A mixed chloride/tri­fluoro­methane­sulfonate ligand species in a ruthenium(II) complex

The compound [2-(amino­meth­yl)pyridine-[kappa]²N,N'][chlorido/tri­fluoro­methane­sulfonato­(0.91/0.09)][(10,11-[eta])-5H-dibenzo[a,d]cyclo­hepten-5-amine-[kappa]N](tri­phenyl­phosphane-[kappa]P)ru­then­ium(II) tri­fluoro­methane­sulfonate di­chloro­methane 0.91-sol­vate, [Ru(CF₃SO₃)_0.09Cl_0.91(C₆H₈N₂)(C₁₅H₁₃N)(C₁₈H₁₅P)]CF₃SO₃·0.91CH₂Cl₂, belongs to a series of Ru^II complexes that had been tested for transfer hydrogenation, hydrogenation of polar bonds and catalytic transfer hydrogenation. The crystal structure determination of this complex revealed disorder in the form of two different anionic ligands sharing the same coordination site, which other spectroscopic methods failed to characterize. The reduced catalytic activity of the title compound was not fully understood until the crystallographic data provided evidence for the mixed ligand species. The crystal structure clearly shows that the majority of the synthesized material has a chloride ligand present. Only a small portion of the material is the expected complex [Ru^II(OTf)(ampy)([eta]²-tropNH₂)(PPh₃)]OTf, where OTf is triflate or tri­fluoro­methane­sul­fon­ate, ampy is 2-(amino­methyl)pyridine and tropNH₂ is 5H-di­benzo[a,d]cyclo­hep­ten-5-amine.

S1. Introduction

The pioneering work of Wilkinson & Stephenson (1966) on ruthenium(II) complexes containing either nitro­gen or phosphane ligands has a well known history. In the mid-1980s, Shvo & Blum (1984, 1985) used Ru^II catalysts to convert simple alcohols to esters and hydrogen and established the possible strategic role of a chemically non-innocent co-operative ligand in the coordination sphere of a metal catalyst. Using commercially available 2-(amino­methyl)­pyridine (ampy), Baratta et al. (2005) reported on Ru^II catalysts with a remarkable acceleration effect for the transfer hydrogenation from propan-2-ol to ketones.

In the past decade, the concept of non-innocent co-operative ligands for such catalytic processes has been further studied and developed by Milstein et al. (2005, 2007). Grützmacher and co-workers [Grützmacher, Annen et al. (2010), Grützmacher, Trincado et al. (2010)] have used this concept with various tropX ligands (X = N, for example) and various metal centres for the catalytic conversion under mild conditions of primary alcohols, polyols and sugars in the presence of water and a hydrogen acceptor to carboxyl­ates as products. Very recently, they have reported (Grützmacher, et al., 2013) the catalytic conversion of water and methanol into CO₂ and H₂ using Ru^II(tropN) complexes.

S2. Experimental

S2.1. Synthesis and crystallization

A precursor of the title compound, (I), was prepared by reacting trans,cis-[RuCl₂(PPh₃)₂(ampy)] (120 mg, 0.15 mmol) (Baratta et al., 2005) and tropNH₂ (tropNH₂ = 5H-dibenzo[a,d]cyclo­hepten-5-amine) (37 mg, 0.18 mmol) (Grützmacher et al., 2004) in a 25 ml two-necked round-bottomed flask which was connected to a reflux condenser with an argon inlet. The second neck was septum-capped. The air and moisture were purged with argon-vacuum cycles for 20 min. Dry and degassed tetra­hydro­furan (THF, 10 ml) was added with a syringe and the reaction mixture was stirred vigorously at 338 K overnight. The yellow suspension was allowed to cool to room temperature and di­ethyl ether (10 ml) was added. The obtained yellow precipitate was filtered, washed with ether (3 × 5 ml) and dried under reduced pressure.

The species [RuCl₂(ampy)(tropNH₂)(PPh₃)], (II), or [RuCl(ampy)(η²-tropNH₂)(PPh₃)]Cl, (III), were expected. All attempts to crystallize these compounds were unsuccessful, mainly due to their poor solubility in common organic solvents. Chlorine abstraction was performed in order to improve the solubility of the product.

The presumed (II) or (III) (~11 µmol) and AgOTf (silver triflate or silver tri­fluoro­methane­sulfonate; 5 mg, 19.5 µmol) were combined in an NMR tube. Dry and degassed di­chloro­methane (DCM, 0.5 ml) was added and the mixture was shaken at room temperature. The progress of the reaction was monitored by means of ³¹P{¹H} NMR. After 4 h, the initial complex reacted almost qu­anti­tatively. ³¹P{¹H} NMR (121.5 MHz, 293 K): δ 55.9 (s, 1P), 54.2 (s, 0.1P); ¹⁹F{¹H} NMR (282.4 MHz, 293 K): δ -76.4 (s, 3F), -75.5 (s, 0.08F). Based on the ³¹P and ¹⁹F NMR analyses in solution, two different species seem to be present. The mixture was filtered and n-hexane was layered on the clear orange filtrate. After slow evaporation of the solvent mixture, re­cta­ngular light-yellow single crystal platelets of (I) were obtained. Only one crystal out of the sample was analyzed. No elemental microanalysis of the whole batch of crystals could be performed as the number of crystal obtained was very few. The crystal structure analysis also shows the presence of two different species. For the rest of crystals obtained, no further analyses were performed.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Most of the H atoms present were found in a difference Fourier map and were refined freely. Those H atoms which after the refinement did not refine properly were placed in idealized positions and refined using a riding model with appropriate displacement parameters of U_iso(H) = 1.2U_eq(parent). Default effective X—H distances for T = 100 K were C—H = 1.00 (NCR₂), 0.99 (methyl­ene), 0.95 (aromatic) and N—H 0.88 Å (amine).

S3. Results and discussion

The title compound, (I) (see Scheme), has been synthesized as part of studies of possible transfer hydrogenation, hydrogenation of polar bonds and hydrogen activation. Compound (I) was mainly tested for catalytic transfer hydrogenation. The catalytic experiments performed did show some activity, but the results were not as competitive as those reported previously by Baratta et al. (2005).

We report herein the crystal structure of (I) which shows a mixed anionic system occupying the same crystallographic position. The cation of (I) has typical o­cta­hedral environment coordination for the six-coordinated central Ru^II atom (Table 1). A C═C π-bond, two N and one P atom are part of the equatorial plane. Another N atom can be found in one of the apical positions. The other apical position is either occupied by a chloride or a OTf^- anion. To balance the charge of the whole complex, one more OTf^- is present as a counter-ion (Fig 1). Complex (I) can be better described as mixture of [Ru^IICl(ampy)(η²-tropNH₂)(PPh₃)]OTf.CH₂Cl₂, (Ia), and [Ru^II(OTf)(ampy)(η²-tropNH₂)(PPh₃)]OTf (OTF is triflate or tri­fluoro­methansiulfonate), (Ib). The structures of (Ia) and (Ib) are shown in Fig. 2.

