The trans influence of the pyridine ligand on ruthenium(II)-porphyrin-carbene complexes

In the two ruthenium(II)-porphyrin-carbene complexes ­(di­benzoyl­carbenyl-[kappa]C)(pyridine-[kappa]N)(5,10,15,20-tetra-p-tolyl­porphyrinato-[kappa]⁴N)­ruthenium(II), [Ru(C₁₅H₁₀O₂)(C₅H₅N)(C₄₈H₃₆N₄)], (I), and (pyridine-[kappa]N)(5,10,15,20-tetra-p-tolyl­porphyrinato-[kappa]⁴N)[bis(3-tri­fluoro­methyl­phenyl)­carbenyl-[kappa]C]­ruthenium(II), [Ru(C₁₅H₈F₆)(C₅H₅N)(C₄₈H₃₆N₄)], (II), the pyridine ligand coordinates to the octahedral Ru atom trans with respect to the carbene ligand. The C(carbene)-Ru-N(pyridine) bonds in (I) coincide with a crystallographic twofold axis. The Ru-C bond lengths of 1.877 (8) and 1.868 (3) Å in (I) and (II), respectively, are slightly longer than those of other ruthenium(II)-porphyrin-carbene complexes, owing to the trans influence of the pyridine ligands.

S1. Comment

Ruthenium(II) porphyrin carbene complexes have been reported as effective catalysts for the production of olefins or cyclopropanes from diazo compounds (Che & Huang, 2002). Assuming that the catalytic reaction would take place at the position trans to the carbene ligand, the ligand-exchange reaction should play an important role in the study of such catalytic reactions. A large amount of Lewis base, PPh₃, pyridine or CO, causes dissociation of the carbene ligand, and the exchange reaction of the axial ligand trans to carbene has been examined using UV-vis spectroscopy in CH₂Cl₂ solution (Galardon et al., 1998). We have synthesized two (porphyrinato)ruthenium(II) carbene complexes coordinated by a pyridine ligand, [Ru(ttp){C(COPh)₂}(py)], (I) and [Ru(ttp){C(3—C₆H₄CF₃)₂}(py)], (II) (where H₂ttp is 5,10,15,20-tetra-p-tolylporphyrin and py is pyridine), and have investigated the trans influence of the axial ligands on the molecular structures in the crystalline state. \sch

The molecular structures of (I) and (II) are shown in Figs. 1 and 2, respectively. The geometry about the Ru atoms is distorted octahedral in both complexes, and the equatorial Ru—N(porphyrin) bond lengths in (I) and (II) are as expected for ruthenium(II) porphyrin complexes. The Ru—C bond length in (II) is longer than that in the five-coordinate derivative [Ru(ttp){C(3—C₆H₄CF₃)₂}] [1.842 (6) Å; Wada et al., 2002]. Compared with analogous ruthenium(II) tetra-p-tolylporphyrin and tetraphenylporphyrin (H₂tpp) carbene complexes, the Ru—C bond trans to the N-donor ligand in (I) and (II) is obviously longer than that trans to an O-donor; an Ru—C bond length of 1.829 (9) Å was observed in [Ru(tpp){C(CO₂Et)₂}(CH₃OH)]·H₂O (Galardon et al., 1998), and a value of 1.845 (3) Å was observed in [Ru(ttp)(CPh₂)(CH₃OH)]·CH₃OH (Kawai et al., 2002). Thus, the N-donor ligand seems to have a larger trans influence than the O-donor ligand in ruthenium(II) porphyrin carbene complexes. In addition, the Ru—N bond trans to the carbene in (I) and (II) is much longer than that trans to a carbonyl group; an Ru—N distance of 2.193 (4) Å was observed in [Ru(tpp)(CO)(py)].1.5(toluene) (Little & Ibers, 1973). Therefore, the trans influence of the carbene ligand is apparently stronger than that of the carbonyl ligand for (porphyrinato)ruthenium(II) complexes. The Ru—C—C angle about the carbene C atom in (I) is closer to 120° than in (II). The pairs of benzoyl [(I)] and 3-trifluoromethylphenyl [(II)] groups assume a face-to-face arrangement in an anti conformation.

The porphyrin rings in these two compounds are slightly distorted into saddle conformations. The largest deviations from the C₂₀N₄ least-squares planes are −0.235 (6) and 0.194 (6) Å at C3 and C8, respectively, for (I), and 0.148 (3) and −0.107 (3) Å at C10 and C13, respectively, for (II). The Ru atoms are displaced out of the least-squares planes toward the carbene ligands by 0.1460 (17) and 0.0603 (6) Å for (I) and (II), respectively. The Ru displacement in (II) is the smallest among ruthenium(II) porphyrin carbene complexes reported to date.

S2. Experimental

For (I), a solution of [Ru(ttp)(CO)(EtOH)] in tetrahydrofuran was irradiated with a 100 W high-pressure mercury lamp under N₂ for 6 h. An equimolar quantity of N₂═C(COPh)₂ was added and the resulting solution refluxed for 6 h. After removal of the solvent in vacuo, the residue was purified by column chromatography on silica gel and eluted with CH₂Cl₂/hexane (2:1), to afford [Ru(ttp){C(COPh)₂}], (I'). Addition of an excess amount of pyridine to a CH₂Cl₂ solution of (I') and evaporation gave compound (I) as a dark-red solid. Compound (II) was prepared according to a procedure similar to that of Kawai et al. (2002). The detailed procedure will be published elsewhere (Wada et al., 2002). Crystals of (I) and (II) were prepared by recrystallization from CH₂Cl₂/cyclohexane (1:1) and CH₂Cl₂/pyridine (1:1) solutions, respectively.

S3. Refinement

All H atoms were placed in geometrically idealized positions, with Csp²—H = 0.93 Å or Csp³—H = 0.96 Å, and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C).

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: CrystalStructure (Molecular Structure Corporation & Rigaku Corporation, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level. H atoms and p-tolyl groups have been omitted for clarity.
	Fig. 2. The molecular structure of (II), showing displacement ellipsoids at the 30% probability level. H atoms and p-tolyl groups have been omitted for clarity.

(I) (dibenzoylcarbenyl-κC)(pyridine-κN)(5,10,15,20-tetra-p-tolylporphyrinato- κ⁴N)ruthenium(II)

Crystal data

[Ru(C48H36N4)(C15H10O2)(C5H5N)]	F(000) = 2216
Mr = 1071.21	Dx = 1.319 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 15.806 (2) Å	θ = 10.8–13.7°
b = 16.6172 (18) Å	µ = 0.34 mm^−1
c = 20.644 (2) Å	T = 296 K
β = 95.872 (10)°	Needle, dark red
V = 5393.7 (10) Å^3	0.20 × 0.12 × 0.10 mm
Z = 4

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.048
Radiation source: rotating Mo anticathode	θmax = 27.5°, θmin = 2.6°
Graphite monochromator	h = 0→20
ω/2θ scans	k = 0→21
6419 measured reflections	l = −26→26
6197 independent reflections	3 standard reflections every 150 reflections
2792 reflections with I > 2σ(I)	intensity decay: 1.5%

