A liquid crystal derived from ­ruthenium(II,III) and a long-chain carboxylate

The title compound, catena-poly[[tetrakis(μ-decanoato-κ²O:O′)diruthenium(II,III)(Ru—Ru)]-μ-octanesulfonato-κ²O:O′], [Ru₂(C₁₀H₁₉O₂)₄(C₈H₁₇O₃S)], is an octane­sulfonate derivative of the mixed-valence complex diruthenium tetradecanoate. The equatorial carboxyl­ate ligands are bidentate, bridging two Ru atoms to form a dinuclear structure. Each of the two independent dinuclear metal complexes in the asymmetric unit is located at an inversion centre. The octane­sulfonate anion bridges the two dinuclear units through axial coordination. The alkyl chains of the carboxyl­ate and sulfonate ligands are arranged in a parallel manner. The global structure can be seen as infinite chains of polar moieties separated by a double layer of non-polar alkyl groups, without interdigitation of the alkyl chains.

S1. Comment

Mixed-valence diruthenium(II,III) tetracarboxylates, [Ru₂(O₂CR)₄X] (X^- is an anion), have been extensively studied in recent years because they exhibit interesting electronic structures, spectroscopic features, magnetic behaviour and liquid crystalline (LC) properties (Aquino, 1998). In particular, LC phases (mesophases) have been obtained with long-chain carboxylates, provided that an appropriate combination of the equatorial carboxylate (RC₂^-) and axial anion (X^-) is used (Cukiernik, Ibn-Elhaj et al., 1998; Chaia et al., 1999; Caplan et al., 1999). For example, aliphatic equatorial carboxylates combined with long-chain axial anions, such as dodecylsulfate or an aliphatic carboxylate, induce mesomorphic behaviour (Cukiernik, Ibn-Elhaj et al., 1998). In some of these cases, a model describing the structural changes taking place through the phase transition has been proposed. As is usual in LC work, these models were based on the structural parameters of the LC phase (obtained from powder X-ray diffraction experiments), on information provided by local spectroscopic probes and on the crystalline structure of short chain (non-mesogenic) analogues.

Of the more than 30 structures of mixed-valence diruthenium carboxylates that are known, the great majority deal with short chain analogues (Bennett et al., 1969; Bino et al., 1979, Togano et al., 1980, Cotton et al., 1988, Barral et al., 1997). The longest chain [Ru₂(O₂CR)₄X] compound for which the molecular structure is known is the non-mesogenic pentanoate derivative [Ru₂(O₂C(CH₂)₃CH₃)₄Cl] (Cukiernik, Luneau et al., 1998). We have now determined the structure of the title ruthenium decanoate derivative with octanesulfonate as the axial anion, [Ru₂{O₂C(CH₂)₈CH₃}₄{O₃S(CH₂)₇CH₃}], (I). This compound is particularly interesting, as it undergoes a transition to a thermotropic hexagonal columnar LC phase at 458 K. We are confident that the crystal structure information we report here will be useful when interpreting the structure of the mesophase of the whole [Ru₂{O₂C(CH₂)_n-2CH₃}₄{O₃S(CH₂)₇CH₃}] series of compounds with n = ?-? Please supply range for n. Is the -2 necessary?. \sch

In compound (I), a Ru₂⁵⁺ metallic centre is bridged by four carboxylate equatorial ligands; the axial positions are occupied by the octanesulfonate anion. The unit cell contains two independent dinuclear complexes, each one located at a crystallographic inversion centre. The Ru atoms are in an environment of approximately C_4v symmetry, while the dinuclear structure exhibits approximate D_{4 h} symmetry.

The Ru—O equatorial bond distances are in the range 2.019–2.034 Å. The average O—C—O bond angle of the carboxylate ligands is 123.1 (3)°, and the O_i—Ru_j—Ru_j' angles (i = 11, 12, 13, 14, 21, 22, 23 or 24 and j = 1 or 2) are nearly 90°. Thus, the pseudo-octahedral environment of the Ru atoms is not significantly distorted, indicating that the dinuclear structure is achieved with little stress around the metal centres.

The Ru—Ru' distance is 2.271 (3) Å (averaged for the two independent dinuclear units), a typical value for mixed-valence diruthenium carboxylates axially coordinated by O atoms (Aquino, 1998). Four alkyl chains from carboxylate ligands are oriented towards the periphery of the polar centre in a zigzag conformation. Two of them are completely extended, while the others rotate around the β-C atom (C12 and C32) in order to align with the former chains. The alkyl chain of the sulfonate ligand also aligns in an extended conformation parallel to the carboxylic alkyl chains.

The alkylsulfonate moiety acts as a bidentate ligand bridging two independent dinuclear units (Fig. 1). The three S—O distances are consistent with double bonds, although the S—O3 bond is significantly shorter than the other two. This can be ascribed to a slight softening of the S—O bonds involved in coordination to the Ru centres (S—O1 and S—O2), arising from p back-donation.

Due to the bridging nature of the octanesulfonate axial anion, the bimetallic centres polymerize in an infinite chain nearly parallel to the b axis. An intermolecular distance along the polymeric structure of 6.755 Å can be calculated, being the distance between two neighbouring dinuclear centres. The corresponding Ru—Ru axes are nearly perpendicular one to each other (91.94°). However, all the aliphatic chains (both carboxylic and sulfonic) of each such polymeric structure are parallel, without interdigitation.

In the global structure, polar chains composed of dinuclear centres and sulfonate axial ligands are separated by non-polar double layers of alkyl chains. An interlayer separation of 26.6 Å can be inferred from the distance between adjacent ab faces. There is no interdigitation between adjacent layers.

S2. Experimental

[Ru₂{O₂C(CH₂)₈CH₃}₄Cl] was synthesized following a method already reported for other homologues of this series (Cukiernik. Luneau et al., 1998). Compound (I) was obtained by a metathesis reaction. A methanol suspension of [Ag{O₃S(CH₂)₇CH₃}] (150 mg) was slowly added to [Ru₂{O₂(CH₂)₈CH₃}₄Cl] (418 mg) dissolved in methanol. The reaction was protected from light and refluxed for 3 h under nitrogen. The AgCl by-product was filtered off while still hot and the solvent was evaporated under vacuum. The pale-brown solid obtained was dissolved in CH₂Cl₂, the solution was filtered on a 0.2 mm porous membrane and, after addition of heptane, the CH₂Cl₂ was evaporated under vacuum. After a couple of hours, a pale-brown solid was filtered, and then washed by suspension on ethylic ether and on distilled water. Brown crystals of (I) were obtained by slow evaporation of a methanolic solution. Characterization was performed by IR spectroscopy (KBr pellets) on an FT—IR Nicolet 150P and by elemental analysis on a Carlo Erba EA1108 analyzer. IR spectroscopic analysis (ν, cm^1-): 1249 (m) (n_S—O SO₃), 1115 (s) (n_S—O SO₃); analysis calculated for Ru₂C₄₈H₉₅SO₁₁: C 53.36, S 2.97, H 8.68%; found: C 53.50, S 2.26, H 8.63%; calculated for Ru₂C₄₀H₇₆ClO₈: C 52.07, H 8.30%; found: C 51.31, H 8.39%.

