Bis(di-2-pyridyl sulfide-[kappa]²N,N')(4-methylpyrimidin-2-yl 2-pyridylmethyl sulfide-[kappa]²N,S)ruthenium(II) bis(hexafluorophosphate) acetonitrile solvate

The crystal structure of the title compound, [Ru(C₁₀H₈N₂S)₂(C₁₁H₁₁N₃S)](PF₆)₂·C₂H₃N, is composed of a bivalent octa­hedral Ru^II complex, two PF₆^- anions and an acetonitrile solvent mol­ecule. Two PF₆^- units are found on a crystallographic binary axis, therefore contributing just one half each to the asymmetric unit cell. The structure displays a peculiar stereochemistry of the cation. Three bidentate ligands around the Ru centre, together with the coordination of the non-symmetric S atom, mean that these two atoms are chiral. This would lead to four stereoisomers, but only an enantiomeric pair was found in the analyzed sample.

S1. Comment

Coordination chemistry of flexible and hemilabile ligands, containing both inert and labile groups, is an active area of research (Slone et al., 1999; Vagg, 1987). N-Heterocyclic donors are often good ligands for many transition metal centres. Hybrid S/N/S ligands consisting of inert pyridine or bipyridine binding groups, connected to labile sulfur binding sites, show S—S switching in addition to S inversion (Abel et al., 1995, and references therein). Thioether ligands containing aromatic heterocyclic N, such as di-2-pyridylsulfide or di-2-pyrimidylsulfide (dps and dprs), usually bind metals in an N,N-bidentate fashion (Bruno et al., 1995, and references therein) and sometimes adopt N-monodentate coordination (Tresoldi et al., 1991, 1992), or N,N- (De Munno et al., 1993; Teles et al. 1999) or N,N,S-bridging coordination (Anderson & Steel, 1998). The flexibility and, in a few cases, the hemilability of dps have been assessed (Tresoldi et al., 1992; De Munno et al. 1993).

Recently, we have demonstrated that dps, under appropriate conditions, binds Ru in an N,S-chelate fashion, leaving one of the pyridine rings uncoordinated (Scopelliti et al., 2001). In such species, some dynamic processes occur, as shown by the temperature dependence of the NMR spectra, but only the restricted rotation of the uncoordinated ring could be studied, whereas the total dynamic stereochemistry remained unclear. On the other hand, we have demonstrated the presence of two invertomers as enantiomeric pairs, (ΔR, ΛS) and (ΔS, ΛR), and obtained quantitative information on the activation energy of the pyramidal inversion around the coordinated S atom (Tresoldi et al., 2002), as well as of the restricted rotation of the pendant ring (Baradello et al., 2004), when the Ru^II centre was N,S-chelated by thioether ligands based on pyridine or pyrimidine and benzyl or phenyl derivatives. We have now turned our attention to metal complexes containing unsymmetrical NSNN thioethers, and we are interested in studying the interchange processes between different conformations and distinct coordination species. In this paper, the reaction of 2-pyridylmethyl-2'-(4-methylpyrimidyl)sulfide (pmprs) with cis-Ru(dps-N,N)₂Cl₂ led to the title compound, [Ru(dps-N,N)₂pmprs](PF₆)₂·C₂H₃N, (I).

The structure of (I) presents two asymmetric atoms, Ru1 and S34, the conventional absolute configurations of which are Δ and R, respectively. Since the space group is centrosymmetric, a racemic mixture crystallizes in the solid state (ΔR and ΛS enantiomers; Fig. 1). The asymmetric unit consists of one cationic complex, one acetonitrile solvent molecule, one entire hexafluorophosphate unit and two further halves of the same anion located on special positions (along the binary axis). The coordination geometry of the Ru^II ion is, as expected, distorted octahedral, with five N atoms and atom S34 as binding sites (Table 1 and Fig. 1). The distortion provoked by an N,S short-bite ligand has already been shown in similar derivatives (Scopelliti et al., 2001). In (I), this effect is not so dramatic, since the five-membered ring presents less strain than the previously analysed four-membered N,S short-bite ligand. This is evident from the geometric comparison of the parameters N—Ru—S [81.8 (1) versus 67.8 (2)°], Ru—N [2.123 (3) versus 2.080 (5) Å] and Ru—S [2.358 (1) versus 2.424 (2) Å] in (I) and the above-mentioned structure, respectively. On the other hand, this is confirmed by an analogue of (I) with the pmprs position occupied by a different 2-pyridylmethylarylsulfide ligand (Baradello et al., 2004). In this case, the geometrical parameters are very close to those measured for (I) [Ru—S 2.370 (1) Å, Ru—N 2.108 (3) Å and N—Ru—S 81.39 (9)°]. The ring formed by the chelation is in an envelope-like conformation, as shown by the puckering parameters (Cremer & Pople, 1975) calculated using the atom sequence from Ru1 to S34 [q₂ = 0.489 (4) Å and ϕ₂ = −37.2 (5)°]. All these data were also compared with Ag (Wang et al., 2001) and Cu (Sillanpää et al., 1994) structures with the symmetric multidentate ligand 2,6-bis(2-pyrimidinylthiomethyl)pyrimidine, which develop (asymmetrically) the same coordination bite shown by pmprs. However, for these structures the other coordination site leads to an enhancement of the distortion. In (I), the Ru—N distances are slightly affected by the pmprs ligand, with the N atoms trans to this group being closer to the metal (Table 1). However, none of the Ru—N distances deviate much from the values reported for similar structures (~2.110 Å).

The two dps ligands display their usual `twisted N,N' inside' conformation, as shown by Bruno et al. (1995), in order to chelate the metal via the lone-pairs of the N atoms. For (I), though, the dps bite angle looks wider with respect to the previously analysed structure Which? [N···N 2.952 (5) and 2.946 (5) Å, and N—Ru—N 89.0 (1) and 89.1 (1)°, for the first and second ligands, respectively]. This is due to the short bite of the pmprs ligand allowing the widening of the dps groups. The boat-like conformation of both dps rings generated through the above-mentioned chelation is shown by the puckering parameters [for ring Ru1/N1–N13, Q = 0.839 (2) Å, θ = 88.2 (2) and ϕ = 0.7 (2)°; for ring Ru1/N14–N26, Q = 0.904 (3) Å, θ = 92.4 (2) and ϕ = 175.7 (3)°].