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.182	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0752P)^2] where P = (Fo^2 + 2Fc^2)/3
6197 reflections	(Δ/σ)max < 0.001
345 parameters	Δρmax = 0.64 e Å^−3
0 restraints	Δρmin = −0.51 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. 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
Ru	0.5000	0.63899 (4)	0.2500	0.0426 (2)
O	0.5512 (3)	0.8122 (3)	0.15859 (19)	0.0658 (11)
N1	0.3831 (3)	0.6273 (3)	0.28244 (19)	0.0447 (10)
N2	0.4442 (3)	0.6359 (3)	0.15594 (19)	0.0461 (10)
N3	0.5000	0.4988 (4)	0.2500	0.0548 (17)
C1	0.3664 (3)	0.6281 (3)	0.3473 (3)	0.0502 (14)
C2	0.2762 (4)	0.6202 (4)	0.3491 (3)	0.0620 (18)
H1	0.2477	0.6183	0.3863	0.074*
C3	0.2402 (4)	0.6161 (4)	0.2871 (3)	0.0627 (17)
H2	0.1825	0.6104	0.2741	0.075*
C4	0.3058 (3)	0.6219 (3)	0.2452 (3)	0.0504 (14)
C5	0.2946 (3)	0.6247 (3)	0.1767 (3)	0.0521 (14)
C6	0.3586 (3)	0.6339 (3)	0.1358 (2)	0.0476 (12)
C7	0.3464 (4)	0.6390 (4)	0.0660 (3)	0.0621 (15)
H3	0.2945	0.6400	0.0403	0.074*
C8	0.4237 (4)	0.6419 (4)	0.0447 (3)	0.0585 (14)
H4	0.4349	0.6454	0.0014	0.070*
C9	0.4866 (3)	0.6387 (4)	0.1003 (2)	0.0503 (12)
C10	0.5739 (3)	0.6348 (3)	0.0990 (2)	0.0491 (12)
C11	0.2044 (4)	0.6154 (3)	0.1448 (3)	0.0529 (15)
C12	0.1617 (4)	0.6767 (4)	0.1099 (3)	0.0675 (17)
H5	0.1884	0.7260	0.1055	0.081*
C13	0.0796 (4)	0.6652 (4)	0.0814 (4)	0.083 (2)
H6	0.0521	0.7069	0.0578	0.100*
C14	0.0377 (4)	0.5932 (4)	0.0871 (4)	0.078 (2)
C15	0.0797 (5)	0.5337 (4)	0.1224 (4)	0.092 (2)
H7	0.0522	0.4850	0.1274	0.110*
C16	0.1611 (4)	0.5433 (4)	0.1506 (3)	0.0741 (19)
H8	0.1879	0.5011	0.1739	0.089*
C17	−0.0516 (5)	0.5811 (5)	0.0537 (5)	0.121 (3)
H9	−0.0707	0.6298	0.0318	0.145*
H10	−0.0894	0.5675	0.0856	0.145*
H11	−0.0512	0.5382	0.0225	0.145*
C18	0.6085 (3)	0.6388 (4)	0.0340 (3)	0.0529 (13)
C19	0.6268 (5)	0.7110 (4)	0.0080 (3)	0.084 (2)
H12	0.6163	0.7582	0.0300	0.101*
C20	0.6611 (5)	0.7148 (4)	−0.0512 (4)	0.095 (3)
H13	0.6733	0.7651	−0.0678	0.114*
C21	0.6774 (4)	0.6491 (5)	−0.0856 (3)	0.0698 (18)
C22	0.6562 (6)	0.5782 (5)	−0.0601 (4)	0.103 (3)
H14	0.6649	0.5314	−0.0832	0.123*
C23	0.6218 (6)	0.5715 (4)	−0.0012 (3)	0.095 (3)
H15	0.6078	0.5212	0.0142	0.114*
C24	0.7157 (5)	0.6553 (5)	−0.1496 (3)	0.099 (3)
H16	0.7224	0.6023	−0.1670	0.118*
H17	0.7702	0.6811	−0.1427	0.118*
H18	0.6787	0.6863	−0.1798	0.118*
C25	0.5000	0.7519 (5)	0.2500	0.0441 (18)
C26	0.4888 (4)	0.7992 (3)	0.1879 (2)	0.0493 (14)
C27	0.4045 (4)	0.8323 (3)	0.1641 (3)	0.0513 (14)
C28	0.3933 (4)	0.8643 (4)	0.1022 (3)	0.0746 (18)
H19	0.4373	0.8629	0.0755	0.089*
C29	0.3153 (6)	0.8989 (5)	0.0800 (4)	0.101 (3)
H20	0.3076	0.9216	0.0386	0.121*
C30	0.2501 (6)	0.8996 (5)	0.1184 (5)	0.094 (3)
H21	0.1985	0.9233	0.1033	0.112*
C31	0.2601 (5)	0.8661 (5)	0.1785 (4)	0.085 (2)
H22	0.2153	0.8665	0.2045	0.102*
C32	0.3371 (4)	0.8311 (4)	0.2014 (3)	0.0652 (17)
H23	0.3433	0.8068	0.2422	0.078*
C33	0.5149 (4)	0.4568 (4)	0.1979 (3)	0.0721 (19)
H24	0.5253	0.4849	0.1606	0.087*
C34	0.5160 (5)	0.3752 (4)	0.1958 (4)	0.096 (2)
H25	0.5274	0.3485	0.1580	0.115*
C35	0.5000	0.3327 (7)	0.2500	0.100 (4)
H26	0.5000	0.2767	0.2500	0.120*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru	0.0424 (4)	0.0448 (4)	0.0412 (3)	0.000	0.0076 (3)	0.000
O	0.069 (3)	0.070 (3)	0.061 (3)	−0.010 (2)	0.018 (2)	0.010 (2)
N1	0.046 (2)	0.053 (3)	0.035 (2)	−0.001 (2)	0.0068 (19)	0.004 (2)
N2	0.046 (2)	0.048 (2)	0.044 (2)	−0.003 (2)	0.0068 (19)	−0.007 (2)
N3	0.048 (4)	0.052 (4)	0.065 (5)	0.000	0.007 (3)	0.000
C1	0.048 (3)	0.042 (3)	0.062 (3)	0.002 (3)	0.017 (3)	−0.003 (3)
C2	0.057 (4)	0.075 (5)	0.058 (4)	0.001 (3)	0.020 (3)	−0.002 (3)
C3	0.042 (3)	0.078 (5)	0.069 (4)	−0.001 (3)	0.012 (3)	0.002 (3)
C4	0.044 (3)	0.050 (4)	0.058 (3)	0.000 (2)	0.007 (3)	0.001 (3)
C5	0.045 (3)	0.050 (4)	0.061 (3)	−0.005 (3)	0.001 (3)	−0.003 (3)
C6	0.047 (3)	0.046 (3)	0.047 (3)	−0.002 (3)	−0.003 (2)	−0.004 (3)
C7	0.055 (3)	0.080 (4)	0.049 (3)	−0.009 (4)	−0.004 (3)	−0.001 (4)
C8	0.069 (4)	0.064 (4)	0.041 (3)	−0.011 (4)	0.003 (3)	−0.013 (3)
C9	0.060 (3)	0.046 (3)	0.045 (3)	−0.007 (3)	0.009 (2)	−0.003 (3)
C10	0.058 (3)	0.046 (3)	0.045 (3)	−0.005 (3)	0.012 (2)	−0.003 (3)
C11	0.047 (3)	0.054 (4)	0.057 (3)	−0.003 (3)	0.000 (3)	−0.008 (3)
C12	0.062 (4)	0.061 (4)	0.076 (4)	−0.014 (3)	−0.007 (3)	0.004 (3)
C13	0.064 (4)	0.067 (5)	0.113 (6)	0.000 (4)	−0.020 (4)	0.008 (4)
C14	0.053 (4)	0.070 (5)	0.106 (6)	−0.011 (4)	−0.010 (4)	0.002 (4)
C15	0.066 (5)	0.060 (5)	0.143 (7)	−0.017 (4)	−0.020 (5)	0.015 (5)
C16	0.055 (4)	0.060 (4)	0.101 (5)	−0.009 (3)	−0.019 (4)	0.007 (4)
C17	0.060 (5)	0.105 (7)	0.187 (10)	−0.020 (5)	−0.033 (5)	0.012 (7)
C18	0.053 (3)	0.053 (3)	0.055 (3)	0.001 (3)	0.014 (3)	0.001 (3)
C19	0.134 (7)	0.052 (4)	0.075 (5)	0.000 (4)	0.057 (5)	−0.006 (3)
C20	0.149 (8)	0.051 (4)	0.098 (6)	−0.005 (4)	0.074 (6)	0.005 (4)
C21	0.086 (5)	0.079 (5)	0.049 (3)	0.009 (4)	0.026 (3)	0.002 (4)
C22	0.183 (9)	0.069 (5)	0.066 (5)	0.012 (5)	0.058 (5)	−0.009 (4)
C23	0.167 (8)	0.057 (4)	0.069 (5)	−0.009 (5)	0.056 (5)	−0.005 (4)
C24	0.132 (7)	0.103 (6)	0.070 (4)	0.006 (5)	0.056 (5)	0.007 (4)
C25	0.036 (4)	0.055 (5)	0.041 (4)	0.000	0.001 (3)	0.000
C26	0.066 (4)	0.041 (3)	0.041 (3)	−0.007 (3)	0.010 (3)	−0.002 (2)
C27	0.059 (4)	0.042 (3)	0.051 (3)	−0.001 (3)	−0.004 (3)	0.008 (2)
C28	0.084 (5)	0.085 (5)	0.052 (3)	−0.022 (4)	−0.012 (3)	0.008 (4)
C29	0.110 (7)	0.093 (6)	0.089 (6)	−0.033 (5)	−0.043 (5)	0.037 (5)
C30	0.082 (6)	0.080 (5)	0.109 (7)	0.013 (5)	−0.036 (5)	0.012 (5)
C31	0.075 (5)	0.096 (6)	0.080 (5)	0.023 (5)	−0.008 (4)	−0.007 (5)
C32	0.064 (4)	0.076 (4)	0.055 (4)	0.014 (3)	0.001 (3)	0.001 (3)
C33	0.076 (5)	0.061 (4)	0.081 (5)	−0.001 (4)	0.012 (4)	−0.013 (4)
C34	0.111 (6)	0.064 (6)	0.112 (7)	0.002 (4)	0.010 (5)	−0.021 (4)
C35	0.114 (10)	0.051 (6)	0.132 (11)	0.000	0.004 (9)	0.000

