supplementary materials


zs2249 scheme

Acta Cryst. (2013). E69, m226    [ doi:10.1107/S160053681300737X ]

cis,cis,cis-(Acetato-[kappa]2O,O')bis[1,2-bis(diphenylphosphanyl)ethane-[kappa]2P,P']ruthenium(II) 0.75-trifluoromethanesulfonate 0.25-chloride

J. Figueira, J. Rodrigues and A. Valkonen

Abstract top

In the title RuII carboxylate compound, [Ru(C2H3O2)(C26H24P2)2](CF3O3S)0.75Cl0.25, the distorted tris-bidentate octahedral stereochemistry about the RuII atom in the complex cation comprises four P-atom donors from two 1,2-bis(diphenylphosphanyl)ethane ligands [Ru-P = 2.2881 (13)-2.3791 (13) Å] and two O-atom donors from the acetate ligand [Ru-O = 2.191 (3) and 2.202 (3) Å]. The disordered counter-anions are located on the same site in the structure in a 3:1 ratio, the expanded formula comprising four complex cations, three trifluoromethanesulfonate anions and one chloride anion, with two such formula units in the unit cell.

Comment top

Ruthenium carboxylate complexes have found increasing interest as building blocks for larger macrocycles (Kilbas et al., 2012), preparation of magnetic materials (Mikuriya et al., 2011), as catalysts (Hiett et al., 2011) and as promising materials for NLO devices (Liu et al., 2012).

In the RuII carboxylate compound, cis-[Ru(η2(CH3CO2) (C26H24P2)2] (CF3O3S)0.75 Cl0.25, the title compound (Fig. 1) the complex cation is formed by three bidentate chelate ligands (two 1,2-bis(diphenylphosphanyl)ethane ligands and one acetato ligand) giving bite angles at the metal of 82.36 (5) and 83.44 (5)° for the phosphines and 59.18 (12)° for the acetate. The observed Ru—P and Ru—O bond distances [range 2.2882 (13)–2.3791 (13) Å and 2.191 (3), 2.202 (3) Å, respectively] result in a distorted octahedral geometry consistent with similar complexes having the cis-configuration (Holle et al., 1997, Lucas et al., 2000, Wyman et al., 2004). The Ru—P bond distances in the title complex are shorter than those in complexes in which the acetate group is trans-related but are well within reported ranges (Holle et al., 1997, Lucas et al., 2000, Wyman et al., 2004).

The disordered counter anions are located on the same site in the structure in a 3:1 ratio, the complete complex unit having the formula 4[Ru(C2H3O2)(C26H24P2)2] (CF3O3S)3 Cl, with two such formula units in the unit cell.

Related literature top

For applications of RuII carboxylate complexes, see: Kilbas et al. (2012); Mikuriya et al. (2011); Hiett et al. (2011); Liu et al. (2012). For similar complexes, see: Holle et al. (1997); Wyman et al. (2004); Lucas et al. (2000).

Experimental top

The title compound was obtained as a by-product in the attempted crystallization of the products of the reaction of [RuCl(dppe)2][PF6] and 1,4-diheptoxy-2,5-diethynylbenzene, using a dichloromethane–diethyl ether solvent mixture at -20 °C.

Refinement top

All H atoms were visible in electron density maps, but they were included at calculated positions and allowed to ride on the C atoms with C—H = 0.95 Å (aromatic), 0.98 Å (methyl) and 0.99 Å (methylene), with Uiso(H) = 1.2 (or 1.5 for methyl) times Ueq(C). Two positions for each of the methyl protons on C54 were found and this disorder was handled by refining these positions constrained over 60° rotational sites with 0.5 site occupancy. The trifluoromethanesulfonate and chloride anions were found to occupy a common site, with occupancies of 0.75 and 0.25, respectively. Small geometrical disorder in the trifluoromethanesulfonate anion was handled by restraining the C—F (1.320 Å), S—C (1.820 Å) and F···F (2.150 Å) distances (s = 0.001). The anisotropic displacement parameters were made equal for S1 and C55.