Since there are no structural data available for either the free or the coordinated 2-pyridylmethyl-2'-(4-methylpyrimidyl)sulfide (pmprs) ligand, ab initio and density functional theory calculations were carried out, using GAUSSIAN98 (Frisch et al., 1998); full geometry optimizations were carried out using the 6–31+G(d,p) basis set in order to obtain comparable data and to study how the molecular geometry of pmprs is modified by coordination to a metal centre. As the hybrid B3LYP method generally works better than the Hartree–Fock one in reproducing the `real' molecular geometry, we compared these calculated values with the experimental X-ray data. As expected, the gas phase conformation of pmprs looks very different from the coordinated one, because of its great conformational flexibility. Nevertheless, we observed a general agreement between the structural parameters, except for the fragment involved in coordination to the metal; the bond distances S34—C35 [1.7728 Å] and S34—C33 [1.8476 Å], and bond angles C33—S34—C35 [103.17°] and N27—C32—C33 [116.14°], can be compared with experimental values for (I) in Table 1.

The crystal packing of (I) is mainly stabilized by intermolecular hydrogen interactions, the acceptor atoms of which are F atoms of the anionic units or the N atom of the solvent molecule, while the donors are several types of C—H groups of the cationic unit. In this way, the complex molecules are mainly held together in an ordered array by the anion and the solvent molecule (Table 2). Other weak dipolar intercation interactions further stabilize the overall solid state structure.

S2. Experimental

Di-2-pyridylsulfide (dps), 2-pyridylmethyl-2'-(4-methylpyrimidyl)sulfide (pmprs) and cis-Ru(dps-N,N)₂Cl₂·2H₂O were prepared according to the methods of Chachaty et al. (1976), Haviv et al. (1983) and Tresoldi et al. (2005), respectively. cis-Ru(dps-N,N)₂Cl₂·2H₂O (0.195 g, 0.33 mmol) and pmprs (0.22 g, 3 mmol) were refluxed in ethanol–water (50 ml, 3:2) under N₂ for 3 h. After filtration of the solution into water (80 ml) containing NH₄PF₆ (0.49 g, 1 mmol) a yellow precipitate was obtained. This was filtered, washed with water (30 ml) and dried overnight. The solid was then dissolved in acetone (15 ml), precipitated with diethyl ether (70 ml), washed with diethyl ether (30 ml) and dried over P₄O₁₀. Yellow crystals of (I) suitable for X-ray structure investigation were obtained from a solution in acetonitrile–ether (3:1) on standing for ca 3 d at 252 K. Analysis, C₃₂H₃₀F₁₂N₈P₂RuS₃ requires: C 37.91, H 3.05, N 11.05%; found: C 37.85, H 3.00, N 11.00%.

S3. Refinement

X-ray diffraction analysis gave a monoclinic crystal system for (I). The space group was assumed to be centrosymmetric during the data-reduction procedure, and confirmed by the subsequent analysis (Orpen et al., 1992). All H atoms were treated as riding, with alkyl C—H distances of 0.98, methyl C—H distances of 0.96 and aromatic C—H distances of 0.93 Å. Their isotropic displacement parameters were fixed by the riding-model technique to U_iso(H) = 1.5U_eq(C) for the methyl group and 1.2U_eq(C) for all others. Intensities were calculated by the profile-fitting procedure (Lehmann & Larsen, 1974). Few refinement troubles were caused, mainly by the intrinsic disorder of the two units in the special position. It was necessary to chose two sites for most of the F atoms and their complementary occupancy factors were obtained by refinement and then fixed.

Computing details

Data collection: XSCANS (Siemens, 1989); cell refinement: XSCANS; data reduction: XPREPW (Bruker, 1997); program(s) used to solve structure: SIR2002 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW (Bruker, 1997); software used to prepare material for publication: PARST97 (Nardelli, 1995) and WinGX-PC (version 1.6.4.05; Farrugia, 1999).

Figures

	Fig. 1. The cation of the (Δ—Ru1, R-S34) isomer of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level for all non-C atoms and at the ??% probability level for C atoms Please provide missing information. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of (I).

Bis(di-2-pyridyl sulfide-κ²N,N')(4-methylpyrimidin-2-yl 2-pyridylmethyl sulfide-κ²N,S)ruthenium(II) bis(hexafluorophosphate) acetonitrile solvate

Crystal data

[Ru(C10H8N2S)2(C11H11N3S)](PF6)2·C2H3N	F(000) = 4112
Mr = 1025.84	Dx = 1.698 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ya	Cell parameters from 30 reflections
a = 23.685 (5) Å	θ = 2.2–16.2°
b = 14.183 (2) Å	µ = 0.72 mm^−1
c = 25.264 (8) Å	T = 298 K
β = 108.941 (16)°	Irregular, yellow
V = 8027 (3) Å^3	0.4 × 0.24 × 0.2 mm
Z = 8

Data collection

Bruker P4 diffractometer	θmax = 25.0°, θmin = 2.1°
ω scans	h = −28→24
8188 measured reflections	k = −16→1
7057 independent reflections	l = −30→24
4940 reflections with I > 2σ(I)	3 standard reflections every 197 reflections
Rint = 0.028	intensity decay: none

Refinement

Refinement on F^2	30 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(Fo^2) + (0.0418P)^2 + 20.1188P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.114	(Δ/σ)max = 0.006
S = 1.03	Δρmax = 0.59 e Å^−3
7057 reflections	Δρmin = −0.38 e Å^−3
572 parameters

