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Acta Cryst. (2008). E64, m483-m484    [ doi:10.1107/S1600536808003978 ]

[mu]3-Carbonato-[kappa]3O:O':O''-tris{([eta]6-benzene)[(R)-1-(1-aminoethyl)naphthyl-[kappa]2C2,N]ruthenium(II)} hexafluoridophosphate dichloromethane solvate

J.-B. Sortais, L. Brelot, M. Pfeffer and L. Barloy

Abstract top

The title compound, [Ru3(C12H12N)3(CO3)(C6H6)3]PF6·CH2Cl2, was obtained unintentionally as the product of an attempted deprotonation of the monomeric parent ruthenium complex [Ru(C12H12N)(C6H6)(C2H3N)]PF6. The carbonate ligand bridges three half-sandwich cycloruthenated fragments, each of them exhibiting a pseudo-tetrahedral geometry. The configuration of the Ru atoms is S. The naphthyl groups of the enantiopure cycloruthenated benzylic amine ligands point in the same direction, adopting a propeller shape.

Comment top

Chiral cycloruthenated half-sandwich complexes have recently experienced a renewed interest because of their catalytic properties applied to asymmetric synthesis (Sortais et al., 2006). Single crystals of the title compound (I) have been obtained while attempting to isolate catalytic intermediates.

The molecular structure of the compound (I) (Fig. 1) consists of a trinuclear cation comprising three pseudotetrahedral ruthenium (II) centres, which are each coordinated by a bridging µ3-carbonato ligand, a η6-benzene ligand and a cyclometallated (R)-(+)-1-(1-naphthyl)ethylamine, together with a non-coordinating hexafluorophosphate anion and one molecule of methylene chloride. The complex crystallizes in the P21 chiral space group, which confirms the presence of a single enantiomer. A partial view showing the coordination sphere of one of the ruthenium atoms is represented Fig. 2, the two others are similar. Its structure is closely related to that of the reported parent complex bearing dimethylphenylphosphine instead of the carbonato ligand (Sortais et al., 2007): SRu configuration, δ conformation of the metallacycle, axial position of the methyl group. The ruthenium atoms and the four atoms belonging to the carbonato are coplanar, the sum of the three Ru···Ccarbonato···Ru angles reaching 359.89°. The three ruthenium atoms form a nearly equilateral triangle with Ru···Ru distances within the 5.2–5.5 Å range. The benzene ligands lie on one side of the corresponding plane and the cycloruthenated on the other side.

A search in the Cambridge Database revealed no previously reported crystal structure of a carbonato-bridged chemically C3-symmetric trinuclear ruthenium complex. Related polynuclear carbonato ruthenium complexes where each oxygen atom is ligated to at least one ruthenium atom exhibit metal-metal bonds (Cotton et al., 1992; Lindsay et al., 1987; Maurette et al., 1999). Interestingly, a closely related monomeric half-sandwich complex where a carbonato ligand chelates the Ru center has been recently reported (Demerseman et al., 2006); we notice that in complex (I) the Ru—O bond distances are longer (2.118 (4)–2.132 (4) Å), probably because of steric repulsions.

Related literature top

For related literature, see: Cotton et al. (1992); Demerseman et al. (2006); Lindsay et al. (1987); Maurette et al. (1999); Sortais et al. (2006, 2007).

Experimental top

{[(R)-1-(1-naphthyl-κC2)-ethylamine-κN](η6-benzene) (acetonitrile-κN)ruthenium(II)} hexafluorophosphate (31 mg, 58 µmol) (Sortais et al., 2007) was dissolved in 4 ml dichloromethane with 3.3 mg (1 equiv.) ground potassium hydroxide (containing potassium carbonate as minor impurity). The suspension was heated to reflux for 1.5 h and evaporated to dryness. Analysis of a sample dissolved in CD2Cl2 by NMR showed only the signals of the starting material, but single crystals of compound (I) had appeared after letting the tube stand for 3 days at room temperature.