In (I), two different ions (Cl^- and OTf^-) occupy the same crystallographic position (Fig. 1). The main part of the structure (91.4%) shows the coordination of the chloride ion and a CH₂Cl₂ solvent molecule. The second portion (8.6%) shows only the OTf^- ion (Fig 2).

While modeling and refining the structural data of the complex, the solution with only the Cl^- (and CH₂Cl₂ molecule) gave reasonable and acceptable results (R = 0.0416, wR = 0.1082 and S = 1.027). The only peculiar situation seen after the refinement was a residual electron density (Q1) of 1.98 e Å^-3 lying ~1 Å from the chloride anion in the direction of the Ru—Cl bond (Fig. 2, left). An absorption correction did not improve the situation and the residual electron density was still observed in the same position.

After refining the chloride anion with an independent variable, the rest of the OTf^- fragment was observed. Q1 was clearly the S atom of the anion and the next three residual electron densities (Q2–Q4) had close contacts to Q1. After assigning a sulfur atom (S2A; Fig. 1) to Q1 and O atoms to the other three Q's, a complete OTf^- ion was observed which could later be taken as part of the refinement. This OTf^- fragment in (Ib) was modeled using SADI constraints in SHELXTL (Sheldrick, 2008) to avoid unstable refinements do to the overlapping of the other portion (Cl^- and CH₂Cl₂). The refinement with these two independent anions clearly improved the overall statistics for the solution (R = 0.0341, wR = 0.0811 and S = 1.031).

Only after elucidating the single-crystal X-ray structure, it was understood why the catalytic activity of (I) was not as promising as expected. The parent complexes [RuCl₂(ampy)(tropNH₂)(PPh₃)], (II), or [RuCl(ampy)(η²-tropNH₂)(PPh₃)]Cl, (III), were sparingly soluble in any organic solvent. The reaction of either one of them with an excess of AgOTf produced (I) and AgCl. Compound (I) is more soluble in organic solvents than the parent complexes (II) and (III), but its solubility is still not good. The single-crystal X-ray determination shows, that the exchange of Cl^- with OTf^- was not completely achieved. The observed low solubility of (I) can be mainly attributed to the high percentage of molecules present in the form (Ia) and the low percentage in the form (Ib). All further experimental attempts to fully extract the chloride anion resulted in the same situation. No further catalytical test were performed on this system.

Related literature

For related literature, see: Baratta et al. (2005); Grützmacher et al. (2004, 2013); Grützmacher, Annen, Bambagioni, Bevilacqua, Filippi, Marchionni, Oberhauser, Schönberg, Vizza & Bianchini (2010); Grützmacher, Trincado, Vizza & Bianchini (2010); Milstein et al. (2005, 2007); Sheldrick (2008); Shvo & Blum (1984, 1985); Wilkinson & Stephenson (1966).

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the Ru^II complex and the two different ions (Cl^- and OTf^-) occupying the same crystallographic position. The counter-ion (OTf^-) and a solvent molecule (CH2Cl2) are also shown. Displacement ellipsoids shown at a 50% probability level. All H atoms have been omitted for clarity.
	Fig. 2. Left: the molecular structure of (Ia), showing the main portion with the Cl^- and CH2Cl2 solvent molecule (91.4%). The highest residual electron density (Q1, before refining the two portions) is also shown. Right: (Ib), showing the OTf^- ion (8.6%). Displacement ellipsoids drawn at the 50% probability level. All H atoms have been omitted for clarity.

[2-(Aminomethyl)pyridine-κ²N,N'][chlorido/trifluoromethanesulfonato(0.91/0.09)][(10,11-η)-5H-dibenzo[a,d]cyclohepten-5-amine-κN](triphenylphosphane-κP)ruthenium(II) trifluoromethanesulfonate dichloromethane 0.91-solvate,

Crystal data

[Ru(Cl)0.91(CF3SO3)0.09(C6H8N2)(C15H13N)(C18H15P)] CF3SO3·0.91CH2Cl2	F(000) = 1933
Mr = 950.79	Dx = 1.610 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6919 reflections
a = 14.374 (3) Å	θ = 2.3–25.0°
b = 15.875 (3) Å	µ = 0.75 mm^−1
c = 17.235 (3) Å	T = 100 K
β = 94.019 (4)°	Platelet, light yellow
V = 3923.1 (12) Å^3	0.30 × 0.15 × 0.02 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	6919 independent reflections
Radiation source: fine-focus sealed tube	5507 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2012)	h = −14→17
Tmin = 0.807, Tmax = 0.985	k = −18→18
37064 measured reflections	l = −20→20

