A five-coordinate ruthenium(II)–porphyrin–carbene complex: [bis(3-trifluoromethylphenyl)methylene-κC](5,10,15,20-tetra-p-tolylporphyrinato-κ⁴N)ruthenium(II)

The stable title tri­fluoro­methyl-substituted carbenyl metalloporphyrin, [Ru(C₁₅H₈F₆)(C₄₈H₃₆N₄)], has a five-coordinate Ru atom which is displaced from the porphyrin N₄ plane towards the axial carbene ligand by 0.230 (3) Å. The Ru—C(carbene) bond coincides with a crystallographic twofold axis and its length of 1.841 (6) Å is notably shorter than the value of 1.868 (3) Å in the pyridine adduct.

S1. Comment

Carbenyl metalloporphyrin chemistry has been developed since the first synthesis of [(tpp)Fe(CCl₂)] (where H₂tpp is 5,10,15,20-tetraphenylporphyrin; Mansuy et al., 1977). Ruthenium(II)-porphyrin-carbene complexes have been reported as effective catalysts for the production of alkenes from ethyl diazoacetate (Collman et al., 1993). In order to investigate the catalytic mechanism, it seems important to isolate a five-coordinate ruthenium(II) porphyrin complex, as well as a six-coordinate adduct with a Lewis base. Recently, we studied the structural details of methanol- or pyridine-ligated six-coordinate ruthenium(II)-porphyrin-carbene complexes obtained from CH₂Cl₂ solution containing the relevant Lewis bases (Kawai et al., 2002; Harada et al., 2003). The title compound, [Ru(ttp){C(3—CF₃C₆H₄)₂}], (I) (where H₂ttp is 5,10,15,20-tetra-p-tolylporphyrin), having a trifluoromethyl-substituted carbene ligand to facilitate examination by ¹⁹F NMR spectroscopy in solution, has been crystallized from CH₂Cl₂-hexane and is herein compared with its pyridine adduct [Ru(ttp){C(3—CF₃C₆H₄)₂}(pyridine)], (II) (Harada et al., 2003). \sch

The molecular structure of (I) features a square-pyramidally five-coordinate Ru atom, as shown in Fig. 1, in contrast with the octahedrally six-coordinate Ru atom in (II). In (I), the Ru—C25 bond coincides with a crystallographic twofold axis, so that the two 3-CF₃ groups of the carbene ligand take an anti conformation, adopting a face-to-face arrangement with the porphyrin plane. The Ru═C bond length of 1.841 (6) Å in (I) is obviously shorter than the value of 1.868 (3) Å in (II). Based on UV-vis and ¹H NMR spectroscopy, Galardon et al. (1998) described how excessive addition of pyridine to a ruthenium(II)-porphyrin-carbene complex caused dissociation of the carbene ligand. Destabilization of the Ru═C bond by the pyridine ligand seems consistent with the longer Ru═C bond length in (II), due to the trans influence of the pyridine ligand.

The angles about the carbene C25 atom in (I) [C26—C25—C26ⁱ 116.1 (5)° and Ru—C25—C26 121.9 (3)°; symmetry code: (i) y, x, −z Is this correct?] are close to the value of 120° for an ideal sp² configuration. The porphyrin ring is in a distorted saddle conformation, as reported for two other five-coordinate ruthenium(II)-porphyrin-carbene complexes, [Ru(P*)(CPh₂)]·2CH₂Cl₂, (III), and [Ru(P*){(C(Ph)CO₂CH₂CH═CH₂}]·3CH₂Cl₂, (IV) {H₂P* is 5,10,15,20-tetrakis[(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro- 1,4:5,8-dimethanoanthracen-9-yl]porphyrin; Che et al., 2001}. In (I), the largest deviations from the C₂₀N₄ least-squares plane are −0.118 (6) and 0.060 (5) Å for atoms C3 and C7, respectively. The Ru atom is displaced out of the N₄ least-squares plane by 0.230 (3) Å toward the carbene ligand, and this is larger than the deviations of 0.19 and 0.22 Å in (III) and (IV), respectively.