Geometric parameters (Å, º)

Ru—N1	2.038 (4)	C25—C26	1.498 (6)
Ru—N2	2.049 (4)	C26—C27	1.479 (8)
Ru—N3	2.329 (7)	C27—C32	1.377 (8)
Ru—C25	1.877 (8)	C27—C28	1.378 (8)
O—C26	1.228 (6)	C28—C29	1.394 (11)
N1—C1	1.392 (6)	C29—C30	1.362 (12)
N1—C4	1.379 (7)	C30—C31	1.354 (10)
N2—C6	1.374 (6)	C31—C32	1.388 (9)
N2—C9	1.387 (6)	C33—C34	1.358 (9)
N3—C33	1.323 (7)	C34—C35	1.369 (9)
C1—C2	1.436 (8)	C2—H1	0.9300
C2—C3	1.347 (8)	C3—H2	0.9300
C3—C4	1.420 (8)	C7—H3	0.9300
C4—C5	1.407 (8)	C8—H4	0.9300
C5—C6	1.391 (7)	C12—H5	0.9300
C6—C7	1.437 (7)	C13—H6	0.9300
C7—C8	1.342 (8)	C15—H7	0.9300
C8—C9	1.440 (7)	C16—H8	0.9300
C9—C10	1.385 (7)	C17—H9	0.9600
C10—C1^i	1.384 (7)	C17—H10	0.9600
C5—C11	1.515 (8)	C17—H11	0.9600
C11—C12	1.383 (8)	C19—H12	0.9300
C12—C13	1.382 (9)	C20—H13	0.9300
C13—C14	1.378 (9)	C22—H14	0.9300
C14—C15	1.360 (9)	C23—H15	0.9300
C15—C16	1.366 (9)	C24—H16	0.9600
C16—C11	1.390 (8)	C24—H17	0.9600
C14—C17	1.520 (9)	C24—H18	0.9600
C10—C18	1.501 (7)	C28—H19	0.9300
C18—C19	1.357 (8)	C29—H20	0.9300
C19—C20	1.388 (8)	C30—H21	0.9300
C20—C21	1.342 (9)	C31—H22	0.9300
C21—C22	1.347 (9)	C32—H23	0.9300
C22—C23	1.386 (9)	C33—H24	0.9300
C23—C18	1.361 (8)	C34—H25	0.9300
C21—C24	1.512 (8)	C35—H26	0.9300
N1—Ru—N1^i	169.1 (2)	C27—C26—C25	120.2 (4)
N1—Ru—N2	89.57 (15)	C32—C27—C28	119.4 (6)
N1—Ru—N2^i	90.16 (15)	C32—C27—C26	122.0 (5)
N1—Ru—N3	84.55 (12)	C28—C27—C26	118.6 (6)
N2^i—Ru—N2	177.1 (3)	C27—C28—C29	119.3 (7)
N2—Ru—N3	88.57 (13)	C30—C29—C28	120.5 (7)
N1—Ru—C25	95.45 (12)	C31—C30—C29	120.4 (7)
N2—Ru—C25	91.43 (13)	C30—C31—C32	120.0 (7)
N3—Ru—C25	180	C27—C32—C31	120.4 (6)
C4—N1—C1	107.1 (4)	N3—C33—C34	123.9 (8)
C4—N1—Ru	127.2 (3)	C33—C34—C35	119.0 (9)
C1—N1—Ru	125.6 (3)	C34—C35—C34^i	117.9 (11)
C6—N2—C9	107.1 (4)	C3—C2—H1	126.1
C6—N2—Ru	127.0 (3)	C1—C2—H1	126.1
C9—N2—Ru	125.9 (3)	C2—C3—H2	125.9
C33—N3—C33^i	116.4 (9)	C4—C3—H2	125.9
C33—N3—Ru	121.8 (4)	C8—C7—H3	126.4
C33^i—N3—Ru	121.8 (4)	C6—C7—H3	126.4
C10^i—C1—N1	126.3 (5)	C7—C8—H4	125.8
C10^i—C1—C2	125.7 (5)	C9—C8—H4	125.8
N1—C1—C2	108.0 (5)	C13—C12—H5	119.8
C3—C2—C1	107.7 (5)	C11—C12—H5	119.8
C2—C3—C4	108.2 (5)	C14—C13—H6	119.3
N1—C4—C5	124.9 (5)	C12—C13—H6	119.3
N1—C4—C3	108.9 (5)	C14—C15—H7	119.0
C5—C4—C3	126.2 (5)	C16—C15—H7	119.0
C6—C5—C4	126.0 (5)	C15—C16—H8	119.5
C6—C5—C11	117.3 (5)	C11—C16—H8	119.5
C4—C5—C11	116.7 (5)	C14—C17—H9	109.5
N2—C6—C5	125.1 (5)	C14—C17—H10	109.5
N2—C6—C7	109.2 (5)	H9—C17—H10	109.5
C5—C6—C7	125.6 (5)	C14—C17—H11	109.5
C8—C7—C6	107.2 (5)	H9—C17—H11	109.5
C7—C8—C9	108.4 (5)	H10—C17—H11	109.5
C10—C9—N2	125.5 (5)	C18—C19—H12	119.8
C10—C9—C8	126.4 (5)	C20—C19—H12	119.8
N2—C9—C8	108.0 (5)	C21—C20—H13	118.6
C1^i—C10—C9	125.9 (5)	C19—C20—H13	118.6
C1^i—C10—C18	116.0 (5)	C21—C22—H14	118.4
C9—C10—C18	118.1 (5)	C23—C22—H14	118.4
C12—C11—C16	117.4 (6)	C18—C23—H15	120.1
C12—C11—C5	122.6 (5)	C22—C23—H15	120.1
C16—C11—C5	120.0 (5)	C21—C24—H16	109.5
C13—C12—C11	120.5 (6)	C21—C24—H17	109.5
C14—C13—C12	121.5 (7)	H16—C24—H17	109.5
C15—C14—C13	117.7 (6)	C21—C24—H18	109.5
C15—C14—C17	121.7 (7)	H16—C24—H18	109.5
C13—C14—C17	120.6 (7)	H17—C24—H18	109.5
C14—C15—C16	122.0 (7)	C27—C28—H19	120.4
C15—C16—C11	121.0 (6)	C29—C28—H19	120.4
C19—C18—C23	117.6 (5)	C30—C29—H20	119.7
C19—C18—C10	120.3 (5)	C28—C29—H20	119.7
C23—C18—C10	122.0 (6)	C31—C30—H21	119.8
C18—C19—C20	120.5 (6)	C29—C30—H21	119.8
C21—C20—C19	122.8 (6)	C30—C31—H22	120.0
C20—C21—C22	115.8 (5)	C32—C31—H22	120.0
C20—C21—C24	121.5 (7)	C27—C32—H23	119.8
C22—C21—C24	122.6 (7)	C31—C32—H23	119.8
C21—C22—C23	123.3 (6)	N3—C33—H24	118.1
C18—C23—C22	119.9 (6)	C34—C33—H24	118.1
C26—C25—C26^i	116.8 (6)	C33—C34—H25	120.5
Ru—C25—C26	121.6 (3)	C35—C34—H25	120.5
O—C26—C27	120.8 (5)	C34—C35—H26	121.1
O—C26—C25	118.9 (5)
N1—Ru—N3—C33	127.1 (4)	C26^i—C25—C26—C27	−81.6 (5)
N2—Ru—N3—C33	37.4 (4)	Ru—C25—C26—C27	98.4 (5)
N1—Ru—C25—C26	−107.1 (3)	O—C26—C27—C32	−168.2 (5)
N2—Ru—C25—C26	−17.4 (3)	C25—C26—C27—C32	9.3 (8)
C26^i—C25—C26—O	95.9 (5)	O—C26—C27—C28	12.6 (8)
Ru—C25—C26—O	−84.1 (5)	C25—C26—C27—C28	−170.0 (6)

Symmetry code: (i) −x+1, y, −z+1/2.