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0348P)^2 + 4.730P] where P = (Fo^2 + 2Fc^2)/3
6919 reflections	(Δ/σ)max = 0.001
633 parameters	Δρmax = 0.91 e Å^−3
19 restraints	Δρmin = −0.60 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	Occ. (<1)
S1A	0.40041 (6)	0.50336 (5)	0.86059 (4)	0.02054 (18)
O1A	0.38103 (17)	0.41953 (13)	0.83163 (13)	0.0285 (5)
O1B	0.40893 (18)	0.50907 (16)	0.94324 (13)	0.0379 (6)
O1C	0.46730 (16)	0.54959 (13)	0.81939 (13)	0.0284 (5)
C1A	0.2919 (2)	0.5577 (2)	0.8339 (2)	0.0307 (8)
F1A	0.22144 (14)	0.52617 (13)	0.87042 (12)	0.0391 (5)
F1B	0.29907 (16)	0.63922 (12)	0.85265 (16)	0.0584 (7)
F1C	0.27027 (15)	0.55322 (15)	0.75829 (13)	0.0505 (6)
Ru1	0.295976 (18)	0.303490 (15)	0.388544 (14)	0.01672 (8)
Cl1	0.21086 (7)	0.32630 (5)	0.50401 (7)	0.0217 (2)	0.914 (2)
S2A	0.1827 (9)	0.3147 (6)	0.5465 (8)	0.036 (3)	0.086 (2)
O2A	0.190 (2)	0.3297 (18)	0.4640 (12)	0.038 (6)*	0.086 (2)
O2B	0.2028 (18)	0.3883 (13)	0.5919 (14)	0.038 (6)*	0.086 (2)
O2C	0.2188 (18)	0.2353 (12)	0.5735 (15)	0.040 (8)*	0.086 (2)
C2A	0.0575 (13)	0.3035 (16)	0.5538 (15)	0.041 (11)*	0.086 (2)
F2A	0.019 (2)	0.2411 (18)	0.5114 (17)	0.077 (7)*	0.086 (2)
F2B	0.044 (2)	0.282 (2)	0.6275 (15)	0.077 (7)*	0.086 (2)
F2C	0.0108 (19)	0.3733 (16)	0.5357 (18)	0.077 (7)*	0.086 (2)
N1	0.3605 (2)	0.20328 (17)	0.45604 (17)	0.0209 (6)
N2	0.34610 (17)	0.25516 (15)	0.28486 (14)	0.0185 (6)
H2A	0.3752	0.2978	0.2597	0.022*
H2B	0.3898	0.2142	0.2974	0.022*
N3	0.19411 (18)	0.21017 (15)	0.35030 (16)	0.0221 (6)
P1	0.21054 (6)	0.41371 (5)	0.32907 (5)	0.01756 (18)
C1	0.4563 (2)	0.21272 (18)	0.49473 (17)	0.0180 (7)
H1	0.4738	0.1587	0.5217	0.022*
C2	0.4592 (2)	0.28222 (18)	0.55465 (18)	0.0191 (7)
C3	0.4299 (2)	0.36354 (19)	0.53325 (18)	0.0196 (7)
C4	0.3972 (2)	0.38813 (19)	0.45401 (18)	0.0191 (7)
C5	0.4365 (2)	0.36026 (19)	0.38720 (18)	0.0185 (7)
C6	0.5154 (2)	0.30079 (19)	0.38592 (16)	0.0175 (6)
C7	0.5260 (2)	0.22997 (18)	0.43529 (17)	0.0178 (7)
C8	0.4367 (2)	0.4272 (2)	0.58989 (19)	0.0225 (7)
C9	0.4737 (2)	0.4115 (2)	0.66425 (19)	0.0229 (7)
C10	0.5033 (2)	0.3312 (2)	0.68424 (18)	0.0232 (7)
H10	0.5294	0.3200	0.7354	0.028*
C11	0.4951 (2)	0.2668 (2)	0.62993 (18)	0.0212 (7)
C12	0.5843 (2)	0.3171 (2)	0.33549 (18)	0.0204 (7)
C13	0.6629 (2)	0.2665 (2)	0.33391 (18)	0.0239 (7)
H13	0.7104	0.2800	0.3004	0.029*
C14	0.6717 (2)	0.1962 (2)	0.38131 (18)	0.0242 (7)
H14	0.7247	0.1606	0.3797	0.029*
C15	0.6032 (2)	0.1782 (2)	0.43093 (18)	0.0214 (7)
C16	0.2721 (2)	0.2192 (2)	0.2317 (2)	0.0226 (7)
C17	0.1999 (2)	0.18044 (18)	0.2775 (2)	0.0240 (7)
C18	0.1396 (3)	0.1194 (2)	0.2458 (2)	0.0311 (8)
C19	0.0718 (3)	0.0878 (2)	0.2901 (3)	0.0393 (10)
C20	0.0668 (3)	0.1160 (2)	0.3648 (2)	0.0377 (9)
H20	0.0210	0.0940	0.3964	0.045*
C21	0.1288 (2)	0.1764 (2)	0.3938 (2)	0.0297 (8)
H21	0.1255	0.1950	0.4459	0.036*
C22	0.0842 (2)	0.40524 (19)	0.33985 (18)	0.0218 (7)
C23	0.0373 (2)	0.4623 (2)	0.3848 (2)	0.0268 (8)
C24	−0.0572 (3)	0.4534 (2)	0.3935 (2)	0.0321 (9)
C25	−0.1061 (3)	0.3884 (3)	0.3574 (2)	0.0344 (9)
C26	−0.0617 (2)	0.3312 (2)	0.3127 (2)	0.0342 (9)
H26	−0.0958	0.2866	0.2874	0.041*
C27	0.0335 (2)	0.3393 (2)	0.3046 (2)	0.0281 (8)
C28	0.2352 (2)	0.52026 (18)	0.36621 (17)	0.0176 (7)
