metal-organic compounds
(2-Aminoethanethiolato-κ2N,S)bis[1,2-bis(diphenylphosphanyl)ethane-κ2P,P′]ruthenium(II) hexafluoridophosphate
aDepartment of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
*Correspondence e-mail: igashira@chem.sci.osaka-u.ac.jp, konno@chem.sci.osaka-u.ac.jp
In the crystal of the title compound, [Ru(C2H6NS)(C26H24P2)2]PF6, the RuII atom is in a slightly distorted octahedral geometry, coordinated by one 2-aminoethanethiolate (aet) and two 1,2-bis(diphenylphosphanyl)ethane (dppe) ligands. The crystal consists of a pair of enantiomers (Δ and Λ) of the compound. The Δ and Λ isomers have the λ and δ conformations for the aet chelate rings and the δ and λ conformations for the dppe chelate rings. The F atoms of the PF6− counter-anion are disordered over three positions, with site occupancies of 0.4, 0.3 and 0.3.
Related literature
For closely related structures, see: Tamura et al. (2007); Matsuura et al. (2006); Hanif et al. (1999). For conformation descriptors of the chelate rings, see: Gispert (2008). For the starting material, see: Bautista et al. (1991). For a description of the Cambridge Structural Database, see: Allen (2002).
Experimental
Crystal data
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Data collection: PROCESS-AUTO (Rigaku, 2000); cell PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Yadokari-XG 2009 (Kabuto et al., 2009); software used to prepare material for publication: Yadokari-XG 2009.
Supporting information
10.1107/S1600536812044273/gk2528sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044273/gk2528Isup2.hkl
To a solution of 0.20 g (0.21 mmol) of [RuCl2(dppe)2] in 200 ml of methanol was added 0.078 g (1.01 mmol) of Haet and 0.338 g (2.07 mmol) of NH4PF6. The mixture was stirred at room temperature for 1 h. The resulting yellow suspension was concentrated to dryness with a rotary evaporator. The residue was washed with water to give a yellow powder of [Ru(aet)(dppe)2]PF6.1.5H2O. Yield 0.178 g (76%). Anal. Calcd for [Ru(aet)(dppe)2]PF6.1.5H2O: C, 58.54; H, 4.64; N, 1.26%. Found: C, 58.73; H, 4.91; N, 1.16%. 1H NMR (400 MHz, DMSO-d6): d, 8.04 (2H, t, J = 8.4 Hz), 7.93 (2H, t, J = 7.9 Hz), 7.72–7.64 (5H, m), 7.54 (2H, t, J = 8.5 Hz), 7.44–7.25 (17H, m), 7.05 (2H, t, J = 7.0 Hz), 6.98–6.89 (6H, m), 6.57 (2H, t, J = 8.3 Hz), 6.31 (2H, t, J = 8.4 Hz), 2.92–2.82 (3H, m), 2.38–2.34 (2H, m), 2.10–2.07 (2H, br m), 1.58 (1H, br s), 1.39 (1H, br s), 1.06 (1H, br s), 0.86 (1H, br s), 0.67 (1H, br s). 31P NMR (202.47 MHz, DMSO-d6): d, p.p.m. 50.25 (1P, d, J = 321.8 Hz), 48.79 (1P, s), 47.34 (1P, s), 29.74 (1P, d, J = 317.1 Hz). IR (KBr, cm-1): 1435 (νPh), 1097 and 745–694 (νP—Ph), 839 (PF6-), 557 (PF6-).
Single crystals of [Ru(aet)(dppe)2]PF6 suitable for X-ray analysis were obtained by the recrystallization of a yellow powder from methanol at room temperature.
H atoms bound to C atoms were placed at calculated positions [C—H = 0.99 (methylene) and 0.95 (phenyl)] and refined as riding with isotropic displacement parameters [Uiso(H) = 1.2Ueq(C)]. H atoms bound to N atoms were located in a difference Fourier map and refined with distance restraint and constrained displacement parameters [N—H = 0.89 (2) Å, Uiso(H) = 1.5Ueq(N)]. The F atoms of the hexafluoridophosphate are disordered over three positions (F1–F6, F7–F12 and F13–F18) with site occupancies of 0.4 (F1–F6) and 0.3 (F7–F12, F13-F18), and refined isotropically.
Data collection: PROCESS-AUTO (Rigaku, 2000); cell
PROCESS-AUTO (Rigaku, 2000); data reduction: PROCESS-AUTO (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Yadokari-XG 2009 (Kabuto et al., 2009); software used to prepare material for publication: Yadokari-XG 2009 (Kabuto et al., 2009).[Ru(C2H6NS)(C26H24P2)2]PF6 | F(000) = 2296 |
Mr = 1118.96 | Dx = 1.533 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: C -2yc | Cell parameters from 15716 reflections |
a = 21.1985 (17) Å | θ = 3.1–27.4° |
b = 11.4000 (9) Å | µ = 0.59 mm−1 |
c = 20.9346 (17) Å | T = 200 K |
β = 106.588 (2)° | Prism, yellow |
V = 4848.6 (7) Å3 | 0.15 × 0.08 × 0.08 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 9513 independent reflections |
Radiation source: fine-focus sealed tube | 7722 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −27→27 |
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995) | k = −14→14 |
Tmin = 0.684, Tmax = 0.954 | l = −27→26 |
23148 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.112 | w = 1/[σ2(Fo2) + (0.0354P)2 + 0.1P] where P = (Fo2 + 2Fc2)/3 |