S3. Refinement

The carboxylate chain labelled C11—C19 is disordered. During the refinement, the corresponding occupancies were allowed to vary so as to add up to 1.0 and the C—C bond distances were restrained to a target value of 1.51 (1) Å. Several H atoms were located in a Fourier difference map. However, they were positioned stereochemically and refined with the riding model. The methyl H atoms were treated in the refinement as rigid bodies and allowed to rotate around the corresponding C—C bond so as to maximize the sum of the observed electron density at the three calculated H-atom positions. As expected, all methyl groups converged to staggered conformations.

Computing details

Data collection: DENZO and SCALEPACK (Otwinowski & Minor, 1997); cell refinement: SCALEPACK; data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1998); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The crystal packing of (I) viewed down a, showing the non-H atom labelling. Only the most populated (61% occupancy) of the two conformations of the C1n chain is shown for clarity.

catena-poly[[tetrakis(decanoato-κ²O:O')diruthenium(II,III)(Ru—Ru)]- µ-octanesulfonato-κ²-O:O']

Crystal data

[Ru2(C10H19O2)4(C8H17O3S)]	Z = 2
Mr = 1080.43	F(000) = 1146
Triclinic, P1	Dx = 1.321 Mg m^−3
a = 8.0020 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.3040 (4) Å	Cell parameters from 8725 reflections
c = 26.7230 (6) Å	θ = 1.0–27.5°
α = 83.427 (2)°	µ = 0.65 mm^−1
β = 85.045 (1)°	T = 120 K
γ = 74.051 (1)°	Thin plate, red
V = 2712.9 (1) Å^3	0.40 × 0.18 × 0.06 mm

Data collection

Nonius KappaCCD area-detector diffractometer	11539 independent reflections
Radiation source: fine-focus sealed tube	8728 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.084
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 1.5°
CCD scans	h = −10→10
Absorption correction: numerical (Spek, 1990)	k = −17→17
Tmin = 0.782, Tmax = 0.965	l = −34→30
31736 measured reflections

Refinement

Refinement on F^2	Primary atom site location: Patterson
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0748P)^2 + 2.5168P] where P = (Fo^2 + 2Fc^2)/3
11539 reflections	(Δ/σ)max = 0.124
647 parameters	Δρmax = 1.04 e Å^−3
18 restraints	Δρmin = −1.67 e Å^−3

Special details

Experimental. The crystals grow in the form of thin plates parallel to (001), that can be easily bent without breaking the crystal.

