Partially oxidized ruthenium phosphine thiol­ates: [Ru(pySO₂)_0.33(pyS)_1.67(dppe)] and [Ru(pySO₂)_0.355(pyS)_1.645(dppp)]

The crystal structures of [1,3-bis­(diphenyl­phosphino)ethane-κ²P,P′](pyridine-2-sulfinato-κ²N,S)(pyridine-2-thiol­ato-κ²N,S)ruthenium(II), [Ru(C₅H₄NO₂S)_0.33(C₅H₄NS)_1.67(C₂₆H₂₄P₂)] or [Ru(pySO₂)_1−x(pyS)_1+x(dppe)] (x = 0.67), (I), and [1,3-bis­(diphenyl­phosphino)propane-κ²P,P′](pyridine-2-sulfinato-κ²N,S)(pyridine-2-thiol­ato-κ²N,S)ruthenium(II), [Ru(C₅H₄NO₂S)_0.355(C₅H₄NS)_1.645(C₂₇H₂₆P₂)] or [Ru(pySO₂)_1−x(pyS)_1+x(dppp)] (x = 0.645), (II), are composed of neutral distorted octa­hedral Ru^II complexes with chelating pyridine-2-thiol­ate, pyridine-2-sulfinate and biphosphine ligands. The S atoms are trans to each other, while pairs of P and N atoms are in cis positions. Partial double-bond character is observed for C—S. The crystal packing consists of monolayers stabilized by C—H...O and C—H...S inter­actions, and is affected by the alkyl-chain lengths.

S1. Comment

Nitric oxide (NO) is relevant for many physiological processes, such as cytotoxicity, neural transmission and blood pressure regulation, and its inbalance relates to diseases, for example cancer, epilepsy, diabetes and arthritis (Ignarro, 2000). S-Nitrosothiols (R-SNO) are believed to play an important role in storing, transporting and releasing NO in the human body (Ignarro, 2000). The ability of transition metal complexes both to scavenge and to release NO has generated new interest in such complexes as potential metallopharmaceuticals (Clarke, 2003). Ruthenium has a high affinity for NO, and some complexes of this metal with coordinated NO have therapeutic use in the treatment of sepsis and in the control of high blood pressure (Clarke, 2003). The ability of {Ru(NO)}⁶ complexes, following the Enemark & Feltham (1974) notation, to form octahedral complexes is well known (Richter-Addo & Legzdins, 1992). Considering the electrophilic character of coordinated NO in a wide range of complexes, biological reducing agents, such as thiols, are able to reduce the NO group, thus promoting its labilization (Bottomley, 1978). Against this background, it is of interest to study the reactions between nitrosyl complexes and ligands containing thiol residues, such as complexes with the general formula [Ru(SpymMe₂,-N,-S)(SpymMe₂,-S)(NO)(P—P)]⁺ (P—P is dppe Please define or c-dppen Please define and SpymMe₂ is ? Please define), recently reported by some of us (Von Poelhsitz et al., 2005).

Extending our previous studies, in the present work complexes with the general formula fac-[RuCl₃(NO)(P—P)] (P—P = dppe or dppp Please define) were chosen as probes to evaluate the interaction between coordinated NO and the 2-mercaptopyridine (pyS^-) ligand. The products were identified by spectroscopic techniques (³¹P NMR, IR and UV–vis) and elemental analysis as the thiolate derivatives [Ru(pyS)₂(P—P)], previously reported by Lobana et al. (1998) and Tiekink et al. (1991). In the present case, the products were obtained by the reaction shown in the scheme, while in the previously reported studies the compounds were obtained by the addition of pyS^- to cis-[RuCl₂(P—P)₂] complexes. Finally, partial oxidation of the [Ru(pyS)₂(P—P)] complexes by air produced the title compounds, (I) and (II), as expected from the well known sulfur-centred reactivity of transition metal thiolates with dioxygen to produce sulfur oxygenates (Dilworth et al., 1992; Grapperhaus & Darensbourg, 1998). In the present cases, occupancy refinement showed that one S atom of each molecule was partially oxidized: the occupancies of atoms O1 and O2 (bonded to S1) refined to 0.330 (5) in (I), to give the formula [Ru(pyS)_1.67(pySO₂)_0.33(dppe)], and to 0.357 (6) in (II), to give the formula [Ru(pyS)_1.64(pySO₂)_0.36(dppp)].

The molecular structures of the title ruthenium (II) complexes, (I) and (II) (Figs. 1 and 2), show the distorted octahedral coordination of the metal centres, with chelating pyS^-, pySO₂^- and biphosphine ligands. The exocyclic S atoms occupy trans-positions, while pairs of P and N atoms are in cis-positions. The distortions from the ideal octahedral geometry arise from both small bite angles for pyS^- and pySO₂^- [average N—Ru—S = 67.3 (3)°] and steric crowding of the bulky biphosphine ligand. The mean Ru—P [2.279 (2) Å], Ru—N [2.139 (7) Å] and Ru—S [2.41 (3) Å] distances are in good agreement with previously reported values for [Ru(pyS)₂(P—P)] complexes (Lobana et al., 1998; Tiekink et al., 1991). The C—S bond distances of 1.758 (3) and 1.731 (3) Å for (I), and 1.767 (4) and 1.744 (4) Å for (II), suggest partial double-bond character for these bonds compared with characteristic single and double C—S bond distances (Pauling, 1960).

Two Ru/N/C/S four-membered rings are present in each complex. Ring A (Ru/N2/C26/S2) contains the non-oxidized S atom. Approximately one-third of rings B (Ru/N1/C12/S1) in the crystal of each complex contain oxidized S atoms. Geometric parameters inside rings A and B are approximately the same. Both rings are constructed by means of an Ru^II ion with S and N atoms from the same pyridine-2-thiolate ligand, tolerating considerable strain to achieve an octahedral coordination of Ru. As a result, the average values of the Ru—N—C [102.3 (8)°] and N—C—S [108.7(1.3)°] angles are distorted from the 120° expected for an sp²-hybridized atom. The observed Ru—S distances in the oxidized complexes (I) and (II) remain close to those observed in the non-oxidized ones.

The two S atoms are trans to each other, with S1—Ru1—S2 angles of 155.87 (3) and 153.87 (4) °, respectively, for (I) and (II). These angles are close to those observed in the series [Ru(pyS)₂(P—P)], where P—P is dppe, dppb [Please define] or dppb [Same as previous ligand?], which have S—Ru—S angles in the range 153.9–155.6° (Lobana et al., 1998). The P2—Ru1—P1 bite angles of 84.45 (3)° for (I) and 90.78 (5)° for (II) are related to the lengths of the alkyl chains.

The crystal packing of both compounds consists of parallel layers of molecules. The layers are stabilized by C—H···O and C—H···S interactions (Tables 2 and 4). For compound (I), these layers are parallel to the (101) planes. The layers in compound (II) lie parallel to the (110) planes. Atom O1 is an acceptor of one hydrogen bond in each complex. Atom O2, on the other hand, is an acceptor of two C—H···O hydrogen bonds in (I), but not in (II).

