A ruthenium(II)-porphyrin-carbene complex with a weakly bonded methanol ligand

The title di­phenyl­carbene porphyrin complex (di­phenyl­carbenyl-[kappa]C)(methanol-[kappa]O)(5,10,15,20-tetra-p-tolyl­por­phy­rin­ato-[kappa]⁴N)ruthenium(II) methanol solvate, [Ru­(C₁₃H₁₀)(C₄₈H₃₆N₄)(CH₄O)]·CH₄O, has a six-coordinate Ru atom with a methanol mol­ecule as the second axial ligand. The carbene fragment is slightly distorted from an ideal sp² configuration, with a C(phenyl)-C(carbene)-C(phenyl) angle of 112.2 (3)°. The Ru-C bond length of 1.845 (3) Å is comparable with other carbene complexes. The two phenyl rings of the carbene ligand are perpendicular to the carbene plane. Methanol solvate mol­ecules link the methanol ligands of adjacent porphyrin complexes via hydrogen bonds.

S1. Comment

Ruthenium carbene complexes have attracted much attention in recent years as catalysts of the cyclopropanation of olefins (Trost et al., 2001). Some ruthenium porphyrin carbene complexes have been reported as effective catalysts because of their higher stereoselectivity and turnover numbers. However, ruthenium porphyrin carbene complexes are so unstable that, since the early investigation by Collman et al. (1985), they have only been characterized using UV-vis or NMR spectroscopy. The first crystal structure of a (porphyrinato)ruthenium(II) carbene complex, [Ru(tpp){C(CO₂Et)₂}(CH₃OH)]·H₂O, (II) (H₂tpp is 5,10,15,20-tetraphenylporphyrin), was determined by Galardon et al. (1998). A methanol molecule was bound to the six-coordinate Ru atom trans to the carbene ligand and could be replaced by other ligands such as PPh₃, pyridine or CO in solution. Che et al. (2001) reported that (porphyrinato)ruthenium(II) diphenyl or phenyl(allyloxycarbonyl) carbene complexes, recrystallized from CH₂Cl₂/CH₃CN in air, contained five-coordinate Ru atoms in the crystalline state. Both cases show that carbene complexes without α- and β-H atoms would be stable enough for isolation and crystallization even in air. We have synthesized a simple carbene complex, [Ru(ttp)(CPh₂)(CH₃OH)]·CH₃OH, (I) (H₂ttp is 5,10,15,20-tetra(p-tolyl)porphyrin), and here we compare its structure with those of some other (porphyrinato)ruthenium(II) carbene complexes. \sch

As shown in Fig. 1, the Ru atom is six-coordinate in (I), similar to (II), while the Ru atoms are square-pyramidally five-coordinate in [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-dimethanoanthracene-9-yl]porphyrin} (Che et al., 2001). The Ru—C(carbene) bond length in (I) is similar to that in (II) [1.829 (9) Å], and the Ru—N(porphyrin) bond lengths are also within the range previously reported for Ru^II porphyrin complexes. A methanol molecule is bonded to the Ru atom trans to the carbene ligand, and is associated with two other methanol solvate molecules through hydrogen bonding. The Ru—O(methanol) bond length in (I) is significantly longer than that in (II) [2.293 (6) Å], perhaps due to the hydrogen bonds.

The carbene fragment in (I) is distorted from an ideal sp² configuration, as the C(phenyl)-C(carbene)-C(phenyl) angle is 112.2 (3)°, similar to that in the diphenylcarbene complex, (III) [112.1 (5)°]. The two phenyl groups are oriented perpendicular to the plane of the carbene fragment, assuming a face-to-face arrangement, as observed in (III). The projection of the phenyl groups onto the porphyrin plane reveals a staggered configuration with regard to the Ru—N bonds; the N2—Ru—C49—C50 and N4—Ru—C49—C56 torsion angles are 27.1 (3) and 26.4 (3)°, respectively. Because of steric repulsion between the porphyrin group and the phenyl groups of the carbene ligand, the porphyrin in (I) is slightly distorted into a saddle conformation, whereas those of (III) and (IV) in the square-pyramidal configuration are severely distorted. The largest deviations from the [C₂₀N₄] least-squares plane in (I) are -0.187 (4) and 0.180 (3) Å for atoms C2 and C7, respectively. The Ru atom is slightly out of this least-squares plane by 0.1139 (7) Å towards the carbene ligand, close to the value of 0.12 Å in (II), but less than the values of 0.19 and 0.22 Å in (III) and (IV), respectively.

S2. Experimental

The title compound was prepared according to the procedure of Galardon et al. (1998). A CH₂Cl₂ solution containing equimolar amounts of [Ru(ttp)(CO)(CH₃OH)] and the diaza compound N₂═CPh₂ was refluxed under N₂ for 3 h. After removal of the solvent in vacuo, the residue was purified by column chromatography on silica gel with toluene as the eluent. The compound is stable in air at room temperature. Crystals of (I) suitable for X-ray diffraction were prepared by recrystallization from CH₂Cl₂/methanol (Ratio?).