Refinement top

The H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with selected atom labels and 50% probability displacement ellipsoids for non-H atoms. The counter-anion and solvent have been omitted for clarity.
[Figure 2] Fig. 2. A partial view of the molecular structure of (I), with 50% probability displacement ellipsoids for non-H atoms. Only the Ru3 atom and its ligands are represented.
µ3-Carbonato-κ3O:O':O''-tris{(η6– benzene)[(R)-1-(1-aminoethyl)naphthyl- κ2C2,N]ruthenium(II)} hexafluoridophosphate dichloromethane solvate top
Crystal data top
[Ru3(C12H12N)3(CO3)(C6H6)3]PF6·CH2Cl2F000 = 1344
Mr = 1338.12Dx = 1.684 Mg m−3
Monoclinic, P21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 6871 reflections
a = 11.4732 (2) Åθ = 1.0–30.0º
b = 19.1377 (5) ŵ = 1.05 mm−1
c = 12.0169 (2) ÅT = 173 (2) K
β = 90.832 (2)ºPrism, yellow
V = 2638.28 (9) Å30.12 × 0.10 × 0.08 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer		12813 independent reflections
Radiation source: fine-focus sealed tube9862 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.050
Detector resolution: 10 pixels mm-1θmax = 30.0º
T = 173(2) Kθmin = 1.7º
φ and ω scansh = −16→16
Absorption correction: nonek = −24→26
15434 measured reflectionsl = −16→16
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.052  w = 1/[σ2(Fo2) + (0.0555P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.132(Δ/σ)max = 0.001
S = 1.06Δρmax = 0.74 e Å−3
12813 reflectionsΔρmin = −0.99 e Å−3
670 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (3)
Secondary atom site location: difference Fourier map
Crystal data top
[Ru3(C12H12N)3(CO3)(C6H6)3]PF6·CH2Cl2V = 2638.28 (9) Å3
Mr = 1338.12Z = 2
Monoclinic, P21Mo Kα
a = 11.4732 (2) ŵ = 1.05 mm−1
b = 19.1377 (5) ÅT = 173 (2) K
c = 12.0169 (2) Å0.12 × 0.10 × 0.08 mm
β = 90.832 (2)º
Data collection top
Nonius KappaCCD
diffractometer		12813 independent reflections
Absorption correction: none9862 reflections with I > 2σ(I)
15434 measured reflectionsRint = 0.050
Refinement top
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.132Δρmax = 0.74 e Å−3
S = 1.06Δρmin = −0.99 e Å−3
12813 reflectionsAbsolute structure: Flack (1983)
670 parametersFlack parameter: 0.01 (3)
1 restraint
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2995 (5)0.8427 (4)0.1246 (5)0.0201 (13)
C20.3807 (5)0.9299 (3)0.3937 (5)0.0219 (13)
C30.4996 (6)0.9276 (4)0.4278 (6)0.0270 (15)
H30.55380.95760.39280.032*
C40.5389 (7)0.8828 (4)0.5104 (6)0.0375 (19)
H40.61890.88300.53180.045*
C50.4618 (6)0.8371 (4)0.5629 (5)0.0294 (16)
C60.5008 (8)0.7871 (5)0.6434 (6)0.048 (2)
H60.58050.78600.66590.057*
C70.4237 (10)0.7409 (5)0.6881 (6)0.058 (3)
H70.45060.70830.74230.070*
C80.3063 (8)0.7404 (5)0.6559 (7)0.051 (2)
H80.25530.70670.68680.061*
C90.2642 (8)0.7874 (4)0.5810 (6)0.041 (2)
H90.18370.78690.56150.049*
C100.3396 (6)0.8376 (4)0.5310 (5)0.0294 (16)
C110.3028 (5)0.8864 (4)0.4492 (5)0.0220 (14)
C120.1760 (5)0.8928 (4)0.4189 (5)0.0261 (15)
H120.14010.84530.41390.031*
C130.1102 (6)0.9370 (5)0.5027 (6)0.039 (2)
H13A0.11500.91480.57610.059*
H13B0.02830.94090.47910.059*
H13C0.14500.98370.50670.059*
C140.2255 (7)1.0778 (5)0.2286 (8)0.050 (2)
H140.14671.08690.24690.060*
C150.3115 (9)1.0883 (5)0.3096 (7)0.049 (2)
H150.29201.10690.38030.059*
C160.4263 (8)1.0714 (5)0.2862 (7)0.045 (2)
H160.48491.07880.34160.055*
C170.4571 (8)1.0442 (5)0.1846 (8)0.050 (2)
H170.53571.03150.17100.060*
C180.3705 (10)1.0354 (5)0.1007 (7)0.055 (3)
H180.39121.01700.03030.066*
C190.2502 (9)1.0543 (4)0.1212 (8)0.055 (3)
H190.19151.05090.06490.066*
C200.4310 (5)0.6561 (3)0.1661 (5)0.0193 (13)
C210.3938 (5)0.6072 (4)0.0840 (5)0.0208 (14)
H210.41240.61510.00830.025*
C220.3320 (6)0.5490 (4)0.1122 (5)0.0263 (15)
H220.30940.51720.05530.032*
C230.3005 (6)0.5347 (4)0.2225 (5)0.0245 (14)
C240.2331 (6)0.4752 (4)0.2510 (6)0.0357 (17)
H240.21150.44260.19480.043*
C250.1992 (6)0.4643 (4)0.3569 (6)0.0382 (19)
H250.15360.42440.37420.046*
C260.2309 (7)0.5115 (4)0.4415 (7)0.0384 (19)
H260.20470.50430.51520.046*
C270.2986 (6)0.5674 (4)0.4181 (5)0.0290 (16)
H270.32210.59760.47690.035*
C280.3360 (5)0.5823 (4)0.3077 (5)0.0240 (14)
C290.4020 (5)0.6425 (4)0.2765 (5)0.0229 (14)
C300.4463 (6)0.6940 (4)0.3622 (5)0.0249 (15)
H300.38750.70040.42200.030*
C310.5616 (6)0.6688 (4)0.4123 (6)0.0364 (18)
H31A0.61900.66390.35320.055*
H31B0.55000.62350.44850.055*
H31C0.58980.70280.46740.055*
C320.6082 (6)0.7174 (4)−0.0141 (6)0.0308 (17)
H320.59180.6831−0.06910.037*
C330.6721 (5)0.6993 (4)0.0846 (5)0.0273 (16)
H330.69570.65240.09770.033*
C340.6991 (5)0.7517 (5)0.1618 (5)0.0321 (16)
H340.74070.74000.22820.039*
C350.6650 (5)0.8231 (4)0.1422 (6)0.0307 (17)
H350.68650.85850.19390.037*
C360.6011 (6)0.8398 (4)0.0483 (6)0.0295 (16)
H360.57800.88680.03520.035*
C370.5697 (6)0.7867 (4)−0.0290 (6)0.0319 (17)
H370.52200.7981−0.09170.038*
C38−0.0018 (5)0.7922 (4)0.1656 (5)0.0210 (14)
