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metal-organic compounds
(η6-Benzene){2-[2-(tert-butylsulfanyl)phenyl]pyridine-κ2N,S}chloridoruthenium(II) hexafluoridophosphate
aGraduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
*Correspondence e-mail: mhiro@sci.osaka-cu.ac.jp
In the title compound, [RuCl(C6H6)(C15H17NS)]PF6, the cation adopts a three-legged piano-stool structure around the Ru(II) atom with an η6-benzene ligand, a chloride ligand and a 2-[2-(tert-butylsulfanyl)phenyl]pyridine (btppy) ligand. The btppy ligand acts as a N,S-bidentate ligand, forming a six-membered ring, which has an The S—Ru—N bite angle is 86.76 (9)°, and the dihedral angle between the pyridine and benzene rings in btppy is 39.8 (2)°. The contains two pairs of racemic with (SRu,SS) and (RRu,RS) configurations, in which the tert-butyl group on the coordinated S atom is distant from the η6-benzene ligand.
Related literature
For general background to the use of chiral N,S-bidentate ligands in asymmetric allylic substitution reactions, see: Mellah et al. (2007). For the synthesis of 2-(2′-(tert-butylthio)phenyl)pyridine, see: Clavier et al. (2003
). For related structures, see: Shibue et al. (2008
); Sau et al. (2010
).
Experimental
Crystal data
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|
Data collection: CrystalClear (Rigaku, 1999); cell CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2006
); program(s) used to solve structure: SIR97 (Altomare et al., 1999
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997
); software used to prepare material for publication: CrystalStructure.
Supporting information
https://doi.org/10.1107/S1600536810049810/fj2364sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810049810/fj2364Isup2.hkl
The btppy ligand was prepared according to a literature procedure (Clavier et al., 2003). For the synthesis of the title compound (I), [RuCl2(C6H6)]2 (51 mg, 0.10 mmol) was added to a deoxygenated solution of btppy (50 mg, 0.21 mmol) in methanol (10 ml). The reaction mixture was refluxed for 6 h under an argon atmosphere. After cooling to room temperature, KPF6 (60 mg, 0.33 mmol) was added. The resulting orange solution was concentrated under reduced pressure. The residue was dissolved in chloroform (10 ml), and the insoluble white solid was removed by filtration. The filtrate was concentrated under reduced pressure, and the resulting brown residue was recrystallized by vapor diffusion of diethyl ether into a dichloromethane solution to afford yellow crystals (19 mg, 15%). Anal. Calcd for C21H23ClF6NPRuS: C, 41.83; H, 3.84; N, 2.32%. Found: C, 41.78; H, 3.82; N, 2.35%. 1H NMR (300 MHz, CDCl3): δ 1.00 (s, 9H, t-Bu), 5.62 (s, 6H, C6H6), 7.51 (ddd, J = 7.5, 6.0, 1.4 Hz, 1H), 7.62 (td, J = 7.6, 1.2 Hz, 1H), 7.77 (td, J = 7.7, 1.2 Hz, 1H), 7.82 (dd, J = 7.9, 1.0 Hz, 1H), 7.84 (dd, J = 7.6, 1.2 Hz, 1H), 8.02 (m, 2H), 9.39 (dd, J = 5.9, 1.2 Hz, 1H).
All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were located on calculated positions with C—H(aromatic) = 0.95 Å and C—H(methyl) = 0.98 Å, and were refined using a riding model with Uiso(H) = 1.2Ueq(C).
Coordination of bidentate ligands bearing thioether sulfur atoms generates η6-C6H6)]CF3SO3 (Shibue et al., 2008). In this complex, PyDBT acts as a N,S-bidentate ligand to form chiral centers at Ru and S atoms. The pyridine and dibenzothiophene planes in PyDBT are twisted with respect to each other, and the dibenzothiophene moiety is in close proximity to the η6-benzene ligand. To clarify the steric interactions around the coordinated S atom, we present here the of the title ruthenium(II) arene complex of 2-(2'-(t-butylthio)phenyl)pyridine (btppy).
at the sulfur center. The of the coordinated S atoms in catalysts would be important in improving enantioselectivities for asymmetric reactions. A variety of chiral N,S-bidentate ligands have been developed and used for asymmetric allylic substitution reactions (Mellah et al., 2007). We previously reported the structurally characterized ruthenium(II) arene complex with 4-(2'-pyridyl)dibenzothiophene (PyDBT), [RuCl(PyDBT)(The η6-C6H6)]+ cation and a hexafluorophosphate anion (Fig. 1). The Ru center of the complex cation is surrounded by a benzene, a btppy and a chloride ligand to form a three-legged piano-stool structure. The btppy ligand acts as a N,S-bidentate ligand to form a six-membered ring. The chelate ring adopts an which is similar to that in the previously reported ruthenium(II) complex [RuCl(PyDBT)(η6-C6H6)]CF3SO3, (II) (Shibue et al., 2008). The S—Ru—N bite angle (86.76 (9)°) is larger than that of (II) (79.20 (7)°, 80.00 (7)°, two independent molecules), which is due to the longer C—S bond in the btppy chelate ring (1.820 (5) Å) compared with the PyDBT chelate ring in (II) (C—S = 1.762 (5), 1.760 (4) Å). The Ru—S (2.3671 (10) Å) and Ru—N (2.122 (3) Å) bond lengths in (I) are slightly shorter than those in (II) (Ru—S, 2.3821 (9), 2.3901 (8) Å; Ru—N, 2.161 (3), 2.164 (3) Å), indicating the higher coordinating ability of btppy. The dihedral angle between the pyridine and benzene rings in btppy (39.8 (2)°) is similar to that in PyDBT of (II) (37.7 (2)°).
of the title compound (I) consists of a [RuCl(btppy)(There are two pair of racemic η6-benzene ligand. An average Ru—C distance of 2.180 (6) Å in (I) is comparable to that in (II) (2.192 (4), 2.180 (4) Å). The Cl—Ru—S angle (93.84 (4)°) in (I) is larger than that in (II) (82.84 (3)°, 84.87 (3)°), and no significant interaction was observed between the t-butyl group and the chloro ligand. Molecular modeling analysis suggests that the other with configurations of (SRu, RS) and (RRu, SS) cause a severe repulsive interaction between the t-butyl group and the benzene ligand. The 1H NMR spectrum of (I) in CDCl3 revealed the presence of a single diastereomer. This suggests that the (SRu, SS) and (RRu, RS) isomers observed in the crystal are retained in solution. Similar stereoselectivity was recently reported for the iridium(III) complex [(η5-C5Me5)Ir(η2-ppy-S-p-tol)(H2O)](OTf)2 (Sau et al., 2010), in which the structure of the chelate ring is analogous to that for btppy in (I).
with (SRu, SS) and (RRu, RS) configurations in the The t-butyl group on the coordinated S atom is placed far from theFor general background to the use of chiral N,S-bidentate ligands in asymmetric allylic substitution reactions, see: Mellah et al. (2007). For the synthesis of 2-(2'-(tert-butylthio)phenyl)pyridine, see: Clavier et al. (2003). For related structures, see: Shibue et al. (2008); Sau et al. (2010).