S3. Refinement

The positions of the methanolic H atoms were refined as rotating methyl and hydroxy groups, with C—H = 0.96 Å and O—H = 0.82 Å, respectively. All remaining H atoms were placed in geometrically idealized positions, with Csp²—H = 0.93 Å and Csp³—H = 0.96 Å. The isotropic displacement parameters of all H atoms were constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C, O).

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 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 have been omitted for clarity.

(diphenylcarbenyl-κC)(methanol-κO)(5,10,15,20-tetra-p-tolylporphyrinato- κ⁴N)ruthenium(II) methanol solvate

Crystal data

[Ru(C48H36N4)(C13H10)(CH4O)]·CH4O	F(000) = 2080
Mr = 1000.17	Dx = 1.295 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.4608 (12) Å	θ = 14.4–15.0°
b = 17.744 (2) Å	µ = 0.35 mm^−1
c = 23.7491 (13) Å	T = 296 K
β = 102.428 (6)°	Prism, dark red
V = 5128.0 (8) Å^3	0.28 × 0.14 × 0.13 mm
Z = 4

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.030
Radiation source: rotating Mo anode	θmax = 27.5°, θmin = 2.7°
Graphite monochromator	h = −16→0
ω/2θ scans	k = 0→23
12304 measured reflections	l = −30→30
11769 independent reflections	3 standard reflections every 150 reflections
6589 reflections with I > 2σ(I)	intensity decay: 0.9%

