rac-cis-Dicarbonyl­chlorido{1-[2-(diphenyl­phosphanyl-κP)benz­yl]-3-(phenyl-κC1)imidazol-2-yl­idene-κC2}ruthenium(II) dichloro­methane monosolvate

Domski, G.J.; Pecak, W.H.; Swenson, D.C.

doi:10.1107/S1600536812036665

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages m1224-m1225

doi:10.1107/S1600536812036665

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rac-cis-Dicarbonylchlorido{1-[2-(diphenylphosphanyl-κP)benzyl]-3-(phenyl-κC¹)imidazol-2-ylidene-κC²}ruthenium(II) dichloromethane monosolvate

Gregory J. Domski,^a ^* Wiktoria H. Pecak ^a ‡ and Dale C. Swenson ^b

^aAugustana College, Department of Chemistry, 639 38th Street, Rock Island, IL 61201, USA, and ^bThe University of Iowa, W437 Chemistry Building, Iowa City, IA 52242-1294, USA
^*Correspondence e-mail: gregdomski@augustana.edu

(Received 13 July 2012; accepted 22 August 2012; online 31 August 2012)

In the title compound, [Ru(C₂₈H₂₂N₂P)Cl(CO)₂]·CH₂Cl₂, the Ru^II atom exhibits a distorted octahedral coordination geometry. The N-phenyl group of the ligand has undergone orthometalation; as a result, the tridentate phosphane-functionalized N-heterocyclic carbene ligand is coordinating in a meridional fashion. This complex is of interest with respect to transfer hydrogenation catalysis and also provides an example of C—H activation behavior in late transition metal complexes. The dichloromethane solvent molecule is disordered over two sets of sites with an occupancy ratio of 0.873 (14):0.127 (14).

Related literature

For a review of transition metal catalysts supported by donor-functionalized N-heterocyclic carbenes, 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 molecule bearing an N-mesityl moiety that has not undergone orthometalation, see: Domski et al. (2012 ).

Experimental

Crystal data

[Ru(C₂₈H₂₂N₂P)Cl(CO)₂]·CH₂Cl₂
M_r = 694.91
Triclinic, $[P \overline 1]$
a = 8.1600 (9) Å
b = 12.1940 (13) Å
c = 14.9713 (16) Å
α = 100.109 (5)°
β = 93.560 (5)°
γ = 93.469 (5)°
V = 1459.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 210 K
0.17 × 0.08 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.862, T_max = 0.974
20414 measured reflections
5349 independent reflections
4214 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.077
S = 1.02
5349 reflections
383 parameters
22 restraints
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected bond lengths (Å)

Ru1—C1	1.860 (4)
Ru1—C2	1.932 (4)
Ru1—C3	2.065 (3)
Ru1—C11	2.129 (3)
Ru1—P1	2.4265 (9)
Ru1—Cl1	2.4737 (9)

Data collection: COLLECT (Nonius, 2000); 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: 10.1107/S1600536812036665/hp2045sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812036665/hp2045Isup2.hkl

checkCIF report

Comment top

Donor-functionalized N-heterocyclic carbenes (NHCs) are employed as ancillary ligands for catalytically active transition metals since they have been shown to prevent common decomposition pathways (e.g. reductive elimination) (Cavell & Normand, 2008). Our research has focused on preparing novel ruthenium(II) complexes supported by donor-functionalized NHCs. In particular we have focused on phosphine-functionalized NHCs since both of these moieties are strong σ-donors and have been shown to effectively stabilize ruthenium(II) at catalytically relevant (i.e. elevated) temperatures. The title compound was exceptionally difficult to characterize via ¹H and ¹³C{¹H} NMR spectroscopy due to extensive overlapping of peaks in the aromatic regions. In order to establish the three-dimensional structure of this molecule we grew single crystals of the title complex and collected X-ray diffraction data. Upon solving the structure we were surprised to find that the N-phenyl moiety of the ligand had undergone orthometalation. While C—H activation by ruthenium(II) is not without precedent, we had not expected this to happen; it would have been difficult to elucidate this behavior without the aid of X-ray crystallography.

In the solid state, the geometry about ruthenium was distorted octahedral with a C(3)–Ru–C(11) bond angle of 77.79 (12)°. The Ru-carbonyl distances were inequivalent with the Ru–C(2) distance being 0.072 (0) Å longer than the Ru–C(1) distance; this observation is consistent with the stronger trans-influence of the NHC relative to chloride.