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ru1	0.54718 (4)	0.56896 (2)	0.481342 (11)	0.02727 (10)
O11	0.7762 (3)	0.5099 (2)	0.51494 (11)	0.0358 (7)
C10	0.7978 (5)	0.4231 (4)	0.54323 (16)	0.0354 (10)
C11	0.9650 (13)	0.3702 (12)	0.5682 (4)	0.031 (3)	0.610 (6)
H11A	1.0630	0.3628	0.5424	0.038*	0.610 (6)
H11B	0.9616	0.2987	0.5826	0.038*	0.610 (6)
C12	0.9986 (9)	0.4295 (6)	0.6099 (2)	0.0351 (17)	0.610 (6)
H12A	1.1229	0.4027	0.6174	0.042*	0.610 (6)
H12B	0.9782	0.5045	0.5971	0.042*	0.610 (6)
C13	0.8889 (13)	0.4225 (8)	0.6589 (3)	0.043 (2)	0.610 (6)
H13A	0.7641	0.4506	0.6521	0.052*	0.610 (6)
H13B	0.9085	0.3479	0.6723	0.052*	0.610 (6)
C14	0.9331 (17)	0.4832 (9)	0.6980 (3)	0.047 (3)	0.610 (6)
H14A	0.8980	0.5589	0.6863	0.057*	0.610 (6)
H14B	1.0609	0.4622	0.7007	0.057*	0.610 (6)
C15	0.8477 (11)	0.4672 (7)	0.7497 (3)	0.049 (2)	0.610 (6)
H15A	0.8792	0.3912	0.7610	0.059*	0.610 (6)
H15B	0.7198	0.4906	0.7474	0.059*	0.610 (6)
C16	0.898 (3)	0.5251 (14)	0.7891 (4)	0.061 (5)	0.610 (6)
H16A	0.8584	0.6014	0.7789	0.073*	0.610 (6)
H16B	1.0263	0.5057	0.7894	0.073*	0.610 (6)
C17	0.8251 (13)	0.5048 (8)	0.8420 (3)	0.070 (3)	0.610 (6)
H17A	0.8587	0.4281	0.8515	0.083*	0.610 (6)
H17B	0.6964	0.5280	0.8421	0.083*	0.610 (6)
C18	0.883 (2)	0.5580 (9)	0.8820 (4)	0.070 (6)	0.610 (6)
H18A	1.0118	0.5356	0.8817	0.084*	0.610 (6)
H18B	0.8478	0.6349	0.8729	0.084*	0.610 (6)
C19	0.8103 (19)	0.5350 (10)	0.9348 (4)	0.109 (5)	0.610 (6)
H19A	0.6836	0.5483	0.9347	0.163*	0.610 (6)
H19B	0.8382	0.5805	0.9574	0.163*	0.610 (6)
H19C	0.8617	0.4613	0.9467	0.163*	0.610 (6)
C11'	0.9790 (15)	0.389 (2)	0.5618 (5)	0.046 (8)	0.390 (6)
H11C	1.0387	0.4456	0.5524	0.056*	0.390 (6)
H11D	1.0478	0.3252	0.5466	0.056*	0.390 (6)
C12'	0.9605 (15)	0.3684 (9)	0.6185 (4)	0.037 (3)	0.390 (6)
H12C	0.8694	0.3309	0.6272	0.045*	0.390 (6)
H12D	1.0716	0.3218	0.6306	0.045*	0.390 (6)
C13'	0.914 (2)	0.4671 (10)	0.6458 (4)	0.041 (4)	0.390 (6)
H13C	0.9979	0.5085	0.6344	0.049*	0.390 (6)
H13D	0.7967	0.5104	0.6365	0.049*	0.390 (6)
C14'	0.914 (3)	0.4445 (11)	0.7027 (5)	0.047 (5)	0.390 (6)
H14C	1.0251	0.3927	0.7110	0.056*	0.390 (6)
H14D	0.8194	0.4105	0.7138	0.056*	0.390 (6)
C15'	0.8910 (18)	0.5362 (10)	0.7336 (5)	0.051 (4)	0.390 (6)
H15C	0.7763	0.5865	0.7273	0.061*	0.390 (6)
H15D	0.9818	0.5727	0.7219	0.061*	0.390 (6)
C16'	0.902 (5)	0.5052 (17)	0.7897 (5)	0.067 (10)	0.390 (6)
H16C	1.0153	0.4533	0.7957	0.080*	0.390 (6)
H16D	0.8094	0.4700	0.8013	0.080*	0.390 (6)
C17'	0.884 (2)	0.5948 (12)	0.8214 (5)	0.063 (4)	0.390 (6)
H17C	0.9735	0.6320	0.8093	0.076*	0.390 (6)
H17D	0.7683	0.6452	0.8171	0.076*	0.390 (6)
C18'	0.904 (7)	0.558 (2)	0.8766 (6)	0.143 (19)	0.390 (6)
H18C	0.8140	0.5210	0.8885	0.172*	0.390 (6)
H18D	1.0191	0.5072	0.8807	0.172*	0.390 (6)
C19'	0.887 (3)	0.6458 (19)	0.9092 (7)	0.115 (8)	0.390 (6)
H19D	0.9738	0.6842	0.8972	0.172*	0.390 (6)
H19E	0.9073	0.6165	0.9442	0.172*	0.390 (6)
H19F	0.7702	0.6939	0.9074	0.172*	0.390 (6)
O12	0.4468 (3)	0.6485 (2)	0.54201 (10)	0.0304 (6)
C20	0.3667 (5)	0.6064 (3)	0.57747 (15)	0.0291 (9)
C21	0.2839 (6)	0.6692 (3)	0.62074 (15)	0.0343 (9)
H21A	0.1564	0.6791	0.6218	0.041*
H21B	0.3055	0.7394	0.6145	0.041*
C22	0.3498 (6)	0.6192 (3)	0.67198 (15)	0.0354 (9)
H22A	0.3194	0.5516	0.6801	0.042*
H22B	0.4782	0.6046	0.6708	0.042*
C23	0.2702 (7)	0.6911 (4)	0.71269 (16)	0.0476 (12)
H23A	0.1424	0.7026	0.7142	0.057*
H23B	0.2944	0.7599	0.7027	0.057*
C24	0.3337 (7)	0.6522 (4)	0.76535 (16)	0.0494 (13)
H24A	0.2972	0.5879	0.7775	0.059*
H24B	0.4625	0.6336	0.7637	0.059*
C25	0.2623 (9)	0.7344 (4)	0.80275 (18)	0.0670 (18)
H25A	0.2960	0.7992	0.7897	0.080*
H25B	0.1336	0.7516	0.8045	0.080*
C26	0.3244 (9)	0.7012 (4)	0.85593 (18)	0.0680 (18)
H26A	0.4531	0.6769	0.8541	0.082*
H26B	0.2795	0.6413	0.8707	0.082*
C27	0.2657 (11)	0.7895 (5)	0.8907 (2)	0.088 (2)
H27A	0.3078	0.8501	0.8755	0.105*
H27B	0.1368	0.8125	0.8932	0.105*
C28	0.3314 (11)	0.7577 (5)	0.9436 (2)	0.089 (2)
H28A	0.4587	0.7259	0.9410	0.106*
H28B	0.2762	0.7039	0.9607	0.106*
C29	0.2913 (12)	0.8519 (6)	0.9757 (2)	0.109 (3)
H29A	0.3425	0.9063	0.9584	0.163*
H29B	0.3409	0.8286	1.0086	0.163*
H29C	0.1649	0.8805	0.9804	0.163*
O13	0.3190 (4)	0.6253 (2)	0.44773 (10)	0.0349 (7)
O14	0.6494 (4)	0.4866 (2)	0.42149 (10)	0.0339 (7)
Ru2	0.12772 (4)	0.94178 (2)	0.489274 (12)	0.02826 (10)
O21	0.2279 (4)	1.0638 (2)	0.46494 (10)	0.0296 (6)