It is interesting to compare these results with the previously reported structures of the non-oxidized compounds [Ru(pyS)₂(dppe)] (Tiekink et al., 1991) and [Ru(pyS)₂(dppp)] (Lobana et al., 1998). The O atoms in the oxidized compound, (II), fill spaces that are empty in the corresponding non-oxidized structure, in such a way that isomorphism is observed between the two species. Similar to (II), compound (I) has a monolayer structure stabilized by C—H···O and C—H···S interactions. [Ru(pyS)₂(dppe)], on the other hand, presents a double-layer structure stabilized by C—H···S interactions. Finally, it is interesting to note that the length of the alkyl groups linking the two P(Ph)₂ units plays an important role in the crystal packing of the compounds discussed here. The packing of the complexes containing the dppp ligand {space group P1 for (II) and [Ru(pyS)₂(dppp)], isomorphous structures} is different from the packing of the crystal structures of the complexes containing the dppe ligand (space groups P2₁/c and P2₁/n for the crystals of the oxidized and non-oxidized species, respectively).

S2. Experimental

A suspension of the corresponding fac-[RuCl₃(NO)(P—P)] precursors (P—P is dppe or dppp) (Batista et al., 1997; Zampieri et al., 2002) (100 mg) in deoxygenated methanol (25 ml) was mixed with a solution of 2-mercaptopyridine (0.48 mmol, 54.0 mg) in methanol (5 ml) containing triethylamine (0.60 mmol, 0.083 ml), previously bubbled with Ar for 10 min. The mixture was heated under reflux for 12 h. The resulting mixture, containing a yellow precipitate, was collected by filtration, washed with methanol and diethyl? ether, and dried under vacuum. The same results can be achieved without heating under reflux if the time of the reaction is increased to 24 h. The [Ru(pyS)₂(P—P)] products were maintained in CH₂Cl₂ solutions and after a few days yellow [(I) is red below - please clarify] crystals of the title complexes, (I) and (II), [Ru(pyS)_{1 + x}(pySO₂)_{1 - x}(P—P)], were grown.

S3. Refinement

H atoms were positioned geometrically and treated as riding, with C—H distances of 0.93–0.97 Å and with U_iso(H) = 1.2–1.5U_eq(C). [Please check added text]

Computing details

Data collection: COLLECT (Nonius, 1999) for (I); CAD-4 EXPRESS (Enraf–Nonius, 1994) for (II). Cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997) for (I); CAD-4 EXPRESS for (II). Data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK for (I); XCAD4 (Harms & Wocadlo, 1995) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A structural representation of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level and most H atoms have been omitted.
	Fig. 2. A structural representation of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level and most H atoms have been omitted.

(I) [1,3-bis(diphenylphosphino)ethane-κ²P,P'](pyridine-2-sulfinato- κ²N,S)(pyridine-2-thiolato-κ²N,S)ruthenium(II)

Crystal data

[Ru(C5H4NO2S)0.33(C5H4NS)1.67(C26H24P2)]	F(000) = 1493.1
Mr = 729.66	Dx = 1.481 Mg m^−3
MonoclinicP21/n	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P2yn	Cell parameters from 80885 reflections
a = 11.4520 (2) Å	θ = 1.0–27.5°
b = 22.3900 (4) Å	µ = 0.73 mm^−1
c = 12.8710 (2) Å	T = 293 K
β = 91.661 (1)°	Prism, red
V = 3298.9 (1) Å^3	0.14 × 0.10 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	7558 independent reflections
Radiation source: fine-focus sealed tube	5481 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.134
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 1.8°
Type of scans	h = −14→14
Absorption correction: multi-scan from symmetry-related measurements (SORTAV; Blessing 1995)	k = −29→29
Tmin = 0.850, Tmax = 0.961	l = −16→16
80383 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0633P)^2] where P = (Fo^2 + 2Fc^2)/3
7558 reflections	(Δ/σ)max = 0.001
407 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.83 e Å^−3

Special details

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. Occupancy parameters were refined for oxygen sites

