Chloro([eta]⁶-p-cymene)(2-methyl-5-oxo-7-phenyl-5,6-di­hydro-2H-1,2,4-triaz­epine-3-thiol­ato-[kappa]²N⁴,S)­ruthenium(II)

The novel title ruthenium(II) complex, [RuCl(C₁₀H₁₄)(C₁₀H₁₀N₃OS)], was synthesized from the reaction of 1,2,4-triazepine, a new class of bidentate ligands, with [Ru(p-cymene)Cl₂]₂. The 1,2,4-triazepine ligand is coordinated to the metal centre through the N-4 and S atoms, forming a four-membered chelate ring. This is the first structural example of a transition metal complex containing a 1,2,4-triazepine ligand.

S1. Comment

Heterocylic compounds have found widespread application in both pharmacology as active drugs (Pauwels et al., 1990; Koop et al., 1991) and chemistry as useful reaction intermediates in organic synthesis (Anderson & Raju, 1989; Steinmeyer & Neef, 1992). They are also good ligands which coordinate readily with transition metals to provide versatile and useful complexes (Ghosh et al., 1998; Wills, 1998; Shi et al., 1999). However, the preparation of transition metal complexes with 1,2,4-tiazepines as ligands is not well documented. This can probably be ascribed to the difficulty of synthesis of these heterocycles and to the triazepine nucleus instability (Ait Itto et al., 1997).

In the course of our research on transition metal complexes (El Firdoussi et al., 1993, 1997; Abouhamza et al., 1999), we report here the crystal structure of a new triazepine based ruthenium(II) complex, namely Chloro(η⁶-p-cymene)(2-methyl-5-oxo-7-phenyl-5,6-dihydro-2H-1,2,4-triazepin- 3-thiolato-κ²N⁴,S)ruthenium(II), (II). This kind of complex which has a great conformational rigidity could lead to catalysts of high selectivity. The title compound was prepared by reaction in 2-propanol of the 1,2,4-triazepine (I) with [Ru(p-cymene)Cl₂]₂ in the presence of triethylamine. Crystals were isolated and characterized by X-ray diffraction. Various complexes of the type [Ru(arene)(heteroatomic ligand)Cl] have been crystallographically characterized (Nishiyama et al., 1989; Suzuki et al., 1996).

Complex (II) is, to the best of our knowledge, the first structural example of a transition metal complex containing a 1,2,4-triazepine ligand. The latter acts as a bidentate ligand (through N1 and S1), forming a four-membered chelate ring. The p-cymene and Cl ligands complete the coordination sphere of the Ru^II atom.

The crystal structure has two similar molecules in its asymmetric unit pseudo-centrosymmetrically arranged, but no additional crystallographic symmetry was found (Le Page, 1987, 1988). Both molecules have the same arrangement and have very close geometries. Average distances involving ruthenium coordination: Ru—N 2.097 (8), Ru—Cl 2.404 (2), Ru—S 2.438 (3) and Ru–centroid 1.67 (1) Å. Average angles involving ruthenium coordination: N—Ru—Cl 85.9 (2), Cl—Ru—S 82.08 (9), N—Ru—S 66.8 (2), N—Ru—centroid 133.0 (3), S—Ru—centroid 135.3 (3) and Cl—Ru—centroid 128.3 (3)°.

S2. Experimental

Complex (II) was prepared by reaction of [Ru(p-cymene)Cl₂]₂, 1,2,4-triazepine (I) and triethyamine (molar ratio 1:4:8) in 2-propanol at 353 K. The resulting solid was filtered off and recrystallized from CHCl₃.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL (Otwinowski & Minor, 1997); data reduction: HKL; program(s) used to solve structure: DIRDIF92 (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1992); software used to prepare material for publication: SHELXL97.

Chloro(η⁶-p-cymene)(2-methyl-5-oxo-7-phenyl-5,6-dihydro-2H-1,2,4-triazepin- 3-thiolato-κ²N⁴,S)ruthenium

Crystal data

[RuCl(C10H14)(C10H11N3OS)]	F(000) = 2048
Mr = 503.01	Dx = 1.592 Mg m^−3
Monoclinic, Cc	Cu Kα radiation, λ = 1.54184 Å
a = 20.647 (2) Å	Cell parameters from 8671 reflections
b = 11.835 (1) Å	θ = 4.3–68.2°
c = 17.275 (2) Å	µ = 8.28 mm^−1
β = 96.253 (5)°	T = 293 K
V = 4196.2 (7) Å^3	Prismatic, colourless
Z = 8	0.7 × 0.2 × 0.2 mm