O22	0.0445 (4)	0.9479 (2)	0.41892 (10)	0.0319 (6)
O23	0.0241 (4)	0.8202 (2)	0.51409 (10)	0.0296 (6)
C30	−0.1327 (6)	0.8421 (3)	0.53318 (14)	0.0303 (9)
C31	−0.2082 (6)	0.7551 (3)	0.55553 (15)	0.0328 (9)
H31A	−0.1124	0.6915	0.5634	0.039*
H31B	−0.2786	0.7390	0.5304	0.039*
C32	−0.3221 (6)	0.7817 (3)	0.60336 (15)	0.0359 (10)
H32A	−0.3634	0.7199	0.6171	0.043*
H32B	−0.4256	0.8398	0.5945	0.043*
C33	−0.2308 (6)	0.8135 (4)	0.64418 (16)	0.0398 (10)
H33A	−0.1216	0.7580	0.6505	0.048*
H33B	−0.1984	0.8787	0.6311	0.048*
C34	−0.3335 (7)	0.8316 (4)	0.69354 (18)	0.0523 (13)
H34A	−0.3523	0.7640	0.7090	0.063*
H34B	−0.4492	0.8802	0.6869	0.063*
C35	−0.2485 (7)	0.8764 (4)	0.73094 (16)	0.0496 (13)
H35A	−0.2382	0.9464	0.7163	0.060*
H35B	−0.1290	0.8307	0.7352	0.060*
C36	−0.3418 (9)	0.8878 (6)	0.7826 (2)	0.078 (2)
H36A	−0.4646	0.9278	0.7783	0.094*
H36B	−0.3416	0.8170	0.7988	0.094*
C37	−0.2641 (8)	0.9419 (5)	0.81750 (19)	0.0681 (18)
H37A	−0.2692	1.0138	0.8019	0.082*
H37B	−0.1398	0.9038	0.8205	0.082*
C38	−0.3520 (11)	0.9496 (7)	0.8704 (2)	0.111 (3)
H38A	−0.4780	0.9833	0.8677	0.133*
H38B	−0.3388	0.8778	0.8873	0.133*
C39	−0.2775 (11)	1.0119 (6)	0.9028 (2)	0.106 (3)
H39A	−0.1571	0.9738	0.9097	0.159*
H39B	−0.3475	1.0213	0.9348	0.159*
H39C	−0.2800	1.0808	0.8849	0.159*
O24	0.2043 (4)	0.9355 (2)	0.55986 (10)	0.0321 (6)
C40	0.1036 (6)	0.9907 (3)	0.59170 (15)	0.0315 (9)
C41	0.1579 (6)	0.9777 (3)	0.64436 (15)	0.0387 (10)
H41A	0.2858	0.9658	0.6432	0.046*
H41B	0.1312	0.9136	0.6617	0.046*
C42	0.0754 (7)	1.0681 (3)	0.67596 (15)	0.0408 (11)
H42A	0.0994	1.1332	0.6590	0.049*
H42B	−0.0524	1.0788	0.6791	0.049*
C43	0.1462 (8)	1.0462 (4)	0.72793 (18)	0.0584 (15)
H43A	0.2738	1.0359	0.7242	0.070*
H43B	0.1249	0.9796	0.7439	0.070*
C44	0.0690 (8)	1.1315 (4)	0.76321 (17)	0.0609 (16)
H44A	0.0912	1.1982	0.7478	0.073*
H44B	−0.0587	1.1422	0.7672	0.073*
C45	0.1444 (9)	1.1048 (5)	0.81501 (19)	0.078 (2)
H45A	0.2719	1.0946	0.8107	0.094*
H45B	0.1236	1.0374	0.8300	0.094*
C46	0.0688 (9)	1.1879 (5)	0.85182 (18)	0.084 (2)
H46A	0.0911	1.2552	0.8374	0.101*
H46B	−0.0589	1.1987	0.8562	0.101*
C47	0.1473 (10)	1.1566 (6)	0.9034 (2)	0.096 (3)
H47A	0.2747	1.1468	0.8989	0.115*
H47B	0.1270	1.0884	0.9173	0.115*
C48	0.0718 (12)	1.2373 (7)	0.9411 (2)	0.117 (4)
H48A	−0.0554	1.2468	0.9463	0.141*
H48B	0.0918	1.3057	0.9276	0.141*
C49	0.1573 (13)	1.2014 (8)	0.9919 (2)	0.149 (5)
H49A	0.1403	1.1327	1.0049	0.223*
H49B	0.1039	1.2526	1.0162	0.223*
H49C	0.2822	1.1958	0.9871	0.223*
S	0.52875 (17)	0.81235 (9)	0.42757 (4)	0.0417 (3)
O1	0.6311 (4)	0.7040 (2)	0.44037 (11)	0.0327 (6)
O2	0.3906 (4)	0.8406 (2)	0.46754 (11)	0.0409 (7)
O3	0.6357 (6)	0.8829 (3)	0.41500 (14)	0.0628 (11)
C50	0.4225 (7)	0.8121 (4)	0.37157 (18)	0.0496 (12)
H50A	0.3273	0.7776	0.3802	0.060*
H50B	0.3692	0.8856	0.3584	0.060*
C51	0.5419 (7)	0.7568 (5)	0.33057 (17)	0.0543 (14)
H51A	0.5882	0.6819	0.3427	0.065*
H51B	0.6416	0.7878	0.3235	0.065*
C52	0.4525 (8)	0.7641 (5)	0.28188 (18)	0.0607 (16)
H52A	0.3420	0.7443	0.2901	0.073*
H52B	0.4226	0.8382	0.2672	0.073*
C53	0.5556 (9)	0.6972 (4)	0.24270 (18)	0.0677 (18)
H53A	0.5767	0.6227	0.2563	0.081*
H53B	0.6703	0.7126	0.2366	0.081*
C54	0.4730 (9)	0.7112 (5)	0.19292 (19)	0.076 (2)
H54A	0.3544	0.7018	0.1997	0.091*
H54B	0.4600	0.7847	0.1785	0.091*
C55	0.5641 (11)	0.6408 (5)	0.1535 (2)	0.090 (3)
H55A	0.5727	0.5673	0.1672	0.108*
H55B	0.6843	0.6480	0.1475	0.108*
C56	0.4825 (13)	0.6593 (6)	0.1039 (2)	0.112 (3)
H56A	0.3621	0.6524	0.1100	0.134*
H56B	0.4744	0.7327	0.0901	0.134*
C57	0.5743 (14)	0.5878 (6)	0.0643 (2)	0.136 (4)
H57A	0.6983	0.5854	0.0613	0.204*
H57B	0.5231	0.6146	0.0318	0.204*
H57C	0.5613	0.5169	0.0740	0.204*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.01993 (18)	0.03526 (19)	0.02970 (18)	−0.00955 (13)	0.00094 (13)	−0.01225 (13)
O11	0.0189 (15)	0.0479 (18)	0.0449 (17)	−0.0099 (13)	−0.0035 (13)	−0.0183 (14)
C10	0.020 (2)	0.053 (3)	0.033 (2)	−0.0045 (19)	−0.0011 (18)	−0.018 (2)
C11	0.020 (5)	0.041 (5)	0.036 (5)	−0.011 (4)	0.006 (4)	−0.015 (5)
C12	0.024 (4)	0.041 (4)	0.040 (4)	−0.009 (3)	−0.004 (3)	−0.002 (3)
C13	0.032 (5)	0.057 (6)	0.034 (5)	−0.001 (5)	−0.004 (4)	−0.003 (4)
C14	0.047 (6)	0.051 (7)	0.044 (5)	−0.012 (6)	−0.005 (4)	−0.006 (5)
C15	0.042 (5)	0.053 (5)	0.046 (5)	0.001 (4)	−0.005 (4)	−0.010 (4)
C16	0.064 (11)	0.051 (7)	0.067 (12)	−0.003 (7)	−0.024 (8)	−0.016 (6)
