(2,6-Bis{1-[4-(dimethyl­amino)phenyl­imino]eth­yl}­pyridine)­dichlorido­(tri­phenyl­phosphine-κP)ruthenium(II): a zigzag chain of fused centrosymmetric R²₂(12) rings

The title compound, [RuCl₂(C₂₅H₂₉N₅)(C₁₈H₁₅P)], a transfer hydrogenation catalyst, is supported by an N,N′,N′′-tridentate pyridine-bridged ligand and triphenyl­phosphine. The Ru^II centre is six-coordinated in a distorted octa­hedral arrangement, with the two Cl atoms located in the axial positions, and the pyridine (py) N atom, the two imino N atoms and the triphenyl­phosphine P atom located in the equatorial plane. The two equatorial Ru—N_imino distances (mean 2.093 Å) are substantially longer than the equatorial Ru—N_py bond [1.954 (4) Å]. It is observed that the N_imino—M—N_py bond angle for the five-membered chelate rings of 2,6-bis(imino)pyridine-based complexes is inversely related to the magnitude of the M—N_py bond. The title structure is stabilized by intra- and inter­molecular C—H...Cl hydrogen bonds, as well as by intra­molecular π–π stacking inter­actions between the aromatic rings belonging to the triphenyl­phosphine ligand and the dimethyl­amino­phenyl fragment. The inter­molecular hydrogen bonds form an R₂²(12) ring and a zigzag chain of fused centrosymmetric rings running parallel to the [100] direction.

S1. Comment

Pydim [2,6-bis(imino)pyridine-based] complexes of the form of (I) display a range of catalytic activity. For example, iron and cobalt complexes have been used in alkene polymerization reactions (Small et al., 1998; Tellmann et al., 2005; Bryliakov et al., 2004; Ionkin et al., 2006). Ruthenium complexes have been studied for potential applications such as optical sensors and chemical catalysis (Bianchini & Lee, 2000; Ertekin et al., 2003; Çetinkaya et al., 1999; Dayan & Çetinkaya, 2007). More recently, Ru^II complexes have been used for transfer hydrogenation reactions of ketones (Dayan & Çetinkaya, 2007).

While Ru^II–pydim complexes have been examined extensively, reports of the structural properties of these compounds are rare in the literature (Ertekin et al., 2003; Özdemir et al., 2007). The necessity of auxiliary ligand L in our [RuCl₂(N,N',N)-L] system (Çetinkaya et al., 1999) prompted us to investigate the influence of PPh₃. Therefore, a single-crystal X-ray structure analysis has been carried out on the title complex, (II).

The molecular structure of complex (II) and the atom-labelling scheme are shown in Fig. 1. Selected geometric parameters are summarized in Table 1. The mononuclear molecule contains an (N¹,N^1'E,N¹,N^1'E)-N¹,N^1'-[1,1'-(pyridine-2,6-diyl)bis (ethan-1-yl-1-ylidene)]bis(N⁴,N⁴-dimethylbenzene-1,4-diamine) ligand with an Ru^II metal centre, one triphenylphosphine ligand and two Cl ligands. The pydim ligand, with its two imine groups in ortho positions with respect to the pyridine N atom, behaves as a symmetrical N,N',N-tridentate chelate. The Ru^II ion is six-coordinated by two imino N atoms, one pyridine N atom, one triphenylphosphine P atom and two Cl atoms (Fig. 1). The five-membered chelate Ru1/N1/C1/C16/N4 and Ru1/N1/C5/C6/N2 rings are planar, and the maximum deviations from their planes are 0.028 (4) and -0.040 (3) Å, respectively, for atoms C1 and N1. These two chelate rings make a small dihedral angle of 2.74 (3)° with one another, indicating that they are nearly coplanar.

The local structure around the Ru^II ion is that of an octahedron, of which the equatorial plane is formed by three N atoms from the pydim ligand (N1, N2 and N4) and the P atom of the triphenylphosphine ligand (P1). The axial positions in the octahedron are occupied by two Cl atoms (Cl1 and Cl2). As can be seen from the trans angles, which range from 154.96 (19) to 175.78 (15)°, and the cis angles, which range from 77.60 (18) to 102.62 (14)°, the coordination octahedron around the Ru^II ion can be visualized as being distorted, with the major distortion arising via the N2—Ru1—N4 angle [154.96 (19)°]. This angle is considerably smaller than the ideal angle of 180°. The N1—Ru—P1 angle, involving the pyridine N and triphenylphosphine P atoms, is normal at 175.78 (15)°. The Ru—N2 and Ru—N4 bond lengths are comparable to the reported values for [RuCl₂(pybox-dihydro)(C₂H₄)] [pybox is bis(hydrooxazolyl)pyridine; Nishiyama et al., 1995]. However, the M—N_py bond [1.954 (4) Å] is somewhat shorter than the M—N_imino bonds, with the formal double bond character of the imino linkages N2═C6 and N4═C16 having been retained [C═N = 1.310 (6) and 1.320 (6) Å, respectively]. When the ruthenium–phosphine distance is compared with the six-coordinate complexes reported in the literature [2.337 (3), 2.3451 (12) and 2.2384 (2) Å; Abbenhuis et al., 1998]. it is seen that the ruthenium–phosphine distance in the solid-state structure of (II) is lengthened significantly to 2.3890 (14) Å, pointing to a weaker Ru—P interaction. This observation is attributed to steric effects of the groups bonded to imino N atoms.