Data collection: CrystalClear (Rigaku, 1999); cell
CrystalClear (Rigaku, 1999); data reduction: CrystalStructure (Rigaku/MSC, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006). ![]() | Fig. 1. The molecular structure of (I) with numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. |
[RuCl(C6H6)(C15H17NS)]PF6 | F(000) = 1208.00 |
Mr = 602.97 | Dx = 1.702 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: C -2yc | Cell parameters from 5146 reflections |
a = 16.638 (4) Å | θ = 4.2–27.5° |
b = 10.5589 (19) Å | µ = 0.99 mm−1 |
c = 14.327 (3) Å | T = 193 K |
β = 110.758 (4)° | Prism, yellow |
V = 2353.6 (8) Å3 | 0.24 × 0.17 × 0.09 mm |
Z = 4 |
Rigaku Mercury diffractometer | 4474 independent reflections |
Radiation source: rotating anode X-ray tube | 4165 reflections with F2 > 2σ(F2) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 7.31 pixels mm-1 | θmax = 27.5°, θmin = 4.2° |
ω scans | h = −21→21 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −13→12 |
Tmin = 0.725, Tmax = 0.914 | l = −18→18 |
11123 measured reflections |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0317P)2 + 6.2745P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.037 | (Δ/σ)max < 0.001 |
wR(F2) = 0.078 | Δρmax = 0.52 e Å−3 |
S = 1.03 | Δρmin = −0.39 e Å−3 |
4474 reflections | Absolute structure: Flack (1983), 1824 Friedel pairs |
291 parameters | Absolute structure parameter: 0.03 (3) |
2 restraints |
[RuCl(C6H6)(C15H17NS)]PF6 | V = 2353.6 (8) Å3 |
Mr = 602.97 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 16.638 (4) Å | µ = 0.99 mm−1 |
b = 10.5589 (19) Å | T = 193 K |
c = 14.327 (3) Å | 0.24 × 0.17 × 0.09 mm |
β = 110.758 (4)° |
Rigaku Mercury diffractometer | 4474 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 4165 reflections with F2 > 2σ(F2) |
Tmin = 0.725, Tmax = 0.914 | Rint = 0.034 |
11123 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.078 | Δρmax = 0.52 e Å−3 |
S = 1.03 | Δρmin = −0.39 e Å−3 |
4474 reflections | Absolute structure: Flack (1983), 1824 Friedel pairs |
291 parameters | Absolute structure parameter: 0.03 (3) |
2 restraints |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Ru1 | 0.440889 (18) | 0.11432 (3) | 0.376620 (19) | 0.02598 (8) | |
Cl1 | 0.45796 (9) | 0.16185 (16) | 0.22110 (9) | 0.0513 (3) | |
S1 | 0.58842 (7) | 0.14331 (10) | 0.47160 (8) | 0.0254 (2) | |
P1 | 0.69584 (11) | 0.73747 (15) | 0.57967 (11) | 0.0475 (3) | |
F1 | 0.6579 (3) | 0.6607 (5) | 0.6493 (3) | 0.0999 (15) | |
F2 | 0.7309 (4) | 0.8098 (5) | 0.5069 (4) | 0.1156 (18) | |
F3 | 0.7809 (3) | 0.7558 (4) | 0.6683 (4) | 0.131 (2) | |
F4 | 0.6641 (4) | 0.8656 (4) | 0.6080 (4) | 0.120 (2) | |
F5 | 0.6079 (3) | 0.7164 (7) | 0.4899 (4) | 0.138 (2) | |
F6 | 0.7296 (3) | 0.6079 (4) | 0.5553 (4) | 0.1003 (16) | |
N1 | 0.4267 (2) | 0.3121 (3) | 0.3922 (3) | 0.0329 (9) | |
C1 | 0.3753 (3) | 0.3726 (5) | 0.3113 (4) | 0.0462 (12) | |
C2 | 0.3601 (4) | 0.5007 (6) | 0.3073 (6) | 0.0675 (19) | |
C3 | 0.4025 (4) | 0.5699 (5) | 0.3912 (6) | 0.066 (2) | |
C4 | 0.4540 (3) | 0.5107 (4) | 0.4763 (5) | 0.0516 (14) | |
C5 | 0.4655 (3) | 0.3802 (4) | 0.4765 (3) | 0.0336 (10) | |
C6 | 0.5200 (3) | 0.3164 (4) | 0.5718 (3) | 0.0369 (11) | |
C7 | 0.5125 (4) | 0.3609 (5) | 0.6596 (4) | 0.0549 (15) | |
C8 | 0.5601 (5) | 0.3089 (7) | 0.7504 (4) | 0.0643 (18) | |
C9 | 0.6163 (4) | 0.2118 (6) | 0.7564 (4) | 0.0589 (18) | |
C10 | 0.6249 (3) | 0.1659 (5) | 0.6696 (3) | 0.0452 (12) | |
C11 | 0.5760 (3) | 0.2207 (4) | 0.5792 (3) | 0.0306 (10) | |
C12 | 0.6615 (2) | 0.2452 (4) | 0.4304 (3) | 0.0346 (10) | |
C13 | 0.6198 (3) | 0.3698 (4) | 0.3827 (4) | 0.0450 (13) | |
C14 | 0.6825 (3) | 0.1590 (6) | 0.3568 (4) | 0.0515 (14) | |
C15 | 0.7403 (3) | 0.2697 (7) | 0.5230 (4) | 0.0566 (17) | |
C16 | 0.4470 (3) | −0.0321 (5) | 0.4865 (4) | 0.0507 (15) | |
C17 | 0.3813 (3) | 0.0508 (5) | 0.4822 (4) | 0.0457 (13) | |
C18 | 0.3169 (3) | 0.0775 (5) | 0.3907 (5) | 0.0519 (15) | |
C19 | 0.3172 (4) | 0.0179 (7) | 0.3037 (4) | 0.069 (2) | |
C20 | 0.3868 (5) | −0.0664 (7) | 0.3120 (6) | 0.076 (2) | |