C39−0.0630 (5)0.8442 (4)0.2251 (5)0.0228 (14)
H39−0.08070.88750.19010.027*
C40−0.0973 (5)0.8328 (4)0.3329 (5)0.0236 (14)
H40−0.13980.86810.37040.028*
C41−0.0710 (6)0.7704 (4)0.3883 (5)0.0276 (16)
C42−0.1033 (7)0.7603 (4)0.5014 (6)0.0367 (18)
H42−0.14510.79560.53960.044*
C43−0.0734 (7)0.6995 (5)0.5543 (6)0.042 (2)
H43−0.09390.69330.62990.051*
C44−0.0146 (8)0.6472 (5)0.5006 (6)0.044 (2)
H440.00510.60560.53970.053*
C450.0157 (6)0.6541 (4)0.3920 (6)0.0366 (18)
H450.05500.61710.35560.044*
C46−0.0113 (6)0.7170 (4)0.3325 (5)0.0251 (14)
C470.0225 (5)0.7292 (4)0.2197 (5)0.0227 (14)
C480.0813 (6)0.6732 (4)0.1515 (6)0.0286 (16)
H480.14270.65010.19870.034*
C49−0.0024 (7)0.6186 (4)0.1104 (7)0.042 (2)
H49A−0.06120.64030.06160.063*
H49B−0.04080.59680.17390.063*
H49C0.04010.58290.06880.063*
C500.0522 (9)0.8959 (5)−0.1028 (7)0.053 (3)
H500.09120.9393−0.09290.063*
C510.1030 (7)0.8457 (6)−0.1663 (6)0.044 (2)
H510.17320.8556−0.20410.053*
C520.0537 (8)0.7825 (5)−0.1752 (6)0.045 (2)
H520.09030.7479−0.21930.053*
C53−0.0490 (8)0.7661 (5)−0.1221 (7)0.050 (2)
H53−0.08000.7202−0.12650.060*
C54−0.1065 (6)0.8179 (7)−0.0621 (6)0.059 (3)
H54−0.17920.8083−0.02830.070*
C55−0.0543 (10)0.8858 (6)−0.0522 (7)0.062 (3)
H55−0.09130.9223−0.01250.075*
C560.6094 (7)0.4920 (5)0.2644 (7)0.046 (2)
H56A0.60050.47190.33980.055*
H56B0.54620.52650.25230.055*
N10.1666 (4)0.9289 (3)0.3070 (4)0.0247 (12)
H1A0.10690.96090.30980.030*
H1B0.14620.89600.25430.030*
N20.4657 (5)0.7614 (3)0.3023 (4)0.0262 (13)
H2A0.52370.78580.33890.031*
H2B0.39860.78760.30540.031*
N30.1387 (4)0.7088 (3)0.0559 (4)0.0232 (12)
H3A0.13680.6791−0.00440.028*
H3B0.21570.71640.07440.028*
O10.3648 (3)0.8835 (2)0.1831 (3)0.0203 (9)
O20.3397 (4)0.7824 (2)0.0963 (4)0.0234 (10)
O30.1951 (3)0.8604 (2)0.0977 (3)0.0218 (10)
F10.0698 (6)0.5255 (4)0.8771 (4)0.093 (2)
F20.2357 (5)0.4880 (4)0.8156 (7)0.110 (3)
F30.2403 (6)0.5770 (4)0.6939 (5)0.089 (2)
F40.2240 (5)0.5996 (3)0.8724 (4)0.0723 (18)
F50.0723 (5)0.6159 (3)0.7598 (6)0.086 (2)
F60.0852 (5)0.5061 (3)0.6993 (4)0.0566 (15)
P10.15655 (17)0.55228 (11)0.78605 (15)0.0312 (4)
Cl10.5964 (2)0.42565 (14)0.1657 (2)0.0600 (6)
Cl20.74437 (19)0.53430 (14)0.2568 (2)0.0589 (6)
Ru10.31904 (4)0.98086 (3)0.25393 (4)0.02012 (12)
Ru20.51234 (4)0.74976 (3)0.13391 (4)0.01916 (12)
Ru30.06260 (4)0.80527 (3)0.00783 (4)0.02022 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.021 (3)0.024 (4)0.016 (3)0.003 (3)0.002 (2)0.003 (3)
C20.027 (3)0.012 (3)0.027 (3)0.000 (3)0.001 (2)−0.004 (3)
C30.024 (3)0.020 (4)0.037 (4)−0.003 (3)−0.001 (3)−0.002 (3)
C40.039 (4)0.030 (5)0.043 (4)0.002 (4)−0.019 (3)−0.009 (4)
C50.046 (4)0.021 (4)0.021 (3)0.008 (3)−0.003 (3)−0.010 (3)
C60.079 (6)0.040 (6)0.023 (4)0.024 (5)−0.014 (4)−0.006 (4)
C70.128 (9)0.028 (5)0.019 (4)0.019 (6)0.015 (5)0.006 (4)
C80.074 (7)0.036 (5)0.044 (5)0.011 (5)0.025 (4)0.011 (4)
C90.061 (5)0.027 (5)0.034 (4)0.006 (4)0.021 (4)0.009 (3)
C100.045 (4)0.026 (4)0.017 (3)0.002 (3)0.007 (3)−0.004 (3)
C110.025 (3)0.017 (3)0.024 (3)0.002 (3)0.004 (2)−0.004 (3)
C120.021 (3)0.026 (4)0.032 (4)−0.007 (3)0.007 (3)0.002 (3)
C130.035 (4)0.054 (6)0.030 (4)0.005 (4)0.006 (3)−0.012 (4)
C140.038 (5)0.019 (4)0.092 (7)0.011 (4)0.001 (4)0.000 (5)
C150.076 (7)0.026 (5)0.046 (5)−0.018 (4)0.007 (4)−0.008 (4)
C160.053 (5)0.028 (5)0.055 (5)−0.020 (4)−0.016 (4)0.008 (4)
C170.046 (5)0.027 (5)0.078 (6)−0.005 (4)0.020 (4)0.017 (5)
C180.111 (9)0.026 (5)0.028 (4)−0.016 (5)0.015 (5)0.011 (4)
C190.075 (7)0.021 (5)0.068 (6)−0.010 (5)−0.047 (5)0.017 (5)
C200.017 (3)0.013 (3)0.029 (3)0.005 (2)0.001 (2)−0.001 (3)
C210.019 (3)0.025 (4)0.019 (3)0.004 (3)−0.004 (2)−0.002 (3)
C220.025 (3)0.026 (4)0.028 (3)−0.001 (3)−0.009 (3)−0.008 (3)
C230.024 (3)0.019 (4)0.030 (3)−0.002 (3)−0.006 (3)−0.002 (3)
C240.030 (4)0.027 (4)0.050 (4)−0.015 (3)−0.008 (3)0.001 (4)
C250.036 (4)0.027 (4)0.052 (5)−0.002 (3)0.006 (3)0.016 (4)
C260.035 (4)0.033 (5)0.047 (5)0.005 (4)0.011 (3)0.013 (4)
C270.032 (4)0.028 (4)0.027 (3)0.009 (3)0.003 (3)−0.001 (3)
C280.022 (3)0.021 (4)0.029 (3)0.007 (3)0.002 (3)0.002 (3)
C290.020 (3)0.027 (4)0.022 (3)0.005 (3)0.002 (2)0.001 (3)
C300.033 (4)0.023 (4)0.019 (3)−0.002 (3)0.003 (3)−0.001 (3)
C310.044 (5)0.037 (5)0.028 (4)0.005 (4)−0.013 (3)−0.004 (4)
C320.030 (4)0.027 (4)0.035 (4)−0.006 (3)0.013 (3)−0.010 (3)
C330.014 (3)0.033 (4)0.036 (4)0.009 (3)0.004 (3)0.006 (3)
C340.013 (3)0.046 (5)0.037 (4)−0.003 (3)−0.006 (2)0.004 (4)
C350.020 (3)0.031 (4)0.041 (4)−0.004 (3)0.001 (3)−0.011 (3)
C360.024 (3)0.018 (4)0.047 (4)−0.001 (3)0.013 (3)0.001 (3)
C370.027 (4)0.040 (5)0.029 (4)0.002 (3)0.003 (3)0.004 (3)
C380.011 (3)0.028 (4)0.024 (3)−0.003 (3)−0.003 (2)0.000 (3)
C390.019 (3)0.017 (4)0.033 (3)0.000 (3)0.000 (3)0.000 (3)
C400.017 (3)0.027 (4)0.027 (3)−0.002 (3)0.007 (2)−0.004 (3)
C410.027 (3)0.032 (4)0.023 (3)−0.008 (3)−0.003 (3)0.002 (3)