Related literature top

For a review of transition metal catalysts supported by donor-functionalized N-heterocyclic carbenes, 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 molecule bearing an N-mesityl moiety that has not undergone orthometalation, 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.

Computing details top

Data collection: COLLECT (Nonius, 2000); 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-Dicarbonylchlorido{1-[2-(diphenylphosphanyl- κP)benzyl]-3-(phenyl-κC¹)imidazol-2-ylidene- κC²}ruthenium(II) dichloromethane monosolvate top

Crystal data top

[Ru(C₂₈H₂₂N₂P)Cl(CO)₂]·CH₂Cl₂	Z = 2
M_r = 694.91	F(000) = 700
Triclinic, P1	D_x = 1.581 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1600 (9) Å	Cell parameters from 5183 reflections
b = 12.1940 (13) Å	θ = 1.0–27.9°
c = 14.9713 (16) Å	µ = 0.90 mm⁻¹
α = 100.109 (5)°	T = 210 K
β = 93.560 (5)°	Plate, colorless
γ = 93.469 (5)°	0.17 × 0.08 × 0.03 mm
V = 1459.9 (3) Å³

Data collection top

Nonius KappaCCD diffractometer	5349 independent reflections
Radiation source: fine-focus sealed tube	4214 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 9 pixels mm^-1	θ_max = 25.5°, θ_min = 2.8°
phi and ω scans	h = −9→9
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997)	k = −14→14
T_min = 0.862, T_max = 0.974	l = −18→18
20414 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0237P)² + 1.1613P] where P = (F_o² + 2F_c²)/3
5349 reflections	(Δ/σ)_max = 0.001
383 parameters	Δρ_max = 0.60 e Å⁻³
22 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Ru(C₂₈H₂₂N₂P)Cl(CO)₂]·CH₂Cl₂	γ = 93.469 (5)°
M_r = 694.91	V = 1459.9 (3) Å³
Triclinic, P1	Z = 2
a = 8.1600 (9) Å	Mo Kα radiation
b = 12.1940 (13) Å	µ = 0.90 mm⁻¹
c = 14.9713 (16) Å	T = 210 K
α = 100.109 (5)°	0.17 × 0.08 × 0.03 mm
β = 93.560 (5)°

Data collection top

Nonius KappaCCD diffractometer	5349 independent reflections
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997)	4214 reflections with I > 2σ(I)
T_min = 0.862, T_max = 0.974	R_int = 0.038
20414 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	22 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.02	Δρ_max = 0.60 e Å⁻³
5349 reflections	Δρ_min = −0.45 e Å⁻³
383 parameters

Special details top

Experimental. The title compound was prepared by allowing 1-phenyl-3-(2-diphenylphosphinobenzyl)-1H-imidazol-3-ium chloride (0.4997 g) (Wang et al., 2005) to react with Ag₂O (0.2502 g) in dry, degassed dichloromethane under a nitrogen atmosphere in the absence of light; 4 Å molecular sieves (approximately 0.5 g) were added to the mixture at the beginning of the reaction. After 24 h, the reaction mixture was filtered through Celite^TM under an atmosphere of nitrogen into a flask containing [Ru(CO)₃Cl₂]₂ (0.1340 g); the reaction mixture was allowed to stir for 24 h in the dark. After stirring overnight, the reaction mixture was filtered through Celite^TM under an atmosphere of dry nitrogen and all volatiles were removed in vacuo. The solid residue was purified via column chromatography (SiO₂, 40:1 CH₂Cl₂/MeOH) to furnish a yellow solid. Single crystals of the title compound were grown by dissolving the crude product in the minimum amount of dichloromethane and allowing diethyl ether to slowly evaporate, condense, and diffuse into the dichloromethane solution.

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 shadowing effects.

