Crystal structure of bis-[μ-(4-meth-oxy-phen-yl)methane-thiol-ato-κ(2) S:S]bis-[chlorido-(η(6)-1-isopropyl-4-methyl-benzene)-ruthenium(II)] chloro-form disolvate.

The mol-ecular structure of the title complex, [Ru2(C8H9OS)2Cl2(C10H14)2]·2CHCl3 or (p-MeC6H4Pr (i) )2Ru2(SCH2-p-C6H5-OCH3)2Cl2·2CHCl3, shows inversion symmetry. The two symmetry-related Ru(II) atoms are bridged by two 4-meth-oxy-α-toluene-thiol-ato [(4-meth-oxy-phen-yl)methane-thiol-ato] units. One chlorido ligand and the p-cymene ligand complete the typical piano-stool coordination environment of the Ru(II) atom. In the crystal, the CH moiety of the chloro-form mol-ecule inter-acts with the chlorido ligand of the dinuclear complex, while one Cl atom of the solvent inter-acts more weakly with the methyl group of the bridging 4-meth-oxy-α-toluene-thiol-ato unit. This assembly leads to the formation of supra-molecular chains extending parallel to [021].

Chemical context

Several series of dinuclear tri­thiol­ato arene ruthenium(II) complexes have been synthesized by our group in recent years (Gras et al., 2010 ▸; Giannini et al., 2011 ▸, 2013a ▸) and investigated for their potential as anti­cancer agents (Giannini et al., 2012 ▸). The in vitro studies showed the IC50 values of the chloride salts of these complexes to be regularly in the nanomolar range, being among the most active ruthenium complexes synthesized to date. The recent discovery of di­thiol­ato complexes (Ibao et al., 2012 ▸) opened new possibilities for the design of thiol­ato-bridged dinuclear arene ruthenium(II) complexes (Giannini et al., 2013b ▸). Herein we report the structure of a neutral di­thio­l­ato complex, p-MeC6H4Pr)2Ru2(SCH2-p-C6H5-OCH3)2Cl2 that crystallized as a chloro­form disolvate.

Structural commentary

The mol­ecular structure of the dinuclear title compound, [RuCl(C8H9OS)(C10H14)]2·2CHCl3, exhibits inversion symmetry and is presented in Fig. 1 ▸. The RuII atom adopts a typical piano-stool coordination geometry with the p-cymene ligand being bound facially, formally occupying three coord­ination sites. The other three positions are occupied by symmetry-related S atoms of two 4-meth­oxy-α-toluene­thiol­ato units and one chlorido ligand. The inter­atomic distances between Ru1 and the two symmetry-related S1 atoms are 2.3778 (10) and 2.3931 (10) Å, between Ru1 and Cl1 2.4284 (12) Å, and between S1 and C1 1.847 (3) Å. The Ru1—S1—Ru1i angle is 100.03 (4)° [symmetry code: (i) –x + 1, –y + 1, –z]. The distance between the metal atom and the associated ring centroid (C1–C6) is 1.684 Å. In agreement with the electronic count, there is no metal–metal bond, the Ru⋯Ru distance in the dinuclear complex mol­ecule being 3.6555 (9) Å.

Figure 1

The mol­ecular structures of the components in the structure of (p-MeC6H4Pr)2Ru2(SCH2-p-C6H5-OCH3)2Cl2·2CHCl3. Displacement ellipsoids are drawn at the 50% probability level.

Supra­molecular features

In the crystal packing of the title compound, the chlorido ligand of the complex inter­acts with the CH moiety of the chloro­form mol­ecule. Moreover, a more weak hydrogen-bonding inter­action is also observed between the meth­oxy group of the 4-meth­oxy-α-toluene­thiol­ato and a chlorine atom of the solvent mol­ecule (Table 1 ▸). These inter­actions give rise to the formation of supra­molecular chains extending parallel to [021] (Fig. 2 ▸).

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C9H9Cl1	0.98	2.66	3.583(4)	157
C8H8CCl4i	0.96	3.03	3.886(5)	150

Symmetry code: (i) .