Data collection

Nonius KappaCCD diffractometer	5007 independent reflections
Radiation source: fine-focus sealed tube	4791 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 9.43 pixels mm^-1	θmax = 68.2°, θmin = 4.3°
ω scans	h = −24→23
Absorption correction: empirical (using intensity measurements) (using ΔF; Parkin et al., 1995)	k = 0→14
Tmin = 0.050, Tmax = 0.189	l = −20→20
8671 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.119	Calculated w = 1/[σ^2(Fo^2) + (0.0718P)^2 + 9.2057P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
5007 reflections	Δρmax = 0.95 e Å^−3
584 parameters	Δρmin = −0.80 e Å^−3
2 restraints	Absolute structure: Flack (1983), Friedel pairs merged
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.467 (14)

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. 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
Ru1	0.50133 (3)	0.33202 (5)	0.49972 (4)	0.0267 (2)
Cl1	0.41055 (12)	0.2478 (3)	0.42157 (16)	0.0529 (7)
S1	0.45099 (11)	0.25636 (19)	0.61058 (15)	0.0352 (6)
O1	0.4188 (4)	0.5740 (6)	0.4445 (4)	0.0504 (19)
N1	0.4322 (4)	0.4410 (7)	0.5401 (5)	0.0298 (18)
N2	0.3796 (4)	0.4311 (7)	0.6584 (5)	0.042 (2)
N3	0.3766 (4)	0.5476 (7)	0.6740 (5)	0.0357 (19)
C1	0.4149 (5)	0.3884 (8)	0.6036 (6)	0.028 (2)
C2	0.3602 (4)	0.6116 (7)	0.6172 (6)	0.030 (2)
C3	0.3393 (5)	0.5683 (9)	0.5373 (6)	0.039 (2)
H31	0.3156	0.6238	0.5040	0.073 (7)*
H32	0.3113	0.5032	0.5415	0.073 (7)*
C4	0.3998 (4)	0.5286 (8)	0.5021 (6)	0.034 (2)
C5	0.3667 (4)	0.7351 (9)	0.6349 (6)	0.033 (2)
C6	0.3658 (5)	0.8144 (9)	0.5742 (7)	0.039 (3)
H6	0.3605	0.7910	0.5226	0.02 (2)*
C7	0.3732 (5)	0.9289 (10)	0.5927 (7)	0.045 (3)
H7	0.3729	0.9817	0.5528	0.04 (3)*
C8	0.3806 (5)	0.9640 (9)	0.6671 (8)	0.049 (3)
H8	0.3846	1.0408	0.6780	0.04 (3)*
C9	0.3824 (6)	0.8884 (10)	0.7269 (8)	0.047 (3)
H9	0.388 (5)	0.904 (8)	0.783 (7)	0.04 (3)*
C10	0.3746 (5)	0.7731 (10)	0.7108 (7)	0.042 (3)
H10	0.375 (7)	0.737 (13)	0.743 (8)	0.073 (7)*
C11	0.3645 (6)	0.3589 (11)	0.7235 (8)	0.055 (3)
H111	0.3250	0.3594	0.7262	0.073 (7)*
H112	0.3865	0.3874	0.7713	0.073 (7)*
H113	0.3784	0.2828	0.7155	0.073 (7)*
C12	0.6004 (5)	0.3370 (7)	0.5571 (6)	0.028 (2)
C13	0.5937 (4)	0.2431 (8)	0.5065 (6)	0.030 (2)
H13	0.610 (7)	0.186 (11)	0.534 (8)	0.073 (7)*
C14	0.5701 (5)	0.2546 (9)	0.4290 (7)	0.037 (2)
