Carbonyl­[di­hydro­bis­(pyrazol-1-yl-κN²)­borato]­hydrido­bis­(tri-p-tolyl­phosphine-κP)­ruthenium(II)

The title compound, [RuH(C₆H₈BN₄)(C₂₁H₂₁P)₂(CO)], possesses two trans-disposed tri-p-tolyl­phosphines in axial positions and the remaining ligands in equatorial positions. The overall geometry of the Ru^II ion is a distorted octahedral structure. The P—Ru—P axis deviates from linearity by about 13°. This distortion arises mainly from the steric congestion between the bulky phosphine moieties and the tetrahedral di­hydro­bis­(pyrazol-1-yl)­borate ligands.

S1. Comment

Our recent structural investigations of several hydridocarbonyl Ru^II complexes containing bidentate anionic dihydrobis(pyrazol-1-yl)borates, [H₂B(pz^*)₂]^- (pz^* = pyrazol-1-yl rings with various substituents), have revealed that these compounds often form novel cyclic dimers consisting of mutual intermolecular hydrogen bonds, namely Ru—C≡O···H, where H belongs to a phenyl or pyrazolyl ring of a neighbouring molecule. We have been interested in this type of hydrogen bonding because this motif can be a good candidate for crystal engineering of organometallic compounds. Both [RuH(CO)(PPh₃)₂(η²-H₂Bpz₂)], (II), and [RuH(CO)(PPh₃)₂(η²-H₂B(4-Brpz)₂)], (III), display respective intermolecular hydrogen-bond dimensions of Ru—C≡O···H_Ph 2.5834 Å and 144.56°, and Ru—C≡O···H_pz 2.5960 Å and 172.23°, where Ph and pz represent the phenyl and the pyrazolyl ring, respectively (Huh, Kim, Park, Youm et al., 1999). It is interesting to note that the sources of the hydrogen bonding (H donor groups) are different in each of the compounds studied. Furthermore, such intermolecular hydrogen bonding leading to the dimeric motif could not be observed when we prepared the compound [RuH(CO)(AsPh₃)₂(η²-H₂Bpz₂)], (IV), using AsPh₃ in place of PPh₃ (Huh, Kim, Park, Park & Jun, 1999).

In this study, an analogous Ru^II complex having substituted phenyl groups in the PPh₃ moieties has been prepared, to test the effect of the structural variation in the PPh₃ moiety on the formation of the dimeric motif. Instead of PPh₃, we have chosen a tri-p-tolylphosphine, P(p—C₆H₄CH₃)₃, whose cone angle is also 145° (Tolman, 1977). This ligand has a methyl group at the para position in each phenyl ring. In our synthesis of the title compound, [RuH(CO){P(p—C₆H₄CH₃)₃}₂(η²-H₂Bpz₂)], (I), we had anticipated obtaining another example of the novel cyclic dimer via the mutual intermolecular hydrogen bonding. Quite unexpectedly, however, we have not been able to obtain the dimeric motif but only the monomeric form in (I). \scheme

Compound (I) shows the same ligand geometry as (II) and (III). The two Ru—P bond distances are also comparable with those of (II) and (III) [2.3578 (12) ~2.3841 (12) Å] (Please clarify). However, the Ru1—P2 length is longer than Ru1—P1 by about 0.025 Å. Although the para-positioned methyl groups of the phosphines do not seem to affect the Ru—P bond distances significantly, they do affect the bond angle of P1—Ru1—P2, whose value is 166.69 (5)°.

The two phosphine ligands are tilted toward the small hydride ligand and this is evident from the H1Ru—Ru1—P1 and H1Ru—Ru1—P2 angles of 85.1 (17) and 81.8 (17)°. This significant deviation from linearity can be attributed to the steric repulsions between the phosphines and the tetrahedral BN₂H₂ moiety, as shown in Fig. 1. The interligand angles of the equatorial donor atoms lie in the range 87.6 (15) to 92.36 (19)° and these values are only slightly different from 90°. The bond distances of Ru1 and other donor atoms are not significantly different from those of complexes (II) and (III). Moreover, the five atoms Ru1, H1Ru, C1, N1 and N3 are almost coplanar: the r.m.s. deviation of these five atoms from the best plane is only 0.035 Å. The angle between the two pyrazolyl rings is 152.2 (4)° (check e.s.d.) and this value is very similar to that in (III).

Two very weak intramolecular hydrogen bonds, C62—H62A···N3 and C62—H62A···N4, have dimensions of 2.549 (4) and 2.508 (5) Å (H···N) and 118.4 (4) and 148.9 (4)° (C—H···N), respectively (check 4 e.s.d.'s).

