.0453 (14)	0.0042 (10)	−0.0057 (11)	−0.0082 (10)
C45	0.0324 (13)	0.0256 (12)	0.0566 (16)	−0.0024 (10)	−0.0102 (14)	−0.0079 (12)
C46	0.0271 (12)	0.0255 (12)	0.0461 (13)	−0.0006 (9)	−0.0040 (11)	−0.0006 (11)
C47	0.0272 (11)	0.0201 (10)	0.0289 (11)	0.0025 (8)	−0.0027 (9)	0.0024 (9)
C48	0.0240 (11)	0.0246 (11)	0.0282 (12)	0.0025 (9)	0.0000 (9)	0.0016 (9)
O49	0.0252 (8)	0.0219 (8)	0.0271 (8)	0.0016 (6)	−0.0018 (6)	0.0005 (6)

Geometric parameters (Å, º) top

Ru—C41	1.827 (2)	C31—C32	1.398 (4)
Ru—C11	2.004 (2)	C31—C36	1.411 (3)
Ru—O49	2.0487 (16)	C32—C33	1.392 (3)
Ru—Cl1	2.3548 (6)	C32—C37	1.517 (4)
Ru—Cl2	2.3600 (6)	C33—C34	1.383 (4)
C11—N12	1.338 (3)	C33—H33	0.9500
C11—N15	1.355 (3)	C34—C35	1.376 (4)
N12—C21	1.443 (3)	C34—C38	1.509 (4)
N12—C13	1.479 (3)	C35—C36	1.401 (4)
C13—C14	1.530 (3)	C35—H35	0.9500
C13—H13A	0.9900	C36—C39	1.493 (4)
C13—H13B	0.9900	C37—H37A	0.9800
C14—N15	1.480 (3)	C37—H37B	0.9800
C14—H14A	0.9900	C37—H37C	0.9800
C14—H14B	0.9900	C38—H38A	0.9800
N15—C31	1.435 (3)	C38—H38B	0.9800
C21—C22	1.393 (3)	C38—H38C	0.9800
C21—C26	1.396 (3)	C39—H39A	0.9800
C22—C23	1.392 (3)	C39—H39B	0.9800
C22—C27	1.502 (3)	C39—H39C	0.9800
C23—C24	1.393 (3)	C41—C42	1.458 (3)
C23—H23	0.9500	C41—H41	0.9500
C24—C25	1.393 (4)	C42—C43	1.398 (3)
C24—C28	1.511 (3)	C42—C47	1.420 (3)
C25—C26	1.398 (3)	C43—C44	1.384 (3)
C25—H25	0.9500	C43—H43	0.9500
C26—C29	1.504 (4)	C44—C45	1.377 (4)
C27—H27A	0.9800	C44—H44	0.9500
C27—H27B	0.9800	C45—C46	1.395 (4)
C27—H27C	0.9800	C45—H45	0.9500
C28—H28A	0.9800	C46—C47	1.393 (3)
C28—H28B	0.9800	C46—H46	0.9500
C28—H28C	0.9800	C47—C48	1.445 (3)
C29—H29A	0.9800	C48—O49	1.242 (3)
C29—H29B	0.9800	C48—H48	0.9500
C29—H29C	0.9800

