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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].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101012689/iz1015sup1.cif
Contains datablocks I, IV, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101012689/iz1015Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101012689/iz1015IVsup3.hkl
Contains datablock IV

CCDC references: 175056; 175057

Comment top

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 top

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).

Experimental top

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.

Refinement top

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 top

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 top
[Figure 1] 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.
[Figure 2] 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)] top
Crystal data top
[(B5H9Os)(C18H15P)2(CO)]F(000) = 1600
Mr = 805.87Dx = 1.544 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 16.0054 (1) ÅCell parameters from 8192 reflections
b = 13.0200 (1) Åθ = 2–33°
c = 17.2445 (1) ŵ = 3.80 mm1
β = 105.29 (1)°T = 153 K
V = 3466.39 (4) Å3Irregular, colourless
Z = 40.25 × 0.20 × 0.08 mm
Data collection top
Bruker SMART Query CCD area-detector
diffractometer
9961 independent reflections
Radiation source: normal-focus sealed tube9460 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ϕ and ω scansθmax = 30.0°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements)
(SADABS; Blessing, 1995)
h = 2222
Tmin = 0.450, Tmax = 0.751k = 1818
31883 measured reflectionsl = 2424
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059 w = 1/[σ2(Fo2) + (0.0182P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
9961 reflectionsΔρmax = 2.20 e Å3
443 parametersΔρmin = 1.78 e Å3
2 restraintsAbsolute structure: Flack, 1983
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.002 (4)
Crystal data top
[(B5H9Os)(C18H15P)2(CO)]V = 3466.39 (4) Å3
Mr = 805.87Z = 4
Monoclinic, CcMo Kα radiation
a = 16.0054 (1) ŵ = 3.80 mm1
b = 13.0200 (1) ÅT = 153 K
c = 17.2445 (1) Å0.25 × 0.20 × 0.08 mm
β = 105.29 (1)°
Data collection top
Bruker SMART Query CCD area-detector
diffractometer
9961 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Blessing, 1995)
9460 reflections with I > 2σ(I)
Tmin = 0.450, Tmax = 0.751Rint = 0.041
31883 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059Δρmax = 2.20 e Å3
S = 1.03Δρmin = 1.78 e Å3
9961 reflectionsAbsolute structure: Flack, 1983
443 parametersAbsolute structure parameter: 0.002 (4)
2 restraints
Special details top