S2. Experimental

[RuHCl(CO)(P(p—C₆H₄CH₃)₃)₃] (324 mg, 0.3 mmol; Stephenson & Wilkinson, 1966) was reacted with K[H₂Bpz₂] (74 mg, 0.4 mmol; Trofimenko, 1970) in boiling toluene (30 ml) solution under a nitrogen atmosphere for 18 h, to give a green solution. After being cooled and filtered, the clear filtrate was evaporated on a rotary evaporator to dryness. The resultant residue was dissolved in a small amount of acetone (5 ml) and this solution was set aside in air. Colourless crystals were obtained in a few days by slow evaporation of the solvent. X-ray quality crystals were collected from the mother liquor, washed with n-hexane and dried in air. Spectroscopic analysis: IR (cm^-1, KBr): ν(BH) 2396, 2344, 2294, ν(CO) 1932; ¹H NMR (293 K, CDCl₃, TMS, Bruker 500 MHz, p.p.m.): δ(Ru—H) -11.8 (t, ²J = 21.5 Hz).

S3. Refinement

All H atoms were included in calculated postions and treated as riding, except for those bonded to B and Ru which were refined with isotropic displacement parameters.

Computing details

Data collection: Kappa-CCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 1998); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.

Figures

Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted for clarity, except those bonded to B and Ru, which are shown as spheres of arbitrary radii.

Carbonyl[dihydrobis(pyrazol-1-yl-κN²)borato]hydridobis- (tri-p-tolylphosphine-κP)ruthenium(II)

Crystal data

[RuH(CO)(C6H8BN4)(C21H21P)2]	Z = 2
Mr = 885.76	F(000) = 920
Triclinic, P1	Dx = 1.340 Mg m^−3
a = 13.3445 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.7089 (2) Å	Cell parameters from 14686 reflections
c = 14.2471 (2) Å	θ = 4.2–25.1°
α = 106.644 (7)°	µ = 0.47 mm^−1
β = 116.816 (8)°	T = 100 K
γ = 90.965 (7)°	Block, pale yellow
V = 2195.85 (6) Å^3	0.25 × 0.15 × 0.10 mm

Data collection

Nonius Kappa-CCD diffractometer	7547 independent reflections
Radiation source: fine-focus sealed tube	4669 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.103
φ scans and ω scans with κ offsets	θmax = 25.1°, θmin = 4.2°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→15
Tmin = 0.891, Tmax = 0.954	k = −16→16
14686 measured reflections	l = −16→14