C420.045 (4)0.035 (5)0.030 (4)0.000 (4)0.003 (3)0.005 (4)
C430.057 (5)0.050 (6)0.020 (4)−0.017 (4)−0.001 (3)0.011 (4)
C440.060 (5)0.037 (5)0.035 (4)−0.010 (4)−0.013 (4)0.017 (4)
C450.036 (4)0.031 (5)0.042 (4)−0.003 (4)−0.013 (3)0.003 (4)
C460.026 (3)0.025 (4)0.024 (3)−0.004 (3)−0.006 (3)0.002 (3)
C470.016 (3)0.023 (4)0.029 (3)0.000 (3)−0.005 (2)0.000 (3)
C480.019 (3)0.028 (4)0.038 (4)0.003 (3)0.001 (3)0.000 (3)
C490.047 (5)0.027 (4)0.052 (5)−0.006 (4)0.012 (4)−0.011 (4)
C500.074 (7)0.033 (5)0.051 (5)−0.017 (5)−0.032 (5)0.016 (4)
C510.037 (4)0.068 (7)0.027 (4)−0.005 (4)0.006 (3)0.009 (4)
C520.052 (5)0.057 (6)0.024 (4)0.009 (5)−0.004 (3)−0.014 (4)
C530.064 (6)0.041 (6)0.044 (5)−0.027 (5)−0.027 (4)0.008 (4)
C540.019 (4)0.132 (11)0.025 (4)0.011 (5)−0.008 (3)0.020 (6)
C550.083 (7)0.077 (8)0.027 (4)0.063 (7)−0.021 (4)−0.010 (5)
C560.045 (5)0.036 (5)0.057 (5)0.007 (4)0.018 (4)0.004 (4)
N10.022 (3)0.027 (3)0.025 (3)−0.007 (2)0.000 (2)−0.005 (3)
N20.025 (3)0.022 (4)0.031 (3)0.000 (2)−0.003 (2)−0.003 (3)
N30.019 (3)0.019 (3)0.032 (3)0.000 (2)−0.005 (2)−0.005 (3)
O10.018 (2)0.016 (2)0.026 (2)0.0002 (18)−0.0048 (17)−0.0036 (19)
O20.019 (2)0.018 (2)0.033 (2)0.0031 (18)−0.0012 (18)−0.005 (2)
O30.013 (2)0.024 (3)0.029 (2)0.0024 (18)−0.0031 (16)−0.005 (2)
F10.136 (6)0.097 (6)0.046 (3)−0.046 (5)0.032 (3)−0.005 (3)
F20.069 (4)0.042 (4)0.219 (8)0.009 (4)−0.056 (5)0.001 (5)
F30.115 (5)0.082 (5)0.072 (4)−0.066 (4)0.045 (3)−0.030 (4)
F40.106 (5)0.052 (4)0.058 (3)−0.011 (3)−0.043 (3)−0.014 (3)
F50.064 (4)0.034 (3)0.158 (6)0.011 (3)−0.037 (4)−0.001 (4)
F60.076 (4)0.044 (3)0.049 (3)−0.031 (3)−0.009 (2)−0.006 (2)
P10.0385 (11)0.0268 (11)0.0282 (9)−0.0024 (8)−0.0040 (8)−0.0021 (8)
Cl10.0737 (16)0.0425 (14)0.0635 (14)0.0017 (13)−0.0093 (12)−0.0031 (12)
Cl20.0362 (11)0.0526 (15)0.0879 (17)−0.0006 (11)0.0012 (10)0.0091 (14)
Ru10.0205 (2)0.0170 (3)0.0229 (2)−0.0008 (2)−0.00081 (18)−0.0004 (2)
Ru20.0149 (2)0.0201 (3)0.0225 (2)0.0010 (2)−0.00019 (17)−0.0030 (2)
Ru30.0163 (2)0.0223 (3)0.0221 (2)0.0002 (2)−0.00065 (17)−0.0025 (2)
Geometric parameters (Å, °) top
C1—O31.281 (7)C33—H330.9500
C1—O11.284 (8)C34—C351.440 (11)
C1—O21.291 (8)C34—Ru22.165 (6)
C2—C111.398 (9)C34—H340.9500
C2—C31.419 (9)C35—C361.373 (10)
C2—Ru12.059 (6)C35—Ru22.245 (7)
C3—C41.382 (10)C35—H350.9500
C3—H30.9500C36—C371.419 (10)
C4—C51.400 (11)C36—Ru22.257 (7)
C4—H40.9500C36—H360.9500
C5—C61.427 (10)C37—Ru22.191 (7)
C5—C101.449 (10)C37—H370.9500
C6—C71.367 (13)C38—C471.397 (9)
C6—H60.9500C38—C391.417 (9)
C7—C81.396 (13)C38—Ru32.060 (6)
C7—H70.9500C39—C401.376 (9)
C8—C91.356 (11)C39—H390.9500
C8—H80.9500C40—C411.399 (10)
C9—C101.431 (10)C40—H400.9500
C9—H90.9500C41—C461.405 (10)
C10—C111.415 (9)C41—C421.427 (9)
C11—C121.500 (9)C42—C431.367 (11)
C12—N11.514 (8)C42—H420.9500
C12—C131.523 (9)C43—C441.374 (12)
C12—H121.0000C43—H430.9500
C13—H13A0.9800C44—C451.361 (11)
C13—H13B0.9800C44—H440.9500
C13—H13C0.9800C45—C461.432 (10)
C14—C151.391 (12)C45—H450.9500
C14—C191.399 (13)C46—C471.433 (9)
C14—Ru12.162 (8)C47—C481.513 (9)
C14—H140.9500C48—N31.497 (9)
C15—C161.388 (12)C48—C491.499 (10)
C15—Ru12.165 (9)C48—H481.0000
C15—H150.9500C49—H49A0.9800
C16—C171.379 (12)C49—H49B0.9800
C16—Ru12.158 (8)C49—H49C0.9800
C16—H160.9500C50—C511.361 (13)
C17—C181.415 (13)C50—C551.387 (14)
C17—Ru12.171 (8)C50—Ru32.187 (8)
C17—H170.9500C50—H500.9500
C18—C191.451 (14)C51—C521.339 (13)
C18—Ru12.205 (7)C51—Ru32.284 (7)
C18—H180.9500C51—H510.9500
C19—Ru12.260 (8)C52—C531.383 (12)
C19—H190.9500C52—Ru32.243 (7)
C20—C291.397 (8)C52—H520.9500
C20—C211.421 (9)C53—C541.398 (14)
C20—Ru22.060 (6)C53—Ru32.140 (7)
C21—C221.366 (9)C53—H530.9500
C21—H210.9500C54—C551.434 (16)
C22—C231.405 (9)C54—Ru32.117 (7)
C22—H220.9500C54—H540.9500
C23—C241.421 (10)C55—Ru32.160 (8)
C23—C281.427 (9)C55—H550.9500
C24—C251.352 (10)C56—Cl11.742 (9)
C24—H240.9500C56—Cl21.751 (8)
C25—C261.405 (11)C56—H56A0.9900
C25—H250.9500C56—H56B0.9900
C26—C271.353 (10)N1—Ru12.119 (5)
C26—H260.9500N1—H1A0.9200
C27—C281.429 (9)N1—H1B0.9200
C27—H270.9500N2—Ru22.112 (5)
C28—C291.432 (10)N2—H2A0.9200
C29—C301.508 (9)N2—H2B0.9200
C30—N21.495 (9)N3—Ru32.119 (6)
C30—C311.523 (10)N3—H3A0.9200
C30—H301.0000N3—H3B0.9200
C31—H31A0.9800O1—Ru12.118 (4)
C31—H31B0.9800O2—Ru22.119 (4)
C31—H31C0.9800O3—Ru32.132 (4)
C32—C371.409 (10)F1—P11.576 (6)
C32—C331.428 (10)F2—P11.566 (7)
C32—Ru22.193 (7)F3—P11.551 (5)
C32—H320.9500F4—P11.572 (5)
C33—C341.397 (10)F5—P11.584 (6)
C33—Ru22.162 (6)F6—P11.585 (5)
O3—C1—O1120.9 (6)C47—C48—H48108.7
O3—C1—O2120.4 (6)C48—C49—H49A109.5
O1—C1—O2118.7 (5)C48—C49—H49B109.5
C11—C2—C3117.5 (6)H49A—C49—H49B109.5
C11—C2—Ru1117.2 (5)C48—C49—H49C109.5
C3—C2—Ru1124.6 (5)H49A—C49—H49C109.5
C4—C3—C2121.9 (7)H49B—C49—H49C109.5
C4—C3—H3119.0C51—C50—C55122.3 (9)
C2—C3—H3119.0C51—C50—Ru376.2 (5)
C3—C4—C5120.6 (7)C55—C50—Ru370.3 (5)
C3—C4—H4119.7C51—C50—H50118.9
C5—C4—H4119.7C55—C50—H50118.9