Computing details top

Data collection: COLLECT (Bruker, 2004); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. Plot of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
cis,cis,cis-(Acetato-κ2O,O')bis[1,2-bis(diphenylphosphanyl)ethane-κ2P,P']ruthenium(II) 0.75-trifluoromethanesulfonate 0.25-chloride top
Crystal data top
[Ru(C2H3O2)(C26H24P2)2](CF3O3S)0.75Cl0.25F(000) = 4432
Mr = 4310.25Dx = 1.451 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 137403 reflections
a = 15.7463 (2) Åθ = 2.9–28.3°
b = 21.8914 (3) ŵ = 0.55 mm1
c = 28.6122 (4) ÅT = 173 K
V = 9862.9 (2) Å3Prism, green-yellow
Z = 20.25 × 0.20 × 0.15 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer with APEXII detector
8662 independent reflections
Radiation source: fine-focus sealed tube7095 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 9 pixels mm-1θmax = 25.0°, θmin = 3.0°
CCD rotation images, thick slices scansh = 1818
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
k = 2526
Tmin = 0.875, Tmax = 0.922l = 3334
16563 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0484P)2 + 43.975P]
where P = (Fo2 + 2Fc2)/3
8662 reflections(Δ/σ)max = 0.001
626 parametersΔρmax = 0.90 e Å3
7 restraintsΔρmin = 1.04 e Å3
Crystal data top
[Ru(C2H3O2)(C26H24P2)2](CF3O3S)0.75Cl0.25V = 9862.9 (2) Å3
Mr = 4310.25Z = 2
Orthorhombic, PbcaMo Kα radiation
a = 15.7463 (2) ŵ = 0.55 mm1
b = 21.8914 (3) ÅT = 173 K
c = 28.6122 (4) Å0.25 × 0.20 × 0.15 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer with APEXII detector
8662 independent reflections
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
7095 reflections with I > 2σ(I)
Tmin = 0.875, Tmax = 0.922Rint = 0.036
16563 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.061 w = 1/[σ2(Fo2) + (0.0484P)2 + 43.975P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.148Δρmax = 0.90 e Å3
S = 1.13Δρmin = 1.04 e Å3
8662 reflectionsAbsolute structure: ?
626 parametersFlack parameter: ?
7 restraintsRogers parameter: ?
H-atom parameters constrained
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ru10.24211 (2)0.986017 (17)0.615267 (13)0.02161 (12)
P10.21047 (8)1.02120 (6)0.68978 (4)0.0250 (3)
P20.38185 (8)0.98385 (6)0.64581 (4)0.0256 (3)
P30.23401 (8)1.08350 (6)0.58676 (4)0.0234 (3)
P40.10573 (8)0.97601 (6)0.58030 (5)0.0268 (3)
O10.2933 (2)0.93092 (15)0.55788 (12)0.0289 (8)
O20.2383 (2)0.88552 (15)0.61809 (11)0.0268 (8)
C10.1295 (3)1.0776 (2)0.70689 (18)0.0318 (12)
C20.0460 (4)1.0689 (3)0.6930 (2)0.0388 (13)
H20.03231.03490.67380.047*
C30.0182 (4)1.1088 (3)0.7068 (2)0.0468 (16)
H30.07471.10280.69620.056*
C40.0006 (5)1.1572 (3)0.7358 (2)0.0533 (18)
H40.04291.18420.74580.064*
C50.0833 (5)1.1659 (3)0.7503 (2)0.0517 (17)
H50.09631.19890.77060.062*
C60.1477 (4)1.1270 (2)0.73574 (19)0.0400 (14)
H60.20451.13420.74550.048*
C70.1886 (3)0.9611 (2)0.73337 (16)0.0255 (11)
C80.1589 (3)0.9772 (2)0.77776 (17)0.0314 (12)
H80.14931.01890.78500.038*
C90.1434 (3)0.9330 (3)0.81120 (18)0.0339 (12)
H90.12290.94450.84110.041*
C100.1576 (3)0.8718 (3)0.80126 (18)0.0351 (13)
H100.14570.84120.82390.042*
C110.1893 (4)0.8560 (2)0.75789 (18)0.0346 (13)
H110.20150.81440.75120.042*
C120.2035 (3)0.8997 (2)0.72447 (17)0.0295 (11)
H120.22400.88770.69460.035*
C130.3081 (3)1.0540 (2)0.71472 (17)0.0297 (12)
H13A0.32161.09320.69920.036*
H13B0.30041.06180.74850.036*