Previously, we have reported the closely related compound, (III), [RuCl₂(pydim)CH₃CN] (Ar = 4-MeOC₆H₄; Çetinkaya et al., 1999). The geometries of the N,N',N ligands in (II) and (III) are very similar. However, the comparison between these structures reveals differences caused by the transition from L = MeCN to L = PPh₃. The Ru—N_py distance in (II) is significantly longer than the corresponding value in (III) [1.906 (7) Å]. This reflects the steric congestion around the ruthenium center and also the greater trans influence of PPh₃; it appears that the stronger π-acceptor ability of PPh₃, in comparison with MeCN, allows it to compete more effectively with the trans pyridyl unit for Ru electron density, and therefore the Ru—N_py bond becomes weakened and extended in complex (II) when compared with (III) (Coe & Glenwright, 2000). The planes of the benzene rings substituted on the bis(imino)pyridine ligand backbone are inclined to the plane of the backbone at 55.11 (20) and 77.87 (19)° for the C8–C13 and C18–C23 rings, respectively, while the dihedral angle between the two benzene planes is 67.90 (17)°. The geometries at the imino N-atom centers are all trigonal planar, the sums of the three bond angles around these centers being 359.8 and 359.9°, and none of the atoms is more than ca 0.03 Å out of its associated RuC₂ plane.

There are several structures reported in the literature containing various transition metal complexes of pydim-based ligands (Britovsek et al., 1999; Dias et al., 2000; Nakayama et al., 2005; Humphries et al., 2005). Inspection of the the M—N bond distances in (II) and in these examples indicates that the two M—N_imino bonds are ca 0.1–0.2 Å longer than the corresponding M—N_py bond within each metal-tridentate chelate unit. Furthermore, it is observed that the N_imino—M—N_py bond angle for the five-membered chelate rings of pydim complexes is inversely related to the magnitude of the M—N_py bond, as expected. As the M—N_py distance increases from 1.833 (3) Å for [CoMe(pydim)] (Ar = 2,6-ⁱPr₂C₆H₃; Humphries et al., 2005) to 1.911 (3) Å for [RhMe(pydim)](OTf)₂ (Ar = 2,6-ⁱPr₂C₆H₃; Dias et al., 2000) to 1.954 (4) Å for (II) to 2.001 (3) Å for [CrCl₃(pydim)] (Ar = C₆F₅; Nakayama et al., 2005) to 2.110 (6) Å for [FeCl₂(pydim)] (Ar = 2,4,6-Me₃C₆H₂; Britovsek et al., 1999), the corresponding inner `bite' angle decreases continually from 81.17 (average) to 79.8 (average) to 77.62 (average) to 76.6 (average) to 72.8° (average), respectively.

Examination of the structure with PLATON (Spek, 2003) reveals that there is an intramolecular π–π stacking interaction between the C18–C23 and C38–C43 rings, with a distance of 3.636 (10) Å between the ring centroids and a perpendicular distance of 3.353 (12) Å between the rings. In the molecular structure of (II), three intramolecular interactions are observed between the phenyl H atoms and Cl atoms (Table 2), which lead to the formation of six-membered rings with graph-set descriptor S(6) (Bernstein et al., 1995). In the crystal structure of (II), pyridine atom C2 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom Cl2 in the molecule at (1 - x, -y, 1 - z), so forming a centrosymmetric R₂²(12) ring centred at (1/2, 0, 1/2). Similarly, pyridine atom C4 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom Cl1 in the molecule at (2 - x, -y, 1 - z), so forming a second centrosymmetric R₂²(12) ring motif centred at (1, 0, 1/2). Propagation by inversion and translation of these two interactions generates a zigzag chain of fused rings running parallel to the [100] direction (Fig. 2). The full geometry of the intra- and intermolecular interactions is given in Table 2.

Related literature

For related literature, see: Abbenhuis et al. (1998); Bernstein et al. (1995); Bianchini & Lee (2000); Britovsek et al. (1999); Bryliakov et al. (2004); Dayan & Çetinkaya (2007); Dias et al. (2000); Ertekin et al. (2003); Humphries et al. (2005); Ionkin et al. (2006); Nakayama et al. (2005); Nishiyama et al. (1995); Sheldrick (1997); Small et al. (1998); Spek (2003); Tellmann et al. (2005); Özdemir et al. (2007); Çetinkaya et al. (1999).

S2. Experimental

The ttitle complex was synthesized by the literature method (Çetinkaya et al., 1999) and X-ray quality crystals were grown from CH₂Cl₂/Et₂O (20 ml, 1:3 v/v).

S3. Refinement

H atoms were positioned geometrically and treated using a riding model, fixing the C—H bond lengths at 0.96 and 0.93 Å for CH₃ and aromatic CH groups, respectively. The U_iso(H) values were constrained as 1.2U_eq (1.5U_eq for methyl groups) of the pivot atom. Riding methyl H atoms on atoms C7 and C17 were allowed to rotate freely during refinement using the AFIX 137 command of SHELXL97 (Sheldrick, 1997). Other methyl H atoms were placed in geometrically idealized positions using the SHELXL97 HFIX 33 command and constrained to ride on their parent atoms.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures

	Fig. 1. : A view of (II), showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity.
	Fig. 2. : Part of the crystal structure of (II), showing the formation of a zigzag chain of fused centrosymmetric R2^2(12) rings along [100]. For clarity, only H atoms involved in hydrogen bonding have been included.