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ru1	0.603182 (16)	0.31438 (3)	0.149985 (14)	0.03261 (10)
N1	0.64974 (16)	0.4389 (3)	0.14460 (14)	0.0345 (9)
C2	0.7058 (2)	0.4514 (4)	0.1809 (2)	0.0436 (12)
H2	0.7218	0.4048	0.2074	0.052*
C3	0.7398 (2)	0.5287 (4)	0.1805 (2)	0.0519 (14)
H3	0.7784	0.5331	0.2056	0.062*
C4	0.7168 (3)	0.6000 (4)	0.1429 (2)	0.0607 (15)
H4	0.7395	0.6531	0.1419	0.073*
C5	0.6591 (2)	0.5909 (4)	0.1067 (2)	0.0515 (14)
H5	0.6421	0.6386	0.0812	0.062*
C6	0.6269 (2)	0.5105 (3)	0.10862 (18)	0.0380 (11)
S7	0.55488 (6)	0.50384 (9)	0.06003 (5)	0.0447 (3)
C8	0.5093 (2)	0.4677 (3)	0.09978 (18)	0.0380 (11)
C9	0.4560 (2)	0.5155 (4)	0.0899 (2)	0.0510 (14)
H9	0.4461	0.5646	0.0641	0.061*
C10	0.4180 (2)	0.4905 (4)	0.1179 (2)	0.0550 (14)
H10	0.3816	0.5212	0.111	0.066*
C11	0.4343 (2)	0.4191 (4)	0.1567 (2)	0.0496 (13)
H11	0.4097	0.4019	0.1772	0.059*
C12	0.4873 (2)	0.3739 (3)	0.16451 (19)	0.0435 (12)
H12	0.498	0.326	0.1911	0.052*
N13	0.52515 (16)	0.3949 (3)	0.13573 (14)	0.0346 (9)
N14	0.62093 (16)	0.3457 (3)	0.23490 (15)	0.0399 (10)
C15	0.6151 (2)	0.4342 (4)	0.2514 (2)	0.0450 (12)
H15	0.6037	0.4808	0.2242	0.054*
C16	0.6252 (2)	0.4597 (4)	0.3060 (2)	0.0564 (15)
H16	0.6213	0.5223	0.3152	0.068*
C17	0.6410 (3)	0.3919 (5)	0.3467 (2)	0.0656 (17)
H17	0.6488	0.4078	0.3841	0.079*
C18	0.6451 (2)	0.3004 (4)	0.3314 (2)	0.0566 (15)
H18	0.654	0.2529	0.3582	0.068*
C19	0.6359 (2)	0.2789 (4)	0.27612 (19)	0.0441 (12)
S20	0.64869 (6)	0.16212 (10)	0.25957 (5)	0.0545 (4)
C21	0.5830 (2)	0.1316 (3)	0.2053 (2)	0.0460 (13)
C22	0.5596 (3)	0.0432 (4)	0.2083 (3)	0.0652 (17)
H22	0.5776	0.0042	0.2387	0.078*
C23	0.5101 (3)	0.0134 (4)	0.1666 (3)	0.0756 (19)
H23	0.495	−0.047	0.1674	0.091*
C24	0.4829 (3)	0.0740 (4)	0.1236 (3)	0.0639 (16)
H24	0.4479	0.057	0.0956	0.077*
C25	0.5089 (2)	0.1607 (4)	0.1228 (2)	0.0466 (13)
H25	0.4899	0.2017	0.0937	0.056*
N26	0.55955 (16)	0.1903 (3)	0.16114 (15)	0.0390 (9)
N27	0.58594 (16)	0.2838 (3)	0.06393 (14)	0.0357 (9)
C28	0.5310 (2)	0.2843 (3)	0.02500 (19)	0.0392 (11)
H28	0.499	0.3035	0.036	0.047*
C29	0.5197 (2)	0.2581 (3)	−0.0296 (2)	0.0473 (13)
H29	0.481	0.2586	−0.0546	0.057*
C30	0.5670 (3)	0.2311 (4)	−0.0464 (2)	0.0536 (14)
H30	0.5607	0.2127	−0.0832	0.064*
C31	0.6234 (2)	0.2315 (4)	−0.0082 (2)	0.0477 (13)
H31	0.6559	0.2146	−0.0192	0.057*
C32	0.6319 (2)	0.2573 (3)	0.04660 (19)	0.0374 (11)
C33	0.6933 (2)	0.2600 (4)	0.08831 (19)	0.0443 (12)
H33A	0.7101	0.3225	0.0887	0.053*
H33B	0.7186	0.2153	0.0775	0.053*
S34	0.69177 (5)	0.23103 (9)	0.15822 (5)	0.0402 (3)
C35	0.6815 (2)	0.1047 (3)	0.1477 (2)	0.0447 (12)
N36	0.7231 (2)	0.0538 (3)	0.18361 (18)	0.0609 (13)
C37	0.7170 (3)	−0.0390 (5)	0.1739 (3)	0.082 (2)
H37	0.7448	−0.0796	0.1974	0.098*
C38	0.6714 (3)	−0.0767 (4)	0.1306 (3)	0.0763 (19)
H38	0.6679	−0.1416	0.1252	0.092*
C39	0.6307 (3)	−0.0152 (4)	0.0952 (3)	0.0609 (15)
N40	0.63615 (19)	0.0774 (3)	0.10443 (18)	0.0490 (11)