C140.3806 (3)1.0085 (3)0.70718 (17)0.0329 (12)
H14A0.37270.97260.72780.039*
H14B0.43551.02790.71520.039*
C150.4262 (3)0.9063 (2)0.64697 (19)0.0315 (12)
C160.4122 (4)0.8679 (3)0.6845 (2)0.0433 (14)
H160.38240.88260.71110.052*
C170.4413 (4)0.8082 (3)0.6836 (3)0.0560 (18)
H170.43160.78250.70980.067*
C180.4840 (4)0.7855 (3)0.6453 (3)0.0528 (18)
H180.50280.74420.64480.063*
C190.4992 (4)0.8237 (3)0.6078 (3)0.0502 (16)
H190.52910.80870.58130.060*
C200.4711 (4)0.8837 (2)0.6086 (2)0.0375 (13)
H200.48250.90970.58270.045*
C210.4649 (3)1.0279 (2)0.61657 (17)0.0265 (11)
C220.5263 (4)1.0605 (3)0.6399 (2)0.0424 (14)
H220.52661.06100.67310.051*
C230.5880 (4)1.0928 (3)0.6155 (3)0.0597 (19)
H230.63111.11420.63210.072*
C240.5868 (4)1.0939 (3)0.5674 (3)0.0537 (17)
H240.62851.11650.55070.064*
C250.5254 (4)1.0622 (3)0.5436 (2)0.0428 (15)
H250.52451.06300.51040.051*
C260.4646 (3)1.0292 (2)0.56764 (18)0.0316 (12)
H260.42241.00720.55090.038*
C270.2689 (3)1.0974 (2)0.52628 (17)0.0283 (11)
C280.2936 (3)1.0509 (2)0.49636 (17)0.0287 (11)
H280.29791.01020.50770.034*
C290.3120 (4)1.0635 (3)0.44953 (19)0.0384 (13)
H290.32961.03150.42930.046*
C300.3045 (5)1.1219 (3)0.4330 (2)0.0507 (17)
H300.31571.13010.40100.061*
C310.2809 (5)1.1685 (3)0.4622 (2)0.0565 (19)
H310.27701.20910.45050.068*
C320.2627 (4)1.1568 (3)0.5087 (2)0.0448 (15)
H320.24601.18920.52880.054*
C330.2783 (3)1.1506 (2)0.61595 (16)0.0230 (10)
C340.3646 (3)1.1632 (2)0.6107 (2)0.0330 (12)
H340.39821.13810.59100.040*
C350.4020 (4)1.2121 (2)0.6338 (2)0.0385 (13)
H350.46101.21990.63040.046*
C360.3526 (4)1.2493 (2)0.6619 (2)0.0382 (13)
H360.37761.28280.67790.046*
C370.2670 (4)1.2376 (2)0.6667 (2)0.0376 (13)
H370.23331.26340.68600.045*
C380.2296 (3)1.1890 (2)0.64379 (17)0.0313 (12)
H380.17041.18180.64710.038*
C390.1203 (3)1.1014 (2)0.57906 (18)0.0296 (11)
H39A0.09261.10610.60990.036*
H39B0.11381.14010.56160.036*
C400.0794 (3)1.0492 (2)0.55215 (18)0.0316 (12)
H40A0.10031.04920.51950.038*
H40B0.01701.05470.55150.038*
C410.0981 (3)0.9187 (2)0.53316 (18)0.0321 (12)
C420.1437 (3)0.9273 (3)0.49147 (19)0.0354 (13)
H420.17610.96350.48710.042*
C430.1415 (4)0.8832 (3)0.4565 (2)0.0426 (15)
H430.17190.88960.42820.051*
C440.0952 (4)0.8303 (3)0.4626 (2)0.0533 (18)
H440.09400.80010.43870.064*
C450.0508 (5)0.8214 (3)0.5037 (3)0.0588 (19)
H450.01890.78500.50780.071*
C460.0521 (4)0.8646 (3)0.5387 (2)0.0468 (15)
H460.02150.85760.56680.056*
C470.0162 (3)0.9537 (3)0.61700 (18)0.0330 (12)
C480.0656 (4)0.9769 (3)0.6110 (2)0.0489 (16)
H480.07721.00490.58650.059*
C490.1296 (4)0.9587 (4)0.6410 (2)0.065 (2)
H490.18500.97520.63740.077*
C500.1147 (4)0.9174 (4)0.6759 (2)0.0580 (19)
H500.15950.90560.69620.070*
C510.0346 (4)0.8929 (3)0.6816 (2)0.0502 (16)
H510.02430.86370.70550.060*
C520.0317 (4)0.9112 (3)0.6520 (2)0.0400 (14)
H520.08700.89450.65590.048*
C530.2719 (3)0.8818 (2)0.57815 (17)0.0269 (11)
C540.2851 (4)0.8208 (2)0.5550 (2)0.0386 (13)
H54A0.32870.82460.53070.058*0.50
H54B0.23170.80730.54080.058*0.50
H54C0.30350.79090.57830.058*0.50
H54D0.24720.79060.56920.058*0.50
H54E0.34420.80790.55910.058*0.50
H54F0.27240.82430.52150.058*0.50
S10.71959 (16)0.70092 (13)0.66161 (10)0.0689 (7)0.75
F10.8095 (8)0.7154 (5)0.5899 (3)0.299 (12)0.75
F20.8041 (9)0.7953 (3)0.6335 (4)0.279 (10)0.75
F30.8855 (5)0.7204 (6)0.6522 (3)0.225 (6)0.75
O30.7261 (3)0.6357 (2)0.6583 (2)0.0504 (15)0.75