(2,6-Bis{1-[4- (dimethylamino)phenylimino]ethyl}pyridine)dichlorido(triphenylphosphine- κP)ruthenium(II)

Crystal data

[RuCl2(C25H29N5)(C18H15P)]	F(000) = 1720
Mr = 833.77	Dx = 1.417 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 20831 reflections
a = 10.2192 (5) Å	θ = 1.5–27.2°
b = 18.3059 (13) Å	µ = 0.62 mm^−1
c = 20.9425 (12) Å	T = 296 K
β = 94.089 (4)°	Thin rod, black
V = 3907.8 (4) Å^3	0.72 × 0.28 × 0.04 mm
Z = 4

Data collection

Stoe IPDS II diffractometer	6869 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	3478 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.121
Detector resolution: 6.67 pixels mm^-1	θmax = 25.0°, θmin = 1.5°
ω scans	h = −12→12
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −21→21
Tmin = 0.893, Tmax = 0.978	l = −24→24
24010 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0123P)^2] where P = (Fo^2 + 2Fc^2)/3
6869 reflections	(Δ/σ)max = 0.001
471 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.44 e Å^−3

Special details

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
Ru1	0.73385 (5)	0.17466 (2)	0.52318 (2)	0.04223 (13)
Cl1	0.91543 (15)	0.15718 (7)	0.60165 (7)	0.0577 (4)
Cl2	0.54902 (14)	0.17907 (9)	0.44560 (7)	0.0590 (4)
P1	0.72432 (16)	0.30149 (7)	0.54931 (7)	0.0479 (4)
N1	0.7526 (5)	0.0703 (2)	0.5065 (2)	0.0474 (12)
N2	0.8555 (4)	0.1739 (3)	0.44538 (19)	0.0499 (11)
N3	0.9965 (7)	0.4116 (3)	0.2930 (3)	0.0880 (19)
N4	0.6135 (4)	0.1283 (2)	0.5873 (2)	0.0496 (12)
N5	0.2724 (6)	0.2669 (3)	0.7507 (3)	0.0798 (17)
C1	0.6920 (6)	0.0215 (3)	0.5425 (3)	0.0539 (16)
C2	0.7129 (7)	−0.0532 (3)	0.5342 (3)	0.0656 (19)
H2	0.6692	−0.0874	0.5577	0.079*
C3	0.7983 (7)	−0.0753 (3)	0.4908 (4)	0.072 (2)
H3	0.8155	−0.1248	0.4862	0.086*
C4	0.8588 (6)	−0.0257 (3)	0.4543 (3)	0.0619 (18)
H4	0.9158	−0.0412	0.4244	0.074*
C5	0.8345 (6)	0.0480 (3)	0.4623 (3)	0.0491 (16)
C6	0.8885 (6)	0.1082 (3)	0.4274 (3)	0.0524 (17)
C7	0.9619 (7)	0.0900 (3)	0.3701 (3)	0.073 (2)
H7A	0.9719	0.1332	0.3451	0.109*
H7B	0.9140	0.0539	0.3447	0.109*
H7C	1.0468	0.0710	0.3839	0.109*
C8	0.8943 (6)	0.2359 (3)	0.4087 (3)	0.0492 (15)
C9	1.0234 (7)	0.2519 (3)	0.3998 (3)	0.073 (2)
H9	1.0894	0.2229	0.4194	0.088*
C10	1.0571 (7)	0.3100 (4)	0.3623 (3)	0.076 (2)
H10	1.1453	0.3200	0.3580	0.091*
C11	0.9622 (8)	0.3540 (3)	0.3308 (3)	0.0652 (19)
C12	0.8331 (7)	0.3382 (3)	0.3414 (3)	0.0671 (18)
H12	0.7668	0.3674	0.3224	0.081*
C13	0.7995 (7)	0.2800 (3)	0.3796 (3)	0.0611 (17)
H13	0.7116	0.2708	0.3855	0.073*
C14	1.1272 (8)	0.4188 (5)	0.2723 (4)	0.133 (4)
H14A	1.1321	0.4618	0.2463	0.199*
H14B	1.1480	0.3766	0.2478	0.199*
H14C	1.1886	0.4229	0.3090	0.199*
C15	0.8968 (9)	0.4574 (4)	0.2619 (3)	0.107 (3)
H15A	0.9374	0.4944	0.2374	0.160*
H15B	0.8470	0.4802	0.2936	0.160*
H15C	0.8396	0.4283	0.2339	0.160*
C16	0.6090 (6)	0.0563 (3)	0.5867 (3)	0.0557 (17)
C17	0.5257 (7)	0.0107 (3)	0.6272 (3)	0.076 (2)