Figure 2

The one dimensional supra­molecular network in the crystal packing of (p-MeC6H4Pr)2Ru2(SCH2-p-C6H5-OCH3)2Cl2·2CHCl3. Only the stronger of the C—H⋯Cl inter­actions is shown (dotted lines).

Synthesis and crystallization

The title complex was obtained from the reaction of 100 mg (0.163 mmol) of (p-MeC6H4Pr)2Ru2Cl4 and 50.3 µl (0.343 mmol) of 4-meth­oxy-α-toluene­thiol in ethanol. The solution was stirred at room temperature for 3 h, afterwards the solvent was reduced to 2 ml in vacuo and the product precipitated by adding hexane. The solid was filtered, washed with hexane and dried in vacuo. X-ray quality crystals were obtained by slow diffusion of diethyl ether into the solution of the title complex in chloro­form.

Yield: 124.2 mg (89%). C36H46Cl2O2Ru2S2: calculated C, 50.99; H, 5.47; found C, 50.76; H, 5.46. ESI MS: (MeOH + CH2Cl2): m/z = 822.8 [M − Cl]+. 1H NMR (400 MHz, CDCl3): δ = 7.49 (d, 3 J = 8 Hz, 2H, SCH2C6H4-p-OCH3), 6.85 (d, 3 J = 8 Hz, 2H, SCH2C6H4-p-OCH3), 5.15–4.89 [m, 8H, p-CH3C6 H 4CH(CH3)2], 4.15 (d, 3 J = 11 Hz, 2H, SCH2C6 H 4-p-OCH3), 3.83 (s, 6H, SCH2C6H4-p-OCH 3), 3.26 (d, 3 J = 11 Hz, 2H, SCH 2C6H4-p-OCH3), 2.86 [sept, 3 J = 8 Hz, 2H, p-CH3C6H4CH(CH3)2], 1.89 [s, 6H, p-CH 3C6H4CH(CH3)2], 1.2 [s, 12H, p-CH3C6H4CH(CH 3)2] p.p.m. 13C NMR (100 MHz, CDCl3): δ = 158.41, 132.89, 131.56, 112.96, 96.97, 83.91, 83.03, 55.32, 35.90, 29.88, 23.50, 21.22, 18.79 p.p.m.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All hydrogen atoms were included in calculated positions and treated as riding atoms, with C—H = 0.93 Å for Caromatic, 0.97 Å for –CH2–, 0.98 Å for –CH–, and 0.96 Å for –CH3, with U iso(H) = 1.2U eq(C) and 1.5U eq(C) for methyl H atoms.

Table 2

Experimental details

Crystal data
Chemical formula	[Ru2(C8H9OS)2Cl2(C10H14)2]2CHCl3
M r	1086.62
Crystal system, space group	Triclinic, P
Temperature (K)	173
a, b, c ()	10.034(2), 10.070(2), 12.124(2)
, , ()	112.75(3), 95.58(3), 98.51(3)
V (3)	1101.2(4)
Z	1
Radiation type	Mo K
(mm1)	1.30
Crystal size (mm)	0.24 0.21 0.19
Data collection
Diffractometer	STOE IPDS
Absorption correction	Empirical (using intensity measurements) (Walker Stuart, 1983 ▸)
T min, T max	0.655, 0.819
No. of measured, independent and observed [I > 2(I)] reflections	13000, 5787, 4504
R int	0.058
(sin /)max (1)	0.689
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.039, 0.092, 0.97
No. of reflections	5787
No. of parameters	239
H-atom treatment	H-atom parameters constrained
max, min (e 3)	0.94, 1.47

Computer programs: EXPOSE, CELL and INTEGRATE (IPDS Software; Stoe Cie, 2000 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014/7 (Sheldrick, 2015 ▸) and ORTEP-3 for Windows (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015017399/wm5217sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017399/wm5217Isup2.hkl