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0531P)^2 + 1.1504P] where P = (Fo^2 + 2Fc^2)/3
11769 reflections	(Δ/σ)max = 0.001
635 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.33 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	0.01297 (2)	0.281035 (16)	0.072200 (11)	0.04669 (9)
O1	−0.0653 (2)	0.39865 (15)	0.03973 (12)	0.0771 (8)
H47	−0.0623	0.4084	0.0064	0.092*
O2	0.0633 (8)	0.5389 (3)	0.0639 (2)	0.214 (3)
H51	0.0458	0.4948	0.0669	0.257*
N1	−0.1422 (2)	0.23654 (15)	0.04885 (11)	0.0506 (7)
N2	−0.0167 (2)	0.30812 (15)	0.15093 (11)	0.0474 (6)
N3	0.1571 (2)	0.33982 (16)	0.09154 (11)	0.0511 (7)
N4	0.0336 (2)	0.26619 (16)	−0.01048 (11)	0.0538 (7)
C1	−0.1840 (3)	0.1980 (2)	−0.00178 (15)	0.0573 (9)
C2	−0.2831 (3)	0.1609 (2)	0.00344 (16)	0.0670 (10)
H1	−0.3270	0.1308	−0.0244	0.080*
C3	−0.3018 (3)	0.1776 (2)	0.05615 (16)	0.0668 (10)
H2	−0.3610	0.1613	0.0710	0.080*
C4	−0.2141 (3)	0.2246 (2)	0.08475 (14)	0.0544 (8)
C5	−0.2014 (3)	0.2530 (2)	0.14107 (15)	0.0537 (8)
C6	−0.1106 (3)	0.29254 (19)	0.17093 (14)	0.0492 (8)
C7	−0.0986 (3)	0.3232 (2)	0.22821 (14)	0.0564 (9)
H3	−0.1510	0.3220	0.2508	0.068*
C8	0.0015 (3)	0.3538 (2)	0.24289 (15)	0.0579 (9)
H4	0.0313	0.3773	0.2777	0.070*
C9	0.0553 (3)	0.34406 (19)	0.19543 (14)	0.0498 (8)
C10	0.1607 (3)	0.36861 (19)	0.19401 (14)	0.0494 (8)
C11	0.2067 (3)	0.36810 (19)	0.14507 (15)	0.0526 (8)
C12	0.3122 (3)	0.3966 (2)	0.14178 (17)	0.0640 (10)
H5	0.3632	0.4181	0.1719	0.077*
C13	0.3252 (3)	0.3870 (2)	0.08743 (17)	0.0682 (11)
H6	0.3856	0.4022	0.0730	0.082*
C14	0.2308 (3)	0.3497 (2)	0.05606 (15)	0.0565 (9)
C15	0.2143 (3)	0.3256 (2)	−0.00151 (15)	0.0585 (9)
C16	0.1229 (3)	0.2875 (2)	−0.03190 (14)	0.0598 (9)
C17	0.1065 (4)	0.2632 (2)	−0.09118 (16)	0.0741 (12)
H7	0.1549	0.2706	−0.1155	0.089*
C18	0.0106 (4)	0.2284 (3)	−0.10461 (16)	0.0739 (12)
H8	−0.0207	0.2075	−0.1403	0.089*
C19	−0.0373 (3)	0.2285 (2)	−0.05408 (14)	0.0591 (9)
C20	−0.1368 (3)	0.1957 (2)	−0.05012 (14)	0.0582 (9)
C21	−0.2917 (3)	0.2370 (2)	0.17190 (15)	0.0552 (9)
C22	−0.2743 (3)	0.1897 (2)	0.21935 (17)	0.0657 (10)
H9	−0.2056	0.1678	0.2324	0.079*
C23	−0.3585 (4)	0.1747 (2)	0.24758 (19)	0.0758 (12)
H10	−0.3452	0.1429	0.2795	0.091*
C24	−0.4605 (4)	0.2057 (3)	0.2296 (2)	0.0753 (12)
C25	−0.4768 (3)	0.2525 (3)	0.1826 (2)	0.0835 (14)
H11	−0.5456	0.2744	0.1698	0.100*
C26	−0.3944 (3)	0.2682 (3)	0.15392 (19)	0.0746 (12)
H12	−0.4083	0.3002	0.1221	0.090*
C27	−0.5521 (4)	0.1916 (4)	0.2610 (3)	0.125 (2)
H13	−0.5268	0.1577	0.2926	0.150*
H14	−0.6139	0.1696	0.2350	0.150*
H15	−0.5738	0.2384	0.2755	0.150*
C28	0.2330 (3)	0.3934 (2)	0.24973 (15)	0.0543 (8)