S = 1.20 | (Δ/σ)max < 0.001 |
9513 reflections | Δρmax = 1.02 e Å−3 |
638 parameters | Δρmin = −0.88 e Å−3 |
4 restraints | Absolute structure: Flack (1983), 3981 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (3) |
[Ru(C2H6NS)(C26H24P2)2]PF6 | V = 4848.6 (7) Å3 |
Mr = 1118.96 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 21.1985 (17) Å | µ = 0.59 mm−1 |
b = 11.4000 (9) Å | T = 200 K |
c = 20.9346 (17) Å | 0.15 × 0.08 × 0.08 mm |
β = 106.588 (2)° |
Rigaku R-AXIS RAPID diffractometer | 9513 independent reflections |
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995) | 7722 reflections with I > 2σ(I) |
Tmin = 0.684, Tmax = 0.954 | Rint = 0.067 |
23148 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.112 | Δρmax = 1.02 e Å−3 |
S = 1.20 | Δρmin = −0.88 e Å−3 |
9513 reflections | Absolute structure: Flack (1983), 3981 Friedel pairs |
638 parameters | Absolute structure parameter: −0.02 (3) |
4 restraints |
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) | |
Ru1 | 0.183683 (18) | 0.68842 (3) | 0.323758 (19) | 0.02092 (10) | |
S1 | 0.29912 (7) | 0.67929 (12) | 0.38742 (8) | 0.0301 (4) | |
N1 | 0.1722 (2) | 0.6281 (4) | 0.4201 (2) | 0.0302 (10) | |
H1 | 0.137 (2) | 0.654 (5) | 0.432 (3) | 0.045* | |
H2 | 0.167 (3) | 0.550 (2) | 0.425 (3) | 0.045* | |
C1 | 0.2930 (3) | 0.6267 (6) | 0.4680 (3) | 0.0429 (16) | |
H3 | 0.3015 | 0.5412 | 0.4710 | 0.052* | |
H4 | 0.3278 | 0.6649 | 0.5039 | 0.052* | |
C2 | 0.2286 (3) | 0.6491 (5) | 0.4800 (3) | 0.0391 (14) | |
H5 | 0.2272 | 0.7315 | 0.4945 | 0.047* | |
H6 | 0.2241 | 0.5977 | 0.5165 | 0.047* | |
P1 | 0.20553 (6) | 0.77721 (11) | 0.23054 (7) | 0.0232 (3) | |
C3 | 0.1951 (3) | 0.9383 (4) | 0.2376 (3) | 0.0271 (12) | |
H7 | 0.2191 | 0.9798 | 0.2101 | 0.032* | |
H8 | 0.1479 | 0.9587 | 0.2203 | 0.032* | |
C4 | 0.2210 (3) | 0.9779 (4) | 0.3095 (3) | 0.0280 (12) | |
H9 | 0.2097 | 1.0614 | 0.3131 | 0.034* | |
H10 | 0.2695 | 0.9704 | 0.3243 | 0.034* | |
P2 | 0.18515 (6) | 0.88868 (11) | 0.36321 (7) | 0.0242 (3) | |
C5 | 0.1565 (2) | 0.7499 (4) | 0.1439 (3) | 0.0259 (12) | |
C6 | 0.1508 (2) | 0.6354 (4) | 0.1183 (3) | 0.0263 (12) | |
H11 | 0.1718 | 0.5727 | 0.1463 | 0.032* | |
C7 | 0.1152 (3) | 0.6119 (5) | 0.0530 (3) | 0.0347 (13) | |
H12 | 0.1113 | 0.5336 | 0.0367 | 0.042* | |
C8 | 0.0855 (3) | 0.7025 (5) | 0.0118 (3) | 0.0401 (14) | |
H13 | 0.0611 | 0.6867 | −0.0331 | 0.048* | |
C9 | 0.0910 (3) | 0.8159 (5) | 0.0354 (3) | 0.0324 (13) | |
H14 | 0.0708 | 0.8782 | 0.0066 | 0.039* | |
C10 | 0.1258 (3) | 0.8400 (5) | 0.1010 (3) | 0.0293 (12) | |
H15 | 0.1289 | 0.9185 | 0.1169 | 0.035* | |
C11 | 0.2893 (2) | 0.7749 (4) | 0.2191 (3) | 0.0242 (11) | |
C12 | 0.3020 (3) | 0.7339 (5) | 0.1614 (3) | 0.0343 (14) | |
H16 | 0.2668 | 0.7031 | 0.1265 | 0.041* | |
C13 | 0.3647 (3) | 0.7372 (6) | 0.1539 (3) | 0.0407 (16) | |
H17 | 0.3723 | 0.7072 | 0.1144 | 0.049* | |
C14 | 0.4161 (3) | 0.7835 (5) | 0.2031 (3) | 0.0381 (15) | |
H18 | 0.4591 | 0.7860 | 0.1978 | 0.046* | |
C15 | 0.4046 (3) | 0.8260 (5) | 0.2602 (4) | 0.0407 (15) | |
H19 | 0.4396 | 0.8602 | 0.2939 | 0.049* | |
C16 | 0.3418 (3) | 0.8194 (5) | 0.2691 (3) | 0.0345 (13) | |
H20 | 0.3350 | 0.8456 | 0.3097 | 0.041* | |
C17 | 0.1085 (3) | 0.9649 (4) | 0.3618 (3) | 0.0300 (12) | |
C18 | 0.0946 (3) | 1.0811 (5) | 0.3404 (3) | 0.0414 (15) | |
H21 | 0.1262 | 1.1246 | 0.3260 | 0.050* | |
C19 | 0.0363 (3) | 1.1332 (5) | 0.3400 (4) | 0.0476 (17) | |
H22 | 0.0280 | 1.2121 | 0.3254 | 0.057* | |
C20 | −0.0103 (3) | 1.0720 (6) | 0.3606 (4) | 0.0460 (17) | |
H23 | −0.0510 | 1.1081 | 0.3594 | 0.055* | |
C21 | 0.0020 (3) | 0.9582 (5) | 0.3828 (3) | 0.0417 (15) | |
H24 | −0.0295 | 0.9164 | 0.3982 | 0.050* | |
C22 | 0.0606 (3) | 0.9053 (5) | 0.3826 (3) | 0.0314 (13) | |
H25 | 0.0683 | 0.8262 | 0.3969 | 0.038* | |
C23 | 0.2367 (3) | 0.9304 (4) | 0.4463 (3) | 0.0304 (12) | |
C24 | 0.3053 (3) | 0.9331 (4) | 0.4623 (3) | 0.0350 (14) | |
H26 | 0.3257 | 0.9182 | 0.4282 | 0.042* | |
C25 | 0.3442 (3) | 0.9567 (5) | 0.5257 (3) | 0.0416 (15) | |
H27 | 0.3907 | 0.9586 | 0.5346 | 0.050* | |
C26 | 0.3164 (3) | 0.9775 (5) | 0.5764 (3) | 0.0435 (16) | |
H28 | 0.3433 | 0.9914 | 0.6205 | 0.052* | |
C27 | 0.2482 (3) | 0.9779 (5) | 0.5621 (3) | 0.0455 (16) | |
H29 | 0.2284 | 0.9956 | 0.5964 | 0.055* | |
C28 | 0.2089 (3) | 0.9527 (4) | 0.4985 (3) | 0.0336 (13) | |
H30 | 0.1624 | 0.9505 | 0.4901 | 0.040* | |
P3 | 0.19576 (6) | 0.48846 (10) | 0.29860 (7) | 0.0233 (3) | |