S2. Experimental

Preparation of [(ttp)Ru(CO)] and the diaza compound N₂═C(3—CF₃C₆H₄)₂ was carried out according to the procedure of Collman et al. (1984) and the modified method for N₂═CPh₂ (Smith & Howard, 1955), respectively. A solution of [(ttp)Ru(CO)] (0.50 g, 0.63 mmol) and a small excess amount of N₂═C(3—CF₃C₆H₄)₂ in CH₂Cl₂ (50 ml) was refluxed under a nitrogen atmosphere for 3 h. After removal of the solvent by rotary evaporation, the residue was chromatographed on a silica-gel column with toluene. A dark-red band was collected and evaporated to dryness. Recrystallization from a CH₂Cl₂-hexane solution gave air-stable dark-purple crystals of (I) (89%). Analysis found: C 70.35, H 4.03, N 5.09%; calculated for C₆₆H₄₄F₆N₄Ru: C 70.58, H 4.14, N 5.23%. Is C₆₆ correct? C₆₃ given in formula below. ¹H NMR (CD₂Cl₂, 500 MHz, δ, p.p.m.): 2.66 (s, 12H), 3.04 (d, 2H), 3.27 (s, 2H), 6.30 (t, 2H), 6.73 (d, 2H), 7.49 (d, 4H), 7.52 (d, 4H), 7.71 (d, 4H), 7.90 (d, 4H), 8.41 (s, 8H). ¹⁹F NMR (CD₂Cl₂, 470 MHz, δ, p.p.m.): −62.88 (s). UV-vis (CH₂Cl₂): λ_max (log ε) 398 (4.98), 427 s h (4.66), 537 (3.93).

S3. Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.96 Å and U_iso(H) = 1.5U_eq(C) for the methyl groups or 0.93 Å and U_iso(H) = 1.2U_eq(C) for the other H atoms.

At a late stage in the refinement, rotational disorder of the CF₃ group was suggested by the rather large U_eq values (0.18–0.22 Ų) of the fluorine atoms and some peaks (0.29—0.35 e Å⁻³) in the differnce Fourier map. Accordingly, the CF₃ group was assumed to be disordered in the two orientations. The fluorine atoms of the major components, F1A, F2A and F3A, were refined anisotropically, and those of the minor, F1B, F2B and F3B, were treated isotropically. The occupancy factors were refined to 0.846 (16) for the major, and 0.154 (16) for the minor.

Computing details

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, 2002); 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. Only one orientation of the disordered CF3 group is drawn. H atoms and p-tolyl groups have been omitted for clarity. Symmetry code: (i) y, x, −z. Is this correct?

(I)

Crystal data

[Ru(C15H8F6)(C48H36N4)]	Dx = 1.393 Mg m^−3
Mr = 1072.09	Mo Kα radiation, λ = 0.71069 Å
Tetragonal, P41212	Cell parameters from 25 reflections
Hall symbol: P 4abw 2nw	θ = 13.4–14.8°
a = 11.817 (3) Å	µ = 0.37 mm^−1
c = 36.608 (4) Å	T = 296 K
V = 5112.0 (19) Å^3	Prism, intense purple
Z = 4	0.25 × 0.23 × 0.20 mm
F(000) = 2192

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.053
Radiation source: rotating Mo anticathode	θmax = 27.5°, θmin = 2.5°
Graphite monochromator	h = 0→15
ω scans	k = 0→10
6817 measured reflections	l = −47→47
5890 independent reflections	3 standard reflections every 150 reflections
4305 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.142	w = 1/[σ^2(Fo^2) + (0.0825P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
5890 reflections	Δρmax = 0.52 e Å^−3
348 parameters	Δρmin = −0.75 e Å^−3
0 restraints	Absolute structure: Flack (1983), 2333 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (5)