H14	0.5617	0.2221	0.3799	0.05 (3)*
C15	0.5529 (5)	0.3660 (10)	0.3963 (7)	0.040 (2)
C16	0.5609 (5)	0.4553 (10)	0.4461 (6)	0.041 (3)
H16	0.5542	0.5185	0.4141	0.07 (4)*
C17	0.5813 (5)	0.4423 (10)	0.5276 (7)	0.040 (3)
H17	0.5893	0.5154	0.5460	0.073 (7)*
C18	0.6256 (5)	0.3143 (10)	0.6420 (6)	0.040 (3)
H18	0.5973	0.2538	0.6574	0.04 (3)*
C19	0.6998 (5)	0.3028 (12)	0.6462 (7)	0.058 (3)
H191	0.7147	0.3556	0.6230	0.073 (7)*
H192	0.7102	0.2327	0.6224	0.073 (7)*
H193	0.7183	0.3032	0.6997	0.073 (7)*
C20	0.6073 (6)	0.4073 (10)	0.6964 (7)	0.058 (3)
H201	0.5740	0.4390	0.6771	0.073 (7)*
H202	0.6423	0.4610	0.7032	0.073 (7)*
H203	0.6000	0.3763	0.7461	0.073 (7)*
C21	0.5247 (7)	0.3805 (12)	0.3124 (7)	0.059 (3)
H211	0.4909	0.4173	0.3107	0.10 (6)*
H212	0.5154	0.3075	0.2897	0.11 (6)*
H213	0.5552	0.4193	0.2837	0.13 (7)*
Ru2	−0.39153 (3)	0.09821 (5)	0.04224 (3)	0.0262 (2)
Cl2	−0.29934 (12)	0.0401 (3)	0.13026 (17)	0.0600 (8)
S2	−0.33700 (12)	0.0103 (2)	−0.05997 (15)	0.0374 (6)
O2	−0.3221 (4)	0.3533 (6)	0.0808 (4)	0.0482 (18)
N21	−0.3269 (4)	0.2078 (7)	−0.0056 (5)	0.0278 (17)
N22	−0.2641 (4)	0.1774 (6)	−0.1137 (5)	0.034 (2)
N23	−0.2616 (4)	0.2893 (7)	−0.1375 (5)	0.0343 (19)
C31	−0.3042 (5)	0.1443 (8)	−0.0587 (6)	0.029 (2)
C32	−0.2502 (4)	0.3664 (9)	−0.0853 (5)	0.035 (2)
C33	−0.2357 (5)	0.3394 (8)	−0.0008 (6)	0.036 (2)
H331	−0.2096	0.2725	0.0119	0.02 (2)*
H332	−0.2200	0.3994	0.0346	0.05 (3)*
C34	−0.2970 (4)	0.3052 (8)	0.0298 (6)	0.033 (2)
C35	−0.2544 (4)	0.4866 (8)	−0.1106 (6)	0.034 (2)
C36	−0.2631 (5)	0.5740 (10)	−0.0608 (7)	0.045 (3)
H36	−0.2640	0.5624	−0.0077	0.08 (4)*
C37	−0.2694 (5)	0.6847 (11)	−0.0881 (10)	0.056 (4)
H37	−0.2886	0.7066	−0.0442	0.16 (10)*
C38	−0.2675 (6)	0.7076 (12)	−0.1650 (9)	0.062 (4)
H38	−0.2788	0.7780	−0.1862	0.073 (7)*
C39	−0.2572 (6)	0.6224 (11)	−0.2162 (8)	0.054 (3)
H39	−0.2643	0.6558	−0.2651	0.06 (3)*
C40	−0.2513 (5)	0.5113 (10)	−0.1917 (6)	0.046 (3)
H40	−0.2508	0.4548	−0.2290	0.03 (2)*
C41	−0.2441 (7)	0.0992 (11)	−0.1707 (8)	0.061 (4)
H411	−0.2251	0.1402	−0.2105	0.073 (7)*
H412	−0.2813	0.0579	−0.1937	0.073 (7)*
H413	−0.2126	0.0474	−0.1458	0.073 (7)*
C42	−0.4880 (5)	0.1199 (10)	−0.0234 (6)	0.032 (2)
C43	−0.4680 (5)	0.0066 (9)	0.0972 (7)	0.040 (3)
H43	−0.4610	−0.0571	0.1285	0.04 (3)*
C44	−0.4862 (4)	0.0135 (9)	0.0163 (6)	0.036 (2)
