rac-cis,cis-Dicarbonyl­dichlorido{1-[2-(diphenyl­phosphan­yl)benz­yl]-3-mesityl­imidazol-2-yl­idene}ruthenium(II) dichloro­methane monosolvate

Domski, G.J.; Hohenboken, S.A.; Swenson, D.C.

doi:10.1107/S1600536812032515

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page m1121

https://doi.org/10.1107/S1600536812032515

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rac-cis,cis-Dicarbonyldichlorido{1-[2-(diphenylphosphanyl)benzyl]-3-mesitylimidazol-2-ylidene}ruthenium(II) dichloromethane monosolvate

Gregory J. Domski,^a ^* Sallie A. Hohenboken ^a and Dale C. Swenson ^b

^aAugustana College, Department of Chemistry, 639 38th Street, Rock Island, IL 61201, USA, and ^bThe University of Iowa, E331 Chemistry Building, Iowa City, IA 52242-1294, USA
^*Correspondence e-mail: gregdomski@augustana.edu

(Received 13 July 2012; accepted 17 July 2012; online 25 July 2012)

The Ru^II atom in the title compound, [RuCl₂(C₃₁H₂₉N₂P)(CO)₂]·CH₂Cl₂, exhibits a distorted octahedral coordination environment. The bond angles of the cis substituents at the Ru^II atom range from 82.72 (9) to 97.20 (3)°. This molecule is of interest in the field of catalytic transfer hydrogenation.

Related literature

For a review of transition metal catalysts supported by donor-functionalized N-heterocyclic carbenes (NHCs), see: Cavell & Normand (2008 ). For the first reported synthesis of the imidazolium chloride pro-ligand, see: Wang et al. (2005 ). For the structure of a similar compound incorporating an orthometalated N-phenyl group, see: Domski et al. (2012 ).

Experimental

Crystal data

[RuCl₂(C₃₁H₂₉N₂P)(CO)₂]·CH₂Cl₂
M_r = 773.45
Monoclinic, C 2/c
a = 22.539 (3) Å
b = 16.4065 (17) Å
c = 19.852 (2) Å
β = 111.004 (5)°
V = 6853.2 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 190 K
0.21 × 0.20 × 0.19 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.842, T_max = 0.855
53042 measured reflections
7865 independent reflections
6109 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.097
S = 1.08
7865 reflections
402 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.99 e Å⁻³

Data collection: COLLECT (Nonius, 1997 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812032515/bt5975sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812032515/bt5975Isup2.hkl

checkCIF report

Comment top

The title compound was prepared in order to prevent orthometalation which we had observed with a similar complex bearing an N-phenyl moiety (Domski et al., 2012) with the ultimate goal of probing the effect of orthometalation on the catalytic behavior of ruthenium(II) complexes supported by phosphine-functionalized NHCs.

The complex exhibited a distorted octahedral geometry about ruthenium with a P1—Ru—Cl1 bond angle of 97.20 (3)°.

Related literature top

For a review of transition metal catalysts supported by donor-functionalized N-heterocyclic carbenes (NHCs), see: Cavell & Normand (2008). For the first reported synthesis of the imidazolium chloride pro-ligand, see: Wang et al. (2005). For the structure of a similar compound incorporating an orthometalated N-phenyl group, see: Domski et al. (2012).

Experimental top

Single crystals suitable for X-ray diffraction studies were grown by vapor diffusion of diethyl ether onto a saturated dichloromethane solution of the title compound.

Structure description top

The complex exhibited a distorted octahedral geometry about ruthenium with a P1—Ru—Cl1 bond angle of 97.20 (3)°.

For a review of transition metal catalysts supported by donor-functionalized N-heterocyclic carbenes (NHCs), see: Cavell & Normand (2008). For the first reported synthesis of the imidazolium chloride pro-ligand, see: Wang et al. (2005). For the structure of a similar compound incorporating an orthometalated N-phenyl group, see: Domski et al. (2012).