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	Occ. (<1)
Ru	0.14034 (3)	0.14034 (3)	0.0000	0.03459 (13)
N1	0.2576 (3)	0.0547 (3)	0.02997 (9)	0.0402 (8)
N2	0.0864 (3)	0.2177 (3)	0.04711 (9)	0.0390 (8)
C1	0.3359 (4)	−0.0219 (4)	0.01690 (13)	0.0427 (11)
C2	0.3957 (4)	−0.0715 (5)	0.04674 (13)	0.0563 (14)
H1	0.4536	−0.1245	0.0451	0.068*
C3	0.3529 (5)	−0.0274 (5)	0.07779 (13)	0.0578 (14)
H2	0.3758	−0.0448	0.1014	0.069*
C4	0.2661 (4)	0.0508 (4)	0.06787 (12)	0.0443 (11)
C5	0.1970 (4)	0.1100 (4)	0.09233 (11)	0.0422 (11)
C6	0.1158 (4)	0.1902 (4)	0.08222 (11)	0.0423 (10)
C7	0.0482 (4)	0.2561 (4)	0.10724 (12)	0.0502 (12)
H3	0.0502	0.2518	0.1326	0.060*
C8	−0.0182 (5)	0.3247 (5)	0.08732 (13)	0.0527 (13)
H4	−0.0693	0.3777	0.0963	0.063*
C9	0.0046 (4)	0.3007 (4)	0.04941 (11)	0.0428 (10)
C10	−0.0455 (4)	0.3560 (5)	0.02015 (12)	0.0463 (10)
C11	0.2124 (4)	0.0834 (4)	0.13196 (11)	0.0460 (10)
C12	0.1853 (6)	−0.0221 (5)	0.14540 (15)	0.0729 (18)
H5	0.1567	−0.0763	0.1295	0.088*
C13	0.1992 (6)	−0.0504 (6)	0.18196 (16)	0.0767 (19)
H6	0.1797	−0.1223	0.1901	0.092*
C14	0.2421 (5)	0.0281 (5)	0.20621 (13)	0.0602 (14)
C15	0.2675 (6)	0.1293 (6)	0.19379 (16)	0.0797 (19)
H7	0.2952	0.1826	0.2102	0.096*
C16	0.2551 (6)	0.1614 (5)	0.15686 (15)	0.0699 (17)
H8	0.2751	0.2338	0.1493	0.084*
C17	0.2584 (6)	−0.0062 (7)	0.24587 (15)	0.089 (2)
H9	0.2152	0.0433	0.2613	0.134*
H10	0.3371	−0.0007	0.2521	0.134*
H11	0.2332	−0.0827	0.2492	0.134*
C18	−0.1347 (5)	0.4426 (4)	0.02864 (12)	0.0521 (12)
C19	−0.2431 (6)	0.4111 (6)	0.0368 (2)	0.082 (2)
H12	−0.2625	0.3349	0.0364	0.099*
C20	−0.3238 (6)	0.4904 (8)	0.0458 (2)	0.093 (2)
H13	−0.3964	0.4655	0.0515	0.112*
C21	−0.3028 (7)	0.6012 (7)	0.04665 (17)	0.086 (2)
C22	−0.1937 (8)	0.6331 (7)	0.0383 (2)	0.105 (3)
H14	−0.1751	0.7095	0.0384	0.126*
C23	−0.1111 (6)	0.5543 (6)	0.0296 (2)	0.088 (2)