C41	0.5815 (3)	−0.0490 (5)	0.0472 (3)	0.100 (3)
H41A	0.581	−0.1167	0.0472	0.15*
H41B	0.5868	−0.0267	0.0132	0.15*
H41C	0.5444	−0.0258	0.0497	0.15*
P1	0.41922 (12)	0.22940 (13)	0.28024 (8)	0.0921 (7)
F1	0.3824 (3)	0.3195 (4)	0.2536 (2)	0.152 (2)
F2	0.4249 (3)	0.2014 (4)	0.2227 (2)	0.171 (2)
F3	0.3616 (3)	0.1705 (5)	0.2668 (3)	0.183 (3)
F4	0.4770 (3)	0.2878 (4)	0.2890 (3)	0.185 (3)
F5	0.4173 (4)	0.2610 (4)	0.3378 (2)	0.190 (3)
F6	0.4528 (3)	0.1392 (4)	0.3059 (3)	0.185 (3)
P2	0.75	0.00392 (19)	0	0.0774 (8)
F7	0.6792 (2)	0.0059 (4)	−0.02475 (19)	0.1265 (17)
F8	0.75	0.1115 (13)	0	0.134 (9)	0.4
F9	0.75	−0.1024 (12)	0	0.200 (14)	0.4
F10	0.7486 (7)	0.0045 (16)	−0.0603 (5)	0.155 (8)	0.4
F8A	0.7551 (5)	0.0782 (9)	−0.0432 (5)	0.181 (7)	0.6
F9A	0.7585 (7)	−0.0758 (8)	−0.0376 (6)	0.207 (6)	0.6
P3	0.75	0.45282 (18)	0	0.0677 (6)
F11	0.68651 (17)	0.4510 (3)	0.00798 (18)	0.1045 (13)
F12	0.7265 (3)	0.4510 (9)	−0.0649 (3)	0.126 (4)	0.63
F13	0.75	0.3387 (6)	0	0.082 (3)	0.63
F14	0.75	0.5622 (10)	0	0.188 (8)	0.63
F12A	0.7205 (6)	0.5352 (11)	−0.0424 (6)	0.107 (5)	0.37
F13A	0.7197 (6)	0.3810 (11)	−0.0452 (9)	0.150 (7)	0.37
C42	0.3262 (5)	0.2504 (7)	0.0827 (4)	0.174 (5)
H42A	0.3481	0.2095	0.1125	0.26*
H42B	0.2873	0.2242	0.0644	0.26*
H42C	0.3221	0.3113	0.0976	0.26*
C43	0.3576 (4)	0.2595 (6)	0.0429 (3)	0.090 (2)
N44	0.3878 (3)	0.2658 (5)	0.0185 (3)	0.112 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.03667 (19)	0.03316 (19)	0.02706 (17)	0.00461 (18)	0.00904 (14)	0.00454 (17)
N1	0.039 (2)	0.035 (2)	0.0305 (19)	0.0044 (18)	0.0123 (17)	0.0030 (17)
C2	0.040 (3)	0.044 (3)	0.043 (3)	−0.001 (2)	0.008 (2)	0.002 (2)
C3	0.043 (3)	0.055 (3)	0.054 (3)	−0.001 (3)	0.010 (2)	0.001 (3)
C4	0.062 (4)	0.053 (3)	0.072 (4)	−0.015 (3)	0.029 (3)	0.002 (3)
C5	0.058 (3)	0.042 (3)	0.057 (3)	0.000 (3)	0.022 (3)	0.012 (3)
C6	0.046 (3)	0.037 (3)	0.033 (2)	0.004 (2)	0.015 (2)	0.002 (2)
S7	0.0483 (7)	0.0477 (7)	0.0352 (6)	0.0051 (6)	0.0095 (5)	0.0124 (6)
C8	0.042 (3)	0.037 (3)	0.032 (2)	0.005 (2)	0.008 (2)	0.001 (2)
C9	0.048 (3)	0.049 (3)	0.053 (3)	0.013 (3)	0.012 (3)	0.010 (3)
C10	0.043 (3)	0.057 (3)	0.067 (4)	0.016 (3)	0.020 (3)	0.003 (3)
C11	0.047 (3)	0.056 (3)	0.051 (3)	0.004 (3)	0.022 (2)	−0.009 (3)
C12	0.054 (3)	0.043 (3)	0.035 (3)	0.002 (3)	0.016 (2)	−0.002 (2)
N13	0.039 (2)	0.036 (2)	0.0296 (19)	0.0054 (18)	0.0122 (17)	0.0034 (17)
N14	0.040 (2)	0.047 (2)	0.030 (2)	0.0058 (19)	0.0082 (17)	0.0021 (18)
C15	0.043 (3)	0.048 (3)	0.041 (3)	0.005 (2)	0.010 (2)	−0.002 (2)
C16	0.062 (4)	0.062 (4)	0.048 (3)	−0.003 (3)	0.021 (3)	−0.017 (3)
C17	0.070 (4)	0.093 (5)	0.033 (3)	0.001 (4)	0.014 (3)	−0.009 (3)
C18	0.056 (3)	0.079 (4)	0.035 (3)	0.008 (3)	0.015 (2)	0.011 (3)
C19	0.038 (3)	0.060 (3)	0.035 (3)	0.008 (2)	0.012 (2)	0.004 (2)
S20	0.0629 (9)	0.0568 (9)	0.0413 (7)	0.0192 (7)	0.0136 (6)	0.0161 (6)