A disordered dichloromethane molecule is included in the structure. The relative occupancy refined to 0.873 (14):0.127 (14). The two disorder sites were restrained to have the same conformation, Uaniso(C41)=Uaniso(C41'). The anisotropic displacement parameters were restrained with the rigid body restraint and the simu restraint.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ru1	0.56260 (3)	0.10472 (2)	0.259925 (18)	0.02297 (9)
Cl1	0.71756 (10)	0.21064 (7)	0.39873 (5)	0.0297 (2)
C1	0.4406 (4)	0.0144 (3)	0.1624 (3)	0.0310 (8)
O1	0.3680 (3)	−0.0442 (2)	0.10503 (18)	0.0505 (7)
C2	0.7517 (4)	0.1111 (3)	0.1890 (2)	0.0300 (8)
O2	0.8606 (3)	0.1083 (2)	0.14529 (19)	0.0503 (7)
C3	0.3718 (4)	0.0743 (2)	0.3387 (2)	0.0242 (7)
N4	0.3856 (3)	−0.0118 (2)	0.38523 (18)	0.0255 (6)
C5	0.2468 (4)	−0.0284 (3)	0.4310 (2)	0.0306 (8)
H5	0.2278	−0.0825	0.4675	0.037*
C6	0.1447 (4)	0.0482 (3)	0.4128 (2)	0.0311 (8)
H6	0.0399	0.0582	0.4344	0.037*
N7	0.2224 (3)	0.1101 (2)	0.35618 (18)	0.0247 (6)
C8	0.1486 (4)	0.1970 (3)	0.3140 (2)	0.0272 (8)
H8A	0.0305	0.1947	0.3229	0.033*
H8B	0.1611	0.1811	0.2484	0.033*
C11	0.6328 (4)	−0.0402 (2)	0.3096 (2)	0.0229 (7)
C12	0.7679 (4)	−0.1015 (3)	0.2936 (2)	0.0312 (8)
H12	0.8445	−0.0801	0.2543	0.037*
C13	0.7943 (4)	−0.1942 (3)	0.3337 (2)	0.0358 (9)
H13	0.8871	−0.2346	0.3207	0.043*
C14	0.6857 (4)	−0.2270 (3)	0.3922 (2)	0.0361 (9)
H14	0.7040	−0.2901	0.4186	0.043*
C15	0.5489 (4)	−0.1671 (3)	0.4124 (2)	0.0315 (8)
H15	0.4744	−0.1879	0.4530	0.038*
C16	0.5262 (4)	−0.0757 (3)	0.3706 (2)	0.0253 (7)
P1	0.46973 (10)	0.27908 (7)	0.22565 (6)	0.0231 (2)
C21	0.3631 (4)	0.3606 (2)	0.3170 (2)	0.0233 (7)
C22	0.2256 (4)	0.3134 (3)	0.3529 (2)	0.0241 (7)
C23	0.1539 (4)	0.3756 (3)	0.4245 (2)	0.0314 (8)
H23	0.0611	0.3442	0.4475	0.038*
C24	0.2149 (4)	0.4827 (3)	0.4629 (2)	0.0354 (9)
H24	0.1661	0.5227	0.5127	0.043*
C25	0.3484 (4)	0.5304 (3)	0.4277 (2)	0.0359 (9)
H25	0.3894	0.6039	0.4524	0.043*
C26	0.4217 (4)	0.4696 (3)	0.3557 (2)	0.0308 (8)
H26	0.5131	0.5025	0.3325	0.037*
C31	0.3271 (4)	0.2636 (3)	0.1239 (2)	0.0248 (7)
C32	0.1787 (4)	0.3131 (3)	0.1231 (2)	0.0365 (9)
H32	0.1491	0.3589	0.1761	0.044*
C33	0.0732 (4)	0.2955 (3)	0.0446 (3)	0.0438 (10)
H33	−0.0280	0.3286	0.0450	0.053*