(II) (pyridine-κN)(5,10,15,20-tetra-p-tolylporphyrinato-κ⁴N)[bis(3- trifluoromethylphenyl)carbenyl-κC]ruthenium(II)

Crystal data

[Ru(C48H36N4)(C15H8F6)(C5H5N)]	F(000) = 2360
Mr = 1151.19	Dx = 1.424 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.4428 (17) Å	θ = 14.9–15.0°
b = 17.3768 (19) Å	µ = 0.36 mm^−1
c = 25.1794 (17) Å	T = 296 K
β = 99.436 (9)°	Prism, dark red
V = 5370.5 (10) Å^3	0.50 × 0.40 × 0.20 mm
Z = 4

Data collection

Rigaku AFC-7R diffractometer	8702 reflections with I > 2σ(I)
Radiation source: rotating Mo anticathode	Rint = 0.018
Graphite monochromator	θmax = 27.5°, θmin = 2.5°
ω scans	h = 0→16
Absorption correction: ψ scan (North et al., 1968)	k = −22→0
Tmin = 0.840, Tmax = 0.930	l = −32→32
12882 measured reflections	3 standard reflections every 150 reflections
12323 independent reflections	intensity decay: 0.5%

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0488P)^2 + 1.7405P] where P = (Fo^2 + 2Fc^2)/3
12323 reflections	(Δ/σ)max = 0.001
721 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. 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
Ru	0.099529 (15)	0.276037 (12)	0.112533 (8)	0.03681 (6)
F1	0.1755 (3)	−0.02171 (17)	0.32508 (10)	0.1254 (10)
F2	0.3033 (2)	0.0438 (2)	0.30258 (10)	0.1422 (13)
F3	0.1773 (3)	0.09841 (19)	0.33376 (10)	0.1470 (13)
F4	0.3295 (2)	−0.01272 (15)	−0.04399 (10)	0.1109 (8)
F5	0.1622 (2)	0.00427 (17)	−0.03831 (10)	0.1122 (9)
F6	0.2485 (3)	0.09030 (15)	−0.07310 (9)	0.1177 (9)
N1	−0.05825 (16)	0.24049 (13)	0.08965 (8)	0.0410 (5)
N2	0.07158 (16)	0.28449 (12)	0.19014 (8)	0.0407 (5)
N3	0.25141 (16)	0.32371 (12)	0.13378 (8)	0.0400 (5)
N4	0.12282 (16)	0.27647 (12)	0.03356 (8)	0.0402 (4)
N5	0.03744 (18)	0.40103 (13)	0.09832 (9)	0.0470 (5)
C1	−0.1032 (2)	0.21636 (15)	0.03845 (10)	0.0434 (6)
C2	−0.2102 (2)	0.18622 (17)	0.04027 (11)	0.0495 (6)
H1	−0.2584	0.1667	0.0112	0.059*
C3	−0.2281 (2)	0.19124 (18)	0.09123 (11)	0.0511 (7)
H2	−0.2907	0.1754	0.1039	0.061*
C4	−0.1332 (2)	0.22545 (16)	0.12274 (10)	0.0435 (6)
C5	−0.1176 (2)	0.23684 (16)	0.17851 (10)	0.0437 (6)
C6	−0.0225 (2)	0.26538 (16)	0.20932 (10)	0.0433 (6)
C7	−0.0056 (2)	0.27736 (18)	0.26690 (11)	0.0541 (7)
H3	−0.0567	0.2697	0.2895	0.065*
C8	0.0976 (2)	0.30171 (18)	0.28176 (11)	0.0520 (7)
H4	0.1309	0.3136	0.3166	0.062*
C9	0.1472 (2)	0.30601 (16)	0.23391 (10)	0.0433 (6)
C10	0.2538 (2)	0.32930 (15)	0.23234 (10)	0.0422 (6)
C11	0.3008 (2)	0.33989 (15)	0.18582 (10)	0.0431 (6)
C12	0.4076 (2)	0.37039 (17)	0.18433 (11)	0.0514 (7)
H5	0.4582	0.3855	0.2139	0.062*
C13	0.4212 (2)	0.37315 (17)	0.13228 (11)	0.0517 (7)
H6	0.4822	0.3918	0.1195	0.062*
C14	0.3247 (2)	0.34220 (15)	0.10003 (10)	0.0436 (6)
C15	0.3093 (2)	0.32987 (15)	0.04438 (10)	0.0439 (6)
C16	0.2162 (2)	0.29682 (15)	0.01416 (10)	0.0424 (6)
C17	0.2036 (2)	0.27733 (16)	−0.04219 (11)	0.0490 (6)
H7	0.2552	0.2845	−0.0646	0.059*
C18	0.1038 (2)	0.24695 (17)	−0.05628 (11)	0.0488 (6)
H8	0.0735	0.2293	−0.0903	0.059*
C19	0.0521 (2)	0.24668 (15)	−0.00914 (10)	0.0423 (6)
C20	−0.0525 (2)	0.21902 (15)	−0.00729 (10)	0.0423 (6)
C21	−0.2073 (2)	0.20829 (16)	0.20679 (10)	0.0461 (6)
C22	−0.1905 (2)	0.14399 (18)	0.23965 (11)	0.0513 (7)
H9	−0.1211	0.1226	0.2474	0.062*
C23	−0.2751 (2)	0.11093 (18)	0.26127 (12)	0.0560 (7)
H10	−0.2616	0.0676	0.2830	0.067*
C24	−0.3792 (2)	0.14130 (19)	0.25103 (12)	0.0568 (7)
C25	−0.3950 (2)	0.2070 (2)	0.21953 (12)	0.0584 (8)
H11	−0.4637	0.2295	0.2129	0.070*
C26	−0.3106 (2)	0.24026 (18)	0.19759 (12)	0.0522 (7)
H12	−0.3236	0.2843	0.1766	0.063*
C27	−0.4726 (3)	0.1042 (2)	0.27239 (16)	0.0828 (11)
H13	−0.5205	0.0803	0.2433	0.099*
H14	−0.5119	0.1427	0.2888	0.099*
H15	−0.4450	0.0660	0.2987	0.099*
C28	0.3276 (2)	0.33959 (16)	0.28545 (10)	0.0450 (6)
C29	0.3615 (3)	0.27619 (18)	0.31649 (12)	0.0594 (8)
H16	0.3352	0.2279	0.3049	0.071*
C30	0.4333 (3)	0.2822 (2)	0.36432 (13)	0.0651 (8)
H17	0.4552	0.2382	0.3842	0.078*
C31	0.4728 (2)	0.3529 (2)	0.38276 (11)	0.0583 (8)
C32	0.4381 (3)	0.4163 (2)	0.35279 (12)	0.0642 (8)
H18	0.4638	0.4646	0.3647	0.077*
C33	0.3647 (3)	0.41023 (18)	0.30450 (12)	0.0591 (8)
H19	0.3409	0.4544	0.2852	0.071*
C34	0.5538 (3)	0.3587 (3)	0.43448 (13)	0.0837 (12)
H20	0.5442	0.3159	0.4573	0.100*
H21	0.5420	0.4059	0.4526	0.100*
H22	0.6265	0.3581	0.4263	0.100*
C35	0.3998 (2)	0.35308 (16)	0.01488 (11)	0.0463 (6)
C36	0.5029 (2)	0.32118 (19)	0.02690 (13)	0.0598 (8)