CCDC reference: 1415346

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ru2(C8H9OS)2Cl2(C10H14)2]·2CHCl3	Z = 1
Mr = 1086.62	F(000) = 548
Triclinic, P1	Dx = 1.639 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.034 (2) Å	Cell parameters from 8000 reflections
b = 10.070 (2) Å	θ = 2.1–28.9°
c = 12.124 (2) Å	µ = 1.30 mm−1
α = 112.75 (3)°	T = 173 K
β = 95.58 (3)°	Block, orange
γ = 98.51 (3)°	0.24 × 0.21 × 0.19 mm
V = 1101.2 (4) Å3

STOE IPDS diffractometer	5787 independent reflections
Radiation source: fine-focus sealed tube	4504 reflections with I > 2σ(I)
Detector resolution: 0.81 pixels mm-1	Rint = 0.058
phi oscillation scans	θmax = 29.3°, θmin = 1.9°
Absorption correction: empirical (using intensity measurements) (Walker & Stuart, 1983)	h = −11→13
Tmin = 0.655, Tmax = 0.819	k = −13→13
13000 measured reflections	l = −16→16

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039	H-atom parameters constrained
wR(F2) = 0.092	w = 1/[σ2(Fo2) + (0.047P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max < 0.001
5787 reflections	Δρmax = 0.94 e Å−3
239 parameters	Δρmin = −1.47 e Å−3

Experimental. A crystal was mounted at 173 K on a Stoe Image Plate Diffraction System (Stoe & Cie, 2000) using Mo Kα graphite monochromated radiation. Image plate distance 100 mm, φ oscillation scans 0 - 180°, step Δφ = 1.2°, 5 minutes per frame.Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement._reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences.

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

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

	x	y	z	Uiso*/Ueq
C1	0.7926 (3)	0.4925 (4)	−0.0177 (3)	0.0255 (6)
H1A	0.8508	0.4762	0.0426	0.031*
H1B	0.7565	0.3986	−0.0855	0.031*
C2	0.8739 (3)	0.5957 (4)	−0.0603 (3)	0.0247 (6)
C3	0.9603 (3)	0.7265 (4)	0.0208 (3)	0.0282 (7)
H3	0.9717	0.7483	0.1035	0.034*
C4	1.0290 (3)	0.8237 (4)	−0.0184 (3)	0.0314 (7)
H4	1.0850	0.9107	0.0376	0.038*
C5	1.0151 (3)	0.7924 (4)	−0.1422 (3)	0.0297 (7)
C6	0.9324 (3)	0.6622 (4)	−0.2252 (3)	0.0326 (7)
H6	0.9230	0.6397	−0.3079	0.039*
C7	0.8633 (3)	0.5650 (4)	−0.1833 (3)	0.0303 (7)
H17	0.8086	0.4771	−0.2393	0.036*
C8	1.0626 (4)	0.8763 (5)	−0.2960 (4)	0.0471 (10)
H8A	1.0848	0.7849	−0.3464	0.071*
H8B	1.1185	0.9558	−0.3056	0.071*
H8C	0.9679	0.8746	−0.3195	0.071*
C9	0.2694 (4)	0.9102 (5)	0.3930 (4)	0.0423 (9)
H9	0.3270	0.8367	0.3788	0.051*
C10	0.5851 (3)	0.3518 (4)	0.2545 (3)	0.0260 (7)
C11	0.4405 (4)	0.2937 (4)	0.2169 (3)	0.0294 (7)
H11	0.3833	0.3152	0.2747	0.035*
C12	0.3845 (3)	0.2066 (4)	0.0967 (3)	0.0273 (7)
H12	0.2906	0.1703	0.0758	0.033*
C13	0.4679 (3)	0.1709 (3)	0.0033 (3)	0.0242 (6)
C14	0.6104 (3)	0.2285 (4)	0.0405 (3)	0.0247 (6)
H14	0.6674	0.2094	−0.0175	0.030*
C15	0.6681 (3)	0.3150 (4)	0.1645 (3)	0.0243 (6)
H15	0.7624	0.3478	0.1864	0.029*
C16	0.6405 (4)	0.4500 (5)	0.3870 (3)	0.0371 (8)
H16	0.5723	0.5092	0.4176	0.044*
C17	0.7731 (5)	0.5567 (5)	0.4064 (4)	0.0516 (11)
H17A	0.8449	0.5032	0.3844	0.077*
H17B	0.7962	0.6241	0.4902	0.077*
H17C	0.7621	0.6105	0.3569	0.077*
C18	0.6510 (5)	0.3546 (6)	0.4589 (4)	0.0528 (12)
H18A	0.5627	0.2956	0.4491	0.079*
H18B	0.6824	0.4168	0.5433	0.079*
H18C	0.7144	0.2918	0.4293	0.079*
C19	0.4071 (4)	0.0830 (4)	−0.1272 (3)	0.0360 (8)
H19A	0.4595	0.1167	−0.1768	0.054*
H19B	0.3145	0.0947	−0.1409	0.054*
H19C	0.4081	−0.0189	−0.1477	0.054*
O1	1.0868 (3)	0.8961 (3)	−0.1727 (3)	0.0419 (6)
S1	0.65082 (7)	0.57453 (8)	0.04876 (7)	0.02020 (15)
Cl1	0.46757 (8)	0.64213 (9)	0.25227 (7)	0.02648 (16)
Cl2	0.33078 (13)	1.05269 (14)	0.53676 (10)	0.0565 (3)
Cl3	0.09992 (13)	0.82576 (14)	0.38522 (11)	0.0576 (3)
Cl4	0.27665 (14)	0.97961 (17)	0.28011 (11)	0.0623 (3)
Ru1	0.50634 (2)	0.41162 (3)	0.10619 (2)	0.01824 (7)