C34	0.1160 (5)	0.2301 (3)	−0.0336 (3)	0.0462 (11)
H34	0.0436	0.2169	−0.0864	0.055*
C35	0.2665 (5)	0.1840 (3)	−0.0341 (3)	0.0422 (10)
H35	0.2982	0.1413	−0.0880	0.051*
C36	0.3710 (4)	0.2001 (3)	0.0444 (2)	0.0338 (8)
H36	0.4725	0.1675	0.0435	0.041*
C41	0.6282 (4)	0.3817 (2)	0.2024 (2)	0.0254 (7)
C42	0.7775 (4)	0.4017 (3)	0.2551 (2)	0.0308 (8)
H42	0.7995	0.3589	0.3003	0.037*
C43	0.8933 (4)	0.4832 (3)	0.2419 (3)	0.0349 (9)
H43	0.9922	0.4973	0.2790	0.042*
C44	0.8630 (4)	0.5444 (3)	0.1737 (3)	0.0380 (9)
H44	0.9428	0.5988	0.1635	0.046*
C45	0.7169 (5)	0.5257 (3)	0.1210 (3)	0.0412 (10)
H45	0.6969	0.5679	0.0751	0.049*
C46	0.5985 (4)	0.4454 (3)	0.1349 (2)	0.0341 (9)
H46	0.4982	0.4337	0.0990	0.041*
C51	0.3690 (10)	−0.3020 (15)	0.1999 (6)	0.0623 (17)	0.873 (14)
H51A	0.4006	−0.3649	0.2282	0.075*	0.873 (14)
H51B	0.4636	−0.2468	0.2081	0.075*	0.873 (14)
Cl3	0.3192 (5)	−0.3489 (3)	0.08393 (18)	0.0632 (8)	0.873 (14)
Cl4	0.2056 (3)	−0.2424 (5)	0.2530 (3)	0.0888 (15)	0.873 (14)
C51'	0.367 (7)	−0.296 (11)	0.196 (4)	0.0623 (17)	0.127 (14)
H51C	0.4704	−0.3223	0.2192	0.075*	0.127 (14)
H51D	0.3909	−0.2204	0.1847	0.075*	0.127 (14)
Cl3'	0.294 (4)	−0.384 (3)	0.0949 (13)	0.087 (5)	0.127 (14)
Cl4'	0.226 (3)	−0.293 (3)	0.2777 (13)	0.094 (6)	0.127 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.02152 (15)	0.02327 (15)	0.02432 (16)	0.00118 (11)	0.00288 (11)	0.00453 (11)
Cl1	0.0307 (5)	0.0306 (5)	0.0274 (5)	−0.0013 (4)	0.0017 (4)	0.0054 (4)
C1	0.0274 (19)	0.0269 (19)	0.043 (2)	0.0078 (16)	0.0102 (17)	0.0122 (18)
O1	0.0582 (19)	0.0437 (16)	0.0441 (17)	−0.0022 (14)	−0.0087 (15)	−0.0008 (14)
C2	0.030 (2)	0.0283 (19)	0.030 (2)	−0.0018 (16)	−0.0002 (17)	0.0030 (16)
O2	0.0388 (16)	0.0631 (19)	0.0481 (18)	−0.0039 (14)	0.0217 (14)	0.0039 (14)
C3	0.0273 (18)	0.0224 (17)	0.0222 (18)	0.0027 (14)	0.0033 (14)	0.0013 (14)
N4	0.0225 (15)	0.0248 (15)	0.0292 (16)	0.0015 (12)	0.0050 (12)	0.0041 (12)
C5	0.032 (2)	0.0321 (19)	0.028 (2)	−0.0039 (16)	0.0085 (16)	0.0078 (16)
C6	0.0265 (19)	0.0314 (19)	0.036 (2)	−0.0021 (16)	0.0100 (16)	0.0060 (16)
N7	0.0195 (14)	0.0251 (15)	0.0294 (16)	0.0002 (11)	0.0072 (12)	0.0037 (12)
C8	0.0207 (17)	0.0324 (19)	0.0300 (19)	0.0039 (14)	0.0024 (15)	0.0094 (15)