H23	0.5167	0.2837	0.0535	0.072*
C37	0.5858 (2)	0.34432 (19)	−0.00010 (14)	0.0631 (8)
H24	0.6546	0.3226	0.0092	0.076*
C38	0.5690 (2)	0.39871 (19)	−0.04031 (12)	0.0568 (7)
C39	0.4658 (3)	0.42957 (18)	−0.05300 (12)	0.0582 (7)
H25	0.4517	0.4659	−0.0804	0.070*
C40	0.3825 (2)	0.40745 (17)	−0.02564 (12)	0.0536 (7)
H26	0.3140	0.4296	−0.0348	0.064*
C41	0.6594 (3)	0.4239 (2)	−0.06927 (16)	0.0825 (11)
H27	0.6375	0.4169	−0.1073	0.099*
H28	0.7233	0.3937	−0.0571	0.099*
H29	0.6753	0.4773	−0.0618	0.099*
C42	−0.1179 (2)	0.18966 (16)	−0.05901 (10)	0.0428 (6)
C43	−0.1274 (3)	0.11240 (18)	−0.06961 (12)	0.0599 (8)
H30	−0.0915	0.0775	−0.0449	0.072*
C44	−0.1897 (3)	0.08560 (18)	−0.11658 (12)	0.0616 (8)
H31	−0.1954	0.0329	−0.1227	0.074*
C45	−0.2432 (2)	0.13562 (18)	−0.15431 (10)	0.0502 (7)
C46	−0.2329 (3)	0.21277 (18)	−0.14392 (11)	0.0585 (8)
H32	−0.2684	0.2477	−0.1688	0.070*
C47	−0.1705 (2)	0.23992 (17)	−0.09700 (11)	0.0531 (7)
H33	−0.1640	0.2927	−0.0911	0.064*
C48	−0.3125 (3)	0.1058 (2)	−0.20524 (13)	0.0747 (10)
H34	−0.3816	0.0888	−0.1973	0.090*
H35	−0.2760	0.0635	−0.2191	0.090*
H36	−0.3239	0.1462	−0.2316	0.090*
C49	0.15061 (19)	0.17531 (15)	0.12378 (9)	0.0399 (5)
C50	0.1107 (2)	0.11845 (15)	0.16059 (11)	0.0448 (6)
C51	0.1672 (2)	0.10765 (17)	0.21242 (11)	0.0527 (7)
H37	0.2275	0.1382	0.2248	0.063*
C52	0.1348 (3)	0.05184 (19)	0.24593 (12)	0.0604 (8)
C53	0.0457 (3)	0.00593 (19)	0.22824 (15)	0.0685 (9)
H38	0.0245	−0.0319	0.2505	0.082*
C54	−0.0116 (3)	0.01678 (19)	0.17714 (16)	0.0692 (9)
H39	−0.0718	−0.0140	0.1650	0.083*
C55	0.0195 (2)	0.07307 (17)	0.14366 (13)	0.0568 (7)
H40	−0.0210	0.0805	0.1096	0.068*
C56	0.1981 (4)	0.0427 (3)	0.30129 (15)	0.0860 (12)
C57	0.2377 (2)	0.14355 (15)	0.09600 (11)	0.0432 (6)
C58	0.2099 (2)	0.10557 (16)	0.04724 (11)	0.0499 (6)
H41	0.1369	0.0998	0.0322	0.060*
C59	0.2903 (3)	0.07613 (17)	0.02087 (13)	0.0585 (8)
C60	0.3989 (3)	0.0830 (2)	0.04397 (16)	0.0719 (10)
H42	0.4530	0.0628	0.0266	0.086*
C61	0.4264 (3)	0.1196 (2)	0.09246 (16)	0.0736 (10)
H43	0.4993	0.1239	0.1080	0.088*
C62	0.3474 (2)	0.14995 (18)	0.11813 (13)	0.0583 (7)
H44	0.3672	0.1752	0.1508	0.070*
C63	0.2578 (4)	0.0400 (2)	−0.03295 (16)	0.0779 (10)
C64	0.0862 (3)	0.45997 (19)	0.12564 (15)	0.0674 (9)
H45	0.1448	0.4499	0.1527	0.081*
C65	0.0549 (3)	0.5351 (2)	0.11612 (18)	0.0832 (11)
H46	0.0911	0.5746	0.1367	0.100*
C66	−0.0297 (3)	0.5511 (2)	0.07625 (16)	0.0786 (10)
H47	−0.0520	0.6016	0.0687	0.094*
C67	−0.0806 (3)	0.4918 (2)	0.04790 (15)	0.0812 (11)
H48	−0.1387	0.5010	0.0204	0.097*
C68	−0.0458 (3)	0.41744 (19)	0.05997 (13)	0.0663 (9)
H49	−0.0822	0.3772	0.0404	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru	0.03286 (10)	0.04300 (11)	0.03268 (10)	0.00014 (9)	−0.00027 (7)	0.00060 (9)
F1	0.165 (3)	0.125 (2)	0.0840 (16)	−0.0253 (19)	0.0128 (16)	0.0513 (16)
F2	0.0933 (19)	0.254 (4)	0.0722 (16)	−0.027 (2)	−0.0091 (14)	0.057 (2)
F3	0.241 (4)	0.133 (2)	0.0640 (15)	−0.002 (2)	0.018 (2)	−0.0082 (16)
F4	0.137 (2)	0.0966 (18)	0.1071 (18)	0.0351 (16)	0.0434 (16)	−0.0270 (14)
F5	0.119 (2)	0.136 (2)	0.0863 (16)	−0.0295 (18)	0.0292 (14)	−0.0496 (15)
F6	0.191 (3)	0.1004 (19)	0.0668 (14)	0.0263 (19)	0.0363 (16)	0.0059 (13)
N1	0.0351 (10)	0.0504 (13)	0.0355 (10)	0.0015 (9)	−0.0007 (8)	−0.0008 (9)
N2	0.0354 (10)	0.0503 (13)	0.0343 (10)	0.0004 (9)	−0.0008 (8)	−0.0030 (9)
N3	0.0356 (10)	0.0452 (12)	0.0372 (10)	−0.0014 (9)	0.0001 (8)	0.0021 (9)
N4	0.0382 (10)	0.0450 (11)	0.0362 (10)	0.0005 (9)	0.0023 (8)	0.0018 (9)
N5	0.0448 (12)	0.0497 (13)	0.0452 (12)	0.0057 (10)	0.0033 (10)	0.0024 (10)
C1	0.0373 (12)	0.0529 (16)	0.0366 (12)	0.0013 (11)	−0.0041 (10)	0.0013 (11)
C2	0.0378 (13)	0.0641 (18)	0.0428 (14)	−0.0042 (12)	−0.0046 (11)	−0.0045 (13)
C3	0.0362 (13)	0.0687 (18)	0.0461 (15)	−0.0051 (13)	0.0002 (11)	−0.0031 (14)
C4	0.0339 (12)	0.0541 (15)	0.0413 (13)	0.0015 (11)	0.0026 (10)	−0.0019 (12)
C5	0.0350 (12)	0.0529 (16)	0.0424 (13)	0.0026 (11)	0.0039 (10)	−0.0029 (11)
C6	0.0364 (12)	0.0533 (16)	0.0398 (13)	0.0022 (11)	0.0052 (10)	−0.0031 (11)
C7	0.0460 (15)	0.077 (2)	0.0394 (14)	−0.0039 (14)	0.0071 (11)	−0.0070 (14)
C8	0.0468 (15)	0.0727 (19)	0.0347 (13)	−0.0021 (13)	0.0013 (11)	−0.0075 (13)
C9	0.0417 (13)	0.0507 (15)	0.0348 (12)	−0.0004 (11)	−0.0015 (10)	−0.0033 (11)
C10	0.0387 (12)	0.0455 (14)	0.0389 (13)	−0.0003 (11)	−0.0034 (10)	−0.0028 (11)
C11	0.0376 (12)	0.0467 (15)	0.0415 (13)	−0.0005 (11)	−0.0033 (10)	0.0029 (11)