C4—C5—C6122.0 (7)Ru3—C50—H50126.6
C4—C5—C10119.5 (6)C52—C51—C50119.9 (8)
C6—C5—C10118.5 (7)C52—C51—Ru371.1 (5)
C7—C6—C5120.1 (9)C50—C51—Ru368.4 (4)
C7—C6—H6119.9C52—C51—H51120.1
C5—C6—H6119.9C50—C51—H51120.1
C6—C7—C8121.5 (8)Ru3—C51—H51133.6
C6—C7—H7119.2C51—C52—C53122.0 (8)
C8—C7—H7119.2C51—C52—Ru374.5 (5)
C9—C8—C7120.8 (8)C53—C52—Ru367.6 (4)
C9—C8—H8119.6C51—C52—H52119.0
C7—C8—H8119.6C53—C52—H52119.0
C8—C9—C10120.8 (8)Ru3—C52—H52131.9
C8—C9—H9119.6C52—C53—C54119.2 (9)
C10—C9—H9119.6C52—C53—Ru375.7 (5)
C11—C10—C9124.0 (7)C54—C53—Ru369.9 (4)
C11—C10—C5117.7 (6)C52—C53—H53120.4
C9—C10—C5118.2 (7)C54—C53—H53120.4
C2—C11—C10122.6 (6)Ru3—C53—H53125.7
C2—C11—C12117.4 (6)C53—C54—C55119.0 (8)
C10—C11—C12120.0 (6)C53—C54—Ru371.7 (4)
C11—C12—N1108.0 (5)C55—C54—Ru372.0 (5)
C11—C12—C13111.9 (6)C53—C54—H54120.5
N1—C12—C13107.7 (6)C55—C54—H54120.5
C11—C12—H12109.7Ru3—C54—H54127.8
N1—C12—H12109.7C50—C55—C54117.3 (8)
C13—C12—H12109.7C50—C55—Ru372.5 (5)
C12—C13—H13A109.5C54—C55—Ru368.8 (5)
C12—C13—H13B109.5C50—C55—H55121.3
H13A—C13—H13B109.5C54—C55—H55121.3
C12—C13—H13C109.5Ru3—C55—H55129.6
H13A—C13—H13C109.5Cl1—C56—Cl2111.6 (4)
H13B—C13—H13C109.5Cl1—C56—H56A109.3
C15—C14—C19122.7 (8)Cl2—C56—H56A109.3
C15—C14—Ru171.3 (5)Cl1—C56—H56B109.3
C19—C14—Ru175.4 (5)Cl2—C56—H56B109.3
C15—C14—H14118.6H56A—C56—H56B108.0
C19—C14—H14118.6C12—N1—Ru1115.6 (4)
Ru1—C14—H14126.7C12—N1—H1A108.4
C16—C15—C14119.3 (8)Ru1—N1—H1A108.4
C16—C15—Ru171.0 (5)C12—N1—H1B108.4
C14—C15—Ru171.1 (5)Ru1—N1—H1B108.4
C16—C15—H15120.3H1A—N1—H1B107.4
C14—C15—H15120.3C30—N2—Ru2114.4 (4)
Ru1—C15—H15130.0C30—N2—H2A108.7
C17—C16—C15121.6 (8)Ru2—N2—H2A108.7
C17—C16—Ru171.9 (5)C30—N2—H2B108.7
C15—C16—Ru171.6 (5)Ru2—N2—H2B108.7
C17—C16—H16119.2H2A—N2—H2B107.6
C15—C16—H16119.2C48—N3—Ru3114.9 (4)
Ru1—C16—H16129.9C48—N3—H3A108.5
C16—C17—C18119.3 (8)Ru3—N3—H3A108.5
C16—C17—Ru170.9 (5)C48—N3—H3B108.5
C18—C17—Ru172.4 (5)Ru3—N3—H3B108.5
C16—C17—H17120.4H3A—N3—H3B107.5
C18—C17—H17120.4C1—O1—Ru1127.5 (4)
Ru1—C17—H17128.5C1—O2—Ru2122.9 (4)
C17—C18—C19120.6 (8)C1—O3—Ru3130.9 (4)
C17—C18—Ru169.8 (4)F3—P1—F292.2 (4)
C19—C18—Ru173.1 (5)F3—P1—F489.5 (3)
C17—C18—H18119.7F2—P1—F491.4 (3)
C19—C18—H18119.7F3—P1—F1178.3 (4)
Ru1—C18—H18129.9F2—P1—F187.6 (4)
C14—C19—C18116.3 (7)F4—P1—F192.3 (3)
C14—C19—Ru167.8 (5)F3—P1—F590.3 (4)
C18—C19—Ru169.0 (4)F2—P1—F5177.5 (4)
C14—C19—H19121.8F4—P1—F589.0 (3)
C18—C19—H19121.8F1—P1—F589.9 (4)
Ru1—C19—H19134.2F3—P1—F691.2 (3)
C29—C20—C21117.6 (6)F2—P1—F690.2 (3)
C29—C20—Ru2117.1 (5)F4—P1—F6178.3 (3)
C21—C20—Ru2125.1 (5)F1—P1—F687.1 (3)
C22—C21—C20121.1 (6)F5—P1—F689.4 (3)
C22—C21—H21119.4C2—Ru1—O180.0 (2)
C20—C21—H21119.4C2—Ru1—N178.9 (2)
C21—C22—C23122.3 (6)O1—Ru1—N185.3 (2)
C21—C22—H22118.8C2—Ru1—C1692.6 (3)
C23—C22—H22118.8O1—Ru1—C16129.5 (3)
C22—C23—C24122.2 (6)N1—Ru1—C16142.6 (3)
C22—C23—C28118.5 (6)C2—Ru1—C14133.2 (3)
C24—C23—C28119.3 (6)O1—Ru1—C14145.5 (3)
C25—C24—C23121.0 (7)N1—Ru1—C1492.0 (3)
C25—C24—H24119.5C16—Ru1—C1467.4 (4)
C23—C24—H24119.5C2—Ru1—C15102.3 (3)
C24—C25—C26120.4 (7)O1—Ru1—C15166.3 (3)
C24—C25—H25119.8N1—Ru1—C15108.4 (3)
C26—C25—H25119.8C16—Ru1—C1537.5 (3)
C27—C26—C25120.1 (7)C14—Ru1—C1537.5 (3)
C27—C26—H26120.0C2—Ru1—C17109.5 (3)
C25—C26—H26120.0O1—Ru1—C1798.7 (3)
C26—C27—C28122.2 (7)N1—Ru1—C17171.2 (3)
C26—C27—H27118.9C16—Ru1—C1737.2 (3)
C28—C27—H27118.9C14—Ru1—C1780.2 (3)
C23—C28—C27116.9 (7)C15—Ru1—C1767.7 (3)
C23—C28—C29118.2 (6)C2—Ru1—C18144.4 (3)
C27—C28—C29124.8 (6)O1—Ru1—C1890.6 (3)
C20—C29—C28122.2 (6)N1—Ru1—C18134.9 (3)
C20—C29—C30116.4 (6)C16—Ru1—C1867.1 (3)
C28—C29—C30121.4 (5)C14—Ru1—C1867.3 (4)
N2—C30—C29106.6 (5)C15—Ru1—C1879.7 (3)
N2—C30—C31109.2 (6)C17—Ru1—C1837.7 (3)
C29—C30—C31110.2 (6)C2—Ru1—C19169.4 (3)
N2—C30—H30110.3O1—Ru1—C19110.5 (3)
C29—C30—H30110.3N1—Ru1—C19102.9 (3)
C31—C30—H30110.3C16—Ru1—C1979.6 (3)
C30—C31—H31A109.5C14—Ru1—C1936.8 (4)
C30—C31—H31B109.5C15—Ru1—C1967.2 (3)
H31A—C31—H31B109.5C17—Ru1—C1968.3 (4)
C30—C31—H31C109.5C18—Ru1—C1937.9 (4)
H31A—C31—H31C109.5C20—Ru2—N277.8 (2)
H31B—C31—H31C109.5C20—Ru2—O282.6 (2)
C37—C32—C33119.4 (7)N2—Ru2—O285.66 (19)
C37—C32—Ru271.2 (4)C20—Ru2—C3392.9 (3)
C33—C32—Ru269.7 (4)N2—Ru2—C33122.5 (2)
C37—C32—H32120.3O2—Ru2—C33150.1 (2)
C33—C32—H32120.3C20—Ru2—C34115.9 (3)
Ru2—C32—H32131.6N2—Ru2—C3496.5 (2)
C34—C33—C32118.9 (7)O2—Ru2—C34161.5 (3)
C34—C33—Ru271.3 (4)C33—Ru2—C3437.7 (3)
C32—C33—Ru272.1 (4)C20—Ru2—C37126.3 (3)
C34—C33—H33120.6N2—Ru2—C37154.9 (3)
C32—C33—H33120.6O2—Ru2—C3790.4 (2)
Ru2—C33—H33128.2C33—Ru2—C3768.5 (3)
C33—C34—C35121.0 (6)C34—Ru2—C3779.8 (3)
C33—C34—Ru271.0 (4)C20—Ru2—C3298.1 (3)
C35—C34—Ru274.0 (4)N2—Ru2—C32160.6 (3)
C33—C34—H34119.5O2—Ru2—C32112.9 (2)
C35—C34—H34119.5C33—Ru2—C3238.3 (3)
Ru2—C34—H34127.6C34—Ru2—C3267.9 (3)
C36—C35—C34119.7 (7)C37—Ru2—C3237.5 (3)
C36—C35—Ru272.7 (4)C20—Ru2—C35153.0 (3)
C34—C35—Ru267.9 (4)N2—Ru2—C3595.8 (2)
C36—C35—H35120.1O2—Ru2—C35123.5 (2)