Computing details top

Data collection: COLLECT (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title complex with ellipsoids drawn at the 50% probability level. Hydrogen atoms and a dichloromethane molecule of crystallization were omitted for clarity.

rac-cis,cis-Dicarbonyldichlorido{1-[2- (diphenylphosphanyl)benzyl]-3-mesitylimidazol-2-ylidene}ruthenium(II) dichloromethane monosolvate top

Crystal data top

[RuCl₂(C₃₁H₂₉N₂P)(CO)₂]·CH₂Cl₂	F(000) = 3136
M_r = 773.45	D_x = 1.499 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 15477 reflections
a = 22.539 (3) Å	θ = 1.0–27.9°
b = 16.4065 (17) Å	µ = 0.85 mm⁻¹
c = 19.852 (2) Å	T = 190 K
β = 111.004 (5)°	Prism, yellow
V = 6853.2 (13) Å³	0.21 × 0.20 × 0.19 mm
Z = 8

Data collection top

Nonius KappaCCD diffractometer	7865 independent reflections
Radiation source: fine-focus sealed tube	6109 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD phi and ω scans	h = −29→29
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −20→21
T_min = 0.842, T_max = 0.855	l = −25→25
53042 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0411P)² + 13.2763P] where P = (F_o² + 2F_c²)/3
7865 reflections	(Δ/σ)_max = 0.002
402 parameters	Δρ_max = 0.98 e Å⁻³
0 restraints	Δρ_min = −0.99 e Å⁻³

Crystal data top

[RuCl₂(C₃₁H₂₉N₂P)(CO)₂]·CH₂Cl₂	V = 6853.2 (13) Å³
M_r = 773.45	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 22.539 (3) Å	µ = 0.85 mm⁻¹
b = 16.4065 (17) Å	T = 190 K
c = 19.852 (2) Å	0.21 × 0.20 × 0.19 mm
β = 111.004 (5)°

Data collection top

Nonius KappaCCD diffractometer	7865 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	6109 reflections with I > 2σ(I)
T_min = 0.842, T_max = 0.855	R_int = 0.043
53042 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0411P)² + 13.2763P] where P = (F_o² + 2F_c²)/3
7865 reflections	Δρ_max = 0.98 e Å⁻³
402 parameters	Δρ_min = −0.99 e Å⁻³

Special details top

Experimental. In a nitrogen-filled glove box, a Schlenk flask was charged with 1-mesityl-3-(2-diphenylphosphinobenzyl)-1H-imidazol-3-ium chloride (0.7625 g), Ag₂O (0.3659 g), and 4 Å molecular seives (ca 0.5 g). The solids were suspended in dry, degassed dichloromethane and allowed to stir overnight in the dark. After 24 h, the reaction mixture was filtered through Celite^TM into a Schlenk flask that had been charged with [Ru(CO)₃Cl₂]₂ (0.4070 g) under a nitrogen atmoshphere. The reaction mixture was allowed to stir at room temperature in the dark overnight. After 24 h, the reaction mixture was filtered through Celite^TM and the volatiles were removed in vacuo to furnish a yellow solid. The crude product was purified by column chromatography (SiO₂, 40:1 CH₂Cl₂/MeOH). Single crystals of the title compound were obtained by slow diffusion of diethyl ether onto a concentrated solution of the yellow powder isolated via column chromatography in dichloromethane.

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.

