cis-Di­chloro­[tris­(di­phenyl­phosphino­ethyl)­amine]­ruthenium(II)-chloro­form-water (1/2.5/1)

In the title compound, [RuCl₂(C₄₂H₄₂NP₃)]·2.5CHCl₃·H₂O, the Ru atom is six-coordinated, to one tetradentate tris­(di­phenyl­phosphinoethyl)­amine ligand and two Cl atoms, in a distorted octahedral arrangement. Molecules of chloro­form and water stabilize the framework through intermolecular hydrogen bonds.

S1. Comment

Tris(diphenylphosphinoethyl)amine (NP₃) is a very interesting polydentate ligand with chelating properties and mixed-donor functionality. Coordination compounds incorporating this ligand and several metal ions have been reported since its initial synthesis (Sacconi & Bertini, 1968). Either a tridentate or tetradentade form of coordination has been observed for NP₃–metal compounds, although unusual mono- (Zank et al.,1997) or bidentate coordination to the same metal can be achieved (Cecconi et al., 1989; Ghilardi & Sacconi, 1975). Specifically for ruthenium–NP₃ complexes, only one structure has been reported previously, viz. [Ru(NP₃)Cl{═ C═C═C(OMe)CH═CPh₂}], (II) (Wolinska et al., 1991), in which the NP₃ ligand exhibits a tetradentade coordination.

The title compound, (I), offers interesting catalytic properties, as shown by Fontal & Suarez (1985) in the case of hydrogenation and hydroformylation, as well as others (Dahlenburg et al., 1991) in 1-alkynes dimerization reactions, but in spite of a good spectroscopic characterization, especially through ¹H and ³¹P NMR spectroscopic analysis, the crystal structure of (I) was hitherto unreported.

From the synthetic point of view, RuCl₂(NP₃) is used as a starting material in the production of alkenyl–allenylidene compounds useful in the preparation of either metal-containing polymers or new polyunsaturated organic substrates (Wolinska et al., 1991). It is interesting to note that the method of synthesis of (I) differs from that reported in the previous literature, where RuCl₂(NP₃) is prepared from RuCl₂(PPh₃)₃ and the NP₃ ligand under reflux in toluene. Complex (I) instead, is obtained by reaction of RuCl₂(dmso)₄ (dmso is dimethyl sulfoxide) and NP₃ in toluene solution. Also, it should be noted that the same reaction with RuCl₂(dmso)₄ and NP₃ but in acetone affords the RuCl₂(NP₃)(dmso) compound where NP₃ seems to act as a tridentade ligand (Taqui-Khan & Rama-Rao, 1988).

The asymmetric unit of (I) consists of one complex molecule, 2.5 chloroform molecules and one water molecule. The Ru atom is coordinated by two Cl atoms and one NP₃ ligand, which is bound through the N and P atoms to complete the octahedral environment of the Ru atom, as depicted in Fig. 1. The coordination geometry is distorted, with bond angles quite similar to those exhibited by analogous complex (II), with P1—Ru—P2 = 165.28 (4)°, N—Ru—Cl1 = 176.1 (1)° and P3—Ru—C1 = 170.3 (1)°. The distances involving the trans P atoms are longer than the distance involving the P atom trans to chlorine (Ru—P3; Table 1). When compared to analogous complex (II), the bond distances involving the trans P atoms are similar, but the Ru—P3 distance in (II) of 2.430 (1) Å is unusually long. This can be attributed to a greater trans effect of the allene ligand due to its π-acceptor nature, compared to the Cl atom in (I). The Cl atoms are in a cis configuration, with longer bond distances compared to the mean value reported for the parent complex cis-RuCl₂(dmso)₄ [Ru—Cl 2.420 (2) Å; Alessio et al., 1988; Attia & Calligaris, 1987]. The arrangement of the internal aromatic rings in the coordinated NP₃ ligand allows for π–π face-to-face interactions with an average centroid–centroid distance of 3.672 (8) Å.

Molecules of chloroform and water are incorporated in the lattice as crystallization solvents; hydrogen-bond analysis, performed with PLATON (Spek, 1999), showed a series of intermolecular and intramolecular contacts (Table 2). A further analysis provided evidence that the chloroform and water molecules interact with the Cl atoms of the complex via C—H···Cl and O—H···Cl hydrogen bonds, respectively. Each coordinated Cl atom (Cl1 and Cl2) serves as an acceptor of four hydrogen-bonds; additionally, direct interactions between complex molecules through C72···Cl2 and C91···Cl2 were observed. These hydrogen bonds may account for the molecular packing and the stability of the structure. Intramolecular interaction could contribute to the distorted environment around the Ru atom also.

In addition, all three chloroform molecules are disordered, this disorder was modelled with two set of positions for molecules 1 and 2, with refined occupation factors of 0.70:0.30 and 0.60:0.40, respectively. Disorder in the third molecule was completely modelled with two set of positions. Refinement of the occupation factor of this molecule reveals a partial occupation of 1/2, distributed between 0.2 and 0.3 for both orientations.

S2. Experimental

The synthesis of (I) was carried out under a nitrogen atmosphere by refluxing a solution of cis-RuCl₂(dmso)₄ (484.53 mg, 1 mmol) with tris(diphenylphosphinoethyl)amine (653.75 mg, 1 mmol) in stirred toluene for 3 h. The resulting orange–yellow mixture was vacuum filtered and evaporated. The yellow solid obtained was washed with ether (yield 85%). ³¹P NMR (CDCl₃, recorded on a Bruker 300 MHz s pectrometer): δ = -27.2 (d), -47.9 (t). Elemental analysis, alculated for C₄₂H₄₂Cl₂NP₃Ru: C 61.0, H 5.09, Cl 8.58, N 1.69, P 11.26%; found: C 60.1, H 5.22, Cl 8.19, N 1.61, P 10.20%. Crystals of (I) were obtained by slow evaporation of a chloroform solution of the complex at room temperature.