H44	−0.4930	−0.0569	−0.0071	0.073 (7)*
C45	−0.4505 (5)	0.1044 (8)	0.1422 (6)	0.037 (3)
C46	−0.4716 (5)	0.2171 (8)	0.0207 (6)	0.036 (2)
H46	−0.4711	0.2870	−0.0037	0.073 (7)*
C47	−0.4536 (5)	0.2095 (11)	0.1040 (7)	0.044 (3)
H47	−0.4369	0.2710	0.1332	0.06 (4)*
C48	−0.5075 (5)	0.1226 (9)	−0.1103 (6)	0.040 (2)
H48	−0.5015	0.0468	−0.1311	0.073 (7)*
C49	−0.5824 (5)	0.1299 (11)	−0.1259 (7)	0.057 (3)
H491	−0.5978	0.1914	−0.0966	0.073 (7)*
H492	−0.6013	0.0605	−0.1104	0.073 (7)*
H493	−0.5947	0.1425	−0.1804	0.073 (7)*
C50	−0.4772 (6)	0.2195 (12)	−0.1507 (7)	0.065 (3)
H501	−0.4326	0.2284	−0.1294	0.073 (7)*
H502	−0.5007	0.2879	−0.1428	0.073 (7)*
H503	−0.4791	0.2040	−0.2054	0.073 (7)*
C51	−0.4297 (7)	0.0938 (12)	0.2274 (7)	0.060 (4)
H511	−0.3839	0.1087	0.2374	0.08 (5)*
H512	−0.4386	0.0186	0.2443	0.20 (11)*
H513	−0.4533	0.1472	0.2554	0.14 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.0262 (3)	0.0247 (4)	0.0291 (4)	0.0012 (3)	0.0028 (3)	−0.0014 (3)
Cl1	0.0382 (13)	0.076 (2)	0.0432 (16)	−0.0151 (12)	0.0005 (11)	−0.0119 (13)
S1	0.0377 (12)	0.0289 (13)	0.0401 (15)	0.0047 (9)	0.0086 (11)	0.0075 (10)
O1	0.066 (5)	0.047 (5)	0.041 (5)	0.021 (4)	0.018 (4)	0.018 (4)
N1	0.038 (4)	0.025 (4)	0.029 (5)	0.002 (3)	0.013 (4)	0.001 (3)
N2	0.046 (5)	0.033 (5)	0.046 (6)	0.004 (4)	0.007 (5)	0.010 (4)
N3	0.036 (4)	0.039 (5)	0.032 (5)	0.007 (4)	0.007 (3)	0.001 (4)
C1	0.033 (5)	0.031 (6)	0.021 (5)	0.004 (4)	0.004 (4)	0.003 (4)
C2	0.029 (4)	0.032 (5)	0.031 (5)	0.011 (4)	0.010 (4)	−0.001 (4)
C3	0.039 (5)	0.035 (6)	0.041 (6)	0.008 (4)	−0.008 (4)	−0.006 (4)
C4	0.036 (5)	0.037 (6)	0.027 (6)	0.012 (4)	−0.003 (4)	−0.002 (4)
C5	0.027 (4)	0.044 (6)	0.030 (6)	0.013 (4)	0.001 (4)	−0.002 (4)
C6	0.031 (5)	0.045 (7)	0.041 (7)	0.005 (4)	0.002 (5)	0.008 (5)
C7	0.031 (5)	0.038 (7)	0.068 (9)	0.011 (4)	0.016 (5)	0.009 (6)
C8	0.046 (6)	0.031 (7)	0.071 (9)	−0.003 (5)	0.006 (6)	−0.005 (5)
C9	0.056 (7)	0.045 (7)	0.041 (8)	−0.001 (5)	0.012 (6)	−0.005 (5)
C10	0.034 (5)	0.043 (7)	0.049 (8)	0.002 (5)	0.003 (5)	0.008 (5)
C11	0.069 (8)	0.048 (7)	0.055 (8)	0.020 (6)	0.038 (6)	0.020 (6)
C12	0.024 (4)	0.028 (6)	0.033 (6)	−0.001 (4)	0.002 (4)	−0.005 (4)
C13	0.023 (4)	0.025 (5)	0.042 (6)	0.003 (4)	0.008 (4)	0.003 (4)
C14	0.041 (5)	0.031 (6)	0.037 (6)	−0.005 (4)	0.001 (5)	−0.002 (5)
C15	0.043 (6)	0.034 (6)	0.043 (7)	−0.002 (5)	0.008 (5)	0.005 (5)