Several low angle reflections were omitted from the final cycles of refinement due to beam-stop beam shadowing effects.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ru1	0.703359 (10)	0.039133 (12)	0.587686 (11)	0.02261 (7)
Cl1	0.66435 (3)	0.17943 (4)	0.58161 (4)	0.03120 (16)
Cl2	0.68354 (4)	0.02104 (5)	0.70046 (4)	0.03544 (17)
C1	0.72360 (14)	−0.06922 (18)	0.58206 (15)	0.0308 (6)
O1	0.73228 (12)	−0.13645 (13)	0.57587 (12)	0.0466 (6)
C2	0.61471 (14)	0.00921 (19)	0.54483 (16)	0.0337 (6)
O2	0.56467 (11)	−0.01302 (18)	0.53158 (14)	0.0582 (7)
C3	0.71699 (12)	0.06780 (15)	0.49266 (14)	0.0233 (5)
N4	0.68600 (11)	0.03936 (13)	0.42422 (12)	0.0266 (5)
C5	0.70667 (14)	0.07903 (18)	0.37477 (16)	0.0327 (6)
H5	0.6921	0.0699	0.3242	0.039*
C6	0.75093 (14)	0.13249 (17)	0.41214 (15)	0.0298 (6)
H6	0.7740	0.1685	0.3932	0.036*
N7	0.75680 (10)	0.12545 (13)	0.48352 (12)	0.0242 (5)
C8	0.80416 (13)	0.17248 (16)	0.54067 (15)	0.0275 (6)
H8A	0.7871	0.1858	0.5789	0.033*
H8B	0.8129	0.2243	0.5204	0.033*
C11	0.63333 (14)	−0.01646 (19)	0.40064 (15)	0.0330 (6)
C12	0.57187 (16)	0.0169 (2)	0.38096 (17)	0.0465 (8)
C13	0.52078 (18)	−0.0363 (3)	0.35720 (19)	0.0618 (12)
H13	0.4788	−0.0153	0.3438	0.074*
C14	0.5295 (2)	−0.1188 (3)	0.3527 (2)	0.0658 (13)
C15	0.5905 (2)	−0.1488 (2)	0.36929 (19)	0.0598 (11)
H15	0.5962	−0.2056	0.3645	0.072*
C16	0.64434 (17)	−0.0981 (2)	0.39303 (17)	0.0418 (8)
C17	0.56132 (18)	0.1068 (3)	0.3862 (2)	0.0619 (11)
H17A	0.5163	0.1169	0.3776	0.093*
H17B	0.5735	0.1358	0.3500	0.093*
H17C	0.5873	0.1262	0.4345	0.093*
C18	0.4727 (2)	−0.1763 (4)	0.3289 (2)	0.103 (2)
H18A	0.4437	−0.1607	0.2806	0.154*
H18B	0.4503	−0.1729	0.3630	0.154*
H18C	0.4874	−0.2323	0.3276	0.154*
C19	0.7094 (2)	−0.1301 (2)	0.4042 (2)	0.0580 (10)
H19A	0.7409	−0.1004	0.4438	0.087*
H19B	0.7186	−0.1226	0.3599	0.087*
H19C	0.7114	−0.1882	0.4161	0.087*
P1	0.81175 (3)	0.06515 (4)	0.66858 (4)	0.02367 (15)
C21	0.87363 (12)	0.06917 (17)	0.62890 (15)	0.0266 (6)
C22	0.86519 (13)	0.12488 (17)	0.57297 (15)	0.0280 (6)
C23	0.91411 (14)	0.1368 (2)	0.54681 (17)	0.0372 (7)
H23	0.9092	0.1761	0.5101	0.045*
C25	0.97763 (15)	0.0365 (2)	0.62788 (19)	0.0442 (8)
H25	1.0156	0.0054	0.6460	0.053*
C24	0.96986 (15)	0.0922 (2)	0.57349 (19)	0.0469 (8)
H24	1.0025	0.1000	0.5544	0.056*
C26	0.93032 (14)	0.02579 (19)	0.65620 (17)	0.0358 (7)
H26	0.9366	−0.0116	0.6947	0.043*
C31	0.82793 (14)	0.16048 (16)	0.72018 (14)	0.0280 (6)
C32	0.88838 (17)	0.1950 (2)	0.74234 (18)	0.0454 (8)
H32	0.9211	0.1686	0.7309	0.055*
C33	0.9013 (2)	0.2668 (2)	0.7806 (2)	0.0579 (10)
H33	0.9428	0.2896	0.7958	0.069*
C34	0.8540 (2)	0.3057 (2)	0.79685 (19)	0.0555 (10)
H34	0.8626	0.3559	0.8224	0.067*
C35	0.79473 (19)	0.2724 (2)	0.77632 (18)	0.0523 (9)
H35	0.7624	0.2993	0.7881	0.063*
C36	0.78110 (16)	0.19921 (19)	0.73826 (16)	0.0388 (7)
H36	0.7399	0.1760	0.7248	0.047*
C41	0.83938 (13)	−0.01377 (17)	0.73767 (16)	0.0294 (6)
C42	0.85110 (14)	−0.09220 (18)	0.71899 (18)	0.0381 (7)
H42	0.8445	−0.1047	0.6701	0.046*
C43	0.87236 (15)	−0.1522 (2)	0.7712 (2)	0.0453 (8)
H43	0.8802	−0.2057	0.7581	0.054*
C44	0.88213 (15)	−0.1345 (2)	0.8424 (2)	0.0479 (9)
H44	0.8973	−0.1756	0.8782	0.057*
C45	0.87005 (15)	−0.0579 (2)	0.86169 (18)	0.0440 (8)
H45	0.8765	−0.0460	0.9107	0.053*
C46	0.84819 (14)	0.0031 (2)	0.80915 (17)	0.0352 (7)
H46	0.8394	0.0560	0.8225	0.042*
C51	0.8875 (3)	−0.2190 (4)	0.4700 (3)	0.1036 (19)
H51B	0.8585	−0.2558	0.4830	0.124*
H51A	0.8671	−0.2054	0.4182	0.124*