O40.6611 (4)0.7297 (4)0.6355 (2)0.081 (2)0.75
O50.7051 (7)0.7148 (3)0.7085 (2)0.103 (3)0.75
C550.8117 (3)0.7352 (3)0.6335 (2)0.0689 (7)0.75
Cl10.8005 (6)0.7210 (6)0.6672 (4)0.108 (4)0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.0256 (2)0.0248 (2)0.0145 (2)0.00014 (16)0.00011 (15)0.00065 (16)
P10.0301 (7)0.0292 (7)0.0157 (6)0.0006 (5)0.0028 (5)0.0011 (5)
P20.0269 (6)0.0310 (7)0.0188 (6)0.0010 (6)0.0008 (5)0.0006 (5)
P30.0282 (7)0.0255 (6)0.0164 (6)0.0016 (5)0.0026 (5)0.0005 (5)
P40.0275 (7)0.0320 (7)0.0210 (7)0.0015 (5)0.0032 (5)0.0002 (6)
O10.0340 (19)0.0292 (19)0.0236 (19)0.0007 (15)0.0014 (15)0.0037 (15)
O20.0330 (19)0.0274 (18)0.0202 (18)0.0001 (15)0.0003 (15)0.0016 (14)
C10.042 (3)0.032 (3)0.021 (3)0.004 (2)0.013 (2)0.007 (2)
C20.045 (3)0.042 (3)0.030 (3)0.007 (3)0.010 (3)0.001 (3)
C30.044 (3)0.052 (4)0.045 (4)0.011 (3)0.019 (3)0.014 (3)
C40.068 (5)0.044 (4)0.048 (4)0.018 (3)0.030 (4)0.016 (3)
C50.081 (5)0.032 (3)0.042 (4)0.015 (3)0.012 (3)0.001 (3)
C60.066 (4)0.029 (3)0.025 (3)0.002 (3)0.011 (3)0.002 (2)
C70.025 (2)0.033 (3)0.019 (2)0.004 (2)0.003 (2)0.002 (2)
C80.036 (3)0.036 (3)0.021 (3)0.002 (2)0.004 (2)0.001 (2)
C90.037 (3)0.044 (3)0.021 (3)0.002 (2)0.005 (2)0.002 (2)
C100.038 (3)0.045 (3)0.022 (3)0.013 (3)0.003 (2)0.007 (2)
C110.050 (3)0.032 (3)0.021 (3)0.007 (3)0.004 (2)0.001 (2)
C120.038 (3)0.038 (3)0.012 (2)0.003 (2)0.001 (2)0.002 (2)
C130.041 (3)0.034 (3)0.014 (2)0.006 (2)0.000 (2)0.003 (2)
C140.033 (3)0.047 (3)0.019 (3)0.006 (2)0.003 (2)0.001 (2)
C150.027 (3)0.032 (3)0.035 (3)0.002 (2)0.006 (2)0.005 (2)
C160.038 (3)0.044 (3)0.048 (4)0.001 (3)0.001 (3)0.010 (3)
C170.048 (4)0.045 (4)0.075 (5)0.001 (3)0.005 (4)0.025 (4)
C180.045 (4)0.026 (3)0.087 (5)0.001 (3)0.017 (4)0.005 (3)
C190.048 (4)0.039 (3)0.063 (4)0.006 (3)0.005 (3)0.012 (3)
C200.046 (3)0.030 (3)0.037 (3)0.003 (3)0.002 (3)0.002 (2)
C210.026 (3)0.027 (3)0.026 (3)0.005 (2)0.001 (2)0.000 (2)
C220.037 (3)0.056 (4)0.034 (3)0.007 (3)0.006 (3)0.010 (3)
C230.041 (4)0.080 (5)0.058 (5)0.025 (3)0.008 (3)0.017 (4)
C240.042 (4)0.057 (4)0.062 (5)0.009 (3)0.015 (3)0.019 (4)
C250.048 (4)0.040 (3)0.040 (4)0.008 (3)0.019 (3)0.006 (3)
C260.038 (3)0.028 (3)0.029 (3)0.005 (2)0.007 (2)0.004 (2)
C270.034 (3)0.030 (3)0.021 (3)0.001 (2)0.001 (2)0.001 (2)
C280.031 (3)0.031 (3)0.024 (3)0.006 (2)0.005 (2)0.003 (2)
C290.049 (3)0.042 (3)0.024 (3)0.005 (3)0.011 (3)0.005 (2)
C300.080 (5)0.051 (4)0.021 (3)0.004 (3)0.015 (3)0.006 (3)
C310.102 (6)0.037 (3)0.030 (3)0.001 (4)0.021 (3)0.005 (3)
C320.077 (4)0.031 (3)0.027 (3)0.002 (3)0.011 (3)0.002 (2)
C330.027 (2)0.023 (2)0.019 (2)0.003 (2)0.001 (2)0.001 (2)
C340.035 (3)0.025 (3)0.039 (3)0.000 (2)0.006 (2)0.005 (2)
C350.035 (3)0.032 (3)0.048 (4)0.003 (2)0.001 (3)0.004 (3)
C360.047 (3)0.029 (3)0.039 (3)0.004 (3)0.003 (3)0.008 (2)
C370.049 (4)0.032 (3)0.032 (3)0.005 (3)0.006 (3)0.012 (2)
C380.037 (3)0.034 (3)0.023 (3)0.001 (2)0.008 (2)0.002 (2)
C390.031 (3)0.032 (3)0.026 (3)0.005 (2)0.002 (2)0.001 (2)
C400.030 (3)0.041 (3)0.024 (3)0.001 (2)0.002 (2)0.002 (2)
C410.032 (3)0.038 (3)0.027 (3)0.006 (2)0.009 (2)0.007 (2)
C420.035 (3)0.044 (3)0.027 (3)0.007 (2)0.007 (2)0.003 (2)
C430.040 (3)0.060 (4)0.028 (3)0.014 (3)0.010 (2)0.011 (3)
C440.060 (4)0.048 (4)0.052 (4)0.010 (3)0.022 (3)0.020 (3)
C450.071 (5)0.043 (4)0.062 (5)0.010 (3)0.011 (4)0.009 (3)
C460.059 (4)0.042 (3)0.039 (4)0.010 (3)0.003 (3)0.001 (3)