H17A	0.4562	0.0401	0.6420	0.114*
H17B	0.5786	−0.0080	0.6633	0.114*
H17C	0.4890	−0.0293	0.6023	0.114*
C18	0.5273 (6)	0.1646 (3)	0.6293 (3)	0.0474 (14)
C19	0.5626 (6)	0.1733 (4)	0.6930 (3)	0.0626 (16)
H19	0.6435	0.1561	0.7098	0.075*
C20	0.4801 (7)	0.2071 (3)	0.7323 (3)	0.0694 (19)
H20	0.5072	0.2127	0.7754	0.083*
C21	0.3576 (7)	0.2332 (3)	0.7106 (3)	0.0601 (17)
C22	0.3221 (6)	0.2239 (3)	0.6453 (3)	0.0646 (17)
H22	0.2408	0.2402	0.6283	0.077*
C23	0.4077 (6)	0.1904 (3)	0.6058 (3)	0.0595 (16)
H23	0.3831	0.1853	0.5624	0.071*
C24	0.3250 (7)	0.2966 (4)	0.8102 (3)	0.112 (3)
H24A	0.2552	0.3171	0.8328	0.168*
H24B	0.3875	0.3341	0.8022	0.168*
H24C	0.3675	0.2586	0.8356	0.168*
C25	0.1526 (8)	0.2972 (4)	0.7230 (3)	0.115 (3)
H25A	0.1038	0.3179	0.7561	0.173*
H25B	0.1016	0.2595	0.7013	0.173*
H25C	0.1719	0.3347	0.6930	0.173*
C26	0.8792 (6)	0.3534 (3)	0.5522 (3)	0.0521 (16)
C27	0.9964 (6)	0.3186 (4)	0.5411 (3)	0.0652 (16)
H27	0.9965	0.2696	0.5296	0.078*
C28	1.1142 (7)	0.3579 (5)	0.5473 (3)	0.087 (2)
H28	1.1924	0.3346	0.5394	0.105*
C29	1.1161 (9)	0.4285 (5)	0.5645 (4)	0.098 (3)
H29	1.1953	0.4537	0.5694	0.118*
C30	1.0005 (9)	0.4635 (4)	0.5749 (4)	0.092 (3)
H30	1.0017	0.5129	0.5852	0.111*
C31	0.8848 (7)	0.4271 (3)	0.5704 (3)	0.077 (2)
H31	0.8082	0.4512	0.5795	0.092*
C32	0.6145 (6)	0.3566 (3)	0.4966 (3)	0.0522 (16)
C33	0.6588 (7)	0.4098 (3)	0.4561 (3)	0.0673 (19)
H33	0.7475	0.4217	0.4589	0.081*
C34	0.5746 (8)	0.4461 (4)	0.4114 (4)	0.086 (2)
H34	0.6070	0.4792	0.3828	0.103*
C35	0.4423 (8)	0.4317 (4)	0.4106 (4)	0.089 (2)
H35	0.3847	0.4567	0.3820	0.107*
C36	0.3946 (7)	0.3824 (4)	0.4503 (3)	0.078 (2)
H36	0.3048	0.3740	0.4496	0.094*
C37	0.4801 (7)	0.3438 (3)	0.4924 (3)	0.0669 (18)
H37	0.4464	0.3084	0.5185	0.080*
C38	0.6808 (6)	0.3292 (3)	0.6299 (3)	0.0528 (14)
C39	0.5802 (7)	0.3757 (3)	0.6430 (3)	0.072 (2)
H39	0.5213	0.3916	0.6100	0.087*
C40	0.5664 (8)	0.3990 (4)	0.7058 (4)	0.089 (2)
H40	0.4985	0.4305	0.7144	0.106*
C41	0.6508 (9)	0.3760 (4)	0.7540 (4)	0.085 (2)
H41	0.6407	0.3919	0.7955	0.103*
C42	0.7520 (7)	0.3291 (4)	0.7424 (3)	0.0797 (19)
H42	0.8091	0.3130	0.7761	0.096*
C43	0.7679 (7)	0.3064 (3)	0.6812 (3)	0.0704 (19)
H43	0.8372	0.2755	0.6733	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.0439 (3)	0.0359 (2)	0.0478 (3)	0.0009 (3)	0.0091 (2)	−0.0019 (3)
Cl1	0.0578 (11)	0.0528 (9)	0.0620 (10)	0.0092 (7)	0.0010 (8)	−0.0030 (7)
Cl2	0.0545 (10)	0.0577 (8)	0.0640 (10)	−0.0063 (9)	−0.0011 (7)	−0.0018 (9)
P1	0.0503 (11)	0.0424 (8)	0.0515 (10)	0.0022 (7)	0.0066 (8)	−0.0005 (7)
N1	0.047 (3)	0.050 (3)	0.045 (3)	0.000 (2)	0.006 (2)	−0.002 (2)
N2	0.052 (3)	0.048 (2)	0.050 (3)	0.005 (3)	0.002 (2)	−0.004 (3)
N3	0.109 (6)	0.069 (4)	0.088 (5)	−0.006 (4)	0.026 (4)	0.023 (3)
N4	0.044 (3)	0.043 (3)	0.061 (3)	0.002 (2)	0.005 (2)	0.001 (2)
N5	0.065 (4)	0.116 (4)	0.060 (4)	0.017 (4)	0.016 (3)	−0.020 (3)