C41—Ru—C11	97.98 (9)	C26—C29—H29C	109.5
C41—Ru—O49	91.12 (8)	H29A—C29—H29C	109.5
C11—Ru—O49	94.35 (8)	H29B—C29—H29C	109.5
C41—Ru—Cl1	89.81 (7)	C32—C31—C36	121.2 (2)
C11—Ru—Cl1	87.90 (7)	C32—C31—N15	118.9 (2)
O49—Ru—Cl1	177.42 (5)	C36—C31—N15	119.7 (2)
C41—Ru—Cl2	111.76 (7)	C33—C32—C31	118.4 (2)
C11—Ru—Cl2	150.16 (7)	C33—C32—C37	119.3 (2)
O49—Ru—Cl2	87.66 (5)	C31—C32—C37	122.2 (2)
Cl1—Ru—Cl2	89.76 (2)	C34—C33—C32	121.9 (2)
N12—C11—N15	108.25 (19)	C34—C33—H33	119.0
N12—C11—Ru	133.55 (16)	C32—C33—H33	119.0
N15—C11—Ru	118.14 (16)	C35—C34—C33	118.4 (2)
C11—N12—C21	126.60 (18)	C35—C34—C38	121.4 (3)
C11—N12—C13	113.14 (19)	C33—C34—C38	120.2 (3)
C21—N12—C13	120.26 (18)	C34—C35—C36	122.8 (2)
N12—C13—C14	102.93 (18)	C34—C35—H35	118.6
N12—C13—H13A	111.2	C36—C35—H35	118.6
C14—C13—H13A	111.2	C35—C36—C31	117.1 (2)
N12—C13—H13B	111.2	C35—C36—C39	120.5 (2)
C14—C13—H13B	111.2	C31—C36—C39	122.4 (2)
H13A—C13—H13B	109.1	C32—C37—H37A	109.5
N15—C14—C13	102.29 (19)	C32—C37—H37B	109.5
N15—C14—H14A	111.3	H37A—C37—H37B	109.5
C13—C14—H14A	111.3	C32—C37—H37C	109.5
N15—C14—H14B	111.3	H37A—C37—H37C	109.5
C13—C14—H14B	111.3	H37B—C37—H37C	109.5
H14A—C14—H14B	109.2	C34—C38—H38A	109.5
C11—N15—C31	123.7 (2)	C34—C38—H38B	109.5
C11—N15—C14	112.87 (19)	H38A—C38—H38B	109.5
C31—N15—C14	120.67 (18)	C34—C38—H38C	109.5
C22—C21—C26	122.7 (2)	H38A—C38—H38C	109.5
C22—C21—N12	118.5 (2)	H38B—C38—H38C	109.5
C26—C21—N12	118.8 (2)	C36—C39—H39A	109.5
C23—C22—C21	117.4 (2)	C36—C39—H39B	109.5
C23—C22—C27	120.8 (2)	H39A—C39—H39B	109.5
C21—C22—C27	121.8 (2)	C36—C39—H39C	109.5
C22—C23—C24	122.1 (2)	H39A—C39—H39C	109.5
C22—C23—H23	118.9	H39B—C39—H39C	109.5
C24—C23—H23	118.9	C42—C41—Ru	127.91 (17)
C25—C24—C23	118.6 (2)	C42—C41—H41	116.0
C25—C24—C28	120.9 (2)	Ru—C41—H41	116.0
C23—C24—C28	120.5 (2)	C43—C42—C47	117.5 (2)
C24—C25—C26	121.4 (2)	C43—C42—C41	118.7 (2)
C24—C25—H25	119.3	C47—C42—C41	123.7 (2)
C26—C25—H25	119.3	C44—C43—C42	121.0 (2)
C21—C26—C25	117.7 (2)	C44—C43—H43	119.5
C21—C26—C29	121.4 (2)	C42—C43—H43	119.5
C25—C26—C29	120.9 (2)	C45—C44—C43	121.5 (2)
C22—C27—H27A	109.5	C45—C44—H44	119.3
C22—C27—H27B	109.5	C43—C44—H44	119.3
H27A—C27—H27B	109.5	C44—C45—C46	119.0 (2)
C22—C27—H27C	109.5	C44—C45—H45	120.5
H27A—C27—H27C	109.5	C46—C45—H45	120.5
H27B—C27—H27C	109.5	C47—C46—C45	120.4 (2)
C24—C28—H28A	109.5	C47—C46—H46	119.8
C24—C28—H28B	109.5	C45—C46—H46	119.8
H28A—C28—H28B	109.5	C46—C47—C42	120.6 (2)
C24—C28—H28C	109.5	C46—C47—C48	117.4 (2)
H28A—C28—H28C	109.5	C42—C47—C48	122.0 (2)
H28B—C28—H28C	109.5	O49—C48—C47	125.4 (2)
C26—C29—H29A	109.5	O49—C48—H48	117.3
C26—C29—H29B	109.5	C47—C48—H48	117.3
H29A—C29—H29B	109.5	C48—O49—Ru	128.47 (15)