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) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0651P)^2] where P = (Fo^2 + 2Fc^2)/3
7547 reflections	(Δ/σ)max = 0.001
541 parameters	Δρmax = 0.73 e Å^−3
0 restraints	Δρmin = −0.99 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1996) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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
Ru1	0.50199 (4)	0.20963 (3)	0.26308 (4)	0.03428 (17)
H1Ru	0.571 (4)	0.327 (3)	0.318 (4)	0.026 (12)*
P1	0.33890 (12)	0.28369 (11)	0.18892 (12)	0.0336 (4)
P2	0.68926 (12)	0.17380 (11)	0.34984 (12)	0.0341 (4)
O1	0.5259 (3)	0.1833 (3)	0.0581 (4)	0.0476 (11)
N1	0.3985 (4)	0.0574 (4)	0.1923 (4)	0.0392 (12)
N2	0.3740 (4)	0.0108 (4)	0.2527 (4)	0.0441 (13)
N3	0.4894 (4)	0.2333 (3)	0.4117 (4)	0.0367 (12)
N4	0.4536 (4)	0.1569 (4)	0.4403 (4)	0.0398 (12)
C1	0.5173 (4)	0.1933 (4)	0.1379 (5)	0.0379 (15)
C2	0.3374 (5)	−0.0029 (4)	0.0846 (5)	0.0455 (16)
H2A	0.3370	0.0123	0.0234	0.055*
C3	0.2758 (5)	−0.0894 (5)	0.0761 (6)	0.0528 (18)
H3A	0.2274	−0.1448	0.0102	0.063*
C4	0.2989 (6)	−0.0789 (5)	0.1824 (6)	0.058 (2)
H4A	0.2680	−0.1261	0.2039	0.070*
C5	0.5074 (5)	0.3217 (5)	0.4932 (5)	0.0426 (15)
H5A	0.5320	0.3880	0.4950	0.051*
C6	0.4861 (5)	0.3049 (5)	0.5739 (5)	0.0449 (16)
H6A	0.4931	0.3545	0.6396	0.054*
C7	0.4520 (5)	0.1981 (5)	0.5366 (5)	0.0447 (15)
H7A	0.4311	0.1608	0.5737	0.054*
C11	0.2787 (4)	0.3282 (4)	0.2815 (5)	0.0350 (14)
C12	0.2789 (4)	0.4330 (4)	0.3300 (5)	0.0375 (14)
H12A	0.3094	0.4842	0.3125	0.045*
C13	0.2344 (5)	0.4621 (4)	0.4038 (5)	0.0396 (15)
H13A	0.2356	0.5334	0.4361	0.047*
C14	0.1887 (5)	0.3903 (4)	0.4314 (5)	0.0397 (15)
C15	0.1935 (4)	0.2864 (4)	0.3873 (5)	0.0373 (14)
H15A	0.1656	0.2357	0.4073	0.045*
C16	0.2384 (4)	0.2565 (4)	0.3147 (4)	0.0355 (14)
H16A	0.2419	0.1855	0.2868	0.043*
C17	0.1360 (5)	0.4212 (5)	0.5077 (5)	0.0522 (18)
H17A	0.0743	0.3660	0.4857	0.078*
H17B	0.1054	0.4850	0.5019	0.078*
H17C	0.1942	0.4326	0.5847	0.078*
C21	0.2162 (4)	0.2040 (4)	0.0564 (5)	0.0354 (14)
C22	0.2241 (5)	0.1871 (4)	−0.0412 (5)	0.0405 (15)
H22A	0.2917	0.2164	−0.0370	0.049*
C23	0.1357 (5)	0.1286 (4)	−0.1441 (5)	0.0422 (15)
H23A	0.1435	0.1186	−0.2091	0.051*
C24	0.0350 (5)	0.0840 (4)	−0.1537 (5)	0.0399 (15)
C25	0.0275 (5)	0.0971 (4)	−0.0576 (5)	0.0417 (15)
H25A	−0.0388	0.0652	−0.0618	0.050*
C26	0.1172 (5)	0.1574 (4)	0.0465 (5)	0.0403 (15)
H26A	0.1098	0.1664	0.1116	0.048*
C27	−0.0633 (5)	0.0218 (5)	−0.2678 (5)	0.0498 (17)
H27A	−0.1199	−0.0147	−0.2582	0.075*
H27B	−0.0340	−0.0284	−0.3094	0.075*
H27C	−0.0989	0.0687	−0.3091	0.075*
C31	0.3552 (5)	0.3954 (4)	0.1487 (4)	0.0373 (15)
C32	0.4588 (5)	0.4331 (4)	0.1570 (5)	0.0405 (15)
H32A	0.5238	0.4022	0.1883	0.049*
C33	0.4675 (5)	0.5145 (4)	0.1203 (5)	0.0423 (15)
H33A	0.5379	0.5375	0.1255	0.051*
C34	0.3751 (5)	0.5634 (4)	0.0759 (5)	0.0409 (15)
C35	0.2733 (5)	0.5269 (4)	0.0690 (5)	0.0431 (15)
H35A	0.2093	0.5597	0.0403	0.052*
C36	0.2631 (5)	0.4442 (5)	0.1026 (5)	0.0421 (15)