C1	0.050 (4)	0.038 (3)	0.073 (5)	−0.003 (3)	0.003 (3)	0.000 (3)
C2	0.065 (5)	0.040 (3)	0.091 (6)	−0.004 (3)	0.003 (4)	0.003 (3)
C3	0.058 (5)	0.043 (3)	0.112 (6)	0.011 (3)	−0.008 (4)	−0.016 (4)
C4	0.053 (5)	0.043 (3)	0.088 (5)	0.011 (3)	−0.003 (4)	−0.015 (3)
C5	0.051 (4)	0.040 (3)	0.056 (4)	0.002 (3)	0.002 (3)	−0.013 (3)
C6	0.049 (4)	0.055 (4)	0.053 (4)	0.007 (3)	0.007 (3)	−0.009 (3)
C7	0.075 (5)	0.093 (5)	0.053 (4)	0.015 (4)	0.021 (4)	−0.015 (4)
C8	0.049 (4)	0.051 (3)	0.048 (4)	−0.003 (3)	0.012 (3)	−0.008 (3)
C9	0.068 (5)	0.087 (5)	0.067 (5)	−0.001 (4)	0.018 (4)	0.013 (4)
C10	0.066 (5)	0.089 (5)	0.075 (5)	−0.002 (4)	0.028 (4)	0.014 (4)
C11	0.081 (6)	0.063 (4)	0.054 (4)	−0.010 (4)	0.022 (4)	−0.002 (3)
C12	0.082 (5)	0.060 (4)	0.061 (4)	0.001 (4)	0.014 (4)	0.012 (3)
C13	0.060 (5)	0.064 (4)	0.061 (4)	−0.004 (3)	0.019 (4)	−0.003 (3)
C14	0.111 (8)	0.146 (7)	0.149 (8)	−0.024 (6)	0.054 (6)	0.060 (6)
C15	0.144 (9)	0.079 (5)	0.100 (6)	−0.015 (5)	0.026 (6)	0.027 (5)
C16	0.047 (4)	0.056 (4)	0.065 (4)	−0.007 (3)	0.009 (3)	0.001 (3)
C17	0.076 (5)	0.057 (4)	0.097 (5)	−0.009 (4)	0.023 (4)	0.013 (4)
C18	0.048 (4)	0.047 (3)	0.049 (4)	0.001 (3)	0.012 (3)	0.003 (3)
C19	0.051 (4)	0.079 (4)	0.059 (4)	0.011 (4)	0.010 (3)	0.006 (4)
C20	0.062 (5)	0.092 (5)	0.055 (4)	−0.003 (4)	0.009 (4)	−0.008 (3)
C21	0.061 (5)	0.074 (4)	0.048 (4)	0.002 (4)	0.017 (4)	−0.004 (3)
C22	0.046 (4)	0.087 (4)	0.060 (5)	0.005 (3)	0.005 (3)	0.000 (4)
C23	0.054 (4)	0.075 (4)	0.050 (4)	0.001 (3)	0.009 (3)	−0.004 (3)
C24	0.103 (6)	0.165 (8)	0.071 (5)	−0.017 (6)	0.035 (5)	−0.046 (5)
C25	0.116 (7)	0.153 (8)	0.080 (6)	0.066 (6)	0.037 (5)	−0.006 (5)
C26	0.053 (4)	0.054 (4)	0.049 (4)	−0.010 (3)	0.003 (3)	−0.001 (3)
C27	0.060 (5)	0.074 (4)	0.061 (4)	−0.003 (4)	0.002 (3)	0.007 (4)
C28	0.047 (5)	0.119 (7)	0.096 (6)	−0.019 (5)	0.002 (4)	0.027 (5)
C29	0.084 (7)	0.102 (7)	0.104 (7)	−0.052 (6)	−0.021 (5)	0.027 (5)
C30	0.103 (7)	0.066 (5)	0.105 (7)	−0.031 (5)	−0.008 (6)	−0.002 (4)
C31	0.087 (6)	0.060 (4)	0.084 (5)	−0.023 (4)	0.018 (4)	−0.009 (4)
C32	0.048 (4)	0.043 (3)	0.066 (4)	0.000 (3)	0.011 (3)	−0.006 (3)
C33	0.067 (5)	0.057 (4)	0.078 (5)	−0.009 (4)	0.009 (4)	0.012 (3)
C34	0.075 (6)	0.078 (5)	0.104 (6)	0.009 (4)	0.007 (5)	0.041 (4)
C35	0.078 (7)	0.095 (6)	0.094 (6)	0.014 (5)	−0.002 (5)	0.029 (5)
C36	0.053 (5)	0.093 (5)	0.088 (6)	0.011 (4)	−0.002 (4)	0.006 (4)
C37	0.056 (5)	0.067 (4)	0.078 (5)	0.005 (4)	0.010 (4)	0.006 (3)
C38	0.063 (4)	0.045 (3)	0.052 (4)	0.007 (3)	0.008 (3)	0.001 (3)
C39	0.083 (6)	0.068 (4)	0.069 (5)	0.015 (4)	0.022 (4)	0.002 (4)
C40	0.107 (7)	0.097 (5)	0.065 (5)	0.026 (5)	0.030 (5)	−0.007 (4)
C41	0.110 (7)	0.095 (5)	0.054 (5)	−0.004 (5)	0.019 (5)	−0.011 (4)
C42	0.097 (6)	0.086 (5)	0.055 (5)	−0.006 (5)	−0.004 (4)	−0.008 (4)
C43	0.079 (5)	0.072 (4)	0.062 (5)	0.006 (4)	0.012 (4)	0.000 (4)