C12	0.0410 (14)	0.0594 (17)	0.0494 (15)	−0.0081 (12)	−0.0055 (12)	0.0011 (13)
C13	0.0420 (14)	0.0581 (17)	0.0524 (16)	−0.0089 (13)	0.0000 (12)	0.0057 (13)
C14	0.0385 (13)	0.0455 (15)	0.0447 (14)	−0.0029 (11)	0.0004 (10)	0.0046 (11)
C15	0.0404 (13)	0.0439 (14)	0.0462 (14)	0.0027 (11)	0.0037 (11)	0.0083 (11)
C16	0.0427 (13)	0.0423 (14)	0.0413 (13)	0.0022 (11)	0.0045 (11)	0.0044 (11)
C17	0.0518 (15)	0.0555 (16)	0.0408 (14)	0.0010 (13)	0.0105 (11)	0.0043 (12)
C18	0.0546 (16)	0.0548 (16)	0.0359 (13)	0.0013 (13)	0.0042 (12)	−0.0001 (12)
C19	0.0441 (14)	0.0446 (14)	0.0359 (12)	0.0033 (11)	−0.0010 (10)	0.0020 (10)
C20	0.0430 (13)	0.0463 (14)	0.0345 (12)	0.0033 (11)	−0.0027 (10)	0.0021 (11)
C21	0.0373 (13)	0.0614 (18)	0.0387 (13)	−0.0013 (12)	0.0040 (10)	−0.0054 (12)
C22	0.0400 (14)	0.0650 (19)	0.0488 (15)	0.0061 (13)	0.0071 (12)	−0.0011 (13)
C23	0.0579 (17)	0.0563 (18)	0.0535 (17)	0.0002 (14)	0.0083 (14)	0.0011 (14)
C24	0.0481 (16)	0.069 (2)	0.0545 (17)	−0.0120 (14)	0.0114 (13)	−0.0113 (15)
C25	0.0353 (14)	0.080 (2)	0.0587 (17)	0.0032 (14)	0.0050 (12)	−0.0100 (16)
C26	0.0425 (14)	0.0620 (18)	0.0509 (16)	0.0032 (13)	0.0037 (12)	−0.0004 (13)
C27	0.061 (2)	0.099 (3)	0.092 (3)	−0.014 (2)	0.0233 (19)	0.005 (2)
C28	0.0378 (13)	0.0569 (16)	0.0378 (13)	−0.0028 (12)	−0.0014 (10)	−0.0013 (12)
C29	0.0632 (18)	0.0551 (17)	0.0525 (16)	−0.0013 (15)	−0.0123 (14)	−0.0001 (14)
C30	0.0636 (19)	0.073 (2)	0.0519 (17)	0.0071 (17)	−0.0120 (14)	0.0051 (16)
C31	0.0438 (15)	0.090 (2)	0.0385 (14)	−0.0006 (15)	−0.0002 (12)	−0.0071 (15)
C32	0.068 (2)	0.068 (2)	0.0523 (17)	−0.0153 (16)	−0.0038 (15)	−0.0139 (15)
C33	0.0686 (19)	0.0535 (18)	0.0507 (16)	−0.0047 (15)	−0.0037 (14)	−0.0001 (14)
C34	0.060 (2)	0.139 (4)	0.0456 (18)	−0.006 (2)	−0.0105 (15)	−0.010 (2)
C35	0.0424 (14)	0.0509 (16)	0.0454 (14)	−0.0022 (12)	0.0062 (11)	0.0043 (12)
C36	0.0511 (16)	0.063 (2)	0.0654 (19)	0.0079 (14)	0.0114 (14)	0.0171 (16)
C37	0.0437 (15)	0.070 (2)	0.077 (2)	0.0100 (15)	0.0147 (15)	0.0049 (17)
C38	0.0519 (17)	0.0621 (19)	0.0594 (18)	−0.0056 (14)	0.0177 (14)	−0.0032 (15)
C39	0.0605 (18)	0.0587 (18)	0.0562 (17)	−0.0047 (15)	0.0115 (14)	0.0128 (14)
C40	0.0466 (15)	0.0564 (17)	0.0576 (17)	0.0058 (13)	0.0084 (13)	0.0114 (14)
C41	0.068 (2)	0.094 (3)	0.092 (3)	−0.010 (2)	0.034 (2)	0.003 (2)
C42	0.0395 (13)	0.0535 (15)	0.0332 (12)	−0.0001 (11)	−0.0007 (10)	0.0007 (11)
C43	0.0683 (19)	0.0545 (18)	0.0495 (16)	0.0107 (15)	−0.0117 (14)	0.0004 (13)
C44	0.074 (2)	0.0494 (17)	0.0550 (17)	0.0077 (15)	−0.0074 (15)	−0.0110 (14)
C45	0.0458 (14)	0.0672 (19)	0.0360 (13)	−0.0027 (13)	0.0018 (11)	−0.0051 (12)
C46	0.0634 (18)	0.064 (2)	0.0416 (15)	0.0024 (15)	−0.0093 (13)	0.0121 (13)
C47	0.0638 (18)	0.0452 (16)	0.0462 (15)	−0.0008 (13)	−0.0032 (13)	0.0056 (12)
C48	0.077 (2)	0.092 (3)	0.0481 (17)	−0.005 (2)	−0.0081 (16)	−0.0104 (17)
C49	0.0361 (12)	0.0438 (14)	0.0370 (12)	−0.0012 (11)	−0.0021 (10)	−0.0008 (10)
C50	0.0439 (14)	0.0434 (14)	0.0479 (14)	0.0006 (11)	0.0095 (11)	0.0011 (11)
C51	0.0538 (16)	0.0574 (17)	0.0471 (15)	−0.0079 (13)	0.0090 (13)	0.0024 (13)
C52	0.0663 (19)	0.064 (2)	0.0546 (17)	0.0023 (16)	0.0203 (15)	0.0112 (15)
C53	0.072 (2)	0.0575 (19)	0.083 (2)	−0.0083 (16)	0.0317 (19)	0.0135 (17)
C54	0.0554 (18)	0.0569 (19)	0.096 (3)	−0.0153 (15)	0.0159 (18)	0.0043 (18)
C55	0.0470 (16)	0.0545 (18)	0.0679 (19)	−0.0045 (13)	0.0063 (14)	0.0008 (15)
C56	0.108 (3)	0.099 (3)	0.054 (2)	−0.012 (3)	0.022 (2)	0.015 (2)
C57	0.0422 (13)	0.0390 (13)	0.0485 (14)	0.0013 (11)	0.0078 (11)	0.0070 (11)
C58	0.0486 (15)	0.0481 (16)	0.0536 (16)	0.0021 (12)	0.0104 (12)	0.0040 (13)
C59	0.069 (2)	0.0481 (17)	0.0644 (19)	0.0068 (14)	0.0272 (16)	0.0036 (14)
C60	0.060 (2)	0.064 (2)	0.101 (3)	0.0096 (16)	0.039 (2)	0.006 (2)
C61	0.0420 (16)	0.074 (2)	0.105 (3)	0.0040 (15)	0.0127 (18)	−0.002 (2)
C62	0.0431 (15)	0.0601 (19)	0.0693 (19)	0.0021 (13)	0.0023 (14)	−0.0007 (15)
C63	0.101 (3)	0.065 (2)	0.076 (2)	0.005 (2)	0.038 (2)	−0.0052 (19)
C64	0.0604 (19)	0.0540 (19)	0.081 (2)	0.0046 (15)	−0.0078 (16)	−0.0046 (16)
C65	0.082 (3)	0.052 (2)	0.110 (3)	0.0036 (18)	0.000 (2)	−0.006 (2)
C66	0.095 (3)	0.052 (2)	0.089 (3)	0.0221 (19)	0.015 (2)	0.0097 (19)
C67	0.086 (3)	0.077 (3)	0.073 (2)	0.029 (2)	−0.0115 (19)	0.0038 (19)
C68	0.071 (2)	0.061 (2)	0.0607 (19)	0.0152 (16)	−0.0086 (16)	−0.0021 (15)

