The nido-osmaboranes [2,2,2-(CO)(PPh₃)₂-nido-2-OsB₅H₉] and [6,6,6-(CO)(PPh₃)₂-nido-6-OsB₉H₁₃]

The structural characterization of the osmahexaborane 2-carbonyl-2,2-bis­(tri­phenyl­phosphine)-nido-2-osmahexaborane(9), [Os(B₅H₉)(C₁₈H₁₅P)₂(CO)], (I), a metallaborane analogue of B₆H₁₀, confirms the structure proposed from NMR spectroscopy. The structure of the osmadecaborane 6-carbonyl-6,6-bis­(tri­phenyl­phosphine)-nido-6-osmadecaborane(13), [Os(B₉H₁₃)(C₁₈H₁₅P)₂(CO)], (IV), is similarly confirmed. The short basal B-B distance of 1.652 (8) Å in (I), not bridged by an H atom, mirrors that in the parent hexaborane(10) [1.626 (4) Å].

S1. Comment

Several metallahexaboranes, species in which a transition metal moiety has replaced a BH group in hexaborane(10), are known (Kennedy, 1984). So far, however, only the species [(PPh₃)₂(CO)-nido-OsB₅H₉], (I) (Bould et al., 1983), and [(PPh₃)₂(CO)-nido-IrB₅H₈], (II) (Greenwood et al., 1979), are available in sufficient yields and stability to be useful reagents. These are important systems because the parent hexaborane(10) is not stable at room temperature and is very air sensitive. Although one report of the derivatization of (II) has been reported (Bould, Rath, Fang & Barton, 1996) correct ref?, species (I) is the only metallahexaborane to have been the subject of significant derivative chemistry, including the construction of polymetallaboranes and studies of cluster degradation. Indeed, structures of several derivatives of (I) have been reported (Bould et al., 1991; Barton et al., 1996, 1997), but until recently crystals of appropriate quality of the parent, (II) surely (I)?, were unavailable. Compound (I) was isolated in high yield (85%) from the reaction of Na[B₅H₈] and [(CO)(PPh₃)₃HClOs]. Minor products also isolated from the reaction mixture were [(CO)H(PPh₃)₂-arachno-OsB₃H₈] (Bould, Rath & Barton, 1996) correct ref? and [(CO)(PPh₃)₂-nido-OsB₄H₇(BH₂·PPh₃)], (III) (Barton et al., 1997). An additional minor reaction by-product was also formed, namely, [(CO)(PPh₃)₂-nido-OsB₉H₁₃], (IV). Herein, we report the structure of the important metallahexaborane starting material, (I), and also of the related osmadecaborane [(CO)(PPh₃)₂-nido-OsB₉H₁₃], (IV), for comparison purposes. \sch

Single-crystal X-ray diffraction analysis confirms the expected pentagonal-based pyramid structure for (I) (Fig. 1) that had been proposed previously from NMR spectrometry (Bould et al., 1983). All cage-bound H atoms were located from the difference map and refined freely in reasonable positions, with the exception of the Os—H—B bridging H atoms, although four bridging H atoms are indicated by NMR spectroscopy and required from electron-counting considerations. The bridging H atoms, which were not located from the difference Fourier syntheses, lie approximately trans to C37 and P1, as indicated by NMR spectroscopy [²J (³¹P - ¹H) (trans) 40 Hz for µH26; Bould et al., 1983].

The short B4—B5 distance of 1.650 (10) Å in (I) compares closely with that in (III) [1.649 (10) Å] and with the basal `single' bond in the parent borane, B₆H₁₀ [1.626 (4) Å; Huffman, 1974]. This determination confirms that the B—B bond opposite the Os atom is the unbridged one. The distances B3—B4 and B5—B6 are 1.754 (6) and 1.734 (6) Å, respectively, suggesting hydrogen-bridged B—B bonds, whereas the shorter B4—B5, at 1.626 (4) Å, does not. Thus the bridging H atoms in (I) are symmetrically disposed, in spite of the observation of four separate resonances in the bridging-hydrogen region of the ¹H NMR spectrum. The latter is clearly due to the asymmetric disposition of the two PPh₃ ligands on Os.

The short B4—B5 distance in (I) implies that the metallaborane species may have some Lewis base character, as has been noted in hexaborane(10) (Solomon & Porter, 1972; Brennan et al., 1973). Some evidence for this has, for example, been adduced in the reaction of (II) with Fe₂(CO)₉ to yield closo-[B₅H₄PPh₃{Fe(CO)₃}{Ir(CO)PPh₃}] via an initial [(PPh₃)₂(CO)IrB₅H₈{µ(Fe(CO)₄)}] intermediate (Bould et al., 1995).

The molecular structure of (IV) is shown in Fig. 2. Again, as with (I), two of the four cage-bound bridging H atoms were not located in the difference map, although they are shown by NMR spectroscopy to be present bridging B9—B8 and B9—B10 (see Experimental). The hydrogen-bridged Os—B distances in (I) and (IV) are comparable: Os2—B3 2.292 (4) and Os2—B6 2.298 (4) Å in (I), and Os6—B5 2.317 (11) and Os6—B7 2.300 (12) Å in (IV). This gives support to the assumption that the two bridging H atoms not located in the X-ray structure are indeed present in (I).

The cluster in (IV) is seen to be a conventional nido-metalladecaborane cage, with the metal vertex in a `prow' position on the open face of the ten-vertex `boat'. The structure of a similar osmadecaborane, [(PMe₂Ph)₃-nido-OsB₉H₁₃], (V), has been previously reported by Beckett et al. (1986). The main variance between the two structures arises from the differing metal ligation sphere. The smaller steric requirement of the PMe₂Ph ligand effects a smaller Os—P distance in (III) surely (V)? compared with (IV) (by ca 0.035 (3) Å). The slight difference between the long B5—B10 and B7—B8 distances in (IV) [2.026 (19) and 1.93 (2) Å, respectively], which might be attributed to the asymmetry introduced by the presence of the equatorial carbonyl ligand, is, however, mirrored in (V) [2.083 (11) versus 2.016 (10) Å]. It is noteworthy that the orientations of the ligands on Os in (IV) and (I) are similar and both asymmetrical. Representations of (I), (II) and (IV) are given in the Scheme to illustrate the orientation of the ligands relative to the boron cages in the three systems.

Related literature

For related literature, see: Barton et al. (1996, 1997); Beckett et al. (1986); Bould et al. (1983, 1991, 1995); Bould, Rath & Barton (1996); Bould, Rath, Fang & Barton (1996); Brennan et al. (1973); Greenwood et al. (1979); Huffman (1974); Kennedy (1984); Nainan & Ryschkewitsch (1969); Sheldrick (1999); Solomon & Porter (1972).

S2. Experimental

Compound (I) was isolated in high yield (85%) from the reaction of Na[B₅H₈] and [(CO)(PPh₃)₃HClOs]. Single crystals of (I) were not grown directly from solutions of the compound; they arose from attempts to grow single crystals of [(PPh₃)₂(CO)-nido-OsB₄H₇(BH₂·PPh₃)], (III). In solution at ambient temperature, (III) loses PPh₃ to form an equilibrium mixture from which (I) preferentially crystallizes. Compound (IV), previously unreported, was isolated as a minor product from the preparation of (I). Soluble residues from the preparation of (I) gave, after reduction in volume, a grey precipitate. Preparative thin-layer chromatography (TLC) of the filtrate (silica gel, Aldrich standard TLC grade, with gypsum binder and fluorescent indicator) gave a series of colourless bands, identified as, in order, [(CO)(PPh₃)₂OsB₄H₈], (III), [(CO)H(PPh₃)₂-arachno-OsB₃H₈] and [BH₃PPh₃] (Bould et al., 1983; Bould, Rath & Barton, 1996 correct ref?; Barton et al., 1997; Nainan & Ryschkewitsch, 1969). Repeated TLC on solutions of the grey precipitate gave an orange band, identified as [6,6,6-(CO)(PPh₃)₂-6-nido-Os(B₉H₁₃)], (IV). Orange single crystals were obtained by diffusion of hexane into a CD₂Cl₂ solution of the compound. NMR data (CD₂Cl₂, 300 K, Bruker 500 AMX spectrometer, p.p.m.) in the above order; assignment δ(¹¹B) [δ(¹H) in square brackets]: B1,3 + 12.5 [+4.42], B2 - 28.5 [-0.26], B4 - 28.2 [+2.04], B5 + 8.9 [+5.27], B7 + 14.5 [+4.90], B(8 or 10) +0.81 [+2.69], B(10 or 8) -2.5 [+2.56], B9 + 6.5 [+2.53]; additional ¹H data, p.p.m/: H(6/5) -10.26 [²J(³¹P-¹H) 35 Hz], H(6/7) -8.80, H(89/910) -4.54 and -4.45; δ(³¹P) +8.7 and +14.9.