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 (Å2) top
xyzUiso*/Ueq
Os20.50112 (1)0.80164 (1)0.27089 (1)0.01393 (3)
H230.50440.80330.37000.017*
P10.60724 (6)0.67533 (9)0.26835 (7)0.01696 (19)
P20.59124 (5)0.94852 (7)0.28822 (5)0.01514 (15)
O0.44307 (19)0.7775 (3)0.09035 (17)0.0304 (6)
C10.5621 (2)0.5612 (3)0.2099 (2)0.0224 (7)
C20.4959 (3)0.5072 (3)0.2305 (3)0.0314 (9)
H2A0.47260.53240.27210.038*
C30.4640 (3)0.4182 (4)0.1915 (4)0.0474 (13)
H3A0.42020.38110.20740.057*
C40.4951 (3)0.3820 (4)0.1290 (4)0.0539 (16)
H4A0.47180.32120.10120.065*
C50.5601 (3)0.4345 (4)0.1072 (3)0.0466 (13)
H5A0.58240.40910.06500.056*
C60.5927 (3)0.5240 (4)0.1465 (3)0.0325 (9)
H6A0.63660.56070.13020.039*
C70.6679 (2)0.6194 (3)0.3641 (2)0.0207 (7)
C80.7004 (2)0.6852 (3)0.4292 (2)0.0229 (7)
H8A0.69100.75720.42310.028*
C90.7467 (2)0.6448 (3)0.5033 (2)0.0252 (8)
H9A0.76850.68950.54750.030*
C100.7609 (2)0.5405 (3)0.5125 (2)0.0292 (8)
H10A0.79210.51350.56310.035*
C110.7299 (3)0.4753 (3)0.4482 (3)0.0345 (9)
H11A0.73980.40350.45450.041*
C120.6840 (3)0.5146 (3)0.3740 (2)0.0302 (8)
H12A0.66350.46940.32980.036*
C130.6914 (2)0.7085 (3)0.2180 (2)0.0217 (7)
C140.6701 (3)0.7659 (4)0.1479 (2)0.0286 (8)
H14A0.61540.79910.13210.034*
C150.7276 (3)0.7760 (4)0.1001 (3)0.0348 (10)
H15A0.71210.81460.05170.042*
C160.8081 (3)0.7284 (4)0.1246 (3)0.0423 (12)
H16A0.84720.73290.09180.051*
C170.8318 (3)0.6752 (4)0.1957 (3)0.0384 (11)
H17A0.88800.64590.21280.046*
C180.7740 (2)0.6637 (4)0.2429 (3)0.0292 (8)
H18A0.79030.62580.29170.035*
C190.7028 (2)0.9426 (3)0.3524 (2)0.0185 (6)
C200.7169 (2)0.9623 (3)0.4342 (2)0.0231 (7)
H20A0.66950.98120.45480.028*
C210.7997 (3)0.9548 (3)0.4863 (3)0.0292 (8)
H21A0.80850.96770.54210.035*
C220.8688 (3)0.9286 (3)0.4565 (3)0.0333 (9)
H22A0.92550.92460.49160.040*
C230.8555 (2)0.9082 (4)0.3756 (3)0.0309 (9)
H23A0.90330.89030.35530.037*
C240.7727 (2)0.9134 (3)0.3231 (2)0.0224 (7)
H24A0.76390.89720.26780.027*
C250.5962 (2)1.0180 (3)0.1969 (2)0.0181 (6)
C260.6693 (2)1.0726 (3)0.1903 (2)0.0235 (7)
H26A0.72201.06700.23130.028*
C270.6651 (3)1.1347 (3)0.1242 (2)0.0289 (8)
H27A0.71521.17080.11980.035*
C280.5889 (3)1.1444 (3)0.0650 (2)0.0277 (8)
H28A0.58641.18730.01980.033*
C290.5152 (3)1.0913 (3)0.0712 (2)0.0248 (7)
H29A0.46231.09800.03040.030*
C300.5194 (3)1.0288 (4)0.1370 (3)0.0215 (9)
H30A0.46920.99280.14120.026*
C310.5505 (2)1.0522 (3)0.3407 (2)0.0184 (6)
C320.4913 (3)1.0363 (4)0.3863 (3)0.0223 (9)
H32A0.46600.97050.38710.027*
C330.4691 (3)1.1159 (4)0.4304 (3)0.0301 (9)
H33A0.42851.10410.46100.036*
C340.5054 (3)1.2125 (3)0.4305 (3)0.0317 (9)
H34A0.49061.26620.46170.038*
C350.5632 (3)1.2305 (3)0.3848 (3)0.0342 (9)
H35A0.58741.29690.38390.041*
C360.5858 (3)1.1510 (3)0.3401 (3)0.0298 (8)
H36A0.62551.16380.30880.036*
C370.4674 (2)0.7903 (3)0.1589 (2)0.0192 (7)
B10.3802 (3)0.7122 (4)0.2865 (3)0.0242 (10)
B30.4699 (3)0.7120 (3)0.3741 (3)0.0223 (8)
B40.3650 (3)0.7230 (4)0.3865 (3)0.0288 (10)
B50.3015 (3)0.7933 (4)0.3151 (3)0.0282 (10)
B60.3559 (3)0.8382 (4)0.2475 (3)0.0239 (8)
H10.354 (3)0.649 (4)0.251 (3)0.028 (12)*
H30.516 (3)0.649 (4)0.406 (3)0.024 (11)*
H40.352 (4)0.660 (5)0.425 (3)0.045 (15)*
H50.232 (4)0.791 (4)0.289 (4)0.042 (16)*
H60.327 (3)0.883 (3)0.192 (2)0.017 (10)*
H340.434 (4)0.765 (5)0.426 (3)0.043 (14)*
H560.319 (3)0.880 (4)0.301 (3)0.027 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Os20.01132 (4)0.01635 (5)0.01419 (5)0.00172 (8)0.00348 (3)0.00039 (8)
P10.0150 (4)0.0181 (5)0.0178 (5)0.0003 (4)0.0044 (3)0.0024 (4)
P20.0123 (3)0.0178 (4)0.0153 (4)0.0014 (3)0.0035 (3)0.0009 (3)
O0.0271 (14)0.0445 (19)0.0183 (13)0.0012 (12)0.0039 (11)0.0027 (12)
C10.0187 (15)0.0193 (18)0.0291 (19)0.0027 (13)0.0061 (14)0.0061 (14)
C20.035 (2)0.023 (2)0.042 (2)0.0080 (16)0.0205 (18)0.0140 (17)
C30.044 (3)0.037 (3)0.071 (4)0.021 (2)0.031 (2)0.024 (2)
C40.044 (3)0.047 (3)0.081 (4)0.023 (2)0.033 (3)0.043 (3)
C50.040 (2)0.050 (3)0.058 (3)0.014 (2)0.027 (2)0.031 (2)
C60.0274 (18)0.038 (2)0.035 (2)0.0095 (17)0.0139 (17)0.0175 (18)
C70.0194 (15)0.0197 (17)0.0233 (17)0.0026 (13)0.0059 (13)0.0006 (13)
C80.0225 (16)0.0220 (19)0.0237 (18)0.0031 (13)0.0049 (14)0.0005 (14)
C90.0198 (16)0.033 (2)0.0202 (17)0.0023 (15)0.0003 (13)0.0030 (14)
C100.0245 (18)0.039 (2)0.0209 (18)0.0078 (16)0.0012 (15)0.0064 (16)
C110.041 (2)0.024 (2)0.035 (2)0.0097 (18)0.0034 (19)0.0029 (17)
C120.036 (2)0.023 (2)0.028 (2)0.0046 (16)0.0026 (16)0.0025 (15)
C130.0152 (14)0.026 (2)0.0250 (18)0.0055 (13)0.0079 (14)0.0098 (14)
C140.0218 (17)0.039 (2)0.027 (2)0.0070 (17)0.0087 (15)0.0032 (17)