C34—C35—H35120.1C33—Ru2—C3568.1 (3)
Ru2—C35—H35132.1C34—Ru2—C3538.1 (3)
C35—C36—C37119.9 (7)C37—Ru2—C3566.0 (3)
C35—C36—Ru271.8 (4)C32—Ru2—C3579.2 (3)
C37—C36—Ru268.9 (4)C20—Ru2—C36163.4 (2)
C35—C36—H36120.1N2—Ru2—C36118.6 (2)
C37—C36—H36120.1O2—Ru2—C3696.0 (2)
Ru2—C36—H36132.2C33—Ru2—C3680.0 (3)
C32—C37—C36120.9 (7)C34—Ru2—C3666.7 (3)
C32—C37—Ru271.3 (4)C37—Ru2—C3637.2 (3)
C36—C37—Ru273.9 (4)C32—Ru2—C3667.1 (3)
C32—C37—H37119.5C35—Ru2—C3635.5 (3)
C36—C37—H37119.5C38—Ru3—C5492.3 (3)
Ru2—C37—H37127.3C38—Ru3—N378.2 (2)
C47—C38—C39117.9 (5)C54—Ru3—N3125.4 (4)
C47—C38—Ru3117.5 (5)C38—Ru3—O381.8 (2)
C39—C38—Ru3124.5 (5)C54—Ru3—O3141.9 (4)
C40—C39—C38121.0 (6)N3—Ru3—O390.30 (19)
C40—C39—H39119.5C38—Ru3—C53114.2 (3)
C38—C39—H39119.5C54—Ru3—C5338.3 (4)
C39—C40—C41121.3 (6)N3—Ru3—C5397.7 (3)
C39—C40—H40119.3O3—Ru3—C53163.2 (3)
C41—C40—H40119.3C38—Ru3—C5599.5 (3)
C40—C41—C46119.8 (6)C54—Ru3—C5539.2 (4)
C40—C41—C42120.7 (7)N3—Ru3—C55164.6 (4)
C46—C41—C42119.5 (7)O3—Ru3—C55104.5 (4)
C43—C42—C41119.4 (7)C53—Ru3—C5569.2 (4)
C43—C42—H42120.3C38—Ru3—C50129.7 (4)
C41—C42—H42120.3C54—Ru3—C5068.1 (4)
C42—C43—C44121.6 (7)N3—Ru3—C50151.0 (3)
C42—C43—H43119.2O3—Ru3—C5087.0 (2)
C44—C43—H43119.2C53—Ru3—C5078.9 (3)
C45—C44—C43120.8 (8)C55—Ru3—C5037.2 (4)
C45—C44—H44119.6C38—Ru3—C52150.1 (3)
C43—C44—H44119.6C54—Ru3—C5266.7 (3)
C44—C45—C46120.3 (8)N3—Ru3—C5296.4 (3)
C44—C45—H45119.8O3—Ru3—C52127.9 (3)
C46—C45—H45119.8C53—Ru3—C5236.7 (3)
C41—C46—C45118.4 (6)C55—Ru3—C5278.0 (3)
C41—C46—C47118.3 (6)C50—Ru3—C5263.7 (4)
C45—C46—C47123.3 (7)C38—Ru3—C51164.6 (3)
C38—C47—C46121.7 (6)C54—Ru3—C5178.1 (3)
C38—C47—C48116.5 (6)N3—Ru3—C51117.2 (3)
C46—C47—C48121.7 (6)O3—Ru3—C5198.2 (3)
N3—C48—C49110.5 (6)C53—Ru3—C5165.0 (3)
N3—C48—C47107.4 (6)C55—Ru3—C5165.5 (3)
C49—C48—C47112.6 (5)C50—Ru3—C5135.4 (3)
N3—C48—H48108.8C52—Ru3—C5134.4 (3)
C49—C48—H48108.8
C11—C2—C3—C41.8 (10)C17—C18—Ru1—C19132.7 (8)
Ru1—C2—C3—C4−168.3 (6)C14—C19—Ru1—C2−23 (2)
C2—C3—C4—C50.8 (11)C18—C19—Ru1—C2109.2 (18)
C3—C4—C5—C6175.9 (7)C14—C19—Ru1—O1165.5 (5)
C3—C4—C5—C10−0.8 (11)C18—C19—Ru1—O1−62.5 (5)
C4—C5—C6—C7−176.4 (7)C14—C19—Ru1—N175.8 (5)
C10—C5—C6—C70.4 (10)C18—C19—Ru1—N1−152.2 (5)
C5—C6—C7—C80.9 (12)C14—C19—Ru1—C16−66.1 (6)
C6—C7—C8—C9−1.9 (13)C18—C19—Ru1—C1665.9 (5)
C7—C8—C9—C101.5 (12)C18—C19—Ru1—C14132.0 (8)
C8—C9—C10—C11177.5 (7)C14—C19—Ru1—C15−29.1 (5)
C8—C9—C10—C5−0.3 (10)C18—C19—Ru1—C15102.9 (6)
C4—C5—C10—C11−1.7 (9)C14—C19—Ru1—C17−103.0 (6)
C6—C5—C10—C11−178.6 (6)C18—C19—Ru1—C1728.9 (5)
C4—C5—C10—C9176.2 (6)C14—C19—Ru1—C18−132.0 (8)
C6—C5—C10—C9−0.7 (9)C29—C20—Ru2—N2−8.2 (5)
C3—C2—C11—C10−4.5 (10)C21—C20—Ru2—N2166.5 (6)
Ru1—C2—C11—C10166.3 (5)C29—C20—Ru2—O2−95.3 (5)
C3—C2—C11—C12175.6 (6)C21—C20—Ru2—O279.4 (5)
Ru1—C2—C11—C12−13.6 (8)C29—C20—Ru2—C33114.4 (5)
C9—C10—C11—C2−173.2 (6)C21—C20—Ru2—C33−70.9 (5)
C5—C10—C11—C24.5 (10)C29—C20—Ru2—C3483.3 (5)
C9—C10—C11—C126.7 (10)C21—C20—Ru2—C34−102.1 (5)
C5—C10—C11—C12−175.6 (6)C29—C20—Ru2—C37179.7 (4)
C2—C11—C12—N118.7 (8)C21—C20—Ru2—C37−5.6 (6)
C10—C11—C12—N1−161.2 (6)C29—C20—Ru2—C32152.5 (5)
C2—C11—C12—C13−99.7 (7)C21—C20—Ru2—C32−32.8 (6)
C10—C11—C12—C1380.4 (8)C29—C20—Ru2—C3570.5 (7)
C19—C14—C15—C16−3.7 (13)C21—C20—Ru2—C35−114.9 (6)
Ru1—C14—C15—C1654.1 (8)C29—C20—Ru2—C36178.5 (7)
C19—C14—C15—Ru1−57.7 (8)C21—C20—Ru2—C36−6.9 (12)
C14—C15—C16—C17−0.2 (13)C30—N2—Ru2—C2022.1 (4)
Ru1—C15—C16—C1754.0 (8)C30—N2—Ru2—O2105.5 (4)
C14—C15—C16—Ru1−54.2 (7)C30—N2—Ru2—C33−63.6 (5)
C15—C16—C17—C182.1 (13)C30—N2—Ru2—C34−93.0 (5)
Ru1—C16—C17—C1855.9 (7)C30—N2—Ru2—C37−172.9 (5)
C15—C16—C17—Ru1−53.8 (7)C30—N2—Ru2—C32−57.6 (9)
C16—C17—C18—C19−0.4 (13)C30—N2—Ru2—C35−131.3 (4)
Ru1—C17—C18—C1954.8 (7)C30—N2—Ru2—C36−160.0 (4)
C16—C17—C18—Ru1−55.2 (7)C1—O2—Ru2—C20139.6 (5)
C15—C14—C19—C185.2 (13)C1—O2—Ru2—N261.3 (5)
Ru1—C14—C19—C18−50.7 (7)C1—O2—Ru2—C33−137.4 (5)
C15—C14—C19—Ru155.9 (8)C1—O2—Ru2—C34−36.3 (9)
C17—C18—C19—C14−3.1 (12)C1—O2—Ru2—C37−93.8 (5)
Ru1—C18—C19—C1450.2 (7)C1—O2—Ru2—C32−124.7 (5)
C17—C18—C19—Ru1−53.2 (7)C1—O2—Ru2—C35−32.7 (5)
C29—C20—C21—C220.1 (9)C1—O2—Ru2—C36−57.0 (5)
Ru2—C20—C21—C22−174.6 (5)C34—C33—Ru2—C20−130.4 (4)
C20—C21—C22—C230.8 (10)C32—C33—Ru2—C2099.4 (4)
C21—C22—C23—C24178.1 (7)C34—C33—Ru2—N2−52.9 (5)
C21—C22—C23—C28−0.8 (10)C32—C33—Ru2—N2176.8 (4)
C22—C23—C24—C25−176.8 (7)C34—C33—Ru2—O2149.3 (5)
C28—C23—C24—C252.0 (11)C32—C33—Ru2—O219.1 (7)
C23—C24—C25—C26−0.5 (12)C32—C33—Ru2—C34−130.2 (7)
C24—C25—C26—C27−2.0 (12)C34—C33—Ru2—C37101.5 (5)
C25—C26—C27—C282.8 (11)C32—C33—Ru2—C37−28.7 (4)
C22—C23—C28—C27177.7 (6)C34—C33—Ru2—C32130.2 (7)
C24—C23—C28—C27−1.2 (9)C34—C33—Ru2—C3529.7 (4)
C22—C23—C28—C290.0 (9)C32—C33—Ru2—C35−100.5 (5)
C24—C23—C28—C29−178.9 (6)C34—C33—Ru2—C3664.7 (4)
C26—C27—C28—C23−1.2 (10)C32—C33—Ru2—C36−65.6 (4)
C26—C27—C28—C29176.3 (7)C33—C34—Ru2—C2057.7 (5)
C21—C20—C29—C28−0.9 (9)C35—C34—Ru2—C20−170.6 (4)
Ru2—C20—C29—C28174.2 (5)C33—C34—Ru2—N2137.3 (4)