C29	0.2453 (2)	0.5884 (2)	0.31748 (19)	0.0264 (8)
H29	0.2387	0.5809	0.2627	0.032*
C30	0.2650 (3)	0.6676 (2)	0.3484 (2)	0.0338 (9)
C31	0.2759 (3)	0.6794 (2)	0.4268 (2)	0.0297 (8)
C32	0.2654 (2)	0.6129 (2)	0.47650 (19)	0.0284 (8)
H32	0.2729	0.6210	0.5312	0.034*
C33	0.2437 (2)	0.5341 (2)	0.44621 (19)	0.0241 (7)
C34	0.2170 (2)	0.42930 (18)	0.22363 (17)	0.0187 (7)
C35	0.1394 (3)	0.4336 (2)	0.1710 (2)	0.0267 (8)
C36	0.1491 (3)	0.4468 (2)	0.0933 (2)	0.0327 (9)
C37	0.2365 (3)	0.4572 (2)	0.0655 (2)	0.0297 (8)
C38	0.3148 (2)	0.45337 (19)	0.11721 (18)	0.0239 (7)
H38	0.3752	0.4602	0.0989	0.029*
C39	0.3050 (2)	0.43958 (18)	0.19505 (18)	0.0211 (7)
H39	0.3590	0.4370	0.2300	0.025*
Cl3	−0.09367 (10)	0.16483 (10)	0.51644 (11)	0.0837 (6)	0.914 (2)
Cl4	−0.01010 (11)	0.28812 (11)	0.62236 (8)	0.0703 (5)	0.914 (2)
C50	−0.0482 (3)	0.2672 (3)	0.5272 (3)	0.0442 (11)	0.914 (2)
H50A	0.0046	0.2737	0.4937	0.053*	0.914 (2)
H50B	−0.0969	0.3085	0.5099	0.053*	0.914 (2)
H1A	0.323 (3)	0.194 (2)	0.492 (2)	0.030 (10)*
H1B	0.360 (2)	0.160 (2)	0.426 (2)	0.031 (10)*
H4	0.373 (2)	0.444 (2)	0.4507 (17)	0.017 (8)*
H5	0.432 (2)	0.3958 (19)	0.3446 (17)	0.016 (8)*
H8	0.419 (2)	0.479 (2)	0.5771 (17)	0.015 (8)*
H9	0.479 (2)	0.456 (2)	0.7017 (18)	0.022 (9)*
H11	0.514 (2)	0.213 (2)	0.6447 (17)	0.015 (8)*
H12	0.583 (2)	0.361 (2)	0.3041 (18)	0.019 (9)*
H15	0.608 (2)	0.131 (2)	0.4639 (18)	0.020 (8)*
H16A	0.300 (2)	0.182 (2)	0.1965 (18)	0.019 (8)*
H16B	0.242 (2)	0.264 (2)	0.1990 (19)	0.029 (9)*
H18	0.149 (2)	0.103 (2)	0.194 (2)	0.034 (10)*
H19	0.029 (3)	0.048 (3)	0.274 (2)	0.052 (12)*
H23	0.069 (2)	0.508 (2)	0.4062 (19)	0.025 (9)*
H24	−0.089 (3)	0.490 (2)	0.423 (2)	0.037 (11)*
H25	−0.170 (3)	0.383 (2)	0.361 (2)	0.039 (11)*
H27	0.057 (2)	0.305 (2)	0.2712 (19)	0.024 (9)*
H30	0.269 (3)	0.712 (3)	0.315 (2)	0.053 (13)*
H31	0.286 (2)	0.733 (2)	0.4452 (19)	0.029 (9)*
H33	0.236 (2)	0.488 (2)	0.4800 (19)	0.031 (10)*
H35	0.083 (2)	0.427 (2)	0.1878 (18)	0.021 (9)*
H36	0.099 (3)	0.450 (2)	0.059 (2)	0.032 (10)*
H37	0.242 (2)	0.469 (2)	0.014 (2)	0.023 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1A	0.0245 (5)	0.0140 (4)	0.0229 (4)	0.0002 (3)	0.0002 (3)	−0.0005 (3)
O1A	0.0369 (15)	0.0135 (11)	0.0359 (13)	−0.0021 (10)	0.0083 (11)	−0.0033 (10)
O1B	0.0441 (17)	0.0441 (16)	0.0249 (13)	−0.0019 (12)	−0.0020 (12)	−0.0052 (11)
O1C	0.0249 (13)	0.0196 (12)	0.0413 (14)	−0.0041 (10)	0.0061 (11)	−0.0010 (10)
C1A	0.026 (2)	0.0225 (19)	0.044 (2)	−0.0001 (15)	0.0037 (17)	0.0082 (15)
F1A	0.0262 (12)	0.0365 (12)	0.0557 (14)	−0.0011 (9)	0.0106 (10)	0.0091 (10)
F1B	0.0461 (15)	0.0149 (11)	0.116 (2)	0.0073 (10)	0.0177 (14)	0.0046 (12)
F1C	0.0354 (13)	0.0697 (16)	0.0442 (14)	−0.0091 (12)	−0.0130 (11)	0.0314 (12)
Ru1	0.01643 (14)	0.01125 (13)	0.02268 (14)	0.00005 (10)	0.00274 (10)	0.00178 (10)
Cl1	0.0234 (5)	0.0205 (5)	0.0218 (6)	0.0007 (4)	0.0061 (4)	0.0029 (4)
S2A	0.056 (9)	0.023 (6)	0.031 (7)	0.017 (5)	0.002 (6)	0.002 (5)
N1	0.0236 (16)	0.0145 (14)	0.0250 (15)	−0.0015 (12)	0.0047 (13)	0.0016 (12)
N2	0.0175 (15)	0.0138 (13)	0.0240 (14)	0.0006 (10)	0.0002 (11)	−0.0001 (10)
N3	0.0150 (14)	0.0150 (14)	0.0359 (16)	0.0005 (11)	−0.0003 (12)	0.0042 (11)
P1	0.0162 (4)	0.0126 (4)	0.0239 (4)	0.0006 (3)	0.0020 (3)	0.0008 (3)