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ru	0.266054 (18)	0.123970 (9)	0.259906 (16)	0.03851 (9)
S1	0.35127 (7)	0.15883 (4)	0.10310 (6)	0.0557 (2)
S2	0.11945 (7)	0.11816 (3)	0.39099 (6)	0.0501 (2)
P1	0.42171 (7)	0.10800 (4)	0.37070 (6)	0.04589 (19)
P2	0.28898 (6)	0.02596 (3)	0.21806 (5)	0.04396 (18)
O1	0.3734 (6)	0.2235 (3)	0.1012 (5)	0.063 (2)	0.330 (5)
O2	0.4097 (6)	0.1228 (3)	0.0389 (6)	0.065 (2)	0.330 (5)
N1	0.1376 (2)	0.14325 (11)	0.14004 (18)	0.0470 (5)
N2	0.22745 (19)	0.20935 (10)	0.32553 (17)	0.0451 (5)
C1	0.4517 (3)	0.02711 (14)	0.3739 (2)	0.0588 (8)
H1A	0.5313	0.0201	0.3987	0.071*
H1B	0.3993	0.0075	0.4209	0.071*
C2	0.4343 (3)	0.00194 (15)	0.2652 (2)	0.0566 (8)
H2A	0.4389	−0.0413	0.2667	0.068*
H2B	0.4939	0.0170	0.2201	0.068*
C12	0.2041 (3)	0.16043 (14)	0.0603 (2)	0.0550 (8)
C13	0.1553 (3)	0.17545 (19)	−0.0352 (3)	0.0810 (11)
H13	0.2015	0.1875	−0.0896	0.097*
C14	0.0353 (4)	0.1720 (2)	−0.0475 (3)	0.0970 (14)
H14	−0.0002	0.1813	−0.1114	0.116*
C15	−0.0318 (3)	0.1548 (2)	0.0335 (3)	0.0819 (11)
H15	−0.1126	0.1526	0.0255	0.098*
C16	0.0225 (3)	0.14095 (16)	0.1266 (3)	0.0595 (8)
H16	−0.0228	0.1296	0.1821	0.071*
C22	0.2593 (3)	0.26631 (14)	0.3159 (2)	0.0523 (7)
H22	0.3180	0.2758	0.2702	0.063*
C23	0.2086 (3)	0.31134 (15)	0.3710 (3)	0.0623 (8)
H23	0.2332	0.3507	0.3639	0.075*
C24	0.1194 (3)	0.29694 (17)	0.4379 (3)	0.0698 (9)
H24	0.0833	0.3268	0.4756	0.084*
C25	0.0850 (3)	0.23878 (16)	0.4479 (2)	0.0624 (8)
H25	0.0246	0.2288	0.4914	0.075*
C26	0.1417 (2)	0.19464 (14)	0.3921 (2)	0.0487 (7)
C31	0.4140 (3)	0.12715 (13)	0.5099 (2)	0.0499 (7)
C32	0.4795 (3)	0.17329 (17)	0.5530 (3)	0.0672 (9)
H32	0.5277	0.1958	0.5112	0.081*
C33	0.4737 (3)	0.18621 (19)	0.6588 (3)	0.0796 (11)
H33	0.5186	0.2170	0.6874	0.096*
C34	0.4021 (3)	0.1537 (2)	0.7209 (3)	0.0770 (11)
H34	0.3986	0.1623	0.7914	0.092*
C35	0.3361 (3)	0.1088 (2)	0.6792 (3)	0.0735 (10)
H35	0.2876	0.0869	0.7215	0.088*
C36	0.3403 (3)	0.09520 (17)	0.5739 (2)	0.0623 (8)
H36	0.2938	0.0647	0.5461	0.075*
C41	0.5651 (3)	0.13984 (16)	0.3395 (2)	0.0528 (7)
C42	0.5726 (3)	0.18750 (16)	0.2722 (2)	0.0622 (8)
H42	0.5048	0.2028	0.2410	0.075*
C43	0.6800 (3)	0.21311 (19)	0.2503 (3)	0.0771 (11)
H43	0.6839	0.2454	0.2050	0.093*
C44	0.7801 (3)	0.1902 (2)	0.2960 (3)	0.0826 (12)
H44	0.8521	0.2067	0.2809	0.099*
C45	0.7749 (3)	0.1431 (2)	0.3637 (3)	0.0844 (12)
H45	0.8429	0.1281	0.3950	0.101*
C46	0.6680 (3)	0.11811 (18)	0.3852 (3)	0.0712 (11)
H46	0.6649	0.0861	0.4312	0.085*
C51	0.1897 (3)	−0.02661 (13)	0.2799 (2)	0.0548 (8)
C52	0.0740 (3)	−0.01224 (18)	0.2840 (3)	0.0756 (10)
H52	0.0483	0.0246	0.2588	0.091*
C53	−0.0065 (4)	−0.0521 (2)	0.3254 (3)	0.0989 (14)
H53	−0.0848	−0.0412	0.3266	0.119*
C54	0.0256 (5)	−0.1048 (2)	0.3629 (3)	0.1005 (16)
H54	−0.0296	−0.1311	0.3883	0.121*
C55	0.1440 (6)	−0.12025 (18)	0.3635 (3)	0.1013 (18)
H55	0.1680	−0.1566	0.3918	0.122*
C56	0.2271 (4)	−0.08153 (17)	0.3221 (3)	0.0781 (11)
H56	0.3056	−0.0921	0.3224	0.094*
C61	0.2791 (3)	−0.00075 (13)	0.0836 (2)	0.0477 (7)
C62	0.1816 (3)	0.01342 (16)	0.0235 (2)	0.0674 (9)
H62	0.1226	0.0362	0.0519	0.081*
C63	0.1700 (4)	−0.0058 (2)	−0.0788 (3)	0.0835 (11)
H63	0.1034	0.0041	−0.1182	0.100*
C64	0.2557 (4)	−0.03916 (19)	−0.1217 (3)	0.0846 (12)
H64	0.2487	−0.0512	−0.1908	0.101*
C65	0.3523 (4)	−0.05481 (16)	−0.0625 (3)	0.0721 (10)
H65	0.4095	−0.0789	−0.0907	0.087*