C21—C20—C29—C30177.9 (6)C35—C34—Ru2—N2−91.0 (4)
Ru2—C20—C29—C30−7.0 (7)C33—C34—Ru2—O2−126.8 (7)
C23—C28—C29—C200.8 (9)C35—C34—Ru2—O24.9 (9)
C27—C28—C29—C20−176.7 (6)C35—C34—Ru2—C33131.7 (6)
C23—C28—C29—C30−177.9 (6)C33—C34—Ru2—C37−67.8 (4)
C27—C28—C29—C304.6 (10)C35—C34—Ru2—C3763.9 (4)
C20—C29—C30—N224.0 (8)C33—C34—Ru2—C32−30.7 (4)
C28—C29—C30—N2−157.2 (6)C35—C34—Ru2—C32101.0 (5)
C20—C29—C30—C31−94.4 (7)C33—C34—Ru2—C35−131.7 (6)
C28—C29—C30—C3184.4 (8)C33—C34—Ru2—C36−104.3 (4)
C37—C32—C33—C34−2.8 (9)C35—C34—Ru2—C3627.4 (4)
Ru2—C32—C33—C34−55.7 (5)C32—C37—Ru2—C20−47.9 (5)
C37—C32—C33—Ru252.9 (6)C36—C37—Ru2—C20−179.4 (4)
C32—C33—C34—C35−0.8 (9)C32—C37—Ru2—N2150.4 (5)
Ru2—C33—C34—C35−56.9 (5)C36—C37—Ru2—N219.0 (8)
C32—C33—C34—Ru256.1 (5)C32—C37—Ru2—O2−129.0 (4)
C33—C34—C35—C362.4 (10)C36—C37—Ru2—O299.5 (4)
Ru2—C34—C35—C36−53.1 (6)C32—C37—Ru2—C3329.3 (4)
C33—C34—C35—Ru255.5 (5)C36—C37—Ru2—C33−102.2 (5)
C34—C35—C36—C37−0.3 (10)C32—C37—Ru2—C3466.8 (5)
Ru2—C35—C36—C37−51.2 (6)C36—C37—Ru2—C34−64.7 (4)
C34—C35—C36—Ru250.9 (5)C36—C37—Ru2—C32−131.5 (6)
C33—C32—C37—C364.9 (10)C32—C37—Ru2—C35104.0 (5)
Ru2—C32—C37—C3657.1 (6)C36—C37—Ru2—C35−27.4 (4)
C33—C32—C37—Ru2−52.2 (6)C32—C37—Ru2—C36131.5 (6)
C35—C36—C37—C32−3.3 (10)C37—C32—Ru2—C20142.8 (4)
Ru2—C36—C37—C32−55.9 (6)C33—C32—Ru2—C20−84.4 (4)
C35—C36—C37—Ru252.5 (6)C37—C32—Ru2—N2−140.9 (7)
C47—C38—C39—C400.1 (9)C33—C32—Ru2—N2−8.1 (10)
Ru3—C38—C39—C40−176.1 (5)C37—C32—Ru2—O257.4 (5)
C38—C39—C40—C411.4 (10)C33—C32—Ru2—O2−169.8 (4)
C39—C40—C41—C46−1.9 (10)C37—C32—Ru2—C33−132.8 (6)
C39—C40—C41—C42177.6 (6)C37—C32—Ru2—C34−102.5 (5)
C40—C41—C42—C43−178.2 (7)C33—C32—Ru2—C3430.3 (4)
C46—C41—C42—C431.3 (11)C33—C32—Ru2—C37132.8 (6)
C41—C42—C43—C44−1.1 (12)C37—C32—Ru2—C35−64.5 (4)
C42—C43—C44—C45−0.2 (13)C33—C32—Ru2—C3568.3 (4)
C43—C44—C45—C461.3 (12)C37—C32—Ru2—C36−29.4 (4)
C40—C41—C46—C45179.2 (6)C33—C32—Ru2—C36103.3 (5)
C42—C41—C46—C45−0.3 (10)C36—C35—Ru2—C20152.2 (5)
C40—C41—C46—C471.0 (9)C34—C35—Ru2—C2018.8 (8)
C42—C41—C46—C47−178.6 (6)C36—C35—Ru2—N2−133.4 (4)
C44—C45—C46—C41−0.9 (10)C34—C35—Ru2—N293.3 (4)
C44—C45—C46—C47177.2 (7)C36—C35—Ru2—O2−44.8 (5)
C39—C38—C47—C46−1.0 (9)C34—C35—Ru2—O2−178.1 (3)
Ru3—C38—C47—C46175.5 (5)C36—C35—Ru2—C33103.9 (4)
C39—C38—C47—C48176.3 (6)C34—C35—Ru2—C33−29.5 (4)
Ru3—C38—C47—C48−7.2 (7)C36—C35—Ru2—C34133.4 (6)
C41—C46—C47—C380.5 (9)C36—C35—Ru2—C3728.6 (4)
C45—C46—C47—C38−177.7 (6)C34—C35—Ru2—C37−104.7 (5)
C41—C46—C47—C48−176.7 (6)C36—C35—Ru2—C3265.6 (4)
C45—C46—C47—C485.2 (10)C34—C35—Ru2—C32−67.8 (4)
C38—C47—C48—N321.1 (8)C34—C35—Ru2—C36−133.4 (6)
C46—C47—C48—N3−161.6 (5)C35—C36—Ru2—C20−131.9 (8)
C38—C47—C48—C49−100.8 (7)C37—C36—Ru2—C201.7 (11)
C46—C47—C48—C4976.5 (8)C35—C36—Ru2—N255.5 (5)
C55—C50—C51—C52−4.5 (13)C37—C36—Ru2—N2−171.0 (4)
Ru3—C50—C51—C5251.1 (8)C35—C36—Ru2—O2143.8 (4)
C55—C50—C51—Ru3−55.6 (7)C37—C36—Ru2—O2−82.6 (4)
C50—C51—C52—C530.4 (13)C35—C36—Ru2—C33−66.2 (4)
Ru3—C51—C52—C5350.3 (7)C37—C36—Ru2—C3367.4 (4)
C50—C51—C52—Ru3−49.8 (7)C35—C36—Ru2—C34−29.2 (4)
C51—C52—C53—C543.4 (12)C37—C36—Ru2—C34104.4 (5)
Ru3—C52—C53—C5456.7 (6)C35—C36—Ru2—C37−133.6 (6)
C51—C52—C53—Ru3−53.3 (8)C35—C36—Ru2—C32−103.9 (5)
C52—C53—C54—C55−3.3 (11)C37—C36—Ru2—C3229.7 (4)
Ru3—C53—C54—C5556.3 (6)C37—C36—Ru2—C35133.6 (6)
C52—C53—C54—Ru3−59.6 (7)C47—C38—Ru3—C54119.8 (6)
C51—C50—C55—C544.5 (12)C39—C38—Ru3—C54−64.0 (6)
Ru3—C50—C55—C54−53.8 (6)C47—C38—Ru3—N3−5.9 (4)
C51—C50—C55—Ru358.3 (7)C39—C38—Ru3—N3170.3 (5)
C53—C54—C55—C50−0.5 (11)C47—C38—Ru3—O3−98.0 (5)
Ru3—C54—C55—C5055.7 (7)C39—C38—Ru3—O378.2 (5)
C53—C54—C55—Ru3−56.2 (6)C47—C38—Ru3—C5387.3 (5)
C11—C12—N1—Ru1−15.9 (7)C39—C38—Ru3—C53−96.6 (6)
C13—C12—N1—Ru1105.3 (5)C47—C38—Ru3—C55158.5 (6)
C29—C30—N2—Ru2−30.4 (6)C39—C38—Ru3—C55−25.3 (6)
C31—C30—N2—Ru288.6 (5)C47—C38—Ru3—C50−177.1 (5)
C49—C48—N3—Ru397.5 (6)C39—C38—Ru3—C50−0.9 (7)
C47—C48—N3—Ru3−25.7 (6)C47—C38—Ru3—C5276.3 (7)
O3—C1—O1—Ru13.7 (8)C39—C38—Ru3—C52−107.6 (8)
O2—C1—O1—Ru1−174.1 (4)C47—C38—Ru3—C51170.9 (9)
O3—C1—O2—Ru2178.5 (4)C39—C38—Ru3—C51−13.0 (14)
O1—C1—O2—Ru2−3.7 (7)C53—C54—Ru3—C38−127.7 (6)
O1—C1—O3—Ru3−177.6 (4)C55—C54—Ru3—C38102.2 (5)
O2—C1—O3—Ru30.2 (8)C53—C54—Ru3—N3−50.5 (6)
C11—C2—Ru1—O1−84.1 (5)C55—C54—Ru3—N3179.3 (4)
C3—C2—Ru1—O186.0 (6)C53—C54—Ru3—O3152.8 (5)
C11—C2—Ru1—N13.0 (5)C55—C54—Ru3—O322.6 (7)
C3—C2—Ru1—N1173.1 (6)C55—C54—Ru3—C53−130.1 (7)
C11—C2—Ru1—C16146.3 (5)C53—C54—Ru3—C55130.1 (7)
C3—C2—Ru1—C16−43.6 (6)C53—C54—Ru3—C50100.0 (6)
C11—C2—Ru1—C1485.2 (6)C55—C54—Ru3—C50−30.1 (5)
C3—C2—Ru1—C14−104.7 (6)C53—C54—Ru3—C5230.4 (5)
C11—C2—Ru1—C15109.7 (5)C55—C54—Ru3—C52−99.8 (6)
C3—C2—Ru1—C15−80.2 (6)C53—C54—Ru3—C5164.5 (6)
C11—C2—Ru1—C17−179.9 (5)C55—C54—Ru3—C51−65.6 (5)
C3—C2—Ru1—C17−9.8 (7)C48—N3—Ru3—C3818.2 (4)
C11—C2—Ru1—C18−161.0 (5)C48—N3—Ru3—C54−66.2 (5)
C3—C2—Ru1—C189.1 (9)C48—N3—Ru3—O399.7 (4)
C11—C2—Ru1—C19103.8 (18)C48—N3—Ru3—C53−95.1 (5)