C1	0.0195 (17)	0.0105 (15)	0.0242 (16)	0.0020 (12)	0.0021 (13)	0.0041 (12)
C2	0.0159 (17)	0.0168 (16)	0.0253 (17)	0.0004 (12)	0.0057 (13)	0.0010 (12)
C3	0.0190 (17)	0.0155 (16)	0.0245 (17)	−0.0009 (13)	0.0034 (13)	0.0016 (13)
C4	0.0220 (18)	0.0110 (15)	0.0241 (17)	0.0006 (13)	−0.0002 (14)	0.0012 (12)
C5	0.0216 (18)	0.0120 (15)	0.0216 (17)	−0.0072 (13)	−0.0021 (13)	0.0053 (13)
C6	0.0181 (17)	0.0189 (16)	0.0151 (15)	−0.0044 (13)	−0.0018 (12)	−0.0037 (12)
C7	0.0207 (18)	0.0152 (15)	0.0172 (16)	−0.0011 (13)	−0.0001 (13)	−0.0025 (12)
C8	0.0251 (19)	0.0138 (17)	0.0289 (19)	0.0021 (14)	0.0030 (14)	0.0028 (13)
C9	0.0239 (19)	0.0221 (18)	0.0232 (17)	−0.0024 (14)	0.0047 (14)	−0.0029 (14)
C10	0.0222 (19)	0.0304 (18)	0.0171 (16)	−0.0012 (14)	0.0029 (14)	0.0051 (13)
C11	0.0206 (18)	0.0191 (17)	0.0244 (18)	0.0038 (14)	0.0046 (14)	0.0050 (14)
C12	0.0228 (18)	0.0198 (17)	0.0186 (16)	−0.0072 (14)	0.0004 (13)	−0.0010 (14)
C13	0.0194 (18)	0.0310 (18)	0.0215 (17)	−0.0064 (15)	0.0025 (14)	−0.0069 (14)
C14	0.0197 (18)	0.0276 (18)	0.0253 (17)	0.0028 (14)	0.0013 (14)	−0.0118 (14)
C15	0.0243 (19)	0.0189 (17)	0.0207 (16)	0.0020 (14)	0.0008 (14)	−0.0007 (13)
C16	0.0227 (19)	0.0165 (17)	0.0280 (18)	−0.0010 (14)	−0.0023 (15)	−0.0031 (14)
C17	0.0195 (18)	0.0121 (16)	0.039 (2)	0.0040 (13)	−0.0063 (15)	−0.0004 (14)
C18	0.026 (2)	0.0210 (18)	0.046 (2)	−0.0033 (15)	−0.0038 (17)	−0.0020 (16)
C19	0.030 (2)	0.027 (2)	0.060 (3)	−0.0103 (17)	−0.007 (2)	−0.0014 (18)
C20	0.021 (2)	0.026 (2)	0.066 (3)	−0.0068 (16)	0.0033 (18)	0.0111 (18)
C21	0.023 (2)	0.0226 (18)	0.044 (2)	0.0024 (14)	0.0042 (16)	0.0071 (15)
C22	0.0176 (18)	0.0195 (17)	0.0285 (18)	0.0030 (13)	0.0027 (14)	0.0070 (13)
C23	0.023 (2)	0.0270 (19)	0.0304 (19)	0.0027 (15)	0.0038 (15)	0.0041 (15)
C24	0.023 (2)	0.043 (2)	0.031 (2)	0.0096 (17)	0.0083 (16)	0.0071 (17)
C25	0.017 (2)	0.047 (2)	0.039 (2)	0.0015 (17)	0.0009 (17)	0.0160 (18)
C26	0.022 (2)	0.034 (2)	0.046 (2)	−0.0067 (16)	−0.0059 (17)	0.0089 (17)
C27	0.024 (2)	0.0216 (18)	0.038 (2)	0.0003 (15)	−0.0031 (16)	0.0051 (16)
C28	0.0136 (16)	0.0153 (15)	0.0243 (17)	0.0019 (12)	0.0033 (13)	−0.0010 (13)
C29	0.035 (2)	0.0202 (17)	0.0239 (18)	−0.0033 (15)	0.0038 (15)	−0.0005 (13)
C30	0.055 (3)	0.0156 (17)	0.032 (2)	−0.0067 (16)	0.0116 (18)	0.0019 (15)
C31	0.034 (2)	0.0201 (19)	0.036 (2)	−0.0044 (15)	0.0063 (16)	−0.0081 (15)
C32	0.033 (2)	0.0286 (19)	0.0241 (18)	0.0075 (15)	0.0031 (15)	−0.0045 (15)
C33	0.026 (2)	0.0185 (17)	0.0280 (18)	0.0048 (14)	0.0066 (15)	0.0005 (14)
C34	0.0226 (18)	0.0098 (15)	0.0239 (17)	0.0046 (13)	0.0027 (14)	0.0008 (12)
C35	0.023 (2)	0.029 (2)	0.029 (2)	0.0055 (15)	0.0033 (16)	−0.0017 (15)
C36	0.028 (2)	0.038 (2)	0.031 (2)	0.0071 (17)	−0.0048 (18)	−0.0006 (16)
C37	0.042 (2)	0.0272 (19)	0.0201 (19)	0.0054 (16)	0.0023 (16)	0.0013 (14)
C38	0.0252 (19)	0.0176 (16)	0.0295 (19)	0.0023 (14)	0.0050 (15)	−0.0014 (13)
C39	0.0222 (18)	0.0140 (16)	0.0270 (18)	0.0020 (13)	0.0007 (14)	−0.0005 (13)
Cl3	0.0509 (9)	0.0730 (10)	0.1287 (14)	−0.0071 (7)	0.0182 (9)	−0.0514 (9)
Cl4	0.0626 (10)	0.0958 (12)	0.0512 (8)	−0.0110 (9)	−0.0062 (7)	−0.0104 (7)
C50	0.041 (3)	0.049 (3)	0.043 (3)	0.014 (2)	0.007 (2)	0.007 (2)