S3. Refinement

All H atoms were placed in calculated positions and allowed for as riding (C—H = 0.93–0.98 Å). Disorder of the chloroform molecules was modelled with two sites for each molecule, and these were refined isotropically constraining C—Cl distances to 1.750 (2) Å. The occupation factors of chloroform molecules 1 and 2 were refined with SHELXTL (Siemens, 1994), option PART. The best model for the third chloroform molecule was obtained by free refinement of the occupation factor for each set of positions, which gives a partial occupation of 0.5. These occupations were fixed during the final refinements. The H atoms of the water molecule were not located in the density map, but were calculated using the HYDROGEN program (Nardelli, 1999).

Computing details

Data collection: COLLECT in UCLA Crystallographic Package (Strouse, 1988); cell refinement: LEAST in UCLA Crystallographic Package; data reduction: REDUCE in UCLA Crystallographic Package; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. View of the title compund, showing the labelling of the non-H atoms and ellipsoids at the 40% probability level.

cis-dicloro [tris-(diphenylphosphinoethyl)amine] ruthenium (II) chloform solvate

Crystal data

[RuCl2(C42H42NP3)]·2.5CHCl3·H2O	F(000) = 2314
Mr = 1140.88	Dx = 1.514 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 17.541 (2) Å	Cell parameters from 80 reflections
b = 12.112 (1) Å	θ = 10–20°
c = 24.950 (3) Å	µ = 0.95 mm^−1
β = 109.26 (1)°	T = 293 K
V = 5004.1 (9) Å^3	Plate, yellow
Z = 4	0.5 × 0.3 × 0.2 mm

Data collection

Nicolet P3/F (Crystal Logic) diffractometer	4795 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
ω scans	h = 0→20
Absorption correction: ψ scan (North et al., 1968)	k = −8→14
Tmin = 0.718, Tmax = 0.827	l = −29→28
10018 measured reflections	3 standard reflections every 97 reflections
8811 independent reflections	intensity decay: 10%

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.223	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0838P)^2 + 23.3179P] where P = (Fo^2 + 2Fc^2)/3
8811 reflections	(Δ/σ)max < 0.001
533 parameters	Δρmax = 1.01 e Å^−3
19 restraints	Δρmin = −1.11 e Å^−3

Special details

Experimental. The crystal was mounted in a sealed glass capillary with a small amount of crystallization solvent.