H15	−0.0380	0.5788	0.0244	0.106*
C24	−0.3917 (8)	0.6862 (8)	0.0565 (2)	0.133 (4)
H16	−0.3595	0.7608	0.0559	0.199*
H17	−0.4198	0.6706	0.0805	0.199*
H18	−0.4527	0.6819	0.0392	0.199*
C25	0.0302 (4)	0.0302 (4)	0.0000	0.0425 (13)
C26	−0.0274 (4)	−0.0060 (4)	0.03397 (12)	0.0465 (11)
C27	−0.1276 (5)	0.0451 (5)	0.04504 (13)	0.0543 (12)
H19	−0.1578	0.1038	0.0312	0.065*
C28	−0.1832 (5)	0.0099 (6)	0.07634 (15)	0.0618 (15)
C29	−0.1416 (7)	−0.0785 (6)	0.09658 (16)	0.0772 (18)
H20	−0.1798	−0.1032	0.1173	0.093*
C30	−0.0428 (6)	−0.1302 (7)	0.08584 (19)	0.084 (2)
H21	−0.0137	−0.1898	0.0995	0.100*
C31	0.0137 (6)	−0.0941 (5)	0.05476 (17)	0.0689 (16)
H22	0.0804	−0.1300	0.0478	0.083*
C32	−0.2874 (7)	0.0704 (9)	0.0880 (2)	0.088 (2)
F1A	−0.3503 (6)	0.1077 (10)	0.0611 (2)	0.146 (4)	0.846 (16)
F2A	−0.3585 (7)	0.0090 (9)	0.1067 (3)	0.166 (5)	0.846 (16)
F3A	−0.2664 (7)	0.1619 (9)	0.1073 (3)	0.181 (5)	0.846 (16)
F1B	−0.300 (3)	0.053 (2)	0.1218 (8)	0.073 (10)*	0.154 (16)
F2B	−0.303 (3)	0.163 (3)	0.0780 (12)	0.096 (13)*	0.154 (16)
F3B	−0.374 (4)	0.020 (4)	0.0750 (13)	0.116 (16)*	0.154 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru	0.03592 (15)	0.03592 (15)	0.03193 (19)	0.0059 (2)	0.00298 (14)	−0.00298 (14)
N1	0.043 (2)	0.045 (2)	0.0330 (18)	0.0077 (17)	0.0027 (16)	0.0005 (15)
N2	0.0388 (19)	0.044 (2)	0.0340 (17)	0.0092 (16)	0.0002 (15)	−0.0054 (15)
C1	0.041 (3)	0.043 (2)	0.044 (2)	0.011 (2)	0.0040 (19)	0.0011 (19)
C2	0.058 (3)	0.061 (3)	0.050 (3)	0.025 (2)	0.001 (2)	0.001 (2)
C3	0.067 (3)	0.065 (3)	0.042 (2)	0.021 (3)	−0.002 (3)	0.009 (2)
C4	0.050 (3)	0.047 (3)	0.035 (2)	0.009 (2)	0.000 (2)	0.0013 (19)
C5	0.050 (3)	0.045 (3)	0.032 (2)	0.005 (2)	0.0000 (19)	−0.0012 (17)
C6	0.046 (3)	0.046 (2)	0.034 (2)	0.004 (2)	0.0027 (18)	−0.0041 (18)
C7	0.058 (3)	0.057 (3)	0.036 (2)	0.011 (2)	0.005 (2)	−0.010 (2)