Geometric parameters (Å, º)

S1A—O1B	1.424 (2)	C12—H12	0.88 (3)
S1A—O1C	1.436 (2)	C13—C14	1.383 (5)
S1A—O1A	1.442 (2)	C13—H13	0.9500
S1A—C1A	1.813 (4)	C14—C15	1.380 (5)
C1A—F1C	1.320 (4)	C14—H14	0.9500
C1A—F1A	1.328 (4)	C15—H15	0.95 (3)
C1A—F1B	1.336 (4)	C16—C17	1.481 (5)
Ru1—O2A	2.11 (3)	C16—H16A	0.95 (3)
Ru1—N1	2.143 (3)	C16—H16B	0.99 (3)
Ru1—N2	2.117 (2)	C17—C18	1.387 (5)
Ru1—N3	2.154 (3)	C18—C19	1.374 (5)
Ru1—C5	2.213 (3)	C18—H18	0.95 (4)
Ru1—C4	2.229 (3)	C19—C20	1.369 (6)
Ru1—P1	2.3332 (8)	C19—H19	0.92 (4)
Ru1—Cl1	2.4351 (13)	C20—C21	1.380 (5)
S2A—O2B	1.424 (16)	C20—H20	0.9500
S2A—O2C	1.428 (16)	C21—H21	0.9500
S2A—O2A	1.453 (16)	C22—C27	1.391 (5)
S2A—C2A	1.821 (17)	C22—C23	1.395 (5)
C2A—F2C	1.321 (18)	C23—C24	1.385 (5)
C2A—F2A	1.328 (18)	C23—H23	0.92 (3)
C2A—F2B	1.342 (19)	C24—C25	1.374 (5)
N1—C1	1.495 (4)	C24—H24	0.92 (4)
N1—H1A	0.87 (4)	C25—C26	1.376 (5)
N1—H1B	0.86 (4)	C25—H25	0.93 (4)
N2—C16	1.469 (4)	C26—C27	1.391 (5)
N2—H2A	0.9200	C26—H26	0.9500
N2—H2B	0.9200	C27—H27	0.88 (3)
N3—C17	1.348 (4)	C28—C29	1.383 (4)
N3—C21	1.352 (4)	C28—C33	1.393 (4)
P1—C28	1.834 (3)	C29—C30	1.388 (5)
P1—C34	1.843 (3)	C29—H29	0.9500
P1—C22	1.843 (3)	C30—C31	1.362 (5)
C1—C7	1.507 (4)	C30—H30	0.91 (4)
C1—C2	1.510 (4)	C31—C32	1.375 (5)
C1—H1	1.0000	C31—H31	0.91 (4)
C2—C11	1.384 (4)	C32—C33	1.383 (5)
C2—C3	1.399 (4)	C32—H32	0.9500
C3—C8	1.404 (4)	C33—H33	0.95 (3)
C3—C4	1.465 (4)	C34—C35	1.389 (5)
C4—C5	1.390 (4)	C34—C39	1.399 (4)
C4—H4	0.95 (3)	C35—C36	1.372 (5)
C5—C6	1.478 (4)	C35—H35	0.89 (3)
C5—H5	0.93 (3)	C36—C37	1.386 (5)
C6—C12	1.387 (4)	C36—H36	0.90 (4)
C6—C7	1.412 (4)	C37—C38	1.388 (5)
C7—C15	1.387 (4)	C37—H37	0.92 (3)
C8—C9	1.376 (5)	C38—C39	1.376 (4)
C8—H8	0.89 (3)	C38—H38	0.9500
C9—C10	1.379 (5)	C39—H39	0.9500
C9—H9	0.95 (3)	Cl3—C50	1.757 (5)
C10—C11	1.385 (5)	Cl4—C50	1.724 (5)
C10—H10	0.9500	C50—H50A	0.9900
C11—H11	0.92 (3)	C50—H50B	0.9900
C12—C13	1.388 (5)	Ru1—ct1	2.109 (3)
P1—Ru1—N1	171.71 (9)	C6—C7—C1	120.4 (3)
P1—Ru1—N2	95.78 (7)	C9—C8—C3	121.4 (3)
P1—Ru1—N3	93.19 (7)	C9—C8—H8	119.1 (19)
P1—Ru1—ct1	96.58 (7)	C3—C8—H8	119.5 (19)
N1—Ru1—N2	91.68 (11)	C8—C9—C10	119.5 (3)
N1—Ru1—N3	85.10 (10)	C8—C9—H9	120.5 (19)
N1—Ru1—ct1	86.3 (1)	C10—C9—H9	120.0 (19)
N2—Ru1—N3	75.92 (10)	C9—C10—C11	120.2 (3)
N2—Ru1—ct1	95.3 (1)	C9—C10—H10	119.9
N3—Ru1—ct1	167.5 (1)	C11—C10—H10	119.9
P1—Ru1—Cl1	88.19 (3)	C2—C11—C10	120.8 (3)
P1—Ru1—O2A	75.1 (7)	C2—C11—H11	120.2 (19)
N1—Ru1—Cl1	83.68 (9)	C10—C11—H11	119.0 (19)
N1—Ru1—O2A	96.6 (7)	C6—C12—C13	121.4 (3)
N2—Ru1—Cl1	164.57 (7)	C6—C12—H12	123 (2)
N2—Ru1—O2A	153.3 (8)	C13—C12—H12	116 (2)
N3—Ru1—Cl1	89.00 (8)	C14—C13—C12	119.8 (3)
N3—Ru1—O2A	79.6 (8)	C14—C13—H13	120.1
O1B—S1A—O1C	116.64 (15)	C12—C13—H13	120.1
O1B—S1A—O1A	113.96 (15)	C15—C14—C13	119.5 (3)
O1C—S1A—O1A	114.85 (14)	C15—C14—H14	120.2
O1B—S1A—C1A	103.64 (16)	C13—C14—H14	120.2
O1C—S1A—C1A	103.01 (15)	C14—C15—C7	121.3 (3)
O1A—S1A—C1A	102.09 (15)	C14—C15—H15	120.7 (19)
F1C—C1A—F1A	108.2 (3)	C7—C15—H15	118.0 (19)
F1C—C1A—F1B	107.5 (3)	N2—C16—C17	109.5 (3)
F1A—C1A—F1B	107.4 (3)	N2—C16—H16A	108.8 (19)
F1C—C1A—S1A	111.4 (3)	C17—C16—H16A	115.1 (19)
F1A—C1A—S1A	111.8 (2)	N2—C16—H16B	110.5 (19)
F1B—C1A—S1A	110.5 (2)	C17—C16—H16B	108 (2)
O2A—Ru1—C5	128.6 (8)	H16A—C16—H16B	105 (3)
N2—Ru1—C5	76.93 (11)	N3—C17—C18	122.3 (3)
N1—Ru1—C5	86.98 (11)	N3—C17—C16	116.2 (3)
N3—Ru1—C5	151.44 (11)	C18—C17—C16	121.4 (3)
O2A—Ru1—C4	92.5 (8)	C19—C18—C17	118.9 (4)
N2—Ru1—C4	113.39 (11)	C19—C18—H18	125 (2)
N1—Ru1—C4	86.00 (11)	C17—C18—H18	116 (2)
N3—Ru1—C4	167.32 (11)	C20—C19—C18	119.3 (4)
C5—Ru1—C4	36.46 (11)	C20—C19—H19	116 (3)
C5—Ru1—P1	98.20 (8)	C18—C19—H19	125 (3)
C4—Ru1—P1	94.32 (8)	C19—C20—C21	119.5 (4)
O2A—Ru1—Cl1	16.7 (7)	C19—C20—H20	120.2