C16	0.044 (6)	0.040 (7)	0.039 (7)	−0.003 (5)	−0.001 (5)	0.010 (5)
C17	0.026 (5)	0.044 (7)	0.052 (8)	−0.012 (5)	0.010 (5)	−0.002 (5)
C18	0.036 (5)	0.051 (7)	0.035 (6)	−0.012 (5)	0.004 (5)	−0.003 (5)
C19	0.046 (6)	0.086 (9)	0.038 (7)	0.010 (6)	−0.011 (5)	−0.005 (6)
C20	0.062 (8)	0.072 (9)	0.039 (7)	0.003 (6)	0.003 (6)	−0.017 (5)
C21	0.060 (8)	0.070 (9)	0.047 (8)	−0.006 (7)	0.002 (6)	0.013 (6)
Ru2	0.0265 (3)	0.0255 (4)	0.0269 (4)	−0.0008 (3)	0.0037 (3)	0.0019 (3)
Cl2	0.0378 (13)	0.091 (2)	0.0508 (18)	0.0139 (14)	0.0010 (12)	0.0214 (15)
S2	0.0424 (13)	0.0289 (13)	0.0432 (16)	−0.0053 (10)	0.0148 (12)	−0.0066 (10)
O2	0.054 (4)	0.051 (5)	0.040 (4)	−0.008 (4)	0.010 (4)	−0.014 (4)
N21	0.031 (4)	0.028 (4)	0.025 (4)	−0.003 (3)	0.006 (3)	−0.003 (3)
N22	0.035 (4)	0.033 (5)	0.036 (5)	−0.005 (3)	0.014 (4)	−0.005 (4)
N23	0.043 (4)	0.035 (5)	0.026 (5)	−0.009 (4)	0.011 (3)	0.000 (3)
C31	0.030 (5)	0.025 (5)	0.033 (6)	0.003 (4)	0.009 (5)	−0.005 (4)
C32	0.028 (5)	0.047 (6)	0.028 (6)	−0.008 (4)	0.000 (4)	−0.003 (4)
C33	0.035 (5)	0.028 (6)	0.042 (7)	−0.001 (4)	−0.005 (4)	−0.011 (4)
C34	0.037 (5)	0.030 (5)	0.030 (6)	0.007 (4)	−0.003 (5)	0.000 (4)
C35	0.027 (4)	0.038 (6)	0.037 (6)	−0.013 (4)	0.003 (4)	0.003 (4)
C36	0.035 (5)	0.054 (7)	0.046 (8)	−0.006 (5)	0.006 (5)	0.000 (6)
C37	0.034 (6)	0.045 (8)	0.089 (12)	−0.007 (5)	0.011 (7)	0.007 (7)
C38	0.041 (6)	0.059 (9)	0.084 (12)	−0.006 (6)	−0.006 (6)	0.014 (8)
C39	0.058 (7)	0.058 (8)	0.043 (8)	−0.009 (6)	0.002 (6)	0.012 (6)
C40	0.053 (6)	0.049 (7)	0.035 (7)	−0.020 (5)	0.006 (5)	0.010 (5)
C41	0.065 (8)	0.078 (10)	0.045 (8)	−0.022 (6)	0.038 (7)	−0.017 (6)
C42	0.024 (5)	0.049 (6)	0.025 (6)	−0.007 (4)	0.010 (4)	0.002 (4)
C43	0.039 (5)	0.034 (6)	0.048 (7)	0.004 (4)	0.015 (5)	0.011 (5)
C44	0.031 (5)	0.035 (6)	0.038 (6)	−0.002 (4)	−0.013 (4)	−0.002 (4)
C45	0.034 (5)	0.043 (7)	0.031 (6)	−0.005 (4)	−0.006 (4)	0.008 (4)
C46	0.040 (5)	0.024 (6)	0.043 (7)	0.001 (4)	−0.003 (5)	0.011 (4)
C47	0.034 (5)	0.045 (7)	0.054 (8)	0.007 (5)	0.014 (5)	−0.008 (6)
C48	0.051 (6)	0.034 (6)	0.037 (6)	0.008 (5)	0.003 (5)	0.001 (5)
C49	0.048 (6)	0.067 (8)	0.052 (8)	0.004 (6)	−0.015 (6)	−0.003 (6)
C50	0.072 (8)	0.091 (10)	0.029 (7)	−0.001 (7)	−0.001 (6)	0.020 (6)
C51	0.068 (8)	0.090 (11)	0.020 (6)	−0.002 (7)	0.004 (6)	0.008 (6)