C17	0.068 (7)	0.081 (7)	0.044 (5)	0.017 (5)	−0.019 (5)	−0.022 (5)
C18	0.084 (11)	0.068 (10)	0.046 (8)	0.010 (8)	−0.021 (8)	−0.026 (7)
C19	0.140 (13)	0.099 (10)	0.063 (7)	0.026 (9)	−0.028 (8)	−0.035 (7)
C11'	0.022 (10)	0.073 (17)	0.038 (10)	−0.005 (9)	−0.004 (8)	0.002 (8)
C12'	0.026 (6)	0.045 (7)	0.042 (7)	−0.012 (5)	−0.013 (5)	0.006 (5)
C13'	0.040 (9)	0.049 (9)	0.026 (7)	0.000 (7)	−0.008 (6)	−0.002 (6)
C14'	0.074 (12)	0.027 (8)	0.043 (8)	−0.022 (8)	−0.006 (7)	0.007 (6)
C15'	0.048 (8)	0.058 (9)	0.048 (8)	−0.012 (7)	−0.003 (6)	−0.018 (7)
C16'	0.10 (2)	0.064 (16)	0.028 (12)	−0.014 (13)	0.009 (12)	−0.006 (8)
C17'	0.066 (10)	0.078 (11)	0.045 (8)	−0.017 (8)	0.001 (7)	−0.011 (7)
C18'	0.23 (5)	0.15 (4)	0.07 (2)	−0.08 (3)	0.00 (3)	−0.01 (2)
C19'	0.120 (19)	0.17 (2)	0.069 (12)	−0.042 (17)	−0.007 (12)	−0.048 (14)
O12	0.0258 (15)	0.0345 (15)	0.0327 (15)	−0.0076 (12)	−0.0019 (12)	−0.0124 (12)
C20	0.019 (2)	0.036 (2)	0.033 (2)	−0.0066 (16)	0.0004 (17)	−0.0111 (17)
C21	0.030 (2)	0.039 (2)	0.033 (2)	−0.0038 (18)	−0.0006 (18)	−0.0124 (17)
C22	0.038 (3)	0.036 (2)	0.031 (2)	−0.0069 (18)	0.0028 (19)	−0.0092 (17)
C23	0.052 (3)	0.051 (3)	0.033 (2)	0.003 (2)	−0.010 (2)	−0.013 (2)
C24	0.065 (4)	0.041 (3)	0.035 (2)	0.002 (2)	−0.009 (2)	−0.008 (2)
C25	0.090 (5)	0.057 (3)	0.037 (3)	0.018 (3)	−0.021 (3)	−0.017 (2)
C26	0.094 (5)	0.058 (3)	0.036 (3)	0.011 (3)	−0.014 (3)	−0.013 (2)
C27	0.137 (7)	0.067 (4)	0.037 (3)	0.024 (4)	−0.034 (4)	−0.018 (3)
C28	0.127 (6)	0.082 (5)	0.038 (3)	0.015 (4)	−0.029 (4)	−0.018 (3)
C29	0.180 (9)	0.090 (5)	0.041 (3)	0.004 (5)	−0.032 (4)	−0.023 (3)
O13	0.0240 (16)	0.0473 (18)	0.0327 (15)	−0.0050 (13)	−0.0035 (13)	−0.0107 (13)
O14	0.0256 (16)	0.0435 (17)	0.0364 (15)	−0.0123 (13)	0.0045 (13)	−0.0167 (13)
Ru2	0.0346 (2)	0.02031 (16)	0.02742 (17)	−0.00524 (13)	0.00640 (14)	−0.00361 (12)
O21	0.0337 (16)	0.0229 (13)	0.0312 (14)	−0.0075 (11)	0.0045 (12)	−0.0036 (11)
O22	0.0388 (17)	0.0249 (14)	0.0286 (14)	−0.0047 (12)	0.0029 (13)	−0.0021 (11)
O23	0.0342 (16)	0.0211 (13)	0.0321 (14)	−0.0072 (11)	0.0101 (13)	−0.0058 (11)
C30	0.040 (3)	0.025 (2)	0.0271 (19)	−0.0115 (17)	0.0020 (18)	−0.0046 (15)
C31	0.038 (2)	0.030 (2)	0.032 (2)	−0.0118 (18)	0.0004 (19)	−0.0034 (17)
C32	0.038 (3)	0.037 (2)	0.033 (2)	−0.0119 (19)	0.0014 (19)	−0.0001 (17)
C33	0.045 (3)	0.043 (3)	0.033 (2)	−0.014 (2)	0.000 (2)	−0.0043 (18)
C34	0.048 (3)	0.065 (3)	0.038 (3)	−0.004 (2)	0.003 (2)	−0.014 (2)
C35	0.054 (3)	0.053 (3)	0.032 (2)	0.002 (2)	−0.001 (2)	−0.006 (2)
C36	0.069 (4)	0.116 (6)	0.040 (3)	−0.001 (4)	0.006 (3)	−0.034 (3)
C37	0.080 (4)	0.071 (4)	0.036 (3)	0.012 (3)	−0.005 (3)	−0.014 (3)
C38	0.097 (6)	0.168 (8)	0.051 (4)	0.008 (5)	0.002 (4)	−0.051 (5)
C39	0.147 (8)	0.103 (6)	0.044 (3)	0.021 (5)	−0.023 (4)	−0.029 (4)
O24	0.0374 (17)	0.0237 (14)	0.0309 (14)	−0.0030 (12)	0.0053 (13)	−0.0030 (11)
C40	0.042 (3)	0.0216 (19)	0.029 (2)	−0.0090 (17)	0.0086 (18)	0.0002 (15)
C41	0.051 (3)	0.028 (2)	0.031 (2)	−0.0009 (19)	0.000 (2)	−0.0010 (17)
C42	0.051 (3)	0.034 (2)	0.030 (2)	0.000 (2)	0.002 (2)	−0.0031 (17)
C43	0.080 (4)	0.045 (3)	0.035 (2)	0.012 (3)	−0.009 (3)	−0.007 (2)
C44	0.072 (4)	0.061 (3)	0.032 (2)	0.015 (3)	−0.003 (3)	−0.011 (2)
C45	0.100 (5)	0.074 (4)	0.030 (3)	0.028 (4)	−0.006 (3)	−0.011 (3)
C46	0.100 (5)	0.092 (5)	0.029 (3)	0.037 (4)	−0.014 (3)	−0.021 (3)
C47	0.113 (6)	0.104 (5)	0.035 (3)	0.038 (4)	−0.014 (3)	−0.016 (3)
C48	0.145 (8)	0.133 (7)	0.030 (3)	0.048 (6)	−0.013 (4)	−0.030 (4)
C49	0.174 (10)	0.194 (10)	0.029 (3)	0.045 (7)	−0.020 (5)	−0.027 (5)
S	0.0465 (7)	0.0398 (6)	0.0407 (6)	−0.0133 (5)	0.0043 (5)	−0.0119 (5)
O1	0.0269 (16)	0.0337 (15)	0.0384 (16)	−0.0082 (12)	−0.0002 (13)	−0.0080 (12)
O2	0.0450 (19)	0.0381 (17)	0.0324 (15)	0.0007 (14)	0.0065 (14)	−0.0100 (13)
O3	0.088 (3)	0.056 (2)	0.055 (2)	−0.041 (2)	0.026 (2)	−0.0176 (17)
C50	0.052 (3)	0.048 (3)	0.041 (3)	0.000 (2)	0.000 (2)	−0.008 (2)
C51	0.048 (3)	0.074 (4)	0.035 (2)	0.000 (3)	−0.002 (2)	−0.022 (2)
C52	0.062 (4)	0.073 (4)	0.035 (2)	0.009 (3)	−0.009 (3)	−0.016 (2)
C53	0.092 (5)	0.062 (4)	0.036 (3)	0.009 (3)	−0.013 (3)	−0.015 (2)
C54	0.101 (5)	0.074 (4)	0.034 (3)	0.012 (3)	−0.015 (3)	−0.011 (3)
C55	0.134 (7)	0.071 (4)	0.039 (3)	0.027 (4)	−0.023 (4)	−0.020 (3)
C56	0.175 (9)	0.094 (5)	0.039 (3)	0.024 (5)	−0.033 (4)	−0.026 (3)
C57	0.240 (11)	0.080 (5)	0.047 (4)	0.046 (6)	−0.047 (5)	−0.027 (3)