C5—Ru1—Cl1	117.33 (8)	C21—C20—H20	120.2
C4—Ru1—Cl1	81.05 (9)	N3—C21—C20	122.0 (4)
O2B—S2A—O2C	119.3 (16)	N3—C21—H21	119.0
O2B—S2A—O2A	112.2 (16)	C20—C21—H21	119.0
O2C—S2A—O2A	114.4 (16)	C27—C22—C23	118.2 (3)
O2B—S2A—C2A	101.9 (14)	C27—C22—P1	120.0 (3)
O2C—S2A—C2A	103.3 (14)	C23—C22—P1	121.7 (3)
O2A—S2A—C2A	102.9 (14)	C24—C23—C22	120.7 (3)
S2A—O2A—Ru1	132.5 (18)	C24—C23—H23	120 (2)
F2C—C2A—F2A	108 (2)	C22—C23—H23	119 (2)
F2C—C2A—F2B	109 (2)	C25—C24—C23	120.1 (4)
F2A—C2A—F2B	105 (2)	C25—C24—H24	118 (2)
F2C—C2A—S2A	112.9 (18)	C23—C24—H24	122 (2)
F2A—C2A—S2A	114.2 (19)	C24—C25—C26	120.4 (4)
F2B—C2A—S2A	107.5 (19)	C24—C25—H25	121 (2)
C1—N1—Ru1	121.19 (19)	C26—C25—H25	118 (2)
C1—N1—H1A	108 (2)	C25—C26—C27	119.6 (4)
Ru1—N1—H1A	105 (2)	C25—C26—H26	120.2
C1—N1—H1B	109 (2)	C27—C26—H26	120.2
Ru1—N1—H1B	106 (2)	C22—C27—C26	121.0 (4)
H1A—N1—H1B	108 (3)	C22—C27—H27	122 (2)
C16—N2—Ru1	113.1 (2)	C26—C27—H27	116 (2)
C16—N2—H2A	109.0	C29—C28—C33	118.2 (3)
Ru1—N2—H2A	109.0	C29—C28—P1	122.3 (2)
C16—N2—H2B	109.0	C33—C28—P1	119.5 (2)
Ru1—N2—H2B	109.0	C28—C29—C30	120.2 (3)
H2A—N2—H2B	107.8	C28—C29—H29	119.9
C17—N3—C21	117.9 (3)	C30—C29—H29	119.9
C17—N3—Ru1	116.1 (2)	C31—C30—C29	120.7 (3)
C21—N3—Ru1	125.9 (2)	C31—C30—H30	121 (3)
C28—P1—C34	101.44 (13)	C29—C30—H30	118 (3)
C28—P1—C22	101.51 (14)	C30—C31—C32	120.2 (3)
C34—P1—C22	103.14 (14)	C30—C31—H31	119 (2)
C28—P1—Ru1	117.09 (10)	C32—C31—H31	121 (2)
C34—P1—Ru1	118.21 (10)	C31—C32—C33	119.4 (3)
C22—P1—Ru1	113.14 (10)	C31—C32—H32	120.3
N1—C1—C7	110.5 (2)	C33—C32—H32	120.3
N1—C1—C2	111.0 (3)	C32—C33—C28	121.2 (3)
C7—C1—C2	110.2 (2)	C32—C33—H33	120 (2)
N1—C1—H1	108.4	C28—C33—H33	119 (2)
C7—C1—H1	108.4	C35—C34—C39	117.9 (3)
C2—C1—H1	108.4	C35—C34—P1	123.9 (3)
C11—C2—C3	119.7 (3)	C39—C34—P1	118.2 (2)
C11—C2—C1	120.2 (3)	C36—C35—C34	120.9 (4)
C3—C2—C1	120.0 (3)	C36—C35—H35	120 (2)
C2—C3—C8	118.4 (3)	C34—C35—H35	120 (2)
C2—C3—C4	124.2 (3)	C35—C36—C37	120.8 (4)
C8—C3—C4	117.3 (3)	C35—C36—H36	121 (2)
C5—C4—C3	124.4 (3)	C37—C36—H36	118 (2)
C5—C4—Ru1	71.16 (17)	C36—C37—C38	119.2 (3)
C3—C4—Ru1	117.8 (2)	C36—C37—H37	120 (2)
C5—C4—H4	114.6 (18)	C38—C37—H37	121 (2)
C3—C4—H4	113.3 (18)	C39—C38—C37	119.9 (3)
Ru1—C4—H4	107.6 (18)	C39—C38—H38	120.0
C4—C5—C6	124.9 (3)	C37—C38—H38	120.0
C4—C5—Ru1	72.38 (18)	C38—C39—C34	121.3 (3)
C6—C5—Ru1	116.3 (2)	C38—C39—H39	119.4
C4—C5—H5	116.9 (19)	C34—C39—H39	119.4
C6—C5—H5	113.0 (19)	Cl4—C50—Cl3	111.7 (3)
Ru1—C5—H5	104.0 (19)	Cl4—C50—H50A	109.3
C12—C6—C7	118.4 (3)	Cl3—C50—H50A	109.3
C12—C6—C5	118.2 (3)	Cl4—C50—H50B	109.3
C7—C6—C5	123.4 (3)	Cl3—C50—H50B	109.3
C15—C7—C6	119.5 (3)	H50A—C50—H50B	107.9
C15—C7—C1	120.1 (3)
O1B—S1A—C1A—F1C	−175.8 (2)	Cl1—Ru1—C4—C3	54.9 (2)
O1C—S1A—C1A—F1C	62.3 (3)	C3—C4—C5—C6	1.2 (5)
O1A—S1A—C1A—F1C	−57.1 (3)	Ru1—C4—C5—C6	−110.2 (3)
O1B—S1A—C1A—F1A	−54.6 (3)	C3—C4—C5—Ru1	111.3 (3)
O1C—S1A—C1A—F1A	−176.6 (2)	O2A—Ru1—C5—C4	8.7 (9)
O1A—S1A—C1A—F1A	64.1 (3)	N2—Ru1—C5—C4	−179.77 (19)
O1B—S1A—C1A—F1B	64.9 (3)	N1—Ru1—C5—C4	−87.34 (19)
O1C—S1A—C1A—F1B	−57.1 (3)	N3—Ru1—C5—C4	−161.4 (2)
O1A—S1A—C1A—F1B	−176.4 (2)	P1—Ru1—C5—C4	86.16 (17)
O2B—S2A—O2A—Ru1	100 (2)	Cl1—Ru1—C5—C4	−6.0 (2)
O2C—S2A—O2A—Ru1	−40 (3)	O2A—Ru1—C5—C6	129.6 (9)
C2A—S2A—O2A—Ru1	−151 (2)	N2—Ru1—C5—C6	−58.9 (2)
N2—Ru1—O2A—S2A	130.7 (18)	N1—Ru1—C5—C6	33.5 (2)
N1—Ru1—O2A—S2A	23 (2)	N3—Ru1—C5—C6	−40.5 (4)
N3—Ru1—O2A—S2A	107 (2)	C4—Ru1—C5—C6	120.9 (3)
C5—Ru1—O2A—S2A	−68 (3)	P1—Ru1—C5—C6	−153.0 (2)
C4—Ru1—O2A—S2A	−63 (2)	Cl1—Ru1—C5—C6	114.8 (2)
P1—Ru1—O2A—S2A	−157 (3)	C4—C5—C6—C12	−138.2 (3)
Cl1—Ru1—O2A—S2A	−16.1 (9)	Ru1—C5—C6—C12	135.7 (2)
O2B—S2A—C2A—F2C	52 (2)	C4—C5—C6—C7	39.5 (4)
O2C—S2A—C2A—F2C	176 (2)	Ru1—C5—C6—C7	−46.6 (4)
O2A—S2A—C2A—F2C	−65 (2)	C12—C6—C7—C15	−1.3 (4)
O2B—S2A—C2A—F2A	176 (2)	C5—C6—C7—C15	−179.0 (3)