H36A	0.1914	0.4199	0.0942	0.051*
C37	0.3848 (6)	0.6538 (5)	0.0385 (6)	0.0563 (18)
H37A	0.4410	0.6469	0.0116	0.084*
H37B	0.4091	0.7181	0.1014	0.084*
H37C	0.3105	0.6552	−0.0216	0.084*
C41	0.7754 (4)	0.2211 (4)	0.2950 (4)	0.0358 (14)
C42	0.7766 (5)	0.3217 (4)	0.2932 (5)	0.0371 (14)
H42A	0.7351	0.3651	0.3218	0.045*
C43	0.8370 (5)	0.3599 (4)	0.2504 (5)	0.0397 (15)
H43A	0.8365	0.4292	0.2506	0.048*
C44	0.8978 (4)	0.2999 (4)	0.2076 (4)	0.0356 (14)
C45	0.8984 (5)	0.1990 (4)	0.2105 (5)	0.0371 (14)
H45A	0.9404	0.1561	0.1823	0.045*
C46	0.8380 (5)	0.1603 (4)	0.2543 (5)	0.0408 (15)
H46A	0.8399	0.0916	0.2562	0.049*
C47	0.9590 (5)	0.3405 (5)	0.1552 (5)	0.0442 (16)
H47A	1.0346	0.3206	0.1800	0.066*
H47B	0.9671	0.4160	0.1779	0.066*
H47C	0.9147	0.3112	0.0739	0.066*
C51	0.7112 (5)	0.0417 (4)	0.3343 (5)	0.0376 (15)
C52	0.6357 (5)	−0.0375 (4)	0.2353 (5)	0.0386 (14)
H52A	0.5758	−0.0203	0.1770	0.046*
C53	0.6478 (5)	−0.1410 (4)	0.2218 (5)	0.0447 (16)
H53A	0.5958	−0.1930	0.1543	0.054*
C54	0.7332 (5)	−0.1693 (5)	0.3040 (6)	0.0482 (17)
C55	0.8099 (6)	−0.0920 (4)	0.4004 (5)	0.0494 (16)
H55A	0.8704	−0.1098	0.4576	0.059*
C56	0.7996 (5)	0.0112 (4)	0.4147 (5)	0.0454 (16)
H56A	0.8544	0.0626	0.4811	0.054*
C57	0.7444 (6)	−0.2813 (5)	0.2890 (6)	0.062 (2)
H57A	0.7291	−0.3170	0.2124	0.094*
H57B	0.6895	−0.3139	0.3037	0.094*
H57C	0.8219	−0.2860	0.3411	0.094*
C61	0.7768 (4)	0.2366 (4)	0.5004 (5)	0.0355 (14)
C62	0.7387 (5)	0.2216 (4)	0.5729 (5)	0.0413 (15)
H62A	0.6668	0.1799	0.5433	0.050*
C63	0.8037 (5)	0.2663 (5)	0.6862 (5)	0.0443 (16)
H63A	0.7746	0.2564	0.7332	0.053*
C64	0.9105 (5)	0.3255 (4)	0.7341 (5)	0.0413 (15)
C65	0.9504 (5)	0.3384 (4)	0.6641 (5)	0.0412 (15)
H65A	1.0238	0.3777	0.6948	0.049*
C66	0.8854 (5)	0.2952 (4)	0.5498 (5)	0.0385 (14)
H66A	0.9153	0.3055	0.5035	0.046*
C67	0.9813 (5)	0.3711 (5)	0.8591 (5)	0.0492 (17)
H67A	1.0605	0.3925	0.8785	0.074*
H67B	0.9778	0.3192	0.8931	0.074*
H67C	0.9514	0.4312	0.8867	0.074*
B1	0.4457 (7)	0.0396 (6)	0.3796 (7)	0.0486 (19)
H1B	0.550 (4)	0.027 (4)	0.406 (4)	0.029 (13)*
H2B	0.412 (5)	−0.010 (5)	0.416 (5)	0.061 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.0289 (3)	0.0320 (3)	0.0352 (3)	−0.00037 (18)	0.0126 (2)	0.0064 (2)
P1	0.0292 (8)	0.0299 (7)	0.0359 (8)	−0.0003 (6)	0.0149 (7)	0.0043 (6)
P2	0.0299 (8)	0.0315 (7)	0.0358 (8)	0.0013 (6)	0.0136 (7)	0.0076 (6)
O1	0.040 (2)	0.053 (3)	0.046 (3)	0.009 (2)	0.019 (2)	0.014 (2)
N1	0.033 (3)	0.041 (3)	0.042 (3)	0.008 (2)	0.018 (2)	0.012 (2)
N2	0.045 (3)	0.036 (3)	0.047 (3)	0.002 (2)	0.025 (3)	0.004 (2)
N3	0.031 (3)	0.035 (3)	0.040 (3)	−0.003 (2)	0.014 (2)	0.011 (2)
N4	0.033 (3)	0.044 (3)	0.039 (3)	0.007 (2)	0.016 (2)	0.011 (2)
C1	0.021 (3)	0.032 (3)	0.047 (4)	0.000 (2)	0.011 (3)	0.001 (3)
C2	0.044 (4)	0.042 (3)	0.043 (4)	0.004 (3)	0.020 (3)	0.004 (3)
C3	0.050 (4)	0.036 (3)	0.051 (4)	−0.004 (3)	0.014 (3)	0.001 (3)
C4	0.062 (4)	0.030 (3)	0.069 (5)	−0.012 (3)	0.027 (4)	0.006 (3)