C470.028 (3)0.044 (3)0.028 (3)0.008 (2)0.001 (2)0.002 (2)
C480.037 (3)0.076 (5)0.034 (3)0.002 (3)0.004 (3)0.011 (3)
C490.031 (3)0.118 (6)0.044 (4)0.004 (4)0.001 (3)0.011 (4)
C500.044 (4)0.096 (6)0.034 (4)0.022 (4)0.008 (3)0.004 (4)
C510.052 (4)0.067 (4)0.031 (3)0.015 (3)0.001 (3)0.007 (3)
C520.036 (3)0.048 (3)0.036 (3)0.010 (3)0.001 (3)0.003 (3)
C530.026 (3)0.032 (3)0.022 (3)0.001 (2)0.006 (2)0.001 (2)
C540.052 (4)0.035 (3)0.029 (3)0.001 (3)0.004 (3)0.007 (2)
S10.0557 (15)0.0781 (17)0.0728 (18)0.0190 (13)0.0043 (12)0.0238 (14)
F10.45 (2)0.272 (15)0.179 (11)0.273 (17)0.189 (14)0.138 (11)
F20.49 (3)0.081 (7)0.270 (17)0.020 (11)0.152 (18)0.030 (9)
F30.090 (7)0.363 (19)0.223 (14)0.031 (9)0.042 (8)0.043 (14)
O30.048 (3)0.040 (3)0.064 (4)0.003 (3)0.010 (3)0.023 (3)
O40.067 (4)0.116 (6)0.059 (4)0.057 (4)0.026 (4)0.017 (4)
O50.230 (10)0.052 (4)0.027 (3)0.059 (5)0.022 (5)0.010 (3)
C550.0557 (15)0.0781 (17)0.0728 (18)0.0190 (13)0.0043 (12)0.0238 (14)
Cl10.063 (6)0.133 (9)0.127 (9)0.010 (6)0.005 (6)0.036 (8)
Geometric parameters (Å, º) top
Ru1—O12.191 (3)C25—C261.383 (8)
Ru1—O22.202 (3)C25—H250.9500
Ru1—P32.2881 (13)C26—H260.9500
Ru1—P12.3211 (13)C27—C281.386 (7)
Ru1—P22.3680 (13)C27—C321.397 (7)
Ru1—P42.3791 (13)C28—C291.398 (7)
P1—C131.841 (5)C28—H280.9500
P1—C11.841 (5)C29—C301.368 (8)
P1—C71.844 (5)C29—H290.9500
P2—C211.827 (5)C30—C311.372 (8)
P2—C141.837 (5)C30—H300.9500
P2—C151.837 (5)C31—C321.385 (8)
P3—C331.828 (5)C31—H310.9500
P3—C271.841 (5)C32—H320.9500
P3—C391.846 (5)C33—C381.390 (7)
P4—C471.825 (5)C33—C341.394 (7)
P4—C401.840 (5)C34—C351.389 (7)
P4—C411.846 (5)C34—H340.9500
O1—C531.267 (6)C35—C361.384 (8)
O2—C531.262 (6)C35—H350.9500
C1—C21.386 (8)C36—C371.379 (8)
C1—C61.391 (8)C36—H360.9500
C2—C31.394 (8)C37—C381.382 (7)
C2—H20.9500C37—H370.9500
C3—C41.378 (9)C38—H380.9500
C3—H30.9500C39—C401.521 (7)
C4—C51.379 (10)C39—H39A0.9900
C4—H40.9500C39—H39B0.9900
C5—C61.388 (8)C40—H40A0.9900
C5—H50.9500C40—H40B0.9900
C6—H60.9500C41—C461.397 (8)
C7—C121.389 (7)C41—C421.405 (8)
C7—C81.398 (7)C42—C431.392 (8)
C8—C91.383 (7)C42—H420.9500
C8—H80.9500C43—C441.380 (9)
C9—C101.387 (8)C43—H430.9500
C9—H90.9500C44—C451.381 (10)
C10—C111.382 (7)C44—H440.9500
C10—H100.9500C45—C461.380 (9)
C11—C121.371 (7)C45—H450.9500
C11—H110.9500C46—H460.9500
C12—H120.9500C47—C521.389 (8)
C13—C141.530 (7)C47—C481.395 (8)
C13—H13A0.9900C48—C491.384 (9)
C13—H13B0.9900C48—H480.9500
C14—H14A0.9900C49—C501.366 (10)
C14—H14B0.9900C49—H490.9500
C15—C161.381 (8)C50—C511.381 (10)
C15—C201.397 (8)C50—H500.9500
C16—C171.386 (9)C51—C521.402 (8)
C16—H160.9500C51—H510.9500
C17—C181.379 (10)C52—H520.9500
C17—H170.9500C53—C541.505 (7)
C18—C191.381 (9)C54—H54A0.9800
C18—H180.9500C54—H54B0.9800
C19—C201.388 (8)C54—H54C0.9800
C19—H190.9500C54—H54D0.9800
C20—H200.9500C54—H54E0.9800
C21—C221.376 (8)C54—H54F0.9800
C21—C261.400 (7)S1—O41.343 (6)
C22—C231.390 (8)S1—O51.394 (6)
C22—H220.9500S1—O31.434 (6)
C23—C241.377 (9)S1—C551.8204 (10)
C23—H230.9500F1—C551.3206 (10)
C24—C251.372 (9)F2—C551.3209 (10)
C24—H240.9500F3—C551.3207 (10)
O1—Ru1—O259.18 (12)C26—C25—H25119.8
O1—Ru1—P3105.48 (10)C25—C26—C21120.4 (5)
O2—Ru1—P3160.60 (9)C25—C26—H26119.8
O1—Ru1—P1161.81 (10)C21—C26—H26119.8
O2—Ru1—P1106.97 (9)C28—C27—C32118.8 (5)
P3—Ru1—P190.34 (5)C28—C27—P3122.9 (4)
O1—Ru1—P285.62 (10)C32—C27—P3118.1 (4)