C29	0.2592 (3)	0.3433 (2)	0.29476 (16)	0.0708 (11)
H16	0.2282	0.2954	0.2910	0.085*
C30	0.3314 (4)	0.3632 (3)	0.34594 (18)	0.0804 (13)
H17	0.3484	0.3280	0.3755	0.096*
C31	0.3779 (3)	0.4329 (3)	0.35364 (18)	0.0731 (12)
C32	0.3491 (3)	0.4839 (3)	0.30915 (19)	0.0758 (12)
H18	0.3785	0.5323	0.3136	0.091*
C33	0.2775 (3)	0.4652 (2)	0.25798 (17)	0.0636 (10)
H19	0.2592	0.5010	0.2289	0.076*
C34	0.4614 (4)	0.4535 (3)	0.4078 (2)	0.1099 (19)
H20	0.4712	0.4117	0.4341	0.132*
H21	0.4357	0.4964	0.4257	0.132*
H22	0.5302	0.4655	0.3980	0.132*
C35	0.3087 (3)	0.3411 (2)	−0.03061 (16)	0.0663 (10)
C36	0.4033 (4)	0.3007 (3)	−0.0180 (2)	0.0884 (15)
H23	0.4077	0.2594	0.0065	0.106*
C37	0.4935 (4)	0.3194 (3)	−0.0405 (2)	0.0975 (16)
H24	0.5570	0.2905	−0.0304	0.117*
C38	0.4923 (5)	0.3775 (3)	−0.0764 (2)	0.0950 (16)
C39	0.3935 (6)	0.4143 (3)	−0.0942 (3)	0.128 (2)
H25	0.3880	0.4520	−0.1218	0.153*
C40	0.3002 (5)	0.3968 (3)	−0.0719 (2)	0.1056 (18)
H26	0.2342	0.4222	−0.0849	0.127*
C41	0.5934 (5)	0.4007 (4)	−0.0983 (3)	0.140 (3)
H27	0.5756	0.4427	−0.1240	0.168*
H28	0.6174	0.3592	−0.1184	0.168*
H29	0.6511	0.4147	−0.0663	0.168*
C42	−0.1969 (3)	0.1517 (2)	−0.10123 (14)	0.0600 (9)
C43	−0.1553 (4)	0.0852 (2)	−0.11704 (18)	0.0819 (14)
H30	−0.0884	0.0674	−0.0960	0.098*
C44	−0.2116 (4)	0.0441 (3)	−0.16408 (19)	0.0862 (14)
H31	−0.1830	−0.0016	−0.1732	0.103*
C45	−0.3078 (4)	0.0696 (2)	−0.19701 (17)	0.0713 (11)
C46	−0.3488 (4)	0.1357 (3)	−0.18149 (17)	0.0825 (13)
H32	−0.4153	0.1536	−0.2030	0.099*
C47	−0.2943 (4)	0.1769 (2)	−0.13460 (17)	0.0783 (13)
H33	−0.3239	0.2223	−0.1255	0.094*
C48	−0.3670 (5)	0.0256 (3)	−0.2489 (2)	0.117 (2)
H34	−0.4331	0.0518	−0.2667	0.140*
H35	−0.3854	−0.0235	−0.2369	0.140*
H36	−0.3203	0.0207	−0.2759	0.140*
C49	0.0744 (3)	0.18900 (19)	0.09689 (13)	0.0475 (8)
C50	0.0461 (3)	0.1456 (2)	0.14529 (16)	0.0580 (9)
C51	0.1031 (4)	0.1557 (2)	0.20130 (17)	0.0797 (13)
H37	0.1589	0.1914	0.2095	0.096*
C52	0.0774 (6)	0.1121 (3)	0.2463 (2)	0.113 (2)
H38	0.1154	0.1191	0.2841	0.135*
C53	−0.0044 (7)	0.0595 (3)	0.2334 (3)	0.119 (2)
H39	−0.0212	0.0303	0.2629	0.143*
C54	−0.0610 (5)	0.0490 (3)	0.1790 (3)	0.109 (2)
H40	−0.1162	0.0128	0.1710	0.131*
C55	−0.0367 (4)	0.0922 (2)	0.1351 (2)	0.0817 (13)
H41	−0.0770	0.0852	0.0977	0.098*
C56	0.1560 (3)	0.1491 (2)	0.07041 (16)	0.0611 (10)
C57	0.1238 (5)	0.0984 (3)	0.0264 (2)	0.1051 (18)
H42	0.0494	0.0892	0.0123	0.126*
C58	0.2007 (8)	0.0610 (4)	0.0031 (3)	0.155 (4)
H43	0.1778	0.0280	−0.0275	0.186*
C59	0.3083 (8)	0.0719 (5)	0.0242 (4)	0.160 (4)
H44	0.3599	0.0451	0.0092	0.192*
C60	0.3419 (5)	0.1222 (4)	0.0674 (4)	0.149 (3)
H45	0.4166	0.1302	0.0815	0.179*