C66	0.3649 (3)	−0.03513 (14)	0.0381 (2)	0.0583 (8)
H66	0.4321	−0.0450	0.0766	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru	0.03591 (14)	0.04269 (15)	0.03704 (14)	−0.00066 (9)	0.00303 (9)	0.00176 (9)
S1	0.0505 (4)	0.0678 (6)	0.0489 (4)	−0.0067 (4)	0.0050 (3)	0.0091 (4)
S2	0.0463 (4)	0.0571 (5)	0.0476 (4)	−0.0038 (3)	0.0104 (3)	0.0026 (3)
P1	0.0405 (4)	0.0549 (5)	0.0421 (4)	0.0016 (3)	−0.0021 (3)	0.0005 (3)
P2	0.0477 (4)	0.0440 (4)	0.0402 (4)	0.0010 (3)	0.0019 (3)	0.0004 (3)
O1	0.069 (5)	0.050 (4)	0.071 (5)	−0.004 (3)	0.012 (3)	0.015 (3)
O2	0.060 (4)	0.063 (5)	0.072 (5)	−0.004 (3)	0.015 (4)	−0.007 (3)
N1	0.0436 (13)	0.0512 (13)	0.0464 (13)	0.0012 (11)	0.0028 (10)	0.0036 (11)
N2	0.0401 (12)	0.0474 (14)	0.0477 (13)	0.0024 (10)	0.0013 (10)	−0.0017 (10)
C1	0.0604 (19)	0.063 (2)	0.0525 (18)	0.0118 (16)	−0.0107 (14)	0.0023 (15)
C2	0.0598 (19)	0.0541 (18)	0.0557 (18)	0.0129 (15)	−0.0022 (14)	−0.0007 (15)
C12	0.0588 (18)	0.057 (2)	0.0495 (17)	0.0027 (14)	0.0062 (14)	0.0109 (14)
C13	0.079 (3)	0.105 (3)	0.059 (2)	0.006 (2)	0.0014 (18)	0.035 (2)
C14	0.084 (3)	0.134 (4)	0.072 (3)	0.017 (3)	−0.020 (2)	0.038 (3)
C15	0.052 (2)	0.111 (3)	0.082 (3)	0.010 (2)	−0.0148 (18)	0.017 (2)
C16	0.0471 (18)	0.069 (2)	0.062 (2)	0.0045 (16)	−0.0005 (15)	0.0066 (17)
C22	0.0486 (17)	0.0538 (19)	0.0543 (18)	−0.0017 (14)	−0.0012 (13)	0.0021 (14)
C23	0.073 (2)	0.0439 (18)	0.069 (2)	0.0007 (16)	−0.0063 (17)	−0.0058 (15)
C24	0.080 (2)	0.062 (2)	0.068 (2)	0.0171 (18)	0.0044 (18)	−0.0133 (17)
C25	0.0612 (19)	0.069 (2)	0.0583 (19)	0.0076 (17)	0.0132 (15)	−0.0089 (16)
C26	0.0465 (16)	0.0565 (18)	0.0431 (15)	0.0046 (13)	0.0009 (12)	−0.0009 (13)
C31	0.0436 (16)	0.063 (2)	0.0433 (16)	0.0041 (13)	−0.0011 (13)	−0.0018 (13)
C32	0.067 (2)	0.075 (2)	0.060 (2)	−0.0070 (18)	0.0046 (16)	−0.0110 (17)
C33	0.080 (3)	0.093 (3)	0.066 (2)	0.001 (2)	−0.0024 (19)	−0.027 (2)
C34	0.072 (2)	0.109 (3)	0.050 (2)	0.016 (2)	0.0000 (18)	−0.017 (2)
C35	0.064 (2)	0.103 (3)	0.054 (2)	0.008 (2)	0.0110 (17)	0.0072 (19)
C36	0.059 (2)	0.075 (2)	0.0525 (18)	−0.0037 (17)	0.0022 (15)	0.0031 (17)
C41	0.0416 (16)	0.072 (2)	0.0447 (16)	−0.0023 (14)	0.0015 (13)	−0.0082 (15)
C42	0.0552 (19)	0.073 (2)	0.0584 (19)	−0.0122 (16)	−0.0023 (15)	−0.0077 (17)
C43	0.069 (2)	0.095 (3)	0.069 (2)	−0.027 (2)	0.0117 (18)	−0.011 (2)
C44	0.049 (2)	0.119 (4)	0.081 (3)	−0.020 (2)	0.0193 (19)	−0.031 (3)
C45	0.0412 (19)	0.127 (4)	0.085 (3)	0.001 (2)	0.0013 (18)	−0.023 (3)
C46	0.0456 (19)	0.105 (3)	0.063 (2)	0.0037 (17)	−0.0034 (16)	−0.0048 (18)
C51	0.079 (2)	0.0458 (17)	0.0403 (16)	−0.0077 (15)	0.0088 (15)	−0.0009 (13)
C52	0.069 (2)	0.079 (3)	0.079 (2)	−0.021 (2)	0.0072 (19)	0.0064 (19)
C53	0.094 (3)	0.103 (4)	0.101 (3)	−0.037 (3)	0.022 (2)	0.008 (3)
C54	0.139 (5)	0.093 (3)	0.071 (3)	−0.052 (3)	0.037 (3)	−0.002 (2)
C55	0.181 (6)	0.064 (3)	0.060 (2)	−0.018 (3)	0.027 (3)	0.0127 (18)
C56	0.113 (3)	0.066 (2)	0.056 (2)	0.001 (2)	0.017 (2)	0.0045 (17)
C61	0.0591 (18)	0.0423 (15)	0.0421 (15)	−0.0054 (13)	0.0088 (13)	0.0013 (12)
C62	0.069 (2)	0.076 (2)	0.0561 (19)	0.0033 (18)	−0.0042 (16)	−0.0175 (17)
C63	0.096 (3)	0.100 (3)	0.054 (2)	−0.011 (2)	−0.012 (2)	−0.015 (2)
C64	0.124 (4)	0.083 (3)	0.047 (2)	−0.021 (3)	0.014 (2)	−0.0149 (19)
C65	0.102 (3)	0.058 (2)	0.058 (2)	−0.003 (2)	0.030 (2)	−0.0055 (16)
C66	0.073 (2)	0.0524 (19)	0.0502 (18)	0.0013 (16)	0.0179 (15)	−0.0002 (14)