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)
Ru	−0.33330 (4)	0.84994 (6)	−0.24476 (3)	0.0334 (2)
Cl1	−0.25206 (13)	0.7588 (2)	−0.29487 (9)	0.0476 (6)
Cl2	−0.40038 (14)	0.67090 (18)	−0.24200 (10)	0.0461 (6)
P1	−0.45084 (13)	0.88285 (19)	−0.32270 (9)	0.0377 (5)
P2	−0.24359 (14)	0.8031 (2)	−0.15485 (9)	0.0385 (5)
P3	−0.28817 (14)	1.02386 (19)	−0.24611 (9)	0.0380 (5)
N	−0.4058 (4)	0.9222 (6)	−0.1972 (3)	0.0385 (17)
C11	−0.4602 (5)	0.9915 (8)	−0.3766 (3)	0.043 (2)
C12	−0.4130 (5)	0.9771 (8)	−0.4109 (4)	0.048 (2)
H12	−0.3795	0.9159	−0.4061	0.058*
C13	−0.4161 (6)	1.0546 (9)	−0.4524 (4)	0.058 (3)
H13	−0.3832	1.0463	−0.4748	0.069*
C14	−0.4672 (7)	1.1435 (9)	−0.4608 (4)	0.063 (3)
H14	−0.4705	1.1937	−0.4897	0.075*
C15	−0.5139 (7)	1.1581 (9)	−0.4262 (4)	0.066 (3)
H15	−0.5474	1.2194	−0.4312	0.079*
C16	−0.5111 (6)	1.0819 (8)	−0.3840 (4)	0.055 (3)
H16	−0.5429	1.0913	−0.3610	0.066*
C21	−0.5006 (5)	0.7707 (8)	−0.3719 (4)	0.043 (2)
C22	−0.5832 (6)	0.7809 (9)	−0.4029 (4)	0.058 (3)
H22	−0.6136	0.8405	−0.3980	0.069*
C23	−0.6176 (8)	0.6957 (12)	−0.4420 (4)	0.078 (4)
H23	−0.6726	0.6994	−0.4621	0.093*
C24	−0.5758 (9)	0.6090 (11)	−0.4520 (5)	0.077 (4)
H24	−0.6005	0.5559	−0.4791	0.092*
C25	−0.4951 (8)	0.6023 (9)	−0.4205 (5)	0.067 (3)
H25	−0.4654	0.5425	−0.4262	0.080*
C26	−0.4562 (7)	0.6816 (8)	−0.3805 (4)	0.053 (3)
H26	−0.4016	0.6750	−0.3599	0.063*
C31	−0.2439 (5)	0.6595 (7)	−0.1324 (4)	0.044 (2)
C32	−0.2608 (6)	0.6265 (9)	−0.0849 (4)	0.056 (3)
H32	−0.2746	0.6799	−0.0629	0.068*
C33	−0.2582 (7)	0.5169 (10)	−0.0682 (5)	0.073 (3)
H33	−0.2702	0.4972	−0.0358	0.088*
C34	−0.2377 (7)	0.4395 (10)	−0.1000 (6)	0.078 (4)
H34	−0.2349	0.3658	−0.0891	0.093*
C35	−0.2210 (7)	0.4675 (10)	−0.1480 (6)	0.074 (3)
H35	−0.2075	0.4134	−0.1697	0.088*
C36	−0.2245 (6)	0.5782 (8)	−0.1640 (5)	0.060 (3)
H36	−0.2134	0.5973	−0.1967	0.072*
C41	−0.1348 (6)	0.8266 (7)	−0.1261 (4)	0.045 (2)
C42	−0.0966 (6)	0.8716 (8)	−0.0720 (4)	0.057 (3)
H42	−0.1271	0.8970	−0.0503	0.068*
C43	−0.0137 (7)	0.8779 (9)	−0.0514 (5)	0.069 (3)
H43	0.0115	0.9074	−0.0155	0.083*
C44	0.0322 (7)	0.8417 (11)	−0.0825 (5)	0.077 (4)
H44	0.0881	0.8463	−0.0677	0.093*
C45	−0.0052 (6)	0.7972 (9)	−0.1371 (5)	0.063 (3)
H45	0.0255	0.7728	−0.1589	0.075*
C46	−0.0881 (6)	0.7908 (8)	−0.1574 (4)	0.051 (2)
H46	−0.1133	0.7615	−0.1933	0.061*
C51	−0.1967 (5)	1.0754 (8)	−0.1911 (4)	0.045 (2)
C52	−0.1220 (6)	1.0506 (8)	−0.1956 (5)	0.056 (3)
H52	−0.1192	1.0080	−0.2259	0.067*
C53	−0.0507 (6)	1.0883 (10)	−0.1555 (5)	0.067 (3)
H53	−0.0010	1.0695	−0.1587	0.081*
C54	−0.0543 (7)	1.1532 (10)	−0.1115 (5)	0.071 (3)
H54	−0.0071	1.1800	−0.0850	0.085*
C55	−0.1264 (7)	1.1777 (9)	−0.1068 (4)	0.063 (3)
H55	−0.1284	1.2205	−0.0764	0.075*
C56	−0.1981 (6)	1.1410 (8)	−0.1462 (4)	0.055 (3)