C21 | 0.4492 (6) | −0.0882 (5) | 0.4002 (7) | 0.068 (2) | |
H1 | 0.3474 | 0.3241 | 0.2528 | 0.055* | |
H2 | 0.3218 | 0.5398 | 0.2487 | 0.081* | |
H3 | 0.3961 | 0.6593 | 0.3903 | 0.079* | |
H4 | 0.4818 | 0.5585 | 0.5351 | 0.062* | |
H7 | 0.4739 | 0.4283 | 0.6569 | 0.066* | |
H8 | 0.5538 | 0.3406 | 0.8095 | 0.077* | |
H9 | 0.6491 | 0.1763 | 0.8193 | 0.071* | |
H10 | 0.6634 | 0.0984 | 0.6720 | 0.054* | |
H13A | 0.5695 | 0.3517 | 0.3231 | 0.054* | |
H13B | 0.6614 | 0.4197 | 0.3638 | 0.054* | |
H13C | 0.6020 | 0.4178 | 0.4306 | 0.054* | |
H14A | 0.6306 | 0.1453 | 0.2980 | 0.062* | |
H14B | 0.7037 | 0.0775 | 0.3887 | 0.062* | |
H14C | 0.7268 | 0.1989 | 0.3362 | 0.062* | |
H15A | 0.7247 | 0.3251 | 0.5687 | 0.068* | |
H15B | 0.7849 | 0.3106 | 0.5036 | 0.068* | |
H15C | 0.7622 | 0.1891 | 0.5563 | 0.068* | |
H16 | 0.4907 | −0.0505 | 0.5488 | 0.061* | |
H17 | 0.3800 | 0.0896 | 0.5415 | 0.055* | |
H18 | 0.2728 | 0.1363 | 0.3876 | 0.062* | |
H19 | 0.2728 | 0.0329 | 0.2413 | 0.083* | |
H20 | 0.3888 | −0.1077 | 0.2539 | 0.091* | |
H21 | 0.4955 | −0.1428 | 0.4034 | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.02434 (16) | 0.02938 (15) | 0.02221 (15) | −0.00544 (19) | 0.00577 (12) | −0.00200 (19) |
Cl1 | 0.0469 (7) | 0.0825 (10) | 0.0235 (5) | −0.0105 (7) | 0.0113 (5) | −0.0022 (6) |
S1 | 0.0239 (5) | 0.0271 (5) | 0.0237 (5) | −0.0005 (4) | 0.0065 (4) | 0.0003 (4) |
P1 | 0.0524 (9) | 0.0479 (8) | 0.0337 (7) | 0.0149 (7) | 0.0047 (6) | −0.0053 (6) |
F1 | 0.124 (4) | 0.100 (3) | 0.094 (3) | 0.014 (3) | 0.062 (3) | 0.023 (2) |
F2 | 0.148 (5) | 0.094 (3) | 0.114 (4) | −0.026 (3) | 0.060 (3) | −0.005 (3) |
F3 | 0.113 (4) | 0.062 (2) | 0.125 (4) | 0.001 (2) | −0.071 (3) | 0.003 (2) |
F4 | 0.196 (6) | 0.076 (3) | 0.098 (3) | 0.084 (3) | 0.064 (4) | 0.020 (2) |
F5 | 0.093 (3) | 0.205 (6) | 0.073 (3) | −0.024 (4) | −0.025 (3) | 0.027 (3) |
F6 | 0.120 (3) | 0.070 (2) | 0.139 (4) | 0.001 (2) | 0.079 (3) | −0.043 (2) |
N1 | 0.020 (2) | 0.036 (2) | 0.041 (2) | 0.0042 (16) | 0.0090 (17) | 0.0089 (19) |
C1 | 0.033 (2) | 0.043 (3) | 0.056 (3) | 0.006 (2) | 0.009 (2) | 0.015 (2) |
C2 | 0.046 (3) | 0.058 (4) | 0.090 (5) | 0.013 (3) | 0.014 (3) | 0.037 (3) |
C3 | 0.056 (4) | 0.027 (2) | 0.116 (6) | 0.012 (2) | 0.031 (4) | 0.022 (3) |
C4 | 0.046 (3) | 0.028 (2) | 0.082 (4) | 0.003 (2) | 0.025 (3) | −0.002 (2) |
C5 | 0.026 (2) | 0.032 (2) | 0.042 (2) | −0.0003 (19) | 0.012 (2) | 0.002 (2) |
C6 | 0.037 (2) | 0.038 (2) | 0.038 (2) | −0.013 (2) | 0.016 (2) | −0.016 (2) |
C7 | 0.066 (4) | 0.053 (3) | 0.051 (3) | −0.008 (2) | 0.027 (3) | −0.025 (2) |
C8 | 0.081 (4) | 0.080 (4) | 0.036 (3) | −0.025 (3) | 0.026 (3) | −0.025 (3) |
C9 | 0.074 (4) | 0.074 (4) | 0.020 (2) | −0.021 (3) | 0.004 (3) | 0.000 (2) |
C10 | 0.050 (3) | 0.050 (3) | 0.029 (2) | −0.003 (2) | 0.006 (2) | 0.002 (2) |
C11 | 0.035 (2) | 0.025 (2) | 0.021 (2) | −0.0133 (18) | −0.004 (2) | 0.0025 (17) |
C12 | 0.022 (2) | 0.048 (2) | 0.033 (2) | −0.006 (2) | 0.010 (2) | 0.005 (2) |
C13 | 0.042 (3) | 0.042 (2) | 0.051 (3) | −0.008 (2) | 0.016 (2) | 0.015 (2) |
C14 | 0.046 (3) | 0.071 (4) | 0.047 (3) | 0.001 (2) | 0.028 (2) | −0.001 (2) |
C15 | 0.033 (3) | 0.079 (4) | 0.053 (4) | −0.017 (2) | 0.008 (2) | 0.008 (3) |
C16 | 0.047 (3) | 0.043 (3) | 0.055 (3) | −0.017 (2) | 0.008 (2) | 0.022 (2) |
C17 | 0.052 (3) | 0.051 (3) | 0.043 (3) | −0.020 (2) | 0.027 (2) | 0.001 (2) |
C18 | 0.030 (2) | 0.047 (3) | 0.078 (4) | −0.005 (2) | 0.019 (3) | 0.018 (3) |
C19 | 0.052 (4) | 0.085 (5) | 0.044 (3) | −0.049 (3) | −0.014 (3) | 0.015 (3) |
C20 | 0.096 (6) | 0.066 (4) | 0.088 (5) | −0.050 (4) | 0.062 (5) | −0.052 (4) |
C21 | 0.062 (5) | 0.027 (2) | 0.123 (9) | −0.009 (3) | 0.042 (6) | 0.000 (3) |
Ru1—Cl1 | 2.3970 (14) | C12—C14 | 1.524 (8) |
Ru1—S1 | 2.3671 (10) | C12—C15 | 1.521 (6) |
Ru1—N1 | 2.122 (3) | C16—C17 | 1.386 (8) |
Ru1—C16 | 2.183 (6) | C16—C21 | 1.383 (12) |
Ru1—C17 | 2.187 (6) | C17—C18 | 1.396 (7) |
Ru1—C18 | 2.178 (6) | C18—C19 | 1.398 (10) |
Ru1—C19 | 2.199 (6) | C19—C20 | 1.432 (12) |
Ru1—C20 | 2.172 (7) | C20—C21 | 1.340 (11) |