O2—Ru1—P289.53 (9)C27—C28—C29120.3 (5)
P3—Ru1—P2101.66 (5)C27—C28—H28119.8
P1—Ru1—P282.36 (5)C29—C28—H28119.8
O1—Ru1—P488.08 (10)C30—C29—C28119.9 (5)
O2—Ru1—P484.19 (9)C30—C29—H29120.1
P3—Ru1—P483.44 (5)C28—C29—H29120.1
P1—Ru1—P4102.89 (5)C29—C30—C31120.5 (5)
P2—Ru1—P4172.77 (5)C29—C30—H30119.7
O1—Ru1—C5329.65 (14)C31—C30—H30119.7
O2—Ru1—C5329.55 (14)C30—C31—C32120.2 (6)
P3—Ru1—C53133.90 (12)C30—C31—H31119.9
P1—Ru1—C53135.75 (12)C32—C31—H31119.9
P2—Ru1—C5387.98 (11)C31—C32—C27120.3 (5)
P4—Ru1—C5384.79 (11)C31—C32—H32119.9
C13—P1—C1102.4 (3)C27—C32—H32119.9
C13—P1—C799.9 (2)C38—C33—C34118.7 (5)
C1—P1—C799.7 (2)C38—C33—P3122.5 (4)
C13—P1—Ru1107.82 (16)C34—C33—P3118.8 (4)
C1—P1—Ru1127.97 (18)C35—C34—C33121.0 (5)
C7—P1—Ru1115.12 (17)C35—C34—H34119.5
C21—P2—C14106.9 (2)C33—C34—H34119.5
C21—P2—C15102.9 (2)C36—C35—C34119.4 (5)
C14—P2—C15105.0 (3)C36—C35—H35120.3
C21—P2—Ru1119.04 (17)C34—C35—H35120.3
C14—P2—Ru1109.69 (18)C37—C36—C35119.9 (5)
C15—P2—Ru1112.26 (17)C37—C36—H36120.1
C33—P3—C27100.5 (2)C35—C36—H36120.1
C33—P3—C39104.8 (2)C36—C37—C38120.8 (5)
C27—P3—C3998.2 (2)C36—C37—H37119.6
C33—P3—Ru1124.40 (16)C38—C37—H37119.6
C27—P3—Ru1118.19 (17)C37—C38—C33120.2 (5)
C39—P3—Ru1107.13 (17)C37—C38—H38119.9
C47—P4—C40108.1 (3)C33—C38—H38119.9
C47—P4—C41100.8 (2)C40—C39—P3108.2 (3)
C40—P4—C41104.9 (2)C40—C39—H39A110.1
C47—P4—Ru1118.71 (18)P3—C39—H39A110.1
C40—P4—Ru1107.88 (17)C40—C39—H39B110.1
C41—P4—Ru1115.37 (17)P3—C39—H39B110.1
C53—O1—Ru191.5 (3)H39A—C39—H39B108.4
C53—O2—Ru191.1 (3)C39—C40—P4109.7 (3)
C2—C1—C6118.2 (5)C39—C40—H40A109.7
C2—C1—P1119.2 (4)P4—C40—H40A109.7
C6—C1—P1122.5 (5)C39—C40—H40B109.7
C1—C2—C3121.4 (6)P4—C40—H40B109.7
C1—C2—H2119.3H40A—C40—H40B108.2
C3—C2—H2119.3C46—C41—C42118.4 (5)
C4—C3—C2119.8 (6)C46—C41—P4121.7 (4)
C4—C3—H3120.1C42—C41—P4119.7 (4)
C2—C3—H3120.1C43—C42—C41120.3 (6)
C3—C4—C5119.4 (6)C43—C42—H42119.8
C3—C4—H4120.3C41—C42—H42119.8
C5—C4—H4120.3C44—C43—C42120.3 (6)
C4—C5—C6120.9 (6)C44—C43—H43119.8
C4—C5—H5119.5C42—C43—H43119.8
C6—C5—H5119.5C43—C44—C45119.6 (6)
C5—C6—C1120.3 (6)C43—C44—H44120.2
C5—C6—H6119.8C45—C44—H44120.2
C1—C6—H6119.8C46—C45—C44121.0 (6)
C12—C7—C8117.8 (5)C46—C45—H45119.5
C12—C7—P1122.3 (4)C44—C45—H45119.5
C8—C7—P1119.8 (4)C45—C46—C41120.4 (6)
C9—C8—C7120.8 (5)C45—C46—H46119.8
C9—C8—H8119.6C41—C46—H46119.8
C7—C8—H8119.6C52—C47—C48119.7 (5)
C8—C9—C10120.4 (5)C52—C47—P4117.3 (4)
C8—C9—H9119.8C48—C47—P4123.0 (4)
C10—C9—H9119.8C49—C48—C47119.4 (6)
C11—C10—C9119.0 (5)C49—C48—H48120.3
C11—C10—H10120.5C47—C48—H48120.3
C9—C10—H10120.5C50—C49—C48121.3 (7)
C12—C11—C10120.7 (5)C50—C49—H49119.3
C12—C11—H11119.7C48—C49—H49119.3
C10—C11—H11119.7C49—C50—C51120.0 (6)
C11—C12—C7121.4 (5)C49—C50—H50120.0
C11—C12—H12119.3C51—C50—H50120.0
C7—C12—H12119.3C50—C51—C52119.8 (6)
C14—C13—P1108.3 (3)C50—C51—H51120.1
C14—C13—H13A110.0C52—C51—H51120.1
P1—C13—H13A110.0C47—C52—C51119.7 (6)
C14—C13—H13B110.0C47—C52—H52120.1
P1—C13—H13B110.0C51—C52—H52120.1
H13A—C13—H13B108.4O2—C53—O1118.1 (4)
C13—C14—P2109.5 (3)O2—C53—C54120.9 (5)
C13—C14—H14A109.8O1—C53—C54121.0 (5)
P2—C14—H14A109.8O2—C53—Ru159.4 (2)
C13—C14—H14B109.8O1—C53—Ru158.8 (2)
P2—C14—H14B109.8C54—C53—Ru1177.0 (4)
H14A—C14—H14B108.2C53—C54—H54A109.5
C16—C15—C20118.6 (5)C53—C54—H54B109.5
C16—C15—P2121.0 (4)H54A—C54—H54B109.5
C20—C15—P2120.3 (4)C53—C54—H54C109.5
C15—C16—C17120.3 (6)H54A—C54—H54C109.5