C150.031 (2)0.046 (3)0.031 (2)0.0153 (19)0.0138 (18)0.0057 (19)
C160.030 (2)0.054 (3)0.051 (3)0.018 (2)0.026 (2)0.022 (2)
C170.0198 (18)0.042 (3)0.057 (3)0.0033 (17)0.0164 (19)0.013 (2)
C180.0182 (16)0.030 (2)0.040 (2)0.0004 (15)0.0090 (16)0.0068 (18)
C190.0151 (14)0.0187 (17)0.0205 (16)0.0042 (12)0.0026 (12)0.0021 (13)
C200.0225 (16)0.0245 (19)0.0199 (17)0.0008 (14)0.0014 (14)0.0004 (14)
C210.0272 (18)0.028 (2)0.027 (2)0.0000 (15)0.0025 (16)0.0016 (16)
C220.0205 (17)0.034 (2)0.037 (2)0.0029 (16)0.0076 (16)0.0014 (17)
C230.0160 (15)0.033 (2)0.041 (2)0.0020 (15)0.0031 (15)0.0020 (18)
C240.0170 (14)0.0235 (18)0.0258 (18)0.0003 (13)0.0043 (13)0.0008 (14)
C250.0180 (14)0.0199 (17)0.0170 (15)0.0011 (12)0.0058 (12)0.0001 (12)
C260.0181 (15)0.029 (2)0.0236 (18)0.0046 (14)0.0063 (13)0.0017 (14)
C270.0276 (18)0.029 (2)0.032 (2)0.0061 (15)0.0117 (16)0.0076 (16)
C280.037 (2)0.026 (2)0.0214 (18)0.0004 (16)0.0105 (16)0.0063 (15)
C290.0261 (17)0.024 (2)0.0204 (18)0.0016 (15)0.0002 (15)0.0035 (15)
C300.0203 (18)0.022 (2)0.022 (2)0.0002 (14)0.0051 (15)0.0022 (16)
C310.0157 (14)0.0229 (18)0.0160 (15)0.0009 (12)0.0031 (12)0.0004 (12)
C320.0228 (18)0.023 (2)0.023 (2)0.0003 (15)0.0105 (16)0.0032 (16)
C330.0285 (19)0.036 (2)0.028 (2)0.0034 (17)0.0124 (17)0.0027 (18)
C340.044 (2)0.025 (2)0.028 (2)0.0122 (17)0.0128 (19)0.0016 (16)
C350.049 (3)0.0166 (18)0.041 (2)0.0042 (18)0.019 (2)0.0027 (17)
C360.036 (2)0.022 (2)0.036 (2)0.0036 (16)0.0181 (18)0.0026 (16)
C370.0118 (13)0.0217 (18)0.0233 (18)0.0015 (12)0.0033 (13)0.0018 (13)
B10.022 (2)0.024 (2)0.027 (2)0.0070 (18)0.0063 (18)0.0030 (19)
B30.0239 (18)0.021 (2)0.024 (2)0.0028 (15)0.0106 (16)0.0045 (15)
B40.026 (2)0.030 (2)0.036 (3)0.0044 (18)0.018 (2)0.0029 (19)
B50.0177 (18)0.030 (2)0.041 (3)0.0028 (16)0.0149 (18)0.0043 (19)
B60.0171 (17)0.030 (2)0.025 (2)0.0003 (16)0.0052 (15)0.0029 (17)
Geometric parameters (Å, º) top
Os2—C371.869 (4)C20—C211.394 (5)
Os2—B32.291 (4)C20—H20A0.9500
Os2—B62.301 (4)C21—C221.381 (6)
Os2—B12.335 (5)C21—H21A0.9500
Os2—P22.3664 (9)C22—C231.381 (6)
Os2—P12.3729 (11)C22—H22A0.9500
Os2—H231.6961C23—C241.395 (5)
P1—C71.831 (4)C23—H23A0.9500
P1—C11.833 (4)C24—H24A0.9500
P1—C131.836 (4)C25—C301.388 (6)
P2—C251.835 (3)C25—C261.399 (5)
P2—C191.838 (3)C26—C271.384 (5)
P2—C311.838 (4)C26—H26A0.9500
O—C371.155 (5)C27—C281.375 (6)
C1—C21.393 (5)C27—H27A0.9500
C1—C61.399 (5)C28—C291.396 (6)
C2—C31.369 (6)C28—H28A0.9500
C2—H2A0.9500C29—C301.383 (6)
C3—C41.384 (7)C29—H29A0.9500
C3—H3A0.9500C30—H30A0.9500
C4—C51.376 (7)C31—C321.398 (5)
C4—H4A0.9500C31—C361.406 (5)
C5—C61.379 (6)C32—C331.386 (6)
C5—H5A0.9500C32—H32A0.9500
C6—H6A0.9500C33—C341.385 (6)
C7—C121.391 (6)C33—H33A0.9500
C7—C81.399 (5)C34—C351.384 (6)
C8—C91.400 (6)C34—H34A0.9500
C8—H8A0.9500C35—C361.393 (6)
C9—C101.379 (6)C35—H35A0.9500
C9—H9A0.9500C36—H36A0.9500
C10—C111.381 (6)B1—B61.777 (7)
C10—H10A0.9500B1—B31.788 (7)
C11—C121.394 (6)B1—B51.808 (7)
C11—H11A0.9500B1—B41.809 (8)
C12—H12A0.9500B1—H11.04 (5)
C13—C141.386 (6)B3—B41.753 (6)
C13—C181.404 (5)B3—H231.3202
C14—C151.394 (6)B3—H31.15 (5)
C14—H14A0.9500B3—H341.37 (6)
C15—C161.391 (7)B4—B51.652 (8)
C15—H15A0.9500B4—H41.10 (6)
C16—C171.371 (8)B4—H341.25 (6)
C16—H16A0.9500B5—B61.730 (6)
C17—C181.392 (6)B5—H51.09 (6)
C17—H17A0.9500B5—H561.20 (5)
C18—H18A0.9500B6—H61.11 (4)
C19—C201.392 (5)B6—H561.33 (4)
C19—C241.396 (5)
C37—Os2—B3134.42 (15)C24—C23—H23A119.6
C37—Os2—B680.32 (15)C23—C24—C19119.6 (4)
B3—Os2—B679.87 (16)C23—C24—H24A120.2
C37—Os2—B193.31 (17)C19—C24—H24A120.2
B3—Os2—B145.46 (18)C30—C25—C26118.8 (3)
B6—Os2—B145.07 (19)C30—C25—P2117.3 (3)
C37—Os2—P2101.22 (11)C26—C25—P2123.1 (3)
B3—Os2—P2124.35 (12)C27—C26—C25120.3 (3)
B6—Os2—P2114.12 (13)C27—C26—H26A119.9
B1—Os2—P2152.23 (15)C25—C26—H26A119.9
C37—Os2—P186.53 (11)C28—C27—C26120.4 (3)
B3—Os2—P188.02 (11)C28—C27—H27A119.8
B6—Os2—P1146.59 (13)C26—C27—H27A119.8
B1—Os2—P1106.00 (16)C27—C28—C29120.0 (3)
P2—Os2—P198.46 (3)C27—C28—H28A120.0
C37—Os2—H23165.0C29—C28—H28A120.0
B3—Os2—H2334.8C30—C29—C28119.6 (4)
B6—Os2—H2386.3C30—C29—H29A120.2
B1—Os2—H2372.3C28—C29—H29A120.2
P2—Os2—H2390.4C29—C30—C25120.9 (4)
P1—Os2—H23101.3C29—C30—H30A119.6
C7—P1—C1102.19 (18)C25—C30—H30A119.6
C7—P1—C13103.80 (17)C32—C31—C36118.3 (4)
C1—P1—C1399.39 (17)C32—C31—P2123.3 (3)
C7—P1—Os2118.11 (12)C36—C31—P2118.2 (3)
C1—P1—Os2113.06 (12)C33—C32—C31120.5 (4)
C13—P1—Os2117.63 (14)C33—C32—H32A119.7
C25—P2—C19106.43 (15)C31—C32—H32A119.7
C25—P2—C3199.31 (16)C34—C33—C32120.7 (4)
C19—P2—C3198.54 (16)C34—C33—H33A119.6
C25—P2—Os2116.90 (11)C32—C33—H33A119.6
C19—P2—Os2120.33 (12)C35—C34—C33119.8 (4)