Ru1—C21 | 2.161 (5) | C1—H1 | 0.950 |
S1—C11 | 1.820 (5) | C2—H2 | 0.950 |
S1—C12 | 1.869 (5) | C3—H3 | 0.950 |
P1—F1 | 1.580 (6) | C4—H4 | 0.950 |
P1—F2 | 1.563 (7) | C7—H7 | 0.950 |
P1—F3 | 1.542 (5) | C8—H8 | 0.950 |
P1—F4 | 1.558 (6) | C9—H9 | 0.950 |
P1—F5 | 1.585 (5) | C10—H10 | 0.950 |
P1—F6 | 1.565 (5) | C13—H13A | 0.980 |
N1—C1 | 1.335 (6) | C13—H13B | 0.980 |
N1—C5 | 1.357 (6) | C13—H13C | 0.980 |
C1—C2 | 1.374 (8) | C14—H14A | 0.980 |
C2—C3 | 1.369 (10) | C14—H14B | 0.980 |
C3—C4 | 1.368 (9) | C14—H14C | 0.980 |
C4—C5 | 1.391 (7) | C15—H15A | 0.980 |
C5—C6 | 1.505 (6) | C15—H15B | 0.980 |
C6—C7 | 1.389 (9) | C15—H15C | 0.980 |
C6—C11 | 1.353 (7) | C16—H16 | 0.950 |
C7—C8 | 1.374 (8) | C17—H17 | 0.950 |
C8—C9 | 1.370 (11) | C18—H18 | 0.950 |
C9—C10 | 1.389 (9) | C19—H19 | 0.950 |
C10—C11 | 1.388 (6) | C20—H20 | 0.950 |
C12—C13 | 1.531 (7) | C21—H21 | 0.950 |
Cl1···C16i | 3.574 (6) | H2···H14Bxiii | 3.292 |
S1···F4ii | 3.502 (5) | H2···H14Cxiii | 2.880 |
F1···C14iii | 3.430 (8) | H2···H15Cxii | 3.534 |
F1···C19iv | 3.365 (8) | H3···F3ix | 3.206 |
F2···C9v | 3.423 (7) | H3···F5 | 3.354 |
F2···C18vi | 3.538 (9) | H3···C14xiii | 3.414 |
F3···C2vii | 3.233 (8) | H3···C16viii | 3.522 |
F3···C19iv | 3.414 (8) | H3···C20viii | 3.090 |
F3···C20iv | 2.962 (9) | H3···C21viii | 2.797 |
F4···S1viii | 3.502 (5) | H3···H8v | 3.222 |
F4···C10viii | 3.415 (8) | H3···H20viii | 3.117 |
F4···C14iii | 3.476 (9) | H3···H21viii | 2.630 |
F4···C16viii | 3.575 (8) | H3···H14Bxiii | 3.308 |
F5···C3 | 3.556 (9) | H3···H14Cxiii | 2.677 |
F5···C4 | 3.310 (9) | H3···H15Bxiii | 3.277 |
F5···C8v | 3.247 (8) | H4···F1 | 3.005 |
F5···C9v | 3.481 (9) | H4···F5 | 2.926 |
F5···C21viii | 3.236 (10) | H7···C2iii | 3.418 |
F6···C13 | 3.545 (6) | H7···H2iii | 3.258 |
F6···C17vi | 3.116 (9) | H7···H13Aiii | 3.303 |
F6···C18vi | 3.194 (10) | H8···F5iii | 2.490 |
F6···C19iv | 3.589 (8) | H8···C3iii | 3.270 |
C2···F3ix | 3.233 (8) | H8···C13iii | 3.292 |
C3···F5 | 3.556 (9) | H8···H3iii | 3.222 |
C4···F5 | 3.310 (9) | H8···H18iv | 3.419 |
C8···F5iii | 3.247 (8) | H8···H20x | 3.560 |
C9···F2iii | 3.423 (7) | H8···H21x | 2.836 |
C9···F5iii | 3.481 (9) | H8···H13Aiii | 3.259 |
C10···F4ii | 3.415 (8) | H8···H13Biii | 3.037 |
C13···F6 | 3.545 (6) | H8···H13Ciii | 3.028 |
C14···F1v | 3.430 (8) | H9···F2iii | 2.550 |
C14···F4v | 3.476 (9) | H9···F5iii | 2.986 |
C16···Cl1x | 3.574 (6) | H9···C14x | 3.595 |
C16···F4ii | 3.575 (8) | H9···H18iv | 2.772 |
C17···F6xi | 3.116 (9) | H9···H21x | 3.207 |
C18···F2xi | 3.538 (9) | H9···H14Ax | 3.413 |
C18···F6xi | 3.194 (10) | H9···H14Bx | 2.891 |
C19···F1xii | 3.365 (8) | H10···F4ii | 2.626 |
C19···F3xii | 3.414 (8) | H10···C1iv | 3.394 |
C19···F6xii | 3.589 (8) | H10···C2iv | 3.328 |
C20···F3xii | 2.962 (9) | H10···H1iv | 2.979 |
C21···F5ii | 3.236 (10) | H10···H2iv | 2.869 |
Cl1···H16i | 2.954 | H10···H14Ax | 3.299 |
Cl1···H15Bxii | 3.425 | H10···H14Bx | 3.474 |
P1···H2vii | 3.491 | H16···Cl1x | 2.954 |
P1···H18vi | 3.584 | H16···F4ii | 2.845 |
P1···H20iv | 3.569 | H16···F5ii | 3.425 |
P1···H14Ciii | 3.589 | H16···H15Bxi | 3.567 |
F1···H4 | 3.005 | H17···F2xi | 3.307 |
F1···H19iv | 2.790 | H17···F3xi | 3.351 |
F1···H13Aiii | 3.313 | H17···F6xi | 2.588 |
F1···H13Biii | 3.170 | H17···H20x | 3.002 |
F1···H14Aiii | 3.103 | H17···H15Bxi | 3.296 |
F1···H14Ciii | 2.916 | H18···P1xi | 3.584 |
F2···H9v | 2.550 | H18···F2xi | 2.758 |
F2···H17vi | 3.307 | H18···F6xi | 2.757 |
F2···H18vi | 2.758 | H18···C8xii | 3.434 |
F2···H14Bviii | 3.243 | H18···C9xii | 3.068 |
F3···H2vii | 2.428 | H18···H8xii | 3.419 |
F3···H3vii | 3.206 | H18···H9xii | 2.772 |
F3···H17vi | 3.351 | H18···H13Bxi | 2.887 |
F3···H19iv | 3.241 | H19···F1xii | 2.790 |
F3···H20iv | 2.369 | H19···F3xii | 3.241 |
F3···H14Ciii | 2.892 | H19···F6xii | 2.910 |
F4···H2vii | 2.863 | H19···H13Bxi | 3.202 |
F4···H10viii | 2.626 | H19···H15Axii | 2.757 |
F4···H16viii | 2.845 | H20···P1xii | 3.569 |
F4···H21viii | 3.262 | H20···F3xii | 2.369 |
F4···H14Aiii | 2.968 | H20···F6xii | 3.127 |