Geometric parameters (Å, º)

Ru—S1	2.3977 (8)	C53—C54	1.322 (6)
Ru—S2	2.4179 (8)	C54—C55	1.399 (7)
Ru—P1	2.2785 (8)	C55—C56	1.404 (6)
Ru—P2	2.2765 (8)	P2—C61	1.832 (3)
Ru—N1	2.144 (2)	C61—C62	1.377 (4)
Ru—N2	2.141 (2)	C61—C66	1.391 (4)
S1—O1	1.470 (6)	C62—C63	1.388 (4)
S1—O2	1.346 (7)	C63—C64	1.363 (5)
S1—C12	1.758 (3)	C64—C65	1.370 (5)
P1—C1	1.844 (3)	C65—C66	1.371 (4)
C1—C2	1.516 (4)	C2—H2A	0.9700
C2—P2	1.835 (3)	C2—H2B	0.9700
N1—C12	1.351 (4)	C1—H1A	0.9700
N1—C16	1.326 (4)	C1—H1B	0.9700
C12—C13	1.378 (4)	C13—H13	0.9300
C13—C14	1.381 (5)	C14—H14	0.9300
C14—C15	1.368 (5)	C15—H15	0.9300
C15—C16	1.369 (4)	C16—H16	0.9300
S2—C26	1.731 (3)	C22—H22	0.9300
N2—C22	1.333 (4)	C23—H23	0.9300
N2—C26	1.363 (3)	C24—H24	0.9300
C22—C23	1.372 (4)	C25—H25	0.9300
C23—C24	1.392 (5)	C32—H32	0.9300
C24—C25	1.368 (5)	C33—H33	0.9300
C25—C26	1.393 (4)	C34—H34	0.9300
P1—C31	1.846 (3)	C35—H35	0.9300
C31—C32	1.384 (4)	C36—H36	0.9300
C31—C36	1.394 (4)	C42—H42	0.9300
C32—C33	1.396 (4)	C43—H43	0.9300
C33—C34	1.371 (5)	C44—H44	0.9300
C34—C35	1.358 (6)	C45—H45	0.9300
C35—C36	1.391 (4)	C46—H46	0.9300
P1—C41	1.845 (3)	C52—H52	0.9300
C41—C42	1.379 (5)	C53—H53	0.9300
C41—C46	1.391 (5)	C54—H54	0.9300
C42—C43	1.394 (4)	C55—H55	0.9300
C43—C44	1.373 (5)	C56—H56	0.9300
C44—C45	1.370 (6)	C62—H62	0.9300
C45—C46	1.381 (5)	C63—H63	0.9300
P2—C51	1.834 (3)	C64—H64	0.9300
C51—C52	1.367 (5)	C65—H65	0.9300
C51—C56	1.405 (5)	C66—H66	0.9300
C52—C53	1.399 (5)
N2—Ru—N1	87.64 (9)	C53—C54—C55	118.8 (4)
N2—Ru—P2	168.65 (6)	C54—C55—C56	120.8 (4)
N1—Ru—P2	96.04 (7)	C55—C56—C51	119.0 (4)
N2—Ru—P1	93.44 (6)	C62—C61—C66	117.5 (3)
N1—Ru—P1	171.78 (6)	C62—C61—P2	118.8 (2)
P2—Ru—P1	84.45 (3)	C66—C61—P2	123.6 (2)
N2—Ru—S1	97.77 (6)	C61—C62—C63	121.0 (3)
N1—Ru—S1	67.44 (6)	C64—C63—C62	120.3 (4)
P2—Ru—S1	93.56 (3)	C63—C64—C65	119.6 (3)
P1—Ru—S1	104.35 (3)	C64—C65—C66	120.3 (3)
N2—Ru—S2	67.50 (6)	C65—C66—C61	121.3 (3)
N1—Ru—S2	92.13 (6)	C1—C2—H2A	110.3
P2—Ru—S2	101.56 (3)	P2—C2—H2A	110.3
P1—Ru—S2	95.81 (3)	C1—C2—H2B	110.3
S1—Ru—S2	155.87 (3)	P2—C2—H2B	110.3
O2—S1—O1	119.4 (4)	H2A—C2—H2B	108.6
O2—S1—C12	108.0 (3)	C2—C1—H1A	109.9
O1—S1—C12	98.0 (3)	P1—C1—H1A	109.9
O2—S1—Ru	122.9 (3)	C2—C1—H1B	109.9
O1—S1—Ru	114.2 (3)	P1—C1—H1B	109.9
C12—S1—Ru	81.97 (10)	H1A—C1—H1B	108.3
C26—S2—Ru	81.25 (9)	C12—C13—H13	121.1
C1—P1—C41	102.59 (16)	C14—C13—H13	121.1
C1—P1—C31	102.75 (14)	C15—C14—H14	119.8
C41—P1—C31	100.91 (13)	C13—C14—H14	119.8
C1—P1—Ru	108.06 (10)	C14—C15—H15	120.6
C41—P1—Ru	119.22 (10)	C16—C15—H15	120.6
C31—P1—Ru	120.81 (10)	N1—C16—H16	119.0
C61—P2—C51	100.29 (13)	C15—C16—H16	119.0
C61—P2—C2	104.32 (14)	N2—C22—H22	118.9
C51—P2—C2	103.62 (15)	C23—C22—H22	118.9
C61—P2—Ru	122.27 (10)	C22—C23—H23	120.7
C51—P2—Ru	116.03 (10)	C24—C23—H23	120.7
C2—P2—Ru	108.30 (11)	C25—C24—H24	120.1
C16—N1—C12	119.5 (3)	C23—C24—H24	120.1
C16—N1—Ru	138.2 (2)	C24—C25—H25	120.4
C12—N1—Ru	102.33 (18)	C26—C25—H25	120.4
C22—N2—C26	119.6 (2)	C31—C32—H32	119.8
C22—N2—Ru	139.2 (2)	C33—C32—H32	119.8
C26—N2—Ru	101.14 (18)	C34—C33—H33	119.8
P1—C1—C2	109.0 (2)	C32—C33—H33	119.8
C1—C2—P2	106.9 (2)	C35—C34—H34	120.1
N1—C12—C13	121.6 (3)	C33—C34—H34	120.1
N1—C12—S1	108.2 (2)	C34—C35—H35	119.6
N1—C16—C15	122.0 (3)	C36—C35—H35	119.6
C13—C12—S1	130.2 (3)	C35—C36—H36	119.9
C12—C13—C14	117.8 (3)	C31—C36—H36	119.9
C14—C15—C16	118.7 (3)	C41—C42—H42	119.4
C15—C14—C13	120.4 (3)	C43—C42—H42	119.4
N2—C22—C23	122.2 (3)	C44—C43—H43	120.3
N2—C26—C25	120.5 (3)	C42—C43—H43	120.3
N2—C26—S2	110.0 (2)	C45—C44—H44	119.7
C22—C23—C24	118.6 (3)	C43—C44—H44	119.7
C23—C24—C25	119.8 (3)	C44—C45—H45	120.2
C24—C25—C26	119.2 (3)	C46—C45—H45	120.2
C25—C26—S2	129.5 (2)	C45—C46—H46	119.4
C32—C31—C36	118.5 (3)	C41—C46—H46	119.4
C32—C31—P1	121.5 (2)	C51—C52—H52	119.5
C36—C31—P1	120.1 (2)	C53—C52—H52	119.5
C31—C32—C33	120.4 (3)	C54—C53—H53	119.0
C34—C33—C32	120.3 (4)	C52—C53—H53	119.0
C35—C34—C33	119.8 (3)	C53—C54—H54	120.6
C34—C35—C36	120.9 (4)	C55—C54—H54	120.6
C35—C36—C31	120.1 (3)	C54—C55—H55	119.6
C42—C41—C46	118.0 (3)	C56—C55—H55	119.6
C42—C41—P1	120.5 (2)	C55—C56—H56	120.5
C46—C41—P1	121.5 (3)	C51—C56—H56	120.5
C41—C42—C43	121.2 (3)	C61—C62—H62	119.5
C44—C43—C42	119.3 (4)	C63—C62—H62	119.5
C45—C44—C43	120.6 (3)	C64—C63—H63	119.8
C44—C45—C46	119.6 (4)	C62—C63—H63	119.8
C45—C46—C41	121.3 (4)	C63—C64—H64	120.2
C52—C51—C56	118.4 (3)	C65—C64—H64	120.2
C52—C51—P2	118.6 (3)	C64—C65—H65	119.9
C56—C51—P2	122.9 (3)	C66—C65—H65	119.9
C51—C52—C53	121.0 (4)	C65—C66—H66	119.4
C54—C53—C52	122.0 (5)	C61—C66—H66	119.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C24—H24···O2^i	0.93	2.45	3.297 (8)	152
C25—H25···O1^i	0.93	2.51	3.280 (7)	141
C65—H65···O2^ii	0.93	2.37	3.130 (8)	139

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

(II) [1,3-bis(diphenylphosphino)propane-κ²P,P'](pyridine-2-sulfinato- κ²N,S)(pyridine-2-thiolato-κ²N,S)ruthenium(II)

Crystal data

[Ru(C5H4NO2S)0.355(C5H4NS)1.645(C26H24P2)]	Z = 2
Mr = 745.31	F(000) = 763.4
TriclinicP1	Dx = 1.476 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 8.818 (5) Å	Cell parameters from 25 reflections
b = 10.245 (4) Å	θ = 33–18°
c = 20.136 (3) Å	µ = 6.05 mm^−1
α = 83.16 (2)°	T = 293 K
β = 81.36 (3)°	Prism, yellow
γ = 70.12 (4)°	0.20 × 0.12 × 0.09 mm
V = 1686.7 (12) Å^3

Data collection

Enraf–Nonius CAD4 diffractometer	4907 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 67.0°, θmin = 2.2°
non–profiled ω/2θ scans	h = −10→10
Absorption correction: analytical (PLATON; Spek, 2003)	k = −12→12
Tmin = 0.42, Tmax = 0.64	l = 0→24
6012 measured reflections	1 standard reflections every 30 min
5837 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.5047P] where P = (Fo^2 + 2Fc^2)/3
5837 reflections	(Δ/σ)max = 0.001
416 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.65 e Å^−3