C5	0.030 (3)	0.042 (3)	0.046 (4)	0.001 (3)	0.013 (3)	0.010 (3)
C6	0.040 (3)	0.053 (4)	0.041 (3)	0.010 (3)	0.021 (3)	0.010 (3)
C7	0.037 (3)	0.055 (4)	0.046 (4)	0.013 (3)	0.018 (3)	0.023 (3)
C11	0.025 (3)	0.030 (3)	0.037 (3)	−0.004 (2)	0.009 (3)	0.004 (2)
C12	0.032 (3)	0.034 (3)	0.038 (3)	0.003 (2)	0.013 (3)	0.006 (3)
C13	0.035 (3)	0.030 (3)	0.045 (3)	0.001 (3)	0.017 (3)	0.003 (3)
C14	0.031 (3)	0.041 (3)	0.037 (3)	0.000 (3)	0.013 (3)	0.003 (3)
C15	0.030 (3)	0.037 (3)	0.038 (3)	0.001 (2)	0.014 (3)	0.006 (3)
C16	0.026 (3)	0.036 (3)	0.037 (3)	0.002 (2)	0.012 (3)	0.005 (3)
C17	0.054 (4)	0.055 (4)	0.049 (4)	0.007 (3)	0.032 (3)	0.005 (3)
C21	0.033 (3)	0.030 (3)	0.044 (3)	0.005 (2)	0.020 (3)	0.010 (3)
C22	0.036 (3)	0.039 (3)	0.043 (3)	0.005 (3)	0.020 (3)	0.005 (3)
C23	0.044 (4)	0.037 (3)	0.038 (3)	0.004 (3)	0.017 (3)	0.007 (3)
C24	0.037 (3)	0.029 (3)	0.041 (3)	0.002 (3)	0.014 (3)	0.004 (3)
C25	0.034 (3)	0.041 (3)	0.037 (3)	−0.008 (3)	0.011 (3)	0.004 (3)
C26	0.042 (3)	0.039 (3)	0.038 (3)	0.003 (3)	0.019 (3)	0.009 (3)
C27	0.040 (3)	0.044 (4)	0.038 (3)	0.000 (3)	0.004 (3)	0.001 (3)
C31	0.037 (3)	0.036 (3)	0.032 (3)	−0.006 (3)	0.015 (3)	0.003 (3)
C32	0.035 (3)	0.042 (3)	0.043 (3)	0.007 (3)	0.018 (3)	0.013 (3)
C33	0.039 (3)	0.037 (3)	0.052 (4)	0.000 (3)	0.024 (3)	0.012 (3)
C34	0.045 (4)	0.031 (3)	0.039 (3)	−0.002 (3)	0.015 (3)	0.010 (3)
C35	0.031 (3)	0.041 (3)	0.042 (3)	0.004 (3)	0.006 (3)	0.012 (3)
C36	0.033 (3)	0.043 (3)	0.042 (3)	−0.002 (3)	0.013 (3)	0.009 (3)
C37	0.055 (4)	0.052 (4)	0.063 (4)	0.004 (3)	0.019 (4)	0.035 (3)
C41	0.030 (3)	0.035 (3)	0.031 (3)	0.001 (2)	0.010 (3)	0.004 (2)
C42	0.037 (3)	0.030 (3)	0.037 (3)	0.004 (3)	0.015 (3)	0.004 (3)
C43	0.035 (3)	0.037 (3)	0.042 (3)	−0.001 (3)	0.015 (3)	0.011 (3)
C44	0.026 (3)	0.037 (3)	0.033 (3)	0.000 (2)	0.008 (2)	0.006 (3)
C45	0.032 (3)	0.037 (3)	0.039 (3)	0.006 (3)	0.017 (3)	0.009 (3)
C46	0.036 (3)	0.037 (3)	0.047 (4)	0.006 (3)	0.019 (3)	0.011 (3)
C47	0.042 (3)	0.045 (3)	0.041 (3)	0.003 (3)	0.019 (3)	0.009 (3)
C51	0.037 (3)	0.034 (3)	0.036 (3)	−0.003 (3)	0.017 (3)	0.004 (3)
C52	0.030 (3)	0.038 (3)	0.037 (3)	0.004 (3)	0.009 (3)	0.009 (3)
C53	0.036 (3)	0.032 (3)	0.056 (4)	0.000 (3)	0.020 (3)	0.003 (3)
C54	0.046 (4)	0.037 (3)	0.061 (4)	0.006 (3)	0.027 (4)	0.014 (3)
C55	0.055 (4)	0.038 (3)	0.045 (4)	0.014 (3)	0.015 (3)	0.016 (3)
C56	0.050 (4)	0.033 (3)	0.041 (4)	0.003 (3)	0.015 (3)	0.006 (3)
C57	0.066 (5)	0.037 (3)	0.080 (5)	0.009 (3)	0.032 (4)	0.017 (3)
C61	0.030 (3)	0.030 (3)	0.039 (3)	0.006 (2)	0.014 (3)	0.006 (3)
C62	0.038 (3)	0.041 (3)	0.041 (3)	0.002 (3)	0.017 (3)	0.012 (3)
C63	0.039 (3)	0.053 (4)	0.038 (3)	0.001 (3)	0.017 (3)	0.015 (3)
C64	0.040 (3)	0.036 (3)	0.037 (3)	0.002 (3)	0.014 (3)	0.004 (3)
C65	0.035 (3)	0.035 (3)	0.042 (3)	−0.004 (3)	0.015 (3)	0.001 (3)
C66	0.033 (3)	0.042 (3)	0.039 (3)	0.004 (3)	0.017 (3)	0.011 (3)
C67	0.050 (4)	0.046 (4)	0.038 (3)	−0.003 (3)	0.014 (3)	0.007 (3)
B1	0.053 (5)	0.038 (4)	0.056 (5)	0.007 (3)	0.025 (4)	0.020 (4)