C29 | 0.1124 (3) | 0.4253 (4) | 0.2654 (3) | 0.0277 (13) | |
H31 | 0.1147 | 0.3537 | 0.2393 | 0.033* | |
H32 | 0.0950 | 0.4028 | 0.3028 | 0.033* | |
C30 | 0.0667 (2) | 0.5138 (4) | 0.2212 (3) | 0.0272 (12) | |
H33 | 0.0208 | 0.4846 | 0.2103 | 0.033* | |
H34 | 0.0785 | 0.5229 | 0.1790 | 0.033* | |
P4 | 0.07221 (7) | 0.65771 (13) | 0.26321 (8) | 0.0236 (3) | |
C31 | 0.2428 (3) | 0.4391 (4) | 0.2423 (3) | 0.0276 (12) | |
C32 | 0.2228 (3) | 0.3441 (5) | 0.2001 (3) | 0.0420 (15) | |
H35 | 0.1823 | 0.3059 | 0.1973 | 0.050* | |
C33 | 0.2627 (3) | 0.3046 (6) | 0.1613 (4) | 0.0479 (17) | |
H36 | 0.2484 | 0.2415 | 0.1310 | 0.057* | |
C34 | 0.3218 (3) | 0.3564 (6) | 0.1672 (3) | 0.0496 (17) | |
H37 | 0.3495 | 0.3269 | 0.1423 | 0.060* | |
C35 | 0.3420 (3) | 0.4508 (5) | 0.2086 (4) | 0.0449 (17) | |
H38 | 0.3830 | 0.4872 | 0.2113 | 0.054* | |
C36 | 0.3034 (3) | 0.4934 (5) | 0.2464 (3) | 0.0337 (13) | |
H39 | 0.3176 | 0.5589 | 0.2750 | 0.040* | |
C37 | 0.2340 (3) | 0.3912 (4) | 0.3691 (3) | 0.0301 (13) | |
C38 | 0.1971 (3) | 0.3350 (4) | 0.4064 (3) | 0.0375 (14) | |
H40 | 0.1508 | 0.3452 | 0.3950 | 0.045* | |
C39 | 0.2292 (3) | 0.2641 (5) | 0.4604 (4) | 0.0464 (17) | |
H41 | 0.2041 | 0.2253 | 0.4851 | 0.056* | |
C40 | 0.2959 (4) | 0.2496 (5) | 0.4783 (3) | 0.0465 (17) | |
H42 | 0.3168 | 0.2019 | 0.5155 | 0.056* | |
C41 | 0.3328 (3) | 0.3040 (5) | 0.4426 (4) | 0.0454 (16) | |
H43 | 0.3791 | 0.2930 | 0.4544 | 0.054* | |
C42 | 0.3018 (3) | 0.3752 (5) | 0.3890 (3) | 0.0393 (15) | |
H44 | 0.3277 | 0.4140 | 0.3652 | 0.047* | |
C43 | 0.0088 (2) | 0.6345 (4) | 0.3075 (3) | 0.0265 (12) | |
C44 | 0.0192 (3) | 0.5576 (5) | 0.3614 (3) | 0.0318 (13) | |
H45 | 0.0601 | 0.5176 | 0.3761 | 0.038* | |
C45 | −0.0281 (3) | 0.5374 (5) | 0.3944 (3) | 0.0347 (13) | |
H46 | −0.0195 | 0.4852 | 0.4312 | 0.042* | |
C46 | −0.0878 (3) | 0.5947 (5) | 0.3726 (3) | 0.0392 (15) | |
H47 | −0.1206 | 0.5820 | 0.3947 | 0.047* | |
C47 | −0.1001 (3) | 0.6699 (5) | 0.3190 (4) | 0.0441 (16) | |
H48 | −0.1413 | 0.7087 | 0.3042 | 0.053* | |
C48 | −0.0525 (3) | 0.6894 (5) | 0.2866 (3) | 0.0388 (15) | |
H49 | −0.0618 | 0.7409 | 0.2494 | 0.047* | |
C49 | 0.0269 (2) | 0.7526 (4) | 0.1944 (3) | 0.0260 (11) | |
C50 | −0.0080 (3) | 0.7093 (5) | 0.1318 (3) | 0.0320 (13) | |
H50 | −0.0092 | 0.6272 | 0.1236 | 0.038* | |
C51 | −0.0407 (3) | 0.7846 (5) | 0.0820 (3) | 0.0353 (13) | |
H51 | −0.0639 | 0.7534 | 0.0397 | 0.042* | |
C52 | −0.0407 (3) | 0.9047 (5) | 0.0917 (3) | 0.0338 (13) | |
H52 | −0.0622 | 0.9560 | 0.0564 | 0.041* | |
C53 | −0.0087 (3) | 0.9477 (5) | 0.1540 (3) | 0.0347 (14) | |
H53 | −0.0096 | 1.0296 | 0.1622 | 0.042* | |
C54 | 0.0249 (2) | 0.8734 (4) | 0.2051 (3) | 0.0283 (12) | |
H54 | 0.0466 | 0.9051 | 0.2477 | 0.034* | |
P5 | 0.54660 (9) | 0.74420 (15) | 0.06486 (10) | 0.0454 (4) | |
F1 | 0.5545 (6) | 0.6026 (9) | 0.0426 (6) | 0.050 (3)* | 0.40 |
F2 | 0.6147 (7) | 0.7668 (12) | 0.0489 (8) | 0.080 (4)* | 0.40 |
F3 | 0.5868 (8) | 0.6925 (13) | 0.1387 (9) | 0.099 (5)* | 0.40 |
F4 | 0.5469 (10) | 0.8632 (12) | 0.0914 (8) | 0.093 (4)* | 0.40 |
F5 | 0.4805 (7) | 0.7031 (11) | 0.0818 (8) | 0.061 (4)* | 0.40 |
F6 | 0.5053 (7) | 0.7599 (12) | −0.0126 (7) | 0.063 (4)* | 0.40 |
F7 | 0.4865 (10) | 0.8345 (18) | 0.0424 (11) | 0.091 (6)* | 0.30 |
F8 | 0.5342 (11) | 0.7245 (15) | 0.1337 (10) | 0.075 (6)* | 0.30 |
F9 | 0.5920 (7) | 0.8583 (10) | 0.1011 (7) | 0.040 (3)* | 0.30 |
F10 | 0.6126 (8) | 0.6707 (13) | 0.0894 (9) | 0.062 (4)* | 0.30 |
F11 | 0.5743 (9) | 0.7863 (13) | 0.0019 (9) | 0.063 (4)* | 0.30 |
F12 | 0.5083 (10) | 0.6387 (15) | 0.0333 (10) | 0.084 (5)* | 0.30 |
F13 | 0.4740 (8) | 0.6838 (14) | 0.0584 (10) | 0.053 (5)* | 0.30 |
F14 | 0.5076 (7) | 0.8755 (11) | 0.0654 (8) | 0.040 (3)* | 0.30 |
F15 | 0.5624 (9) | 0.7389 (13) | 0.1454 (8) | 0.043 (4)* | 0.30 |
F16 | 0.6071 (8) | 0.8210 (16) | 0.0700 (10) | 0.073 (5)* | 0.30 |
F17 | 0.5809 (9) | 0.6314 (14) | 0.0656 (9) | 0.056 (4)* | 0.30 |
F18 | 0.5308 (11) | 0.7675 (15) | −0.0113 (9) | 0.057 (5)* | 0.30 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01844 (17) | 0.02342 (17) | 0.0212 (2) | −0.00033 (19) | 0.00615 (14) | 0.00016 (19) |
S1 | 0.0202 (7) | 0.0355 (8) | 0.0317 (10) | 0.0002 (6) | 0.0031 (7) | −0.0012 (6) |
N1 | 0.030 (2) | 0.036 (2) | 0.025 (3) | 0.003 (2) | 0.009 (2) | 0.005 (2) |
C1 | 0.032 (3) | 0.051 (4) | 0.036 (4) | −0.005 (3) | −0.005 (3) | 0.001 (3) |
C2 | 0.041 (3) | 0.042 (3) | 0.029 (4) | 0.003 (3) | 0.002 (3) | 0.007 (3) |