Special details

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. Occupancy parameters were refined for oxygen sites.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ru	0.17357 (3)	0.34834 (2)	0.263041 (11)	0.03791 (8)
S1	0.14651 (11)	0.13425 (9)	0.24268 (5)	0.0569 (2)
S2	0.31785 (10)	0.49163 (9)	0.29680 (4)	0.0502 (2)
P1	−0.08754 (9)	0.44768 (8)	0.30981 (4)	0.04195 (18)
P2	0.10366 (10)	0.43780 (8)	0.15862 (4)	0.04307 (18)
O1	0.0606 (10)	0.1320 (8)	0.1920 (5)	0.080 (3)	0.357 (6)
O2	0.1432 (11)	0.0402 (8)	0.3034 (4)	0.079 (3)	0.357 (6)
N1	0.3980 (3)	0.2037 (3)	0.22261 (13)	0.0475 (6)
N2	0.2627 (3)	0.2782 (3)	0.35801 (13)	0.0465 (6)
C1	−0.2303 (4)	0.4216 (4)	0.25979 (18)	0.0529 (8)
H1A	−0.2002	0.3231	0.2537	0.064*
H1B	−0.3382	0.4506	0.2844	0.064*
C2	−0.2349 (4)	0.5020 (4)	0.19070 (18)	0.0589 (9)
H2A	−0.3352	0.5105	0.1735	0.071*
H2B	−0.2355	0.5951	0.1959	0.071*
C3	−0.0921 (4)	0.4336 (4)	0.13916 (17)	0.0558 (8)
H3A	−0.1125	0.4809	0.0951	0.067*
H3B	−0.0850	0.3376	0.1372	0.067*
C12	0.3560 (4)	0.0929 (3)	0.21455 (17)	0.0517 (8)
C13	0.4691 (5)	−0.0274 (4)	0.1888 (2)	0.0668 (10)
H13	0.4382	−0.1030	0.1829	0.080*
C14	0.6273 (5)	−0.0312 (5)	0.1726 (2)	0.0763 (12)
H14	0.7051	−0.1103	0.1553	0.092*
C15	0.6711 (5)	0.0816 (5)	0.1817 (2)	0.0737 (11)
H15	0.7783	0.0794	0.1714	0.088*
C16	0.5527 (4)	0.1979 (4)	0.20636 (19)	0.0580 (9)
H16	0.5813	0.2750	0.2119	0.070*
C22	0.2611 (4)	0.1758 (4)	0.40609 (18)	0.0576 (9)
H22	0.2071	0.1144	0.4010	0.069*
C23	0.3375 (5)	0.1597 (5)	0.4624 (2)	0.0732 (12)
H23	0.3343	0.0889	0.4955	0.088*
C24	0.4185 (5)	0.2491 (5)	0.4695 (2)	0.0777 (13)
H24	0.4706	0.2389	0.5076	0.093*
C25	0.4232 (4)	0.3531 (5)	0.4209 (2)	0.0668 (10)
H25	0.4792	0.4134	0.4251	0.080*
C26	0.3418 (4)	0.3667 (4)	0.36479 (17)	0.0491 (7)
C31	−0.1849 (4)	0.6324 (3)	0.32752 (16)	0.0480 (7)
C32	−0.3525 (5)	0.6964 (4)	0.33382 (19)	0.0623 (9)
H32	−0.4191	0.6448	0.3300	0.075*
C33	−0.4212 (5)	0.8354 (4)	0.3457 (2)	0.0725 (12)
H33	−0.5335	0.8764	0.3493	0.087*
C34	−0.3270 (6)	0.9138 (4)	0.3521 (2)	0.0748 (12)
H34	−0.3744	1.0075	0.3600	0.090*
C35	−0.1622 (6)	0.8528 (4)	0.3469 (2)	0.0741 (12)
H35	−0.0967	0.9054	0.3508	0.089*
C36	−0.0915 (5)	0.7113 (4)	0.33574 (19)	0.0608 (9)
H36	0.0206	0.6701	0.3338	0.073*
C41	−0.1289 (4)	0.3595 (4)	0.39198 (17)	0.0500 (8)
C42	−0.1404 (5)	0.2268 (4)	0.3955 (2)	0.0632 (9)
H42	−0.1384	0.1870	0.3560	0.076*
C43	−0.1549 (5)	0.1533 (5)	0.4571 (2)	0.0765 (12)
H43	−0.1625	0.0646	0.4588	0.092*
C44	−0.1580 (6)	0.2103 (5)	0.5156 (2)	0.0818 (13)
H44	−0.1675	0.1605	0.5569	0.098*
C45	−0.1469 (6)	0.3418 (5)	0.5131 (2)	0.0797 (13)
H45	−0.1492	0.3810	0.5528	0.096*
C46	−0.1323 (5)	0.4161 (4)	0.45131 (19)	0.0645 (10)
H46	−0.1248	0.5048	0.4500	0.077*
C51	0.0884 (4)	0.6187 (3)	0.13165 (17)	0.0503 (8)
C52	0.1032 (5)	0.7050 (4)	0.1757 (2)	0.0633 (9)
H52	0.1169	0.6721	0.2202	0.076*
C53	0.0981 (5)	0.8401 (4)	0.1550 (3)	0.0755 (12)
H53	0.1066	0.8971	0.1859	0.091*
C54	0.0813 (6)	0.8895 (4)	0.0912 (3)	0.0818 (13)
H54	0.0805	0.9796	0.0773	0.098*
C55	0.0652 (7)	0.8061 (5)	0.0462 (3)	0.0959 (16)
H55	0.0522	0.8406	0.0018	0.115*
C56	0.0679 (6)	0.6718 (4)	0.0658 (2)	0.0762 (12)
H56	0.0559	0.6167	0.0347	0.091*
C61	0.2468 (4)	0.3491 (3)	0.08892 (16)	0.0501 (8)
C62	0.2251 (5)	0.2472 (4)	0.0569 (2)	0.0719 (11)
H62	0.1323	0.2222	0.0698	0.086*
C63	0.3390 (7)	0.1802 (6)	0.0056 (3)	0.0949 (16)
H63	0.3219	0.1113	−0.0155	0.114*
C64	0.4737 (7)	0.2149 (6)	−0.0134 (2)	0.1006 (18)
H64	0.5486	0.1718	−0.0485	0.121*