C61	0.2661 (4)	0.1615 (3)	0.0908 (3)	0.0998 (16)
H46	0.2897	0.1962	0.1202	0.120*
C62	−0.1688 (5)	0.4222 (3)	0.0499 (3)	0.142 (3)
H48	−0.1938	0.4657	0.0267	0.170*
H49	−0.1610	0.4347	0.0899	0.170*
H50	−0.2212	0.3822	0.0399	0.170*
C63	0.0931 (6)	0.5676 (4)	0.1135 (3)	0.151 (3)
H52	0.0328	0.5665	0.1328	0.181*
H53	0.1156	0.6188	0.1100	0.181*
H54	0.1535	0.5392	0.1354	0.181*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru	0.05534 (16)	0.04805 (15)	0.03828 (13)	0.00454 (15)	0.01360 (10)	−0.00024 (13)
O1	0.098 (2)	0.0691 (18)	0.0658 (17)	0.0234 (16)	0.0221 (16)	0.0111 (14)
O2	0.394 (10)	0.121 (4)	0.112 (4)	−0.048 (5)	0.018 (5)	0.027 (3)
N1	0.0539 (17)	0.0579 (18)	0.0393 (14)	0.0086 (13)	0.0087 (12)	−0.0027 (12)
N2	0.0503 (17)	0.0505 (16)	0.0434 (15)	0.0026 (13)	0.0146 (13)	−0.0042 (12)
N3	0.0594 (18)	0.0530 (17)	0.0446 (15)	0.0019 (14)	0.0191 (13)	0.0020 (13)
N4	0.0652 (19)	0.0546 (19)	0.0440 (15)	0.0093 (14)	0.0170 (14)	0.0025 (13)
C1	0.062 (2)	0.061 (2)	0.0452 (19)	0.0066 (18)	0.0027 (17)	−0.0079 (16)
C2	0.063 (2)	0.076 (3)	0.058 (2)	−0.003 (2)	0.0026 (19)	−0.014 (2)
C3	0.057 (2)	0.082 (3)	0.061 (2)	−0.006 (2)	0.0117 (19)	−0.012 (2)
C4	0.0484 (19)	0.064 (2)	0.0497 (18)	0.0022 (18)	0.0082 (15)	−0.0043 (18)
C5	0.051 (2)	0.062 (2)	0.0491 (19)	0.0049 (17)	0.0138 (16)	−0.0010 (16)
C6	0.052 (2)	0.054 (2)	0.0441 (17)	0.0040 (16)	0.0156 (15)	−0.0033 (15)
C7	0.059 (2)	0.070 (2)	0.0447 (18)	−0.0041 (19)	0.0205 (16)	−0.0110 (17)
C8	0.067 (2)	0.063 (2)	0.0459 (19)	−0.0072 (19)	0.0173 (17)	−0.0131 (17)
C9	0.056 (2)	0.0484 (19)	0.0465 (18)	−0.0013 (16)	0.0143 (16)	−0.0052 (15)
C10	0.055 (2)	0.0468 (19)	0.0478 (18)	−0.0019 (16)	0.0134 (16)	−0.0025 (15)
C11	0.055 (2)	0.050 (2)	0.055 (2)	−0.0021 (16)	0.0179 (17)	0.0013 (16)
C12	0.065 (2)	0.066 (2)	0.066 (2)	−0.012 (2)	0.024 (2)	−0.008 (2)
C13	0.072 (3)	0.071 (3)	0.071 (3)	−0.010 (2)	0.035 (2)	−0.002 (2)
C14	0.063 (2)	0.054 (2)	0.056 (2)	0.0019 (18)	0.0218 (18)	0.0050 (17)
C15	0.074 (3)	0.057 (2)	0.051 (2)	0.010 (2)	0.0287 (19)	0.0115 (17)
C16	0.077 (3)	0.061 (2)	0.0448 (18)	0.011 (2)	0.0215 (18)	0.0023 (18)
C17	0.092 (3)	0.088 (3)	0.049 (2)	0.009 (3)	0.030 (2)	0.000 (2)
C18	0.098 (3)	0.085 (3)	0.0418 (19)	0.008 (3)	0.022 (2)	−0.006 (2)
C19	0.077 (3)	0.061 (2)	0.0399 (17)	0.012 (2)	0.0129 (17)	−0.0002 (17)
C20	0.072 (3)	0.058 (2)	0.0407 (18)	0.0135 (19)	0.0036 (17)	−0.0031 (15)
C21	0.049 (2)	0.067 (2)	0.052 (2)	−0.0067 (17)	0.0142 (16)	−0.0157 (17)
C22	0.060 (2)	0.076 (3)	0.066 (2)	0.011 (2)	0.026 (2)	0.000 (2)
C23	0.079 (3)	0.079 (3)	0.078 (3)	0.004 (2)	0.037 (2)	0.003 (2)
C24	0.059 (3)	0.080 (3)	0.094 (3)	−0.010 (2)	0.034 (2)	−0.016 (2)