C8	0.055 (3)	0.063 (3)	0.040 (2)	0.016 (2)	0.006 (2)	−0.015 (2)
C9	0.047 (3)	0.045 (3)	0.037 (2)	0.007 (2)	0.0058 (19)	−0.0090 (19)
C10	0.047 (3)	0.045 (2)	0.047 (2)	0.011 (2)	−0.0009 (19)	−0.010 (2)
C11	0.052 (3)	0.051 (3)	0.035 (2)	0.009 (2)	0.0039 (19)	−0.004 (2)
C12	0.112 (5)	0.061 (3)	0.046 (3)	−0.007 (3)	−0.007 (3)	−0.001 (3)
C13	0.109 (5)	0.068 (4)	0.053 (3)	−0.001 (4)	0.007 (3)	0.015 (3)
C14	0.069 (4)	0.076 (4)	0.036 (2)	0.012 (3)	0.000 (2)	0.007 (3)
C15	0.111 (5)	0.080 (4)	0.048 (3)	−0.024 (4)	−0.023 (3)	−0.001 (3)
C16	0.092 (5)	0.066 (4)	0.052 (3)	−0.013 (3)	−0.017 (3)	0.008 (3)
C17	0.102 (5)	0.121 (6)	0.044 (3)	0.020 (4)	−0.011 (3)	0.011 (4)
C18	0.055 (3)	0.059 (3)	0.043 (2)	0.018 (3)	−0.002 (2)	−0.006 (2)
C19	0.071 (4)	0.075 (4)	0.101 (5)	0.017 (3)	0.022 (4)	0.002 (4)
C20	0.062 (4)	0.116 (7)	0.101 (6)	0.046 (4)	0.021 (4)	0.011 (5)
C21	0.095 (5)	0.107 (6)	0.056 (3)	0.064 (5)	−0.007 (3)	−0.022 (4)
C22	0.117 (7)	0.066 (4)	0.131 (7)	0.034 (5)	−0.011 (5)	−0.037 (5)
C23	0.064 (4)	0.066 (4)	0.135 (6)	0.016 (3)	−0.007 (4)	−0.036 (4)
C24	0.145 (9)	0.160 (9)	0.093 (5)	0.112 (7)	0.001 (5)	−0.027 (6)
C25	0.0405 (18)	0.0405 (18)	0.047 (3)	0.007 (2)	0.001 (2)	−0.001 (2)
C26	0.049 (3)	0.043 (3)	0.047 (2)	−0.011 (2)	0.003 (2)	−0.0003 (19)
C27	0.053 (3)	0.061 (3)	0.049 (3)	−0.006 (3)	0.004 (2)	0.006 (2)
C28	0.060 (3)	0.076 (4)	0.049 (3)	−0.019 (3)	0.007 (3)	0.006 (3)
C29	0.084 (4)	0.092 (4)	0.056 (3)	−0.025 (4)	0.010 (3)	0.021 (3)
C30	0.086 (5)	0.089 (5)	0.077 (4)	−0.016 (4)	0.002 (4)	0.032 (4)
C31	0.071 (4)	0.062 (4)	0.073 (4)	0.002 (3)	0.001 (3)	0.014 (3)
C32	0.079 (5)	0.120 (7)	0.066 (4)	−0.002 (5)	0.021 (4)	0.016 (5)
F1A	0.087 (4)	0.244 (12)	0.105 (5)	0.056 (6)	0.032 (4)	0.051 (6)
F2A	0.093 (5)	0.224 (8)	0.181 (9)	0.012 (6)	0.075 (6)	0.110 (7)
F3A	0.126 (6)	0.189 (9)	0.226 (12)	0.018 (6)	0.037 (7)	−0.112 (8)