C65	0.5009 (7)	0.3143 (6)	0.0189 (3)	0.1032 (18)
H65	0.5957	0.3364	0.0066	0.124*
C66	0.3869 (6)	0.3819 (5)	0.0699 (2)	0.0791 (13)
H66	0.4054	0.4497	0.0913	0.095*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru	0.03239 (13)	0.03682 (13)	0.04540 (14)	−0.01097 (10)	−0.00205 (9)	−0.01083 (9)
S1	0.0509 (5)	0.0456 (5)	0.0764 (6)	−0.0171 (4)	−0.0005 (4)	−0.0174 (4)
S2	0.0425 (4)	0.0502 (5)	0.0623 (5)	−0.0183 (4)	−0.0071 (4)	−0.0110 (4)
P1	0.0328 (4)	0.0427 (4)	0.0502 (4)	−0.0110 (3)	−0.0011 (3)	−0.0116 (3)
P2	0.0431 (4)	0.0428 (4)	0.0451 (4)	−0.0141 (4)	−0.0044 (3)	−0.0111 (3)
O1	0.072 (5)	0.061 (5)	0.120 (7)	−0.024 (4)	−0.030 (5)	−0.029 (5)
O2	0.089 (6)	0.052 (5)	0.099 (6)	−0.032 (4)	0.007 (5)	−0.008 (4)
N2	0.0349 (13)	0.0492 (15)	0.0521 (15)	−0.0089 (12)	−0.0035 (11)	−0.0084 (12)
N1	0.0412 (15)	0.0449 (15)	0.0533 (15)	−0.0090 (12)	−0.0032 (12)	−0.0099 (12)
C1	0.0383 (17)	0.060 (2)	0.065 (2)	−0.0191 (16)	−0.0040 (15)	−0.0159 (17)
C2	0.0413 (18)	0.071 (2)	0.068 (2)	−0.0156 (17)	−0.0158 (16)	−0.0141 (18)
C3	0.053 (2)	0.068 (2)	0.0546 (19)	−0.0248 (18)	−0.0104 (16)	−0.0147 (17)
C12	0.0498 (19)	0.0468 (18)	0.0543 (19)	−0.0078 (15)	−0.0035 (15)	−0.0147 (15)
C13	0.072 (3)	0.047 (2)	0.074 (2)	−0.0049 (19)	−0.007 (2)	−0.0203 (18)
C14	0.065 (3)	0.064 (3)	0.077 (3)	0.009 (2)	0.004 (2)	−0.020 (2)
C15	0.044 (2)	0.077 (3)	0.082 (3)	0.001 (2)	0.0072 (19)	−0.015 (2)
C16	0.0410 (19)	0.059 (2)	0.069 (2)	−0.0097 (17)	−0.0005 (16)	−0.0115 (18)
C22	0.0446 (19)	0.059 (2)	0.061 (2)	−0.0099 (17)	−0.0039 (16)	0.0040 (17)
C23	0.055 (2)	0.085 (3)	0.063 (2)	−0.007 (2)	−0.0055 (19)	0.013 (2)
C24	0.058 (2)	0.111 (4)	0.052 (2)	−0.009 (2)	−0.0138 (18)	−0.005 (2)
C25	0.047 (2)	0.090 (3)	0.065 (2)	−0.017 (2)	−0.0131 (17)	−0.021 (2)
C26	0.0338 (16)	0.056 (2)	0.0546 (18)	−0.0083 (15)	−0.0027 (14)	−0.0149 (15)
C31	0.0472 (18)	0.0450 (17)	0.0457 (16)	−0.0077 (15)	−0.0003 (14)	−0.0092 (14)
C32	0.051 (2)	0.061 (2)	0.064 (2)	−0.0052 (18)	−0.0024 (17)	−0.0078 (18)
C33	0.061 (2)	0.066 (3)	0.063 (2)	0.013 (2)	−0.0010 (19)	−0.0067 (19)
C34	0.091 (3)	0.049 (2)	0.062 (2)	0.003 (2)	0.004 (2)	−0.0133 (18)
C35	0.086 (3)	0.056 (2)	0.079 (3)	−0.020 (2)	0.001 (2)	−0.024 (2)
C36	0.055 (2)	0.055 (2)	0.068 (2)	−0.0106 (18)	−0.0001 (18)	−0.0201 (18)
C41	0.0324 (16)	0.0519 (19)	0.060 (2)	−0.0092 (14)	0.0039 (14)	−0.0073 (15)
C42	0.057 (2)	0.058 (2)	0.074 (2)	−0.0223 (19)	0.0041 (18)	−0.0088 (18)
C43	0.068 (3)	0.067 (3)	0.091 (3)	−0.028 (2)	0.004 (2)	0.006 (2)
C44	0.073 (3)	0.075 (3)	0.079 (3)	−0.013 (2)	0.008 (2)	0.012 (2)
C45	0.090 (3)	0.077 (3)	0.055 (2)	−0.008 (3)	−0.002 (2)	−0.008 (2)
C46	0.070 (3)	0.054 (2)	0.062 (2)	−0.0127 (19)	−0.0021 (19)	−0.0044 (17)
C51	0.0456 (18)	0.0440 (17)	0.0583 (19)	−0.0103 (15)	−0.0068 (15)	−0.0051 (15)
C52	0.071 (3)	0.0468 (19)	0.071 (2)	−0.0156 (18)	−0.011 (2)	−0.0098 (17)
C53	0.078 (3)	0.043 (2)	0.105 (3)	−0.015 (2)	−0.019 (3)	−0.011 (2)
C54	0.075 (3)	0.046 (2)	0.119 (4)	−0.016 (2)	−0.012 (3)	0.007 (2)
C55	0.119 (4)	0.070 (3)	0.094 (3)	−0.026 (3)	−0.033 (3)	0.027 (3)
C56	0.099 (3)	0.061 (2)	0.071 (3)	−0.024 (2)	−0.029 (2)	0.004 (2)
C61	0.054 (2)	0.0475 (18)	0.0450 (17)	−0.0121 (16)	−0.0012 (14)	−0.0074 (14)
C62	0.073 (3)	0.072 (3)	0.071 (3)	−0.022 (2)	0.005 (2)	−0.031 (2)
C63	0.100 (4)	0.097 (4)	0.084 (3)	−0.023 (3)	0.012 (3)	−0.050 (3)
C64	0.115 (5)	0.092 (4)	0.072 (3)	−0.013 (3)	0.026 (3)	−0.026 (3)
C65	0.090 (4)	0.098 (4)	0.110 (4)	−0.033 (3)	0.038 (3)	−0.017 (3)
C66	0.076 (3)	0.076 (3)	0.083 (3)	−0.030 (2)	0.023 (2)	−0.023 (2)