Geometric parameters (Å, º)

Ru—N1	2.049 (2)	C47—C42	1.379 (4)
Ru—N2	2.046 (2)	C45—C48	1.514 (4)
Ru—N3	2.052 (2)	C49—C50	1.494 (4)
Ru—N4	2.056 (2)	C49—C57	1.489 (3)
Ru—N5	2.313 (2)	C50—C51	1.390 (4)
Ru—C49	1.868 (3)	C51—C52	1.388 (4)
F1—C56	1.321 (4)	C52—C53	1.379 (5)
F2—C56	1.304 (5)	C53—C54	1.378 (5)
F3—C56	1.321 (5)	C54—C55	1.387 (4)
F4—C63	1.340 (4)	C55—C50	1.390 (4)
F5—C63	1.329 (4)	C52—C56	1.493 (5)
F6—C63	1.327 (4)	C57—C58	1.387 (4)
N1—C1	1.383 (3)	C58—C59	1.386 (4)
N1—C4	1.374 (3)	C59—C60	1.387 (5)
N2—C6	1.378 (3)	C60—C61	1.369 (5)
N2—C9	1.378 (3)	C61—C62	1.368 (4)
N3—C11	1.382 (3)	C62—C57	1.391 (4)
N3—C14	1.383 (3)	C59—C63	1.488 (5)
N4—C16	1.378 (3)	C64—C65	1.373 (5)
N4—C19	1.374 (3)	C65—C66	1.359 (5)
N5—C64	1.324 (4)	C66—C67	1.351 (5)
N5—C68	1.326 (3)	C67—C68	1.380 (5)
C1—C2	1.439 (4)	C2—H1	0.9300
C2—C3	1.341 (4)	C3—H2	0.9300
C3—C4	1.439 (3)	C7—H3	0.9300
C4—C5	1.400 (3)	C8—H4	0.9300
C5—C6	1.395 (3)	C12—H5	0.9300
C6—C7	1.446 (4)	C13—H6	0.9300
C7—C8	1.345 (4)	C17—H7	0.9300
C8—C9	1.443 (4)	C18—H8	0.9300
C9—C10	1.394 (3)	C22—H9	0.9300
C10—C11	1.404 (4)	C23—H10	0.9300
C11—C12	1.437 (4)	C25—H11	0.9300
C12—C13	1.350 (4)	C26—H12	0.9300
C13—C14	1.439 (3)	C27—H13	0.9600
C14—C15	1.399 (4)	C27—H14	0.9600
C15—C16	1.401 (4)	C27—H15	0.9600
C16—C17	1.442 (4)	C29—H16	0.9300
C17—C18	1.343 (4)	C30—H17	0.9300
C18—C19	1.440 (4)	C32—H18	0.9300
C19—C20	1.396 (4)	C33—H19	0.9300
C20—C1	1.401 (4)	C34—H20	0.9600
C5—C21	1.504 (4)	C34—H21	0.9600
C21—C22	1.386 (4)	C34—H22	0.9600
C22—C23	1.387 (4)	C36—H23	0.9300
C23—C24	1.384 (4)	C37—H24	0.9300
C24—C25	1.386 (4)	C39—H25	0.9300
C25—C26	1.389 (4)	C40—H26	0.9300
C26—C21	1.384 (4)	C41—H27	0.9600
C24—C27	1.503 (4)	C41—H28	0.9600
C10—C28	1.504 (3)	C41—H29	0.9600
C28—C29	1.376 (4)	C43—H30	0.9300
C29—C30	1.381 (4)	C44—H31	0.9300
C30—C31	1.375 (5)	C46—H32	0.9300
C31—C32	1.365 (5)	C47—H33	0.9300
C32—C33	1.400 (4)	C48—H34	0.9600
C33—C28	1.370 (4)	C48—H35	0.9600
C31—C34	1.514 (4)	C48—H36	0.9600
C15—C35	1.502 (4)	C51—H37	0.9300
C35—C36	1.385 (4)	C53—H38	0.9300
C36—C37	1.385 (4)	C54—H39	0.9300
C37—C38	1.376 (4)	C55—H40	0.9300
C38—C39	1.380 (4)	C58—H41	0.9300
C39—C40	1.389 (4)	C60—H42	0.9300
C40—C35	1.381 (4)	C61—H43	0.9300
C38—C41	1.503 (4)	C62—H44	0.9300
C20—C42	1.507 (3)	C64—H45	0.9300
C42—C43	1.370 (4)	C65—H46	0.9300
C43—C44	1.384 (4)	C66—H47	0.9300
C44—C45	1.376 (4)	C67—H48	0.9300
C45—C46	1.368 (4)	C68—H49	0.9300
C46—C47	1.386 (4)
N1—Ru—N2	89.15 (8)	C54—C55—C50	120.6 (3)
N1—Ru—N3	173.72 (8)	F2—C56—F3	105.8 (4)
N1—Ru—N4	90.55 (8)	F2—C56—F1	106.8 (4)
N2—Ru—N3	90.89 (8)	F3—C56—F1	105.2 (3)
N2—Ru—N4	175.36 (8)	F2—C56—C52	113.3 (3)
N3—Ru—N4	88.90 (8)	F3—C56—C52	111.9 (4)
N1—Ru—N5	87.66 (8)	F1—C56—C52	113.3 (4)
N2—Ru—N5	88.60 (8)	C58—C57—C62	118.6 (3)
N3—Ru—N5	86.06 (8)	C58—C57—C49	119.8 (2)
N4—Ru—N5	86.75 (8)	C62—C57—C49	121.6 (2)
C49—Ru—N1	92.68 (10)	C59—C58—C57	120.3 (3)
C49—Ru—N2	91.69 (10)	C58—C59—C60	119.9 (3)
C49—Ru—N3	93.60 (9)	C58—C59—C63	118.8 (3)
C49—Ru—N4	92.96 (10)	C60—C59—C63	121.3 (3)
C49—Ru—N5	179.56 (10)	C61—C60—C59	119.9 (3)
C4—N1—C1	107.3 (2)	C62—C61—C60	120.4 (3)
C4—N1—Ru	126.97 (16)	C61—C62—C57	120.9 (3)
C1—N1—Ru	125.14 (17)	F6—C63—F5	105.4 (4)
C6—N2—C9	107.0 (2)	F6—C63—F4	105.7 (3)
C6—N2—Ru	127.21 (16)	F5—C63—F4	105.9 (3)
C9—N2—Ru	125.65 (17)	F6—C63—C59	113.2 (3)
C11—N3—C14	107.5 (2)	F5—C63—C59	113.3 (3)
C11—N3—Ru	125.21 (16)	F4—C63—C59	112.7 (3)
C14—N3—Ru	127.28 (16)	N5—C64—C65	123.5 (3)
C19—N4—C16	106.8 (2)	C66—C65—C64	119.1 (4)
C19—N4—Ru	125.58 (17)	C67—C66—C65	118.2 (3)
C16—N4—Ru	127.18 (16)	C66—C67—C68	119.7 (3)
C64—N5—C68	116.7 (3)	N5—C68—C67	122.7 (3)
C64—N5—Ru	122.20 (19)	C1—C2—H1	126.1
C68—N5—Ru	121.0 (2)	C3—C2—H1	126.1
N1—C1—C20	126.1 (2)	C2—C3—H2	126.1
N1—C1—C2	108.4 (2)	C4—C3—H2	126.1
C20—C1—C2	125.6 (2)	C8—C7—H3	126.3
C3—C2—C1	107.9 (2)	C6—C7—H3	126.3
C2—C3—C4	107.7 (2)	C7—C8—H4	126.2
N1—C4—C5	125.8 (2)	C9—C8—H4	126.2
N1—C4—C3	108.8 (2)	C13—C12—H5	126.2
C5—C4—C3	125.4 (2)	C11—C12—H5	126.2
C6—C5—C4	125.0 (2)	C12—C13—H6	126.0
C6—C5—C21	118.8 (2)	C14—C13—H6	126.0
C4—C5—C21	115.9 (2)	C18—C17—H7	126.3
N2—C6—C5	125.6 (2)	C16—C17—H7	126.3
N2—C6—C7	108.9 (2)	C17—C18—H8	126.2
C5—C6—C7	125.4 (2)	C19—C18—H8	126.2
C8—C7—C6	107.4 (2)	C21—C22—H9	119.4
C7—C8—C9	107.6 (2)	C23—C22—H9	119.4
N2—C9—C10	125.7 (2)	C24—C23—H10	119.4
N2—C9—C8	108.9 (2)	C22—C23—H10	119.4
C10—C9—C8	125.3 (2)	C24—C25—H11	119.2
C9—C10—C11	126.2 (2)	C26—C25—H11	119.2
C9—C10—C28	117.1 (2)	C21—C26—H12	119.7
C11—C10—C28	116.7 (2)	C25—C26—H12	119.7
N3—C11—C10	125.7 (2)	C24—C27—H13	109.5
N3—C11—C12	108.6 (2)	C24—C27—H14	109.5
C10—C11—C12	125.7 (2)	H13—C27—H14	109.5