Geometric parameters (Å, º)

Ru—N1	2.036 (4)	C17—H10	0.9600
Ru—N2	2.053 (3)	C17—H11	0.9600
Ru—C25	1.841 (6)	C18—C23	1.349 (8)
N1—C1	1.380 (6)	C18—C19	1.367 (9)
N1—C4	1.392 (5)	C19—C20	1.377 (9)
N2—C6	1.371 (6)	C19—H12	0.9300
N2—C9	1.380 (6)	C20—C21	1.333 (11)
C1—C10^i	1.405 (6)	C20—H13	0.9300
C1—C2	1.427 (7)	C21—C22	1.377 (12)
C2—C3	1.349 (7)	C21—C24	1.498 (8)
C2—H1	0.9300	C22—C23	1.386 (9)
C3—C4	1.427 (7)	C22—H14	0.9300
C3—H2	0.9300	C23—H15	0.9300
C4—C5	1.400 (6)	C24—H16	0.9600
C5—C6	1.399 (6)	C24—H17	0.9600
C5—C11	1.495 (6)	C24—H18	0.9600
C6—C7	1.443 (6)	C25—C26^i	1.480 (5)
C7—C8	1.343 (7)	C25—C26	1.480 (5)
C7—H3	0.9300	C26—C31	1.379 (8)
C8—C9	1.442 (6)	C26—C27	1.390 (8)
C8—H4	0.9300	C27—C28	1.385 (7)
C9—C10	1.387 (6)	C27—H19	0.9300
C10—C1^i	1.405 (6)	C28—C29	1.372 (9)
C10—C18	1.502 (7)	C28—C32	1.487 (10)
C11—C12	1.379 (8)	C29—C30	1.375 (10)
C11—C16	1.391 (8)	C29—H20	0.9300
C12—C13	1.389 (8)	C30—C31	1.386 (9)
C12—H5	0.9300	C30—H21	0.9300
C13—C14	1.380 (9)	C31—H22	0.9300
C13—H6	0.9300	C32—F1A	1.311 (11)
C14—C15	1.314 (9)	C32—F2A	1.303 (10)
C14—C17	1.519 (7)	C32—F3A	1.314 (12)
C15—C16	1.412 (8)	C32—F1B	1.26 (3)
C15—H7	0.9300	C32—F2B	1.16 (4)
C16—H8	0.9300	C32—F3B	1.28 (4)
C17—H9	0.9600
N1—Ru—C25	97.47 (11)	C23—C18—C19	117.1 (5)
N2—Ru—C25	95.47 (11)	C23—C18—C10	121.8 (6)
N1—Ru—N1^i	165.1 (2)	C19—C18—C10	121.1 (5)
N1—Ru—N2	88.84 (14)	C18—C19—C20	121.1 (7)
N1—Ru—N2^i	89.74 (14)	C18—C19—H12	119.5
N2—Ru—N2^i	169.1 (2)	C20—C19—H12	119.5
C1—N1—C4	106.0 (4)	C21—C20—C19	123.0 (7)
C1—N1—Ru	126.5 (3)	C21—C20—H13	118.5
C4—N1—Ru	127.1 (3)	C19—C20—H13	118.5
C6—N2—C9	106.8 (3)	C20—C21—C22	116.0 (6)
C6—N2—Ru	127.2 (3)	C20—C21—C24	122.3 (8)
C9—N2—Ru	125.8 (3)	C22—C21—C24	121.8 (8)
N1—C1—C10^i	125.3 (4)	C21—C22—C23	121.8 (8)
N1—C1—C2	109.6 (4)	C21—C22—H14	119.1
C10^i—C1—C2	125.0 (4)	C23—C22—H14	119.1
C3—C2—C1	107.5 (4)	C18—C23—C22	121.1 (7)
C3—C2—H1	126.2	C18—C23—H15	119.4
C1—C2—H1	126.2	C22—C23—H15	119.4
C2—C3—C4	107.7 (4)	C21—C24—H16	109.5
C2—C3—H2	126.1	C21—C24—H17	109.5
C4—C3—H2	126.1	H16—C24—H17	109.5
N1—C4—C5	125.3 (4)	C21—C24—H18	109.5
N1—C4—C3	109.1 (4)	H16—C24—H18	109.5
C5—C4—C3	125.5 (4)	H17—C24—H18	109.5
C6—C5—C4	124.8 (4)	C26—C25—C26^i	116.1 (5)
C6—C5—C11	118.8 (4)	Ru—C25—C26	121.9 (3)