Geometric parameters (Å, º)

Ru1—C1	1.837 (6)	C23—C24	1.399 (7)
Ru1—N1	2.173 (4)	C24—C25	1.378 (8)
Ru1—N3	2.132 (4)	C24—C27	1.528 (7)
Ru1—P1	2.3448 (17)	C25—C26	1.407 (7)
Ru1—P2	2.3699 (17)	C31—C36	1.394 (9)
Ru1—H1Ru	1.62 (4)	C31—C32	1.409 (7)
P1—C11	1.807 (5)	C32—C33	1.384 (9)
P1—C31	1.824 (6)	C33—C34	1.391 (9)
P1—C21	1.846 (5)	C34—C35	1.390 (8)
P2—C51	1.806 (6)	C34—C37	1.506 (9)
P2—C61	1.832 (5)	C35—C36	1.377 (9)
P2—C41	1.851 (5)	C41—C46	1.382 (7)
O1—C1	1.164 (6)	C41—C42	1.387 (8)
N1—N2	1.348 (7)	C42—C43	1.381 (8)
N1—C2	1.351 (7)	C43—C44	1.374 (7)
N2—C4	1.367 (7)	C44—C45	1.395 (8)
N2—B1	1.536 (9)	C44—C47	1.520 (7)
N3—C5	1.344 (6)	C45—C46	1.397 (8)
N3—N4	1.378 (6)	C51—C56	1.396 (9)
N4—C7	1.335 (7)	C51—C52	1.410 (7)
N4—B1	1.568 (8)	C52—C53	1.399 (8)
C2—C3	1.376 (8)	C53—C54	1.375 (10)
C3—C4	1.364 (9)	C54—C55	1.386 (8)
C5—C6	1.379 (8)	C54—C57	1.509 (9)
C6—C7	1.395 (8)	C55—C56	1.389 (8)
C11—C16	1.400 (8)	C61—C66	1.399 (7)
C11—C12	1.404 (7)	C61—C62	1.399 (8)
C12—C13	1.395 (7)	C62—C63	1.374 (8)
C13—C14	1.384 (8)	C63—C64	1.387 (7)
C14—C15	1.398 (7)	C64—C65	1.372 (8)
C14—C17	1.513 (7)	C64—C67	1.509 (8)
C15—C16	1.387 (7)	C65—C66	1.383 (8)
C21—C26	1.387 (7)	B1—H2B	1.16 (6)
C21—C22	1.396 (7)	B1—H1B	1.30 (5)
C22—C23	1.385 (7)
H1Ru—Ru1—C1	90.4 (15)	C26—C21—C22	117.2 (5)
H1Ru—Ru1—N1	175.2 (15)	C26—C21—P1	125.0 (4)
H1Ru—Ru1—N3	87.6 (15)	C22—C21—P1	117.8 (4)
H1Ru—Ru1—P1	85.1 (17)	C23—C22—C21	121.5 (5)
H1Ru—Ru1—P2	81.8 (17)	C22—C23—C24	120.9 (5)
C1—Ru1—N1	92.36 (19)	C25—C24—C23	118.2 (5)
C1—Ru1—N3	177.85 (19)	C25—C24—C27	121.2 (5)
C1—Ru1—P1	90.02 (19)	C23—C24—C27	120.6 (5)
C1—Ru1—P2	88.00 (18)	C24—C25—C26	120.5 (5)
N1—Ru1—P1	90.98 (14)	C21—C26—C25	121.6 (5)
N1—Ru1—P2	102.26 (14)	C36—C31—C32	116.8 (6)
N3—Ru1—P1	90.53 (14)	C36—C31—P1	120.9 (4)
N3—Ru1—P2	90.99 (14)	C32—C31—P1	122.2 (5)
N3—Ru1—N1	89.71 (16)	C33—C32—C31	121.1 (6)
P1—Ru1—P2	166.69 (5)	C32—C33—C34	121.4 (5)
C11—P1—C31	103.9 (3)	C35—C34—C33	117.4 (6)
C11—P1—C21	104.0 (2)	C35—C34—C37	120.9 (6)
C31—P1—C21	98.4 (3)	C33—C34—C37	121.7 (5)
C11—P1—Ru1	114.0 (2)	C36—C35—C34	121.6 (6)
C31—P1—Ru1	116.53 (19)	C35—C36—C31	121.6 (5)
C21—P1—Ru1	117.83 (18)	C46—C41—C42	118.1 (5)
C51—P2—C61	101.5 (3)	C46—C41—P2	123.0 (5)
C51—P2—C41	103.5 (2)	C42—C41—P2	118.8 (4)
C61—P2—C41	102.1 (2)	C43—C42—C41	121.1 (5)
C51—P2—Ru1	119.72 (18)	C44—C43—C42	121.5 (6)
C61—P2—Ru1	118.14 (17)	C43—C44—C45	117.8 (5)
C41—P2—Ru1	109.6 (2)	C43—C44—C47	121.2 (5)
N2—N1—C2	106.8 (5)	C45—C44—C47	121.0 (5)
N2—N1—Ru1	123.3 (3)	C44—C45—C46	120.9 (5)
C2—N1—Ru1	129.5 (4)	C41—C46—C45	120.5 (6)
N1—N2—C4	108.9 (5)	C56—C51—C52	116.5 (5)
N1—N2—B1	123.2 (5)	C56—C51—P2	124.3 (4)
C4—N2—B1	125.8 (6)	C52—C51—P2	119.2 (5)