C11	0.0239 (17)	0.0229 (17)	0.0205 (17)	−0.0043 (14)	−0.0023 (14)	0.0037 (14)
C12	0.0271 (19)	0.033 (2)	0.033 (2)	0.0019 (15)	0.0021 (16)	0.0051 (16)
C13	0.031 (2)	0.033 (2)	0.044 (2)	0.0115 (16)	0.0010 (17)	0.0047 (17)
C14	0.043 (2)	0.0267 (19)	0.039 (2)	0.0057 (17)	−0.0032 (18)	0.0087 (17)
C15	0.033 (2)	0.0266 (18)	0.035 (2)	0.0010 (15)	0.0010 (16)	0.0059 (16)
C16	0.0247 (18)	0.0212 (17)	0.0275 (19)	0.0026 (14)	−0.0018 (15)	−0.0011 (14)
P1	0.0227 (4)	0.0234 (4)	0.0232 (5)	0.0011 (4)	0.0026 (4)	0.0045 (4)
C21	0.0227 (17)	0.0233 (17)	0.0241 (18)	0.0077 (14)	−0.0011 (14)	0.0038 (14)
C22	0.0214 (17)	0.0244 (17)	0.0279 (19)	0.0081 (14)	−0.0006 (14)	0.0070 (14)
C23	0.0246 (18)	0.037 (2)	0.035 (2)	0.0095 (15)	0.0053 (16)	0.0102 (17)
C24	0.037 (2)	0.037 (2)	0.031 (2)	0.0128 (17)	0.0066 (17)	−0.0027 (17)
C25	0.039 (2)	0.0268 (19)	0.040 (2)	0.0050 (16)	0.0053 (18)	−0.0015 (17)
C26	0.0282 (19)	0.0265 (18)	0.037 (2)	0.0016 (15)	0.0020 (16)	0.0031 (16)
C31	0.0258 (18)	0.0249 (18)	0.0243 (18)	−0.0014 (14)	0.0013 (14)	0.0071 (15)
C32	0.034 (2)	0.044 (2)	0.034 (2)	0.0090 (17)	0.0017 (17)	0.0109 (17)
C33	0.030 (2)	0.060 (3)	0.047 (3)	0.0102 (19)	−0.0033 (19)	0.023 (2)
C34	0.049 (3)	0.050 (2)	0.039 (2)	−0.006 (2)	−0.018 (2)	0.015 (2)
C35	0.060 (3)	0.034 (2)	0.030 (2)	0.0030 (19)	−0.0057 (19)	0.0008 (17)
C36	0.041 (2)	0.0298 (19)	0.030 (2)	0.0033 (16)	−0.0035 (17)	0.0039 (16)
C41	0.0269 (18)	0.0207 (17)	0.0279 (19)	0.0032 (14)	0.0048 (15)	0.0009 (14)
C42	0.0282 (19)	0.0305 (19)	0.035 (2)	0.0023 (15)	0.0011 (16)	0.0098 (16)
C43	0.0258 (19)	0.031 (2)	0.047 (2)	−0.0009 (16)	−0.0001 (17)	0.0053 (17)
C44	0.035 (2)	0.030 (2)	0.049 (2)	−0.0072 (16)	0.0095 (18)	0.0071 (18)
C45	0.048 (2)	0.034 (2)	0.043 (2)	−0.0028 (18)	−0.0022 (19)	0.0145 (18)
C46	0.035 (2)	0.034 (2)	0.033 (2)	−0.0031 (16)	−0.0018 (17)	0.0084 (17)
C51	0.064 (3)	0.064 (3)	0.053 (3)	0.013 (2)	−0.004 (2)	−0.006 (2)
Cl3	0.0649 (14)	0.0762 (16)	0.0465 (10)	0.0169 (12)	−0.0063 (8)	0.0052 (9)
Cl4	0.0406 (10)	0.120 (3)	0.0799 (18)	−0.0128 (13)	0.0074 (11)	−0.0469 (16)
C51'	0.064 (3)	0.064 (3)	0.053 (3)	0.013 (2)	−0.004 (2)	−0.006 (2)
Cl3'	0.079 (8)	0.090 (10)	0.083 (7)	0.027 (8)	−0.006 (6)	−0.009 (7)
Cl4'	0.065 (9)	0.140 (15)	0.083 (8)	−0.005 (10)	0.014 (6)	0.038 (11)