F4···H14Ciii | 3.133 | H20···C8i | 3.569 |
F5···H3 | 3.354 | H20···H3ii | 3.117 |
F5···H4 | 2.926 | H20···H8i | 3.560 |
F5···H8v | 2.490 | H20···H17i | 3.002 |
F5···H9v | 2.986 | H21···F4ii | 3.262 |
F5···H16viii | 3.425 | H21···F5ii | 2.366 |
F5···H21viii | 2.366 | H21···C3ii | 3.382 |
F5···H13C | 3.258 | H21···C8i | 3.272 |
F6···H17vi | 2.588 | H21···C9i | 3.465 |
F6···H18vi | 2.757 | H21···H3ii | 2.630 |
F6···H19iv | 2.910 | H21···H8i | 2.836 |
F6···H20iv | 3.127 | H21···H9i | 3.207 |
F6···H13B | 3.249 | H13A···F1v | 3.313 |
F6···H13C | 3.006 | H13A···H7v | 3.303 |
F6···H15A | 2.996 | H13A···H8v | 3.259 |
F6···H15B | 3.425 | H13B···F1v | 3.170 |
C1···H10xii | 3.394 | H13B···F6 | 3.249 |
C1···H18 | 3.414 | H13B···C8v | 3.428 |
C1···H13A | 3.183 | H13B···C18vi | 2.986 |
C1···H13C | 3.579 | H13B···C19vi | 3.181 |
C1···H15Cxii | 3.527 | H13B···H8v | 3.037 |
C2···H7v | 3.418 | H13B···H18vi | 2.887 |
C2···H10xii | 3.328 | H13B···H19vi | 3.202 |
C2···H14Bxiii | 3.308 | H13C···F5 | 3.258 |
C2···H14Cxiii | 3.182 | H13C···F6 | 3.006 |
C3···H8v | 3.270 | H13C···H8v | 3.028 |
C3···H21viii | 3.382 | H14A···F1v | 3.103 |
C3···H14Bxiii | 3.296 | H14A···F4v | 2.968 |
C3···H14Cxiii | 3.065 | H14A···H9i | 3.413 |
C8···H18iv | 3.434 | H14A···H10i | 3.299 |
C8···H20x | 3.569 | H14B···F2ii | 3.243 |
C8···H21x | 3.272 | H14B···C2xiv | 3.308 |
C8···H13Biii | 3.428 | H14B···C3xiv | 3.296 |
C9···H18iv | 3.068 | H14B···H2xiv | 3.292 |
C9···H21x | 3.465 | H14B···H3xiv | 3.308 |
C10···H1iv | 3.466 | H14B···H9i | 2.891 |
C13···H8v | 3.292 | H14B···H10i | 3.474 |
C14···H2xiv | 3.449 | H14C···P1v | 3.589 |
C14···H3xiv | 3.414 | H14C···F1v | 2.916 |
C14···H9i | 3.595 | H14C···F3v | 2.892 |
C15···H1iv | 3.293 | H14C···F4v | 3.133 |
C16···H3ii | 3.522 | H14C···C2xiv | 3.182 |
C16···H15Bxi | 3.250 | H14C···C3xiv | 3.065 |
C17···H15Bxi | 3.074 | H14C···H2xiv | 2.880 |
C18···H13Bxi | 2.986 | H14C···H3xiv | 2.677 |
C18···H15Bxi | 3.384 | H15A···F6 | 2.996 |
C19···H13Bxi | 3.181 | H15A···C19iv | 3.575 |
C19···H15Axii | 3.575 | H15A···H1iv | 3.129 |
C20···H3ii | 3.090 | H15A···H19iv | 2.757 |
C21···H3ii | 2.797 | H15B···Cl1iv | 3.425 |
H1···C10xii | 3.466 | H15B···F6 | 3.425 |
H1···C15xii | 3.293 | H15B···C16vi | 3.250 |
H1···H10xii | 2.979 | H15B···C17vi | 3.074 |
H1···H15Axii | 3.129 | H15B···C18vi | 3.384 |
H1···H15Cxii | 2.671 | H15B···H3xiv | 3.277 |
H2···P1ix | 3.491 | H15B···H16vi | 3.567 |
H2···F3ix | 2.428 | H15B···H17vi | 3.296 |
H2···F4ix | 2.863 | H15C···C1iv | 3.527 |
H2···C14xiii | 3.449 | H15C···H1iv | 2.671 |
H2···H7v | 3.258 | H15C···H2iv | 3.534 |
H2···H10xii | 2.869 | ||
Cl1—Ru1—S1 | 93.84 (4) | S1—C12—C14 | 102.1 (3) |
Cl1—Ru1—N1 | 86.89 (14) | S1—C12—C15 | 106.2 (4) |
Cl1—Ru1—C16 | 145.87 (18) | C13—C12—C14 | 112.5 (4) |
Cl1—Ru1—C17 | 159.90 (13) | C13—C12—C15 | 110.9 (4) |
Cl1—Ru1—C18 | 123.49 (17) | C14—C12—C15 | 111.5 (4) |
Cl1—Ru1—C19 | 93.14 (19) | Ru1—C16—C17 | 71.7 (3) |
Cl1—Ru1—C20 | 87.4 (2) | Ru1—C16—C21 | 70.6 (4) |
Cl1—Ru1—C21 | 109.3 (3) | C17—C16—C21 | 120.1 (5) |
S1—Ru1—N1 | 86.76 (9) | Ru1—C17—C16 | 71.4 (4) |
S1—Ru1—C16 | 84.44 (15) | Ru1—C17—C18 | 71.0 (4) |
S1—Ru1—C17 | 105.91 (13) | C16—C17—C18 | 120.0 (5) |
S1—Ru1—C18 | 142.48 (17) | Ru1—C18—C17 | 71.7 (3) |
S1—Ru1—C19 | 159.70 (19) | Ru1—C18—C19 | 72.2 (4) |
S1—Ru1—C20 | 123.2 (2) | C17—C18—C19 | 120.1 (5) |
S1—Ru1—C21 | 92.4 (2) | Ru1—C19—C18 | 70.5 (3) |
N1—Ru1—C16 | 126.9 (2) | Ru1—C19—C20 | 69.8 (4) |
N1—Ru1—C17 | 97.7 (2) | C18—C19—C20 | 117.7 (5) |
N1—Ru1—C18 | 91.25 (19) | Ru1—C20—C19 | 71.9 (4) |
N1—Ru1—C19 | 112.7 (2) | Ru1—C20—C21 | 71.5 (4) |
N1—Ru1—C20 | 149.9 (2) | C19—C20—C21 | 121.2 (8) |
N1—Ru1—C21 | 163.8 (3) | Ru1—C21—C16 | 72.3 (3) |
C16—Ru1—C17 | 37.0 (2) | Ru1—C21—C20 | 72.4 (4) |
C16—Ru1—C18 | 67.1 (2) | C16—C21—C20 | 120.8 (8) |
C16—Ru1—C19 | 79.1 (2) | N1—C1—H1 | 118.0 |
C16—Ru1—C20 | 65.9 (2) | C2—C1—H1 | 118.0 |
C16—Ru1—C21 | 37.1 (3) | C1—C2—H2 | 121.3 |
C17—Ru1—C18 | 37.3 (2) | C3—C2—H2 | 121.3 |
C17—Ru1—C19 | 67.0 (2) | C2—C3—H3 | 119.9 |