Cl12	0.89756 (8)	−0.12965 (10)	0.52043 (9)	0.1097 (5)
Cl11	0.95810 (9)	−0.27001 (8)	0.48306 (7)	0.0993 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.02264 (11)	0.02248 (11)	0.02245 (12)	−0.00064 (8)	0.00778 (9)	0.00257 (8)
Cl1	0.0356 (4)	0.0259 (3)	0.0350 (4)	0.0041 (3)	0.0161 (3)	0.0041 (3)
Cl2	0.0377 (4)	0.0426 (4)	0.0292 (4)	−0.0005 (3)	0.0158 (3)	0.0074 (3)
C1	0.0334 (15)	0.0323 (16)	0.0241 (15)	−0.0065 (12)	0.0069 (12)	0.0018 (12)
O1	0.0576 (15)	0.0300 (12)	0.0451 (14)	0.0001 (10)	0.0099 (12)	−0.0012 (10)
C2	0.0309 (16)	0.0417 (17)	0.0277 (16)	−0.0002 (13)	0.0094 (13)	0.0029 (13)
O2	0.0288 (13)	0.096 (2)	0.0461 (15)	−0.0127 (13)	0.0087 (11)	0.0031 (14)
C3	0.0234 (13)	0.0207 (12)	0.0259 (14)	0.0016 (10)	0.0089 (11)	0.0030 (10)
N4	0.0280 (12)	0.0290 (12)	0.0216 (12)	−0.0029 (10)	0.0074 (10)	−0.0017 (9)
C5	0.0377 (16)	0.0375 (16)	0.0241 (15)	−0.0016 (13)	0.0125 (13)	0.0006 (12)
C6	0.0351 (15)	0.0328 (15)	0.0253 (14)	−0.0002 (12)	0.0156 (12)	0.0035 (12)
N7	0.0271 (11)	0.0227 (11)	0.0233 (12)	−0.0012 (9)	0.0094 (9)	0.0001 (9)
C8	0.0311 (14)	0.0266 (13)	0.0260 (14)	−0.0046 (11)	0.0119 (12)	−0.0007 (11)
C11	0.0314 (15)	0.0433 (17)	0.0218 (14)	−0.0114 (13)	0.0066 (12)	−0.0024 (12)
C12	0.0356 (17)	0.074 (2)	0.0263 (16)	−0.0062 (17)	0.0067 (14)	0.0025 (16)
C13	0.0363 (19)	0.111 (4)	0.0307 (19)	−0.022 (2)	0.0034 (15)	−0.002 (2)
C14	0.059 (3)	0.106 (4)	0.0304 (19)	−0.047 (3)	0.0138 (18)	−0.014 (2)
C15	0.092 (3)	0.052 (2)	0.040 (2)	−0.037 (2)	0.028 (2)	−0.0159 (17)
C16	0.057 (2)	0.0421 (18)	0.0282 (16)	−0.0172 (16)	0.0176 (15)	−0.0090 (13)
C17	0.049 (2)	0.078 (3)	0.053 (2)	0.025 (2)	0.0124 (19)	0.018 (2)
C18	0.090 (4)	0.160 (5)	0.053 (3)	−0.092 (4)	0.019 (3)	−0.020 (3)
C19	0.084 (3)	0.0394 (19)	0.061 (2)	0.0014 (19)	0.038 (2)	−0.0089 (17)
P1	0.0234 (3)	0.0244 (3)	0.0224 (3)	0.0005 (3)	0.0072 (3)	0.0008 (3)
C21	0.0225 (13)	0.0288 (13)	0.0284 (14)	−0.0017 (11)	0.0091 (11)	−0.0027 (11)
C22	0.0267 (14)	0.0310 (14)	0.0264 (14)	−0.0073 (11)	0.0095 (12)	−0.0070 (11)
C23	0.0326 (16)	0.0475 (18)	0.0337 (17)	−0.0091 (13)	0.0144 (14)	−0.0021 (14)
C25	0.0243 (15)	0.059 (2)	0.048 (2)	0.0048 (14)	0.0111 (14)	−0.0013 (16)
C24	0.0290 (16)	0.069 (2)	0.048 (2)	−0.0061 (16)	0.0198 (15)	−0.0029 (18)
C26	0.0287 (15)	0.0429 (17)	0.0345 (17)	0.0016 (13)	0.0098 (13)	0.0002 (13)
C31	0.0356 (15)	0.0262 (14)	0.0198 (13)	−0.0006 (11)	0.0071 (12)	0.0006 (11)
C32	0.049 (2)	0.0439 (19)	0.044 (2)	−0.0121 (16)	0.0175 (16)	−0.0131 (15)
C33	0.070 (3)	0.052 (2)	0.052 (2)	−0.030 (2)	0.022 (2)	−0.0216 (18)
C34	0.089 (3)	0.0314 (17)	0.0350 (19)	−0.0025 (18)	0.008 (2)	−0.0074 (14)
C35	0.066 (2)	0.048 (2)	0.0330 (18)	0.0184 (18)	0.0063 (17)	−0.0109 (15)
C36	0.0393 (17)	0.0433 (18)	0.0292 (16)	0.0057 (14)	0.0067 (14)	−0.0062 (13)
C41	0.0200 (13)	0.0308 (14)	0.0340 (16)	0.0006 (11)	0.0056 (12)	0.0060 (12)
C42	0.0335 (16)	0.0335 (16)	0.0408 (18)	0.0033 (13)	0.0056 (14)	0.0076 (13)
C43	0.0368 (18)	0.0343 (17)	0.057 (2)	0.0075 (14)	0.0080 (16)	0.0144 (15)
C44	0.0339 (17)	0.050 (2)	0.057 (2)	0.0072 (15)	0.0137 (16)	0.0301 (17)
C45	0.0353 (17)	0.060 (2)	0.0353 (18)	−0.0006 (15)	0.0111 (14)	0.0189 (16)
C46	0.0306 (15)	0.0409 (17)	0.0345 (17)	−0.0001 (13)	0.0121 (13)	0.0073 (13)
C51	0.110 (5)	0.108 (4)	0.095 (4)	−0.045 (4)	0.038 (4)	−0.044 (3)
Cl12	0.1207 (12)	0.1043 (11)	0.1156 (12)	−0.0406 (9)	0.0562 (10)	−0.0495 (9)
Cl11	0.1521 (14)	0.0775 (8)	0.0702 (8)	−0.0089 (9)	0.0423 (9)	0.0073 (6)

