Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113019057/sf3205sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113019057/sf3205Isup2.hkl |
CCDC reference: 962899
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 RuII 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 RuII 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 RuII(tropN) complexes.
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.
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 Uiso(H) = 1.2Ueq(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).
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 RuII 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 [RuIICl(ampy)(η2-tropNH2)(PPh3)]OTf.CH2Cl2, (Ia), and [RuII(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.
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).
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).
[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) Å3 | 0.30 × 0.15 × 0.02 mm |
Z = 4 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0348P)2 + 4.730P] where P = (Fo2 + 2Fc2)/3 |
6919 reflections | (Δ/σ)max = 0.001 |
633 parameters | Δρmax = 0.91 e Å−3 |
19 restraints | Δρmin = −0.60 e Å−3 |
[Ru(Cl)0.91(CF3SO3)0.09(C6H8N2)(C15H13N)(C18H15P)] CF3SO3·0.91CH2Cl2 | V = 3923.1 (12) Å3 |
Mr = 950.79 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.374 (3) Å | µ = 0.75 mm−1 |
b = 15.875 (3) Å | T = 100 K |
c = 17.235 (3) Å | 0.30 × 0.15 × 0.02 mm |
β = 94.019 (4)° |
Bruker APEXII CCD diffractometer | 6919 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2012) | 5507 reflections with I > 2σ(I) |
Tmin = 0.807, Tmax = 0.985 | Rint = 0.046 |
37064 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 19 restraints |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.91 e Å−3 |
6919 reflections | Δρmin = −0.60 e Å−3 |
633 parameters |
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. |
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)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
Experimental details
Crystal data | |
Chemical formula | [Ru(Cl)0.91(CF3SO3)0.09(C6H8N2)(C15H13N)(C18H15P)] CF3SO3·0.91CH2Cl2 |
Mr | 950.79 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 14.374 (3), 15.875 (3), 17.235 (3) |
β (°) | 94.019 (4) |
V (Å3) | 3923.1 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.75 |
Crystal size (mm) | 0.30 × 0.15 × 0.02 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Bruker, 2012) |
Tmin, Tmax | 0.807, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 37064, 6919, 5507 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.082, 1.03 |
No. of reflections | 6919 |
No. of parameters | 633 |
No. of restraints | 19 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.91, −0.60 |
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Ru1—O2A | 2.11 (3) | Ru1—P1 | 2.3332 (8) |
Ru1—N1 | 2.143 (3) | Ru1—Cl1 | 2.4351 (13) |
Ru1—N2 | 2.117 (2) | Ru1—ct1 | 2.109 (3) |
Ru1—N3 | 2.154 (3) | ||
P1—Ru1—N1 | 171.71 (9) | N3—Ru1—ct1 | 167.5 (1) |
P1—Ru1—N2 | 95.78 (7) | P1—Ru1—Cl1 | 88.19 (3) |
P1—Ru1—N3 | 93.19 (7) | P1—Ru1—O2A | 75.1 (7) |
P1—Ru1—ct1 | 96.58 (7) | N1—Ru1—Cl1 | 83.68 (9) |
N1—Ru1—N2 | 91.68 (11) | N1—Ru1—O2A | 96.6 (7) |
N1—Ru1—N3 | 85.10 (10) | N2—Ru1—Cl1 | 164.57 (7) |
N1—Ru1—ct1 | 86.3 (1) | N2—Ru1—O2A | 153.3 (8) |
N2—Ru1—N3 | 75.92 (10) | N3—Ru1—Cl1 | 89.00 (8) |
N2—Ru1—ct1 | 95.3 (1) | N3—Ru1—O2A | 79.6 (8) |
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