C17—Ru1—C20 | 78.7 (3) | C4—C3—H3 | 119.9 |
C17—Ru1—C21 | 67.0 (3) | C3—C4—H4 | 120.1 |
C18—Ru1—C19 | 37.2 (2) | C5—C4—H4 | 120.1 |
C18—Ru1—C20 | 67.7 (3) | C6—C7—H7 | 119.5 |
C18—Ru1—C21 | 79.6 (3) | C8—C7—H7 | 119.5 |
C19—Ru1—C20 | 38.2 (3) | C7—C8—H8 | 119.7 |
C19—Ru1—C21 | 67.3 (3) | C9—C8—H8 | 119.7 |
C20—Ru1—C21 | 36.0 (3) | C8—C9—H9 | 120.3 |
Ru1—S1—C11 | 98.00 (15) | C10—C9—H9 | 120.3 |
Ru1—S1—C12 | 123.42 (13) | C9—C10—H10 | 120.7 |
C11—S1—C12 | 106.9 (2) | C11—C10—H10 | 120.7 |
F1—P1—F2 | 177.5 (2) | C12—C13—H13A | 109.5 |
F1—P1—F3 | 90.0 (3) | C12—C13—H13B | 109.5 |
F1—P1—F4 | 91.8 (3) | C12—C13—H13C | 109.5 |
F1—P1—F5 | 88.8 (3) | H13A—C13—H13B | 109.5 |
F1—P1—F6 | 87.0 (3) | H13A—C13—H13C | 109.5 |
F2—P1—F3 | 92.1 (3) | H13B—C13—H13C | 109.5 |
F2—P1—F4 | 89.5 (3) | C12—C14—H14A | 109.5 |
F2—P1—F5 | 89.0 (3) | C12—C14—H14B | 109.5 |
F2—P1—F6 | 91.7 (3) | C12—C14—H14C | 109.5 |
F3—P1—F4 | 88.5 (2) | H14A—C14—H14B | 109.5 |
F3—P1—F5 | 178.8 (3) | H14A—C14—H14C | 109.5 |
F3—P1—F6 | 89.8 (2) | H14B—C14—H14C | 109.5 |
F4—P1—F5 | 91.8 (3) | C12—C15—H15A | 109.5 |
F4—P1—F6 | 177.9 (2) | C12—C15—H15B | 109.5 |
F5—P1—F6 | 89.8 (3) | C12—C15—H15C | 109.5 |
Ru1—N1—C1 | 116.1 (3) | H15A—C15—H15B | 109.5 |
Ru1—N1—C5 | 125.4 (3) | H15A—C15—H15C | 109.5 |
C1—N1—C5 | 118.4 (4) | H15B—C15—H15C | 109.5 |
N1—C1—C2 | 124.0 (5) | Ru1—C16—H16 | 130.3 |
C1—C2—C3 | 117.3 (6) | C17—C16—H16 | 120.0 |
C2—C3—C4 | 120.3 (5) | C21—C16—H16 | 120.0 |
C3—C4—C5 | 119.8 (5) | Ru1—C17—H17 | 130.2 |
N1—C5—C4 | 120.1 (4) | C16—C17—H17 | 120.0 |
N1—C5—C6 | 121.0 (4) | C18—C17—H17 | 120.0 |
C4—C5—C6 | 118.9 (4) | Ru1—C18—H18 | 128.4 |
C5—C6—C7 | 116.9 (4) | C17—C18—H18 | 119.9 |
C5—C6—C11 | 125.6 (5) | C19—C18—H18 | 119.9 |
C7—C6—C11 | 117.5 (4) | Ru1—C19—H19 | 130.9 |
C6—C7—C8 | 121.1 (6) | C18—C19—H19 | 121.2 |
C7—C8—C9 | 120.6 (6) | C20—C19—H19 | 121.2 |
C8—C9—C10 | 119.3 (5) | Ru1—C20—H20 | 129.7 |
C9—C10—C11 | 118.5 (5) | C19—C20—H20 | 119.4 |
S1—C11—C6 | 123.5 (3) | C21—C20—H20 | 119.4 |
S1—C11—C10 | 113.5 (3) | Ru1—C21—H21 | 127.9 |
C6—C11—C10 | 122.9 (5) | C16—C21—H21 | 119.6 |
S1—C12—C13 | 113.2 (3) | C20—C21—H21 | 119.6 |
Cl1—Ru1—S1—C11 | 141.23 (14) | C18—Ru1—C17—C16 | 132.5 (5) |
Cl1—Ru1—S1—C12 | 24.8 (2) | C17—Ru1—C19—C18 | 29.6 (3) |
Cl1—Ru1—N1—C1 | 45.1 (4) | C17—Ru1—C19—C20 | −101.3 (5) |
Cl1—Ru1—N1—C5 | −134.7 (4) | C19—Ru1—C17—C16 | 102.9 (3) |
Cl1—Ru1—C16—C17 | −145.4 (2) | C19—Ru1—C17—C18 | −29.6 (3) |
Cl1—Ru1—C16—C21 | −12.8 (6) | C17—Ru1—C20—C19 | 67.0 (4) |
Cl1—Ru1—C17—C16 | 112.0 (4) | C17—Ru1—C20—C21 | −66.1 (6) |
Cl1—Ru1—C17—C18 | −20.4 (6) | C20—Ru1—C17—C16 | 64.7 (3) |
Cl1—Ru1—C18—C17 | 171.7 (2) | C20—Ru1—C17—C18 | −67.8 (3) |
Cl1—Ru1—C18—C19 | 40.4 (4) | C17—Ru1—C21—C16 | −28.8 (4) |
Cl1—Ru1—C19—C18 | −147.3 (3) | C17—Ru1—C21—C20 | 102.9 (6) |
Cl1—Ru1—C19—C20 | 81.9 (4) | C21—Ru1—C17—C16 | 28.9 (3) |
Cl1—Ru1—C20—C19 | −98.3 (4) | C21—Ru1—C17—C18 | −103.6 (4) |
Cl1—Ru1—C20—C21 | 128.5 (6) | C18—Ru1—C19—C20 | −130.9 (6) |
Cl1—Ru1—C21—C16 | 172.4 (3) | C19—Ru1—C18—C17 | 131.4 (5) |
Cl1—Ru1—C21—C20 | −55.9 (7) | C18—Ru1—C20—C19 | 29.6 (4) |
S1—Ru1—N1—C1 | 139.1 (4) | C18—Ru1—C20—C21 | −103.5 (7) |
S1—Ru1—N1—C5 | −40.7 (4) | C20—Ru1—C18—C17 | 101.0 (4) |
N1—Ru1—S1—C11 | 54.57 (19) | C20—Ru1—C18—C19 | −30.4 (4) |
N1—Ru1—S1—C12 | −61.8 (2) | C18—Ru1—C21—C16 | −65.6 (4) |
S1—Ru1—C16—C17 | 126.0 (3) | C18—Ru1—C21—C20 | 66.1 (6) |
S1—Ru1—C16—C21 | −101.5 (4) | C21—Ru1—C18—C17 | 65.4 (4) |
C16—Ru1—S1—C11 | −73.0 (2) | C21—Ru1—C18—C19 | −66.0 (4) |
C16—Ru1—S1—C12 | 170.6 (2) | C19—Ru1—C20—C21 | −133.1 (9) |
S1—Ru1—C17—C16 | −56.9 (3) | C20—Ru1—C19—C18 | 130.9 (6) |
S1—Ru1—C17—C18 | 170.7 (3) | C19—Ru1—C21—C16 | −102.4 (5) |
C17—Ru1—S1—C11 | −42.6 (2) | C19—Ru1—C21—C20 | 29.3 (6) |
C17—Ru1—S1—C12 | −159.0 (2) | C21—Ru1—C19—C18 | 103.2 (5) |
S1—Ru1—C18—C17 | −14.9 (4) | C21—Ru1—C19—C20 | −27.7 (5) |
S1—Ru1—C18—C19 | −146.2 (3) | C20—Ru1—C21—C16 | −131.7 (9) |
C18—Ru1—S1—C11 | −33.3 (3) | C21—Ru1—C20—C19 | 133.1 (9) |
C18—Ru1—S1—C12 | −149.7 (3) | Ru1—S1—C11—C6 | −46.4 (4) |