C31—P2—Os2111.87 (11)C35—C34—H34A120.1
C2—C1—C6118.1 (3)C33—C34—H34A120.1
C2—C1—P1119.1 (3)C34—C35—C36120.0 (4)
C6—C1—P1122.8 (3)C34—C35—H35A120.0
C3—C2—C1120.8 (4)C36—C35—H35A120.0
C3—C2—H2A119.6C35—C36—C31120.7 (4)
C1—C2—H2A119.6C35—C36—H36A119.6
C2—C3—C4120.4 (4)C31—C36—H36A119.6
C2—C3—H3A119.8O—C37—Os2175.2 (3)
C4—C3—H3A119.8B6—B1—B3111.6 (3)
C5—C4—C3119.7 (4)B6—B1—B557.7 (3)
C5—C4—H4A120.1B3—B1—B5103.5 (4)
C3—C4—H4A120.1B6—B1—B4102.6 (4)
C4—C5—C6120.1 (4)B3—B1—B458.3 (3)
C4—C5—H5A119.9B5—B1—B454.3 (3)
C6—C5—H5A120.0B6—B1—Os266.5 (2)
C5—C6—C1120.7 (4)B3—B1—Os266.0 (2)
C5—C6—H6A119.6B5—B1—Os2113.5 (3)
C1—C6—H6A119.6B4—B1—Os2113.3 (3)
C12—C7—C8119.0 (3)B6—B1—H1119 (3)
C12—C7—P1122.6 (3)B3—B1—H1127 (3)
C8—C7—P1118.4 (3)B5—B1—H1115 (3)
C7—C8—C9119.8 (4)B4—B1—H1120 (3)
C7—C8—H8A120.1Os2—B1—H1122 (3)
C9—C8—H8A120.1B4—B3—B161.4 (3)
C10—C9—C8120.5 (4)B4—B3—Os2117.8 (3)
C10—C9—H9A119.8B1—B3—Os268.6 (2)
C8—C9—H9A119.8B4—B3—H23111.2
C9—C10—C11119.9 (4)B1—B3—H23102.0
C9—C10—H10A120.0Os2—B3—H2347.1
C11—C10—H10A120.0B4—B3—H3121 (2)
C10—C11—C12120.2 (4)B1—B3—H3133 (2)
C10—C11—H11A119.9Os2—B3—H3120 (2)
C12—C11—H11A119.9H23—B3—H3116.9
C7—C12—C11120.6 (4)B4—B3—H3445 (2)
C7—C12—H12A119.7B1—B3—H3499 (2)
C11—C12—H12A119.7Os2—B3—H34117 (3)
C14—C13—C18119.1 (4)H23—B3—H3480.4
C14—C13—P1119.8 (3)H3—B3—H34112 (3)
C18—C13—P1120.4 (3)B5—B4—B3112.0 (3)
C13—C14—C15121.2 (4)B5—B4—B162.8 (3)
C13—C14—H14A119.4B3—B4—B160.2 (3)
C15—C14—H14A119.4B5—B4—H4133 (3)
C16—C15—C14118.7 (5)B3—B4—H4110 (3)
C16—C15—H15A120.6B1—B4—H4127 (3)
C14—C15—H15A120.6B5—B4—H34116 (3)
C17—C16—C15120.8 (4)B3—B4—H3451 (3)
C17—C16—H16A119.6B1—B4—H34103 (3)
C15—C16—H16A119.6H4—B4—H34106 (4)
C16—C17—C18120.5 (4)B4—B5—B6111.7 (3)
C16—C17—H17A119.7B4—B5—B162.9 (3)
C18—C17—H17A119.7B6—B5—B160.2 (3)
C17—C18—C13119.6 (4)B4—B5—H5131 (3)
C17—C18—H18A120.2B6—B5—H5112 (3)
C13—C18—H18A120.2B1—B5—H5126 (3)
C20—C19—C24119.1 (3)B4—B5—H56123 (2)
C20—C19—P2118.3 (3)B6—B5—H5650 (2)
C24—C19—P2122.5 (3)B1—B5—H56106 (2)
C19—C20—C21120.8 (4)H5—B5—H56102 (3)
C19—C20—H20A119.6B5—B6—B162.0 (3)
C21—C20—H20A119.6B5—B6—Os2118.5 (3)
C22—C21—C20119.7 (4)B1—B6—Os268.5 (2)
C22—C21—H21A120.1B5—B6—H6126 (2)
C20—C21—H21A120.1B1—B6—H6144 (2)
C23—C22—C21119.9 (3)Os2—B6—H6116 (2)
C23—C22—H22A120.0B5—B6—H5644 (2)
C21—C22—H22A120.0B1—B6—H56102 (2)
C22—C23—C24120.9 (4)Os2—B6—H56125.0 (19)
C22—C23—H23A119.6H6—B6—H56103 (3)
(IV) [6-carbonyl-6,6-bis(triphenylphosphine)-nido-6-osmadecaborane(13)] top
Crystal data top
[(B9H13Os)(C18H15P)2(CO)]F(000) = 1696
Mr = 853.14Dx = 1.526 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.4617 (1) ÅCell parameters from 8192 reflections
b = 15.6821 (1) Åθ = 2–25°
c = 22.6315 (3) ŵ = 3.55 mm1
β = 91.08 (1)°T = 223 K
V = 3712.29 (7) Å3Irregular, orange
Z = 40.28 × 0.20 × 0.04 mm
Data collection top
Bruker SMART Query CCD area-detector
diffractometer
6483 independent reflections
Radiation source: normal-focus sealed tube5001 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.01
ϕ and ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements)
(SADABS; Blessing, 1995)
h = 1212
Tmin = 0.436, Tmax = 0.871k = 1818
74813 measured reflectionsl = 2626
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.18 w = 1/[σ2(Fo2) + (0.0197P)2 + 26.7668P]
where P = (Fo2 + 2Fc2)/3
6483 reflections(Δ/σ)max = 0.002
491 parametersΔρmax = 1.26 e Å3
36 restraintsΔρmin = 1.16 e Å3
Crystal data top
[(B9H13Os)(C18H15P)2(CO)]V = 3712.29 (7) Å3
Mr = 853.14Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.4617 (1) ŵ = 3.55 mm1
b = 15.6821 (1) ÅT = 223 K
c = 22.6315 (3) Å0.28 × 0.20 × 0.04 mm
β = 91.08 (1)°
Data collection top
Bruker SMART Query CCD area-detector
diffractometer
6483 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Blessing, 1995)
5001 reflections with I > 2σ(I)
Tmin = 0.436, Tmax = 0.871Rint = 0.01
74813 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05736 restraints
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.18 w = 1/[σ2(Fo2) + (0.0197P)2 + 26.7668P]
where P = (Fo2 + 2Fc2)/3
6483 reflectionsΔρmax = 1.26 e Å3
491 parametersΔρmin = 1.16 e Å3
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Os60.11446 (3)0.22460 (2)0.13120 (2)0.03850 (12)
P10.0532 (2)0.32366 (14)0.14111 (11)0.0399 (5)
P20.0107 (2)0.09573 (14)0.15819 (10)0.0364 (5)
O10.2200 (8)0.2474 (5)0.2554 (4)0.084 (3)
B10.3129 (12)0.1735 (13)0.0156 (6)0.083 (5)
H10.348 (11)0.105 (7)0.010 (5)0.100*
B20.2998 (11)0.1722 (8)0.0920 (6)0.053 (3)
H20.349 (9)0.123 (6)0.117 (4)0.063*
B30.4027 (13)0.2443 (9)0.0580 (6)0.071 (4)