Geometric parameters (Å, º) top

Ru1—C1	1.860 (4)	C23—H23	0.9400
Ru1—C2	1.932 (4)	C24—C25	1.381 (5)
Ru1—C3	2.065 (3)	C24—H24	0.9400
Ru1—C11	2.129 (3)	C25—C26	1.386 (5)
Ru1—P1	2.4265 (9)	C25—H25	0.9400
Ru1—Cl1	2.4737 (9)	C26—H26	0.9400
C1—O1	1.127 (4)	C31—C36	1.381 (5)
C2—O2	1.135 (4)	C31—C32	1.386 (4)
C3—N7	1.345 (4)	C32—C33	1.391 (5)
C3—N4	1.364 (4)	C32—H32	0.9400
N4—C5	1.382 (4)	C33—C34	1.373 (5)
N4—C16	1.432 (4)	C33—H33	0.9400
C5—C6	1.340 (5)	C34—C35	1.382 (5)
C5—H5	0.9400	C34—H34	0.9400
C6—N7	1.387 (4)	C35—C36	1.386 (5)
C6—H6	0.9400	C35—H35	0.9400
N7—C8	1.465 (4)	C36—H36	0.9400
C8—C22	1.518 (4)	C41—C42	1.394 (4)
C8—H8A	0.9800	C41—C46	1.396 (4)
C8—H8B	0.9800	C42—C43	1.378 (4)
C11—C12	1.379 (4)	C42—H42	0.9400
C11—C16	1.404 (4)	C43—C44	1.384 (5)
C12—C13	1.391 (5)	C43—H43	0.9400
C12—H12	0.9400	C44—C45	1.373 (5)
C13—C14	1.374 (5)	C44—H44	0.9400
C13—H13	0.9400	C45—C46	1.385 (5)
C14—C15	1.391 (5)	C45—H45	0.9400
C14—H14	0.9400	C46—H46	0.9400
C15—C16	1.387 (4)	C51—Cl4	1.728 (10)
C15—H15	0.9400	C51—Cl3	1.744 (7)
P1—C31	1.834 (3)	C51—H51A	0.9800
P1—C41	1.836 (3)	C51—H51B	0.9800
P1—C21	1.841 (3)	C51'—Cl4'	1.727 (11)
C21—C26	1.396 (4)	C51'—Cl3'	1.744 (8)
C21—C22	1.409 (4)	C51'—H51C	0.9800
C22—C23	1.383 (4)	C51'—H51D	0.9800
C23—C24	1.380 (5)