Geometric parameters (Å, º) top

Ru1—C1	1.849 (3)	P1—C41	1.826 (3)
Ru1—C2	1.934 (3)	P1—C21	1.832 (3)
Ru1—C3	2.071 (3)	P1—C31	1.833 (3)
Ru1—P1	2.4325 (8)	C21—C26	1.392 (4)
Ru1—Cl1	2.4515 (7)	C21—C22	1.398 (4)
Ru1—Cl2	2.4529 (8)	C22—C23	1.391 (4)
C1—O1	1.135 (4)	C23—C24	1.384 (5)
C2—O2	1.123 (4)	C23—H23	0.9500
C3—N7	1.360 (3)	C25—C24	1.377 (5)
C3—N4	1.368 (3)	C25—C26	1.383 (4)
N4—C5	1.390 (4)	C25—H25	0.9500
N4—C11	1.438 (4)	C24—H24	0.9500
C5—C6	1.336 (4)	C26—H26	0.9500
C5—H5	0.9500	C31—C36	1.385 (4)
C6—N7	1.380 (3)	C31—C32	1.393 (4)
C6—H6	0.9500	C32—C33	1.376 (5)
N7—C8	1.467 (3)	C32—H32	0.9500
C8—C22	1.510 (4)	C33—C34	1.376 (6)
C8—H8A	0.9900	C33—H33	0.9500
C8—H8B	0.9900	C34—C35	1.363 (6)
C11—C16	1.380 (5)	C34—H34	0.9500
C11—C12	1.408 (5)	C35—C36	1.393 (4)
C12—C13	1.386 (5)	C35—H35	0.9500
C12—C17	1.503 (5)	C36—H36	0.9500
C13—C14	1.376 (6)	C41—C46	1.388 (4)
C13—H13	0.9500	C41—C42	1.390 (4)
C14—C15	1.385 (6)	C42—C43	1.385 (4)
C14—C18	1.522 (5)	C42—H42	0.9500
C15—C16	1.407 (5)	C43—C44	1.381 (5)
C15—H15	0.9500	C43—H43	0.9500
C16—C19	1.498 (5)	C44—C45	1.369 (5)
C17—H17A	0.9800	C44—H44	0.9500
C17—H17B	0.9800	C45—C46	1.401 (4)
C17—H17C	0.9800	C45—H45	0.9500
C18—H18A	0.9800	C46—H46	0.9500
C18—H18B	0.9800	C51—Cl11	1.733 (6)
C18—H18C	0.9800	C51—Cl12	1.744 (5)
C19—H19A	0.9800	C51—H51B	0.9900
C19—H19B	0.9800	C51—H51A	0.9900
C19—H19C	0.9800