S3. Refinement

For (I), cluster-associated H atoms were located from the difference Fourier syntheses and refined freely, with the exception of the bridging atom H23, which was located from the Fourier synthesis and for which the positional parameters were treated as riding on Os2. Bridging atom H26 could not be located. For (IV), cage H atoms were located from the difference Fourier synthesis and, for some, the positions were refined, while for the rest an appropriate riding model was used. The H atoms bridging B8—B9 and B9—B10 could not be located. One of the phenyl rings (C8—C13) in (IV) is disordered. This was resolved and the disorder atoms were refined with anisotropic displacement parameter constraints (EADP command in SHELXTL; Sheldrick, 1999). Non-boron-cage H atoms for both compounds were included in their idealized geometry and refined with appropriate riding models (AFIX command in SHELXTL). The highest residual peaks were found close to the Os atoms [0.89 and 0.99 Å for (I) and (IV), respectively]. Please provide CIF-format data for bonds and angles involving H atoms for both compounds.

Computing details

For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 1999); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A perspective view of a single molecule of (I), with displacement ellipsoids drawn at the 40% probability level and H atoms shown as small spheres of arbitrary radii. The phenyl groups, with the exception of the ipso C atoms, have been omitted to aid clarity. The Os2—H—B6 bridging H atom, shown to be present by NMR spectrometry, was not located from the X-ray data.
	Fig. 2. A perspective view of a single molecule of (IV), with displacement ellipsoids drawn at the 40% probability level and H atoms shown as small spheres of arbitrary radii. The phenyl groups, with the exception of the ipso C atoms, have been omitted to aid clarity. The two H atoms bridging B9—H—B8 and B9—H—B10, shown to be present by NMR spectrometry, were not located from the X-ray data.

(I) [2-carbonyl-2,2-bis(triphenylphosphine)-nido-2-osmahexaborane(9)]

Crystal data

[(B5H9Os)(C18H15P)2(CO)]	F(000) = 1600
Mr = 805.87	Dx = 1.544 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 16.0054 (1) Å	Cell parameters from 8192 reflections
b = 13.0200 (1) Å	θ = 2–33°
c = 17.2445 (1) Å	µ = 3.80 mm^−1
β = 105.29 (1)°	T = 153 K
V = 3466.39 (4) Å^3	Irregular, colourless
Z = 4	0.25 × 0.20 × 0.08 mm

Data collection

Bruker SMART Query CCD area-detector diffractometer	9961 independent reflections
Radiation source: normal-focus sealed tube	9460 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ϕ and ω scans	θmax = 30.0°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995)	h = −22→22
Tmin = 0.450, Tmax = 0.751	k = −18→18
31883 measured reflections	l = −24→24

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)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.059	w = 1/[σ^2(Fo^2) + (0.0182P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
9961 reflections	Δρmax = 2.20 e Å^−3
443 parameters	Δρmin = −1.78 e Å^−3
2 restraints	Absolute structure: Flack, 1983
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.002 (4)