Geometric parameters (Å, º)

Ru1—N1	1.954 (4)	C17—H17B	0.9600
Ru1—N4	2.067 (4)	C17—H17C	0.9600
Ru1—N2	2.119 (4)	C18—C19	1.366 (7)
Ru1—P1	2.3890 (14)	C18—C23	1.369 (7)
Ru1—Cl2	2.4034 (17)	C19—C20	1.368 (7)
Ru1—Cl1	2.4106 (17)	C19—H19	0.9300
P1—C32	1.821 (6)	C20—C21	1.386 (8)
P1—C26	1.843 (6)	C20—H20	0.9300
P1—C38	1.847 (5)	C21—C22	1.399 (8)
N1—C1	1.348 (6)	C22—C23	1.389 (7)
N1—C5	1.355 (6)	C22—H22	0.9300
N2—C6	1.310 (6)	C23—H23	0.9300
N2—C8	1.443 (7)	C24—H24A	0.9600
N3—C11	1.379 (7)	C24—H24B	0.9600
N3—C14	1.439 (9)	C24—H24C	0.9600
N3—C15	1.439 (9)	C25—H25A	0.9600
N4—C16	1.320 (6)	C25—H25B	0.9600
N4—C18	1.448 (6)	C25—H25C	0.9600
N5—C21	1.396 (7)	C26—C27	1.390 (8)
N5—C24	1.428 (7)	C26—C31	1.402 (7)
N5—C25	1.430 (8)	C27—C28	1.400 (8)
C1—C2	1.398 (7)	C27—H27	0.9300
C1—C16	1.446 (7)	C28—C29	1.343 (9)
C2—C3	1.365 (8)	C28—H28	0.9300
C2—H2	0.9300	C29—C30	1.375 (10)
C3—C4	1.363 (8)	C29—H29	0.9300
C3—H3	0.9300	C30—C31	1.355 (9)
C4—C5	1.384 (7)	C30—H30	0.9300
C4—H4	0.9300	C31—H31	0.9300
C5—C6	1.452 (7)	C32—C37	1.390 (8)
C6—C7	1.498 (7)	C32—C33	1.389 (7)
C7—H7A	0.9600	C33—C34	1.393 (8)
C7—H7B	0.9600	C33—H33	0.9300
C7—H7C	0.9600	C34—C35	1.376 (9)
C8—C13	1.370 (8)	C34—H34	0.9300
C8—C9	1.377 (8)	C35—C36	1.342 (8)
C9—C10	1.379 (8)	C35—H35	0.9300
C9—H9	0.9300	C36—C37	1.389 (8)
C10—C11	1.391 (8)	C36—H36	0.9300
C10—H10	0.9300	C37—H37	0.9300
C11—C12	1.384 (8)	C38—C39	1.377 (7)
C12—C13	1.390 (7)	C38—C43	1.408 (8)
C12—H12	0.9300	C39—C40	1.401 (8)
C13—H13	0.9300	C39—H39	0.9300
C14—H14A	0.9600	C40—C41	1.347 (9)
C14—H14B	0.9600	C40—H40	0.9300
C14—H14C	0.9600	C41—C42	1.378 (9)
C15—H15A	0.9600	C41—H41	0.9300
C15—H15B	0.9600	C42—C43	1.370 (7)
C15—H15C	0.9600	C42—H42	0.9300
C16—C17	1.498 (7)	C43—H43	0.9300
C17—H17A	0.9600
N1—Ru1—N4	77.64 (17)	C1—C16—C17	120.0 (5)
N1—Ru1—N2	77.60 (18)	C16—C17—H17A	109.5
N4—Ru1—N2	154.96 (19)	C16—C17—H17B	109.5
N1—Ru1—P1	175.78 (15)	H17A—C17—H17B	109.5
N4—Ru1—P1	102.35 (12)	C16—C17—H17C	109.5
N2—Ru1—P1	102.62 (14)	H17A—C17—H17C	109.5
N1—Ru1—Cl2	89.68 (14)	H17B—C17—H17C	109.5
N4—Ru1—Cl2	88.73 (13)	C19—C18—C23	118.5 (5)
N2—Ru1—Cl2	87.50 (12)	C19—C18—N4	121.1 (5)
P1—Ru1—Cl2	94.54 (6)	C23—C18—N4	120.4 (5)
N1—Ru1—Cl1	84.93 (14)	C18—C19—C20	120.7 (6)
N4—Ru1—Cl1	88.13 (13)	C18—C19—H19	119.7
N2—Ru1—Cl1	93.32 (12)	C20—C19—H19	119.7
P1—Ru1—Cl1	90.85 (5)	C19—C20—C21	122.6 (6)
Cl2—Ru1—Cl1	174.23 (5)	C19—C20—H20	118.7
C32—P1—C26	103.0 (2)	C21—C20—H20	118.7
C32—P1—C38	102.9 (3)	C20—C21—N5	122.7 (6)
C26—P1—C38	95.2 (3)	C20—C21—C22	116.4 (6)
C32—P1—Ru1	115.64 (18)	N5—C21—C22	120.9 (6)
C26—P1—Ru1	117.4 (2)	C23—C22—C21	120.4 (6)
C38—P1—Ru1	119.52 (19)	C23—C22—H22	119.8
C1—N1—C5	121.0 (5)	C21—C22—H22	119.8
C1—N1—Ru1	119.5 (3)	C18—C23—C22	121.4 (6)
C5—N1—Ru1	119.4 (4)	C18—C23—H23	119.3
C6—N2—C8	118.9 (4)	C22—C23—H23	119.3
C6—N2—Ru1	113.8 (4)	N5—C24—H24A	109.5
C8—N2—Ru1	127.1 (3)	N5—C24—H24B	109.5
C11—N3—C14	121.5 (7)	H24A—C24—H24B	109.5
C11—N3—C15	120.3 (7)	N5—C24—H24C	109.5
C14—N3—C15	116.9 (6)	H24A—C24—H24C	109.5
C16—N4—C18	116.3 (5)	H24B—C24—H24C	109.5
C16—N4—Ru1	115.2 (4)	N5—C25—H25A	109.5
C18—N4—Ru1	128.4 (3)	N5—C25—H25B	109.5