C21	0.057 (3)	0.040 (3)	0.046 (3)	0.010 (3)	0.024 (2)	0.015 (2)
C22	0.076 (4)	0.052 (4)	0.075 (4)	0.005 (3)	0.034 (3)	0.021 (3)
C23	0.089 (5)	0.052 (4)	0.097 (5)	−0.014 (4)	0.045 (4)	0.015 (4)
C24	0.064 (4)	0.053 (4)	0.080 (4)	−0.014 (3)	0.031 (3)	−0.003 (3)
C25	0.052 (3)	0.048 (3)	0.043 (3)	−0.002 (3)	0.020 (2)	0.007 (2)
N26	0.043 (2)	0.036 (2)	0.039 (2)	0.004 (2)	0.0149 (18)	0.0037 (19)
N27	0.044 (2)	0.033 (2)	0.032 (2)	0.0044 (18)	0.0148 (17)	0.0062 (16)
C28	0.040 (3)	0.036 (3)	0.038 (3)	0.005 (2)	0.009 (2)	0.004 (2)
C29	0.057 (3)	0.043 (3)	0.034 (3)	−0.001 (3)	0.004 (2)	0.000 (2)
C30	0.080 (4)	0.050 (3)	0.034 (3)	−0.001 (3)	0.023 (3)	−0.006 (2)
C31	0.058 (3)	0.048 (3)	0.043 (3)	0.005 (3)	0.024 (3)	0.004 (2)
C32	0.046 (3)	0.032 (3)	0.038 (3)	0.000 (2)	0.019 (2)	0.005 (2)
C33	0.045 (3)	0.044 (3)	0.049 (3)	0.008 (2)	0.023 (2)	0.007 (2)
S34	0.0386 (7)	0.0412 (7)	0.0388 (7)	0.0066 (6)	0.0099 (5)	0.0045 (6)
C35	0.057 (3)	0.044 (3)	0.040 (3)	0.012 (3)	0.026 (2)	0.007 (2)
N36	0.078 (3)	0.054 (3)	0.049 (3)	0.027 (3)	0.018 (2)	0.013 (2)
C37	0.122 (6)	0.056 (4)	0.074 (4)	0.031 (4)	0.039 (4)	0.015 (4)
C38	0.120 (6)	0.036 (3)	0.094 (5)	0.006 (4)	0.063 (4)	0.005 (3)
C39	0.070 (4)	0.050 (4)	0.075 (4)	−0.007 (3)	0.039 (3)	−0.006 (3)
N40	0.051 (3)	0.040 (3)	0.054 (3)	−0.001 (2)	0.015 (2)	−0.002 (2)
C41	0.095 (5)	0.081 (5)	0.119 (6)	−0.027 (4)	0.026 (5)	−0.035 (5)
P1	0.162 (2)	0.0557 (11)	0.0660 (11)	−0.0228 (13)	0.0467 (13)	0.0003 (9)
F1	0.198 (6)	0.121 (4)	0.148 (4)	0.024 (4)	0.071 (4)	0.041 (4)
F2	0.304 (7)	0.128 (4)	0.120 (4)	−0.031 (5)	0.123 (4)	−0.029 (3)
F3	0.168 (5)	0.173 (6)	0.216 (7)	−0.070 (5)	0.071 (5)	0.008 (5)
F4	0.191 (6)	0.152 (5)	0.226 (7)	−0.081 (5)	0.088 (5)	−0.051 (5)
F5	0.343 (9)	0.158 (5)	0.087 (3)	0.028 (6)	0.096 (5)	−0.013 (3)
F6	0.257 (8)	0.088 (4)	0.187 (6)	0.030 (4)	0.039 (5)	0.038 (4)
P2	0.113 (2)	0.0677 (16)	0.0555 (14)	0	0.0326 (14)	0
F7	0.114 (3)	0.158 (4)	0.102 (3)	−0.037 (3)	0.028 (3)	0.024 (3)
F8	0.115 (13)	0.068 (10)	0.25 (2)	0	0.108 (17)	0
F9	0.19 (2)	0.035 (8)	0.25 (2)	0	−0.106 (18)	0
F10	0.121 (10)	0.30 (2)	0.051 (6)	0.095 (13)	0.040 (7)	0.027 (11)
F8A	0.156 (10)	0.187 (11)	0.155 (11)	−0.102 (9)	−0.012 (8)	0.111 (9)
F9A	0.345 (15)	0.156 (10)	0.209 (11)	−0.134 (10)	0.216 (11)	−0.131 (9)
P3	0.0703 (15)	0.0638 (15)	0.0841 (17)	0	0.0458 (13)	0
F11	0.084 (3)	0.119 (3)	0.136 (3)	0.023 (2)	0.070 (2)	0.012 (3)
F12	0.086 (5)	0.232 (11)	0.070 (4)	0.042 (7)	0.039 (4)	0.055 (6)
F13	0.085 (7)	0.048 (5)	0.137 (9)	0	0.068 (6)	0
F14	0.228 (19)	0.079 (9)	0.30 (2)	0	0.143 (16)	0
F12A	0.077 (8)	0.107 (11)	0.118 (12)	−0.007 (8)	0.007 (8)	0.057 (10)
F13A	0.102 (10)	0.102 (11)	0.28 (2)	−0.035 (9)	0.111 (12)	−0.090 (12)
C42	0.210 (10)	0.196 (11)	0.158 (9)	−0.115 (9)	0.119 (8)	−0.101 (8)
C43	0.082 (5)	0.095 (6)	0.098 (6)	−0.003 (4)	0.033 (4)	−0.012 (5)
N44	0.086 (4)	0.135 (6)	0.126 (6)	0.011 (4)	0.051 (4)	0.009 (5)