H56	−0.2472	1.1606	−0.1423	0.066*
C61	−0.2705 (6)	1.0884 (9)	−0.3081 (4)	0.050 (2)
C62	−0.2948 (7)	1.1965 (9)	−0.3249 (5)	0.064 (3)
H62	−0.3245	1.2357	−0.3065	0.076*
C63	−0.2752 (8)	1.2449 (11)	−0.3681 (5)	0.078 (4)
H63	−0.2918	1.3166	−0.3796	0.094*
C64	−0.2307 (8)	1.1860 (12)	−0.3943 (5)	0.082 (4)
H64	−0.2182	1.2181	−0.4242	0.098*
C65	−0.2051 (7)	1.0842 (12)	−0.3781 (5)	0.075 (3)
H65	−0.1727	1.0483	−0.3956	0.090*
C66	−0.2255 (6)	1.0304 (10)	−0.3358 (4)	0.058 (3)
H66	−0.2097	0.9577	−0.3260	0.069*
C71	−0.4924 (6)	0.8907 (8)	−0.2246 (4)	0.049 (2)
H711	−0.5248	0.9266	−0.2049	0.059*
H712	−0.4980	0.8115	−0.2214	0.059*
C72	−0.5237 (5)	0.9234 (8)	−0.2873 (4)	0.046 (2)
H721	−0.5321	1.0026	−0.2905	0.055*
H722	−0.5751	0.8876	−0.3058	0.055*
C81	−0.3793 (6)	0.8758 (8)	−0.1379 (4)	0.046 (2)
H811	−0.3970	0.7997	−0.1392	0.055*
H812	−0.4047	0.9173	−0.1151	0.055*
C82	−0.2879 (6)	0.8808 (8)	−0.1100 (4)	0.047 (2)
H821	−0.2722	0.8487	−0.0723	0.056*
H822	−0.2696	0.9568	−0.1067	0.056*
C91	−0.3996 (6)	1.0476 (7)	−0.1921 (4)	0.042 (2)
H911	−0.4525	1.0765	−0.1953	0.050*
H912	−0.3636	1.0657	−0.1543	0.050*
C92	−0.3702 (5)	1.1060 (7)	−0.2344 (4)	0.044 (2)
H921	−0.3503	1.1788	−0.2204	0.053*
H922	−0.4142	1.1147	−0.2699	0.053*
O	0.3225 (8)	0.5235 (11)	0.3028 (6)	0.185 (7)
H1O	0.2714	0.5244	0.2880	0.222*
H2O	0.3406	0.4743	0.2859	0.222*
C1A	0.0398 (2)	0.6052 (5)	0.2053 (3)	0.095 (4)*
H1A	0.0435	0.6122	0.1671	0.114*
Cl1A	0.0416 (5)	0.4661 (6)	0.2247 (4)	0.155 (3)*	0.70
Cl2A	0.1205 (3)	0.6730 (5)	0.2550 (2)	0.1021 (17)*	0.70
Cl3A	−0.0460 (3)	0.6736 (7)	0.2094 (4)	0.1068 (18)*	0.70
Cl11	0.0128 (12)	0.4700 (7)	0.1820 (9)	0.155 (3)*	0.30
Cl21	0.1220 (6)	0.6264 (13)	0.2672 (4)	0.1021 (17)*	0.30
Cl31	−0.0566 (6)	0.6554 (17)	0.1983 (9)	0.1068 (18)*	0.30
C2B	0.2345 (3)	0.3280 (6)	0.4177 (3)	0.092 (4)*
H2B	0.2366	0.3101	0.3799	0.110*
Cl1B	0.3322 (3)	0.3360 (7)	0.4668 (3)	0.100 (2)*	0.60
Cl2B	0.1742 (5)	0.2324 (7)	0.4378 (4)	0.128 (3)*	0.60
Cl3B	0.1844 (8)	0.4536 (8)	0.4160 (6)	0.194 (5)*	0.60
Cl12	0.3246 (3)	0.2772 (7)	0.4658 (3)	0.071 (2)*	0.40
Cl22	0.1556 (6)	0.2898 (12)	0.4422 (5)	0.124 (4)*	0.40
Cl32	0.2358 (13)	0.4725 (6)	0.4202 (8)	0.191 (7)*	0.40
C3C	0.0000	0.5000	0.0000	0.045 (16)*	0.20
H3CA	0.0442	0.5137	0.0342	0.054*	0.20
Cl1C	−0.0495 (16)	0.6276 (11)	−0.0124 (13)	0.140 (9)*	0.20
Cl2C	0.0464 (17)	0.427 (3)	−0.0413 (12)	0.166 (12)*	0.20
Cl3C	−0.0618 (12)	0.412 (2)	0.0232 (11)	0.132 (8)*	0.20
C3CA	0.0402 (13)	0.4921 (13)	0.0224 (7)	0.065 (10)*	0.30
H3CB	0.0961	0.4898	0.0455	0.078*	0.30
Cl13	0.0097 (15)	0.3889 (17)	−0.0293 (10)	0.166 (8)*	0.30
Cl23	0.0090 (13)	0.6153 (13)	−0.0151 (8)	0.138 (6)*	0.30
Cl33	−0.0282 (15)	0.479 (3)	0.0597 (10)	0.196 (9)*	0.30