O2C—S2A—C2A—F2A	−60 (2)	C12—C6—C7—C1	176.0 (3)
O2A—S2A—C2A—F2A	59 (2)	C5—C6—C7—C1	−1.7 (4)
O2B—S2A—C2A—F2B	−69 (2)	N1—C1—C7—C15	−124.2 (3)
O2C—S2A—C2A—F2B	56 (2)	C2—C1—C7—C15	112.7 (3)
O2A—S2A—C2A—F2B	175 (2)	N1—C1—C7—C6	58.4 (3)
O2A—Ru1—N1—C1	−112.7 (8)	C2—C1—C7—C6	−64.6 (3)
N2—Ru1—N1—C1	92.7 (2)	C2—C3—C8—C9	1.9 (5)
N3—Ru1—N1—C1	168.4 (3)	C4—C3—C8—C9	−174.7 (3)
C5—Ru1—N1—C1	15.9 (2)	C3—C8—C9—C10	−1.2 (5)
C4—Ru1—N1—C1	−20.6 (2)	C8—C9—C10—C11	−0.5 (5)
Cl1—Ru1—N1—C1	−102.1 (2)	C3—C2—C11—C10	−0.7 (5)
O2A—Ru1—N2—C16	1.0 (16)	C1—C2—C11—C10	176.1 (3)
N1—Ru1—N2—C16	109.4 (2)	C9—C10—C11—C2	1.5 (5)
N3—Ru1—N2—C16	24.9 (2)	C7—C6—C12—C13	−1.1 (4)
C5—Ru1—N2—C16	−164.1 (2)	C5—C6—C12—C13	176.7 (3)
C4—Ru1—N2—C16	−164.2 (2)	C6—C12—C13—C14	2.5 (5)
P1—Ru1—N2—C16	−67.0 (2)	C12—C13—C14—C15	−1.4 (5)
Cl1—Ru1—N2—C16	37.3 (4)	C13—C14—C15—C7	−1.1 (5)
O2A—Ru1—N3—C17	157.4 (7)	C6—C7—C15—C14	2.5 (5)
N2—Ru1—N3—C17	−11.9 (2)	C1—C7—C15—C14	−174.9 (3)
N1—Ru1—N3—C17	−104.9 (2)	Ru1—N2—C16—C17	−33.6 (3)
C5—Ru1—N3—C17	−30.4 (3)	C21—N3—C17—C18	2.3 (4)
C4—Ru1—N3—C17	−150.5 (4)	Ru1—N3—C17—C18	179.1 (2)
P1—Ru1—N3—C17	83.2 (2)	C21—N3—C17—C16	179.8 (3)
Cl1—Ru1—N3—C17	171.4 (2)	Ru1—N3—C17—C16	−3.3 (3)
O2A—Ru1—N3—C21	−26.0 (7)	N2—C16—C17—N3	23.9 (4)
N2—Ru1—N3—C21	164.6 (3)	N2—C16—C17—C18	−158.6 (3)
N1—Ru1—N3—C21	71.7 (3)	N3—C17—C18—C19	−0.3 (5)
C5—Ru1—N3—C21	146.1 (3)	C16—C17—C18—C19	−177.7 (3)
C4—Ru1—N3—C21	26.1 (6)	C17—C18—C19—C20	−1.4 (5)
P1—Ru1—N3—C21	−100.2 (2)	C18—C19—C20—C21	1.0 (6)
Cl1—Ru1—N3—C21	−12.1 (2)	C17—N3—C21—C20	−2.7 (5)
O2A—Ru1—P1—C28	80.0 (8)	Ru1—N3—C21—C20	−179.2 (2)
N2—Ru1—P1—C28	−125.48 (13)	C19—C20—C21—N3	1.0 (5)
N3—Ru1—P1—C28	158.37 (13)	C28—P1—C22—C27	167.8 (3)
C5—Ru1—P1—C28	−47.89 (14)	C34—P1—C22—C27	63.0 (3)
C4—Ru1—P1—C28	−11.41 (14)	Ru1—P1—C22—C27	−65.8 (3)
Cl1—Ru1—P1—C28	69.47 (12)	C28—P1—C22—C23	−14.1 (3)
O2A—Ru1—P1—C34	−158.2 (8)	C34—P1—C22—C23	−118.9 (3)
N2—Ru1—P1—C34	−3.66 (13)	Ru1—P1—C22—C23	112.2 (3)
N3—Ru1—P1—C34	−79.81 (14)	C27—C22—C23—C24	−0.4 (5)
C5—Ru1—P1—C34	73.93 (14)	P1—C22—C23—C24	−178.5 (3)
C4—Ru1—P1—C34	110.41 (14)	C22—C23—C24—C25	−0.4 (5)
Cl1—Ru1—P1—C34	−168.71 (12)	C23—C24—C25—C26	0.3 (5)
O2A—Ru1—P1—C22	−37.5 (8)	C24—C25—C26—C27	0.5 (5)
N2—Ru1—P1—C22	116.98 (13)	C23—C22—C27—C26	1.2 (5)
N3—Ru1—P1—C22	40.83 (14)	P1—C22—C27—C26	179.3 (3)
C5—Ru1—P1—C22	−165.43 (14)	C25—C26—C27—C22	−1.3 (5)
C4—Ru1—P1—C22	−128.95 (14)	C34—P1—C28—C29	5.2 (3)
Cl1—Ru1—P1—C22	−48.07 (12)	C22—P1—C28—C29	−101.0 (3)
Ru1—N1—C1—C7	−59.9 (3)	Ru1—P1—C28—C29	135.3 (2)
Ru1—N1—C1—C2	62.7 (3)	C34—P1—C28—C33	−175.2 (3)
N1—C1—C2—C11	127.5 (3)	C22—P1—C28—C33	78.7 (3)
C7—C1—C2—C11	−109.8 (3)	Ru1—P1—C28—C33	−45.0 (3)
N1—C1—C2—C3	−55.7 (4)	C33—C28—C29—C30	1.1 (5)
C7—C1—C2—C3	67.1 (4)	P1—C28—C29—C30	−179.2 (3)
C11—C2—C3—C8	−0.9 (5)	C28—C29—C30—C31	0.9 (6)
C1—C2—C3—C8	−177.8 (3)	C29—C30—C31—C32	−1.5 (6)
C11—C2—C3—C4	175.4 (3)	C30—C31—C32—C33	0.0 (6)
C1—C2—C3—C4	−1.4 (5)	C31—C32—C33—C28	2.0 (5)
C2—C3—C4—C5	−39.6 (5)	C29—C28—C33—C32	−2.5 (5)
C8—C3—C4—C5	136.8 (3)	P1—C28—C33—C32	177.8 (3)
C2—C3—C4—Ru1	45.7 (4)	C28—P1—C34—C35	−104.2 (3)
C8—C3—C4—Ru1	−137.9 (3)	C22—P1—C34—C35	0.7 (3)
O2A—Ru1—C4—C5	−173.2 (7)	Ru1—P1—C34—C35	126.4 (2)
N2—Ru1—C4—C5	0.2 (2)	C28—P1—C34—C39	74.2 (2)
N1—Ru1—C4—C5	90.34 (19)	C22—P1—C34—C39	179.0 (2)
N3—Ru1—C4—C5	135.9 (4)	Ru1—P1—C34—C39	−55.3 (3)
P1—Ru1—C4—C5	−97.96 (17)	C39—C34—C35—C36	0.5 (5)
Cl1—Ru1—C4—C5	174.56 (18)	P1—C34—C35—C36	178.8 (3)
O2A—Ru1—C4—C3	67.1 (7)	C34—C35—C36—C37	−0.7 (5)
N2—Ru1—C4—C3	−119.5 (2)	C35—C36—C37—C38	0.5 (5)
N1—Ru1—C4—C3	−29.4 (2)	C36—C37—C38—C39	−0.2 (5)
N3—Ru1—C4—C3	16.2 (6)	C37—C38—C39—C34	−0.1 (5)
C5—Ru1—C4—C3	−119.7 (3)	C35—C34—C39—C38	−0.1 (4)
P1—Ru1—C4—C3	142.3 (2)	P1—C34—C39—C38	−178.5 (2)