C3—C2—Ru1—C19−86.1 (19)C48—N3—Ru3—C55−64.6 (12)
C1—O1—Ru1—C2125.6 (5)C48—N3—Ru3—C50−176.0 (5)
C1—O1—Ru1—N146.1 (5)C48—N3—Ru3—C52−132.1 (5)
C1—O1—Ru1—C16−149.2 (5)C48—N3—Ru3—C51−160.9 (5)
C1—O1—Ru1—C14−40.6 (7)C1—O3—Ru3—C38103.6 (5)
C1—O1—Ru1—C15−133.5 (11)C1—O3—Ru3—C54−173.3 (5)
C1—O1—Ru1—C17−125.9 (5)C1—O3—Ru3—N325.5 (5)
C1—O1—Ru1—C18−88.9 (5)C1—O3—Ru3—C53−93.2 (12)
C1—O1—Ru1—C19−55.9 (6)C1—O3—Ru3—C55−158.7 (5)
C12—N1—Ru1—C27.8 (5)C1—O3—Ru3—C50−125.6 (6)
C12—N1—Ru1—O188.5 (5)C1—O3—Ru3—C52−72.8 (6)
C12—N1—Ru1—C16−71.9 (7)C1—O3—Ru3—C51−92.0 (6)
C12—N1—Ru1—C14−126.0 (5)C52—C53—Ru3—C38−170.8 (5)
C12—N1—Ru1—C15−91.6 (5)C54—C53—Ru3—C3860.1 (6)
C12—N1—Ru1—C18174.7 (5)C52—C53—Ru3—C54129.0 (8)
C12—N1—Ru1—C19−161.5 (5)C52—C53—Ru3—N3−90.4 (6)
C17—C16—Ru1—C2119.6 (5)C54—C53—Ru3—N3140.6 (6)
C15—C16—Ru1—C2−106.9 (5)C52—C53—Ru3—O327.4 (14)
C17—C16—Ru1—O140.3 (6)C54—C53—Ru3—O3−101.7 (12)
C15—C16—Ru1—O1173.9 (4)C52—C53—Ru3—C5597.9 (6)
C17—C16—Ru1—N1−165.4 (5)C54—C53—Ru3—C55−31.1 (6)
C15—C16—Ru1—N1−31.8 (7)C52—C53—Ru3—C5060.5 (6)
C17—C16—Ru1—C14−104.1 (6)C54—C53—Ru3—C50−68.6 (6)
C15—C16—Ru1—C1429.5 (5)C54—C53—Ru3—C52−129.0 (8)
C17—C16—Ru1—C15−133.6 (8)C52—C53—Ru3—C5126.1 (5)
C15—C16—Ru1—C17133.6 (8)C54—C53—Ru3—C51−103.0 (6)
C17—C16—Ru1—C18−30.2 (5)C50—C55—Ru3—C38148.3 (5)
C15—C16—Ru1—C18103.4 (6)C54—C55—Ru3—C38−81.9 (5)
C17—C16—Ru1—C19−67.7 (6)C50—C55—Ru3—C54−129.7 (8)
C15—C16—Ru1—C1965.9 (6)C50—C55—Ru3—N3−131.7 (11)
C15—C14—Ru1—C241.7 (7)C54—C55—Ru3—N3−2.0 (14)
C19—C14—Ru1—C2174.4 (5)C50—C55—Ru3—O364.5 (6)
C15—C14—Ru1—O1−157.1 (4)C54—C55—Ru3—O3−165.8 (4)
C19—C14—Ru1—O1−24.4 (8)C50—C55—Ru3—C53−99.2 (6)
C15—C14—Ru1—N1118.3 (5)C54—C55—Ru3—C5330.5 (5)
C19—C14—Ru1—N1−109.0 (5)C54—C55—Ru3—C50129.7 (8)
C15—C14—Ru1—C16−29.5 (5)C50—C55—Ru3—C52−62.0 (6)
C19—C14—Ru1—C16103.2 (6)C54—C55—Ru3—C5267.7 (5)
C19—C14—Ru1—C15132.7 (8)C50—C55—Ru3—C51−28.1 (5)
C15—C14—Ru1—C17−65.9 (6)C54—C55—Ru3—C51101.6 (5)
C19—C14—Ru1—C1766.7 (6)C51—C50—Ru3—C38−174.5 (4)
C15—C14—Ru1—C18−103.0 (6)C55—C50—Ru3—C38−42.3 (7)
C19—C14—Ru1—C1829.7 (5)C51—C50—Ru3—C54−100.6 (6)
C15—C14—Ru1—C19−132.7 (8)C55—C50—Ru3—C5431.6 (6)
C16—C15—Ru1—C278.0 (5)C51—C50—Ru3—N323.6 (9)
C14—C15—Ru1—C2−150.3 (5)C55—C50—Ru3—N3155.8 (6)
C16—C15—Ru1—O1−20.2 (14)C51—C50—Ru3—O3108.8 (5)
C14—C15—Ru1—O1111.5 (12)C55—C50—Ru3—O3−119.0 (6)
C16—C15—Ru1—N1160.3 (5)C51—C50—Ru3—C53−62.2 (6)
C14—C15—Ru1—N1−68.1 (5)C55—C50—Ru3—C5370.1 (6)
C14—C15—Ru1—C16131.7 (8)C51—C50—Ru3—C55−132.2 (8)
C16—C15—Ru1—C14−131.7 (8)C51—C50—Ru3—C52−26.7 (5)
C16—C15—Ru1—C17−28.2 (5)C55—C50—Ru3—C52105.5 (6)
C14—C15—Ru1—C17103.5 (6)C55—C50—Ru3—C51132.2 (8)
C16—C15—Ru1—C18−65.7 (5)C51—C52—Ru3—C38152.0 (6)
C14—C15—Ru1—C1866.0 (6)C53—C52—Ru3—C3816.9 (10)
C16—C15—Ru1—C19−103.1 (6)C51—C52—Ru3—C54103.5 (7)
C14—C15—Ru1—C1928.5 (5)C53—C52—Ru3—C54−31.6 (6)
C16—C17—Ru1—C2−67.2 (6)C51—C52—Ru3—N3−130.6 (5)
C18—C17—Ru1—C2162.1 (5)C53—C52—Ru3—N394.3 (6)
C16—C17—Ru1—O1−149.6 (5)C51—C52—Ru3—O3−35.2 (6)
C18—C17—Ru1—O179.6 (6)C53—C52—Ru3—O3−170.3 (5)
C18—C17—Ru1—C16−130.7 (8)C51—C52—Ru3—C53135.1 (8)
C16—C17—Ru1—C1465.4 (6)C51—C52—Ru3—C5564.0 (6)
C18—C17—Ru1—C14−65.4 (6)C53—C52—Ru3—C55−71.1 (7)
C16—C17—Ru1—C1528.4 (5)C51—C52—Ru3—C5027.4 (5)
C18—C17—Ru1—C15−102.3 (6)C53—C52—Ru3—C50−107.7 (7)
C16—C17—Ru1—C18130.7 (8)C53—C52—Ru3—C51−135.1 (8)
C16—C17—Ru1—C19101.7 (6)C52—C51—Ru3—C38−118.4 (11)
C18—C17—Ru1—C19−29.1 (6)C50—C51—Ru3—C3816.1 (14)
C17—C18—Ru1—C2−29.9 (8)C52—C51—Ru3—C54−65.9 (6)
C19—C18—Ru1—C2−162.6 (5)C50—C51—Ru3—C5468.7 (6)
C17—C18—Ru1—O1−103.5 (6)C52—C51—Ru3—N358.0 (6)
C19—C18—Ru1—O1123.8 (5)C50—C51—Ru3—N3−167.4 (5)
C17—C18—Ru1—N1172.6 (5)C52—C51—Ru3—O3152.6 (5)
C19—C18—Ru1—N139.9 (7)C50—C51—Ru3—O3−72.8 (5)
C17—C18—Ru1—C1629.8 (5)C52—C51—Ru3—C53−27.7 (5)
C19—C18—Ru1—C16−102.9 (6)C50—C51—Ru3—C53106.8 (6)
C17—C18—Ru1—C14103.8 (6)C52—C51—Ru3—C55−105.1 (6)
C19—C18—Ru1—C14−28.9 (5)C50—C51—Ru3—C5529.5 (6)
C17—C18—Ru1—C1566.8 (6)C52—C51—Ru3—C50−134.5 (8)
C19—C18—Ru1—C15−65.9 (5)C50—C51—Ru3—C52134.5 (8)
C19—C18—Ru1—C17−132.7 (8)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···F6i0.922.373.245 (7)159
N1—H1B···O30.922.092.860 (7)141
N2—H2B···O10.922.382.967 (7)122
N3—H3A···F4ii0.922.363.202 (8)153
N3—H3B···O20.921.922.739 (7)148
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x, y, z−1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···F6i0.922.373.245 (7)159
N1—H1B···O30.922.092.860 (7)141
N2—H2B···O10.922.382.967 (7)122
N3—H3A···F4ii0.922.363.202 (8)153
N3—H3B···O20.921.922.739 (7)148
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x, y, z−1.
Acknowledgements top

The authors thank André De Cian for his contribution to this work, and the CNRS for financial support. The authors are also indebted to the Ministère de l'Education Nationale for a fellowship granted to JBS.

references
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