C13—C12—C11	107.6 (2)	C24—C27—H15	109.5
C12—C13—C14	108.0 (2)	H13—C27—H15	109.5
N3—C14—C15	125.7 (2)	H14—C27—H15	109.5
N3—C14—C13	108.3 (2)	C28—C29—H16	119.1
C15—C14—C13	125.9 (2)	C30—C29—H16	119.1
C14—C15—C16	124.9 (2)	C31—C30—H17	119.8
C14—C15—C35	117.6 (2)	C29—C30—H17	119.8
C16—C15—C35	117.5 (2)	C31—C32—H18	119.3
N4—C16—C15	125.7 (2)	C33—C32—H18	119.3
N4—C16—C17	109.1 (2)	C28—C33—H19	119.8
C15—C16—C17	125.3 (2)	C32—C33—H19	119.8
C18—C17—C16	107.4 (2)	C31—C34—H20	109.5
C17—C18—C19	107.6 (2)	C31—C34—H21	109.5
N4—C19—C20	125.8 (2)	H20—C34—H21	109.5
N4—C19—C18	109.2 (2)	C31—C34—H22	109.5
C20—C19—C18	125.0 (2)	H20—C34—H22	109.5
C19—C20—C1	125.9 (2)	H21—C34—H22	109.5
C19—C20—C42	117.5 (2)	C37—C36—H23	119.5
C1—C20—C42	116.6 (2)	C35—C36—H23	119.5
C26—C21—C22	118.0 (3)	C38—C37—H24	119.2
C26—C21—C5	122.0 (3)	C36—C37—H24	119.2
C22—C21—C5	119.8 (2)	C38—C39—H25	119.4
C21—C22—C23	121.2 (3)	C40—C39—H25	119.4
C24—C23—C22	121.1 (3)	C35—C40—H26	119.4
C23—C24—C25	117.5 (3)	C39—C40—H26	119.4
C23—C24—C27	121.7 (3)	C38—C41—H27	109.5
C25—C24—C27	120.9 (3)	C38—C41—H28	109.5
C24—C25—C26	121.6 (3)	H27—C41—H28	109.5
C21—C26—C25	120.5 (3)	C38—C41—H29	109.5
C33—C28—C29	117.7 (2)	H27—C41—H29	109.5
C33—C28—C10	122.6 (3)	H28—C41—H29	109.5
C29—C28—C10	119.7 (2)	C42—C43—H30	119.5
C28—C29—C30	121.9 (3)	C44—C43—H30	119.5
C31—C30—C29	120.5 (3)	C45—C44—H31	119.4
C32—C31—C30	118.1 (3)	C43—C44—H31	119.4
C32—C31—C34	121.8 (3)	C45—C46—H32	119.4
C30—C31—C34	120.0 (3)	C47—C46—H32	119.4
C31—C32—C33	121.4 (3)	C42—C47—H33	119.6
C28—C33—C32	120.4 (3)	C46—C47—H33	119.6
C40—C35—C36	117.5 (3)	C45—C48—H34	109.5
C40—C35—C15	120.7 (2)	C45—C48—H35	109.5
C36—C35—C15	121.8 (2)	H34—C48—H35	109.5
C37—C36—C35	121.0 (3)	C45—C48—H36	109.5
C38—C37—C36	121.7 (3)	H34—C48—H36	109.5
C37—C38—C39	117.5 (3)	H35—C48—H36	109.5
C37—C38—C41	121.4 (3)	C52—C51—H37	119.6
C39—C38—C41	121.1 (3)	C50—C51—H37	119.6
C38—C39—C40	121.3 (3)	C54—C53—H38	120.4
C35—C40—C39	121.2 (3)	C52—C53—H38	120.4
C43—C42—C47	118.0 (2)	C53—C54—H39	119.6
C43—C42—C20	121.1 (2)	C55—C54—H39	119.6
C47—C42—C20	120.8 (3)	C54—C55—H40	119.7
C42—C43—C44	121.0 (3)	C50—C55—H40	119.7
C45—C44—C43	121.2 (3)	C59—C58—H41	119.8
C46—C45—C44	117.8 (3)	C57—C58—H41	119.8
C46—C45—C48	121.3 (3)	C61—C60—H42	120.1
C44—C45—C48	120.8 (3)	C59—C60—H42	120.1
C45—C46—C47	121.3 (3)	C62—C61—H43	119.8
C42—C47—C46	120.8 (3)	C60—C61—H43	119.8
C50—C49—C57	112.8 (2)	C61—C62—H44	119.5
Ru—C49—C50	125.04 (18)	C57—C62—H44	119.5
Ru—C49—C57	122.13 (18)	N5—C64—H45	118.2
C55—C50—C51	118.2 (3)	C65—C64—H45	118.2
C55—C50—C49	121.5 (2)	C66—C65—H46	120.4
C51—C50—C49	120.2 (2)	C64—C65—H46	120.4
C52—C51—C50	120.8 (3)	C67—C66—H47	120.9
C53—C52—C51	120.4 (3)	C65—C66—H47	120.9
C53—C52—C56	120.9 (3)	C66—C67—H48	120.2
C51—C52—C56	118.7 (3)	C68—C67—H48	120.2
C54—C53—C52	119.2 (3)	N5—C68—H49	118.6
C53—C54—C55	120.7 (3)	C67—C68—H49	118.6
C49—Ru—N1—C4	86.4 (2)	C14—C15—C35—C40	−119.7 (3)
N5—Ru—N1—C4	−93.9 (2)	C16—C15—C35—C40	60.9 (4)
C49—Ru—N1—C1	−83.4 (2)	C19—C20—C42—C43	100.9 (3)
N5—Ru—N1—C1	96.3 (2)	C1—C20—C42—C43	−79.5 (3)
C49—Ru—N2—C6	−89.3 (2)	C19—C20—C42—C47	−79.5 (3)
N5—Ru—N2—C6	91.0 (2)	C1—C20—C42—C47	100.2 (3)
C49—Ru—N2—C9	86.1 (2)	N1—Ru—C49—C57	123.7 (2)
N5—Ru—N2—C9	−93.5 (2)	N2—Ru—C49—C57	−147.1 (2)
C49—Ru—N3—C11	−84.6 (2)	N3—Ru—C49—C57	−56.1 (2)
N5—Ru—N3—C11	95.7 (2)	N4—Ru—C49—C57	33.0 (2)
C49—Ru—N3—C14	92.2 (2)	N1—Ru—C49—C50	−56.4 (2)
N5—Ru—N3—C14	−87.5 (2)	N2—Ru—C49—C50	32.8 (2)
C49—Ru—N4—C16	−88.4 (2)	N3—Ru—C49—C50	123.8 (2)
N5—Ru—N4—C16	91.3 (2)	N4—Ru—C49—C50	−147.1 (2)
C49—Ru—N4—C19	82.5 (2)	C57—C49—C50—C51	82.8 (3)
N5—Ru—N4—C19	−97.9 (2)	Ru—C49—C50—C51	−97.1 (3)
N1—Ru—N5—C64	150.7 (3)	C57—C49—C50—C55	−94.6 (3)
N2—Ru—N5—C64	61.5 (3)	Ru—C49—C50—C55	85.5 (3)
N3—Ru—N5—C64	−29.5 (3)	C51—C52—C56—F1	−166.2 (3)
N4—Ru—N5—C64	−118.6 (3)	C53—C52—C56—F1	13.9 (6)
N1—Ru—N5—C68	−33.1 (2)	C51—C52—C56—F2	−44.3 (5)
N2—Ru—N5—C68	−122.3 (2)	C53—C52—C56—F2	135.7 (4)
N3—Ru—N5—C68	146.7 (2)	C51—C52—C56—F3	75.1 (5)
N4—Ru—N5—C68	57.6 (2)	C53—C52—C56—F3	−104.8 (4)
C4—C5—C21—C22	108.7 (3)	C50—C49—C57—C58	88.7 (3)
C6—C5—C21—C22	−65.4 (4)	Ru—C49—C57—C58	−91.4 (3)
C4—C5—C21—C26	−65.6 (4)	C50—C49—C57—C62	−90.4 (3)
C6—C5—C21—C26	120.3 (3)	Ru—C49—C57—C62	89.5 (3)
C5—C21—C22—C23	−172.4 (3)	C58—C59—C63—F4	−153.5 (3)
C5—C21—C26—C25	172.6 (3)	C60—C59—C63—F4	28.7 (5)
C9—C10—C28—C29	69.6 (4)	C58—C59—C63—F5	−33.3 (5)
C11—C10—C28—C29	−106.9 (3)	C60—C59—C63—F5	149.0 (3)
C9—C10—C28—C33	−111.2 (3)	C58—C59—C63—F6	86.7 (4)
C11—C10—C28—C33	72.2 (4)	C60—C59—C63—F6	−91.1 (4)
C14—C15—C35—C36	60.4 (4)	Ru—N5—C64—C65	176.4 (3)
C16—C15—C35—C36	−119.0 (3)	Ru—N5—C68—C67	−175.6 (3)