Geometric parameters (Å, º)

Ru1—N1	2.099 (8)	Ru2—N21	2.095 (8)
Ru1—C17	2.119 (10)	Ru2—C46	2.171 (9)
Ru1—C13	2.171 (9)	Ru2—C47	2.194 (11)
Ru1—C14	2.174 (12)	Ru2—C42	2.196 (10)
Ru1—C12	2.174 (9)	Ru2—C44	2.199 (9)
Ru1—C16	2.180 (11)	Ru2—C43	2.213 (11)
Ru1—C15	2.214 (12)	Ru2—C45	2.219 (12)
Ru1—Cl1	2.404 (2)	Ru2—Cl2	2.404 (2)
Ru1—S1	2.446 (3)	Ru2—S2	2.429 (3)
S1—C1	1.731 (10)	S2—C31	1.724 (10)
O1—C4	1.230 (12)	O2—C34	1.212 (12)
N1—C1	1.342 (13)	N21—C31	1.310 (13)
N1—C4	1.364 (12)	N21—C34	1.415 (12)
N2—C1	1.354 (14)	N22—C31	1.383 (14)
N2—N3	1.406 (12)	N22—N23	1.391 (11)
N2—C11	1.473 (14)	N22—C41	1.444 (14)
N3—C2	1.257 (12)	N23—C32	1.287 (12)
C2—C3	1.492 (14)	C32—C35	1.488 (14)
C2—C5	1.496 (14)	C32—C33	1.492 (14)
C3—C4	1.522 (14)	C33—C34	1.481 (14)
C3—H31	0.9697	C33—H331	0.9688
C3—H32	0.9702	C33—H332	0.9694
C5—C10	1.378 (16)	C35—C36	1.371 (16)
C5—C6	1.406 (14)	C35—C40	1.438 (15)
C6—C7	1.396 (15)	C36—C37	1.394 (17)
C6—H6	0.9300	C36—H36	0.9300
C7—C8	1.344 (16)	C37—C38	1.36 (2)
C7—H7	0.9300	C37—H37	0.9305
C8—C9	1.364 (17)	C38—C39	1.37 (2)
C8—H8	0.9300	C38—H38	0.9299
C9—C10	1.398 (17)	C39—C40	1.383 (16)
C9—H9	0.98 (11)	C39—H39	0.9301
C10—H10	0.70 (14)	C40—H40	0.9300
C11—H111	0.8200	C41—H411	0.9600
C11—H112	0.9600	C41—H412	0.9600
C11—H113	0.9600	C41—H413	0.9600
C12—C17	1.387 (15)	C42—C46	1.401 (15)
C12—C13	1.412 (13)	C42—C44	1.432 (15)
C12—C18	1.525 (16)	C42—C48	1.512 (16)
C13—C14	1.381 (15)	C43—C44	1.410 (15)
C13—H13	0.87 (13)	C43—C45	1.419 (15)
C14—C15	1.463 (15)	C43—H43	0.9299
C14—H14	0.9303	C44—H44	0.9298
C15—C16	1.361 (16)	C45—C47	1.406 (16)
C15—C21	1.511 (16)	C45—C51	1.494 (16)
C16—C17	1.434 (16)	C46—C47	1.448 (16)
C16—H16	0.9302	C46—H46	0.9301
C17—H17	0.9300	C47—H47	0.9297
C18—C20	1.522 (16)	C48—C50	1.513 (17)
C18—C19	1.532 (15)	C48—C49	1.543 (15)
C18—H18	0.9798	C48—H48	0.9794
C19—H191	0.8200	C49—H491	0.9600
C19—H192	0.9600	C49—H492	0.9600
C19—H193	0.9600	C49—H493	0.9600
C20—H201	0.8200	C50—H501	0.9600
C20—H202	0.9600	C50—H502	0.9600
C20—H203	0.9599	C50—H503	0.9600
C21—H211	0.8200	C51—H511	0.9600
C21—H212	0.9601	C51—H512	0.9600
C21—H213	0.9599	C51—H513	0.9600
N1—Ru1—C17	95.0 (4)	N21—Ru2—C46	92.1 (3)
N1—Ru1—C13	154.9 (3)	N21—Ru2—C47	104.6 (4)
C17—Ru1—C13	68.2 (4)	C46—Ru2—C47	38.8 (4)
N1—Ru1—C14	162.8 (3)	N21—Ru2—C42	107.7 (3)
C17—Ru1—C14	81.2 (4)	C46—Ru2—C42	37.4 (4)
C13—Ru1—C14	37.1 (4)	C47—Ru2—C42	68.7 (4)
N1—Ru1—C12	118.1 (3)	N21—Ru2—C44	142.4 (3)
C17—Ru1—C12	37.7 (4)	C46—Ru2—C44	67.5 (4)
C13—Ru1—C12	37.9 (3)	C47—Ru2—C44	79.6 (4)
C14—Ru1—C12	68.2 (4)	C42—Ru2—C44	38.0 (4)
N1—Ru1—C16	99.6 (3)	N21—Ru2—C43	171.1 (4)
C17—Ru1—C16	38.9 (4)	C46—Ru2—C43	79.9 (4)
C13—Ru1—C16	79.3 (4)	C47—Ru2—C43	66.6 (5)