H30.516 (10)0.240 (6)0.072 (4)0.085*
B40.3619 (17)0.2673 (14)0.0170 (7)0.101 (5)
H40.454 (13)0.246 (8)0.051 (6)0.121*
B50.1630 (11)0.1549 (8)0.0442 (5)0.050 (3)
H50.115 (9)0.096 (6)0.029 (4)0.060*
H560.075 (8)0.207 (6)0.068 (4)0.060*
B70.3100 (11)0.2834 (9)0.1105 (7)0.068 (4)
H70.375 (10)0.315 (6)0.147 (4)0.081*
H670.172 (10)0.313 (6)0.108 (4)0.081*
B80.3455 (16)0.3468 (10)0.0398 (7)0.092 (5)
H80.41700.41540.04520.111*
B90.2314 (16)0.3380 (13)0.0178 (8)0.114 (7)
H90.20260.38380.05800.136*
B100.2055 (16)0.2272 (13)0.0270 (7)0.103 (6)
H100.159 (12)0.228 (8)0.073 (6)0.124*
C10.1748 (8)0.2389 (6)0.2087 (5)0.054 (3)
C20.0018 (9)0.4309 (5)0.1624 (4)0.045 (2)
C30.1242 (8)0.4531 (6)0.1773 (4)0.045 (2)
H3A0.18790.41090.17830.054*
C40.1564 (9)0.5373 (6)0.1907 (4)0.051 (2)
H4A0.24160.55130.20060.061*
C50.0647 (10)0.6001 (6)0.1895 (5)0.061 (3)
H5A0.08680.65690.19790.074*
C60.0609 (10)0.5786 (7)0.1755 (5)0.070 (3)
H6A0.12440.62100.17560.085*
C70.0935 (9)0.4958 (6)0.1616 (5)0.062 (3)
H7A0.17880.48270.15130.075*
C80.1305 (7)0.3459 (5)0.0696 (4)0.042 (2)
C110.2348 (11)0.3868 (9)0.0419 (5)0.087 (4)
H11A0.26820.39080.08060.104*
C90.0595 (19)0.3687 (10)0.0218 (7)0.076 (7)0.610 (10)
H9A0.02980.36840.02710.091*0.610 (10)
C100.1054 (16)0.3918 (12)0.0329 (10)0.075 (7)0.610 (10)
H10A0.05070.41030.06270.090*0.610 (10)
C120.3158 (16)0.3763 (16)0.0032 (6)0.091 (7)0.610 (10)
H120.40450.38360.00180.109*0.610 (10)
C130.2609 (12)0.3540 (11)0.0570 (7)0.060 (4)0.610 (10)
H130.31690.34340.08810.072*0.610 (10)
C9'0.084 (3)0.4160 (16)0.0401 (13)0.076 (7)0.390 (10)
H9'0.02020.45120.05700.091*0.390 (10)
C10'0.135 (2)0.4319 (19)0.0159 (14)0.075 (7)0.390 (10)
H10'0.09940.47670.03770.090*0.390 (10)
C12'0.265 (3)0.3130 (19)0.0079 (11)0.091 (7)0.390 (10)
H12'0.32710.27720.02540.109*0.390 (10)
C13'0.217 (2)0.2848 (16)0.0477 (9)0.060 (4)0.390 (10)
H13'0.23960.23380.06670.072*0.390 (10)
C140.1820 (8)0.3111 (5)0.1942 (4)0.041 (2)
C150.1684 (11)0.3461 (7)0.2490 (5)0.067 (3)
H15A0.09500.37860.25780.080*
C160.2602 (12)0.3354 (7)0.2926 (5)0.075 (3)
H16A0.24750.35860.33060.090*
C170.3685 (11)0.2905 (6)0.2788 (6)0.069 (3)
H17A0.43270.28430.30700.083*
C180.3843 (11)0.2538 (7)0.2234 (6)0.072 (3)
H18A0.45880.22260.21430.086*
C190.2920 (9)0.2630 (7)0.1820 (5)0.061 (3)
H19A0.30250.23680.14480.074*
C200.0986 (8)0.0011 (5)0.1381 (4)0.041 (2)
C210.0474 (9)0.0656 (6)0.1040 (4)0.046 (2)
H21A0.03510.05910.08750.055*
C220.1153 (10)0.1404 (6)0.0936 (4)0.057 (3)
H22A0.07870.18390.07020.069*
C230.2354 (11)0.1500 (7)0.1174 (5)0.064 (3)
H23A0.28220.20010.11040.077*
C240.2872 (10)0.0860 (7)0.1516 (5)0.062 (3)
H24A0.36940.09330.16840.075*
C250.2217 (9)0.0114 (6)0.1621 (4)0.048 (2)
H25A0.25940.03210.18500.058*
C260.0092 (8)0.0785 (6)0.2374 (4)0.044 (2)
C270.0404 (10)0.1444 (7)0.2746 (4)0.062 (3)
H27A0.04720.19990.25910.074*
C280.0619 (12)0.1320 (8)0.3336 (5)0.076 (3)
H28A0.08490.17830.35750.091*
C290.0499 (10)0.0518 (8)0.3580 (5)0.064 (3)
H29A0.06060.04350.39880.077*
C300.0224 (9)0.0150 (7)0.3223 (4)0.058 (3)
H30A0.01740.07020.33840.069*
C310.0014 (8)0.0035 (6)0.2622 (4)0.051 (2)
H31A0.01790.05060.23830.061*
C320.1498 (8)0.0770 (5)0.1274 (4)0.039 (2)
C330.1737 (9)0.0861 (8)0.0683 (4)0.066 (3)
H33A0.10720.10340.04370.079*
C340.2943 (10)0.0704 (8)0.0435 (5)0.078 (4)
H34A0.30760.07480.00240.093*
C350.3935 (9)0.0485 (6)0.0793 (5)0.057 (3)
H35A0.47610.03990.06330.068*
C360.3704 (9)0.0395 (7)0.1377 (5)0.063 (3)
H36A0.43780.02340.16220.075*
C370.2497 (9)0.0534 (6)0.1630 (5)0.053 (2)
H37A0.23630.04670.20390.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Os60.0303 (2)0.0371 (2)0.0479 (2)0.0012 (2)0.0065 (1)0.0054 (2)
P10.0346 (12)0.0330 (12)0.0517 (14)0.0004 (10)0.0055 (10)0.0041 (11)
P20.0355 (12)0.0365 (12)0.0372 (13)0.0040 (10)0.0000 (10)0.0040 (10)
O10.099 (6)0.081 (6)0.072 (5)0.020 (4)0.047 (5)0.023 (4)
B10.047 (7)0.150 (15)0.053 (8)0.025 (9)0.011 (6)0.012 (9)
B20.044 (6)0.049 (7)0.065 (8)0.009 (6)0.001 (6)0.003 (6)
B30.063 (8)0.073 (10)0.077 (9)0.008 (7)0.006 (7)0.002 (7)
B40.087 (11)0.140 (16)0.076 (10)0.014 (12)0.013 (9)0.004 (11)
B50.043 (6)0.053 (7)0.055 (7)0.003 (5)0.005 (5)0.010 (6)
B70.037 (6)0.054 (7)0.111 (11)0.006 (6)0.007 (7)0.002 (8)
B80.106 (13)0.082 (11)0.088 (11)0.020 (9)0.012 (9)0.039 (9)
B90.081 (11)0.133 (16)0.126 (15)0.024 (11)0.028 (10)0.075 (13)
B100.098 (12)0.136 (15)0.076 (10)0.057 (12)0.019 (9)0.051 (11)
C10.037 (5)0.043 (5)0.083 (8)0.006 (4)0.007 (5)0.001 (5)
C20.045 (5)0.032 (5)0.059 (6)0.002 (4)0.004 (4)0.002 (4)
C30.036 (5)0.046 (5)0.052 (6)0.001 (4)0.009 (4)0.003 (4)