C1—Ru1—C2	88.15 (13)	H19A—C19—H19B	109.5
C1—Ru1—C3	92.46 (11)	C16—C19—H19C	109.5
C2—Ru1—C3	97.13 (11)	H19A—C19—H19C	109.5
C1—Ru1—P1	89.86 (9)	H19B—C19—H19C	109.5
C2—Ru1—P1	165.93 (9)	C41—P1—C21	103.96 (13)
C3—Ru1—P1	96.87 (7)	C41—P1—C31	103.84 (13)
C1—Ru1—Cl1	172.69 (9)	C21—P1—C31	100.37 (13)
C2—Ru1—Cl1	85.46 (9)	C41—P1—Ru1	111.28 (9)
C3—Ru1—Cl1	84.81 (7)	C21—P1—Ru1	117.49 (9)
P1—Ru1—Cl1	97.20 (3)	C31—P1—Ru1	118.04 (9)
C1—Ru1—Cl2	93.92 (9)	C26—C21—C22	119.2 (3)
C2—Ru1—Cl2	82.72 (9)	C26—C21—P1	123.3 (2)
C3—Ru1—Cl2	173.60 (7)	C22—C21—P1	117.2 (2)
P1—Ru1—Cl2	83.52 (3)	C23—C22—C21	119.2 (3)
Cl1—Ru1—Cl2	88.80 (3)	C23—C22—C8	119.5 (3)
O1—C1—Ru1	175.8 (3)	C21—C22—C8	121.3 (2)
O2—C2—Ru1	168.0 (3)	C24—C23—C22	121.0 (3)
N7—C3—N4	103.4 (2)	C24—C23—H23	119.5
N7—C3—Ru1	126.86 (19)	C22—C23—H23	119.5
N4—C3—Ru1	129.61 (19)	C24—C25—C26	120.2 (3)
C3—N4—C5	111.1 (2)	C24—C25—H25	119.9
C3—N4—C11	127.5 (2)	C26—C25—H25	119.9
C5—N4—C11	121.0 (2)	C25—C24—C23	119.6 (3)
C6—C5—N4	106.7 (2)	C25—C24—H24	120.2
C6—C5—H5	126.6	C23—C24—H24	120.2
N4—C5—H5	126.6	C25—C26—C21	120.7 (3)
C5—C6—N7	107.0 (2)	C25—C26—H26	119.7
C5—C6—H6	126.5	C21—C26—H26	119.7
N7—C6—H6	126.5	C36—C31—C32	118.8 (3)
C3—N7—C6	111.7 (2)	C36—C31—P1	121.3 (2)
C3—N7—C8	126.5 (2)	C32—C31—P1	120.0 (2)
C6—N7—C8	121.7 (2)	C33—C32—C31	120.8 (3)
N7—C8—C22	110.8 (2)	C33—C32—H32	119.6
N7—C8—H8A	109.5	C31—C32—H32	119.6
C22—C8—H8A	109.5	C32—C33—C34	119.9 (4)
N7—C8—H8B	109.5	C32—C33—H33	120.1
C22—C8—H8B	109.5	C34—C33—H33	120.1
H8A—C8—H8B	108.1	C35—C34—C33	120.1 (3)
C16—C11—C12	123.0 (3)	C35—C34—H34	119.9
C16—C11—N4	119.6 (3)	C33—C34—H34	119.9
C12—C11—N4	117.2 (3)	C34—C35—C36	120.7 (3)
C13—C12—C11	117.7 (4)	C34—C35—H35	119.7
C13—C12—C17	120.6 (4)	C36—C35—H35	119.7
C11—C12—C17	121.8 (3)	C31—C36—C35	119.7 (3)
C14—C13—C12	121.4 (4)	C31—C36—H36	120.1
C14—C13—H13	119.3	C35—C36—H36	120.1
C12—C13—H13	119.3	C46—C41—C42	119.0 (3)
C13—C14—C15	119.1 (3)	C46—C41—P1	120.8 (2)
C13—C14—C18	120.4 (5)	C42—C41—P1	120.2 (2)
C15—C14—C18	120.4 (5)	C43—C42—C41	120.4 (3)
C14—C15—C16	122.2 (4)	C43—C42—H42	119.8
C14—C15—H15	118.9	C41—C42—H42	119.8
C16—C15—H15	118.9	C44—C43—C42	120.1 (3)
C11—C16—C15	116.4 (3)	C44—C43—H43	119.9
C11—C16—C19	121.9 (3)	C42—C43—H43	119.9
C15—C16—C19	121.5 (3)	C45—C44—C43	120.3 (3)
C12—C17—H17A	109.5	C45—C44—H44	119.9
C12—C17—H17B	109.5	C43—C44—H44	119.9
H17A—C17—H17B	109.5	C44—C45—C46	120.0 (3)
C12—C17—H17C	109.5	C44—C45—H45	120.0
H17A—C17—H17C	109.5	C46—C45—H45	120.0
H17B—C17—H17C	109.5	C41—C46—C45	120.2 (3)
C14—C18—H18A	109.5	C41—C46—H46	119.9
C14—C18—H18B	109.5	C45—C46—H46	119.9
H18A—C18—H18B	109.5	Cl11—C51—Cl12	113.4 (3)
C14—C18—H18C	109.5	Cl11—C51—H51B	108.9
H18A—C18—H18C	109.5	Cl12—C51—H51B	108.9
H18B—C18—H18C	109.5	Cl11—C51—H51A	108.9
C16—C19—H19A	109.5	Cl12—C51—H51A	108.9
C16—C19—H19B	109.5	H51B—C51—H51A	107.7