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 > 2σ(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
Os2	0.50112 (1)	0.80164 (1)	0.27089 (1)	0.01393 (3)
H23	0.5044	0.8033	0.3700	0.017*
P1	0.60724 (6)	0.67533 (9)	0.26835 (7)	0.01696 (19)
P2	0.59124 (5)	0.94852 (7)	0.28822 (5)	0.01514 (15)
O	0.44307 (19)	0.7775 (3)	0.09035 (17)	0.0304 (6)
C1	0.5621 (2)	0.5612 (3)	0.2099 (2)	0.0224 (7)
C2	0.4959 (3)	0.5072 (3)	0.2305 (3)	0.0314 (9)
H2A	0.4726	0.5324	0.2721	0.038*
C3	0.4640 (3)	0.4182 (4)	0.1915 (4)	0.0474 (13)
H3A	0.4202	0.3811	0.2074	0.057*
C4	0.4951 (3)	0.3820 (4)	0.1290 (4)	0.0539 (16)
H4A	0.4718	0.3212	0.1012	0.065*
C5	0.5601 (3)	0.4345 (4)	0.1072 (3)	0.0466 (13)
H5A	0.5824	0.4091	0.0650	0.056*
C6	0.5927 (3)	0.5240 (4)	0.1465 (3)	0.0325 (9)
H6A	0.6366	0.5607	0.1302	0.039*
C7	0.6679 (2)	0.6194 (3)	0.3641 (2)	0.0207 (7)
C8	0.7004 (2)	0.6852 (3)	0.4292 (2)	0.0229 (7)
H8A	0.6910	0.7572	0.4231	0.028*
C9	0.7467 (2)	0.6448 (3)	0.5033 (2)	0.0252 (8)
H9A	0.7685	0.6895	0.5475	0.030*
C10	0.7609 (2)	0.5405 (3)	0.5125 (2)	0.0292 (8)
H10A	0.7921	0.5135	0.5631	0.035*
C11	0.7299 (3)	0.4753 (3)	0.4482 (3)	0.0345 (9)
H11A	0.7398	0.4035	0.4545	0.041*
C12	0.6840 (3)	0.5146 (3)	0.3740 (2)	0.0302 (8)
H12A	0.6635	0.4694	0.3298	0.036*
C13	0.6914 (2)	0.7085 (3)	0.2180 (2)	0.0217 (7)
C14	0.6701 (3)	0.7659 (4)	0.1479 (2)	0.0286 (8)
H14A	0.6154	0.7991	0.1321	0.034*
C15	0.7276 (3)	0.7760 (4)	0.1001 (3)	0.0348 (10)
H15A	0.7121	0.8146	0.0517	0.042*
C16	0.8081 (3)	0.7284 (4)	0.1246 (3)	0.0423 (12)
H16A	0.8472	0.7329	0.0918	0.051*
C17	0.8318 (3)	0.6752 (4)	0.1957 (3)	0.0384 (11)
H17A	0.8880	0.6459	0.2128	0.046*
C18	0.7740 (2)	0.6637 (4)	0.2429 (3)	0.0292 (8)
H18A	0.7903	0.6258	0.2917	0.035*
C19	0.7028 (2)	0.9426 (3)	0.3524 (2)	0.0185 (6)
C20	0.7169 (2)	0.9623 (3)	0.4342 (2)	0.0231 (7)
H20A	0.6695	0.9812	0.4548	0.028*
C21	0.7997 (3)	0.9548 (3)	0.4863 (3)	0.0292 (8)
H21A	0.8085	0.9677	0.5421	0.035*
C22	0.8688 (3)	0.9286 (3)	0.4565 (3)	0.0333 (9)
H22A	0.9255	0.9246	0.4916	0.040*
C23	0.8555 (2)	0.9082 (4)	0.3756 (3)	0.0309 (9)
H23A	0.9033	0.8903	0.3553	0.037*
C24	0.7727 (2)	0.9134 (3)	0.3231 (2)	0.0224 (7)
H24A	0.7639	0.8972	0.2678	0.027*
C25	0.5962 (2)	1.0180 (3)	0.1969 (2)	0.0181 (6)
C26	0.6693 (2)	1.0726 (3)	0.1903 (2)	0.0235 (7)
H26A	0.7220	1.0670	0.2313	0.028*
C27	0.6651 (3)	1.1347 (3)	0.1242 (2)	0.0289 (8)
H27A	0.7152	1.1708	0.1198	0.035*
C28	0.5889 (3)	1.1444 (3)	0.0650 (2)	0.0277 (8)
H28A	0.5864	1.1873	0.0198	0.033*
C29	0.5152 (3)	1.0913 (3)	0.0712 (2)	0.0248 (7)
H29A	0.4623	1.0980	0.0304	0.030*
C30	0.5194 (3)	1.0288 (4)	0.1370 (3)	0.0215 (9)
H30A	0.4692	0.9928	0.1412	0.026*
C31	0.5505 (2)	1.0522 (3)	0.3407 (2)	0.0184 (6)
C32	0.4913 (3)	1.0363 (4)	0.3863 (3)	0.0223 (9)
H32A	0.4660	0.9705	0.3871	0.027*
C33	0.4691 (3)	1.1159 (4)	0.4304 (3)	0.0301 (9)
H33A	0.4285	1.1041	0.4610	0.036*
C34	0.5054 (3)	1.2125 (3)	0.4305 (3)	0.0317 (9)
H34A	0.4906	1.2662	0.4617	0.038*
C35	0.5632 (3)	1.2305 (3)	0.3848 (3)	0.0342 (9)
H35A	0.5874	1.2969	0.3839	0.041*
C36	0.5858 (3)	1.1510 (3)	0.3401 (3)	0.0298 (8)
H36A	0.6255	1.1638	0.3088	0.036*
C37	0.4674 (2)	0.7903 (3)	0.1589 (2)	0.0192 (7)
B1	0.3802 (3)	0.7122 (4)	0.2865 (3)	0.0242 (10)
B3	0.4699 (3)	0.7120 (3)	0.3741 (3)	0.0223 (8)
B4	0.3650 (3)	0.7230 (4)	0.3865 (3)	0.0288 (10)
B5	0.3015 (3)	0.7933 (4)	0.3151 (3)	0.0282 (10)
B6	0.3559 (3)	0.8382 (4)	0.2475 (3)	0.0239 (8)
H1	0.354 (3)	0.649 (4)	0.251 (3)	0.028 (12)*
H3	0.516 (3)	0.649 (4)	0.406 (3)	0.024 (11)*
H4	0.352 (4)	0.660 (5)	0.425 (3)	0.045 (15)*
H5	0.232 (4)	0.791 (4)	0.289 (4)	0.042 (16)*
H6	0.327 (3)	0.883 (3)	0.192 (2)	0.017 (10)*
H34	0.434 (4)	0.765 (5)	0.426 (3)	0.043 (14)*
H56	0.319 (3)	0.880 (4)	0.301 (3)	0.027 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Os2	0.01132 (4)	0.01635 (5)	0.01419 (5)	−0.00172 (8)	0.00348 (3)	−0.00039 (8)
P1	0.0150 (4)	0.0181 (5)	0.0178 (5)	−0.0003 (4)	0.0044 (3)	−0.0024 (4)
P2	0.0123 (3)	0.0178 (4)	0.0153 (4)	−0.0014 (3)	0.0035 (3)	0.0009 (3)
O	0.0271 (14)	0.0445 (19)	0.0183 (13)	−0.0012 (12)	0.0039 (11)	−0.0027 (12)
C1	0.0187 (15)	0.0193 (18)	0.0291 (19)	−0.0027 (13)	0.0061 (14)	−0.0061 (14)
C2	0.035 (2)	0.023 (2)	0.042 (2)	−0.0080 (16)	0.0205 (18)	−0.0140 (17)
C3	0.044 (3)	0.037 (3)	0.071 (4)	−0.021 (2)	0.031 (2)	−0.024 (2)
C4	0.044 (3)	0.047 (3)	0.081 (4)	−0.023 (2)	0.033 (3)	−0.043 (3)
C5	0.040 (2)	0.050 (3)	0.058 (3)	−0.014 (2)	0.027 (2)	−0.031 (2)
C6	0.0274 (18)	0.038 (2)	0.035 (2)	−0.0095 (17)	0.0139 (17)	−0.0175 (18)
C7	0.0194 (15)	0.0197 (17)	0.0233 (17)	0.0026 (13)	0.0059 (13)	−0.0006 (13)
C8	0.0225 (16)	0.0220 (19)	0.0237 (18)	0.0031 (13)	0.0049 (14)	0.0005 (14)
C9	0.0198 (16)	0.033 (2)	0.0202 (17)	0.0023 (15)	0.0003 (13)	−0.0030 (14)
C10	0.0245 (18)	0.039 (2)	0.0209 (18)	0.0078 (16)	0.0012 (15)	0.0064 (16)
C11	0.041 (2)	0.024 (2)	0.035 (2)	0.0097 (18)	0.0034 (19)	0.0029 (17)
C12	0.036 (2)	0.023 (2)	0.028 (2)	0.0046 (16)	0.0026 (16)	−0.0025 (15)
C13	0.0152 (14)	0.026 (2)	0.0250 (18)	−0.0055 (13)	0.0079 (14)	−0.0098 (14)
C14	0.0218 (17)	0.039 (2)	0.027 (2)	−0.0070 (17)	0.0087 (15)	−0.0032 (17)
C15	0.031 (2)	0.046 (3)	0.031 (2)	−0.0153 (19)	0.0138 (18)	−0.0057 (19)
C16	0.030 (2)	0.054 (3)	0.051 (3)	−0.018 (2)	0.026 (2)	−0.022 (2)
C17	0.0198 (18)	0.042 (3)	0.057 (3)	−0.0033 (17)	0.0164 (19)	−0.013 (2)
C18	0.0182 (16)	0.030 (2)	0.040 (2)	0.0004 (15)	0.0090 (16)	−0.0068 (18)
C19	0.0151 (14)	0.0187 (17)	0.0205 (16)	−0.0042 (12)	0.0026 (12)	0.0021 (13)
C20	0.0225 (16)	0.0245 (19)	0.0199 (17)	−0.0008 (14)	0.0014 (14)	0.0004 (14)
C21	0.0272 (18)	0.028 (2)	0.027 (2)	0.0000 (15)	−0.0025 (16)	−0.0016 (16)
C22	0.0205 (17)	0.034 (2)	0.037 (2)	0.0029 (16)	−0.0076 (16)	0.0014 (17)
C23	0.0160 (15)	0.033 (2)	0.041 (2)	0.0020 (15)	0.0031 (15)	−0.0020 (18)
C24	0.0170 (14)	0.0235 (18)	0.0258 (18)	0.0003 (13)	0.0043 (13)	−0.0008 (14)
C25	0.0180 (14)	0.0199 (17)	0.0170 (15)	−0.0011 (12)	0.0058 (12)	0.0001 (12)
C26	0.0181 (15)	0.029 (2)	0.0236 (18)	−0.0046 (14)	0.0063 (13)	0.0017 (14)
C27	0.0276 (18)	0.029 (2)	0.032 (2)	−0.0061 (15)	0.0117 (16)	0.0076 (16)
C28	0.037 (2)	0.026 (2)	0.0214 (18)	0.0004 (16)	0.0105 (16)	0.0063 (15)
C29	0.0261 (17)	0.024 (2)	0.0204 (18)	0.0016 (15)	−0.0002 (15)	0.0035 (15)
C30	0.0203 (18)	0.022 (2)	0.022 (2)	0.0002 (14)	0.0051 (15)	0.0022 (16)
C31	0.0157 (14)	0.0229 (18)	0.0160 (15)	0.0009 (12)	0.0031 (12)	−0.0004 (12)
C32	0.0228 (18)	0.023 (2)	0.023 (2)	−0.0003 (15)	0.0105 (16)	−0.0032 (16)
C33	0.0285 (19)	0.036 (2)	0.028 (2)	0.0034 (17)	0.0124 (17)	−0.0027 (18)
C34	0.044 (2)	0.025 (2)	0.028 (2)	0.0122 (17)	0.0128 (19)	−0.0016 (16)
C35	0.049 (3)	0.0166 (18)	0.041 (2)	−0.0042 (18)	0.019 (2)	−0.0027 (17)
C36	0.036 (2)	0.022 (2)	0.036 (2)	−0.0036 (16)	0.0181 (18)	−0.0026 (16)
C37	0.0118 (13)	0.0217 (18)	0.0233 (18)	−0.0015 (12)	0.0033 (13)	0.0018 (13)
B1	0.022 (2)	0.024 (2)	0.027 (2)	−0.0070 (18)	0.0063 (18)	−0.0030 (19)
B3	0.0239 (18)	0.021 (2)	0.024 (2)	−0.0028 (15)	0.0106 (16)	0.0045 (15)
B4	0.026 (2)	0.030 (2)	0.036 (3)	−0.0044 (18)	0.018 (2)	0.0029 (19)
B5	0.0177 (18)	0.030 (2)	0.041 (3)	−0.0028 (16)	0.0149 (18)	−0.0043 (19)
B6	0.0171 (17)	0.030 (2)	0.025 (2)	−0.0003 (16)	0.0052 (15)	−0.0029 (17)

Geometric parameters (Å, º)