C21—N5—C24	118.8 (6)	H25A—C25—H25B	109.5
C21—N5—C25	118.6 (6)	N5—C25—H25C	109.5
C24—N5—C25	117.6 (6)	H25A—C25—H25C	109.5
N1—C1—C2	119.8 (5)	H25B—C25—H25C	109.5
N1—C1—C16	112.4 (5)	C27—C26—C31	117.8 (6)
C2—C1—C16	127.8 (6)	C27—C26—P1	120.4 (5)
C3—C2—C1	118.9 (6)	C31—C26—P1	121.6 (5)
C3—C2—H2	120.5	C26—C27—C28	119.7 (7)
C1—C2—H2	120.5	C26—C27—H27	120.2
C4—C3—C2	120.9 (5)	C28—C27—H27	120.2
C4—C3—H3	119.6	C29—C28—C27	121.0 (8)
C2—C3—H3	119.6	C29—C28—H28	119.5
C3—C4—C5	119.3 (6)	C27—C28—H28	119.5
C3—C4—H4	120.3	C28—C29—C30	119.7 (8)
C5—C4—H4	120.3	C28—C29—H29	120.2
N1—C5—C4	120.0 (6)	C30—C29—H29	120.2
N1—C5—C6	112.9 (5)	C31—C30—C29	121.1 (7)
C4—C5—C6	127.1 (6)	C31—C30—H30	119.5
N2—C6—C5	116.0 (5)	C29—C30—H30	119.5
N2—C6—C7	126.0 (5)	C30—C31—C26	120.7 (7)
C5—C6—C7	117.5 (5)	C30—C31—H31	119.6
C6—C7—H7A	109.5	C26—C31—H31	119.6
C6—C7—H7B	109.5	C37—C32—C33	116.2 (6)
H7A—C7—H7B	109.5	C37—C32—P1	120.6 (5)
C6—C7—H7C	109.5	C33—C32—P1	123.0 (5)
H7A—C7—H7C	109.5	C32—C33—C34	122.2 (7)
H7B—C7—H7C	109.5	C32—C33—H33	118.9
C13—C8—C9	118.0 (6)	C34—C33—H33	118.9
C13—C8—N2	119.2 (5)	C35—C34—C33	118.4 (7)
C9—C8—N2	122.8 (6)	C35—C34—H34	120.8
C8—C9—C10	121.4 (6)	C33—C34—H34	120.8
C8—C9—H9	119.3	C36—C35—C34	121.4 (7)
C10—C9—H9	119.3	C36—C35—H35	119.3
C9—C10—C11	121.5 (6)	C34—C35—H35	119.3
C9—C10—H10	119.2	C35—C36—C37	119.7 (7)
C11—C10—H10	119.2	C35—C36—H36	120.2
N3—C11—C12	122.5 (7)	C37—C36—H36	120.2
N3—C11—C10	121.2 (7)	C36—C37—C32	122.0 (6)
C12—C11—C10	116.3 (6)	C36—C37—H37	119.0
C11—C12—C13	122.1 (6)	C32—C37—H37	119.0
C11—C12—H12	119.0	C39—C38—C43	118.2 (6)
C13—C12—H12	119.0	C39—C38—P1	125.7 (5)
C8—C13—C12	120.7 (6)	C43—C38—P1	115.8 (4)
C8—C13—H13	119.6	C38—C39—C40	120.1 (7)
C12—C13—H13	119.6	C38—C39—H39	119.9
N3—C14—H14A	109.5	C40—C39—H39	119.9
N3—C14—H14B	109.5	C41—C40—C39	120.4 (7)
H14A—C14—H14B	109.5	C41—C40—H40	119.8
N3—C14—H14C	109.5	C39—C40—H40	119.8
H14A—C14—H14C	109.5	C40—C41—C42	120.7 (7)
H14B—C14—H14C	109.5	C40—C41—H41	119.6
N3—C15—H15A	109.5	C42—C41—H41	119.6
N3—C15—H15B	109.5	C43—C42—C41	119.6 (6)
H15A—C15—H15B	109.5	C43—C42—H42	120.2
N3—C15—H15C	109.5	C41—C42—H42	120.2
H15A—C15—H15C	109.5	C42—C43—C38	120.9 (6)
H15B—C15—H15C	109.5	C42—C43—H43	119.6
N4—C16—C1	115.1 (5)	C38—C43—H43	119.6
N4—C16—C17	124.9 (6)
N4—Ru1—P1—C32	−100.4 (3)	C9—C10—C11—C12	2.8 (9)
N2—Ru1—P1—C32	77.8 (3)	N3—C11—C12—C13	−179.9 (6)
Cl2—Ru1—P1—C32	−10.7 (2)	C10—C11—C12—C13	−2.2 (9)
Cl1—Ru1—P1—C32	171.4 (2)	C9—C8—C13—C12	1.1 (9)
N4—Ru1—P1—C26	137.7 (2)	N2—C8—C13—C12	−176.9 (5)
N2—Ru1—P1—C26	−44.2 (2)	C11—C12—C13—C8	0.4 (9)
Cl2—Ru1—P1—C26	−132.6 (2)	C18—N4—C16—C1	177.6 (5)
Cl1—Ru1—P1—C26	49.4 (2)	Ru1—N4—C16—C1	1.6 (7)
N4—Ru1—P1—C38	23.4 (3)	C18—N4—C16—C17	−2.0 (9)
N2—Ru1—P1—C38	−158.4 (2)	Ru1—N4—C16—C17	−177.9 (5)
Cl2—Ru1—P1—C38	113.1 (2)	N1—C1—C16—N4	−4.3 (8)
Cl1—Ru1—P1—C38	−64.8 (2)	C2—C1—C16—N4	176.1 (6)
N4—Ru1—N1—C1	−3.4 (4)	N1—C1—C16—C17	175.3 (6)
N2—Ru1—N1—C1	−179.7 (5)	C2—C1—C16—C17	−4.3 (10)
Cl2—Ru1—N1—C1	−92.2 (4)	C16—N4—C18—C19	82.8 (7)
Cl1—Ru1—N1—C1	85.8 (4)	Ru1—N4—C18—C19	−101.9 (6)
N4—Ru1—N1—C5	−178.3 (5)	C16—N4—C18—C23	−96.5 (7)