Geometric parameters (Å, º)

Ru1—O12	2.023 (3)	Ru2—O24	2.019 (3)
Ru1—O14	2.028 (3)	Ru2—O21	2.021 (3)
Ru1—O13	2.020 (3)	Ru2—O23	2.035 (3)
Ru1—O11	2.029 (3)	Ru2—O22	2.034 (3)
Ru1—O1	2.228 (3)	Ru2—O2	2.233 (3)
Ru1—Ru1^i	2.2680 (6)	Ru2—Ru2^ii	2.2732 (6)
O11—C10	1.284 (5)	O21—C30^ii	1.278 (5)
C10—O13^i	1.265 (5)	O22—C40^ii	1.275 (5)
C10—C11	1.504 (8)	O23—C30	1.282 (5)
C10—C11'	1.505 (9)	C30—O21^ii	1.278 (5)
C11—C12	1.518 (9)	C30—C31	1.491 (6)
C11—H11A	0.9900	C31—C32	1.521 (6)
C11—H11B	0.9900	C31—H31A	0.9900
C12—C13	1.522 (8)	C31—H31B	0.9900
C12—H12A	0.9900	C32—C33	1.522 (6)
C12—H12B	0.9900	C32—H32A	0.9900
C13—C14	1.510 (8)	C32—H32B	0.9900
C13—H13A	0.9900	C33—C34	1.500 (6)
C13—H13B	0.9900	C33—H33A	0.9900
C14—C15	1.507 (8)	C33—H33B	0.9900
C14—H14A	0.9900	C34—C35	1.515 (7)
C14—H14B	0.9900	C34—H34A	0.9900
C15—C16	1.514 (9)	C34—H34B	0.9900
C15—H15A	0.9900	C35—C36	1.515 (7)
C15—H15B	0.9900	C35—H35A	0.9900
C16—C17	1.504 (9)	C35—H35B	0.9900
C16—H16A	0.9900	C36—C37	1.508 (8)
C16—H16B	0.9900	C36—H36A	0.9900
C17—C18	1.516 (8)	C36—H36B	0.9900
C17—H17A	0.9900	C37—C38	1.524 (8)
C17—H17B	0.9900	C37—H37A	0.9900
C18—C19	1.512 (9)	C37—H37B	0.9900
C18—H18A	0.9900	C38—C39	1.52 (1)
C18—H18B	0.9900	C38—H38A	0.9900
C19—H19A	0.9800	C38—H38B	0.9900
C19—H19B	0.9800	C39—H39A	0.9800
C19—H19C	0.9800	C39—H39B	0.9800
C11'—C12'	1.51 (1)	C39—H39C	0.9800
C11'—H11C	0.9900	O24—C40	1.270 (5)
C11'—H11D	0.9900	C40—O22^ii	1.275 (5)
C12'—C13'	1.516 (9)	C40—C41	1.486 (5)
C12'—H12C	0.9900	C41—C42	1.515 (6)
C12'—H12D	0.9900	C41—H41A	0.9900
C13'—C14'	1.516 (9)	C41—H41B	0.9900
C13'—H13C	0.9900	C42—C43	1.512 (6)
C13'—H13D	0.9900	C42—H42A	0.9900
C14'—C15'	1.512 (9)	C42—H42B	0.9900
C14'—H14C	0.9900	C43—C44	1.522 (6)
C14'—H14D	0.9900	C43—H43A	0.9900
C15'—C16'	1.51 (1)	C43—H43B	0.9900
C15'—H15C	0.9900	C44—C45	1.523 (7)
C15'—H15D	0.9900	C44—H44A	0.9900
C16'—C17'	1.51 (1)	C44—H44B	0.9900
C16'—H16C	0.9900	C45—C46	1.528 (7)
C16'—H16D	0.9900	C45—H45A	0.9900
C17'—C18'	1.51 (1)	C45—H45B	0.9900
C17'—H17C	0.9900	C46—C47	1.530 (7)
C17'—H17D	0.9900	C46—H46A	0.9900
C18'—C19'	1.51 (1)	C46—H46B	0.9900
C18'—H18C	0.9900	C47—C48	1.525 (8)
C18'—H18D	0.9900	C47—H47A	0.9900
C19'—H19D	0.9800	C47—H47B	0.9900
C19'—H19E	0.9800	C48—C49	1.540 (8)
C19'—H19F	0.9800	C48—H48A	0.9900
O12—C20	1.262 (5)	C48—H48B	0.9900
C20—O14^i	1.275 (5)	C49—H49A	0.9800
C20—C21	1.502 (5)	C49—H49B	0.9800
C21—C22	1.523 (5)	C49—H49C	0.9800
C21—H21A	0.9900	S—O3	1.430 (4)
C21—H21B	0.9900	S—O1	1.467 (3)
C22—C23	1.513 (6)	S—O2	1.471 (3)
C22—H22A	0.9900	S—C50	1.785 (5)
C22—H22B	0.9900	C50—C51	1.507 (6)
C23—C24	1.523 (6)	C50—H50A	0.9900
C23—H23A	0.9900	C50—H50B	0.9900
C23—H23B	0.9900	C51—C52	1.519 (6)
C24—C25	1.526 (6)	C51—H51A	0.9900
C24—H24A	0.9900	C51—H51B	0.9900
C24—H24B	0.9900	C52—C53	1.493 (7)
C25—C26	1.523 (6)	C52—H52A	0.9900
C25—H25A	0.9900	C52—H52B	0.9900
C25—H25B	0.9900	C53—C54	1.506 (7)
C26—C27	1.528 (7)	C53—H53A	0.9900
C26—H26A	0.9900	C53—H53B	0.9900
C26—H26B	0.9900	C54—C55	1.495 (7)
C27—C28	1.524 (7)	C54—H54A	0.9900
C27—H27A	0.9900	C54—H54B	0.9900
C27—H27B	0.9900	C55—C56	1.494 (8)
C28—C29	1.545 (8)	C55—H55A	0.9900
C28—H28A	0.9900	C55—H55B	0.9900
C28—H28B	0.9900	C56—C57	1.510 (9)
C29—H29A	0.9800	C56—H56A	0.9900
C29—H29B	0.9800	C56—H56B	0.9900
C29—H29C	0.9800	C57—H57A	0.9800
O13—C10^i	1.265 (5)	C57—H57B	0.9800
O14—C20^i	1.275 (5)	C57—H57C	0.9800
O12—Ru1—O14	178.8 (1)	O24—Ru2—O22	178.6 (1)
O12—Ru1—O13	90.8 (1)	O21—Ru2—O22	88.7 (1)
O14—Ru1—O13	89.9 (1)	O23—Ru2—O22	91.4 (1)
O12—Ru1—O11	89.8 (1)	O24—Ru2—O2	89.3 (1)
O14—Ru1—O11	89.5 (1)	O21—Ru2—O2	85.5 (1)
O13—Ru1—O11	179.0 (1)	O23—Ru2—O2	95.2 (1)
O12—Ru1—O1	93.1 (1)	O22—Ru2—O2	91.9 (1)
O14—Ru1—O1	87.8 (1)	O24—Ru2—Ru2^ii	89.59 (8)