Os2—C37	1.869 (4)	C20—C21	1.394 (5)
Os2—B3	2.291 (4)	C20—H20A	0.9500
Os2—B6	2.301 (4)	C21—C22	1.381 (6)
Os2—B1	2.335 (5)	C21—H21A	0.9500
Os2—P2	2.3664 (9)	C22—C23	1.381 (6)
Os2—P1	2.3729 (11)	C22—H22A	0.9500
Os2—H23	1.6961	C23—C24	1.395 (5)
P1—C7	1.831 (4)	C23—H23A	0.9500
P1—C1	1.833 (4)	C24—H24A	0.9500
P1—C13	1.836 (4)	C25—C30	1.388 (6)
P2—C25	1.835 (3)	C25—C26	1.399 (5)
P2—C19	1.838 (3)	C26—C27	1.384 (5)
P2—C31	1.838 (4)	C26—H26A	0.9500
O—C37	1.155 (5)	C27—C28	1.375 (6)
C1—C2	1.393 (5)	C27—H27A	0.9500
C1—C6	1.399 (5)	C28—C29	1.396 (6)
C2—C3	1.369 (6)	C28—H28A	0.9500
C2—H2A	0.9500	C29—C30	1.383 (6)
C3—C4	1.384 (7)	C29—H29A	0.9500
C3—H3A	0.9500	C30—H30A	0.9500
C4—C5	1.376 (7)	C31—C32	1.398 (5)
C4—H4A	0.9500	C31—C36	1.406 (5)
C5—C6	1.379 (6)	C32—C33	1.386 (6)
C5—H5A	0.9500	C32—H32A	0.9500
C6—H6A	0.9500	C33—C34	1.385 (6)
C7—C12	1.391 (6)	C33—H33A	0.9500
C7—C8	1.399 (5)	C34—C35	1.384 (6)
C8—C9	1.400 (6)	C34—H34A	0.9500
C8—H8A	0.9500	C35—C36	1.393 (6)
C9—C10	1.379 (6)	C35—H35A	0.9500
C9—H9A	0.9500	C36—H36A	0.9500
C10—C11	1.381 (6)	B1—B6	1.777 (7)
C10—H10A	0.9500	B1—B3	1.788 (7)
C11—C12	1.394 (6)	B1—B5	1.808 (7)
C11—H11A	0.9500	B1—B4	1.809 (8)
C12—H12A	0.9500	B1—H1	1.04 (5)
C13—C14	1.386 (6)	B3—B4	1.753 (6)
C13—C18	1.404 (5)	B3—H23	1.3202
C14—C15	1.394 (6)	B3—H3	1.15 (5)
C14—H14A	0.9500	B3—H34	1.37 (6)
C15—C16	1.391 (7)	B4—B5	1.652 (8)
C15—H15A	0.9500	B4—H4	1.10 (6)
C16—C17	1.371 (8)	B4—H34	1.25 (6)
C16—H16A	0.9500	B5—B6	1.730 (6)
C17—C18	1.392 (6)	B5—H5	1.09 (6)
C17—H17A	0.9500	B5—H56	1.20 (5)
C18—H18A	0.9500	B6—H6	1.11 (4)
C19—C20	1.392 (5)	B6—H56	1.33 (4)
C19—C24	1.396 (5)
C37—Os2—B3	134.42 (15)	C24—C23—H23A	119.6
C37—Os2—B6	80.32 (15)	C23—C24—C19	119.6 (4)
B3—Os2—B6	79.87 (16)	C23—C24—H24A	120.2
C37—Os2—B1	93.31 (17)	C19—C24—H24A	120.2
B3—Os2—B1	45.46 (18)	C30—C25—C26	118.8 (3)
B6—Os2—B1	45.07 (19)	C30—C25—P2	117.3 (3)
C37—Os2—P2	101.22 (11)	C26—C25—P2	123.1 (3)
B3—Os2—P2	124.35 (12)	C27—C26—C25	120.3 (3)
B6—Os2—P2	114.12 (13)	C27—C26—H26A	119.9
B1—Os2—P2	152.23 (15)	C25—C26—H26A	119.9
C37—Os2—P1	86.53 (11)	C28—C27—C26	120.4 (3)
B3—Os2—P1	88.02 (11)	C28—C27—H27A	119.8
B6—Os2—P1	146.59 (13)	C26—C27—H27A	119.8
B1—Os2—P1	106.00 (16)	C27—C28—C29	120.0 (3)
P2—Os2—P1	98.46 (3)	C27—C28—H28A	120.0
C37—Os2—H23	165.0	C29—C28—H28A	120.0
B3—Os2—H23	34.8	C30—C29—C28	119.6 (4)
B6—Os2—H23	86.3	C30—C29—H29A	120.2
B1—Os2—H23	72.3	C28—C29—H29A	120.2
P2—Os2—H23	90.4	C29—C30—C25	120.9 (4)
P1—Os2—H23	101.3	C29—C30—H30A	119.6
C7—P1—C1	102.19 (18)	C25—C30—H30A	119.6
C7—P1—C13	103.80 (17)	C32—C31—C36	118.3 (4)
C1—P1—C13	99.39 (17)	C32—C31—P2	123.3 (3)
C7—P1—Os2	118.11 (12)	C36—C31—P2	118.2 (3)
C1—P1—Os2	113.06 (12)	C33—C32—C31	120.5 (4)
C13—P1—Os2	117.63 (14)	C33—C32—H32A	119.7
C25—P2—C19	106.43 (15)	C31—C32—H32A	119.7
C25—P2—C31	99.31 (16)	C34—C33—C32	120.7 (4)
C19—P2—C31	98.54 (16)	C34—C33—H33A	119.6
C25—P2—Os2	116.90 (11)	C32—C33—H33A	119.6
C19—P2—Os2	120.33 (12)	C35—C34—C33	119.8 (4)
C31—P2—Os2	111.87 (11)	C35—C34—H34A	120.1
C2—C1—C6	118.1 (3)	C33—C34—H34A	120.1
C2—C1—P1	119.1 (3)	C34—C35—C36	120.0 (4)
C6—C1—P1	122.8 (3)	C34—C35—H35A	120.0
C3—C2—C1	120.8 (4)	C36—C35—H35A	120.0
C3—C2—H2A	119.6	C35—C36—C31	120.7 (4)
C1—C2—H2A	119.6	C35—C36—H36A	119.6
C2—C3—C4	120.4 (4)	C31—C36—H36A	119.6
C2—C3—H3A	119.8	O—C37—Os2	175.2 (3)
C4—C3—H3A	119.8	B6—B1—B3	111.6 (3)
C5—C4—C3	119.7 (4)	B6—B1—B5	57.7 (3)
C5—C4—H4A	120.1	B3—B1—B5	103.5 (4)
C3—C4—H4A	120.1	B6—B1—B4	102.6 (4)
C4—C5—C6	120.1 (4)	B3—B1—B4	58.3 (3)
C4—C5—H5A	119.9	B5—B1—B4	54.3 (3)
C6—C5—H5A	120.0	B6—B1—Os2	66.5 (2)
C5—C6—C1	120.7 (4)	B3—B1—Os2	66.0 (2)
C5—C6—H6A	119.6	B5—B1—Os2	113.5 (3)
C1—C6—H6A	119.6	B4—B1—Os2	113.3 (3)
C12—C7—C8	119.0 (3)	B6—B1—H1	119 (3)
C12—C7—P1	122.6 (3)	B3—B1—H1	127 (3)
C8—C7—P1	118.4 (3)	B5—B1—H1	115 (3)
C7—C8—C9	119.8 (4)	B4—B1—H1	120 (3)
C7—C8—H8A	120.1	Os2—B1—H1	122 (3)
C9—C8—H8A	120.1	B4—B3—B1	61.4 (3)
C10—C9—C8	120.5 (4)	B4—B3—Os2	117.8 (3)
C10—C9—H9A	119.8	B1—B3—Os2	68.6 (2)
C8—C9—H9A	119.8	B4—B3—H23	111.2
C9—C10—C11	119.9 (4)	B1—B3—H23	102.0
C9—C10—H10A	120.0	Os2—B3—H23	47.1
C11—C10—H10A	120.0	B4—B3—H3	121 (2)
C10—C11—C12	120.2 (4)	B1—B3—H3	133 (2)
C10—C11—H11A	119.9	Os2—B3—H3	120 (2)
C12—C11—H11A	119.9	H23—B3—H3	116.9
C7—C12—C11	120.6 (4)	B4—B3—H34	45 (2)
C7—C12—H12A	119.7	B1—B3—H34	99 (2)
C11—C12—H12A	119.7	Os2—B3—H34	117 (3)
C14—C13—C18	119.1 (4)	H23—B3—H34	80.4
C14—C13—P1	119.8 (3)	H3—B3—H34	112 (3)
C18—C13—P1	120.4 (3)	B5—B4—B3	112.0 (3)
C13—C14—C15	121.2 (4)	B5—B4—B1	62.8 (3)
C13—C14—H14A	119.4	B3—B4—B1	60.2 (3)
C15—C14—H14A	119.4	B5—B4—H4	133 (3)
C16—C15—C14	118.7 (5)	B3—B4—H4	110 (3)
C16—C15—H15A	120.6	B1—B4—H4	127 (3)
C14—C15—H15A	120.6	B5—B4—H34	116 (3)
C17—C16—C15	120.8 (4)	B3—B4—H34	51 (3)
C17—C16—H16A	119.6	B1—B4—H34	103 (3)
C15—C16—H16A	119.6	H4—B4—H34	106 (4)
C16—C17—C18	120.5 (4)	B4—B5—B6	111.7 (3)
C16—C17—H17A	119.7	B4—B5—B1	62.9 (3)
C18—C17—H17A	119.7	B6—B5—B1	60.2 (3)
C17—C18—C13	119.6 (4)	B4—B5—H5	131 (3)
C17—C18—H18A	120.2	B6—B5—H5	112 (3)
C13—C18—H18A	120.2	B1—B5—H5	126 (3)
C20—C19—C24	119.1 (3)	B4—B5—H56	123 (2)
C20—C19—P2	118.3 (3)	B6—B5—H56	50 (2)
C24—C19—P2	122.5 (3)	B1—B5—H56	106 (2)
C19—C20—C21	120.8 (4)	H5—B5—H56	102 (3)
C19—C20—H20A	119.6	B5—B6—B1	62.0 (3)
C21—C20—H20A	119.6	B5—B6—Os2	118.5 (3)
C22—C21—C20	119.7 (4)	B1—B6—Os2	68.5 (2)
C22—C21—H21A	120.1	B5—B6—H6	126 (2)
C20—C21—H21A	120.1	B1—B6—H6	144 (2)
C23—C22—C21	119.9 (3)	Os2—B6—H6	116 (2)
C23—C22—H22A	120.0	B5—B6—H56	44 (2)
C21—C22—H22A	120.0	B1—B6—H56	102 (2)
C22—C23—C24	120.9 (4)	Os2—B6—H56	125.0 (19)
C22—C23—H23A	119.6	H6—B6—H56	103 (3)