	U11	U22	U33	U12	U13	U23
C1	0.0191 (14)	0.0273 (18)	0.0344 (17)	0.0071 (12)	0.0081 (12)	0.0157 (15)
C2	0.0176 (13)	0.0288 (18)	0.0326 (16)	0.0072 (12)	0.0081 (12)	0.0157 (14)
C3	0.0246 (15)	0.0313 (19)	0.0302 (16)	0.0052 (13)	0.0046 (13)	0.0140 (15)
C4	0.0245 (16)	0.0288 (19)	0.0375 (18)	0.0003 (13)	0.0042 (14)	0.0120 (16)
C5	0.0234 (15)	0.0292 (19)	0.0413 (19)	0.0046 (13)	0.0132 (14)	0.0180 (16)
C6	0.0268 (16)	0.042 (2)	0.0302 (17)	0.0061 (15)	0.0091 (13)	0.0154 (16)
C7	0.0265 (16)	0.0290 (19)	0.0327 (17)	0.0021 (13)	0.0087 (14)	0.0100 (15)
C8	0.045 (2)	0.057 (3)	0.054 (2)	0.0045 (19)	0.0187 (19)	0.038 (2)
C9	0.048 (2)	0.040 (2)	0.037 (2)	0.0147 (19)	0.0076 (18)	0.0118 (18)
C10	0.0295 (16)	0.0318 (18)	0.0266 (15)	0.0132 (13)	0.0079 (13)	0.0191 (15)
C11	0.0337 (17)	0.0343 (19)	0.0338 (17)	0.0137 (14)	0.0159 (14)	0.0236 (16)
C12	0.0243 (15)	0.0214 (17)	0.0428 (19)	0.0030 (12)	0.0072 (13)	0.0202 (15)
C13	0.0315 (16)	0.0122 (14)	0.0285 (15)	0.0005 (12)	0.0010 (13)	0.0101 (13)
C14	0.0282 (15)	0.0224 (16)	0.0331 (16)	0.0141 (13)	0.0139 (13)	0.0162 (14)
C15	0.0236 (14)	0.0250 (17)	0.0311 (16)	0.0118 (12)	0.0055 (12)	0.0160 (14)
C16	0.044 (2)	0.047 (2)	0.0249 (16)	0.0214 (18)	0.0061 (15)	0.0161 (17)
C17	0.056 (3)	0.050 (3)	0.034 (2)	0.009 (2)	−0.0070 (19)	0.006 (2)
C18	0.063 (3)	0.079 (4)	0.036 (2)	0.034 (3)	0.015 (2)	0.035 (2)
C19	0.046 (2)	0.0240 (19)	0.0357 (19)	0.0037 (15)	0.0020 (16)	0.0123 (16)
O1	0.0349 (14)	0.0449 (17)	0.0514 (16)	−0.0023 (12)	0.0138 (12)	0.0275 (14)
S1	0.0175 (3)	0.0209 (4)	0.0245 (4)	0.0040 (3)	0.0043 (3)	0.0116 (3)
Cl1	0.0281 (4)	0.0250 (4)	0.0260 (4)	0.0070 (3)	0.0072 (3)	0.0088 (3)
Cl2	0.0583 (7)	0.0529 (7)	0.0386 (5)	0.0077 (5)	0.0022 (5)	0.0004 (5)
Cl3	0.0537 (6)	0.0547 (7)	0.0578 (7)	0.0009 (5)	0.0024 (5)	0.0211 (6)
Cl4	0.0711 (8)	0.0793 (9)	0.0511 (6)	0.0268 (7)	0.0240 (6)	0.0348 (7)
Ru1	0.01758 (11)	0.01881 (13)	0.02142 (12)	0.00467 (8)	0.00493 (8)	0.01074 (10)