P1 | 0.0218 (6) | 0.0257 (6) | 0.0225 (8) | −0.0015 (5) | 0.0071 (6) | 0.0001 (6) |
C3 | 0.029 (3) | 0.026 (2) | 0.028 (3) | 0.001 (2) | 0.010 (2) | 0.005 (2) |
C4 | 0.027 (3) | 0.031 (3) | 0.029 (3) | −0.004 (2) | 0.013 (3) | 0.001 (2) |
P2 | 0.0249 (7) | 0.0241 (6) | 0.0241 (8) | −0.0012 (5) | 0.0078 (6) | −0.0014 (6) |
C5 | 0.016 (2) | 0.031 (3) | 0.031 (3) | 0.001 (2) | 0.008 (2) | 0.002 (2) |
C6 | 0.025 (3) | 0.028 (3) | 0.026 (3) | −0.002 (2) | 0.007 (2) | −0.001 (2) |
C7 | 0.037 (3) | 0.040 (3) | 0.027 (3) | −0.008 (2) | 0.007 (3) | −0.007 (3) |
C8 | 0.046 (4) | 0.049 (4) | 0.023 (4) | −0.007 (3) | 0.007 (3) | −0.004 (3) |
C9 | 0.023 (3) | 0.048 (3) | 0.023 (3) | −0.003 (2) | 0.002 (2) | 0.007 (3) |
C10 | 0.025 (3) | 0.035 (3) | 0.031 (3) | −0.006 (2) | 0.012 (3) | 0.002 (2) |
C11 | 0.023 (2) | 0.022 (2) | 0.029 (3) | −0.001 (2) | 0.009 (2) | 0.002 (2) |
C12 | 0.028 (3) | 0.051 (3) | 0.027 (4) | −0.004 (3) | 0.013 (3) | −0.002 (3) |
C13 | 0.031 (3) | 0.063 (4) | 0.032 (4) | 0.004 (3) | 0.015 (3) | 0.012 (3) |
C14 | 0.024 (3) | 0.043 (3) | 0.051 (4) | 0.004 (2) | 0.017 (3) | 0.010 (3) |
C15 | 0.024 (3) | 0.045 (3) | 0.052 (4) | −0.007 (3) | 0.009 (3) | −0.008 (3) |
C16 | 0.026 (3) | 0.043 (3) | 0.033 (4) | 0.001 (2) | 0.006 (3) | −0.004 (3) |
C17 | 0.036 (3) | 0.026 (3) | 0.031 (3) | 0.004 (2) | 0.014 (3) | −0.006 (2) |
C18 | 0.038 (3) | 0.037 (3) | 0.045 (4) | 0.002 (3) | 0.004 (3) | 0.000 (3) |
C19 | 0.032 (3) | 0.040 (3) | 0.067 (5) | 0.010 (3) | 0.008 (3) | 0.008 (3) |
C20 | 0.029 (3) | 0.050 (4) | 0.056 (5) | 0.012 (3) | 0.007 (3) | −0.009 (3) |
C21 | 0.034 (3) | 0.047 (4) | 0.048 (4) | −0.004 (3) | 0.018 (3) | −0.003 (3) |
C22 | 0.025 (3) | 0.034 (3) | 0.034 (4) | 0.005 (2) | 0.007 (3) | 0.001 (2) |
C23 | 0.039 (3) | 0.020 (2) | 0.029 (3) | 0.002 (2) | 0.004 (3) | 0.000 (2) |
C24 | 0.037 (3) | 0.026 (3) | 0.039 (4) | −0.001 (2) | 0.005 (3) | 0.000 (3) |
C25 | 0.037 (3) | 0.042 (3) | 0.036 (4) | 0.004 (3) | −0.005 (3) | −0.006 (3) |
C26 | 0.053 (4) | 0.034 (3) | 0.032 (4) | 0.004 (3) | −0.006 (3) | −0.008 (3) |
C27 | 0.067 (5) | 0.043 (3) | 0.023 (4) | 0.013 (3) | 0.007 (3) | −0.004 (3) |
C28 | 0.042 (3) | 0.030 (3) | 0.027 (3) | 0.005 (2) | 0.007 (3) | −0.003 (2) |
P3 | 0.0215 (6) | 0.0231 (6) | 0.0253 (8) | 0.0010 (5) | 0.0069 (6) | 0.0006 (6) |
C29 | 0.030 (3) | 0.022 (2) | 0.032 (3) | −0.002 (2) | 0.009 (3) | 0.000 (2) |
C30 | 0.022 (3) | 0.029 (3) | 0.032 (3) | −0.001 (2) | 0.011 (2) | 0.001 (2) |
P4 | 0.0194 (7) | 0.0261 (6) | 0.0254 (9) | −0.0009 (6) | 0.0064 (6) | 0.0002 (6) |
C31 | 0.026 (3) | 0.030 (3) | 0.027 (3) | 0.012 (2) | 0.008 (2) | 0.002 (2) |
C32 | 0.039 (3) | 0.053 (4) | 0.033 (4) | −0.001 (3) | 0.009 (3) | −0.009 (3) |
C33 | 0.053 (4) | 0.059 (4) | 0.034 (4) | 0.012 (3) | 0.018 (3) | −0.013 (3) |
C34 | 0.049 (4) | 0.067 (4) | 0.039 (4) | 0.024 (3) | 0.023 (3) | 0.005 (4) |
C35 | 0.039 (4) | 0.045 (4) | 0.059 (5) | 0.013 (3) | 0.027 (3) | 0.005 (3) |
C36 | 0.032 (3) | 0.029 (3) | 0.041 (4) | 0.004 (2) | 0.013 (3) | 0.003 (3) |
C37 | 0.036 (3) | 0.028 (3) | 0.029 (4) | 0.004 (2) | 0.013 (3) | 0.003 (2) |
C38 | 0.046 (3) | 0.029 (3) | 0.041 (4) | 0.002 (2) | 0.018 (3) | 0.011 (3) |
C39 | 0.061 (4) | 0.034 (3) | 0.049 (5) | 0.011 (3) | 0.023 (4) | 0.017 (3) |
C40 | 0.071 (5) | 0.036 (3) | 0.031 (4) | 0.018 (3) | 0.012 (4) | 0.007 (3) |
C41 | 0.054 (4) | 0.037 (3) | 0.043 (4) | 0.017 (3) | 0.010 (3) | 0.008 (3) |
C42 | 0.038 (3) | 0.038 (3) | 0.041 (4) | 0.011 (3) | 0.010 (3) | 0.008 (3) |
C43 | 0.021 (3) | 0.028 (3) | 0.031 (3) | −0.001 (2) | 0.009 (2) | 0.001 (2) |
C44 | 0.028 (3) | 0.036 (3) | 0.035 (4) | −0.003 (2) | 0.014 (3) | 0.000 (3) |
C45 | 0.039 (3) | 0.036 (3) | 0.033 (4) | −0.008 (2) | 0.018 (3) | −0.002 (3) |
C46 | 0.035 (3) | 0.043 (3) | 0.051 (4) | −0.009 (3) | 0.031 (3) | −0.004 (3) |
C47 | 0.029 (3) | 0.052 (4) | 0.056 (5) | 0.009 (3) | 0.020 (3) | 0.006 (3) |
C48 | 0.024 (3) | 0.046 (3) | 0.053 (4) | 0.008 (2) | 0.021 (3) | 0.011 (3) |
C49 | 0.015 (2) | 0.032 (3) | 0.030 (3) | −0.004 (2) | 0.006 (2) | 0.001 (2) |
C50 | 0.025 (3) | 0.038 (3) | 0.032 (3) | −0.004 (2) | 0.006 (3) | −0.002 (3) |
C51 | 0.024 (3) | 0.047 (3) | 0.031 (4) | 0.001 (2) | 0.001 (3) | 0.007 (3) |
C52 | 0.024 (3) | 0.045 (3) | 0.029 (3) | −0.001 (2) | 0.000 (2) | 0.011 (3) |
C53 | 0.029 (3) | 0.029 (3) | 0.048 (4) | 0.002 (2) | 0.014 (3) | 0.011 (3) |
C54 | 0.023 (3) | 0.031 (3) | 0.029 (3) | −0.003 (2) | 0.004 (2) | 0.003 (2) |