(IV) [6-carbonyl-6,6-bis(triphenylphosphine)-nido-6-osmadecaborane(13)]

Crystal data

[(B9H13Os)(C18H15P)2(CO)]	F(000) = 1696
Mr = 853.14	Dx = 1.526 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.4617 (1) Å	Cell parameters from 8192 reflections
b = 15.6821 (1) Å	θ = 2–25°
c = 22.6315 (3) Å	µ = 3.55 mm^−1
β = 91.08 (1)°	T = 223 K
V = 3712.29 (7) Å^3	Irregular, orange
Z = 4	0.28 × 0.20 × 0.04 mm

Data collection

Bruker SMART Query CCD area-detector diffractometer	6483 independent reflections
Radiation source: normal-focus sealed tube	5001 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.01
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995)	h = −12→12
Tmin = 0.436, Tmax = 0.871	k = −18→18
74813 measured reflections	l = −26→26

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0197P)^2 + 26.7668P] where P = (Fo^2 + 2Fc^2)/3
6483 reflections	(Δ/σ)max = 0.002
491 parameters	Δρmax = 1.26 e Å^−3
36 restraints	Δρmin = −1.16 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 > 2σ(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)
Os6	0.11446 (3)	0.22460 (2)	0.13120 (2)	0.03850 (12)
P1	−0.0532 (2)	0.32366 (14)	0.14111 (11)	0.0399 (5)
P2	0.0107 (2)	0.09573 (14)	0.15819 (10)	0.0364 (5)
O1	0.2200 (8)	0.2474 (5)	0.2554 (4)	0.084 (3)
B1	0.3129 (12)	0.1735 (13)	0.0156 (6)	0.083 (5)
H1	0.348 (11)	0.105 (7)	−0.010 (5)	0.100*
B2	0.2998 (11)	0.1722 (8)	0.0920 (6)	0.053 (3)
H2	0.349 (9)	0.123 (6)	0.117 (4)	0.063*
B3	0.4027 (13)	0.2443 (9)	0.0580 (6)	0.071 (4)
H3	0.516 (10)	0.240 (6)	0.072 (4)	0.085*
B4	0.3619 (17)	0.2673 (14)	−0.0170 (7)	0.101 (5)
H4	0.454 (13)	0.246 (8)	−0.051 (6)	0.121*
B5	0.1630 (11)	0.1549 (8)	0.0442 (5)	0.050 (3)
H5	0.115 (9)	0.096 (6)	0.029 (4)	0.060*
H56	0.075 (8)	0.207 (6)	0.068 (4)	0.060*
B7	0.3100 (11)	0.2834 (9)	0.1105 (7)	0.068 (4)
H7	0.375 (10)	0.315 (6)	0.147 (4)	0.081*
H67	0.172 (10)	0.313 (6)	0.108 (4)	0.081*
B8	0.3455 (16)	0.3468 (10)	0.0398 (7)	0.092 (5)
H8	0.4170	0.4154	0.0452	0.111*
B9	0.2314 (16)	0.3380 (13)	−0.0178 (8)	0.114 (7)
H9	0.2026	0.3838	−0.0580	0.136*
B10	0.2055 (16)	0.2272 (13)	−0.0270 (7)	0.103 (6)
H10	0.159 (12)	0.228 (8)	−0.073 (6)	0.124*
C1	0.1748 (8)	0.2389 (6)	0.2087 (5)	0.054 (3)
C2	−0.0018 (9)	0.4309 (5)	0.1624 (4)	0.045 (2)
C3	0.1242 (8)	0.4531 (6)	0.1773 (4)	0.045 (2)
H3A	0.1879	0.4109	0.1783	0.054*
C4	0.1564 (9)	0.5373 (6)	0.1907 (4)	0.051 (2)
H4A	0.2416	0.5513	0.2006	0.061*
C5	0.0647 (10)	0.6001 (6)	0.1895 (5)	0.061 (3)
H5A	0.0868	0.6569	0.1979	0.074*
C6	−0.0609 (10)	0.5786 (7)	0.1755 (5)	0.070 (3)
H6A	−0.1244	0.6210	0.1756	0.085*
C7	−0.0935 (9)	0.4958 (6)	0.1616 (5)	0.062 (3)
H7A	−0.1788	0.4827	0.1513	0.075*
C8	−0.1305 (7)	0.3459 (5)	0.0696 (4)	0.042 (2)
C11	−0.2348 (11)	0.3868 (9)	−0.0419 (5)	0.087 (4)
H11A	−0.2682	0.3908	−0.0806	0.104*
C9	−0.0595 (19)	0.3687 (10)	0.0218 (7)	0.076 (7)	0.610 (10)
H9A	0.0298	0.3684	0.0271	0.091*	0.610 (10)
C10	−0.1054 (16)	0.3918 (12)	−0.0329 (10)	0.075 (7)	0.610 (10)
H10A	−0.0507	0.4103	−0.0627	0.090*	0.610 (10)
C12	−0.3158 (16)	0.3763 (16)	0.0032 (6)	0.091 (7)	0.610 (10)
H12	−0.4045	0.3836	−0.0018	0.109*	0.610 (10)
C13	−0.2609 (12)	0.3540 (11)	0.0570 (7)	0.060 (4)	0.610 (10)
H13	−0.3169	0.3434	0.0881	0.072*	0.610 (10)
C9'	−0.084 (3)	0.4160 (16)	0.0401 (13)	0.076 (7)	0.390 (10)
H9'	−0.0202	0.4512	0.0570	0.091*	0.390 (10)
C10'	−0.135 (2)	0.4319 (19)	−0.0159 (14)	0.075 (7)	0.390 (10)
H10'	−0.0994	0.4767	−0.0377	0.090*	0.390 (10)
C12'	−0.265 (3)	0.3130 (19)	−0.0079 (11)	0.091 (7)	0.390 (10)
H12'	−0.3271	0.2772	−0.0254	0.109*	0.390 (10)
C13'	−0.217 (2)	0.2848 (16)	0.0477 (9)	0.060 (4)	0.390 (10)
H13'	−0.2396	0.2338	0.0667	0.072*	0.390 (10)
C14	−0.1820 (8)	0.3111 (5)	0.1942 (4)	0.041 (2)
C15	−0.1684 (11)	0.3461 (7)	0.2490 (5)	0.067 (3)
H15A	−0.0950	0.3786	0.2578	0.080*
C16	−0.2602 (12)	0.3354 (7)	0.2926 (5)	0.075 (3)
H16A	−0.2475	0.3586	0.3306	0.090*
C17	−0.3685 (11)	0.2905 (6)	0.2788 (6)	0.069 (3)
H17A	−0.4327	0.2843	0.3070	0.083*
C18	−0.3843 (11)	0.2538 (7)	0.2234 (6)	0.072 (3)
H18A	−0.4588	0.2226	0.2143	0.086*
C19	−0.2920 (9)	0.2630 (7)	0.1820 (5)	0.061 (3)
H19A	−0.3025	0.2368	0.1448	0.074*
C20	0.0986 (8)	−0.0011 (5)	0.1381 (4)	0.041 (2)
C21	0.0474 (9)	−0.0656 (6)	0.1040 (4)	0.046 (2)
H21A	−0.0351	−0.0591	0.0875	0.055*
C22	0.1153 (10)	−0.1404 (6)	0.0936 (4)	0.057 (3)
H22A	0.0787	−0.1839	0.0702	0.069*
C23	0.2354 (11)	−0.1500 (7)	0.1174 (5)	0.064 (3)
H23A	0.2822	−0.2001	0.1104	0.077*
C24	0.2872 (10)	−0.0860 (7)	0.1516 (5)	0.062 (3)
H24A	0.3694	−0.0933	0.1684	0.075*
C25	0.2217 (9)	−0.0114 (6)	0.1621 (4)	0.048 (2)
H25A	0.2594	0.0321	0.1850	0.058*
C26	−0.0092 (8)	0.0785 (6)	0.2374 (4)	0.044 (2)