C1—Ru1—C2	91.19 (14)	C22—C21—P1	121.2 (2)
C1—Ru1—C3	87.39 (13)	C23—C22—C21	119.4 (3)
C2—Ru1—C3	171.22 (13)	C23—C22—C8	118.1 (3)
C1—Ru1—C11	89.85 (13)	C21—C22—C8	122.5 (3)
C2—Ru1—C11	93.55 (13)	C24—C23—C22	121.8 (3)
C3—Ru1—C11	77.79 (12)	C24—C23—H23	119.1
C1—Ru1—P1	95.28 (10)	C22—C23—H23	119.1
C2—Ru1—P1	93.06 (10)	C23—C24—C25	119.3 (3)
C3—Ru1—P1	95.70 (9)	C23—C24—H24	120.3
C11—Ru1—P1	171.55 (9)	C25—C24—H24	120.3
C1—Ru1—Cl1	174.32 (10)	C24—C25—C26	119.8 (3)
C2—Ru1—Cl1	92.23 (10)	C24—C25—H25	120.1
C3—Ru1—Cl1	88.54 (9)	C26—C25—H25	120.1
C11—Ru1—Cl1	85.41 (8)	C25—C26—C21	121.6 (3)
P1—Ru1—Cl1	89.07 (3)	C25—C26—H26	119.2
O1—C1—Ru1	177.0 (3)	C21—C26—H26	119.2
O2—C2—Ru1	175.9 (3)	C36—C31—C32	118.8 (3)
N7—C3—N4	104.1 (3)	C36—C31—P1	118.1 (3)
N7—C3—Ru1	139.1 (2)	C32—C31—P1	123.1 (3)
N4—C3—Ru1	116.6 (2)	C31—C32—C33	120.5 (4)
C3—N4—C5	111.4 (3)	C31—C32—H32	119.8
C3—N4—C16	116.8 (3)	C33—C32—H32	119.8
C5—N4—C16	131.4 (3)	C34—C33—C32	120.3 (4)
C6—C5—N4	106.2 (3)	C34—C33—H33	119.8
C6—C5—H5	126.9	C32—C33—H33	119.8
N4—C5—H5	126.9	C33—C34—C35	119.3 (3)
C5—C6—N7	107.3 (3)	C33—C34—H34	120.3
C5—C6—H6	126.4	C35—C34—H34	120.3
N7—C6—H6	126.4	C34—C35—C36	120.5 (4)
C3—N7—C6	111.1 (3)	C34—C35—H35	119.8
C3—N7—C8	123.5 (3)	C36—C35—H35	119.8
C6—N7—C8	125.3 (3)	C31—C36—C35	120.5 (3)
N7—C8—C22	112.9 (2)	C31—C36—H36	119.7
N7—C8—H8A	109.0	C35—C36—H36	119.7
C22—C8—H8A	109.0	C42—C41—C46	118.6 (3)
N7—C8—H8B	109.0	C42—C41—P1	120.5 (2)
C22—C8—H8B	109.0	C46—C41—P1	120.8 (2)
H8A—C8—H8B	107.8	C43—C42—C41	121.0 (3)
C12—C11—C16	115.6 (3)	C43—C42—H42	119.5
C12—C11—Ru1	130.3 (2)	C41—C42—H42	119.5
C16—C11—Ru1	114.0 (2)	C42—C43—C44	119.6 (3)
C11—C12—C13	122.0 (3)	C42—C43—H43	120.2
C11—C12—H12	119.0	C44—C43—H43	120.2
C13—C12—H12	119.0	C45—C44—C43	120.2 (3)
C14—C13—C12	120.4 (3)	C45—C44—H44	119.9
C14—C13—H13	119.8	C43—C44—H44	119.9
C12—C13—H13	119.8	C44—C45—C46	120.6 (3)
C13—C14—C15	120.2 (3)	C44—C45—H45	119.7
C13—C14—H14	119.9	C46—C45—H45	119.7
C15—C14—H14	119.9	C45—C46—C41	120.0 (3)
C16—C15—C14	117.7 (3)	C45—C46—H46	120.0
C16—C15—H15	121.2	C41—C46—H46	120.0
C14—C15—H15	121.2	Cl4—C51—Cl3	111.5 (8)
C15—C16—C11	124.0 (3)	Cl4—C51—H51A	109.3
C15—C16—N4	121.3 (3)	Cl3—C51—H51A	109.3
C11—C16—N4	114.7 (3)	Cl4—C51—H51B	109.3
C31—P1—C41	101.78 (14)	Cl3—C51—H51B	109.3
C31—P1—C21	104.91 (14)	H51A—C51—H51B	108.0
C41—P1—C21	102.61 (14)	Cl4'—C51'—Cl3'	111.4 (9)
C31—P1—Ru1	114.52 (10)	Cl4'—C51'—H51C	109.4
C41—P1—Ru1	116.91 (10)	Cl3'—C51'—H51C	109.4
C21—P1—Ru1	114.40 (10)	Cl4'—C51'—H51D	109.3
C26—C21—C22	118.1 (3)	Cl3'—C51'—H51D	109.3
C26—C21—P1	120.6 (2)	H51C—C51'—H51D	108.0