C1—C2	1.503 (4)	C11—H11	0.9300
C1—S1	1.847 (3)	C12—C13	1.439 (5)
C1—H1A	0.9700	C12—Ru1	2.194 (3)
C1—H1B	0.9700	C12—H12	0.9300
C2—C7	1.391 (5)	C13—C14	1.418 (5)
C2—C3	1.396 (5)	C13—C19	1.492 (5)
C3—C4	1.372 (5)	C13—Ru1	2.208 (3)
C3—H3	0.9300	C14—C15	1.422 (5)
C4—C5	1.397 (5)	C14—Ru1	2.173 (3)
C4—H4	0.9300	C14—H14	0.9300
C5—O1	1.369 (4)	C15—Ru1	2.204 (3)
C5—C6	1.384 (5)	C15—H15	0.9300
C6—C7	1.396 (5)	C16—C17	1.517 (6)
C6—H6	0.9300	C16—C18	1.534 (5)
C7—H17	0.9300	C16—H16	0.9800
C8—O1	1.421 (5)	C17—H17A	0.9600
C8—H8A	0.9600	C17—H17B	0.9600
C8—H8B	0.9600	C17—H17C	0.9600
C8—H8C	0.9600	C18—H18A	0.9600
C9—Cl2	1.752 (4)	C18—H18B	0.9600
C9—Cl3	1.761 (5)	C18—H18C	0.9600
C9—Cl4	1.764 (4)	C19—H19A	0.9600
C9—H9	0.9800	C19—H19B	0.9600
C10—C15	1.406 (4)	C19—H19C	0.9600
C10—C11	1.438 (5)	S1—Ru1	2.3778 (10)
C10—C16	1.517 (5)	S1—Ru1i	2.3931 (10)
C10—Ru1	2.219 (3)	Cl1—Ru1	2.4284 (12)
C11—C12	1.384 (5)	Ru1—S1i	2.3931 (10)
C11—Ru1	2.196 (3)
C2—C1—S1	108.8 (2)	C14—C15—Ru1	69.85 (16)
C2—C1—H1A	109.9	C10—C15—H15	119.4
S1—C1—H1A	109.9	C14—C15—H15	119.4
C2—C1—H1B	109.9	Ru1—C15—H15	131.6
S1—C1—H1B	109.9	C17—C16—C10	113.6 (3)
H1A—C1—H1B	108.3	C17—C16—C18	112.9 (4)
C7—C2—C3	117.4 (3)	C10—C16—C18	109.4 (4)
C7—C2—C1	120.7 (3)	C17—C16—H16	106.9
C3—C2—C1	121.9 (3)	C10—C16—H16	106.9
C4—C3—C2	121.6 (3)	C18—C16—H16	106.9
C4—C3—H3	119.2	C16—C17—H17A	109.5
C2—C3—H3	119.2	C16—C17—H17B	109.5
C3—C4—C5	120.3 (3)	H17A—C17—H17B	109.5
C3—C4—H4	119.9	C16—C17—H17C	109.5
C5—C4—H4	119.9	H17A—C17—H17C	109.5
O1—C5—C6	124.3 (3)	H17B—C17—H17C	109.5
O1—C5—C4	116.1 (3)	C16—C18—H18A	109.5
C6—C5—C4	119.6 (3)	C16—C18—H18B	109.5
C5—C6—C7	119.2 (3)	H18A—C18—H18B	109.5
C5—C6—H6	120.4	C16—C18—H18C	109.5