C27	−0.0404 (10)	0.1444 (7)	0.2746 (4)	0.062 (3)
H27A	−0.0472	0.1999	0.2591	0.074*
C28	−0.0619 (12)	0.1320 (8)	0.3336 (5)	0.076 (3)
H28A	−0.0849	0.1783	0.3575	0.091*
C29	−0.0499 (10)	0.0518 (8)	0.3580 (5)	0.064 (3)
H29A	−0.0606	0.0435	0.3988	0.077*
C30	−0.0224 (9)	−0.0150 (7)	0.3223 (4)	0.058 (3)
H30A	−0.0174	−0.0702	0.3384	0.069*
C31	−0.0014 (8)	−0.0035 (6)	0.2622 (4)	0.051 (2)
H31A	0.0179	−0.0506	0.2383	0.061*
C32	−0.1498 (8)	0.0770 (5)	0.1274 (4)	0.039 (2)
C33	−0.1737 (9)	0.0861 (8)	0.0683 (4)	0.066 (3)
H33A	−0.1072	0.1034	0.0437	0.079*
C34	−0.2943 (10)	0.0704 (8)	0.0435 (5)	0.078 (4)
H34A	−0.3076	0.0748	0.0024	0.093*
C35	−0.3935 (9)	0.0485 (6)	0.0793 (5)	0.057 (3)
H35A	−0.4761	0.0399	0.0633	0.068*
C36	−0.3704 (9)	0.0395 (7)	0.1377 (5)	0.063 (3)
H36A	−0.4378	0.0234	0.1622	0.075*
C37	−0.2497 (9)	0.0534 (6)	0.1630 (5)	0.053 (2)
H37A	−0.2363	0.0467	0.2039	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Os6	0.0303 (2)	0.0371 (2)	0.0479 (2)	0.0012 (2)	−0.0065 (1)	−0.0054 (2)
P1	0.0346 (12)	0.0330 (12)	0.0517 (14)	−0.0004 (10)	−0.0055 (10)	−0.0041 (11)
P2	0.0355 (12)	0.0365 (12)	0.0372 (13)	0.0040 (10)	0.0000 (10)	−0.0040 (10)
O1	0.099 (6)	0.081 (6)	0.072 (5)	0.020 (4)	−0.047 (5)	−0.023 (4)
B1	0.047 (7)	0.150 (15)	0.053 (8)	−0.025 (9)	0.011 (6)	0.012 (9)
B2	0.044 (6)	0.049 (7)	0.065 (8)	0.009 (6)	0.001 (6)	0.003 (6)
B3	0.063 (8)	0.073 (10)	0.077 (9)	0.008 (7)	−0.006 (7)	0.002 (7)
B4	0.087 (11)	0.140 (16)	0.076 (10)	−0.014 (12)	−0.013 (9)	−0.004 (11)
B5	0.043 (6)	0.053 (7)	0.055 (7)	−0.003 (5)	0.005 (5)	−0.010 (6)
B7	0.037 (6)	0.054 (7)	0.111 (11)	−0.006 (6)	−0.007 (7)	0.002 (8)
B8	0.106 (13)	0.082 (11)	0.088 (11)	−0.020 (9)	−0.012 (9)	0.039 (9)
B9	0.081 (11)	0.133 (16)	0.126 (15)	−0.024 (11)	−0.028 (10)	0.075 (13)
B10	0.098 (12)	0.136 (15)	0.076 (10)	−0.057 (12)	−0.019 (9)	0.051 (11)
C1	0.037 (5)	0.043 (5)	0.083 (8)	0.006 (4)	−0.007 (5)	0.001 (5)
C2	0.045 (5)	0.032 (5)	0.059 (6)	−0.002 (4)	−0.004 (4)	−0.002 (4)
C3	0.036 (5)	0.046 (5)	0.052 (6)	0.001 (4)	−0.009 (4)	−0.003 (4)
C4	0.044 (5)	0.044 (5)	0.065 (7)	−0.002 (4)	−0.010 (5)	−0.010 (5)
C5	0.058 (6)	0.040 (5)	0.085 (8)	−0.007 (5)	−0.010 (6)	−0.013 (5)
C6	0.052 (6)	0.052 (6)	0.108 (9)	0.009 (5)	−0.013 (6)	−0.029 (6)
C7	0.038 (5)	0.049 (6)	0.100 (9)	0.002 (5)	−0.015 (5)	−0.023 (6)
C8	0.031 (4)	0.045 (5)	0.051 (6)	0.000 (4)	0.002 (4)	−0.008 (4)
C11	0.077 (9)	0.138 (12)	0.044 (7)	0.008 (8)	−0.013 (6)	0.005 (7)
C9	0.060 (10)	0.083 (16)	0.084 (15)	−0.010 (12)	−0.030 (10)	0.044 (13)
C10	0.073 (12)	0.063 (16)	0.088 (15)	0.001 (10)	−0.004 (11)	0.036 (12)
C12	0.035 (10)	0.18 (2)	0.059 (10)	0.011 (10)	−0.013 (8)	0.002 (13)
C13	0.047 (8)	0.076 (11)	0.057 (9)	−0.002 (8)	0.001 (7)	0.020 (9)
C9'	0.060 (10)	0.083 (16)	0.084 (15)	−0.010 (12)	−0.030 (10)	0.044 (13)
C10'	0.073 (12)	0.063 (16)	0.088 (15)	0.001 (10)	−0.004 (11)	0.036 (12)
C12'	0.035 (10)	0.18 (2)	0.059 (10)	0.011 (10)	−0.013 (8)	0.002 (13)
C13'	0.047 (8)	0.076 (11)	0.057 (9)	−0.002 (8)	0.001 (7)	0.020 (9)
C14	0.039 (5)	0.030 (4)	0.053 (6)	0.004 (4)	0.003 (4)	0.003 (4)
C15	0.063 (7)	0.058 (7)	0.080 (8)	−0.015 (6)	0.020 (6)	−0.013 (6)
C16	0.104 (10)	0.043 (6)	0.079 (8)	−0.009 (7)	0.033 (7)	−0.013 (6)
C17	0.077 (8)	0.031 (6)	0.100 (10)	0.013 (5)	0.042 (7)	0.023 (6)
C18	0.055 (6)	0.073 (8)	0.088 (9)	−0.012 (6)	0.007 (6)	0.028 (7)
C19	0.056 (6)	0.059 (6)	0.068 (7)	−0.010 (5)	−0.005 (5)	0.015 (6)
C20	0.047 (5)	0.039 (5)	0.039 (5)	0.002 (4)	−0.005 (4)	0.005 (4)
C21	0.044 (5)	0.056 (6)	0.038 (5)	0.009 (5)	−0.002 (4)	−0.005 (4)
C22	0.066 (7)	0.052 (6)	0.054 (6)	0.004 (5)	0.002 (5)	−0.015 (5)
C23	0.069 (7)	0.060 (7)	0.063 (7)	0.019 (6)	0.019 (6)	0.003 (6)
C24	0.047 (6)	0.068 (7)	0.072 (7)	0.021 (5)	0.001 (5)	0.021 (6)
C25	0.051 (6)	0.046 (5)	0.049 (6)	−0.002 (5)	−0.006 (5)	0.003 (5)
C26	0.041 (5)	0.056 (6)	0.035 (5)	−0.002 (4)	−0.004 (4)	−0.004 (4)
C27	0.077 (7)	0.069 (7)	0.039 (6)	0.020 (6)	−0.002 (5)	−0.001 (5)
C28	0.093 (9)	0.091 (9)	0.043 (6)	0.021 (7)	0.008 (6)	−0.006 (6)
C29	0.061 (7)	0.090 (9)	0.041 (6)	0.005 (6)	0.009 (5)	0.007 (6)
C30	0.046 (6)	0.075 (7)	0.052 (6)	−0.010 (5)	0.003 (5)	0.015 (6)
C31	0.041 (5)	0.060 (6)	0.051 (6)	0.001 (5)	0.000 (4)	−0.008 (5)
C32	0.030 (4)	0.030 (4)	0.055 (6)	0.002 (4)	−0.004 (4)	−0.002 (4)
C33	0.037 (5)	0.115 (10)	0.045 (6)	−0.018 (6)	0.000 (5)	0.005 (6)
C34	0.051 (7)	0.120 (11)	0.062 (7)	−0.014 (7)	−0.020 (6)	0.007 (7)
C35	0.034 (5)	0.061 (6)	0.076 (8)	0.006 (5)	−0.002 (5)	−0.015 (6)
C36	0.042 (6)	0.067 (7)	0.079 (8)	−0.011 (5)	0.014 (6)	0.012 (6)
C37	0.049 (6)	0.053 (6)	0.058 (6)	−0.011 (5)	0.007 (5)	0.005 (5)