C5—N3—N4	105.2 (4)	C53—C52—C51	120.8 (6)
C5—N3—Ru1	129.6 (4)	C54—C53—C52	121.5 (5)
N4—N3—Ru1	125.1 (3)	C53—C54—C55	118.2 (6)
C7—N4—N3	109.9 (4)	C53—C54—C57	121.0 (5)
C7—N4—B1	127.1 (5)	C55—C54—C57	120.8 (7)
N3—N4—B1	121.5 (4)	C54—C55—C56	120.9 (7)
O1—C1—Ru1	179.3 (5)	C55—C56—C51	122.0 (5)
N1—C2—C3	110.3 (6)	C66—C61—C62	116.5 (5)
C4—C3—C2	105.4 (5)	C66—C61—P2	123.5 (4)
C3—C4—N2	108.6 (6)	C62—C61—P2	119.8 (4)
N3—C5—C6	112.0 (5)	C63—C62—C61	120.9 (5)
C5—C6—C7	103.9 (5)	C62—C63—C64	122.0 (5)
N4—C7—C6	108.9 (5)	C65—C64—C63	117.7 (5)
C16—C11—C12	117.4 (5)	C65—C64—C67	121.6 (5)
C16—C11—P1	119.1 (4)	C63—C64—C67	120.7 (5)
C12—C11—P1	123.3 (4)	C64—C65—C66	121.1 (5)
C13—C12—C11	120.2 (5)	C65—C66—C61	121.7 (5)
C14—C13—C12	122.0 (5)	H2B—B1—H1B	107 (4)
C13—C14—C15	117.8 (5)	H2B—B1—N2	113 (3)
C13—C14—C17	122.2 (5)	H1B—B1—N2	110 (2)
C15—C14—C17	120.0 (5)	H2B—B1—N4	109 (3)
C16—C15—C14	120.7 (5)	H1B—B1—N4	106 (2)
C15—C16—C11	121.6 (5)	N2—B1—N4	111.5 (6)
H1Ru—Ru1—P1—C11	−86.3 (15)	C31—P1—C21—C26	−129.6 (5)
C1—Ru1—P1—C11	−176.7 (2)	Ru1—P1—C21—C26	104.4 (5)
N3—Ru1—P1—C11	1.2 (2)	C11—P1—C21—C22	158.6 (5)
N1—Ru1—P1—C11	91.0 (2)	C31—P1—C21—C22	51.9 (5)
P2—Ru1—P1—C11	−95.3 (3)	Ru1—P1—C21—C22	−74.1 (5)
H1Ru—Ru1—P1—C31	34.8 (15)	C26—C21—C22—C23	1.7 (9)
C1—Ru1—P1—C31	−55.6 (2)	P1—C21—C22—C23	−179.7 (5)
N3—Ru1—P1—C31	122.4 (2)	C21—C22—C23—C24	−0.2 (9)
N1—Ru1—P1—C31	−147.9 (2)	C22—C23—C24—C25	−2.0 (9)
P2—Ru1—P1—C31	25.8 (3)	C22—C23—C24—C27	178.5 (6)
H1Ru—Ru1—P1—C21	151.4 (15)	C23—C24—C25—C26	2.5 (9)
C1—Ru1—P1—C21	61.0 (3)	C27—C24—C25—C26	−177.9 (6)
N3—Ru1—P1—C21	−121.0 (2)	C22—C21—C26—C25	−1.1 (9)
N1—Ru1—P1—C21	−31.3 (2)	P1—C21—C26—C25	−179.6 (5)
P2—Ru1—P1—C21	142.4 (3)	C24—C25—C26—C21	−1.0 (10)
H1Ru—Ru1—P2—C51	−178.2 (15)	C11—P1—C31—C36	−54.4 (5)
C1—Ru1—P2—C51	−87.5 (3)	C21—P1—C31—C36	52.3 (5)
N3—Ru1—P2—C51	94.4 (2)	Ru1—P1—C31—C36	179.3 (4)
N1—Ru1—P2—C51	4.5 (2)	C11—P1—C31—C32	128.9 (4)
P1—Ru1—P2—C51	−169.1 (3)	C21—P1—C31—C32	−124.4 (4)
H1Ru—Ru1—P2—C61	57.3 (15)	Ru1—P1—C31—C32	2.6 (5)
C1—Ru1—P2—C61	148.0 (3)	C36—C31—C32—C33	−0.4 (8)
N3—Ru1—P2—C61	−30.1 (2)	P1—C31—C32—C33	176.5 (4)
N1—Ru1—P2—C61	−120.0 (2)	C31—C32—C33—C34	1.3 (8)
P1—Ru1—P2—C61	66.4 (3)	C32—C33—C34—C35	−0.5 (8)
H1Ru—Ru1—P2—C41	−59.0 (15)	C32—C33—C34—C37	178.4 (5)
C1—Ru1—P2—C41	31.7 (2)	C33—C34—C35—C36	−1.2 (8)
N3—Ru1—P2—C41	−146.4 (2)	C37—C34—C35—C36	179.9 (5)
N1—Ru1—P2—C41	123.7 (2)	C34—C35—C36—C31	2.2 (8)
P1—Ru1—P2—C41	−49.9 (3)	C32—C31—C36—C35	−1.3 (8)
H1Ru—Ru1—N1—N2	−68 (21)	P1—C31—C36—C35	−178.2 (4)
C1—Ru1—N1—N2	167.1 (5)	C51—P2—C41—C46	0.0 (5)
N3—Ru1—N1—N2	−12.3 (4)	C61—P2—C41—C46	105.1 (5)
P1—Ru1—N1—N2	−102.9 (4)	Ru1—P2—C41—C46	−128.8 (5)
P2—Ru1—N1—N2	78.6 (4)	C51—P2—C41—C42	179.1 (4)