P5 | 0.0505 (10) | 0.0507 (10) | 0.0380 (11) | −0.0106 (8) | 0.0173 (9) | −0.0057 (8) |
Ru1—N1 | 2.209 (5) | C28—H30 | 0.9500 |
Ru1—P1 | 2.3586 (14) | P3—C31 | 1.835 (5) |
Ru1—P4 | 2.3672 (15) | P3—C37 | 1.838 (6) |
Ru1—P3 | 2.3698 (13) | P3—C29 | 1.850 (5) |
Ru1—P2 | 2.4249 (13) | C29—C30 | 1.517 (7) |
Ru1—S1 | 2.4317 (15) | C29—H31 | 0.9900 |
S1—C1 | 1.831 (7) | C29—H32 | 0.9900 |
N1—C2 | 1.484 (8) | C30—P4 | 1.849 (5) |
N1—H1 | 0.90 (2) | C30—H33 | 0.9900 |
N1—H2 | 0.91 (2) | C30—H34 | 0.9900 |
C1—C2 | 1.478 (8) | P4—C49 | 1.837 (6) |
C1—H3 | 0.9900 | P4—C43 | 1.856 (5) |
C1—H4 | 0.9900 | C31—C32 | 1.386 (8) |
C2—H5 | 0.9900 | C31—C36 | 1.406 (7) |
C2—H6 | 0.9900 | C32—C33 | 1.404 (9) |
P1—C5 | 1.842 (6) | C32—H35 | 0.9500 |
P1—C11 | 1.859 (5) | C33—C34 | 1.358 (9) |
P1—C3 | 1.860 (5) | C33—H36 | 0.9500 |
C3—C4 | 1.517 (8) | C34—C35 | 1.372 (9) |
C3—H7 | 0.9900 | C34—H37 | 0.9500 |
C3—H8 | 0.9900 | C35—C36 | 1.379 (8) |
C4—P2 | 1.833 (5) | C35—H38 | 0.9500 |
C4—H9 | 0.9900 | C36—H39 | 0.9500 |
C4—H10 | 0.9900 | C37—C42 | 1.390 (8) |
P2—C23 | 1.834 (6) | C37—C38 | 1.407 (8) |
P2—C17 | 1.835 (5) | C38—C39 | 1.397 (8) |
C5—C10 | 1.396 (7) | C38—H40 | 0.9500 |
C5—C6 | 1.403 (7) | C39—C40 | 1.366 (9) |
C6—C7 | 1.386 (8) | C39—H41 | 0.9500 |
C6—H11 | 0.9500 | C40—C41 | 1.375 (10) |
C7—C8 | 1.378 (8) | C40—H42 | 0.9500 |
C7—H12 | 0.9500 | C41—C42 | 1.388 (8) |
C8—C9 | 1.377 (8) | C41—H43 | 0.9500 |
C8—H13 | 0.9500 | C42—H44 | 0.9500 |
C9—C10 | 1.389 (8) | C43—C48 | 1.395 (7) |
C9—H14 | 0.9500 | C43—C44 | 1.396 (8) |
C10—H15 | 0.9500 | C44—C45 | 1.389 (7) |
C11—C16 | 1.388 (8) | C44—H45 | 0.9500 |
C11—C12 | 1.389 (8) | C45—C46 | 1.380 (8) |
C12—C13 | 1.385 (8) | C45—H46 | 0.9500 |
C12—H16 | 0.9500 | C46—C47 | 1.376 (9) |
C13—C14 | 1.373 (9) | C46—H47 | 0.9500 |
C13—H17 | 0.9500 | C47—C48 | 1.386 (8) |
C14—C15 | 1.375 (9) | C47—H48 | 0.9500 |
C14—H18 | 0.9500 | C48—H49 | 0.9500 |
C15—C16 | 1.396 (8) | C49—C54 | 1.398 (7) |
C15—H19 | 0.9500 | C49—C50 | 1.400 (8) |
C16—H20 | 0.9500 | C50—C51 | 1.375 (8) |
C17—C22 | 1.391 (7) | C50—H50 | 0.9500 |
C17—C18 | 1.403 (7) | C51—C52 | 1.384 (8) |
C18—C19 | 1.369 (8) | C51—H51 | 0.9500 |
C18—H21 | 0.9500 | C52—C53 | 1.378 (8) |
C19—C20 | 1.375 (9) | C52—H52 | 0.9500 |
C19—H22 | 0.9500 | C53—C54 | 1.390 (8) |
C20—C21 | 1.377 (9) | C53—H53 | 0.9500 |
C20—H23 | 0.9500 | C54—H54 | 0.9500 |
C21—C22 | 1.381 (7) | P5—F4 | 1.466 (14) |
C21—H24 | 0.9500 | P5—F17 | 1.475 (14) |
C22—H25 | 0.9500 | P5—F12 | 1.495 (17) |
C23—C24 | 1.396 (8) | P5—F16 | 1.531 (16) |
C23—C28 | 1.405 (8) | P5—F8 | 1.552 (19) |
C24—C25 | 1.375 (8) | P5—F18 | 1.555 (18) |
C24—H26 | 0.9500 | P5—F10 | 1.585 (15) |
C25—C26 | 1.374 (9) | P5—F2 | 1.592 (13) |
C25—H27 | 0.9500 | P5—F7 | 1.601 (19) |
C26—C27 | 1.390 (9) | P5—F5 | 1.610 (13) |
C26—H28 | 0.9500 | P5—F6 | 1.617 (14) |
C27—C28 | 1.384 (8) | P5—F15 | 1.623 (15) |
C27—H29 | 0.9500 | ||
N1—Ru1—P1 | 171.03 (13) | C25—C26—H28 | 120.5 |
N1—Ru1—P4 | 95.14 (13) | C27—C26—H28 | 120.5 |
P1—Ru1—P4 | 91.27 (5) | C28—C27—C26 | 120.6 (6) |
N1—Ru1—P3 | 87.17 (13) | C28—C27—H29 | 119.7 |
P1—Ru1—P3 | 99.77 (5) | C26—C27—H29 | 119.7 |
P4—Ru1—P3 | 83.88 (5) | C27—C28—C23 | 121.0 (6) |
N1—Ru1—P2 | 88.63 (13) | C27—C28—H30 | 119.5 |
P1—Ru1—P2 | 83.76 (5) | C23—C28—H30 | 119.5 |
P4—Ru1—P2 | 103.62 (5) | C31—P3—C37 | 97.8 (2) |
P3—Ru1—P2 | 171.71 (5) | C31—P3—C29 | 105.9 (3) |
N1—Ru1—S1 | 80.92 (13) | C37—P3—C29 | 102.8 (3) |
P1—Ru1—S1 | 93.86 (5) | C31—P3—Ru1 | 123.39 (17) |
P4—Ru1—S1 | 169.03 (5) | C37—P3—Ru1 | 116.92 (18) |
P3—Ru1—S1 | 85.70 (5) | C29—P3—Ru1 | 107.81 (16) |
P2—Ru1—S1 | 86.59 (5) | C30—C29—P3 | 110.2 (3) |
C1—S1—Ru1 | 101.18 (19) | C30—C29—H31 | 109.6 |
C2—N1—Ru1 | 116.7 (4) | P3—C29—H31 | 109.6 |
C2—N1—H1 | 104 (4) | C30—C29—H32 | 109.6 |
Ru1—N1—H1 | 118 (4) | P3—C29—H32 | 109.6 |
C2—N1—H2 | 99 (4) | H31—C29—H32 | 108.1 |
Ru1—N1—H2 | 118 (4) | C29—C30—P4 | 111.0 (4) |
H1—N1—H2 | 98 (5) | C29—C30—H33 | 109.4 |
C2—C1—S1 | 114.3 (4) | P4—C30—H33 | 109.4 |
C2—C1—H3 | 108.7 | C29—C30—H34 | 109.4 |
S1—C1—H3 | 108.7 | P4—C30—H34 | 109.4 |
C2—C1—H4 | 108.7 | H33—C30—H34 | 108.0 |
S1—C1—H4 | 108.7 | C49—P4—C30 | 101.7 (3) |
H3—C1—H4 | 107.6 | C49—P4—C43 | 100.6 (2) |
C1—C2—N1 | 112.9 (5) | C30—P4—C43 | 98.9 (2) |
C1—C2—H5 | 109.0 | C49—P4—Ru1 | 123.42 (16) |
N1—C2—H5 | 109.0 | C30—P4—Ru1 | 107.70 (17) |
C1—C2—H6 | 109.0 | C43—P4—Ru1 | 120.52 (19) |
N1—C2—H6 | 109.0 | C32—C31—C36 | 119.3 (5) |
H5—C2—H6 | 107.8 | C32—C31—P3 | 121.7 (4) |
C5—P1—C11 | 99.3 (2) | C36—C31—P3 | 118.7 (4) |