C4—C5—C11	116.4 (4)	C31—C26—C27	117.9 (5)
N2—C6—C5	125.6 (4)	C31—C26—C25	121.3 (5)
N2—C6—C7	109.1 (4)	C27—C26—C25	120.7 (4)
C5—C6—C7	125.3 (4)	C28—C27—C26	121.0 (5)
C8—C7—C6	107.7 (4)	C28—C27—H19	119.5
C8—C7—H3	126.1	C26—C27—H19	119.5
C6—C7—H3	126.1	C29—C28—C27	120.4 (6)
C7—C8—C9	107.1 (4)	C29—C28—C32	120.5 (6)
C7—C8—H4	126.4	C27—C28—C32	119.1 (6)
C9—C8—H4	126.4	C28—C29—C30	119.2 (6)
N2—C9—C10	125.9 (4)	C28—C29—H20	120.4
N2—C9—C8	109.2 (4)	C30—C29—H20	120.4
C10—C9—C8	124.8 (4)	C29—C30—C31	120.5 (7)
C9—C10—C1^i	125.5 (4)	C29—C30—H21	119.8
C9—C10—C18	117.5 (4)	C31—C30—H21	119.8
C1^i—C10—C18	117.0 (4)	C26—C31—C30	121.0 (6)
C12—C11—C16	116.7 (5)	C26—C31—H22	119.5
C12—C11—C5	120.5 (5)	C30—C31—H22	119.5
C16—C11—C5	122.7 (5)	C28—C32—F1A	114.5 (7)
C11—C12—C13	122.3 (6)	C28—C32—F2A	114.6 (8)
C11—C12—H5	118.9	C28—C32—F3A	113.2 (8)
C13—C12—H5	118.9	C28—C32—F1B	107.4 (15)
C14—C13—C12	120.1 (6)	C28—C32—F2B	119 (2)
C14—C13—H6	119.9	C28—C32—F3B	109.4 (18)
C12—C13—H6	119.9	F1A—C32—F2A	102.4 (9)
C15—C14—C13	118.2 (5)	F2A—C32—F3A	107.4 (9)
C15—C14—C17	123.0 (6)	F3A—C32—F1A	103.5 (11)
C13—C14—C17	118.8 (6)	F1B—C32—F2B	116 (3)
C14—C15—C16	123.5 (6)	F2B—C32—F3B	101 (3)
C14—C15—H7	118.2	F3B—C32—F1B	101 (3)
C16—C15—H7	118.2	F1A—C32—F1B	136.6 (16)
C11—C16—C15	119.1 (6)	F1A—C32—F2B	50 (2)
C11—C16—H8	120.4	F1A—C32—F3B	55 (2)
C15—C16—H8	120.4	F2A—C32—F1B	47.3 (13)
C14—C17—H9	109.5	F2A—C32—F2B	126 (2)
C14—C17—H10	109.5	F2A—C32—F3B	54 (2)
H9—C17—H10	109.5	F3A—C32—F1B	68.4 (13)
C14—C17—H11	109.5	F3A—C32—F2B	55 (2)
H9—C17—H11	109.5	F3A—C32—F3B	137.3 (19)
H10—C17—H11	109.5
C25—Ru—N1—C1	85.2 (4)	C16—C11—C12—C13	0.1 (10)
N1^i—Ru—N1—C1	−94.8 (4)	C5—C11—C12—C13	179.5 (6)
N2—Ru—N1—C1	−179.5 (4)	C11—C12—C13—C14	−0.4 (11)
N2^i—Ru—N1—C1	−10.3 (4)	C12—C13—C14—C15	0.8 (11)
C25—Ru—N1—C4	−86.3 (4)	C12—C13—C14—C17	−178.9 (6)
N1^i—Ru—N1—C4	93.7 (4)	C13—C14—C15—C16	−1.1 (11)
N2—Ru—N1—C4	9.1 (4)	C17—C14—C15—C16	178.6 (7)
N2^i—Ru—N1—C4	178.2 (4)	C12—C11—C16—C15	−0.3 (9)
C25—Ru—N2—C6	86.7 (4)	C5—C11—C16—C15	−179.6 (6)
N1—Ru—N2—C6	−10.7 (4)	C14—C15—C16—C11	0.9 (12)
N1^i—Ru—N2—C6	−175.8 (4)	C9—C10—C18—C23	98.3 (7)
N2^i—Ru—N2—C6	−93.3 (4)	C1^i—C10—C18—C23	−83.3 (7)
C25—Ru—N2—C9	−86.6 (4)	C9—C10—C18—C19	−79.6 (7)