S1—Ru1—C19—C18 | 102.8 (6) | Ru1—S1—C11—C10 | 129.0 (3) |
S1—Ru1—C19—C20 | −28.1 (8) | Ru1—S1—C12—C13 | 41.4 (4) |
C19—Ru1—S1—C11 | −108.9 (6) | Ru1—S1—C12—C14 | −79.8 (3) |
C19—Ru1—S1—C12 | 134.6 (6) | Ru1—S1—C12—C15 | 163.3 (3) |
S1—Ru1—C20—C19 | 168.7 (3) | C11—S1—C12—C13 | −70.6 (3) |
S1—Ru1—C20—C21 | 35.6 (7) | C11—S1—C12—C14 | 168.2 (2) |
C20—Ru1—S1—C11 | −129.3 (3) | C11—S1—C12—C15 | 51.3 (4) |
C20—Ru1—S1—C12 | 114.3 (3) | C12—S1—C11—C6 | 82.3 (4) |
S1—Ru1—C21—C16 | 77.5 (4) | C12—S1—C11—C10 | −102.3 (4) |
S1—Ru1—C21—C20 | −150.8 (6) | Ru1—N1—C1—C2 | −178.6 (6) |
C21—Ru1—S1—C11 | −109.3 (3) | Ru1—N1—C5—C4 | 177.3 (4) |
C21—Ru1—S1—C12 | 134.3 (3) | Ru1—N1—C5—C6 | −3.9 (7) |
N1—Ru1—C16—C17 | 44.3 (3) | C1—N1—C5—C4 | −2.5 (8) |
N1—Ru1—C16—C21 | 176.8 (4) | C1—N1—C5—C6 | 176.3 (5) |
C16—Ru1—N1—C1 | −140.3 (4) | C5—N1—C1—C2 | 1.2 (10) |
C16—Ru1—N1—C5 | 39.9 (5) | N1—C1—C2—C3 | 1.7 (12) |
N1—Ru1—C17—C16 | −145.7 (3) | C1—C2—C3—C4 | −3.3 (12) |
N1—Ru1—C17—C18 | 81.8 (3) | C2—C3—C4—C5 | 2.1 (12) |
C17—Ru1—N1—C1 | −115.3 (4) | C3—C4—C5—N1 | 0.9 (10) |
C17—Ru1—N1—C5 | 64.9 (4) | C3—C4—C5—C6 | −177.9 (6) |
N1—Ru1—C18—C17 | −101.2 (3) | N1—C5—C6—C7 | −140.0 (5) |
N1—Ru1—C18—C19 | 127.5 (3) | N1—C5—C6—C11 | 40.7 (8) |
C18—Ru1—N1—C1 | −78.4 (4) | C4—C5—C6—C7 | 38.8 (8) |
C18—Ru1—N1—C5 | 101.8 (4) | C4—C5—C6—C11 | −140.5 (6) |
N1—Ru1—C19—C18 | −59.3 (4) | C5—C6—C7—C8 | −179.6 (6) |
N1—Ru1—C19—C20 | 169.8 (4) | C5—C6—C11—S1 | −5.3 (7) |
C19—Ru1—N1—C1 | −47.0 (5) | C5—C6—C11—C10 | 179.7 (5) |
C19—Ru1—N1—C5 | 133.2 (4) | C7—C6—C11—S1 | 175.4 (4) |
N1—Ru1—C20—C19 | −19.0 (8) | C7—C6—C11—C10 | 0.5 (8) |
N1—Ru1—C20—C21 | −152.1 (6) | C11—C6—C7—C8 | −0.3 (8) |
C20—Ru1—N1—C1 | −34.4 (8) | C6—C7—C8—C9 | 0.1 (8) |
C20—Ru1—N1—C5 | 145.8 (6) | C7—C8—C9—C10 | −0.1 (9) |
N1—Ru1—C21—C16 | −9.2 (12) | C8—C9—C10—C11 | 0.2 (7) |
N1—Ru1—C21—C20 | 122.5 (8) | C9—C10—C11—S1 | −175.8 (5) |
C21—Ru1—N1—C1 | −133.4 (9) | C9—C10—C11—C6 | −0.4 (8) |
C21—Ru1—N1—C5 | 46.8 (11) | Ru1—C16—C17—C18 | 53.7 (5) |
C16—Ru1—C17—C18 | −132.5 (5) | Ru1—C16—C21—C20 | −56.0 (7) |
C17—Ru1—C16—C21 | 132.6 (5) | C17—C16—C21—Ru1 | 53.9 (6) |
C16—Ru1—C18—C17 | 28.8 (3) | C17—C16—C21—C20 | −2.1 (11) |
C16—Ru1—C18—C19 | −102.6 (4) | C21—C16—C17—Ru1 | −53.4 (6) |
C18—Ru1—C16—C17 | −29.0 (3) | C21—C16—C17—C18 | 0.3 (8) |
C18—Ru1—C16—C21 | 103.5 (5) | Ru1—C17—C18—C19 | 55.7 (6) |
C16—Ru1—C19—C18 | 66.3 (3) | C16—C17—C18—Ru1 | −53.9 (5) |
C16—Ru1—C19—C20 | −64.6 (5) | C16—C17—C18—C19 | 1.8 (9) |
C19—Ru1—C16—C17 | −66.0 (3) | Ru1—C18—C19—C20 | 53.3 (6) |
C19—Ru1—C16—C21 | 66.6 (5) | C17—C18—C19—Ru1 | −55.4 (5) |
C16—Ru1—C20—C19 | 103.6 (5) | C17—C18—C19—C20 | −2.2 (10) |
C16—Ru1—C20—C21 | −29.6 (6) | Ru1—C19—C20—C21 | 54.0 (7) |
C20—Ru1—C16—C17 | −103.8 (4) | C18—C19—C20—Ru1 | −53.6 (6) |
C20—Ru1—C16—C21 | 28.8 (5) | C18—C19—C20—C21 | 0.4 (11) |
C16—Ru1—C21—C20 | 131.7 (9) | Ru1—C20—C21—C16 | 55.9 (6) |
C21—Ru1—C16—C17 | −132.6 (5) | C19—C20—C21—Ru1 | −54.2 (7) |
C17—Ru1—C18—C19 | −131.4 (5) | C19—C20—C21—C16 | 1.7 (13) |
Symmetry codes: (i) x, −y, z−1/2; (ii) x, y−1, z; (iii) x, −y+1, z+1/2; (iv) x+1/2, −y+1/2, z+1/2; (v) x, −y+1, z−1/2; (vi) x+1/2, y+1/2, z; (vii) x+1/2, −y+3/2, z+1/2; (viii) x, y+1, z; (ix) x−1/2, −y+3/2, z−1/2; (x) x, −y, z+1/2; (xi) x−1/2, y−1/2, z; (xii) x−1/2, −y+1/2, z−1/2; (xiii) x−1/2, y+1/2, z; (xiv) x+1/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [RuCl(C6H6)(C15H17NS)]PF6 |
Mr | 602.97 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 193 |
a, b, c (Å) | 16.638 (4), 10.5589 (19), 14.327 (3) |
β (°) | 110.758 (4) |
V (Å3) | 2353.6 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.99 |
Crystal size (mm) | 0.24 × 0.17 × 0.09 |
Data collection | |
Diffractometer | Rigaku Mercury |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.725, 0.914 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 11123, 4474, 4165 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.078, 1.03 |
No. of reflections | 4474 |
No. of parameters | 291 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.39 |