C7—C6—H6	120.4	H18A—C18—H18C	109.5
C2—C7—C6	121.9 (3)	H18B—C18—H18C	109.5
C2—C7—H17	119.0	C13—C19—H19A	109.5
C6—C7—H17	119.0	C13—C19—H19B	109.5
O1—C8—H8A	109.5	H19A—C19—H19B	109.5
O1—C8—H8B	109.5	C13—C19—H19C	109.5
H8A—C8—H8B	109.5	H19A—C19—H19C	109.5
O1—C8—H8C	109.5	H19B—C19—H19C	109.5
H8A—C8—H8C	109.5	C5—O1—C8	117.6 (3)
H8B—C8—H8C	109.5	C1—S1—Ru1	111.36 (10)
Cl2—C9—Cl3	110.4 (2)	C1—S1—Ru1i	109.65 (11)
Cl2—C9—Cl4	110.0 (2)	Ru1—S1—Ru1i	100.03 (4)
Cl3—C9—Cl4	109.8 (2)	C14—Ru1—C12	67.73 (12)
Cl2—C9—H9	108.8	C14—Ru1—C11	79.89 (12)
Cl3—C9—H9	108.8	C12—Ru1—C11	36.75 (14)
Cl4—C9—H9	108.8	C14—Ru1—C15	37.92 (12)
C15—C10—C11	117.4 (3)	C12—Ru1—C15	79.44 (12)
C15—C10—C16	123.3 (3)	C11—Ru1—C15	67.08 (12)
C11—C10—C16	119.3 (3)	C14—Ru1—C13	37.76 (12)
C15—C10—Ru1	70.89 (16)	C12—Ru1—C13	38.17 (12)
C11—C10—Ru1	70.12 (16)	C11—Ru1—C13	68.07 (13)
C16—C10—Ru1	129.3 (2)	C15—Ru1—C13	68.35 (13)
C12—C11—C10	121.5 (3)	C14—Ru1—C10	68.23 (12)
C12—C11—Ru1	71.54 (17)	C12—Ru1—C10	67.85 (13)
C10—C11—Ru1	71.86 (17)	C11—Ru1—C10	38.02 (13)
C12—C11—H11	119.2	C15—Ru1—C10	37.08 (11)
C10—C11—H11	119.2	C13—Ru1—C10	81.53 (13)
Ru1—C11—H11	130.0	C14—Ru1—S1	96.92 (8)
C11—C12—C13	121.6 (3)	C12—Ru1—S1	159.60 (10)
C11—C12—Ru1	71.71 (19)	C11—Ru1—S1	157.71 (10)
C13—C12—Ru1	71.44 (17)	C15—Ru1—S1	96.80 (8)
C11—C12—H12	119.2	C13—Ru1—S1	121.79 (9)
C13—C12—H12	119.2	C10—Ru1—S1	120.29 (9)
Ru1—C12—H12	130.4	C14—Ru1—S1i	113.67 (9)
C14—C13—C12	116.8 (3)	C12—Ru1—S1i	93.66 (9)
C14—C13—C19	121.5 (3)	C11—Ru1—S1i	121.67 (10)
C12—C13—C19	121.7 (3)	C15—Ru1—S1i	151.25 (9)
C14—C13—Ru1	69.78 (18)	C13—Ru1—S1i	88.92 (9)
C12—C13—Ru1	70.38 (18)	C10—Ru1—S1i	159.68 (9)