C1—Ru1—C2—O2	77.2 (14)	C3—Ru1—P1—C21	−17.66 (12)
C3—Ru1—C2—O2	169.5 (14)	Cl1—Ru1—P1—C21	−103.27 (10)
P1—Ru1—C2—O2	−4.8 (18)	Cl2—Ru1—P1—C21	168.76 (10)
Cl1—Ru1—C2—O2	−106.3 (14)	C1—Ru1—P1—C31	−164.73 (13)
Cl2—Ru1—C2—O2	−17.0 (14)	C2—Ru1—P1—C31	−82.9 (4)
C1—Ru1—C3—N7	−123.9 (2)	C3—Ru1—P1—C31	102.81 (12)
C2—Ru1—C3—N7	147.6 (2)	Cl1—Ru1—P1—C31	17.20 (10)
P1—Ru1—C3—N7	−33.8 (2)	Cl2—Ru1—P1—C31	−70.76 (10)
Cl1—Ru1—C3—N7	62.9 (2)	C41—P1—C21—C26	−6.8 (3)
C1—Ru1—C3—N4	61.6 (2)	C31—P1—C21—C26	100.4 (3)
C2—Ru1—C3—N4	−26.9 (3)	Ru1—P1—C21—C26	−130.2 (2)
P1—Ru1—C3—N4	151.7 (2)	C41—P1—C21—C22	179.6 (2)
Cl1—Ru1—C3—N4	−111.6 (2)	C31—P1—C21—C22	−73.2 (2)
N7—C3—N4—C5	0.0 (3)	Ru1—P1—C21—C22	56.2 (2)
Ru1—C3—N4—C5	175.5 (2)	C26—C21—C22—C23	−1.2 (4)
N7—C3—N4—C11	−172.7 (3)	P1—C21—C22—C23	172.7 (2)
Ru1—C3—N4—C11	2.7 (4)	C26—C21—C22—C8	179.0 (3)
C3—N4—C5—C6	0.1 (3)	P1—C21—C22—C8	−7.1 (3)
C11—N4—C5—C6	173.4 (3)	N7—C8—C22—C23	94.5 (3)
N4—C5—C6—N7	−0.2 (3)	N7—C8—C22—C21	−85.7 (3)
N4—C3—N7—C6	−0.1 (3)	C21—C22—C23—C24	2.4 (4)
Ru1—C3—N7—C6	−175.79 (19)	C8—C22—C23—C24	−177.8 (3)
N4—C3—N7—C8	−176.3 (2)	C26—C25—C24—C23	−0.7 (5)
Ru1—C3—N7—C8	8.1 (4)	C22—C23—C24—C25	−1.4 (5)
C5—C6—N7—C3	0.2 (3)	C24—C25—C26—C21	1.9 (5)
C5—C6—N7—C8	176.6 (2)	C22—C21—C26—C25	−0.9 (4)
C3—N7—C8—C22	83.6 (3)	P1—C21—C26—C25	−174.4 (2)
C6—N7—C8—C22	−92.2 (3)	C41—P1—C31—C36	−96.4 (3)
C3—N4—C11—C16	−97.6 (3)	C21—P1—C31—C36	156.2 (2)
C5—N4—C11—C16	90.3 (3)	Ru1—P1—C31—C36	27.3 (3)
C3—N4—C11—C12	87.2 (4)	C41—P1—C31—C32	83.2 (3)
C5—N4—C11—C12	−84.9 (3)	C21—P1—C31—C32	−24.1 (3)
C16—C11—C12—C13	4.1 (5)	Ru1—P1—C31—C32	−153.1 (2)
N4—C11—C12—C13	179.1 (3)	C36—C31—C32—C33	−0.9 (5)
C16—C11—C12—C17	−176.7 (3)	P1—C31—C32—C33	179.5 (3)
N4—C11—C12—C17	−1.7 (4)	C31—C32—C33—C34	−0.6 (6)
C11—C12—C13—C14	−0.2 (5)	C32—C33—C34—C35	1.3 (6)
C17—C12—C13—C14	−179.4 (4)	C33—C34—C35—C36	−0.6 (6)
C12—C13—C14—C15	−2.8 (6)	C32—C31—C36—C35	1.6 (5)
C12—C13—C14—C18	177.9 (3)	P1—C31—C36—C35	−178.8 (2)
C13—C14—C15—C16	2.1 (6)	C34—C35—C36—C31	−0.9 (5)
C18—C14—C15—C16	−178.6 (3)	C21—P1—C41—C46	123.2 (2)
C12—C11—C16—C15	−4.7 (5)	C31—P1—C41—C46	18.6 (3)
N4—C11—C16—C15	−179.6 (3)	Ru1—P1—C41—C46	−109.4 (2)
C12—C11—C16—C19	171.0 (3)	C21—P1—C41—C42	−57.6 (3)
N4—C11—C16—C19	−3.9 (4)	C31—P1—C41—C42	−162.3 (2)
C14—C15—C16—C11	1.5 (5)	Ru1—P1—C41—C42	69.8 (2)
C14—C15—C16—C19	−174.2 (3)	C46—C41—C42—C43	−1.2 (4)
C1—Ru1—P1—C41	−44.83 (14)	P1—C41—C42—C43	179.7 (2)
C2—Ru1—P1—C41	37.0 (4)	C41—C42—C43—C44	−0.1 (5)
C3—Ru1—P1—C41	−137.30 (13)	C42—C43—C44—C45	0.9 (5)
Cl1—Ru1—P1—C41	137.09 (11)	C43—C44—C45—C46	−0.5 (5)
Cl2—Ru1—P1—C41	49.13 (11)	C42—C41—C46—C45	1.5 (4)
C1—Ru1—P1—C21	74.80 (14)	P1—C41—C46—C45	−179.3 (2)
C2—Ru1—P1—C21	156.6 (4)	C44—C45—C46—C41	−0.7 (5)