C40.044 (5)0.044 (5)0.065 (7)0.002 (4)0.010 (5)0.010 (5)
C50.058 (6)0.040 (5)0.085 (8)0.007 (5)0.010 (6)0.013 (5)
C60.052 (6)0.052 (6)0.108 (9)0.009 (5)0.013 (6)0.029 (6)
C70.038 (5)0.049 (6)0.100 (9)0.002 (5)0.015 (5)0.023 (6)
C80.031 (4)0.045 (5)0.051 (6)0.000 (4)0.002 (4)0.008 (4)
C110.077 (9)0.138 (12)0.044 (7)0.008 (8)0.013 (6)0.005 (7)
C90.060 (10)0.083 (16)0.084 (15)0.010 (12)0.030 (10)0.044 (13)
C100.073 (12)0.063 (16)0.088 (15)0.001 (10)0.004 (11)0.036 (12)
C120.035 (10)0.18 (2)0.059 (10)0.011 (10)0.013 (8)0.002 (13)
C130.047 (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)
C140.039 (5)0.030 (4)0.053 (6)0.004 (4)0.003 (4)0.003 (4)
C150.063 (7)0.058 (7)0.080 (8)0.015 (6)0.020 (6)0.013 (6)
C160.104 (10)0.043 (6)0.079 (8)0.009 (7)0.033 (7)0.013 (6)
C170.077 (8)0.031 (6)0.100 (10)0.013 (5)0.042 (7)0.023 (6)
C180.055 (6)0.073 (8)0.088 (9)0.012 (6)0.007 (6)0.028 (7)
C190.056 (6)0.059 (6)0.068 (7)0.010 (5)0.005 (5)0.015 (6)
C200.047 (5)0.039 (5)0.039 (5)0.002 (4)0.005 (4)0.005 (4)
C210.044 (5)0.056 (6)0.038 (5)0.009 (5)0.002 (4)0.005 (4)
C220.066 (7)0.052 (6)0.054 (6)0.004 (5)0.002 (5)0.015 (5)
C230.069 (7)0.060 (7)0.063 (7)0.019 (6)0.019 (6)0.003 (6)
C240.047 (6)0.068 (7)0.072 (7)0.021 (5)0.001 (5)0.021 (6)
C250.051 (6)0.046 (5)0.049 (6)0.002 (5)0.006 (5)0.003 (5)
C260.041 (5)0.056 (6)0.035 (5)0.002 (4)0.004 (4)0.004 (4)
C270.077 (7)0.069 (7)0.039 (6)0.020 (6)0.002 (5)0.001 (5)
C280.093 (9)0.091 (9)0.043 (6)0.021 (7)0.008 (6)0.006 (6)
C290.061 (7)0.090 (9)0.041 (6)0.005 (6)0.009 (5)0.007 (6)
C300.046 (6)0.075 (7)0.052 (6)0.010 (5)0.003 (5)0.015 (6)
C310.041 (5)0.060 (6)0.051 (6)0.001 (5)0.000 (4)0.008 (5)
C320.030 (4)0.030 (4)0.055 (6)0.002 (4)0.004 (4)0.002 (4)
C330.037 (5)0.115 (10)0.045 (6)0.018 (6)0.000 (5)0.005 (6)
C340.051 (7)0.120 (11)0.062 (7)0.014 (7)0.020 (6)0.007 (7)
C350.034 (5)0.061 (6)0.076 (8)0.006 (5)0.002 (5)0.015 (6)
C360.042 (6)0.067 (7)0.079 (8)0.011 (5)0.014 (6)0.012 (6)
C370.049 (6)0.053 (6)0.058 (6)0.011 (5)0.007 (5)0.005 (5)
Geometric parameters (Å, º) top
Os6—C11.866 (11)C11—C101.367 (14)
Os6—B22.299 (11)C11—C10'1.382 (18)
Os6—B72.300 (12)C11—C12'1.428 (17)
Os6—B52.317 (11)C11—H11A0.9400
Os6—P12.357 (2)C9—C101.367 (14)
Os6—P22.379 (2)C9—H9A0.9400
Os6—H561.51 (8)C10—H10A0.9400
Os6—H671.61 (10)C12—C131.381 (13)
P1—C21.828 (9)C12—H120.9400
P1—C81.829 (9)C13—H130.9400
P1—C141.833 (9)C9'—C10'1.389 (18)
P2—C261.829 (9)C9'—H9'0.9400
P2—C321.830 (8)C10'—H10'0.9400
P2—C201.837 (9)C12'—C13'1.418 (17)
O1—C11.159 (12)C12'—H12'0.9400
B1—B101.69 (2)C13'—H13'0.9400
B1—B41.73 (2)C14—C151.361 (13)
B1—B51.732 (16)C14—C191.400 (13)
B1—B31.73 (2)C15—C161.400 (14)
B1—B21.737 (18)C15—H15A0.9400
B1—H11.28 (11)C16—C171.367 (16)
B2—B31.749 (19)C16—H16A0.9400
B2—B71.796 (17)C17—C181.387 (16)
B2—B51.798 (16)C17—H17A0.9400
B2—H21.09 (9)C18—C191.366 (14)
B3—B71.66 (2)C18—H18A0.9400
B3—B81.76 (2)C19—H19A0.9400
B3—B41.78 (2)C20—C211.375 (12)
B3—H31.22 (11)C20—C251.396 (12)
B4—B91.76 (3)C21—C221.394 (13)
B4—B101.76 (2)C21—H21A0.9400
B4—B81.80 (3)C22—C231.366 (14)
B4—H41.29 (13)C22—H22A0.9400
B5—B102.026 (19)C23—C241.374 (15)
B5—H51.11 (9)C23—H23A0.9400
B5—H561.35 (9)C24—C251.379 (13)
B7—B81.93 (2)C24—H24A0.9400
B7—H71.18 (10)C25—H25A0.9400
B7—H671.52 (10)C26—C271.376 (13)
B8—B91.76 (2)C26—C311.405 (13)
B8—H81.3151C27—C281.372 (13)
B9—B101.77 (3)C27—H27A0.9400
B9—H91.1933C28—C291.378 (15)
B10—H101.14 (13)C28—H28A0.9400
C2—C31.398 (12)C29—C301.358 (14)
C2—C71.399 (12)C29—H29A0.9400
C3—C41.394 (12)C30—C311.392 (13)
C3—H3A0.9400C30—H30A0.9400
C4—C51.375 (13)C31—H31A0.9400
C4—H4A0.9400C32—C331.362 (12)
C5—C61.386 (13)C32—C371.382 (12)
C5—H5A0.9400C33—C341.393 (13)
C6—C71.378 (13)C33—H33A0.9400
C6—H6A0.9400C34—C351.373 (14)
C7—H7A0.9400C34—H34A0.9400
C8—C91.370 (14)C35—C361.346 (14)
C8—C9'1.381 (18)C35—H35A0.9400
C8—C131.395 (12)C36—C371.393 (13)
C8—C13'1.403 (17)C36—H36A0.9400
C11—C121.348 (13)C37—H37A0.9400
C1—Os6—B297.7 (4)B1—B10—B460.0 (10)
C1—Os6—B781.8 (5)B1—B10—B9108.9 (12)
B2—Os6—B746.0 (4)B4—B10—B959.7 (10)
C1—Os6—B5141.3 (4)B1—B10—B554.7 (7)
B2—Os6—B545.8 (4)B4—B10—B5108.4 (10)
B7—Os6—B578.8 (5)B9—B10—B5119.5 (12)
C1—Os6—P194.0 (3)B1—B10—H10142 (7)
B2—Os6—P1155.1 (3)B4—B10—H10120 (7)
B7—Os6—P1114.9 (3)B9—B10—H1099 (7)
B5—Os6—P1124.5 (3)B5—B10—H10129 (7)
C1—Os6—P290.5 (3)O1—C1—Os6175.6 (9)
B2—Os6—P2100.8 (3)C3—C2—C7117.7 (8)
B7—Os6—P2143.6 (3)C3—C2—P1124.4 (7)
B5—Os6—P285.8 (3)C7—C2—P1117.8 (7)
P1—Os6—P2101.04 (8)C4—C3—C2120.7 (8)
C1—Os6—H56175 (3)C4—C3—H3A119.6
B2—Os6—H5678 (3)C2—C3—H3A119.6
B7—Os6—H5696 (3)C5—C4—C3120.5 (9)
B5—Os6—H5634 (3)C5—C4—H4A119.8