C1—Ru1—C3—N7	−80.2 (4)	Cl1—Ru1—P1—C41	63.93 (12)
C11—Ru1—C3—N7	−170.6 (4)	C1—Ru1—P1—C21	120.34 (15)
P1—Ru1—C3—N7	14.8 (3)	C2—Ru1—P1—C21	−148.19 (14)
Cl1—Ru1—C3—N7	103.8 (3)	C3—Ru1—P1—C21	32.44 (14)
C1—Ru1—C3—N4	94.1 (2)	Cl1—Ru1—P1—C21	−56.00 (11)
C11—Ru1—C3—N4	3.7 (2)	C31—P1—C21—C26	−111.9 (3)
P1—Ru1—C3—N4	−170.9 (2)	C41—P1—C21—C26	−5.9 (3)
Cl1—Ru1—C3—N4	−81.9 (2)	Ru1—P1—C21—C26	121.7 (2)
N7—C3—N4—C5	−0.2 (3)	C31—P1—C21—C22	71.3 (3)
Ru1—C3—N4—C5	−176.4 (2)	C41—P1—C21—C22	177.3 (2)
N7—C3—N4—C16	172.8 (2)	Ru1—P1—C21—C22	−55.0 (3)
Ru1—C3—N4—C16	−3.3 (3)	C26—C21—C22—C23	0.0 (4)
C3—N4—C5—C6	0.1 (4)	P1—C21—C22—C23	176.8 (2)
C16—N4—C5—C6	−171.7 (3)	C26—C21—C22—C8	178.1 (3)
N4—C5—C6—N7	0.1 (4)	P1—C21—C22—C8	−5.1 (4)
N4—C3—N7—C6	0.3 (3)	N7—C8—C22—C23	−92.6 (3)
Ru1—C3—N7—C6	175.1 (3)	N7—C8—C22—C21	89.3 (4)
N4—C3—N7—C8	−175.0 (3)	C21—C22—C23—C24	−1.0 (5)
Ru1—C3—N7—C8	−0.2 (5)	C8—C22—C23—C24	−179.2 (3)
C5—C6—N7—C3	−0.3 (4)	C22—C23—C24—C25	1.8 (5)
C5—C6—N7—C8	174.9 (3)	C23—C24—C25—C26	−1.5 (5)
C3—N7—C8—C22	−74.5 (4)	C24—C25—C26—C21	0.6 (5)
C6—N7—C8—C22	110.9 (3)	C22—C21—C26—C25	0.2 (5)
C1—Ru1—C11—C12	91.5 (3)	P1—C21—C26—C25	−176.6 (3)
C2—Ru1—C11—C12	0.3 (3)	C41—P1—C31—C36	76.7 (3)
C3—Ru1—C11—C12	178.9 (3)	C21—P1—C31—C36	−176.7 (2)
Cl1—Ru1—C11—C12	−91.6 (3)	Ru1—P1—C31—C36	−50.4 (3)
C1—Ru1—C11—C16	−90.8 (2)	C41—P1—C31—C32	−102.9 (3)
C2—Ru1—C11—C16	178.0 (2)	C21—P1—C31—C32	3.8 (3)
C3—Ru1—C11—C16	−3.5 (2)	Ru1—P1—C31—C32	130.0 (2)
Cl1—Ru1—C11—C16	86.0 (2)	C36—C31—C32—C33	2.4 (5)
C16—C11—C12—C13	1.5 (5)	P1—C31—C32—C33	−178.0 (3)
Ru1—C11—C12—C13	179.1 (2)	C31—C32—C33—C34	−1.0 (5)
C11—C12—C13—C14	−0.7 (5)	C32—C33—C34—C35	−1.4 (6)
C12—C13—C14—C15	−0.5 (5)	C33—C34—C35—C36	2.3 (5)
C13—C14—C15—C16	0.9 (5)	C32—C31—C36—C35	−1.6 (5)
C14—C15—C16—C11	−0.1 (5)	P1—C31—C36—C35	178.8 (3)
C14—C15—C16—N4	177.8 (3)	C34—C35—C36—C31	−0.8 (5)
C12—C11—C16—C15	−1.1 (5)	C31—P1—C41—C42	−167.7 (3)
Ru1—C11—C16—C15	−179.1 (2)	C21—P1—C41—C42	83.9 (3)
C12—C11—C16—N4	−179.1 (3)	Ru1—P1—C41—C42	−42.1 (3)
Ru1—C11—C16—N4	2.9 (3)	C31—P1—C41—C46	15.8 (3)
C3—N4—C16—C15	−177.9 (3)	C21—P1—C41—C46	−92.6 (3)
C5—N4—C16—C15	−6.5 (5)	Ru1—P1—C41—C46	141.4 (2)
C3—N4—C16—C11	0.2 (4)	C46—C41—C42—C43	0.6 (5)
C5—N4—C16—C11	171.6 (3)	P1—C41—C42—C43	−176.0 (3)
C1—Ru1—P1—C31	−0.83 (16)	C41—C42—C43—C44	−1.7 (5)
C2—Ru1—P1—C31	90.64 (15)	C42—C43—C44—C45	1.6 (6)
C3—Ru1—P1—C31	−88.73 (14)	C43—C44—C45—C46	−0.4 (6)
Cl1—Ru1—P1—C31	−177.17 (12)	C44—C45—C46—C41	−0.7 (6)
C1—Ru1—P1—C41	−119.73 (16)	C42—C41—C46—C45	0.6 (5)
C2—Ru1—P1—C41	−28.25 (15)	P1—C41—C46—C45	177.2 (3)
C3—Ru1—P1—C41	152.38 (14)

Experimental details

Crystal data
Chemical formula	[Ru(C₂₈H₂₂N₂P)Cl(CO)₂]·CH₂Cl₂
M_r	694.91
Crystal system, space group	Triclinic, P1
Temperature (K)	210
a, b, c (Å)	8.1600 (9), 12.1940 (13), 14.9713 (16)
α, β, γ (°)	100.109 (5), 93.560 (5), 93.469 (5)
V (Å³)	1459.9 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.17 × 0.08 × 0.03

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.862, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	20414, 5349, 4214
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.077, 1.02
No. of reflections	5349
No. of parameters	383
No. of restraints	22
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.45

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ru1—C1	1.860 (4)	Ru1—C11	2.129 (3)
Ru1—C2	1.932 (4)	Ru1—P1	2.4265 (9)
Ru1—C3	2.065 (3)	Ru1—Cl1	2.4737 (9)

Footnotes

‡Current address: University of Illinois at Chicago, Department of Chemistry, 845 West Taylor Street, MC 111, Chicago, IL 60607, USA.

Acknowledgements

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

References

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Nonius (2000). 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., Wang, L.-X., Xie, J.-H. & Zhou, Q.-L. (2005). Tetrahedron, pp. 259–266. CrossRef Google Scholar

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