Geometric parameters (Å, º)

Ru—S1	2.3739 (12)	C55—C54	1.369 (7)
Ru—S2	2.4502 (12)	C54—C53	1.335 (6)
Ru—P1	2.2819 (16)	C53—C52	1.385 (5)
Ru—P2	2.2775 (10)	P2—C61	1.838 (3)
Ru—N1	2.141 (3)	C61—C62	1.370 (5)
Ru—N2	2.129 (3)	C61—C66	1.376 (5)
S1—O1	1.365 (8)	C62—C63	1.392 (6)
S1—O2	1.468 (8)	C63—C64	1.343 (7)
S1—C12	1.767 (4)	C64—C65	1.374 (7)
P1—C1	1.829 (3)	C65—C66	1.389 (6)
C2—C1	1.529 (5)	C3—H3A	0.9700
C3—C2	1.528 (5)	C3—H3B	0.9700
P2—C3	1.842 (3)	C2—H2A	0.9700
N1—C12	1.341 (4)	C2—H2B	0.9700
N1—C16	1.337 (4)	C1—H1A	0.9700
C16—C15	1.377 (5)	C1—H1B	0.9700
C15—C14	1.377 (6)	C56—H56	0.9300
C14—C13	1.372 (6)	C55—H55	0.9300
C13—C12	1.393 (5)	C54—H54	0.9300
S2—C26	1.744 (4)	C53—H53	0.9300
N2—C22	1.342 (4)	C52—H52	0.9300
N2—C26	1.348 (4)	C62—H62	0.9300
C22—C23	1.370 (5)	C63—H63	0.9300
C23—C24	1.369 (6)	C64—H64	0.9300
C24—C25	1.365 (6)	C65—H65	0.9300
C25—C26	1.397 (5)	C66—H66	0.9300
P1—C31	1.846 (3)	C36—H36	0.9300
C31—C32	1.391 (5)	C35—H35	0.9300
C31—C36	1.372 (5)	C34—H34	0.9300
C36—C35	1.401 (5)	C33—H33	0.9300
C35—C34	1.366 (6)	C32—H32	0.9300
C34—C33	1.365 (6)	C46—H46	0.9300
C33—C32	1.380 (5)	C45—H45	0.9300
P1—C41	1.837 (3)	C44—H44	0.9300
C41—C42	1.390 (5)	C43—H43	0.9300
C41—C46	1.381 (5)	C42—H42	0.9300
C46—C45	1.392 (5)	C22—H22	0.9300
C45—C44	1.378 (6)	C23—H23	0.9300
C44—C43	1.369 (6)	C24—H24	0.9300
C43—C42	1.386 (6)	C25—H25	0.9300
P2—C51	1.834 (3)	C16—H16	0.9300
C51—C52	1.372 (5)	C15—H15	0.9300
C51—C56	1.386 (5)	C14—H14	0.9300
C56—C55	1.379 (6)	C13—H13	0.9300
N2—Ru—N1	85.12 (11)	C62—C61—C66	118.1 (4)
N2—Ru—P2	172.37 (7)	C62—C61—P2	123.3 (3)
N1—Ru—P2	92.43 (8)	C66—C61—P2	118.5 (3)
N2—Ru—P1	93.59 (8)	C61—C62—C63	121.3 (4)
N1—Ru—P1	163.70 (8)	C64—C63—C62	120.0 (5)
P2—Ru—P1	90.78 (5)	C63—C64—C65	120.0 (5)
N2—Ru—S1	95.72 (8)	C64—C65—C66	120.1 (5)
N1—Ru—S1	67.45 (8)	C61—C66—C65	120.5 (4)
P2—Ru—S1	89.98 (4)	C2—C3—H3A	108.9
P1—Ru—S1	96.60 (5)	P2—C3—H3A	108.9
N2—Ru—S2	66.89 (8)	C2—C3—H3B	108.9
N1—Ru—S2	90.88 (8)	P2—C3—H3B	108.9
P2—Ru—S2	105.99 (4)	H3A—C3—H3B	107.7
P1—Ru—S2	103.57 (5)	C3—C2—H2A	108.8
S1—Ru—S2	153.87 (4)	C1—C2—H2A	108.8
O1—S1—O2	119.1 (5)	C3—C2—H2B	108.8
O1—S1—C12	111.5 (4)	C1—C2—H2B	108.8
O2—S1—C12	103.2 (4)	H2A—C2—H2B	107.7
O1—S1—Ru	118.9 (3)	C2—C1—P1	113.1 (2)
O2—S1—Ru	113.8 (3)	C2—C1—H1A	109.0
C12—S1—Ru	82.50 (12)	P1—C1—H1A	109.0
C26—S2—Ru	80.46 (11)	C2—C1—H1B	109.0
C1—P1—C41	102.86 (16)	P1—C1—H1B	109.0
C1—P1—C31	101.85 (16)	H1A—C1—H1B	107.8
C41—P1—C31	101.50 (15)	C55—C56—H56	120.0
C1—P1—Ru	110.61 (12)	C51—C56—H56	120.0
C41—P1—Ru	111.48 (11)	C54—C55—H55	119.5
C31—P1—Ru	125.89 (12)	C56—C55—H55	119.5
C51—P2—C61	99.91 (16)	C53—C54—H54	120.3
C51—P2—C3	101.19 (17)	C55—C54—H54	120.3
C61—P2—C3	102.56 (16)	C54—C53—H53	119.6
C51—P2—Ru	119.60 (11)	C52—C53—H53	119.6
C61—P2—Ru	114.40 (12)	C51—C52—H52	119.4
C3—P2—Ru	116.46 (12)	C53—C52—H52	119.4
C16—N1—C12	119.1 (3)	C61—C62—H62	119.3
C16—N1—Ru	138.0 (2)	C63—C62—H62	119.3
C12—N1—Ru	102.9 (2)	C64—C63—H63	120.0
C22—N2—C26	119.6 (3)	C62—C63—H63	120.0
C22—N2—Ru	137.5 (2)	C63—C64—H64	120.0
C26—N2—Ru	102.9 (2)	C65—C64—H64	120.0
C2—C1—P1	113.1 (2)	C64—C65—H65	120.0
C3—C2—C1	113.6 (3)	C66—C65—H65	120.0
C2—C3—P2	113.3 (2)	C61—C66—H66	119.8
N1—C12—C13	121.7 (3)	C65—C66—H66	119.8
N1—C12—S1	107.2 (2)	C31—C36—H36	119.5
C13—C12—S1	131.2 (3)	C35—C36—H36	119.5
C14—C13—C12	118.2 (4)	C34—C35—H35	119.9
C13—C14—C15	120.2 (4)	C36—C35—H35	119.9
C14—C15—C16	118.5 (4)	C33—C34—H34	120.4
N1—C16—C15	122.2 (4)	C35—C34—H34	120.4
N2—C22—C23	121.3 (4)	C34—C33—H33	119.5
C24—C23—C22	119.3 (4)	C32—C33—H33	119.5
C25—C24—C23	120.4 (4)	C33—C32—H32	119.6
C24—C25—C26	118.3 (4)	C31—C32—H32	119.6
N2—C26—C25	121.0 (3)	C41—C46—H46	119.7
N2—C26—S2	109.6 (2)	C45—C46—H46	119.7
C25—C26—S2	129.3 (3)	C44—C45—H45	120.0
C36—C31—C32	117.6 (3)	C46—C45—H45	120.0
C36—C31—P1	120.1 (3)	C43—C44—H44	120.2
C32—C31—P1	122.3 (3)	C45—C44—H44	120.2
C33—C32—C31	120.8 (4)	C44—C43—H43	119.8
C34—C33—C32	121.1 (4)	C42—C43—H43	119.8
C33—C34—C35	119.2 (4)	C43—C42—H42	119.7
C34—C35—C36	120.2 (4)	C41—C42—H42	119.7
C31—C36—C35	121.1 (4)	N2—C22—H22	119.3
C46—C41—C42	118.5 (3)	C23—C22—H22	119.3
C46—C41—P1	121.2 (3)	C24—C23—H23	120.3
C42—C41—P1	120.0 (3)	C22—C23—H23	120.3
C43—C42—C41	120.6 (4)	C25—C24—H24	119.8
C44—C43—C42	120.5 (4)	C23—C24—H24	119.8
C43—C44—C45	119.7 (4)	C24—C25—H25	120.8
C44—C45—C46	120.1 (4)	C26—C25—H25	120.8
C41—C46—C45	120.7 (4)	N1—C16—H16	118.9
C52—C51—C56	117.6 (3)	C15—C16—H16	118.9
C52—C51—P2	120.8 (3)	C14—C15—H15	120.7
C56—C51—P2	121.5 (3)	C16—C15—H15	120.7
C51—C52—C53	121.2 (4)	C13—C14—H14	119.9
C54—C53—C52	120.8 (4)	C15—C14—H14	119.9
C53—C54—C55	119.3 (4)	C14—C13—H13	120.9
C54—C55—C56	121.0 (5)	C12—C13—H13	120.9
C55—C56—C51	120.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C53—H53···O1^i	0.93	2.32	3.065 (8)	137

Symmetry code: (i) x, y+1, z.