C5—P1—C3 | 101.4 (2) | C31—C32—C33 | 119.6 (6) |
C11—P1—C3 | 99.4 (2) | C31—C32—H35 | 120.2 |
C5—P1—Ru1 | 123.58 (17) | C33—C32—H35 | 120.2 |
C11—P1—Ru1 | 121.42 (18) | C34—C33—C32 | 120.1 (6) |
C3—P1—Ru1 | 107.59 (18) | C34—C33—H36 | 120.0 |
C4—C3—P1 | 110.8 (4) | C32—C33—H36 | 120.0 |
C4—C3—H7 | 109.5 | C33—C34—C35 | 120.8 (6) |
P1—C3—H7 | 109.5 | C33—C34—H37 | 119.6 |
C4—C3—H8 | 109.5 | C35—C34—H37 | 119.6 |
P1—C3—H8 | 109.5 | C34—C35—C36 | 120.6 (6) |
H7—C3—H8 | 108.1 | C34—C35—H38 | 119.7 |
C3—C4—P2 | 110.4 (3) | C36—C35—H38 | 119.7 |
C3—C4—H9 | 109.6 | C35—C36—C31 | 119.5 (5) |
P2—C4—H9 | 109.6 | C35—C36—H39 | 120.3 |
C3—C4—H10 | 109.6 | C31—C36—H39 | 120.3 |
P2—C4—H10 | 109.6 | C42—C37—C38 | 117.6 (5) |
H9—C4—H10 | 108.1 | C42—C37—P3 | 120.1 (4) |
C4—P2—C23 | 101.5 (3) | C38—C37—P3 | 122.2 (4) |
C4—P2—C17 | 104.3 (2) | C39—C38—C37 | 119.6 (6) |
C23—P2—C17 | 100.2 (3) | C39—C38—H40 | 120.2 |
C4—P2—Ru1 | 106.29 (18) | C37—C38—H40 | 120.2 |
C23—P2—Ru1 | 120.91 (17) | C40—C39—C38 | 121.2 (6) |
C17—P2—Ru1 | 121.00 (17) | C40—C39—H41 | 119.4 |
C10—C5—C6 | 117.8 (5) | C38—C39—H41 | 119.4 |
C10—C5—P1 | 122.4 (4) | C39—C40—C41 | 120.1 (6) |
C6—C5—P1 | 119.7 (4) | C39—C40—H42 | 119.9 |
C7—C6—C5 | 121.3 (5) | C41—C40—H42 | 119.9 |
C7—C6—H11 | 119.4 | C40—C41—C42 | 119.4 (6) |
C5—C6—H11 | 119.4 | C40—C41—H43 | 120.3 |
C8—C7—C6 | 119.7 (5) | C42—C41—H43 | 120.3 |
C8—C7—H12 | 120.1 | C41—C42—C37 | 122.0 (6) |
C6—C7—H12 | 120.1 | C41—C42—H44 | 119.0 |
C9—C8—C7 | 120.1 (6) | C37—C42—H44 | 119.0 |
C9—C8—H13 | 119.9 | C48—C43—C44 | 116.9 (5) |
C7—C8—H13 | 119.9 | C48—C43—P4 | 121.4 (4) |
C8—C9—C10 | 120.5 (5) | C44—C43—P4 | 121.6 (4) |
C8—C9—H14 | 119.7 | C45—C44—C43 | 122.5 (5) |
C10—C9—H14 | 119.7 | C45—C44—H45 | 118.8 |
C9—C10—C5 | 120.6 (5) | C43—C44—H45 | 118.8 |
C9—C10—H15 | 119.7 | C46—C45—C44 | 118.8 (5) |
C5—C10—H15 | 119.7 | C46—C45—H46 | 120.6 |
C16—C11—C12 | 117.8 (5) | C44—C45—H46 | 120.6 |
C16—C11—P1 | 119.2 (4) | C47—C46—C45 | 120.4 (5) |
C12—C11—P1 | 123.0 (4) | C47—C46—H47 | 119.8 |
C13—C12—C11 | 121.3 (6) | C45—C46—H47 | 119.8 |
C13—C12—H16 | 119.3 | C46—C47—C48 | 120.3 (5) |
C11—C12—H16 | 119.3 | C46—C47—H48 | 119.9 |
C14—C13—C12 | 120.5 (6) | C48—C47—H48 | 119.9 |
C14—C13—H17 | 119.8 | C47—C48—C43 | 121.2 (6) |
C12—C13—H17 | 119.8 | C47—C48—H49 | 119.4 |
C13—C14—C15 | 119.1 (5) | C43—C48—H49 | 119.4 |
C13—C14—H18 | 120.4 | C54—C49—C50 | 117.7 (5) |
C15—C14—H18 | 120.4 | C54—C49—P4 | 119.2 (4) |
C14—C15—C16 | 120.7 (6) | C50—C49—P4 | 123.0 (4) |
C14—C15—H19 | 119.7 | C51—C50—C49 | 120.5 (5) |
C16—C15—H19 | 119.7 | C51—C50—H50 | 119.8 |
C11—C16—C15 | 120.6 (6) | C49—C50—H50 | 119.8 |
C11—C16—H20 | 119.7 | C50—C51—C52 | 121.9 (6) |
C15—C16—H20 | 119.7 | C50—C51—H51 | 119.1 |
C22—C17—C18 | 117.0 (5) | C52—C51—H51 | 119.1 |
C22—C17—P2 | 119.1 (4) | C53—C52—C51 | 118.0 (5) |
C18—C17—P2 | 123.9 (4) | C53—C52—H52 | 121.0 |
C19—C18—C17 | 121.3 (6) | C51—C52—H52 | 121.0 |
C19—C18—H21 | 119.3 | C52—C53—C54 | 121.1 (5) |
C17—C18—H21 | 119.3 | C52—C53—H53 | 119.4 |
C18—C19—C20 | 120.4 (6) | C54—C53—H53 | 119.4 |
C18—C19—H22 | 119.8 | C53—C54—C49 | 120.7 (5) |
C20—C19—H22 | 119.8 | C53—C54—H54 | 119.7 |
C19—C20—C21 | 119.9 (5) | C49—C54—H54 | 119.7 |
C19—C20—H23 | 120.0 | F17—P5—F16 | 95.6 (11) |
C21—C20—H23 | 120.0 | F12—P5—F8 | 94.6 (10) |
C20—C21—C22 | 119.6 (5) | F17—P5—F18 | 97.0 (9) |
C20—C21—H24 | 120.2 | F16—P5—F18 | 84.6 (11) |
C22—C21—H24 | 120.2 | F12—P5—F10 | 92.0 (9) |
C21—C22—C17 | 121.7 (5) | F8—P5—F10 | 89.5 (9) |
C21—C22—H25 | 119.2 | F4—P5—F2 | 91.4 (8) |
C17—C22—H25 | 119.2 | F12—P5—F7 | 95.8 (11) |
C24—C23—C28 | 116.7 (5) | F8—P5—F7 | 92.0 (10) |
C24—C23—P2 | 122.0 (5) | F10—P5—F7 | 171.9 (10) |
C28—C23—P2 | 121.1 (4) | F4—P5—F5 | 95.4 (8) |
C25—C24—C23 | 122.2 (6) | F2—P5—F5 | 172.3 (7) |
C25—C24—H26 | 118.9 | F4—P5—F6 | 102.7 (9) |
C23—C24—H26 | 118.9 | F2—P5—F6 | 92.0 (8) |
C26—C25—C24 | 120.5 (6) | F5—P5—F6 | 89.8 (8) |
C26—C25—H27 | 119.7 | F17—P5—F15 | 90.1 (9) |
C24—C25—H27 | 119.7 | F16—P5—F15 | 91.6 (10) |
C25—C26—C27 | 118.9 (6) | F18—P5—F15 | 172.2 (8) |
N1—Ru1—S1—C1 | 1.0 (2) | C25—C26—C27—C28 | 2.8 (9) |
P1—Ru1—S1—C1 | 173.7 (2) | C26—C27—C28—C23 | −2.4 (9) |
P4—Ru1—S1—C1 | −68.6 (4) | C24—C23—C28—C27 | 1.0 (8) |
P3—Ru1—S1—C1 | −86.8 (2) | P2—C23—C28—C27 | 176.4 (4) |
P2—Ru1—S1—C1 | 90.2 (2) | N1—Ru1—P3—C31 | −152.5 (2) |
P4—Ru1—N1—C2 | −169.9 (4) | P1—Ru1—P3—C31 | 21.8 (2) |
P3—Ru1—N1—C2 | 106.5 (4) | P4—Ru1—P3—C31 | 112.0 (2) |