C25	0.047 (2)	0.102 (4)	0.101 (4)	0.007 (2)	0.017 (2)	−0.010 (3)
C26	0.058 (2)	0.092 (3)	0.073 (3)	0.007 (2)	0.011 (2)	0.003 (2)
C27	0.096 (4)	0.133 (5)	0.168 (6)	−0.014 (4)	0.076 (4)	−0.009 (4)
C28	0.053 (2)	0.059 (2)	0.0519 (19)	−0.0042 (17)	0.0134 (16)	−0.0073 (17)
C29	0.083 (3)	0.073 (3)	0.055 (2)	−0.012 (2)	0.012 (2)	0.004 (2)
C30	0.084 (3)	0.096 (3)	0.055 (2)	−0.004 (3)	0.001 (2)	0.010 (2)
C31	0.060 (3)	0.099 (3)	0.059 (2)	−0.006 (2)	0.011 (2)	−0.011 (2)
C32	0.074 (3)	0.074 (3)	0.077 (3)	−0.012 (2)	0.011 (2)	−0.016 (2)
C33	0.062 (2)	0.063 (2)	0.064 (2)	−0.0057 (19)	0.0091 (19)	−0.0057 (19)
C34	0.092 (4)	0.160 (6)	0.071 (3)	−0.022 (4)	0.001 (3)	−0.019 (3)
C35	0.081 (3)	0.070 (3)	0.059 (2)	0.004 (2)	0.037 (2)	0.006 (2)
C36	0.084 (3)	0.091 (3)	0.100 (4)	0.013 (3)	0.041 (3)	0.031 (3)
C37	0.086 (3)	0.111 (4)	0.108 (4)	0.012 (3)	0.048 (3)	0.015 (3)
C38	0.112 (4)	0.089 (3)	0.105 (4)	−0.009 (3)	0.070 (3)	−0.005 (3)
C39	0.175 (6)	0.101 (4)	0.139 (5)	0.012 (4)	0.103 (5)	0.040 (4)
C40	0.122 (4)	0.105 (4)	0.108 (4)	0.027 (3)	0.066 (4)	0.039 (3)
C41	0.141 (5)	0.149 (6)	0.161 (6)	−0.045 (5)	0.104 (5)	−0.022 (5)
C42	0.075 (3)	0.061 (2)	0.0424 (18)	0.010 (2)	0.0095 (18)	−0.0019 (17)
C43	0.093 (3)	0.076 (3)	0.066 (3)	0.029 (3)	−0.007 (2)	−0.012 (2)
C44	0.109 (4)	0.068 (3)	0.078 (3)	0.019 (3)	0.011 (3)	−0.021 (2)
C45	0.083 (3)	0.073 (3)	0.055 (2)	−0.002 (2)	0.009 (2)	−0.012 (2)
C46	0.091 (3)	0.086 (3)	0.058 (2)	0.018 (3)	−0.012 (2)	−0.007 (2)
C47	0.095 (3)	0.066 (3)	0.063 (2)	0.024 (2)	−0.007 (2)	−0.013 (2)
C48	0.135 (5)	0.113 (4)	0.089 (4)	−0.002 (4)	−0.004 (3)	−0.043 (3)
C49	0.050 (2)	0.0484 (18)	0.0422 (17)	−0.0043 (15)	0.0063 (15)	−0.0034 (14)
C50	0.071 (2)	0.047 (2)	0.061 (2)	0.0134 (19)	0.0258 (19)	0.0065 (17)
C51	0.121 (4)	0.063 (3)	0.055 (2)	0.010 (3)	0.019 (2)	0.003 (2)
C52	0.203 (7)	0.081 (4)	0.064 (3)	0.040 (4)	0.049 (4)	0.014 (3)
C53	0.193 (7)	0.078 (4)	0.114 (5)	0.028 (4)	0.094 (5)	0.032 (4)
C54	0.115 (5)	0.078 (3)	0.155 (6)	0.004 (3)	0.077 (4)	0.034 (4)
C55	0.081 (3)	0.068 (3)	0.101 (3)	0.002 (2)	0.030 (3)	0.021 (3)
C56	0.073 (3)	0.057 (2)	0.055 (2)	0.017 (2)	0.0203 (19)	0.0116 (18)
C57	0.133 (5)	0.106 (4)	0.071 (3)	0.048 (4)	0.011 (3)	−0.023 (3)
C58	0.217 (9)	0.158 (7)	0.089 (4)	0.114 (7)	0.032 (5)	−0.013 (4)
C59	0.204 (9)	0.164 (8)	0.149 (7)	0.107 (8)	0.119 (7)	0.047 (6)
C60	0.095 (5)	0.129 (6)	0.250 (10)	0.046 (4)	0.097 (6)	0.052 (6)
C61	0.071 (3)	0.087 (3)	0.149 (5)	0.015 (3)	0.040 (3)	0.006 (3)
C62	0.143 (6)	0.106 (5)	0.191 (7)	0.064 (4)	0.070 (5)	0.047 (4)
C63	0.205 (8)	0.148 (6)	0.093 (5)	0.046 (6)	0.022 (5)	0.002 (4)