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru	0.0347 (4)	0.0352 (4)	0.0323 (4)	0.0004 (3)	0.0139 (3)	−0.0023 (3)
Cl1	0.0478 (13)	0.0558 (14)	0.0461 (13)	0.0014 (11)	0.0248 (11)	−0.0108 (11)
Cl2	0.0498 (13)	0.0391 (13)	0.0519 (13)	−0.0073 (10)	0.0201 (11)	0.0001 (10)
P1	0.0362 (12)	0.0396 (13)	0.0381 (12)	−0.0003 (10)	0.0134 (10)	−0.0024 (10)
P2	0.0417 (13)	0.0419 (13)	0.0320 (12)	0.0033 (10)	0.0122 (10)	0.0012 (10)
P3	0.0400 (13)	0.0355 (13)	0.0369 (12)	−0.0024 (10)	0.0106 (10)	−0.0010 (10)
N	0.034 (4)	0.045 (4)	0.039 (4)	0.003 (3)	0.015 (3)	0.003 (3)
C11	0.046 (5)	0.049 (6)	0.031 (4)	−0.017 (5)	0.009 (4)	−0.002 (4)
C12	0.044 (5)	0.058 (6)	0.037 (5)	−0.003 (5)	0.007 (4)	0.004 (5)
C13	0.059 (6)	0.073 (8)	0.045 (6)	−0.009 (6)	0.021 (5)	−0.005 (5)
C14	0.082 (8)	0.052 (6)	0.046 (6)	−0.006 (6)	0.010 (5)	0.014 (5)
C15	0.076 (8)	0.062 (7)	0.052 (6)	0.016 (6)	0.013 (6)	0.018 (6)
C16	0.056 (6)	0.054 (6)	0.054 (6)	0.016 (5)	0.016 (5)	0.009 (5)
C21	0.044 (5)	0.045 (5)	0.036 (5)	−0.004 (4)	0.009 (4)	−0.003 (4)
C22	0.054 (6)	0.067 (7)	0.051 (6)	−0.013 (5)	0.015 (5)	−0.003 (5)
C23	0.084 (9)	0.104 (10)	0.037 (6)	−0.049 (8)	0.008 (6)	−0.005 (6)
C24	0.119 (12)	0.069 (8)	0.046 (6)	−0.035 (8)	0.030 (7)	−0.014 (6)
C25	0.091 (9)	0.051 (7)	0.066 (7)	−0.002 (6)	0.034 (7)	−0.009 (6)
C26	0.065 (7)	0.055 (6)	0.041 (5)	−0.018 (5)	0.022 (5)	−0.008 (4)
C31	0.042 (5)	0.038 (5)	0.050 (5)	0.002 (4)	0.014 (4)	0.001 (4)
C32	0.065 (7)	0.056 (7)	0.056 (6)	0.005 (5)	0.030 (5)	0.006 (5)
C33	0.079 (8)	0.073 (8)	0.071 (8)	0.003 (7)	0.027 (7)	0.024 (7)
C34	0.069 (8)	0.054 (7)	0.118 (11)	0.012 (6)	0.042 (8)	0.021 (7)
C35	0.073 (8)	0.054 (7)	0.110 (10)	0.011 (6)	0.051 (8)	0.005 (7)
C36	0.070 (7)	0.046 (6)	0.071 (7)	0.008 (5)	0.034 (6)	0.000 (5)
C41	0.056 (6)	0.038 (5)	0.040 (5)	0.014 (4)	0.014 (4)	0.001 (4)
C42	0.068 (7)	0.051 (6)	0.046 (6)	0.007 (5)	0.012 (5)	0.000 (5)
C43	0.055 (7)	0.065 (8)	0.060 (7)	−0.004 (6)	−0.020 (6)	−0.012 (6)
C44	0.045 (6)	0.087 (9)	0.085 (9)	−0.005 (7)	0.002 (6)	0.002 (7)
C45	0.039 (6)	0.068 (7)	0.079 (8)	0.001 (5)	0.017 (5)	−0.008 (6)
C46	0.046 (6)	0.051 (6)	0.054 (6)	0.004 (5)	0.015 (5)	−0.006 (5)
C51	0.044 (5)	0.049 (6)	0.036 (5)	−0.005 (4)	0.005 (4)	0.005 (4)
C52	0.051 (6)	0.048 (6)	0.066 (7)	−0.002 (5)	0.016 (5)	0.002 (5)
C53	0.040 (6)	0.085 (8)	0.066 (7)	−0.006 (6)	0.003 (5)	0.011 (7)
C54	0.060 (7)	0.062 (7)	0.073 (8)	−0.013 (6)	−0.001 (6)	−0.010 (6)
C55	0.062 (7)	0.055 (7)	0.055 (6)	0.000 (5)	−0.002 (5)	−0.015 (5)
C56	0.053 (6)	0.047 (6)	0.055 (6)	−0.002 (5)	0.005 (5)	−0.012 (5)
C61	0.044 (5)	0.061 (7)	0.041 (5)	−0.019 (5)	0.008 (4)	0.003 (5)
C62	0.062 (7)	0.054 (7)	0.065 (7)	−0.013 (5)	0.009 (6)	0.014 (6)
C63	0.079 (9)	0.069 (8)	0.068 (8)	−0.020 (7)	0.001 (7)	0.022 (7)
C64	0.080 (9)	0.105 (11)	0.065 (8)	−0.012 (8)	0.030 (7)	0.029 (8)
C65	0.067 (8)	0.102 (10)	0.062 (7)	−0.012 (7)	0.031 (6)	0.017 (7)
C66	0.062 (7)	0.070 (7)	0.046 (6)	0.000 (6)	0.025 (5)	0.012 (5)
C71	0.051 (6)	0.053 (6)	0.052 (6)	0.002 (5)	0.029 (5)	0.001 (5)
C72	0.042 (5)	0.052 (6)	0.043 (5)	−0.001 (5)	0.013 (4)	−0.006 (4)
C81	0.060 (6)	0.047 (6)	0.036 (5)	0.008 (5)	0.023 (4)	−0.001 (4)
C82	0.056 (6)	0.052 (6)	0.035 (5)	0.016 (5)	0.018 (4)	0.000 (4)
C91	0.047 (5)	0.040 (5)	0.040 (5)	0.009 (4)	0.016 (4)	−0.009 (4)
C92	0.048 (5)	0.033 (5)	0.049 (5)	0.002 (4)	0.012 (4)	−0.005 (4)
O	0.149 (11)	0.149 (12)	0.234 (16)	0.028 (10)	0.032 (11)	−0.076 (11)