N2—Ru1—N1—C5	5.4 (4)	Ru1—N4—C18—C23	78.8 (6)
Cl2—Ru1—N1—C5	92.9 (4)	C23—C18—C19—C20	0.0 (9)
Cl1—Ru1—N1—C5	−89.1 (4)	N4—C18—C19—C20	−179.4 (5)
N1—Ru1—N2—C6	−3.6 (4)	C18—C19—C20—C21	0.8 (10)
N4—Ru1—N2—C6	−12.2 (7)	C19—C20—C21—N5	179.2 (6)
P1—Ru1—N2—C6	172.1 (4)	C19—C20—C21—C22	−0.6 (9)
Cl2—Ru1—N2—C6	−93.8 (4)	C24—N5—C21—C20	20.4 (9)
Cl1—Ru1—N2—C6	80.5 (4)	C25—N5—C21—C20	175.1 (7)
N1—Ru1—N2—C8	171.0 (5)	C24—N5—C21—C22	−159.8 (6)
N4—Ru1—N2—C8	162.4 (4)	C25—N5—C21—C22	−5.1 (9)
P1—Ru1—N2—C8	−13.3 (5)	C20—C21—C22—C23	−0.3 (9)
Cl2—Ru1—N2—C8	80.8 (4)	N5—C21—C22—C23	179.9 (5)
Cl1—Ru1—N2—C8	−104.9 (4)	C19—C18—C23—C22	−0.8 (9)
N1—Ru1—N4—C16	0.8 (4)	N4—C18—C23—C22	178.5 (5)
N2—Ru1—N4—C16	9.4 (7)	C21—C22—C23—C18	1.0 (9)
P1—Ru1—N4—C16	−174.9 (4)	C32—P1—C26—C27	−129.9 (4)
Cl2—Ru1—N4—C16	90.8 (4)	C38—P1—C26—C27	125.5 (5)
Cl1—Ru1—N4—C16	−84.4 (4)	Ru1—P1—C26—C27	−1.7 (5)
N1—Ru1—N4—C18	−174.5 (5)	C32—P1—C26—C31	55.2 (6)
N2—Ru1—N4—C18	−165.9 (4)	C38—P1—C26—C31	−49.4 (5)
P1—Ru1—N4—C18	9.8 (5)	Ru1—P1—C26—C31	−176.5 (4)
Cl2—Ru1—N4—C18	−84.6 (5)	C31—C26—C27—C28	−1.0 (9)
Cl1—Ru1—N4—C18	100.3 (5)	P1—C26—C27—C28	−176.1 (5)
C5—N1—C1—C2	−0.4 (9)	C26—C27—C28—C29	0.7 (10)
Ru1—N1—C1—C2	−175.2 (5)	C27—C28—C29—C30	−1.4 (12)
C5—N1—C1—C16	180.0 (6)	C28—C29—C30—C31	2.5 (13)
Ru1—N1—C1—C16	5.2 (7)	C29—C30—C31—C26	−2.9 (12)
N1—C1—C2—C3	2.2 (10)	C27—C26—C31—C30	2.1 (10)
C16—C1—C2—C3	−178.2 (6)	P1—C26—C31—C30	177.1 (5)
C1—C2—C3—C4	−2.5 (10)	C26—P1—C32—C37	−166.8 (5)
C2—C3—C4—C5	1.1 (10)	C38—P1—C32—C37	−68.3 (5)
C1—N1—C5—C4	−1.1 (9)	Ru1—P1—C32—C37	63.8 (5)
Ru1—N1—C5—C4	173.6 (4)	C26—P1—C32—C33	17.1 (6)
C1—N1—C5—C6	178.9 (5)	C38—P1—C32—C33	115.6 (5)
Ru1—N1—C5—C6	−6.3 (7)	Ru1—P1—C32—C33	−112.2 (5)
C3—C4—C5—N1	0.8 (9)	C37—C32—C33—C34	−3.1 (9)
C3—C4—C5—C6	−179.3 (6)	P1—C32—C33—C34	173.2 (5)
C8—N2—C6—C5	−173.7 (6)	C32—C33—C34—C35	4.4 (11)
Ru1—N2—C6—C5	1.4 (7)	C33—C34—C35—C36	−2.1 (12)
C8—N2—C6—C7	−1.6 (9)	C34—C35—C36—C37	−1.1 (12)
Ru1—N2—C6—C7	173.5 (5)	C35—C36—C37—C32	2.4 (10)
N1—C5—C6—N2	2.9 (8)	C33—C32—C37—C36	−0.3 (9)
C4—C5—C6—N2	−177.0 (6)	P1—C32—C37—C36	−176.6 (5)
N1—C5—C6—C7	−169.9 (5)	C32—P1—C38—C39	5.1 (6)
C4—C5—C6—C7	10.1 (10)	C26—P1—C38—C39	109.8 (6)
C6—N2—C8—C13	118.5 (6)	Ru1—P1—C38—C39	−124.6 (5)
Ru1—N2—C8—C13	−55.9 (7)	C32—P1—C38—C43	−167.7 (5)
C6—N2—C8—C9	−59.4 (7)	C26—P1—C38—C43	−63.1 (5)
Ru1—N2—C8—C9	126.3 (5)	Ru1—P1—C38—C43	62.5 (5)
C13—C8—C9—C10	−0.5 (9)	C43—C38—C39—C40	−0.1 (9)
N2—C8—C9—C10	177.3 (5)	P1—C38—C39—C40	−172.7 (5)
C8—C9—C10—C11	−1.4 (10)	C38—C39—C40—C41	−0.3 (11)
C14—N3—C11—C12	−167.6 (7)	C39—C40—C41—C42	−0.1 (12)
C15—N3—C11—C12	−1.1 (10)	C40—C41—C42—C43	0.9 (11)
C14—N3—C11—C10	14.8 (10)	C41—C42—C43—C38	−1.2 (10)
C15—N3—C11—C10	−178.7 (6)	C39—C38—C43—C42	0.8 (9)
C9—C10—C11—N3	−179.5 (6)	P1—C38—C43—C42	174.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C43—H43···Cl1	0.93	2.78	3.587 (6)	145
C13—H13···Cl2	0.93	2.73	3.518 (6)	143
C27—H27···Cl1	0.93	2.72	3.343 (7)	126
C2—H2···Cl2^i	0.93	2.79	3.580 (6)	144
C4—H4···Cl1^ii	0.93	2.81	3.588 (6)	142

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