P1—Os6—H5691 (3)C3—C4—H4A119.8
P2—Os6—H5688 (3)C4—C5—C6119.3 (9)
C1—Os6—H6795 (3)C4—C5—H5A120.4
B2—Os6—H6782 (4)C6—C5—H5A120.4
B7—Os6—H6741 (4)C7—C6—C5120.7 (10)
B5—Os6—H6792 (3)C7—C6—H6A119.6
P1—Os6—H6775 (4)C5—C6—H6A119.6
P2—Os6—H67174 (3)C6—C7—C2121.0 (9)
H56—Os6—H6787 (5)C6—C7—H7A119.5
C2—P1—C8100.5 (4)C2—C7—H7A119.5
C2—P1—C1498.2 (4)C9—C8—C9'37.7 (12)
C8—P1—C14106.4 (4)C9—C8—C13110.9 (13)
C2—P1—Os6114.5 (3)C9'—C8—C13100.5 (14)
C8—P1—Os6111.0 (3)C9—C8—C13'104.8 (13)
C14—P1—Os6123.3 (3)C9'—C8—C13'127 (2)
C26—P2—C32103.2 (4)C13—C8—C13'50.8 (12)
C26—P2—C20100.8 (4)C9—C8—P1120.8 (10)
C32—P2—C20103.5 (4)C9'—C8—P1115.1 (15)
C26—P2—Os6116.0 (3)C13—C8—P1127.8 (9)
C32—P2—Os6117.3 (3)C13'—C8—P1117.0 (11)
C20—P2—Os6113.9 (3)C12—C11—C10121.9 (15)
B10—B1—B462.1 (10)C12—C11—C10'102.8 (18)
B10—B1—B572.6 (9)C10—C11—C10'33.9 (13)
B4—B1—B5125.5 (13)C12—C11—C12'49.1 (15)
B10—B1—B3110.1 (14)C10—C11—C12'101.3 (15)
B4—B1—B361.9 (9)C10'—C11—C12'111 (2)
B5—B1—B3112.7 (11)C12—C11—H11A119.0
B10—B1—B2120.6 (12)C10—C11—H11A119.0
B4—B1—B2117.7 (13)C10'—C11—H11A128.9
B5—B1—B262.4 (7)C12'—C11—H11A118.3
B3—B1—B260.5 (8)C10—C9—C8126.7 (18)
B10—B1—H1111 (5)C10—C9—H9A116.7
B4—B1—H1116 (5)C8—C9—H9A116.7
B5—B1—H1107 (5)C11—C10—C9116.7 (18)
B3—B1—H1129 (5)C11—C10—H10A121.6
B2—B1—H1118 (5)C9—C10—H10A121.6
B1—B2—B359.6 (8)C11—C12—C13116.2 (14)
B1—B2—B7102.5 (10)C11—C12—H12121.9
B3—B2—B756.0 (7)C13—C12—H12121.9
B1—B2—B558.7 (7)C12—C13—C8126.3 (13)
B3—B2—B5108.8 (9)C12—C13—H13116.8
B7—B2—B5109.3 (8)C8—C13—H13116.8
B1—B2—Os6117.6 (8)C8—C9'—C10'117 (3)
B3—B2—Os6118.0 (7)C8—C9'—H9'121.7
B7—B2—Os667.0 (6)C10'—C9'—H9'121.7
B5—B2—Os667.6 (5)C11—C10'—C9'125 (3)
B1—B2—H2119 (5)C11—C10'—H10'117.5
B3—B2—H2114 (5)C9'—C10'—H10'117.5
B7—B2—H2123 (5)C13'—C12'—C11131 (2)
B5—B2—H2125 (5)C13'—C12'—H12'114.6
Os6—B2—H2116 (5)C11—C12'—H12'114.6
B7—B3—B1108.3 (10)C8—C13'—C12'108.4 (18)
B7—B3—B263.4 (8)C8—C13'—H13'125.8
B1—B3—B259.8 (8)C12'—C13'—H13'125.8
B7—B3—B868.4 (9)C15—C14—C19118.0 (9)
B1—B3—B8106.1 (11)C15—C14—P1119.3 (7)
B2—B3—B8118.9 (10)C19—C14—P1122.7 (8)
B7—B3—B4118.3 (11)C14—C15—C16122.2 (10)
B1—B3—B458.9 (9)C14—C15—H15A118.9
B2—B3—B4114.3 (11)C16—C15—H15A118.9
B8—B3—B461.2 (10)C17—C16—C15118.5 (11)
B7—B3—H3114 (5)C17—C16—H16A120.8
B1—B3—H3128 (5)C15—C16—H16A120.8
B2—B3—H3117 (5)C16—C17—C18120.3 (10)
B8—B3—H3116 (5)C16—C17—H17A119.8
B4—B3—H3118 (5)C18—C17—H17A119.8
B1—B4—B9107.7 (12)C19—C18—C17120.2 (11)
B1—B4—B1057.9 (9)C19—C18—H18A119.9
B9—B4—B1060.3 (11)C17—C18—H18A119.9
B1—B4—B359.2 (9)C18—C19—C14120.7 (11)
B9—B4—B3108.0 (13)C18—C19—H19A119.7
B10—B4—B3104.8 (12)C14—C19—H19A119.7
B1—B4—B8104.5 (12)C21—C20—C25118.7 (8)
B9—B4—B859.1 (11)C21—C20—P2123.7 (7)
B10—B4—B8103.7 (13)C25—C20—P2117.5 (7)
B3—B4—B858.9 (8)C20—C21—C22121.3 (9)
B1—B4—H4105 (6)C20—C21—H21A119.3
B9—B4—H4139 (6)C22—C21—H21A119.3
B10—B4—H4122 (6)C23—C22—C21119.6 (10)
B3—B4—H4110 (6)C23—C22—H22A120.2
B8—B4—H4134 (6)C21—C22—H22A120.2
B1—B5—B258.9 (7)C22—C23—C24119.5 (10)
B1—B5—B1052.8 (8)C22—C23—H23A120.3
B2—B5—B10102.1 (8)C24—C23—H23A120.3
B1—B5—Os6116.9 (8)C23—C24—C25121.7 (10)
B2—B5—Os666.6 (5)C23—C24—H24A119.2
B10—B5—Os6117.8 (8)C25—C24—H24A119.2
B1—B5—H5115 (5)C24—C25—C20119.3 (9)
B2—B5—H5132 (5)C24—C25—H25A120.4
B10—B5—H5109 (5)C20—C25—H25A120.4
Os6—B5—H5124 (5)C27—C26—C31117.1 (9)
B1—B5—H56133 (4)C27—C26—P2121.5 (8)
B2—B5—H56102 (4)C31—C26—P2121.3 (7)
B10—B5—H5698 (4)C28—C27—C26122.2 (10)
Os6—B5—H5638 (4)C28—C27—H27A118.9
H5—B5—H56109 (6)C26—C27—H27A118.9
B3—B7—B260.6 (8)C27—C28—C29120.3 (11)
B3—B7—B858.2 (9)C27—C28—H28A119.9
B2—B7—B8108.6 (10)C29—C28—H28A119.9
B3—B7—Os6122.0 (9)C30—C29—C28119.0 (10)
B2—B7—Os667.0 (5)C30—C29—H29A120.5
B8—B7—Os6124.2 (8)C28—C29—H29A120.5
B3—B7—H7109 (5)C29—C30—C31121.3 (10)
B2—B7—H7128 (5)C29—C30—H30A119.3
B8—B7—H7104 (5)C31—C30—H30A119.3
Os6—B7—H7122 (5)C30—C31—C26120.0 (9)
B3—B7—H67131 (4)C30—C31—H31A120.0
B2—B7—H67104 (4)C26—C31—H31A120.0
B8—B7—H6790 (4)C33—C32—C37118.2 (8)
Os6—B7—H6744 (4)C33—C32—P2120.5 (7)
H7—B7—H67116 (6)C37—C32—P2121.3 (7)
B9—B8—B3108.9 (12)C32—C33—C34121.7 (10)
B9—B8—B459.2 (11)C32—C33—H33A119.1
B3—B8—B459.9 (10)C34—C33—H33A119.1
B9—B8—B7115.9 (11)C35—C34—C33119.6 (10)
B3—B8—B753.5 (7)C35—C34—H34A120.2
B4—B8—B7105.0 (11)C33—C34—H34A120.2
B9—B8—H8120.7C36—C35—C34118.9 (9)
B3—B8—H8122.3C36—C35—H35A120.6
B4—B8—H8124.8C34—C35—H35A120.6
B7—B8—H8117.6C35—C36—C37122.1 (10)
B8—B9—B461.7 (10)C35—C36—H36A119.0
B8—B9—B10105.3 (11)C37—C36—H36A119.0
B4—B9—B1060.0 (11)C32—C37—C36119.5 (9)
B8—B9—H9132.5C32—C37—H37A120.3
B4—B9—H9124.9C36—C37—H37A120.3
B10—B9—H9117.8