C19—C13—Ru1	128.3 (2)	S1—Ru1—S1i	79.97 (4)
C13—C14—C15	121.5 (3)	C14—Ru1—Cl1	155.31 (10)
C13—C14—Ru1	72.46 (17)	C12—Ru1—Cl1	117.94 (9)
C15—C14—Ru1	72.23 (17)	C11—Ru1—Cl1	92.05 (10)
C13—C14—H14	119.3	C15—Ru1—Cl1	117.51 (10)
C15—C14—H14	119.3	C13—Ru1—Cl1	155.93 (9)
Ru1—C14—H14	128.4	C10—Ru1—Cl1	91.04 (9)
C10—C15—C14	121.1 (3)	S1—Ru1—Cl1	81.71 (4)
C10—C15—Ru1	72.04 (17)	S1i—Ru1—Cl1	90.48 (4)
S1—C1—C2—C7	−105.6 (3)	C11—C12—C13—Ru1	−53.5 (3)
S1—C1—C2—C3	73.2 (3)	C12—C13—C14—C15	1.2 (4)
C7—C2—C3—C4	2.1 (5)	C19—C13—C14—C15	178.6 (3)
C1—C2—C3—C4	−176.7 (3)	Ru1—C13—C14—C15	55.3 (2)
C2—C3—C4—C5	−0.9 (5)	C12—C13—C14—Ru1	−54.1 (2)
C3—C4—C5—O1	179.6 (3)	C19—C13—C14—Ru1	123.3 (3)
C3—C4—C5—C6	−0.5 (5)	C11—C10—C15—C14	2.4 (4)
O1—C5—C6—C7	−179.6 (3)	C16—C10—C15—C14	−176.8 (3)
C4—C5—C6—C7	0.6 (5)	Ru1—C10—C15—C14	−51.8 (3)
C3—C2—C7—C6	−2.0 (5)	C11—C10—C15—Ru1	54.2 (2)
C1—C2—C7—C6	176.8 (3)	C16—C10—C15—Ru1	−125.0 (3)
C5—C6—C7—C2	0.7 (5)	C13—C14—C15—C10	−2.7 (4)
C15—C10—C11—C12	−0.8 (4)	Ru1—C14—C15—C10	52.8 (3)
C16—C10—C11—C12	178.4 (3)	C13—C14—C15—Ru1	−55.4 (2)
Ru1—C10—C11—C12	53.7 (3)	C15—C10—C16—C17	25.9 (5)
C15—C10—C11—Ru1	−54.6 (2)	C11—C10—C16—C17	−153.3 (3)
C16—C10—C11—Ru1	124.7 (3)	Ru1—C10—C16—C17	−65.9 (4)
C10—C11—C12—C13	−0.5 (5)	C15—C10—C16—C18	−101.2 (4)
Ru1—C11—C12—C13	53.3 (3)	C11—C10—C16—C18	79.6 (4)
C10—C11—C12—Ru1	−53.9 (3)	Ru1—C10—C16—C18	167.0 (3)
C11—C12—C13—C14	0.3 (4)	C6—C5—O1—C8	7.4 (5)
Ru1—C12—C13—C14	53.8 (2)	C4—C5—O1—C8	−172.7 (3)
C11—C12—C13—C19	−177.0 (3)	C2—C1—S1—Ru1	175.94 (19)
Ru1—C12—C13—C19	−123.6 (3)	C2—C1—S1—Ru1i	66.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cl1	0.98	2.66	3.583 (4)	157
C8—H8C···Cl4ii	0.96	3.03	3.886 (5)	150