Geometric parameters (Å, º)

Ru—N1	2.051 (3)	C30—C31	1.362 (6)
Ru—N2	2.040 (2)	C30—H17	0.9300
Ru—N3	2.042 (3)	C31—C32	1.379 (6)
Ru—N4	2.051 (3)	C31—C34	1.516 (6)
Ru—C49	1.845 (3)	C32—C33	1.384 (5)
Ru—O1	2.362 (3)	C32—H18	0.9300
O1—C62	1.424 (6)	C33—H19	0.9300
O1—H47	0.8200	C34—H20	0.9600
O2—C63	1.264 (7)	C34—H21	0.9600
O2—H51	0.8200	C34—H22	0.9600
N1—C1	1.384 (4)	C35—C36	1.356 (6)
N1—C4	1.380 (4)	C35—C40	1.381 (6)
N2—C6	1.382 (4)	C36—C37	1.385 (6)
N2—C9	1.386 (4)	C36—H23	0.9300
N3—C11	1.382 (4)	C37—C38	1.336 (7)
N3—C14	1.384 (4)	C37—H24	0.9300
N4—C16	1.373 (5)	C38—C39	1.377 (8)
N4—C19	1.380 (4)	C38—C41	1.520 (6)
C1—C20	1.399 (5)	C39—C40	1.411 (7)
C1—C2	1.429 (5)	C39—H25	0.9300
C2—C3	1.354 (5)	C40—H26	0.9300
C2—H1	0.9300	C41—H27	0.9600
C3—C4	1.425 (5)	C41—H28	0.9600
C3—H2	0.9300	C41—H29	0.9600
C4—C5	1.406 (5)	C42—C43	1.372 (5)
C5—C6	1.389 (5)	C42—C47	1.374 (5)
C5—C21	1.496 (5)	C43—C44	1.391 (6)
C6—C7	1.443 (4)	C43—H30	0.9300
C7—C8	1.336 (5)	C44—C45	1.360 (6)
C7—H3	0.9300	C44—H31	0.9300
C8—C9	1.441 (4)	C45—C46	1.362 (6)
C8—H4	0.9300	C45—C48	1.509 (6)
C9—C10	1.391 (5)	C46—C47	1.382 (5)
C10—C11	1.402 (4)	C46—H32	0.9300
C10—C28	1.498 (5)	C47—H33	0.9300
C11—C12	1.427 (5)	C48—H34	0.9600
C12—C13	1.346 (5)	C48—H35	0.9600
C12—H5	0.9300	C48—H36	0.9600
C13—C14	1.415 (5)	C49—C56	1.485 (5)
C13—H6	0.9300	C49—C50	1.488 (5)
C14—C15	1.405 (5)	C50—C51	1.378 (5)
C15—C16	1.387 (5)	C50—C55	1.384 (6)
C15—C35	1.512 (5)	C51—C52	1.410 (6)
C16—C17	1.444 (5)	C51—H37	0.9300
C17—C18	1.322 (6)	C52—C53	1.367 (8)
C17—H7	0.9300	C52—H38	0.9300
C18—C19	1.451 (5)	C53—C54	1.345 (8)
C18—H8	0.9300	C53—H39	0.9300
C19—C20	1.391 (5)	C54—C55	1.378 (6)
C20—C42	1.501 (5)	C54—H40	0.9300
C21—C26	1.376 (5)	C55—H41	0.9300
C21—C22	1.384 (5)	C56—C61	1.370 (6)
C22—C23	1.387 (5)	C56—C57	1.372 (6)
C22—H9	0.9300	C57—C58	1.375 (8)
C23—C24	1.366 (6)	C57—H42	0.9300
C23—H10	0.9300	C58—C59	1.341 (11)
C24—C25	1.371 (6)	C58—H43	0.9300
C24—C27	1.513 (6)	C59—C60	1.356 (11)
C25—C26	1.378 (6)	C59—H44	0.9300
C25—H11	0.9300	C60—C61	1.383 (8)
C26—H12	0.9300	C60—H45	0.9300
C27—H13	0.9600	C61—H46	0.9300
C27—H14	0.9600	C62—H48	0.9600
C27—H15	0.9600	C62—H49	0.9600
C28—C29	1.375 (5)	C62—H50	0.9600
C28—C33	1.386 (5)	C63—H52	0.9600
C29—C30	1.393 (5)	C63—H53	0.9600
C29—H16	0.9300	C63—H54	0.9600
N1—Ru—N2	89.57 (11)	C28—C29—H16	119.5
N1—Ru—N3	171.76 (11)	C30—C29—H16	119.5
N1—Ru—N4	89.80 (11)	C31—C30—C29	121.5 (4)
N1—Ru—O1	87.29 (11)	C31—C30—H17	119.2
N2—Ru—N3	89.85 (11)	C29—C30—H17	119.2
N2—Ru—N4	172.91 (11)	C30—C31—C32	117.4 (4)
N2—Ru—O1	86.99 (10)	C30—C31—C34	121.8 (5)
N3—Ru—N4	89.76 (11)	C32—C31—C34	120.7 (5)
N3—Ru—O1	84.47 (11)	C31—C32—C33	121.8 (4)
N4—Ru—O1	85.93 (10)	C31—C32—H18	119.1
C49—Ru—N1	92.74 (13)	C33—C32—H18	119.1
C49—Ru—N2	93.55 (13)	C32—C33—C28	120.5 (4)
C49—Ru—N3	95.50 (13)	C32—C33—H19	119.7
C49—Ru—N4	93.53 (12)	C28—C33—H19	119.7
C49—Ru—O1	179.46 (12)	C31—C34—H20	109.5
C62—O1—Ru	122.0 (3)	C31—C34—H21	109.5
C62—O1—H47	109.5	H20—C34—H21	109.5
Ru—O1—H47	113.6	C31—C34—H22	109.5
C63—O2—H51	109.5	H20—C34—H22	109.5
C4—N1—C1	106.7 (3)	H21—C34—H22	109.5
C4—N1—Ru	126.3 (2)	C36—C35—C40	117.7 (4)
C1—N1—Ru	125.6 (2)	C36—C35—C15	121.8 (4)
C6—N2—C9	106.7 (3)	C40—C35—C15	120.4 (4)
C6—N2—Ru	127.0 (2)	C35—C36—C37	121.8 (4)
C9—N2—Ru	126.3 (2)	C35—C36—H23	119.1
C11—N3—C14	106.9 (3)	C37—C36—H23	119.1
C11—N3—Ru	126.1 (2)	C38—C37—C36	122.2 (5)
C14—N3—Ru	126.4 (2)	C38—C37—H24	118.9
C16—N4—C19	107.1 (3)	C36—C37—H24	118.9
C16—N4—Ru	126.7 (2)	C37—C38—C39	116.6 (5)
C19—N4—Ru	126.1 (2)	C37—C38—C41	122.1 (6)
N1—C1—C20	125.6 (4)	C39—C38—C41	121.3 (5)
N1—C1—C2	108.8 (3)	C38—C39—C40	122.4 (5)
C20—C1—C2	125.6 (3)	C38—C39—H25	118.8
C3—C2—C1	107.7 (3)	C40—C39—H25	118.8
C3—C2—H1	126.2	C35—C40—C39	118.7 (5)