Geometric parameters (Å, º)

Ru1—N14	2.095 (4)	C29—C30	1.375 (7)
Ru1—N13	2.102 (4)	C29—H29	0.93
Ru1—N26	2.106 (4)	C30—C31	1.372 (7)
Ru1—N1	2.109 (4)	C30—H30	0.93
Ru1—N27	2.123 (4)	C31—C32	1.383 (6)
Ru1—S34	2.3581 (13)	C31—H31	0.93
N1—C6	1.354 (5)	C32—C33	1.494 (6)
N1—C2	1.357 (5)	C33—S34	1.825 (5)
C2—C3	1.362 (7)	C33—H33A	0.97
C2—H2	0.93	C33—H33B	0.97
C3—C4	1.373 (7)	S34—C35	1.816 (5)
C3—H3	0.93	C35—N36	1.316 (6)
C4—C5	1.381 (7)	C35—N40	1.318 (6)
C4—H4	0.93	N36—C37	1.338 (8)
C5—C6	1.382 (7)	C37—C38	1.370 (9)
C5—H5	0.93	C37—H37	0.93
C6—S7	1.751 (5)	C38—C39	1.389 (8)
S7—C8	1.772 (5)	C38—H38	0.93
C8—N13	1.346 (5)	C39—N40	1.332 (7)
C8—C9	1.383 (6)	C39—C41	1.464 (8)
C9—C10	1.360 (7)	C41—H41A	0.96
C9—H9	0.93	C41—H41B	0.96
C10—C11	1.375 (7)	C41—H41C	0.96
C10—H10	0.93	P1—F6	1.535 (6)
C11—C12	1.364 (7)	P1—F5	1.536 (5)
C11—H11	0.93	P1—F3	1.541 (6)
C12—N13	1.359 (6)	P1—F2	1.553 (5)
C12—H12	0.93	P1—F4	1.554 (6)
N14—C15	1.343 (6)	P1—F1	1.570 (6)
N14—C19	1.366 (6)	P2—F9	1.508 (17)
C15—C16	1.369 (7)	P2—F10	1.514 (12)
C15—H15	0.93	P2—F10^i	1.514 (12)
C16—C17	1.370 (8)	P2—F8	1.525 (19)
C16—H16	0.93	P2—F9A	1.531 (10)
C17—C18	1.366 (8)	P2—F9A^i	1.531 (10)
C17—H17	0.93	P2—F8A	1.550 (9)
C18—C19	1.377 (7)	P2—F8A^i	1.550 (9)
C18—H18	0.93	P2—F7^i	1.589 (5)
C19—S20	1.758 (5)	P2—F7	1.589 (5)
S20—C21	1.761 (5)	P3—F13A	1.525 (15)
C21—N26	1.357 (6)	P3—F13A^i	1.525 (15)
C21—C22	1.383 (7)	P3—F14	1.551 (15)
C22—C23	1.365 (8)	P3—F12	1.552 (7)
C22—H22	0.93	P3—F12^i	1.552 (7)
C23—C24	1.372 (8)	P3—F11^i	1.581 (4)
C23—H23	0.93	P3—F11	1.581 (4)
C24—C25	1.378 (7)	P3—F12A^i	1.585 (13)
C24—H24	0.93	P3—F12A	1.585 (13)
C25—N26	1.342 (6)	P3—F13	1.619 (9)
C25—H25	0.93	C42—C43	1.437 (11)
N27—C32	1.351 (6)	C42—H42A	0.96
N27—C28	1.352 (5)	C42—H42B	0.96
C28—C29	1.367 (6)	C42—H42C	0.96
C28—H28	0.93	C43—N44	1.089 (9)
N14—Ru1—N13	86.18 (14)	S34—C33—H33B	109.5
N14—Ru1—N26	89.08 (15)	H33A—C33—H33B	108.1
N13—Ru1—N26	91.97 (14)	C35—S34—C33	97.2 (2)
N14—Ru1—N1	87.34 (14)	C35—S34—Ru1	114.10 (17)
N13—Ru1—N1	89.05 (14)	C33—S34—Ru1	95.64 (16)
N26—Ru1—N1	176.20 (14)	N36—C35—N40	129.5 (5)
N14—Ru1—N27	179.37 (16)	N36—C35—S34	114.0 (4)
N13—Ru1—N27	93.98 (14)	N40—C35—S34	116.5 (4)
N26—Ru1—N27	91.52 (14)	C35—N36—C37	113.7 (5)
N1—Ru1—N27	92.05 (14)	N36—C37—C38	122.7 (6)
N14—Ru1—S34	97.98 (11)	N36—C37—H37	118.7
N13—Ru1—S34	174.46 (10)	C38—C37—H37	118.7
N26—Ru1—S34	91.75 (10)	C37—C38—C39	118.1 (6)
N1—Ru1—S34	87.50 (10)	C37—C38—H38	121
N27—Ru1—S34	81.82 (10)	C39—C38—H38	121
C6—N1—C2	116.4 (4)	N40—C39—C38	119.9 (6)
C6—N1—Ru1	124.6 (3)	N40—C39—C41	118.2 (6)
C2—N1—Ru1	118.9 (3)	C38—C39—C41	121.9 (6)
N1—C2—C3	123.5 (5)	C35—N40—C39	116.2 (5)
N1—C2—H2	118.2	C39—C41—H41A	109.5
C3—C2—H2	118.2	C39—C41—H41B	109.5
C2—C3—C4	119.6 (5)	H41A—C41—H41B	109.5
C2—C3—H3	120.2	C39—C41—H41C	109.5
C4—C3—H3	120.2	H41A—C41—H41C	109.5
C3—C4—C5	118.3 (5)	H41B—C41—H41C	109.5
C3—C4—H4	120.8	F6—P1—F5	90.8 (4)
C5—C4—H4	120.8	F6—P1—F3	86.7 (4)
C4—C5—C6	119.5 (5)	F5—P1—F3	94.0 (4)
C4—C5—H5	120.2	F6—P1—F2	89.5 (4)
C6—C5—H5	120.2	F5—P1—F2	176.3 (4)
N1—C6—C5	122.5 (4)	F3—P1—F2	89.7 (4)
N1—C6—S7	121.1 (3)	F6—P1—F4	94.2 (4)
C5—C6—S7	116.3 (4)	F5—P1—F4	90.3 (4)
C6—S7—C8	104.6 (2)	F3—P1—F4	175.6 (4)
N13—C8—C9	122.4 (4)	F2—P1—F4	86.0 (4)
N13—C8—S7	121.1 (3)	F6—P1—F1	177.7 (4)
C9—C8—S7	116.4 (4)	F5—P1—F1	89.2 (3)