P2—Ru1—N1—C2 | −66.4 (4) | S1—Ru1—P3—C31 | −71.4 (2) |
S1—Ru1—N1—C2 | 20.4 (4) | N1—Ru1—P3—C37 | −31.4 (2) |
Ru1—S1—C1—C2 | −22.2 (5) | P1—Ru1—P3—C37 | 142.8 (2) |
S1—C1—C2—N1 | 41.0 (6) | P4—Ru1—P3—C37 | −126.9 (2) |
Ru1—N1—C2—C1 | −40.8 (6) | S1—Ru1—P3—C37 | 49.7 (2) |
P4—Ru1—P1—C5 | −23.9 (2) | N1—Ru1—P3—C29 | 83.6 (2) |
P3—Ru1—P1—C5 | 60.1 (2) | P1—Ru1—P3—C29 | −102.1 (2) |
P2—Ru1—P1—C5 | −127.5 (2) | P4—Ru1—P3—C29 | −11.8 (2) |
S1—Ru1—P1—C5 | 146.40 (19) | S1—Ru1—P3—C29 | 164.7 (2) |
P4—Ru1—P1—C11 | −153.23 (19) | C31—P3—C29—C30 | −95.6 (4) |
P3—Ru1—P1—C11 | −69.21 (19) | C37—P3—C29—C30 | 162.4 (4) |
P2—Ru1—P1—C11 | 103.22 (19) | Ru1—P3—C29—C30 | 38.3 (4) |
S1—Ru1—P1—C11 | 17.08 (19) | P3—C29—C30—P4 | −49.2 (5) |
P4—Ru1—P1—C3 | 93.51 (18) | C29—C30—P4—C49 | 168.7 (4) |
P3—Ru1—P1—C3 | 177.52 (18) | C29—C30—P4—C43 | −88.4 (4) |
P2—Ru1—P1—C3 | −10.05 (18) | C29—C30—P4—Ru1 | 37.7 (4) |
S1—Ru1—P1—C3 | −96.19 (18) | N1—Ru1—P4—C49 | 144.9 (3) |
C5—P1—C3—C4 | 169.2 (4) | P1—Ru1—P4—C49 | −28.8 (2) |
C11—P1—C3—C4 | −89.1 (4) | P3—Ru1—P4—C49 | −128.5 (2) |
Ru1—P1—C3—C4 | 38.2 (4) | P2—Ru1—P4—C49 | 55.1 (2) |
P1—C3—C4—P2 | −51.7 (4) | S1—Ru1—P4—C49 | −146.7 (4) |
C3—C4—P2—C23 | 168.0 (4) | N1—Ru1—P4—C30 | −97.4 (2) |
C3—C4—P2—C17 | −88.2 (4) | P1—Ru1—P4—C30 | 88.91 (19) |
C3—C4—P2—Ru1 | 40.8 (4) | P3—Ru1—P4—C30 | −10.79 (19) |
N1—Ru1—P2—C4 | 161.9 (2) | P2—Ru1—P4—C30 | 172.79 (19) |
P1—Ru1—P2—C4 | −13.36 (19) | S1—Ru1—P4—C30 | −29.0 (4) |
P4—Ru1—P2—C4 | −103.16 (19) | N1—Ru1—P4—C43 | 14.7 (2) |
S1—Ru1—P2—C4 | 80.90 (19) | P1—Ru1—P4—C43 | −159.01 (19) |
N1—Ru1—P2—C23 | 47.2 (3) | P3—Ru1—P4—C43 | 101.30 (19) |
P1—Ru1—P2—C23 | −128.0 (2) | P2—Ru1—P4—C43 | −75.12 (19) |
P4—Ru1—P2—C23 | 142.2 (2) | S1—Ru1—P4—C43 | 83.1 (4) |
S1—Ru1—P2—C23 | −33.8 (2) | C37—P3—C31—C32 | 86.9 (5) |
N1—Ru1—P2—C17 | −79.7 (3) | C29—P3—C31—C32 | −18.9 (5) |
P1—Ru1—P2—C17 | 105.1 (2) | Ru1—P3—C31—C32 | −143.6 (4) |
P4—Ru1—P2—C17 | 15.3 (2) | C37—P3—C31—C36 | −87.8 (5) |
S1—Ru1—P2—C17 | −160.6 (2) | C29—P3—C31—C36 | 166.5 (4) |
C11—P1—C5—C10 | −98.7 (4) | Ru1—P3—C31—C36 | 41.8 (5) |
C3—P1—C5—C10 | 3.0 (5) | C36—C31—C32—C33 | −1.0 (9) |
Ru1—P1—C5—C10 | 123.3 (4) | P3—C31—C32—C33 | −175.6 (5) |
C11—P1—C5—C6 | 79.1 (4) | C31—C32—C33—C34 | 2.6 (10) |
C3—P1—C5—C6 | −179.2 (4) | C32—C33—C34—C35 | −2.9 (11) |
Ru1—P1—C5—C6 | −58.9 (4) | C33—C34—C35—C36 | 1.5 (10) |
C10—C5—C6—C7 | −1.0 (7) | C34—C35—C36—C31 | 0.1 (10) |
P1—C5—C6—C7 | −178.9 (4) | C32—C31—C36—C35 | −0.3 (9) |
C5—C6—C7—C8 | 1.0 (8) | P3—C31—C36—C35 | 174.4 (5) |
C6—C7—C8—C9 | −0.1 (9) | C31—P3—C37—C42 | 43.7 (5) |
C7—C8—C9—C10 | −0.7 (9) | C29—P3—C37—C42 | 152.1 (5) |
C8—C9—C10—C5 | 0.7 (8) | Ru1—P3—C37—C42 | −90.1 (5) |
C6—C5—C10—C9 | 0.1 (7) | C31—P3—C37—C38 | −139.2 (5) |
P1—C5—C10—C9 | 178.0 (4) | C29—P3—C37—C38 | −30.8 (6) |
C5—P1—C11—C16 | 164.8 (4) | Ru1—P3—C37—C38 | 87.0 (5) |
C3—P1—C11—C16 | 61.4 (5) | C42—C37—C38—C39 | −1.4 (9) |
Ru1—P1—C11—C16 | −56.0 (5) | P3—C37—C38—C39 | −178.6 (5) |
C5—P1—C11—C12 | −13.1 (5) | C37—C38—C39—C40 | 1.0 (10) |
C3—P1—C11—C12 | −116.4 (5) | C38—C39—C40—C41 | −0.8 (10) |
Ru1—P1—C11—C12 | 126.1 (4) | C39—C40—C41—C42 | 1.1 (10) |
C16—C11—C12—C13 | 0.0 (9) | C40—C41—C42—C37 | −1.6 (10) |
P1—C11—C12—C13 | 177.9 (5) | C38—C37—C42—C41 | 1.7 (9) |
C11—C12—C13—C14 | −1.3 (10) | P3—C37—C42—C41 | 179.0 (5) |
C12—C13—C14—C15 | 0.3 (10) | C49—P4—C43—C48 | −2.9 (5) |
C13—C14—C15—C16 | 1.8 (9) | C30—P4—C43—C48 | −106.6 (5) |
C12—C11—C16—C15 | 2.1 (8) | Ru1—P4—C43—C48 | 136.7 (4) |
P1—C11—C16—C15 | −175.8 (4) | C49—P4—C43—C44 | 174.3 (4) |
C14—C15—C16—C11 | −3.1 (9) | C30—P4—C43—C44 | 70.5 (5) |
C4—P2—C17—C22 | 162.9 (5) | Ru1—P4—C43—C44 | −46.1 (5) |
C23—P2—C17—C22 | −92.3 (5) | C48—C43—C44—C45 | −1.5 (8) |
Ru1—P2—C17—C22 | 43.5 (6) | P4—C43—C44—C45 | −178.7 (4) |
C4—P2—C17—C18 | −16.6 (6) | C43—C44—C45—C46 | 0.7 (9) |
C23—P2—C17—C18 | 88.2 (5) | C44—C45—C46—C47 | 0.2 (9) |
Ru1—P2—C17—C18 | −136.1 (5) | C45—C46—C47—C48 | −0.3 (10) |
C22—C17—C18—C19 | −0.1 (9) | C46—C47—C48—C43 | −0.6 (10) |
P2—C17—C18—C19 | 179.5 (5) | C44—C43—C48—C47 | 1.4 (9) |
C17—C18—C19—C20 | −0.2 (11) | P4—C43—C48—C47 | 178.7 (5) |
C18—C19—C20—C21 | 1.1 (11) | C30—P4—C49—C54 | −174.5 (4) |
C19—C20—C21—C22 | −1.8 (10) | C43—P4—C49—C54 | 84.0 (4) |
C20—C21—C22—C17 | 1.5 (10) | Ru1—P4—C49—C54 | −54.0 (5) |
C18—C17—C22—C21 | −0.6 (9) | C30—P4—C49—C50 | 7.9 (5) |
P2—C17—C22—C21 | 179.8 (5) | C43—P4—C49—C50 | −93.6 (5) |
C4—P2—C23—C24 | −47.9 (5) | Ru1—P4—C49—C50 | 128.4 (4) |