C1—C2—H1	126.2	C35—C40—H26	120.7
C2—C3—C4	107.6 (4)	C39—C40—H26	120.7
C2—C3—H2	126.2	C38—C41—H27	109.5
C4—C3—H2	126.2	C38—C41—H28	109.5
N1—C4—C5	125.2 (3)	H27—C41—H28	109.5
N1—C4—C3	109.2 (3)	C38—C41—H29	109.5
C5—C4—C3	125.5 (3)	H27—C41—H29	109.5
C6—C5—C4	125.4 (3)	H28—C41—H29	109.5
C6—C5—C21	117.5 (3)	C43—C42—C47	117.5 (4)
C4—C5—C21	117.0 (3)	C43—C42—C20	121.1 (4)
N2—C6—C5	125.6 (3)	C47—C42—C20	121.4 (3)
N2—C6—C7	109.0 (3)	C42—C43—C44	121.0 (4)
C5—C6—C7	125.4 (3)	C42—C43—H30	119.5
C8—C7—C6	107.5 (3)	C44—C43—H30	119.5
C8—C7—H3	126.2	C45—C44—C43	121.2 (4)
C6—C7—H3	126.2	C45—C44—H31	119.4
C7—C8—C9	108.2 (3)	C43—C44—H31	119.4
C7—C8—H4	125.9	C44—C45—C46	117.8 (4)
C9—C8—H4	125.9	C44—C45—C48	120.9 (4)
N2—C9—C10	125.8 (3)	C46—C45—C48	121.3 (4)
N2—C9—C8	108.5 (3)	C45—C46—C47	121.7 (4)
C10—C9—C8	125.6 (3)	C45—C46—H32	119.1
C9—C10—C11	125.1 (3)	C47—C46—H32	119.1
C9—C10—C28	117.5 (3)	C42—C47—C46	120.8 (4)
C11—C10—C28	117.3 (3)	C42—C47—H33	119.6
N3—C11—C10	125.7 (3)	C46—C47—H33	119.6
N3—C11—C12	108.2 (3)	C45—C48—H34	109.5
C10—C11—C12	126.1 (3)	C45—C48—H35	109.5
C13—C12—C11	108.1 (4)	H34—C48—H35	109.5
C13—C12—H5	126.0	C45—C48—H36	109.5
C11—C12—H5	126.0	H34—C48—H36	109.5
C12—C13—C14	107.8 (3)	H35—C48—H36	109.5
C12—C13—H6	126.1	C50—C49—C56	112.2 (3)
C14—C13—H6	126.1	Ru—C49—C50	123.5 (2)
N3—C14—C15	125.3 (3)	Ru—C49—C56	124.2 (2)
N3—C14—C13	108.9 (3)	C51—C50—C55	117.8 (4)
C15—C14—C13	125.8 (3)	C51—C50—C49	121.3 (4)
C16—C15—C14	125.9 (3)	C55—C50—C49	120.8 (4)
C16—C15—C35	118.9 (3)	C50—C51—C52	120.4 (5)
C14—C15—C35	115.2 (4)	C50—C51—H37	119.8
N4—C16—C15	125.6 (3)	C52—C51—H37	119.8
N4—C16—C17	108.9 (4)	C51—C52—C53	119.0 (5)
C15—C16—C17	125.5 (4)	C53—C52—H38	120.5
C18—C17—C16	107.8 (4)	C51—C52—H38	120.5
C18—C17—H7	126.1	C52—C53—C54	121.4 (5)
C16—C17—H7	126.1	C54—C53—H39	119.3
C17—C18—C19	108.1 (4)	C52—C53—H39	119.3
C17—C18—H8	125.9	C53—C54—C55	119.6 (6)
C19—C18—H8	125.9	C53—C54—H40	120.2
N4—C19—C20	126.0 (3)	C55—C54—H40	120.2
N4—C19—C18	108.1 (4)	C50—C55—C54	121.8 (5)
C20—C19—C18	125.9 (4)	C54—C55—H41	119.1
C19—C20—C1	125.6 (3)	C50—C55—H41	119.1
C19—C20—C42	117.4 (3)	C49—C56—C57	121.3 (4)
C1—C20—C42	117.0 (4)	C57—C56—C61	118.8 (4)
C26—C21—C22	118.0 (4)	C49—C56—C61	119.9 (4)
C26—C21—C5	121.3 (4)	C56—C57—C58	120.5 (6)
C22—C21—C5	120.7 (3)	C56—C57—H42	119.8
C21—C22—C23	120.5 (4)	C58—C57—H42	119.8
C21—C22—H9	119.8	C59—C58—C57	120.5 (7)
C23—C22—H9	119.8	C59—C58—H43	119.7
C24—C23—C22	121.5 (4)	C57—C58—H43	119.7
C24—C23—H10	119.3	C58—C59—C60	119.9 (7)
C22—C23—H10	119.3	C58—C59—H44	120.1
C23—C24—C25	117.6 (4)	C60—C59—H44	120.1
C23—C24—C27	122.0 (5)	C59—C60—C61	120.6 (7)
C25—C24—C27	120.4 (5)	C59—C60—H45	119.7
C24—C25—C26	121.9 (4)	C61—C60—H45	119.7
C24—C25—H11	119.0	C56—C61—C60	119.7 (6)
C26—C25—H11	119.0	C56—C61—H46	120.2
C21—C26—C25	120.5 (4)	C60—C61—H46	120.2
C21—C26—H12	119.7	O1—C62—H48	109.5
C25—C26—H12	119.7	O1—C62—H49	109.5
C24—C27—H13	109.5	H48—C62—H49	109.5
C24—C27—H14	109.5	O1—C62—H50	109.5
H13—C27—H14	109.5	H48—C62—H50	109.5
C24—C27—H15	109.5	H49—C62—H50	109.5
H13—C27—H15	109.5	O2—C63—H52	109.5
H14—C27—H15	109.5	O2—C63—H53	109.5
C29—C28—C33	117.6 (4)	H52—C63—H53	109.5
C29—C28—C10	119.6 (3)	O2—C63—H54	109.5
C33—C28—C10	122.8 (3)	H52—C63—H54	109.5
C28—C29—C30	121.0 (4)	H53—C63—H54	109.5
N2—Ru—O1—C62	−49.9 (4)	N2—Ru—C49—C50	27.1 (3)
N3—Ru—O1—C62	−140.0 (4)	N2—Ru—C49—C56	−153.9 (3)
N1—Ru—O1—C62	39.8 (4)	N3—Ru—C49—C50	117.3 (3)
N4—Ru—O1—C62	129.8 (4)	N3—Ru—C49—C56	−63.7 (3)
N1—Ru—C49—C50	−62.6 (3)	N4—Ru—C49—C50	−152.6 (3)
N1—Ru—C49—C56	116.4 (3)	N4—Ru—C49—C56	26.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H47···O2^i	0.82	1.91	2.704 (5)	163
O2—H51···O1	0.82	2.20	2.949 (6)	151

Symmetry code: (i) −x, −y+1, −z.