C15—C16—H16119.8H54B—C54—H54C109.5
C17—C16—H16119.8C53—C54—H54D109.5
C18—C17—C16121.1 (6)H54A—C54—H54D141.1
C18—C17—H17119.4H54B—C54—H54D56.3
C16—C17—H17119.4H54C—C54—H54D56.3
C17—C18—C19118.9 (6)C53—C54—H54E109.5
C17—C18—H18120.5H54A—C54—H54E56.3
C19—C18—H18120.5H54B—C54—H54E141.1
C18—C19—C20120.4 (6)H54C—C54—H54E56.3
C18—C19—H19119.8H54D—C54—H54E109.5
C20—C19—H19119.8C53—C54—H54F109.5
C19—C20—C15120.6 (6)H54A—C54—H54F56.3
C19—C20—H20119.7H54B—C54—H54F56.3
C15—C20—H20119.7H54C—C54—H54F141.1
C22—C21—C26118.5 (5)H54D—C54—H54F109.5
C22—C21—P2123.7 (4)H54E—C54—H54F109.5
C26—C21—P2117.8 (4)O4—S1—O5108.7 (5)
C21—C22—C23120.8 (6)O4—S1—O3118.6 (5)
C21—C22—H22119.6O5—S1—O3107.0 (4)
C23—C22—H22119.6O4—S1—C5596.1 (5)
C24—C23—C22120.0 (6)O5—S1—C55117.8 (5)
C24—C23—H23120.0O3—S1—C55108.9 (3)
C22—C23—H23120.0F1—C55—F3108.95 (12)
C25—C24—C23119.9 (6)F1—C55—F2108.94 (12)
C25—C24—H24120.0F3—C55—F2108.90 (12)
C23—C24—H24120.0F1—C55—S1105.2 (8)
C24—C25—C26120.3 (6)F3—C55—S1114.9 (7)
C24—C25—H25119.8F2—C55—S1109.8 (8)
O1—Ru1—P1—C1371.7 (4)Ru1—P2—C15—C1686.8 (5)
O2—Ru1—P1—C13109.8 (2)C21—P2—C15—C2039.5 (5)
P3—Ru1—P1—C1379.07 (18)C14—P2—C15—C20151.2 (4)
P2—Ru1—P1—C1322.64 (18)Ru1—P2—C15—C2089.7 (4)
P4—Ru1—P1—C13162.41 (18)C20—C15—C16—C170.8 (9)
C53—Ru1—P1—C13101.8 (2)P2—C15—C16—C17175.7 (5)
O1—Ru1—P1—C1165.8 (4)C15—C16—C17—C180.6 (10)
O2—Ru1—P1—C1127.7 (2)C16—C17—C18—C191.3 (10)
P3—Ru1—P1—C143.4 (2)C17—C18—C19—C200.6 (9)
P2—Ru1—P1—C1145.1 (2)C18—C19—C20—C150.8 (9)
P4—Ru1—P1—C140.0 (2)C16—C15—C20—C191.4 (8)
C53—Ru1—P1—C1135.8 (3)P2—C15—C20—C19175.1 (5)
O1—Ru1—P1—C738.7 (4)C14—P2—C21—C2214.6 (5)
O2—Ru1—P1—C70.7 (2)C15—P2—C21—C2295.7 (5)
P3—Ru1—P1—C7170.47 (17)Ru1—P2—C21—C22139.5 (4)
P2—Ru1—P1—C787.81 (17)C14—P2—C21—C26164.1 (4)
P4—Ru1—P1—C787.13 (18)C15—P2—C21—C2685.6 (4)
C53—Ru1—P1—C78.7 (2)Ru1—P2—C21—C2639.3 (4)
O1—Ru1—P2—C2171.3 (2)C26—C21—C22—C231.6 (9)
O2—Ru1—P2—C21130.4 (2)P2—C21—C22—C23179.7 (5)
P3—Ru1—P2—C2133.60 (19)C21—C22—C23—C241.8 (11)
P1—Ru1—P2—C21122.36 (19)C22—C23—C24—C250.9 (11)
C53—Ru1—P2—C21100.9 (2)C23—C24—C25—C260.1 (10)
O1—Ru1—P2—C14165.2 (2)C24—C25—C26—C210.3 (8)
O2—Ru1—P2—C14106.1 (2)C22—C21—C26—C250.6 (8)
P3—Ru1—P2—C1489.9 (2)P2—C21—C26—C25179.3 (4)
P1—Ru1—P2—C141.1 (2)C33—P3—C27—C28143.8 (4)
C53—Ru1—P2—C14135.6 (2)C39—P3—C27—C28109.4 (5)
O1—Ru1—P2—C1548.9 (2)Ru1—P3—C27—C285.1 (5)
O2—Ru1—P2—C1510.2 (2)C33—P3—C27—C3242.2 (5)
P3—Ru1—P2—C15153.83 (19)C39—P3—C27—C3264.5 (5)
P1—Ru1—P2—C15117.4 (2)Ru1—P3—C27—C32179.0 (4)
C53—Ru1—P2—C1519.3 (2)C32—C27—C28—C290.2 (8)
O1—Ru1—P3—C33128.3 (2)P3—C27—C28—C29174.1 (4)
O2—Ru1—P3—C33163.8 (3)C27—C28—C29—C300.9 (9)
P1—Ru1—P3—C3342.56 (19)C28—C29—C30—C311.5 (10)
P2—Ru1—P3—C3339.7 (2)C29—C30—C31—C321.3 (12)
P4—Ru1—P3—C33145.49 (19)C30—C31—C32—C270.5 (11)
C53—Ru1—P3—C33138.3 (2)C28—C27—C32—C310.0 (9)
O1—Ru1—P3—C270.1 (2)P3—C27—C32—C31174.2 (5)
O2—Ru1—P3—C2735.6 (4)C27—P3—C33—C38127.6 (4)
P1—Ru1—P3—C27170.76 (19)C39—P3—C33—C3826.1 (5)
P2—Ru1—P3—C2788.49 (19)Ru1—P3—C33—C3897.2 (4)
P4—Ru1—P3—C2786.31 (19)C27—P3—C33—C3453.4 (4)
C53—Ru1—P3—C2710.1 (3)C39—P3—C33—C34154.9 (4)
O1—Ru1—P3—C39109.4 (2)Ru1—P3—C33—C3481.8 (4)
O2—Ru1—P3—C3973.9 (3)C38—C33—C34—C352.0 (8)
P1—Ru1—P3—C3979.72 (18)P3—C33—C34—C35177.1 (4)
P2—Ru1—P3—C39161.99 (18)C33—C34—C35—C361.0 (9)
P4—Ru1—P3—C3923.22 (18)C34—C35—C36—C370.1 (9)
C53—Ru1—P3—C3999.5 (2)C35—C36—C37—C380.2 (9)