C41—Ru—C11—N12	−5.8 (3)	C14—N15—C31—C32	−81.5 (3)
O49—Ru—C11—N12	85.9 (2)	C11—N15—C31—C36	−106.7 (3)
Cl1—Ru—C11—N12	−95.3 (2)	C14—N15—C31—C36	93.5 (3)
Cl2—Ru—C11—N12	178.85 (15)	C36—C31—C32—C33	4.1 (4)
C41—Ru—C11—N15	170.79 (18)	N15—C31—C32—C33	179.0 (2)
O49—Ru—C11—N15	−97.46 (18)	C36—C31—C32—C37	−173.4 (2)
Cl1—Ru—C11—N15	81.27 (17)	N15—C31—C32—C37	1.4 (3)
Cl2—Ru—C11—N15	−4.6 (3)	C31—C32—C33—C34	−1.6 (4)
N15—C11—N12—C21	179.8 (2)	C37—C32—C33—C34	176.1 (2)
Ru—C11—N12—C21	−3.4 (4)	C32—C33—C34—C35	−1.2 (4)
N15—C11—N12—C13	0.3 (3)	C32—C33—C34—C38	179.8 (3)
Ru—C11—N12—C13	177.2 (2)	C33—C34—C35—C36	1.6 (4)
C11—N12—C13—C14	4.1 (3)	C38—C34—C35—C36	−179.5 (3)
C21—N12—C13—C14	−175.4 (2)	C34—C35—C36—C31	0.9 (4)
N12—C13—C14—N15	−6.4 (3)	C34—C35—C36—C39	−178.3 (2)
N12—C11—N15—C31	−166.3 (2)	C32—C31—C36—C35	−3.7 (4)
Ru—C11—N15—C31	16.3 (3)	N15—C31—C36—C35	−178.6 (2)
N12—C11—N15—C14	−5.1 (3)	C32—C31—C36—C39	175.4 (2)
Ru—C11—N15—C14	177.51 (17)	N15—C31—C36—C39	0.6 (4)
C13—C14—N15—C11	7.4 (3)	C11—Ru—C41—C42	106.4 (2)
C13—C14—N15—C31	169.2 (2)	O49—Ru—C41—C42	11.9 (2)
C11—N12—C21—C22	−91.5 (3)	Cl1—Ru—C41—C42	−165.7 (2)
C13—N12—C21—C22	87.9 (3)	Cl2—Ru—C41—C42	−76.1 (2)
C11—N12—C21—C26	91.2 (3)	Ru—C41—C42—C43	171.49 (18)
C13—N12—C21—C26	−89.4 (3)	Ru—C41—C42—C47	−8.6 (3)
C26—C21—C22—C23	−1.8 (3)	C47—C42—C43—C44	−0.2 (3)
N12—C21—C22—C23	−178.94 (19)	C41—C42—C43—C44	179.7 (2)
C26—C21—C22—C27	178.3 (2)	C42—C43—C44—C45	−0.5 (4)
N12—C21—C22—C27	1.1 (3)	C43—C44—C45—C46	0.7 (4)
C21—C22—C23—C24	0.9 (3)	C44—C45—C46—C47	−0.3 (4)
C27—C22—C23—C24	−179.2 (2)	C45—C46—C47—C42	−0.3 (4)
C22—C23—C24—C25	0.4 (4)	C45—C46—C47—C48	−179.0 (2)
C22—C23—C24—C28	−179.0 (2)	C43—C42—C47—C46	0.5 (3)
C23—C24—C25—C26	−0.9 (4)	C41—C42—C47—C46	−179.3 (2)
C28—C24—C25—C26	178.6 (2)	C43—C42—C47—C48	179.2 (2)
C22—C21—C26—C25	1.4 (3)	C41—C42—C47—C48	−0.7 (3)
N12—C21—C26—C25	178.5 (2)	C46—C47—C48—O49	179.8 (2)
C22—C21—C26—C29	−179.5 (2)	C42—C47—C48—O49	1.1 (4)
N12—C21—C26—C29	−2.4 (3)	C47—C48—O49—Ru	7.0 (3)
C24—C25—C26—C21	0.0 (3)	C41—Ru—O49—C48	−11.70 (19)
C24—C25—C26—C29	−179.1 (2)	C11—Ru—O49—C48	−109.79 (19)
C11—N15—C31—C32	78.3 (3)	Cl2—Ru—O49—C48	100.04 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C29—H29C···Cl1	0.98	2.67	3.634 (3)	166
C39—H39C···Cl1	0.98	2.76	3.371 (3)	121
C37—H37A···O49	0.98	2.39	3.268 (3)	150
C13—H13B···Cl1ⁱ	0.99	2.94	3.395 (2)	109
C14—H14A···Cl1ⁱ	0.99	2.90	3.324 (3)	107
C27—H27A···Cl2ⁱ	0.98	2.85	3.724 (3)	149
C37—H37C···Cl2ⁱ	0.98	2.88	3.736 (3)	146
C25—H25···Cl1ⁱⁱ	0.95	2.98	3.831 (3)	150
C29—H29A···Cl1ⁱⁱ	0.98	2.71	3.673 (3)	169
C46—H46···Cl2ⁱⁱⁱ	0.95	3.04	3.553 (2)	115
C48—H48···O49ⁱⁱⁱ	0.95	2.50	3.014 (3)	114