Geometric parameters (Å, º)

Os6—C1	1.866 (11)	C11—C10	1.367 (14)
Os6—B2	2.299 (11)	C11—C10'	1.382 (18)
Os6—B7	2.300 (12)	C11—C12'	1.428 (17)
Os6—B5	2.317 (11)	C11—H11A	0.9400
Os6—P1	2.357 (2)	C9—C10	1.367 (14)
Os6—P2	2.379 (2)	C9—H9A	0.9400
Os6—H56	1.51 (8)	C10—H10A	0.9400
Os6—H67	1.61 (10)	C12—C13	1.381 (13)
P1—C2	1.828 (9)	C12—H12	0.9400
P1—C8	1.829 (9)	C13—H13	0.9400
P1—C14	1.833 (9)	C9'—C10'	1.389 (18)
P2—C26	1.829 (9)	C9'—H9'	0.9400
P2—C32	1.830 (8)	C10'—H10'	0.9400
P2—C20	1.837 (9)	C12'—C13'	1.418 (17)
O1—C1	1.159 (12)	C12'—H12'	0.9400
B1—B10	1.69 (2)	C13'—H13'	0.9400
B1—B4	1.73 (2)	C14—C15	1.361 (13)
B1—B5	1.732 (16)	C14—C19	1.400 (13)
B1—B3	1.73 (2)	C15—C16	1.400 (14)
B1—B2	1.737 (18)	C15—H15A	0.9400
B1—H1	1.28 (11)	C16—C17	1.367 (16)
B2—B3	1.749 (19)	C16—H16A	0.9400
B2—B7	1.796 (17)	C17—C18	1.387 (16)
B2—B5	1.798 (16)	C17—H17A	0.9400
B2—H2	1.09 (9)	C18—C19	1.366 (14)
B3—B7	1.66 (2)	C18—H18A	0.9400
B3—B8	1.76 (2)	C19—H19A	0.9400
B3—B4	1.78 (2)	C20—C21	1.375 (12)
B3—H3	1.22 (11)	C20—C25	1.396 (12)
B4—B9	1.76 (3)	C21—C22	1.394 (13)
B4—B10	1.76 (2)	C21—H21A	0.9400
B4—B8	1.80 (3)	C22—C23	1.366 (14)
B4—H4	1.29 (13)	C22—H22A	0.9400
B5—B10	2.026 (19)	C23—C24	1.374 (15)
B5—H5	1.11 (9)	C23—H23A	0.9400
B5—H56	1.35 (9)	C24—C25	1.379 (13)
B7—B8	1.93 (2)	C24—H24A	0.9400
B7—H7	1.18 (10)	C25—H25A	0.9400
B7—H67	1.52 (10)	C26—C27	1.376 (13)
B8—B9	1.76 (2)	C26—C31	1.405 (13)
B8—H8	1.3151	C27—C28	1.372 (13)
B9—B10	1.77 (3)	C27—H27A	0.9400
B9—H9	1.1933	C28—C29	1.378 (15)
B10—H10	1.14 (13)	C28—H28A	0.9400
C2—C3	1.398 (12)	C29—C30	1.358 (14)
C2—C7	1.399 (12)	C29—H29A	0.9400
C3—C4	1.394 (12)	C30—C31	1.392 (13)
C3—H3A	0.9400	C30—H30A	0.9400
C4—C5	1.375 (13)	C31—H31A	0.9400
C4—H4A	0.9400	C32—C33	1.362 (12)
C5—C6	1.386 (13)	C32—C37	1.382 (12)
C5—H5A	0.9400	C33—C34	1.393 (13)
C6—C7	1.378 (13)	C33—H33A	0.9400
C6—H6A	0.9400	C34—C35	1.373 (14)
C7—H7A	0.9400	C34—H34A	0.9400
C8—C9	1.370 (14)	C35—C36	1.346 (14)
C8—C9'	1.381 (18)	C35—H35A	0.9400
C8—C13	1.395 (12)	C36—C37	1.393 (13)
C8—C13'	1.403 (17)	C36—H36A	0.9400
C11—C12	1.348 (13)	C37—H37A	0.9400
C1—Os6—B2	97.7 (4)	B1—B10—B4	60.0 (10)
C1—Os6—B7	81.8 (5)	B1—B10—B9	108.9 (12)
B2—Os6—B7	46.0 (4)	B4—B10—B9	59.7 (10)
C1—Os6—B5	141.3 (4)	B1—B10—B5	54.7 (7)
B2—Os6—B5	45.8 (4)	B4—B10—B5	108.4 (10)
B7—Os6—B5	78.8 (5)	B9—B10—B5	119.5 (12)
C1—Os6—P1	94.0 (3)	B1—B10—H10	142 (7)
B2—Os6—P1	155.1 (3)	B4—B10—H10	120 (7)
B7—Os6—P1	114.9 (3)	B9—B10—H10	99 (7)
B5—Os6—P1	124.5 (3)	B5—B10—H10	129 (7)
C1—Os6—P2	90.5 (3)	O1—C1—Os6	175.6 (9)
B2—Os6—P2	100.8 (3)	C3—C2—C7	117.7 (8)
B7—Os6—P2	143.6 (3)	C3—C2—P1	124.4 (7)
B5—Os6—P2	85.8 (3)	C7—C2—P1	117.8 (7)
P1—Os6—P2	101.04 (8)	C4—C3—C2	120.7 (8)
C1—Os6—H56	175 (3)	C4—C3—H3A	119.6
B2—Os6—H56	78 (3)	C2—C3—H3A	119.6
B7—Os6—H56	96 (3)	C5—C4—C3	120.5 (9)
B5—Os6—H56	34 (3)	C5—C4—H4A	119.8
P1—Os6—H56	91 (3)	C3—C4—H4A	119.8
P2—Os6—H56	88 (3)	C4—C5—C6	119.3 (9)
C1—Os6—H67	95 (3)	C4—C5—H5A	120.4
B2—Os6—H67	82 (4)	C6—C5—H5A	120.4
B7—Os6—H67	41 (4)	C7—C6—C5	120.7 (10)
B5—Os6—H67	92 (3)	C7—C6—H6A	119.6
P1—Os6—H67	75 (4)	C5—C6—H6A	119.6
P2—Os6—H67	174 (3)	C6—C7—C2	121.0 (9)
H56—Os6—H67	87 (5)	C6—C7—H7A	119.5
C2—P1—C8	100.5 (4)	C2—C7—H7A	119.5
C2—P1—C14	98.2 (4)	C9—C8—C9'	37.7 (12)
C8—P1—C14	106.4 (4)	C9—C8—C13	110.9 (13)
C2—P1—Os6	114.5 (3)	C9'—C8—C13	100.5 (14)
C8—P1—Os6	111.0 (3)	C9—C8—C13'	104.8 (13)
C14—P1—Os6	123.3 (3)	C9'—C8—C13'	127 (2)
C26—P2—C32	103.2 (4)	C13—C8—C13'	50.8 (12)
C26—P2—C20	100.8 (4)	C9—C8—P1	120.8 (10)
C32—P2—C20	103.5 (4)	C9'—C8—P1	115.1 (15)
C26—P2—Os6	116.0 (3)	C13—C8—P1	127.8 (9)
C32—P2—Os6	117.3 (3)	C13'—C8—P1	117.0 (11)
C20—P2—Os6	113.9 (3)	C12—C11—C10	121.9 (15)
B10—B1—B4	62.1 (10)	C12—C11—C10'	102.8 (18)
B10—B1—B5	72.6 (9)	C10—C11—C10'	33.9 (13)
B4—B1—B5	125.5 (13)	C12—C11—C12'	49.1 (15)
B10—B1—B3	110.1 (14)	C10—C11—C12'	101.3 (15)
B4—B1—B3	61.9 (9)	C10'—C11—C12'	111 (2)
B5—B1—B3	112.7 (11)	C12—C11—H11A	119.0