C10—C9—C8	119.9 (5)	F3—P1—F1	91.0 (4)
C10—C9—H9	120.1	F2—P1—F1	90.7 (3)
C8—C9—H9	120.1	F4—P1—F1	88.2 (4)
C9—C10—C11	118.8 (5)	F9—P2—F10	90.3 (9)
C9—C10—H10	120.6	F9—P2—F10^i	90.3 (9)
C11—C10—H10	120.6	F10—P2—F10^i	179.3 (17)
C12—C11—C10	118.9 (5)	F9—P2—F8	180
C12—C11—H11	120.6	F10—P2—F8	89.7 (9)
C10—C11—H11	120.6	F10^i—P2—F8	89.7 (9)
N13—C12—C11	123.7 (5)	F10—P2—F9A	49.0 (8)
N13—C12—H12	118.1	F10^i—P2—F9A	131.6 (13)
C11—C12—H12	118.1	F8—P2—F9A	137.6 (5)
C8—N13—C12	116.2 (4)	F9A—P2—F9A^i	84.8 (9)
C8—N13—Ru1	124.7 (3)	F9A—P2—F8A	90.5 (7)
C12—N13—Ru1	119.1 (3)	F9A^i—P2—F8A	174.2 (9)
C15—N14—C19	116.0 (4)	F9—P2—F8A^i	132.8 (6)
C15—N14—Ru1	120.6 (3)	F9A—P2—F8A^i	174.2 (9)
C19—N14—Ru1	123.3 (3)	F9A^i—P2—F8A^i	90.5 (7)
N14—C15—C16	123.9 (5)	F8A—P2—F8A^i	94.4 (12)
N14—C15—H15	118	F9—P2—F7^i	91.0 (2)
C16—C15—H15	118	F10—P2—F7^i	94.1 (6)
C15—C16—C17	119.1 (5)	F10^i—P2—F7^i	85.9 (6)
C15—C16—H16	120.4	F8—P2—F7^i	89.0 (2)
C17—C16—H16	120.4	F9A—P2—F7^i	85.6 (6)
C18—C17—C16	118.8 (5)	F9A^i—P2—F7^i	96.0 (6)
C18—C17—H17	120.6	F8A—P2—F7^i	87.2 (5)
C16—C17—H17	120.6	F8A^i—P2—F7^i	91.4 (5)
C17—C18—C19	119.7 (5)	F9—P2—F7	91.0 (2)
C17—C18—H18	120.2	F10—P2—F7	85.9 (6)
C19—C18—H18	120.2	F10^i—P2—F7	94.1 (6)
N14—C19—C18	122.4 (5)	F8—P2—F7	89.0 (2)
N14—C19—S20	119.6 (3)	F9A—P2—F7	96.0 (6)
C18—C19—S20	117.9 (4)	F9A^i—P2—F7	85.6 (6)
C19—S20—C21	103.9 (2)	F8A—P2—F7	91.4 (5)
N26—C21—C22	122.4 (5)	F8A^i—P2—F7	87.2 (5)
N26—C21—S20	120.8 (4)	F7^i—P2—F7	177.9 (4)
C22—C21—S20	116.6 (4)	F13A—P3—F13A^i	96.3 (16)
C23—C22—C21	119.9 (6)	F14—P3—F12	90.9 (5)
C23—C22—H22	120	F14—P3—F12^i	90.9 (5)
C21—C22—H22	120	F12—P3—F12^i	178.1 (10)
C22—C23—C24	118.7 (6)	F13A—P3—F11^i	97.4 (5)
C22—C23—H23	120.6	F13A^i—P3—F11^i	81.3 (5)
C24—C23—H23	120.6	F14—P3—F11^i	90.95 (19)
C23—C24—C25	118.4 (6)	F12—P3—F11^i	83.9 (3)
C23—C24—H24	120.8	F12^i—P3—F11^i	96.0 (3)
C25—C24—H24	120.8	F13A—P3—F11	81.3 (5)
N26—C25—C24	124.6 (5)	F13A^i—P3—F11	97.4 (5)
N26—C25—H25	117.7	F14—P3—F11	90.95 (19)
C24—C25—H25	117.7	F12—P3—F11	96.0 (3)
C25—N26—C21	115.7 (4)	F12^i—P3—F11	83.9 (3)
C25—N26—Ru1	121.9 (3)	F11^i—P3—F11	178.1 (4)
C21—N26—Ru1	122.3 (3)	F13A—P3—F12A^i	174.3 (12)
C32—N27—C28	116.8 (4)	F13A^i—P3—F12A^i	89.3 (9)
C32—N27—Ru1	118.8 (3)	F11^i—P3—F12A^i	82.4 (6)
C28—N27—Ru1	124.3 (3)	F11—P3—F12A^i	99.0 (6)
N27—C28—C29	124.0 (5)	F13A—P3—F12A	89.3 (9)
N27—C28—H28	118	F13A^i—P3—F12A	174.3 (12)
C29—C28—H28	118	F11^i—P3—F12A	99.0 (6)
C28—C29—C30	118.3 (5)	F11—P3—F12A	82.4 (6)
C28—C29—H29	120.8	F12A^i—P3—F12A	85.1 (12)
C30—C29—H29	120.8	F14—P3—F13	180.000 (2)
C31—C30—C29	119.2 (5)	F12—P3—F13	89.1 (5)
C31—C30—H30	120.4	F12^i—P3—F13	89.1 (5)
C29—C30—H30	120.4	F11^i—P3—F13	89.05 (19)
C30—C31—C32	119.8 (5)	F11—P3—F13	89.05 (19)
C30—C31—H31	120.1	F12A^i—P3—F13	137.5 (6)
C32—C31—H31	120.1	F12A—P3—F13	137.5 (6)
N27—C32—C31	121.9 (4)	C43—C42—H42A	109.5
N27—C32—C33	117.8 (4)	C43—C42—H42B	109.5
C31—C32—C33	120.3 (4)	H42A—C42—H42B	109.5
C32—C33—S34	110.9 (3)	C43—C42—H42C	109.5
C32—C33—H33A	109.5	H42A—C42—H42C	109.5
S34—C33—H33A	109.5	H42B—C42—H42C	109.5
C32—C33—H33B	109.5	N44—C43—C42	171.0 (10)
N14—Ru1—N1—C6	−123.9 (4)	N26—C21—C22—C23	−1.9 (9)
N13—Ru1—N1—C6	−37.7 (4)	S20—C21—C22—C23	−177.5 (5)
N27—Ru1—N1—C6	56.3 (4)	C21—C22—C23—C24	−2.9 (9)
S34—Ru1—N1—C6	138.0 (3)	C22—C23—C24—C25	3.4 (9)