C14—Ru1—C16	67.0 (4)	C42—Ru2—C43	68.3 (4)
C12—Ru1—C16	68.2 (4)	C44—Ru2—C43	37.3 (4)
N1—Ru1—C15	124.1 (4)	N21—Ru2—C45	135.5 (3)
C17—Ru1—C15	68.9 (4)	C46—Ru2—C45	68.9 (4)
C13—Ru1—C15	68.6 (4)	C47—Ru2—C45	37.1 (4)
C14—Ru1—C15	38.9 (4)	C42—Ru2—C45	81.6 (4)
C12—Ru1—C15	81.5 (4)	C44—Ru2—C45	67.9 (4)
C16—Ru1—C15	36.1 (4)	C43—Ru2—C45	37.3 (4)
N1—Ru1—Cl1	85.7 (2)	N21—Ru2—Cl2	86.1 (2)
C17—Ru1—Cl1	157.5 (3)	C46—Ru2—Cl2	146.0 (3)
C13—Ru1—Cl1	117.1 (3)	C47—Ru2—Cl2	109.2 (3)
C14—Ru1—Cl1	91.5 (3)	C42—Ru2—Cl2	166.1 (3)
C12—Ru1—Cl1	154.8 (2)	C44—Ru2—Cl2	128.6 (3)
C16—Ru1—Cl1	118.7 (3)	C43—Ru2—Cl2	98.1 (3)
C15—Ru1—Cl1	92.1 (3)	C45—Ru2—Cl2	88.9 (3)
N1—Ru1—S1	66.5 (2)	N21—Ru2—S2	67.2 (2)
C17—Ru1—S1	115.8 (3)	C46—Ru2—S2	123.9 (3)
C13—Ru1—S1	103.1 (3)	C47—Ru2—S2	162.2 (3)
C14—Ru1—S1	130.2 (3)	C42—Ru2—S2	98.1 (3)
C12—Ru1—S1	96.4 (3)	C44—Ru2—S2	97.4 (3)
C16—Ru1—S1	152.3 (3)	C43—Ru2—S2	120.7 (3)
C15—Ru1—S1	168.8 (3)	C45—Ru2—S2	156.4 (3)
Cl1—Ru1—S1	85.19 (9)	Cl2—Ru2—S2	86.53 (10)
C1—S1—Ru1	80.3 (4)	C31—S2—Ru2	79.0 (3)
C1—N1—C4	125.9 (8)	C31—N21—C34	126.7 (8)
C1—N1—Ru1	103.8 (6)	C31—N21—Ru2	102.3 (6)
C4—N1—Ru1	128.5 (7)	C34—N21—Ru2	126.9 (7)
C1—N2—N3	122.5 (8)	C31—N22—N23	121.1 (8)
C1—N2—C11	119.5 (9)	C31—N22—C41	121.6 (8)
N3—N2—C11	113.9 (9)	N23—N22—C41	112.7 (9)
C2—N3—N2	117.1 (8)	C32—N23—N22	118.5 (8)
N1—C1—N2	127.6 (8)	N21—C31—N22	127.2 (9)
N1—C1—S1	108.9 (7)	N21—C31—S2	111.5 (7)
N2—C1—S1	123.3 (7)	N22—C31—S2	121.0 (7)
N3—C2—C3	122.7 (9)	N23—C32—C35	118.1 (9)
N3—C2—C5	114.8 (8)	N23—C32—C33	122.4 (9)
C3—C2—C5	122.4 (8)	C35—C32—C33	119.5 (8)
C2—C3—C4	108.0 (7)	C34—C33—C32	108.6 (7)
C2—C3—H31	113.1	C34—C33—H331	99.9
C4—C3—H31	110.8	C32—C33—H331	116.4
C2—C3—H32	108.6	C34—C33—H332	102.5
C4—C3—H32	107.9	C32—C33—H332	118.5
H31—C3—H32	108.4	H331—C33—H332	108.4
O1—C4—N1	122.7 (9)	O2—C34—N21	119.8 (9)
O1—C4—C3	122.4 (8)	O2—C34—C33	125.6 (9)
N1—C4—C3	114.9 (9)	N21—C34—C33	114.7 (8)
C10—C5—C6	118.8 (10)	C36—C35—C40	118.7 (10)
C10—C5—C2	120.8 (9)	C36—C35—C32	123.0 (10)
C6—C5—C2	120.4 (9)	C40—C35—C32	118.3 (10)
C7—C6—C5	119.0 (11)	C35—C36—C37	120.7 (12)
C7—C6—H6	120.5	C35—C36—H36	121.8
C5—C6—H6	120.5	C37—C36—H36	117.5
C8—C7—C6	121.1 (11)	C38—C37—C36	120.4 (14)
C8—C7—H7	119.5	C38—C37—H37	143.3
C6—C7—H7	119.5	C36—C37—H37	91.0
C7—C8—C9	120.8 (11)	C37—C38—C39	120.4 (13)
C7—C8—H8	119.6	C37—C38—H38	122.0
C9—C8—H8	119.6	C39—C38—H38	117.1
C8—C9—C10	119.8 (11)	C38—C39—C40	121.1 (13)
C8—C9—H9	128 (5)	C38—C39—H39	104.7
C10—C9—H9	112 (5)	C40—C39—H39	133.0
C5—C10—C9	120.4 (10)	C39—C40—C35	118.7 (12)
C5—C10—H10	123 (10)	C39—C40—H40	118.6
C9—C10—H10	116 (10)	C35—C40—H40	122.2
N2—C11—H111	109.5	N22—C41—H411	109.5