Geometric parameters (Å, º)

Ru—N	2.188 (7)	C61—C66	1.399 (14)
Ru—P3	2.254 (2)	C62—C63	1.367 (15)
Ru—P2	2.346 (2)	C62—H62	0.9300
Ru—P1	2.355 (2)	C63—C64	1.372 (18)
Ru—Cl1	2.447 (2)	C63—H63	0.9300
Ru—Cl2	2.479 (2)	C64—C65	1.328 (18)
P1—C72	1.844 (9)	C64—H64	0.9300
P1—C21	1.846 (9)	C65—C66	1.384 (14)
P1—C11	1.850 (9)	C65—H65	0.9300
P2—C82	1.820 (8)	C66—H66	0.9300
P2—C41	1.827 (10)	C71—C72	1.528 (12)
P2—C31	1.828 (9)	C71—H711	0.9700
P3—C51	1.842 (9)	C71—H712	0.9700
P3—C61	1.848 (10)	C72—H721	0.9700
P3—C92	1.849 (9)	C72—H722	0.9700
N—C71	1.494 (11)	C81—C82	1.523 (13)
N—C81	1.507 (10)	C81—H811	0.9700
N—C91	1.524 (11)	C81—H812	0.9700
C11—C12	1.382 (12)	C82—H821	0.9700
C11—C16	1.386 (13)	C82—H822	0.9700
C12—C13	1.387 (13)	C91—C92	1.498 (12)
C12—H12	0.9300	C91—H911	0.9700
C13—C14	1.373 (15)	C91—H912	0.9700
C13—H13	0.9300	C92—H921	0.9700
C14—C15	1.383 (15)	C92—H922	0.9700
C14—H14	0.9300	O—H1O	0.8495
C15—C16	1.388 (14)	O—H2O	0.8494
C15—H15	0.9300	C1A—Cl11	1.7494 (10)
C16—H16	0.9300	C1A—Cl31	1.7496 (10)
C21—C26	1.388 (13)	C1A—Cl2A	1.7497 (11)
C21—C22	1.406 (13)	C1A—Cl21	1.7499 (11)
C22—C23	1.410 (15)	C1A—Cl3A	1.7503 (10)
C22—H22	0.9300	C1A—Cl1A	1.7506 (10)
C23—C24	1.352 (18)	C1A—H1A	0.9800
C23—H23	0.9300	C2B—Cl22	1.7495 (10)
C24—C25	1.376 (17)	C2B—Cl1B	1.7498 (11)
C24—H24	0.9300	C2B—Cl3B	1.7499 (10)
C25—C26	1.391 (14)	C2B—Cl12	1.7501 (11)
C25—H25	0.9300	C2B—Cl32	1.7503 (11)
C26—H26	0.9300	C2B—Cl2B	1.7505 (10)
C31—C32	1.373 (13)	C2B—H2B	0.9800
C31—C36	1.373 (13)	C3C—Cl1C^i	1.7496 (10)
C32—C33	1.388 (15)	C3C—Cl1C	1.7496 (10)
C32—H32	0.9300	C3C—Cl2C	1.7500 (10)
C33—C34	1.352 (17)	C3C—Cl2C^i	1.7500 (10)
C33—H33	0.9300	C3C—Cl3C^i	1.7500 (10)
C34—C35	1.364 (16)	C3C—Cl3C	1.7500 (10)
C34—H34	0.9300	C3C—H3CA	0.9600
C35—C36	1.394 (15)	Cl1C—Cl2C^i	1.48 (4)
C35—H35	0.9300	Cl1C—Cl3C^i	2.11 (3)
C36—H36	0.9300	Cl2C—Cl1C^i	1.48 (4)
C41—C46	1.375 (12)	Cl2C—Cl3C^i	2.00 (4)
C41—C42	1.402 (13)	Cl3C—Cl2C^i	2.00 (4)
C42—C43	1.375 (14)	Cl3C—Cl1C^i	2.11 (3)
C42—H42	0.9300	C3CA—C3CA^i	1.50 (4)
C43—C44	1.361 (16)	C3CA—Cl23^i	1.54 (3)
C43—H43	0.9300	C3CA—Cl13^i	1.72 (3)
C44—C45	1.410 (16)	C3CA—Cl13	1.7500 (10)
C44—H44	0.9300	C3CA—Cl23	1.7500 (10)
C45—C46	1.375 (13)	C3CA—Cl33	1.7500 (10)
C45—H45	0.9300	C3CA—Cl33^i	2.02 (3)
C46—H46	0.9300	C3CA—H3CA	0.3817
C51—C56	1.380 (13)	C3CA—H3CB	0.9600
C51—C52	1.385 (13)	Cl13—Cl23^i	1.26 (3)
C52—C53	1.394 (14)	Cl13—C3CA^i	1.72 (3)
C52—H52	0.9300	Cl13—Cl33^i	1.85 (3)
C53—C54	1.369 (16)	Cl23—Cl13^i	1.26 (3)
C53—H53	0.9300	Cl23—C3CA^i	1.54 (3)
C54—C55	1.341 (15)	Cl23—Cl33^i	1.70 (3)
C54—H54	0.9300	Cl23—H3CA	1.7052
C55—C56	1.389 (13)	Cl33—Cl23^i	1.70 (3)
C55—H55	0.9300	Cl33—Cl13^i	1.85 (3)
C56—H56	0.9300	Cl33—C3CA^i	2.02 (3)
C61—C62	1.397 (14)	Cl33—H3CA	1.6523
N—Ru—P3	84.5 (2)	N—C81—C82	111.8 (7)
N—Ru—P2	84.55 (19)	N—C81—H811	109.3
P3—Ru—P2	96.44 (9)	C82—C81—H811	109.3
N—Ru—P1	82.68 (19)	N—C81—H812	109.3
P3—Ru—P1	92.61 (8)	C82—C81—H812	109.3
P2—Ru—P1	163.56 (8)	H811—C81—H812	107.9
N—Ru—Cl1	176.6 (2)	C81—C82—P2	107.3 (6)
P3—Ru—Cl1	98.47 (9)	C81—C82—H821	110.3
P2—Ru—Cl1	93.41 (8)	P2—C82—H821	110.3
P1—Ru—Cl1	98.81 (8)	C81—C82—H822	110.3
N—Ru—Cl2	88.2 (2)	P2—C82—H822	110.3
P3—Ru—Cl2	171.89 (9)	H821—C82—H822	108.5
P2—Ru—Cl2	86.38 (8)	C92—C91—N	116.2 (7)
P1—Ru—Cl2	82.92 (8)	C92—C91—H911	108.2
Cl1—Ru—Cl2	88.93 (8)	N—C91—H911	108.2
C72—P1—C21	105.4 (4)	C92—C91—H912	108.2
C72—P1—C11	104.5 (4)	N—C91—H912	108.2
C21—P1—C11	97.5 (4)	H911—C91—H912	107.4
C72—P1—Ru	101.9 (3)	C91—C92—P3	108.9 (6)