Experimental details

(I)(IV)
Crystal data
Chemical formula[(B5H9Os)(C18H15P)2(CO)][(B9H13Os)(C18H15P)2(CO)]
Mr805.87853.14
Crystal system, space groupMonoclinic, CcMonoclinic, P21/n
Temperature (K)153223
a, b, c (Å)16.0054 (1), 13.0200 (1), 17.2445 (1)10.4617 (1), 15.6821 (1), 22.6315 (3)
β (°) 105.29 (1) 91.08 (1)
V3)3466.39 (4)3712.29 (7)
Z44
Radiation typeMo KαMo Kα
µ (mm1)3.803.55
Crystal size (mm)0.25 × 0.20 × 0.080.28 × 0.20 × 0.04
Data collection
DiffractometerBruker SMART Query CCD area-detector
diffractometer
Bruker SMART Query CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Blessing, 1995)
Empirical (using intensity measurements)
(SADABS; Blessing, 1995)
Tmin, Tmax0.450, 0.7510.436, 0.871
No. of measured, independent and
observed [I > 2σ(I)] reflections
31883, 9961, 9460 74813, 6483, 5001
Rint0.0410.01
(sin θ/λ)max1)0.7030.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.059, 1.03 0.057, 0.116, 1.18
No. of reflections99616483
No. of parameters443491
No. of restraints236
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0182P)2]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0197P)2 + 26.7668P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)2.20, 1.781.26, 1.16
Absolute structureFlack, 1983?
Absolute structure parameter0.002 (4)?

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXTL (Sheldrick, 1999), SHELXTL.

Selected geometric parameters (Å, º) for (I) top
Os2—C371.869 (4)B1—B61.777 (7)
Os2—B32.291 (4)B1—B31.788 (7)
Os2—B62.301 (4)B1—B51.808 (7)
Os2—B12.335 (5)B1—B41.809 (8)
Os2—P22.3664 (9)B3—B41.753 (6)
Os2—P12.3729 (11)B4—B51.652 (8)
O—C371.155 (5)B5—B61.730 (6)
C37—Os2—B3134.42 (15)B1—Os2—P2152.23 (15)
C37—Os2—B680.32 (15)C37—Os2—P186.53 (11)
B3—Os2—B679.87 (16)B3—Os2—P188.02 (11)
C37—Os2—B193.31 (17)B6—Os2—P1146.59 (13)
B3—Os2—B145.46 (18)B1—Os2—P1106.00 (16)
B6—Os2—B145.07 (19)P2—Os2—P198.46 (3)
C37—Os2—P2101.22 (11)B5—B4—B3112.0 (3)
B3—Os2—P2124.35 (12)B4—B5—B6111.7 (3)
B6—Os2—P2114.12 (13)
Selected geometric parameters (Å, º) for (IV) top
Os6—C11.866 (11)Os6—P22.379 (2)
Os6—B22.299 (11)O1—C11.159 (12)
Os6—B72.300 (12)B5—B102.026 (19)
Os6—B52.317 (11)B7—B81.93 (2)
Os6—P12.357 (2)
C1—Os6—B297.7 (4)C1—Os6—P290.5 (3)
C1—Os6—B781.8 (5)B2—Os6—P2100.8 (3)
C1—Os6—P194.0 (3)P1—Os6—P2101.04 (8)
B2—Os6—P1155.1 (3)
 

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