O13—Ru1—O1	87.7 (1)	O21—Ru2—Ru2^ii	89.01 (8)
O11—Ru1—O1	93.1 (1)	O23—Ru2—Ru2^ii	90.28 (8)
O12—Ru1—Ru1^i	89.10 (8)	O22—Ru2—Ru2^ii	89.36 (8)
O14—Ru1—Ru1^i	90.00 (8)	O2—Ru2—Ru2^ii	174.33 (9)
O13—Ru1—Ru1^i	89.38 (9)	C30^ii—O21—Ru2	119.9 (3)
O11—Ru1—Ru1^i	89.83 (9)	C40^ii—O22—Ru2	118.7 (3)
O1—Ru1—Ru1^i	176.36 (7)	C30—O23—Ru2	117.9 (2)
C10—O11—Ru1	118.2 (2)	O21^ii—C30—O23	122.9 (4)
O13^i—C10—O11	123.0 (3)	O21^ii—C30—C31	117.7 (4)
O13^i—C10—C11	114.4 (8)	O23—C30—C31	119.4 (3)
O11—C10—C11	122.5 (8)	C30—C31—C32	112.8 (3)
O13^i—C10—C11'	127 (1)	C30—C31—H31A	109.0
O11—C10—C11'	110 (1)	C32—C31—H31A	109.0
C10—C11—C12	113.2 (8)	C30—C31—H31B	109.0
C10—C11—H11A	108.9	C32—C31—H31B	109.0
C12—C11—H11A	108.9	H31A—C31—H31B	107.8
C10—C11—H11B	108.9	C31—C32—C33	114.1 (4)
C12—C11—H11B	108.9	C31—C32—H32A	108.7
H11A—C11—H11B	107.7	C33—C32—H32A	108.7
C13—C12—C11	115.8 (9)	C31—C32—H32B	108.7
C13—C12—H12A	108.3	C33—C32—H32B	108.7
C11—C12—H12A	108.3	H32A—C32—H32B	107.6
C13—C12—H12B	108.3	C34—C33—C32	115.8 (4)
C11—C12—H12B	108.3	C34—C33—H33A	108.3
H12A—C12—H12B	107.4	C32—C33—H33A	108.3
C14—C13—C12	111.7 (7)	C34—C33—H33B	108.3
C14—C13—H13A	109.3	C32—C33—H33B	108.3
C12—C13—H13A	109.3	H33A—C33—H33B	107.4
C14—C13—H13B	109.3	C33—C34—C35	114.4 (4)
C12—C13—H13B	109.3	C33—C34—H34A	108.7
H13A—C13—H13B	107.9	C35—C34—H34A	108.7
C13—C14—C15	114.4 (8)	C33—C34—H34B	108.7
C13—C14—H14A	108.7	C35—C34—H34B	108.7
C15—C14—H14A	108.7	H34A—C34—H34B	107.6
C13—C14—H14B	108.7	C34—C35—C36	115.8 (5)
C15—C14—H14B	108.7	C34—C35—H35A	108.3
H14A—C14—H14B	107.6	C36—C35—H35A	108.3
C14—C15—C16	114.1 (9)	C34—C35—H35B	108.3
C14—C15—H15A	108.7	C36—C35—H35B	108.3
C16—C15—H15A	108.7	H35A—C35—H35B	107.4
C14—C15—H15B	108.7	C37—C36—C35	114.7 (6)
C16—C15—H15B	108.7	C37—C36—H36A	108.6
H15A—C15—H15B	107.6	C35—C36—H36A	108.6
C15—C16—C17	116 (1)	C37—C36—H36B	108.6
C15—C16—H16A	108.4	C35—C36—H36B	108.6
C17—C16—H16A	108.4	H36A—C36—H36B	107.6
C15—C16—H16B	108.4	C36—C37—C38	115.2 (6)
C17—C16—H16B	108.4	C36—C37—H37A	108.5
H16A—C16—H16B	107.5	C38—C37—H37A	108.5
C16—C17—C18	116 (1)	C36—C37—H37B	108.5
C16—C17—H17A	108.4	C38—C37—H37B	108.5
C18—C17—H17A	108.4	H37A—C37—H37B	107.5
C16—C17—H17B	108.4	C39—C38—C37	113.1 (7)
C18—C17—H17B	108.4	C39—C38—H38A	109.0
H17A—C17—H17B	107.5	C37—C38—H38A	109.0
C19—C18—C17	114 (1)	C39—C38—H38B	109.0
C19—C18—H18A	108.7	C37—C38—H38B	109.0
C17—C18—H18A	108.7	H38A—C38—H38B	107.8
C19—C18—H18B	108.6	C38—C39—H39A	109.5
C17—C18—H18B	108.6	C38—C39—H39B	109.5
H18A—C18—H18B	107.6	H39A—C39—H39B	109.5
C10—C11'—C12'	106.8 (9)	C38—C39—H39C	109.5
C10—C11'—H11C	110.4	H39A—C39—H39C	109.5
C12'—C11'—H11C	110.4	H39B—C39—H39C	109.5
C10—C11'—H11D	110.4	C40—O24—Ru2	119.3 (3)
C12'—C11'—H11D	110.4	O22^ii—C40—O24	123.0 (4)
H11C—C11'—H11D	108.6	O22^ii—C40—C41	119.0 (4)
C13'—C12'—C11'	114 (2)	O24—C40—C41	117.9 (4)
C13'—C12'—H12C	108.9	C40—C41—C42	116.3 (3)
C11'—C12'—H12C	108.9	C40—C41—H41A	108.2
C13'—C12'—H12D	108.9	C42—C41—H41A	108.2
C11'—C12'—H12D	108.9	C40—C41—H41B	108.2
H12C—C12'—H12D	107.7	C42—C41—H41B	108.2
C14'—C13'—C12'	113 (1)	H41A—C41—H41B	107.4
C14'—C13'—H13C	109.0	C43—C42—C41	110.8 (4)
C12'—C13'—H13C	109.0	C43—C42—H42A	109.5
C14'—C13'—H13D	109.0	C41—C42—H42A	109.5
C12'—C13'—H13D	109.0	C43—C42—H42B	109.5
H13C—C13'—H13D	107.8	C41—C42—H42B	109.5
C13'—C14'—C15'	118 (1)	H42A—C42—H42B	108.1
C13'—C14'—H14C	107.9	C42—C43—C44	115.1 (4)
C15'—C14'—H14C	107.9	C42—C43—H43A	108.5
C13'—C14'—H14D	107.9	C44—C43—H43A	108.5
C15'—C14'—H14D	107.9	C42—C43—H43B	108.5
H14C—C14'—H14D	107.2	C44—C43—H43B	108.5
C14'—C15'—C16'	114 (1)	H43A—C43—H43B	107.5
C14'—C15'—H15C	108.8	C45—C44—C43	112.7 (4)
C16'—C15'—H15C	108.9	C45—C44—H44A	109.1
C14'—C15'—H15D	108.8	C43—C44—H44A	109.1