O1—Ru1—P4—C47131.8 (2)C36—C37—C38—C330.8 (8)
O2—Ru1—P4—C4772.6 (2)C34—C33—C38—C371.8 (8)
P3—Ru1—P4—C47122.4 (2)P3—C33—C38—C37177.2 (4)
P1—Ru1—P4—C4733.6 (2)C33—P3—C39—C40176.6 (3)
C53—Ru1—P4—C47102.2 (2)C27—P3—C39—C4073.3 (4)
O1—Ru1—P4—C40104.9 (2)Ru1—P3—C39—C4049.6 (4)
O2—Ru1—P4—C40164.1 (2)P3—C39—C40—P451.2 (4)
P3—Ru1—P4—C400.93 (18)C47—P4—C40—C3998.5 (4)
P1—Ru1—P4—C4089.78 (19)C41—P4—C40—C39154.5 (4)
C53—Ru1—P4—C40134.4 (2)Ru1—P4—C40—C3931.0 (4)
O1—Ru1—P4—C4112.0 (2)C47—P4—C41—C4618.4 (5)
O2—Ru1—P4—C4147.2 (2)C40—P4—C41—C46130.7 (5)
P3—Ru1—P4—C41117.8 (2)Ru1—P4—C41—C46110.8 (5)
P1—Ru1—P4—C41153.4 (2)C47—P4—C41—C42165.6 (4)
C53—Ru1—P4—C4117.5 (2)C40—P4—C41—C4253.3 (5)
O2—Ru1—O1—C531.5 (3)Ru1—P4—C41—C4265.2 (4)
P3—Ru1—O1—C53165.5 (3)C46—C41—C42—C431.0 (8)
P1—Ru1—O1—C5344.9 (5)P4—C41—C42—C43177.2 (4)
P2—Ru1—O1—C5393.6 (3)C41—C42—C43—C440.7 (8)
P4—Ru1—O1—C5382.8 (3)C42—C43—C44—C450.3 (9)
O1—Ru1—O2—C531.6 (3)C43—C44—C45—C460.2 (10)
P3—Ru1—O2—C5339.1 (4)C44—C45—C46—C410.5 (10)
P1—Ru1—O2—C53168.6 (3)C42—C41—C46—C450.9 (9)
P2—Ru1—O2—C5386.7 (3)P4—C41—C46—C45177.0 (5)
P4—Ru1—O2—C5389.7 (3)C40—P4—C47—C52160.4 (4)
C13—P1—C1—C2178.6 (4)C41—P4—C47—C5289.8 (5)
C7—P1—C1—C279.0 (4)Ru1—P4—C47—C5237.2 (5)
Ru1—P1—C1—C253.9 (5)C40—P4—C47—C4820.1 (6)
C13—P1—C1—C65.5 (5)C41—P4—C47—C4889.6 (5)
C7—P1—C1—C697.0 (4)Ru1—P4—C47—C48143.3 (5)
Ru1—P1—C1—C6130.1 (4)C52—C47—C48—C492.1 (10)
C6—C1—C2—C31.1 (8)P4—C47—C48—C49178.4 (5)
P1—C1—C2—C3177.2 (4)C47—C48—C49—C501.4 (11)
C1—C2—C3—C41.9 (9)C48—C49—C50—C510.2 (12)
C2—C3—C4—C51.0 (9)C49—C50—C51—C521.0 (11)
C3—C4—C5—C60.6 (9)C48—C47—C52—C511.3 (9)
C4—C5—C6—C11.4 (9)P4—C47—C52—C51179.2 (5)
C2—C1—C6—C50.6 (8)C50—C51—C52—C470.2 (9)
P1—C1—C6—C5175.4 (4)Ru1—O2—C53—O12.6 (4)
C13—P1—C7—C12105.0 (4)Ru1—O2—C53—C54176.5 (4)
C1—P1—C7—C12150.5 (4)Ru1—O1—C53—O22.6 (4)
Ru1—P1—C7—C1210.1 (5)Ru1—O1—C53—C54176.5 (4)
C13—P1—C7—C872.6 (4)O1—Ru1—C53—O2177.3 (5)
C1—P1—C7—C831.9 (5)P3—Ru1—C53—O2163.1 (2)
Ru1—P1—C7—C8172.3 (3)P1—Ru1—C53—O215.7 (3)
C12—C7—C8—C91.3 (8)P2—Ru1—C53—O292.6 (3)
P1—C7—C8—C9179.0 (4)P4—Ru1—C53—O287.4 (3)
C7—C8—C9—C100.4 (8)O2—Ru1—C53—O1177.3 (5)
C8—C9—C10—C111.5 (8)P3—Ru1—C53—O119.6 (3)
C9—C10—C11—C122.5 (8)P1—Ru1—C53—O1161.6 (2)
C10—C11—C12—C71.6 (8)P2—Ru1—C53—O184.7 (3)
C8—C7—C12—C110.3 (8)P4—Ru1—C53—O195.3 (3)
P1—C7—C12—C11177.9 (4)O4—S1—C55—F164.2 (5)
C1—P1—C13—C14174.7 (3)O5—S1—C55—F1179.1 (5)
C7—P1—C13—C1472.3 (4)O3—S1—C55—F158.9 (5)
Ru1—P1—C13—C1448.2 (4)O4—S1—C55—F3176.0 (6)
P1—C13—C14—P249.5 (4)O5—S1—C55—F361.1 (6)
C21—P2—C14—C13100.1 (4)O3—S1—C55—F360.9 (6)
C15—P2—C14—C13151.1 (4)O4—S1—C55—F252.9 (6)
Ru1—P2—C14—C1330.3 (4)O5—S1—C55—F262.1 (6)
C21—P2—C15—C16144.0 (5)O3—S1—C55—F2176.0 (5)
C14—P2—C15—C1632.3 (5)
Acknowledgements top

The authors thank the Fundação para a Ciência e a Tecnologia (FCT) for JF's PhD grant (SFRH/BD/29325/2006), the pluriannual base funding of CQM (PEst-OE/QUI/UI0674/2011), research project PTDC/CTM/098451/2008 and Academy Professor Kari Rissanen for some practical advice and financial aid from his Academy of Finland funding (project Nos. 130629, 122350 and 140718). The Portuguese Mass Spectrometry Network – RNEM 2013 and the Portuguese Nuclear Magnetic Resonance Network – PTNMR 2013 and the support of Vidamar Resorts are acknowledged.

references
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