C17—P2—C23—C24 | −155.0 (4) | C54—C49—C50—C51 | 2.8 (7) |
Ru1—P2—C23—C24 | 69.2 (5) | P4—C49—C50—C51 | −179.6 (4) |
C4—P2—C23—C28 | 136.9 (4) | C49—C50—C51—C52 | −0.4 (8) |
C17—P2—C23—C28 | 29.8 (5) | C50—C51—C52—C53 | −2.2 (8) |
Ru1—P2—C23—C28 | −106.0 (4) | C51—C52—C53—C54 | 2.4 (8) |
C28—C23—C24—C25 | −0.2 (8) | C52—C53—C54—C49 | 0.0 (8) |
P2—C23—C24—C25 | −175.5 (4) | C50—C49—C54—C53 | −2.6 (7) |
C23—C24—C25—C26 | 0.7 (9) | P4—C49—C54—C53 | 179.7 (4) |
C24—C25—C26—C27 | −1.9 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F11i | 0.90 (2) | 2.34 (4) | 3.198 (17) | 159 (6) |
Symmetry code: (i) x−1/2, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ru(C2H6NS)(C26H24P2)2]PF6 |
Mr | 1118.96 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 200 |
a, b, c (Å) | 21.1985 (17), 11.4000 (9), 20.9346 (17) |
β (°) | 106.588 (2) |
V (Å3) | 4848.6 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.59 |
Crystal size (mm) | 0.15 × 0.08 × 0.08 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Rigaku, 1995) |
Tmin, Tmax | 0.684, 0.954 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23148, 9513, 7722 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.112, 1.20 |
No. of reflections | 9513 |
No. of parameters | 638 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.02, −0.88 |
Absolute structure | Flack (1983), 3981 Friedel pairs |
Absolute structure parameter | −0.02 (3) |
Computer programs: PROCESS-AUTO (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Yadokari-XG 2009 (Kabuto et al., 2009).
Ru1—N1 | 2.209 (5) | Ru1—P3 | 2.3698 (13) |
Ru1—P1 | 2.3586 (14) | Ru1—P2 | 2.4249 (13) |
Ru1—P4 | 2.3672 (15) | Ru1—S1 | 2.4317 (15) |
N1—Ru1—P1 | 171.03 (13) | P4—Ru1—S1 | 169.03 (5) |
P3—Ru1—P2 | 171.71 (5) |
Acknowledgements
This work was supported by a Grant-in-Aid for Science Research (grant No. 23350026) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.
References
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It has been recognized that the preparation of ruthenium complexes having non-bridging aliphatic thiolato group(s) is difficult because of the high reactivity of a thiolato group bound to a metal center. For example, the direct reaction of RuII with 2-aminoethanethiol (Haet) led to the formation of thiolato-bridged trinuclear complex, [Ru{Ru(aet)3}2]2+ (Matsuura et al., 2006), and furthermore, the reaction of [Ag{Ru(aet)(bpy)2}2]3+ (bpy = 2,2'-bipyridine) with HCl did not give an expected mononuclear complex, [Ru(aet)(bpy)2]+, but produced a dinuclear complex with a disulfide bond, [Ru2(cysta)(bpy)4]4+ (cysta = cystamine) (Tamura et al., 2007). Here, we report the synthesis and crystal structure of [Ru(aet)(dppe)2]PF6, which is a quite rare example of a crystallographically characterized ruthenium(II) complex with an aliphatic thiolato donor. The use of the bulky diphenylphosphine ligand seems to be responsible for the successful isolation of this compound.
The reaction of [RuCl2(dppe)2] (Bautista et al., 1991) with excess Haet in methanol in the presence of NH4PF6 gave a yellow powder of [Ru(aet)(dppe)2]PF6. Single-crystals suitable for X-ray analysis were obtained by the recrystallization of the yellow powder from methanol.
The compound crystallized in a non-centrosymmetric space group Cc, the asymmetric unit of which contains one complex cation and one PF6- anion. The Ru atom is in an NP4S octahedral geometry coordinated by two dppe-κP,P and one aet-κN,S ligands (Fig. 1). The Ru–S [2.431 (2) Å] and Ru–N [2.212 (5) Å] bond distances are slightly longer than those of the related ruthenium(II) complexes with aet ligand(s) (Ru–S = 2.291–2.394 Å, Ru–N = 2.133–2.212 Å) (Tamura et al., 2007; Matsuura et al., 2006; Hanif et al., 1999). On the other hand, the Ru–P bond distances (average 2.380 Å) are similar to those of ruthenium(II) complexes with dppe ligands (av. 2.32 Å), as found in the Cambridge Structural Database (Allen, 2002). Consistent with the space group Cc, the crystal consists of a pair of enantiomers (Δ and Λ) of the ruthenium(II) complex. Two dppe P,P-chelate rings in the complex adopt an ob conformation (δ for Δ isomer, λ for Λ isomer), while its N,S-aet chelate ring has a lel conformation (λ for Δ isomer, δ for Λ isomer). It may be interesting to note that no significant specific intermolecular interactions have been found, except for very weak N-H···F interactions between the complex cations and PF6- anions (Fig. 2).