N2—C11—H112	109.4	N22—C41—H412	109.5
H111—C11—H112	109.2	H411—C41—H412	109.5
N2—C11—H113	110.0	N22—C41—H413	109.5
H111—C11—H113	109.3	H411—C41—H413	109.5
H112—C11—H113	109.5	H412—C41—H413	109.5
C17—C12—C13	118.3 (10)	C46—C42—C44	118.0 (9)
C17—C12—C18	124.5 (9)	C46—C42—C48	123.1 (10)
C13—C12—C18	117.2 (8)	C44—C42—C48	118.9 (9)
C17—C12—Ru1	69.0 (6)	C46—C42—Ru2	70.3 (6)
C13—C12—Ru1	70.9 (5)	C44—C42—Ru2	71.1 (5)
C18—C12—Ru1	129.8 (7)	C48—C42—Ru2	130.1 (7)
C14—C13—C12	121.6 (9)	C44—C43—C45	121.3 (9)
C14—C13—Ru1	71.6 (6)	C44—C43—Ru2	70.8 (6)
C12—C13—Ru1	71.2 (5)	C45—C43—Ru2	71.5 (6)
C14—C13—H13	133 (9)	C44—C43—H43	129.2
C12—C13—H13	106 (9)	C45—C43—H43	109.2
Ru1—C13—H13	134 (9)	Ru2—C43—H43	124.9
C13—C14—C15	120.6 (9)	C43—C44—C42	121.0 (9)
C13—C14—Ru1	71.3 (6)	C43—C44—Ru2	71.9 (5)
C15—C14—Ru1	72.0 (6)	C42—C44—Ru2	70.9 (5)
C13—C14—H14	148.7	C43—C44—H44	112.9
C15—C14—H14	90.4	C42—C44—H44	125.8
Ru1—C14—H14	128.2	Ru2—C44—H44	125.9
C16—C15—C14	116.6 (10)	C47—C45—C43	118.0 (11)
C16—C15—C21	121.7 (11)	C47—C45—C51	122.0 (11)
C14—C15—C21	121.6 (11)	C43—C45—C51	120.0 (10)
C16—C15—Ru1	70.6 (7)	C47—C45—Ru2	70.5 (7)
C14—C15—Ru1	69.1 (6)	C43—C45—Ru2	71.1 (7)
C21—C15—Ru1	128.7 (8)	C51—C45—Ru2	129.9 (8)
C15—C16—C17	122.7 (10)	C42—C46—C47	120.7 (10)
C15—C16—Ru1	73.3 (7)	C42—C46—Ru2	72.3 (6)
C17—C16—Ru1	68.2 (6)	C47—C46—Ru2	71.5 (6)
C15—C16—H16	104.4	C42—C46—H46	119.8
C17—C16—H16	132.7	C47—C46—H46	119.5
Ru1—C16—H16	137.3	Ru2—C46—H46	127.5
C12—C17—C16	119.9 (11)	C45—C47—C46	120.9 (11)
C12—C17—Ru1	73.3 (6)	C45—C47—Ru2	72.4 (7)
C16—C17—Ru1	72.8 (6)	C46—C47—Ru2	69.8 (6)
C12—C17—H17	132.6	C45—C47—H47	116.3
C16—C17—H17	104.9	C46—C47—H47	122.0
Ru1—C17—H17	139.0	Ru2—C47—H47	122.1
C20—C18—C12	112.6 (9)	C42—C48—C50	113.3 (9)
C20—C18—C19	110.5 (9)	C42—C48—C49	109.2 (9)
C12—C18—C19	107.3 (9)	C50—C48—C49	109.5 (9)
C20—C18—H18	99.4	C42—C48—H48	108.3
C12—C18—H18	103.7	C50—C48—H48	116.8
C19—C18—H18	123.1	C49—C48—H48	98.7
C18—C19—H191	109.5	C48—C49—H491	109.5
C18—C19—H192	108.9	C48—C49—H492	109.5
H191—C19—H192	109.7	H491—C49—H492	109.5
C18—C19—H193	109.6	C48—C49—H493	109.5
H191—C19—H193	109.7	H491—C49—H493	109.5
H192—C19—H193	109.5	H492—C49—H493	109.5
C18—C20—H201	109.5	C48—C50—H501	109.5
C18—C20—H202	108.6	C48—C50—H502	109.5
H201—C20—H202	109.4	H501—C50—H502	109.5
C18—C20—H203	110.5	C48—C50—H503	109.5
H201—C20—H203	109.4	H501—C50—H503	109.5
H202—C20—H203	109.5	H502—C50—H503	109.5
C15—C21—H211	109.5	C45—C51—H511	109.5
C15—C21—H212	109.2	C45—C51—H512	109.5
H211—C21—H212	109.3	H511—C51—H512	109.5
C15—C21—H213	110.1	C45—C51—H513	109.5
H211—C21—H213	109.2	H511—C51—H513	109.5
H212—C21—H213	109.5	H512—C51—H513	109.5