B10—B1—B2	120.6 (12)	C10—C11—H11A	119.0
B4—B1—B2	117.7 (13)	C10'—C11—H11A	128.9
B5—B1—B2	62.4 (7)	C12'—C11—H11A	118.3
B3—B1—B2	60.5 (8)	C10—C9—C8	126.7 (18)
B10—B1—H1	111 (5)	C10—C9—H9A	116.7
B4—B1—H1	116 (5)	C8—C9—H9A	116.7
B5—B1—H1	107 (5)	C11—C10—C9	116.7 (18)
B3—B1—H1	129 (5)	C11—C10—H10A	121.6
B2—B1—H1	118 (5)	C9—C10—H10A	121.6
B1—B2—B3	59.6 (8)	C11—C12—C13	116.2 (14)
B1—B2—B7	102.5 (10)	C11—C12—H12	121.9
B3—B2—B7	56.0 (7)	C13—C12—H12	121.9
B1—B2—B5	58.7 (7)	C12—C13—C8	126.3 (13)
B3—B2—B5	108.8 (9)	C12—C13—H13	116.8
B7—B2—B5	109.3 (8)	C8—C13—H13	116.8
B1—B2—Os6	117.6 (8)	C8—C9'—C10'	117 (3)
B3—B2—Os6	118.0 (7)	C8—C9'—H9'	121.7
B7—B2—Os6	67.0 (6)	C10'—C9'—H9'	121.7
B5—B2—Os6	67.6 (5)	C11—C10'—C9'	125 (3)
B1—B2—H2	119 (5)	C11—C10'—H10'	117.5
B3—B2—H2	114 (5)	C9'—C10'—H10'	117.5
B7—B2—H2	123 (5)	C13'—C12'—C11	131 (2)
B5—B2—H2	125 (5)	C13'—C12'—H12'	114.6
Os6—B2—H2	116 (5)	C11—C12'—H12'	114.6
B7—B3—B1	108.3 (10)	C8—C13'—C12'	108.4 (18)
B7—B3—B2	63.4 (8)	C8—C13'—H13'	125.8
B1—B3—B2	59.8 (8)	C12'—C13'—H13'	125.8
B7—B3—B8	68.4 (9)	C15—C14—C19	118.0 (9)
B1—B3—B8	106.1 (11)	C15—C14—P1	119.3 (7)
B2—B3—B8	118.9 (10)	C19—C14—P1	122.7 (8)
B7—B3—B4	118.3 (11)	C14—C15—C16	122.2 (10)
B1—B3—B4	58.9 (9)	C14—C15—H15A	118.9
B2—B3—B4	114.3 (11)	C16—C15—H15A	118.9
B8—B3—B4	61.2 (10)	C17—C16—C15	118.5 (11)
B7—B3—H3	114 (5)	C17—C16—H16A	120.8
B1—B3—H3	128 (5)	C15—C16—H16A	120.8
B2—B3—H3	117 (5)	C16—C17—C18	120.3 (10)
B8—B3—H3	116 (5)	C16—C17—H17A	119.8
B4—B3—H3	118 (5)	C18—C17—H17A	119.8
B1—B4—B9	107.7 (12)	C19—C18—C17	120.2 (11)
B1—B4—B10	57.9 (9)	C19—C18—H18A	119.9
B9—B4—B10	60.3 (11)	C17—C18—H18A	119.9
B1—B4—B3	59.2 (9)	C18—C19—C14	120.7 (11)
B9—B4—B3	108.0 (13)	C18—C19—H19A	119.7
B10—B4—B3	104.8 (12)	C14—C19—H19A	119.7
B1—B4—B8	104.5 (12)	C21—C20—C25	118.7 (8)
B9—B4—B8	59.1 (11)	C21—C20—P2	123.7 (7)
B10—B4—B8	103.7 (13)	C25—C20—P2	117.5 (7)
B3—B4—B8	58.9 (8)	C20—C21—C22	121.3 (9)
B1—B4—H4	105 (6)	C20—C21—H21A	119.3
B9—B4—H4	139 (6)	C22—C21—H21A	119.3
B10—B4—H4	122 (6)	C23—C22—C21	119.6 (10)
B3—B4—H4	110 (6)	C23—C22—H22A	120.2
B8—B4—H4	134 (6)	C21—C22—H22A	120.2
B1—B5—B2	58.9 (7)	C22—C23—C24	119.5 (10)
B1—B5—B10	52.8 (8)	C22—C23—H23A	120.3
B2—B5—B10	102.1 (8)	C24—C23—H23A	120.3
B1—B5—Os6	116.9 (8)	C23—C24—C25	121.7 (10)
B2—B5—Os6	66.6 (5)	C23—C24—H24A	119.2
B10—B5—Os6	117.8 (8)	C25—C24—H24A	119.2
B1—B5—H5	115 (5)	C24—C25—C20	119.3 (9)
B2—B5—H5	132 (5)	C24—C25—H25A	120.4
B10—B5—H5	109 (5)	C20—C25—H25A	120.4
Os6—B5—H5	124 (5)	C27—C26—C31	117.1 (9)
B1—B5—H56	133 (4)	C27—C26—P2	121.5 (8)
B2—B5—H56	102 (4)	C31—C26—P2	121.3 (7)
B10—B5—H56	98 (4)	C28—C27—C26	122.2 (10)
Os6—B5—H56	38 (4)	C28—C27—H27A	118.9
H5—B5—H56	109 (6)	C26—C27—H27A	118.9
B3—B7—B2	60.6 (8)	C27—C28—C29	120.3 (11)
B3—B7—B8	58.2 (9)	C27—C28—H28A	119.9
B2—B7—B8	108.6 (10)	C29—C28—H28A	119.9
B3—B7—Os6	122.0 (9)	C30—C29—C28	119.0 (10)
B2—B7—Os6	67.0 (5)	C30—C29—H29A	120.5
B8—B7—Os6	124.2 (8)	C28—C29—H29A	120.5
B3—B7—H7	109 (5)	C29—C30—C31	121.3 (10)
B2—B7—H7	128 (5)	C29—C30—H30A	119.3
B8—B7—H7	104 (5)	C31—C30—H30A	119.3
Os6—B7—H7	122 (5)	C30—C31—C26	120.0 (9)
B3—B7—H67	131 (4)	C30—C31—H31A	120.0
B2—B7—H67	104 (4)	C26—C31—H31A	120.0
B8—B7—H67	90 (4)	C33—C32—C37	118.2 (8)
Os6—B7—H67	44 (4)	C33—C32—P2	120.5 (7)
H7—B7—H67	116 (6)	C37—C32—P2	121.3 (7)
B9—B8—B3	108.9 (12)	C32—C33—C34	121.7 (10)
B9—B8—B4	59.2 (11)	C32—C33—H33A	119.1
B3—B8—B4	59.9 (10)	C34—C33—H33A	119.1
B9—B8—B7	115.9 (11)	C35—C34—C33	119.6 (10)
B3—B8—B7	53.5 (7)	C35—C34—H34A	120.2
B4—B8—B7	105.0 (11)	C33—C34—H34A	120.2
B9—B8—H8	120.7	C36—C35—C34	118.9 (9)
B3—B8—H8	122.3	C36—C35—H35A	120.6
B4—B8—H8	124.8	C34—C35—H35A	120.6
B7—B8—H8	117.6	C35—C36—C37	122.1 (10)
B8—B9—B4	61.7 (10)	C35—C36—H36A	119.0
B8—B9—B10	105.3 (11)	C37—C36—H36A	119.0
B4—B9—B10	60.0 (11)	C32—C37—C36	119.5 (9)
B8—B9—H9	132.5	C32—C37—H37A	120.3
B4—B9—H9	124.9	C36—C37—H37A	120.3
B10—B9—H9	117.8