N1—Ru—N2—C9	176.1 (4)	C1^i—C10—C18—C19	98.8 (7)
N1^i—Ru—N2—C9	10.9 (4)	C23—C18—C19—C20	−0.2 (11)
N2^i—Ru—N2—C9	93.4 (4)	C10—C18—C19—C20	177.8 (6)
C4—N1—C1—C10^i	179.9 (5)	C18—C19—C20—C21	0.8 (13)
Ru—N1—C1—C10^i	7.0 (8)	C19—C20—C21—C22	−0.5 (12)
C4—N1—C1—C2	−1.6 (6)	C19—C20—C21—C24	−180.0 (8)
Ru—N1—C1—C2	−174.6 (3)	C20—C21—C22—C23	−0.3 (12)
N1—C1—C2—C3	1.2 (6)	C24—C21—C22—C23	179.1 (8)
C10^i—C1—C2—C3	179.6 (6)	C19—C18—C23—C22	−0.6 (11)
C1—C2—C3—C4	−0.3 (7)	C10—C18—C23—C22	−178.6 (7)
C1—N1—C4—C5	−175.8 (5)	C21—C22—C23—C18	0.9 (13)
Ru—N1—C4—C5	−2.9 (7)	N1—Ru—C25—C26^i	−114.7 (3)
C1—N1—C4—C3	1.5 (6)	N1^i—Ru—C25—C26^i	65.3 (3)
Ru—N1—C4—C3	174.3 (3)	N2—Ru—C25—C26^i	155.7 (3)
C2—C3—C4—N1	−0.8 (7)	N2^i—Ru—C25—C26^i	−24.3 (3)
C2—C3—C4—C5	176.5 (5)	N1—Ru—C25—C26	65.3 (3)
N1—C4—C5—C6	−6.3 (8)	N1^i—Ru—C25—C26	−114.7 (3)
C3—C4—C5—C6	176.9 (5)	N2—Ru—C25—C26	−24.3 (3)
N1—C4—C5—C11	173.4 (5)	N2^i—Ru—C25—C26	155.7 (3)
C3—C4—C5—C11	−3.4 (8)	C26^i—C25—C26—C31	89.2 (5)
C9—N2—C6—C5	−179.5 (5)	Ru—C25—C26—C31	−90.8 (5)
Ru—N2—C6—C5	6.3 (7)	C26^i—C25—C26—C27	−88.0 (4)
C9—N2—C6—C7	1.5 (5)	Ru—C25—C26—C27	92.0 (4)
Ru—N2—C6—C7	−172.8 (3)	C31—C26—C27—C28	1.2 (8)
C4—C5—C6—N2	4.5 (8)	C25—C26—C27—C28	178.5 (5)
C11—C5—C6—N2	−175.1 (4)	C26—C27—C28—C29	−1.7 (9)
C4—C5—C6—C7	−176.6 (5)	C26—C27—C28—C32	177.3 (6)
C11—C5—C6—C7	3.7 (8)	C27—C28—C29—C30	1.4 (10)
N2—C6—C7—C8	−1.9 (6)	C32—C28—C29—C30	−177.7 (7)
C5—C6—C7—C8	179.0 (5)	C28—C29—C30—C31	−0.6 (11)
C6—C7—C8—C9	1.5 (6)	C27—C26—C31—C30	−0.4 (9)
C6—N2—C9—C10	177.2 (5)	C25—C26—C31—C30	−177.7 (6)
Ru—N2—C9—C10	−8.4 (7)	C29—C30—C31—C26	0.0 (11)
C6—N2—C9—C8	−0.6 (6)	C29—C28—C32—F2B	157 (3)
Ru—N2—C9—C8	173.8 (3)	C27—C28—C32—F2B	−22 (3)
C7—C8—C9—N2	−0.6 (6)	C29—C28—C32—F1B	21.8 (19)
C7—C8—C9—C10	−178.5 (5)	C27—C28—C32—F1B	−157.3 (16)
N2—C9—C10—C1^i	0.7 (9)	C29—C28—C32—F3B	−87 (3)
C8—C9—C10—C1^i	178.1 (5)	C27—C28—C32—F3B	93 (3)
N2—C9—C10—C18	178.9 (5)	C29—C28—C32—F2A	−28.6 (13)
C8—C9—C10—C18	−3.6 (8)	C27—C28—C32—F2A	152.3 (10)
C6—C5—C11—C12	113.7 (6)	C29—C28—C32—F1A	−146.6 (10)
C4—C5—C11—C12	−66.0 (7)	C27—C28—C32—F1A	34.3 (13)
C6—C5—C11—C16	−67.0 (7)	C29—C28—C32—F3A	95.1 (11)
C4—C5—C11—C16	113.3 (6)	C27—C28—C32—F3A	−83.9 (10)

Symmetry code: (i) y, x, −z.