C21—P1—Ru	121.2 (3)	C91—C92—H921	109.9
C11—P1—Ru	124.3 (3)	P3—C92—H921	109.9
C82—P2—C41	106.3 (4)	C91—C92—H922	109.9
C82—P2—C31	104.9 (4)	P3—C92—H922	109.9
C41—P2—C31	97.8 (4)	H921—C92—H922	108.3
C82—P2—Ru	100.1 (3)	H1O—O—H2O	107.8
C41—P2—Ru	128.5 (3)	Cl11—C1A—Cl31	98.4 (10)
C31—P2—Ru	117.0 (3)	Cl11—C1A—Cl2A	137.9 (8)
C51—P3—C61	97.8 (4)	Cl31—C1A—Cl2A	115.9 (8)
C51—P3—C92	103.4 (4)	Cl11—C1A—Cl21	118.9 (9)
C61—P3—C92	104.9 (5)	Cl31—C1A—Cl21	121.7 (10)
C51—P3—Ru	122.0 (3)	Cl2A—C1A—Cl21	21.0 (5)
C61—P3—Ru	124.4 (3)	Cl11—C1A—Cl3A	108.6 (8)
C92—P3—Ru	101.8 (3)	Cl31—C1A—Cl3A	11.6 (9)
C71—N—C81	107.0 (7)	Cl2A—C1A—Cl3A	104.3 (4)
C71—N—C91	109.1 (7)	Cl21—C1A—Cl3A	110.7 (6)
C81—N—C91	107.3 (7)	Cl11—C1A—Cl1A	33.8 (7)
C71—N—Ru	109.5 (5)	Cl31—C1A—Cl1A	106.9 (9)
C81—N—Ru	109.7 (5)	Cl2A—C1A—Cl1A	108.6 (5)
C91—N—Ru	114.0 (5)	Cl21—C1A—Cl1A	87.8 (7)
C12—C11—C16	120.5 (9)	Cl3A—C1A—Cl1A	112.2 (6)
C12—C11—P1	115.6 (7)	Cl11—C1A—H1A	81.7
C16—C11—P1	123.9 (7)	Cl31—C1A—H1A	104.2
C11—C12—C13	119.6 (10)	Cl2A—C1A—H1A	110.5
C11—C12—H12	120.2	Cl21—C1A—H1A	123.0
C13—C12—H12	120.2	Cl3A—C1A—H1A	110.5
C14—C13—C12	120.4 (10)	Cl1A—C1A—H1A	110.5
C14—C13—H13	119.8	Cl22—C2B—Cl1B	118.3 (6)
C12—C13—H13	119.8	Cl22—C2B—Cl3B	77.9 (7)
C13—C14—C15	119.8 (10)	Cl1B—C2B—Cl3B	109.7 (7)
C13—C14—H14	120.1	Cl22—C2B—Cl12	107.8 (6)
C15—C14—H14	120.1	Cl1B—C2B—Cl12	23.9 (3)
C14—C15—C16	120.5 (10)	Cl3B—C2B—Cl12	130.9 (7)
C14—C15—H15	119.7	Cl22—C2B—Cl32	104.7 (10)
C16—C15—H15	119.7	Cl1B—C2B—Cl32	85.5 (8)
C11—C16—C15	119.1 (10)	Cl3B—C2B—Cl32	29.8 (7)
C11—C16—H16	120.5	Cl12—C2B—Cl32	109.2 (8)
C15—C16—H16	120.5	Cl22—C2B—Cl2B	26.1 (5)
C26—C21—C22	120.8 (9)	Cl1B—C2B—Cl2B	112.4 (5)
C26—C21—P1	120.6 (7)	Cl3B—C2B—Cl2B	103.7 (7)
C22—C21—P1	118.5 (7)	Cl12—C2B—Cl2B	93.7 (5)
C21—C22—C23	116.4 (11)	Cl32—C2B—Cl2B	130.8 (9)
C21—C22—H22	121.8	Cl22—C2B—H2B	124.3
C23—C22—H22	121.8	Cl1B—C2B—H2B	110.3
C24—C23—C22	124.2 (12)	Cl3B—C2B—H2B	110.3
C24—C23—H23	117.9	Cl12—C2B—H2B	105.6
C22—C23—H23	117.9	Cl32—C2B—H2B	104.6
C23—C24—C25	117.4 (11)	Cl2B—C2B—H2B	110.3
C23—C24—H24	121.3	Cl1C^i—C3C—Cl1C	180.0 (16)
C25—C24—H24	121.3	Cl1C^i—C3C—Cl2C	50.0 (16)
C24—C25—C26	122.4 (11)	Cl1C—C3C—Cl2C	130.0 (16)
C24—C25—H25	118.8	Cl1C^i—C3C—Cl2C^i	130.0 (16)
C26—C25—H25	118.8	Cl1C—C3C—Cl2C^i	50.0 (16)
C21—C26—C25	118.8 (10)	Cl2C—C3C—Cl2C^i	180.0 (13)
C21—C26—H26	120.6	Cl1C^i—C3C—Cl3C^i	105.7 (12)
C25—C26—H26	120.6	Cl1C—C3C—Cl3C^i	74.3 (12)
C32—C31—C36	116.8 (9)	Cl2C—C3C—Cl3C^i	69.7 (16)
C32—C31—P2	124.4 (7)	Cl2C^i—C3C—Cl3C^i	110.3 (16)
C36—C31—P2	118.7 (7)	Cl1C^i—C3C—Cl3C	74.3 (12)
C31—C32—C33	122.9 (10)	Cl1C—C3C—Cl3C	105.7 (12)
C31—C32—H32	118.6	Cl2C—C3C—Cl3C	110.3 (16)
C33—C32—H32	118.6	Cl2C^i—C3C—Cl3C	69.7 (16)
C34—C33—C32	118.4 (11)	Cl3C^i—C3C—Cl3C	180.0 (13)
C34—C33—H33	120.8	Cl1C^i—C3C—H3CA	77.7
C32—C33—H33	120.8	Cl1C—C3C—H3CA	102.3
C33—C34—C35	121.2 (11)	Cl2C—C3C—H3CA	102.4
C33—C34—H34	119.4	Cl2C^i—C3C—H3CA	77.6
C35—C34—H34	119.4	Cl3C^i—C3C—H3CA	77.4
C34—C35—C36	119.3 (12)	Cl3C—C3C—H3CA	102.6
C34—C35—H35	120.4	Cl2C^i—Cl1C—C3C	65.0 (8)
C36—C35—H35	120.4	Cl2C^i—Cl1C—Cl3C^i	104.8 (14)
C31—C36—C35	121.4 (11)	C3C—Cl1C—Cl3C^i	52.9 (6)
C31—C36—H36	119.3	Cl1C^i—Cl2C—C3C	65.0 (8)
C35—C36—H36	119.3	Cl1C^i—Cl2C—Cl3C^i	105.6 (15)
C46—C41—C42	118.9 (9)	C3C—Cl2C—Cl3C^i	55.1 (8)
C46—C41—P2	118.0 (7)	C3C—Cl3C—Cl2C^i	55.1 (8)
C42—C41—P2	123.0 (8)	C3C—Cl3C—Cl1C^i	52.8 (6)
C43—C42—C41	119.5 (10)	Cl2C^i—Cl3C—Cl1C^i	100.8 (10)
C43—C42—H42	120.2	C3CA^i—C3CA—Cl23^i	70.5 (14)