Absolute structure | Flack (1983), 1824 Friedel pairs |
Absolute structure parameter | 0.03 (3) |
Computer programs: CrystalClear (Rigaku, 1999), CrystalStructure (Rigaku/MSC, 2006), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).
Ru1—Cl1 | 2.3970 (14) | Ru1—C19 | 2.199 (6) |
Ru1—S1 | 2.3671 (10) | Ru1—C20 | 2.172 (7) |
Ru1—N1 | 2.122 (3) | Ru1—C21 | 2.161 (5) |
Ru1—C16 | 2.183 (6) | S1—C11 | 1.820 (5) |
Ru1—C17 | 2.187 (6) | S1—C12 | 1.869 (5) |
Ru1—C18 | 2.178 (6) | ||
Cl1—Ru1—S1 | 93.84 (4) | Ru1—S1—C12 | 123.42 (13) |
Cl1—Ru1—N1 | 86.89 (14) | C11—S1—C12 | 106.9 (2) |
S1—Ru1—N1 | 86.76 (9) | Ru1—N1—C1 | 116.1 (3) |
Ru1—S1—C11 | 98.00 (15) | Ru1—N1—C5 | 125.4 (3) |
References
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Coordination of bidentate ligands bearing thioether sulfur atoms generates chirality at the sulfur center. The chirality of the coordinated S atoms in catalysts would be important in improving enantioselectivities for asymmetric reactions. A variety of chiral N,S-bidentate ligands have been developed and used for asymmetric allylic substitution reactions (Mellah et al., 2007). We previously reported the structurally characterized ruthenium(II) arene complex with 4-(2'-pyridyl)dibenzothiophene (PyDBT), [RuCl(PyDBT)(η6-C6H6)]CF3SO3 (Shibue et al., 2008). In this complex, PyDBT acts as a N,S-bidentate ligand to form chiral centers at Ru and S atoms. The pyridine and dibenzothiophene planes in PyDBT are twisted with respect to each other, and the dibenzothiophene moiety is in close proximity to the η6-benzene ligand. To clarify the steric interactions around the coordinated S atom, we present here the crystal structure of the title ruthenium(II) arene complex of 2-(2'-(t-butylthio)phenyl)pyridine (btppy).
The asymmetric unit of the title compound (I) consists of a [RuCl(btppy)(η6-C6H6)]+ cation and a hexafluorophosphate anion (Fig. 1). The Ru center of the complex cation is surrounded by a benzene, a btppy and a chloride ligand to form a three-legged piano-stool structure. The btppy ligand acts as a N,S-bidentate ligand to form a six-membered ring. The chelate ring adopts an envelope conformation, which is similar to that in the previously reported ruthenium(II) complex [RuCl(PyDBT)(η6-C6H6)]CF3SO3, (II) (Shibue et al., 2008). The S—Ru—N bite angle (86.76 (9)°) is larger than that of (II) (79.20 (7)°, 80.00 (7)°, two independent molecules), which is due to the longer C—S bond in the btppy chelate ring (1.820 (5) Å) compared with the PyDBT chelate ring in (II) (C—S = 1.762 (5), 1.760 (4) Å). The Ru—S (2.3671 (10) Å) and Ru—N (2.122 (3) Å) bond lengths in (I) are slightly shorter than those in (II) (Ru—S, 2.3821 (9), 2.3901 (8) Å; Ru—N, 2.161 (3), 2.164 (3) Å), indicating the higher coordinating ability of btppy. The dihedral angle between the pyridine and benzene rings in btppy (39.8 (2)°) is similar to that in PyDBT of (II) (37.7 (2)°).
There are two pair of racemic diastereomers with (SRu, SS) and (RRu, RS) configurations in the unit cell. The t-butyl group on the coordinated S atom is placed far from the η6-benzene ligand. An average Ru—C distance of 2.180 (6) Å in (I) is comparable to that in (II) (2.192 (4), 2.180 (4) Å). The Cl—Ru—S angle (93.84 (4)°) in (I) is larger than that in (II) (82.84 (3)°, 84.87 (3)°), and no significant interaction was observed between the t-butyl group and the chloro ligand. Molecular modeling analysis suggests that the other diastereomers with configurations of (SRu, RS) and (RRu, SS) cause a severe repulsive interaction between the t-butyl group and the benzene ligand. The 1H NMR spectrum of (I) in CDCl3 revealed the presence of a single diastereomer. This suggests that the (SRu, SS) and (RRu, RS) isomers observed in the crystal are retained in solution. Similar stereoselectivity was recently reported for the iridium(III) complex [(η5-C5Me5)Ir(η2-ppy-S-p-tol)(H2O)](OTf)2 (Sau et al., 2010), in which the structure of the chelate ring is analogous to that for btppy in (I).