C16'—C15'—H15D	108.7	C45—C44—H44B	109.1
H15C—C15'—H15D	107.7	C43—C44—H44B	109.1
C15'—C16'—C17'	115 (1)	H44A—C44—H44B	107.8
C15'—C16'—H16C	108.6	C44—C45—C46	114.4 (4)
C17'—C16'—H16C	108.6	C44—C45—H45A	108.7
C15'—C16'—H16D	108.5	C46—C45—H45A	108.7
C17'—C16'—H16D	108.5	C44—C45—H45B	108.7
H16C—C16'—H16D	107.5	C46—C45—H45B	108.7
C18'—C17'—C16'	112 (1)	H45A—C45—H45B	107.6
C18'—C17'—H17C	109.1	C47—C46—C45	112.2 (5)
C16'—C17'—H17C	109.1	C47—C46—H46A	109.2
C18'—C17'—H17D	109.1	C45—C46—H46A	109.2
C16'—C17'—H17D	109.2	C47—C46—H46B	109.2
H17C—C17'—H17D	107.9	C45—C46—H46B	109.2
C19'—C18'—C17'	114 (2)	H46A—C46—H46B	107.9
C19'—C18'—H18C	108.8	C46—C47—C48	113.3 (5)
C17'—C18'—H18C	108.8	C46—C47—H47A	108.9
C19'—C18'—H18D	108.9	C48—C47—H47A	108.9
C17'—C18'—H18D	108.9	C46—C47—H47B	108.9
H18C—C18'—H18D	107.7	C48—C47—H47B	108.9
C18'—C19'—H19D	109.4	H47A—C47—H47B	107.7
C18'—C19'—H19E	109.5	C47—C48—C49	110.6 (6)
H19D—C19'—H19E	109.5	C47—C48—H48A	109.5
C18'—C19'—H19F	109.5	C49—C48—H48A	109.5
H19D—C19'—H19F	109.5	C47—C48—H48B	109.5
H19E—C19'—H19F	109.5	C49—C48—H48B	109.5
C20—O12—Ru1	119.3 (2)	H48A—C48—H48B	108.1
O12—C20—O14^i	123.6 (4)	C48—C49—H49A	109.5
O12—C20—C21	118.6 (4)	C48—C49—H49B	109.5
O14^i—C20—C21	117.8 (4)	H49A—C49—H49B	109.5
C20—C21—C22	114.2 (3)	C48—C49—H49C	109.5
C20—C21—H21A	108.7	H49A—C49—H49C	109.5
C22—C21—H21A	108.7	H49B—C49—H49C	109.5
C20—C21—H21B	108.7	O3—S—O1	112.5 (2)
C22—C21—H21B	108.7	O3—S—O2	116.4 (2)
H21A—C21—H21B	107.6	O1—S—O2	108.32 (18)
C23—C22—C21	110.7 (3)	O3—S—C50	105.8 (3)
C23—C22—H22A	109.5	O1—S—C50	106.7 (2)
C21—C22—H22A	109.5	O2—S—C50	106.5 (2)
C23—C22—H22B	109.5	S—O1—Ru1	129.6 (2)
C21—C22—H22B	109.5	S—O2—Ru2	147.4 (2)
H22A—C22—H22B	108.1	C51—C50—S	113.8 (4)
C22—C23—C24	115.6 (4)	C51—C50—H50A	108.8
C22—C23—H23A	108.4	S—C50—H50A	108.8
C24—C23—H23A	108.4	C51—C50—H50B	108.8
C22—C23—H23B	108.4	S—C50—H50B	108.8
C24—C23—H23B	108.4	H50A—C50—H50B	107.7
H23A—C23—H23B	107.4	C50—C51—C52	113.1 (4)
C25—C24—C23	112.1 (4)	C50—C51—H51A	109.0
C25—C24—H24A	109.2	C52—C51—H51A	109.0
C23—C24—H24A	109.2	C50—C51—H51B	109.0
C25—C24—H24B	109.2	C52—C51—H51B	109.0
C23—C24—H24B	109.2	H51A—C51—H51B	107.8
H24A—C24—H24B	107.9	C53—C52—C51	115.5 (4)
C26—C25—C24	114.7 (4)	C53—C52—H52A	108.4
C26—C25—H25A	108.6	C51—C52—H52A	108.4
C24—C25—H25A	108.6	C53—C52—H52B	108.4
C26—C25—H25B	108.6	C51—C52—H52B	108.4
C24—C25—H25B	108.6	H52A—C52—H52B	107.5
H25A—C25—H25B	107.6	C52—C53—C54	115.4 (5)
C25—C26—C27	113.1 (4)	C52—C53—H53A	108.4
C25—C26—H26A	109.0	C54—C53—H53A	108.4
C27—C26—H26A	109.0	C52—C53—H53B	108.4
C25—C26—H26B	109.0	C54—C53—H53B	108.4
C27—C26—H26B	109.0	H53A—C53—H53B	107.5
H26A—C26—H26B	107.8	C55—C54—C53	117.7 (5)
C28—C27—C26	113.3 (5)	C55—C54—H54A	107.9
C28—C27—H27A	108.9	C53—C54—H54A	107.9
C26—C27—H27A	108.9	C55—C54—H54B	107.9
C28—C27—H27B	108.9	C53—C54—H54B	107.9
C26—C27—H27B	108.9	H54A—C54—H54B	107.2
H27A—C27—H27B	107.7	C54—C55—C56	116.4 (5)
C27—C28—C29	112.3 (5)	C54—C55—H55A	108.2
C27—C28—H28A	109.2	C56—C55—H55A	108.2
C29—C28—H28A	109.2	C54—C55—H55B	108.2
C27—C28—H28B	109.2	C56—C55—H55B	108.2
C29—C28—H28B	109.2	H55A—C55—H55B	107.3
H28A—C28—H28B	107.9	C57—C56—C55	116.3 (6)
C28—C29—H29A	109.5	C57—C56—H56A	108.2
C28—C29—H29B	109.5	C55—C56—H56A	108.2
H29A—C29—H29B	109.5	C57—C56—H56B	108.2
C28—C29—H29C	109.5	C55—C56—H56B	108.2
H29A—C29—H29C	109.5	H56A—C56—H56B	107.4
H29B—C29—H29C	109.5	C56—C57—H57A	109.5
C10^i—O13—Ru1	119.5 (3)	C56—C57—H57B	109.5
C20^i—O14—Ru1	117.9 (3)	H57A—C57—H57B	109.5
O24—Ru2—O21	92.3 (1)	C56—C57—H57C	109.5
O24—Ru2—O23	87.6 (1)	H57A—C57—H57C	109.5
O21—Ru2—O23	179.3 (1)	H57B—C57—H57C	109.5

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+2, −z+1.