N14—Ru1—N1—C2	53.2 (3)	C23—C24—C25—N26	0.8 (9)
N13—Ru1—N1—C2	139.5 (3)	C24—C25—N26—C21	−5.3 (7)
N27—Ru1—N1—C2	−126.6 (3)	C24—C25—N26—Ru1	170.1 (4)
S34—Ru1—N1—C2	−44.9 (3)	C22—C21—N26—C25	5.8 (7)
C6—N1—C2—C3	−3.3 (7)	S20—C21—N26—C25	−178.8 (4)
Ru1—N1—C2—C3	179.3 (4)	C22—C21—N26—Ru1	−169.5 (4)
N1—C2—C3—C4	1.8 (8)	S20—C21—N26—Ru1	5.9 (5)
C2—C3—C4—C5	0.5 (8)	N14—Ru1—N26—C25	139.8 (4)
C3—C4—C5—C6	−1.1 (8)	N13—Ru1—N26—C25	53.6 (4)
C2—N1—C6—C5	2.7 (7)	N27—Ru1—N26—C25	−40.4 (4)
Ru1—N1—C6—C5	179.9 (4)	S34—Ru1—N26—C25	−122.3 (4)
C2—N1—C6—S7	−179.5 (3)	N14—Ru1—N26—C21	−45.2 (4)
Ru1—N1—C6—S7	−2.3 (5)	N13—Ru1—N26—C21	−131.3 (4)
C4—C5—C6—N1	−0.5 (8)	N27—Ru1—N26—C21	134.6 (4)
C4—C5—C6—S7	−178.5 (4)	S34—Ru1—N26—C21	52.8 (4)
N1—C6—S7—C8	49.0 (4)	N13—Ru1—N27—C32	159.3 (3)
C5—C6—S7—C8	−133.0 (4)	N26—Ru1—N27—C32	−108.7 (3)
C6—S7—C8—N13	−47.8 (4)	N1—Ru1—N27—C32	70.1 (3)
C6—S7—C8—C9	135.0 (4)	S34—Ru1—N27—C32	−17.1 (3)
N13—C8—C9—C10	1.4 (8)	N13—Ru1—N27—C28	−24.3 (4)
S7—C8—C9—C10	178.6 (4)	N26—Ru1—N27—C28	67.8 (4)
C8—C9—C10—C11	1.5 (8)	N1—Ru1—N27—C28	−113.4 (4)
C9—C10—C11—C12	−1.9 (8)	S34—Ru1—N27—C28	159.4 (4)
C10—C11—C12—N13	−0.5 (8)	C32—N27—C28—C29	1.3 (7)
C9—C8—N13—C12	−3.6 (7)	Ru1—N27—C28—C29	−175.2 (4)
S7—C8—N13—C12	179.3 (3)	N27—C28—C29—C30	−1.1 (7)
C9—C8—N13—Ru1	176.7 (4)	C28—C29—C30—C31	−0.2 (8)
S7—C8—N13—Ru1	−0.4 (5)	C29—C30—C31—C32	1.2 (8)
C11—C12—N13—C8	3.2 (7)	C28—N27—C32—C31	−0.2 (6)
C11—C12—N13—Ru1	−177.1 (4)	Ru1—N27—C32—C31	176.5 (3)
N14—Ru1—N13—C8	126.3 (4)	C28—N27—C32—C33	177.6 (4)
N26—Ru1—N13—C8	−144.7 (4)	Ru1—N27—C32—C33	−5.7 (5)
N1—Ru1—N13—C8	38.9 (4)	C30—C31—C32—N27	−1.0 (7)
N27—Ru1—N13—C8	−53.1 (4)	C30—C31—C32—C33	−178.7 (5)
N14—Ru1—N13—C12	−53.3 (3)	N27—C32—C33—S34	33.7 (5)
N26—Ru1—N13—C12	35.7 (3)	C31—C32—C33—S34	−148.5 (4)
N1—Ru1—N13—C12	−140.7 (3)	C32—C33—S34—C35	75.9 (4)
N27—Ru1—N13—C12	127.3 (3)	C32—C33—S34—Ru1	−39.4 (3)
N13—Ru1—N14—C15	−46.3 (4)	N14—Ru1—S34—C35	107.7 (2)
N26—Ru1—N14—C15	−138.4 (4)	N26—Ru1—S34—C35	18.4 (2)
N1—Ru1—N14—C15	42.9 (4)	N1—Ru1—S34—C35	−165.4 (2)
S34—Ru1—N14—C15	130.0 (3)	N27—Ru1—S34—C35	−72.9 (2)
N13—Ru1—N14—C19	130.4 (4)	N14—Ru1—S34—C33	−151.9 (2)
N26—Ru1—N14—C19	38.4 (4)	N26—Ru1—S34—C33	118.82 (19)
N1—Ru1—N14—C19	−140.4 (4)	N1—Ru1—S34—C33	−64.91 (19)
S34—Ru1—N14—C19	−53.2 (4)	N27—Ru1—S34—C33	27.53 (19)
C19—N14—C15—C16	2.1 (7)	C33—S34—C35—N36	123.0 (4)
Ru1—N14—C15—C16	179.1 (4)	Ru1—S34—C35—N36	−137.5 (3)
N14—C15—C16—C17	−1.3 (8)	C33—S34—C35—N40	−53.7 (4)
C15—C16—C17—C18	−1.3 (8)	Ru1—S34—C35—N40	45.8 (4)
C16—C17—C18—C19	2.8 (8)	N40—C35—N36—C37	−0.5 (8)
C15—N14—C19—C18	−0.4 (7)	S34—C35—N36—C37	−176.7 (4)
Ru1—N14—C19—C18	−177.3 (4)	C35—N36—C37—C38	−0.3 (9)
C15—N14—C19—S20	−176.5 (3)	N36—C37—C38—C39	1.1 (10)
Ru1—N14—C19—S20	6.6 (5)	C37—C38—C39—N40	−1.1 (9)
C17—C18—C19—N14	−2.0 (8)	C37—C38—C39—C41	178.5 (6)
C17—C18—C19—S20	174.1 (4)	N36—C35—N40—C39	0.5 (8)
N14—C19—S20—C21	−54.7 (4)	S34—C35—N40—C39	176.6 (4)
C18—C19—S20—C21	129.0 (4)	C38—C39—N40—C35	0.4 (8)
C19—S20—C21—N26	47.8 (4)	C41—C39—N40—C35	−179.2 (5)
C19—S20—C21—C22	−136.6 (4)

Symmetry code: (i) −x+3/2, y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···F7^ii	0.93	2.50	3.399 (7)	163
C11—H11···F1	0.93	2.51	3.385 (8)	156
C28—H28···N44	0.93	2.58	3.353 (8)	141

Symmetry code: (ii) x, −y+1/2, z+1/2.