Symmetry codes: (i) x, −y+1, z+1/2; (ii) −y+1, x, −z; (iii) −x, −y+1, z.

Experimental details

Crystal data
Chemical formula	[RuCl₂(C₈H₆O)(C₂₁H₂₆N₂)]·C₄H₁₀O
M_r	670.66
Crystal system, space group	Tetragonal, P4c2
Temperature (K)	100
a, c (Å)	19.8603 (4), 15.6582 (7)
V (Å³)	6176.1 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.71
Crystal size (mm)	0.43 × 0.25 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.78, 0.86
No. of measured, independent and observed [I > 2σ(I)] reflections	90504, 8992, 7306
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.067, 1.01
No. of reflections	8992
No. of parameters	322
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.31
Absolute structure	Flack (1983), 4175 Friedel pairs
Absolute structure parameter	−0.02 (2)

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SADABS and XPREP (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C29—H29C···Cl1	0.98	2.67	3.634 (3)	166.3
C39—H39C···Cl1	0.98	2.76	3.371 (3)	121.2
C37—H37A···O49	0.98	2.39	3.268 (3)	149.5
C13—H13B···Cl1ⁱ	0.99	2.94	3.395 (2)	109.1
C14—H14A···Cl1ⁱ	0.99	2.90	3.324 (3)	106.5
C27—H27A···Cl2ⁱ	0.98	2.85	3.724 (3)	149.0
C37—H37C···Cl2ⁱ	0.98	2.88	3.736 (3)	146.3
C25—H25···Cl1ⁱⁱ	0.95	2.98	3.831 (3)	149.9
C29—H29A···Cl1ⁱⁱ	0.98	2.71	3.673 (3)	168.7
C46—H46···Cl2ⁱⁱⁱ	0.95	3.04	3.553 (2)	115.4
C48—H48···O49ⁱⁱⁱ	0.95	2.50	3.014 (3)	114.1

Symmetry codes: (i) x, −y+1, z+1/2; (ii) −y+1, x, −z; (iii) −x, −y+1, z.

Acknowledgements

Financial support by the EC Project `EuMet' (grant No. CPFP 211468-2) is gratefully acknowledged.

References

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