H1Ru—Ru1—N1—C2	104 (21)	C61—P2—C41—C42	−75.7 (5)
C1—Ru1—N1—C2	−21.1 (5)	Ru1—P2—C41—C42	50.3 (5)
N3—Ru1—N1—C2	159.5 (5)	C46—C41—C42—C43	1.0 (8)
P1—Ru1—N1—C2	69.0 (5)	P2—C41—C42—C43	−178.3 (4)
P2—Ru1—N1—C2	−109.5 (5)	C41—C42—C43—C44	0.3 (9)
C2—N1—N2—C4	0.8 (6)	C42—C43—C44—C45	−1.2 (8)
Ru1—N1—N2—C4	174.3 (4)	C42—C43—C44—C47	176.8 (5)
C2—N1—N2—B1	164.9 (5)	C43—C44—C45—C46	0.8 (8)
Ru1—N1—N2—B1	−21.6 (7)	C47—C44—C45—C46	−177.2 (5)
H1Ru—Ru1—N3—C5	14.9 (18)	C42—C41—C46—C45	−1.4 (8)
C1—Ru1—N3—C5	35 (7)	P2—C41—C46—C45	177.8 (4)
N1—Ru1—N3—C5	−161.2 (5)	C44—C45—C46—C41	0.5 (9)
P1—Ru1—N3—C5	−70.2 (5)	C61—P2—C51—C56	−16.8 (5)
P2—Ru1—N3—C5	96.6 (5)	C41—P2—C51—C56	88.8 (5)
H1Ru—Ru1—N3—N4	−168.9 (18)	Ru1—P2—C51—C56	−148.9 (4)
C1—Ru1—N3—N4	−149 (6)	C61—P2—C51—C52	163.5 (4)
N1—Ru1—N3—N4	15.1 (4)	C41—P2—C51—C52	−90.9 (4)
P1—Ru1—N3—N4	106.0 (4)	Ru1—P2—C51—C52	31.4 (5)
P2—Ru1—N3—N4	−87.2 (4)	C56—C51—C52—C53	2.4 (8)
C5—N3—N4—C7	−1.0 (6)	P2—C51—C52—C53	−177.9 (4)
Ru1—N3—N4—C7	−178.0 (4)	C51—C52—C53—C54	0.0 (9)
C5—N3—N4—B1	−168.0 (5)	C52—C53—C54—C55	−1.8 (9)
Ru1—N3—N4—B1	15.0 (7)	C52—C53—C54—C57	179.2 (5)
H1Ru—Ru1—C1—O1	−91 (42)	C53—C54—C55—C56	1.2 (9)
N3—Ru1—C1—O1	−110 (41)	C57—C54—C55—C56	−179.8 (6)
N1—Ru1—C1—O1	86 (42)	C54—C55—C56—C51	1.2 (9)
P1—Ru1—C1—O1	−5 (42)	C52—C51—C56—C55	−3.0 (8)
P2—Ru1—C1—O1	−172 (100)	P2—C51—C56—C55	177.3 (4)
N2—N1—C2—C3	−1.4 (7)	C51—P2—C61—C66	101.1 (5)
Ru1—N1—C2—C3	−174.4 (4)	C41—P2—C61—C66	−5.5 (6)
N1—C2—C3—C4	1.5 (8)	Ru1—P2—C61—C66	−125.8 (5)
C2—C3—C4—N2	−1.0 (8)	C51—P2—C61—C62	−74.7 (5)
N1—N2—C4—C3	0.1 (7)	C41—P2—C61—C62	178.7 (5)
B1—N2—C4—C3	−163.5 (6)	Ru1—P2—C61—C62	58.4 (5)
N4—N3—C5—C6	0.9 (7)	C66—C61—C62—C63	2.7 (9)
Ru1—N3—C5—C6	177.7 (4)	P2—C61—C62—C63	178.8 (5)
N3—C5—C6—C7	−0.4 (7)	C61—C62—C63—C64	−1.8 (10)
N3—N4—C7—C6	0.7 (7)	C62—C63—C64—C65	−0.1 (9)
B1—N4—C7—C6	166.9 (6)	C62—C63—C64—C67	−178.2 (6)
C5—C6—C7—N4	−0.2 (7)	C63—C64—C65—C66	1.0 (9)
C31—P1—C11—C16	170.1 (4)	C67—C64—C65—C66	179.1 (6)
C21—P1—C11—C16	67.6 (5)	C64—C65—C66—C61	0.0 (9)
Ru1—P1—C11—C16	−62.0 (5)	C62—C61—C66—C65	−1.8 (9)
C31—P1—C11—C12	−15.6 (6)	P2—C61—C66—C65	−177.8 (5)
C21—P1—C11—C12	−118.1 (5)	N1—N2—B1—H2B	−179 (3)
Ru1—P1—C11—C12	112.3 (5)	C4—N2—B1—H2B	−18 (3)
C16—C11—C12—C13	−3.3 (8)	N1—N2—B1—H1B	−59 (2)
P1—C11—C12—C13	−177.8 (4)	C4—N2—B1—H1B	102 (2)
C11—C12—C13—C14	−0.3 (9)	N1—N2—B1—N4	57.7 (7)
C12—C13—C14—C15	3.3 (9)	C4—N2—B1—N4	−141.0 (6)
C12—C13—C14—C17	−177.4 (6)	C7—N4—B1—H2B	16 (4)
C13—C14—C15—C16	−2.6 (9)	N3—N4—B1—H2B	−179 (3)
C17—C14—C15—C16	178.0 (5)	C7—N4—B1—H1B	−99 (2)
C14—C15—C16—C11	−1.0 (9)	N3—N4—B1—H1B	66 (2)
C12—C11—C16—C15	4.0 (8)	C7—N4—B1—N2	141.9 (6)
P1—C11—C16—C15	178.7 (4)	N3—N4—B1—N2	−53.4 (7)
C11—P1—C21—C26	−22.9 (6)