C41—C42—H42	120.2	C3CA^i—C3CA—Cl13^i	65.4 (12)
C44—C43—C42	121.3 (10)	Cl23^i—C3CA—Cl13^i	115.8 (18)
C44—C43—H43	119.4	C3CA^i—C3CA—Cl13	63.6 (14)
C42—C43—H43	119.4	Cl23^i—C3CA—Cl13	44.4 (10)
C43—C44—C45	120.1 (10)	Cl13^i—C3CA—Cl13	129.0 (15)
C43—C44—H44	120.0	C3CA^i—C3CA—Cl23	55.9 (11)
C45—C44—H44	120.0	Cl23^i—C3CA—Cl23	126.4 (15)
C46—C45—C44	118.3 (10)	Cl13^i—C3CA—Cl23	42.4 (9)
C46—C45—H45	120.8	Cl13—C3CA—Cl23	104.4 (13)
C44—C45—H45	120.8	C3CA^i—C3CA—Cl33	76.6 (18)
C41—C46—C45	122.0 (10)	Cl23^i—C3CA—Cl33	61.9 (13)
C41—C46—H46	119.0	Cl13^i—C3CA—Cl33	64.2 (14)
C45—C46—H46	119.0	Cl13—C3CA—Cl33	103.3 (16)
C56—C51—C52	117.4 (9)	Cl23—C3CA—Cl33	102.4 (15)
C56—C51—P3	123.8 (8)	C3CA^i—C3CA—Cl33^i	57.4 (10)
C52—C51—P3	118.8 (7)	Cl23^i—C3CA—Cl33^i	99.2 (13)
C51—C52—C53	121.3 (10)	Cl13^i—C3CA—Cl33^i	93.9 (13)
C51—C52—H52	119.4	Cl13—C3CA—Cl33^i	58.1 (12)
C53—C52—H52	119.4	Cl23—C3CA—Cl33^i	53.0 (11)
C54—C53—C52	119.8 (11)	Cl33—C3CA—Cl33^i	134.0 (14)
C54—C53—H53	120.1	C3CA^i—C3CA—H3CA	112.3
C52—C53—H53	120.1	Cl23^i—C3CA—H3CA	128.7
C55—C54—C53	119.4 (10)	Cl13^i—C3CA—H3CA	47.4
C55—C54—H54	120.3	Cl13—C3CA—H3CA	172.2
C53—C54—H54	120.3	Cl23—C3CA—H3CA	77.0
C54—C55—C56	121.8 (10)	Cl33—C3CA—H3CA	69.0
C54—C55—H55	119.1	Cl33^i—C3CA—H3CA	126.2
C56—C55—H55	119.1	C3CA^i—C3CA—H3CB	167.7
C51—C56—C55	120.3 (10)	Cl23^i—C3CA—H3CB	117.9
C51—C56—H56	119.9	Cl13^i—C3CA—H3CB	114.7
C55—C56—H56	119.9	Cl13—C3CA—H3CB	115.1
C62—C61—C66	119.2 (10)	Cl23—C3CA—H3CB	115.1
C62—C61—P3	122.0 (9)	Cl33—C3CA—H3CB	115.0
C66—C61—P3	118.6 (8)	Cl33^i—C3CA—H3CB	110.9
C63—C62—C61	120.6 (12)	H3CA—C3CA—H3CB	70.4
C63—C62—H62	119.7	Cl23^i—Cl13—C3CA^i	69.9 (13)
C61—C62—H62	119.7	Cl23^i—Cl13—C3CA	58.8 (13)
C62—C63—C64	118.8 (12)	C3CA^i—Cl13—C3CA	51.0 (15)
C62—C63—H63	120.6	Cl23^i—Cl13—Cl33^i	121.9 (17)
C64—C63—H63	120.6	C3CA^i—Cl13—Cl33^i	58.6 (9)
C65—C64—C63	121.8 (12)	C3CA—Cl13—Cl33^i	68.3 (13)
C65—C64—H64	119.1	Cl13^i—Cl23—C3CA^i	76.8 (13)
C63—C64—H64	119.1	Cl13^i—Cl23—Cl33^i	135.7 (17)
C64—C65—C66	121.5 (13)	C3CA^i—Cl23—Cl33^i	65.2 (9)
C64—C65—H65	119.3	Cl13^i—Cl23—C3CA	67.7 (15)
C66—C65—H65	119.3	C3CA^i—Cl23—C3CA	53.6 (15)
C65—C66—C61	118.0 (11)	Cl33^i—Cl23—C3CA	71.7 (14)
C65—C66—H66	121.0	Cl13^i—Cl23—H3CA	58.2
C61—C66—H66	121.0	C3CA^i—Cl23—H3CA	62.1
N—C71—C72	111.7 (7)	Cl33^i—Cl23—H3CA	83.5
N—C71—H711	109.3	C3CA—Cl23—H3CA	12.6
C72—C71—H711	109.3	Cl23^i—Cl33—C3CA	52.9 (11)
N—C71—H712	109.3	Cl23^i—Cl33—Cl13^i	102.3 (13)
C72—C71—H712	109.3	C3CA—Cl33—Cl13^i	57.2 (12)
H711—C71—H712	107.9	Cl23^i—Cl33—C3CA^i	55.3 (9)
C71—C72—P1	110.4 (6)	C3CA—Cl33—C3CA^i	46.0 (14)
C71—C72—H721	109.6	Cl13^i—Cl33—C3CA^i	53.6 (8)
P1—C72—H721	109.6	Cl23^i—Cl33—H3CA	65.0
C71—C72—H722	109.6	C3CA—Cl33—H3CA	12.5
P1—C72—H722	109.6	Cl13^i—Cl33—H3CA	50.1
H721—C72—H722	108.1	C3CA^i—Cl33—H3CA	53.2

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2B—H2B···Cl1^i	0.98	2.38	3.349 (7)	171
C26—H26···Cl1	0.93	2.78	3.635 (12)	153
C66—H66···Cl1	0.93	2.71	3.521 (11)	146
C71—H712···Cl2	0.97	2.58	3.216 (10)	122
C72—H721···Cl2^ii	0.97	2.62	3.455 (10)	144
C91—H911···Cl2^ii	0.97	2.79	3.666 (11)	151
C46—H46···Cl1	0.93	2.88	3.698 (9)	148
C15—H15···Cl12^iii	0.93	2.89	3.511 (11)	126
C66—H66···Cl31^iv	0.93	2.89	3.590 (18)	133
C54—H54···Cl22^iv	0.93	2.73	3.545 (15)	146
C54—H54···Cl13^v	0.93	2.87	3.50 (2)	126
O—H1O···Cl21	0.85	2.78	3.46 (2)	151
O—H2O···Cl2^i	0.85	2.46	3.31 (2)	176

Symmetry codes: (i) −x, −y+1, −z; (ii) −x−1, y+1/2, −z−1/2; (iii) x−1, y+1, z−1; (iv) x, −y+3/2, z−1/2; (v) x, y+1, z.