Experimental details

Crystal data
Chemical formula	[RuCl₂(C₃₁H₂₉N₂P)(CO)₂]·CH₂Cl₂
M_r	773.45
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	190
a, b, c (Å)	22.539 (3), 16.4065 (17), 19.852 (2)
β (°)	111.004 (5)
V (Å³)	6853.2 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.21 × 0.20 × 0.19

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.842, 0.855
No. of measured, independent and observed [I > 2σ(I)] reflections	53042, 7865, 6109
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.097, 1.08
No. of reflections	7865
No. of parameters	402
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0411P)² + 13.2763P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.98, −0.99

Computer programs: COLLECT (Nonius, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors wish to thank Augustana College for financial support. Additionally, GJD would like to thank Sam Alvarado for early progress on the synthesis of imidazolium chloride pro-ligands.

References

Cavell, K. J. & Normand, A. T. (2008). Eur. J. Inorg. Chem. pp. 2781–2800. Google Scholar
Domski, G. J., Pecak, W. H. & Swenson, D. C. (2012). Acta Cryst. E68. Submitted (HP2045). CrossRef IUCr Journals Google Scholar
Nonius (1997). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, A.-E., Wange, L.-X., Xie, J.-H. & Zhou, Q.-L. (2005). Tetrahedron, pp. 259–266. Web of Science CrossRef Google Scholar

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