Hydrido-sulfido-bridged triangular Os₃ cluster compounds with different phosphine ligand substitution patterns

In the course of our studies of trinuclear osmium cluster complexes with bridging sulfido and hydrido ligands, the new compounds Os₃(μ-H)(μ-SR)(CO)₉(PHCy₂) (Cy = cyclo­hexyl) with R = phenyl, (I) (nona­carbonyl-1κ³C,2κ³C,3κ³C-di­cyclo­hexyl­phosphine-3κP-μ-hydrido-1:2κ²H-μ-phenyl­thio-1:2κ²S-triangulo-triosmium), [Os₃H(C₆H₅S)(C₁₂H₂₃P)(CO)₉], and R = naphthyl, (II) [nona­carbonyl-1κ³C,2κ²C,3κ⁴C-di­cyclo­hexyl­phosphine-2κP-μ-hydrido-1:2κ²H-μ-(2-naphthyl­thio)-1:2κ²S-triangulo-triosmium], [Os₃H(C₁₀H₇S)(C₁₂H₂₃P)(CO)₉], were prepared. We report on these two phosphine-substituted complexes, which exhibit perceptible changes of the Os—Os bond parameters due to the ligand-substitution pattern.

S1. Comment

Structure reports on triangular Os₃(µ-H)(µ-SR)(CO)_10-nL_n (n = 0 or 1) compounds show rather differing patterns of Os—Os distances, and the positions of the µ-H atoms, though confirmed by spectroscopic methods, have not been determined (Adams & Dawoodi, 1981; Brodie et al., 1983; Ditzel et al., 1987; Holden et al., 1983; Monari et al., 1996). We present here the structures of two similar compounds, (I) and (II), together with details of the µ-H atoms. \sch

The molecular structure of (I) (Fig. 1) depicts a triangular arrangement of the three Os atoms. Of these, Os2 and Os3 each have three terminal carbonyl groups and the common bridging µ-H and µ-S atoms as ligands. The CO groups show ecliptic arrangement with torsion angles C5—Os2—Os3—C7 − 0.2 (5), C6—Os2—Os3—C8 − 2.2 (7) and C4—Os2—Os3—C9 − 6.4 (6)°. The third metal atom, Os1, has two axially and one equatorially attached CO groups, as well as the equatorially positioned PHCy₂ ligand. Considering two Os—Os bonds for each metal atom, Os1 thus reaches a sixfold distorted octahedral coordination, whereas the two bridged atoms Os2 and Os3 have sevenfold coordination.

The two planes Os₂µ-H and Os₂µ-S form a dihedral angle of 52.0 (1)°, and the dihedral angles with the central Os₃ ring are 73.7 (1) for the Os₂µ-S plane and 125.7 (1)° for Os₂µ-H. Two edges, Os1—Os3 = 2.8678 (7) and Os2—Os3 = 2.8674 (7) Å, are equal and clearly longer than the Os1—Os2 edge of 2.8382 (7) Å. One of the long edges is bridged by the two µ-H and µ-S ligands, and the short Os—Os edge has the PHCy₂ ligand in the trans position.

The sulfido bridge is symmetric, with equal Os—S bond lengths of 2.412 (3) and 2.413 (3) Å, and compares well with that known from the above-mentioned related Os₃-clusters. The S—C_phenyl distance of 1.803 (10) Å is consistent with a single bond and the plane of the phenyl ring is nearly perpendicular to the Os₃ plane at an angle of 85.0 (1)°.

The molecular structure of (II) (Fig. 2) is closely related to that of (I) but with substitution of a naphthyl group rather than a phenyl group attached to the µ-S ligand. The deciding difference, however, is the position of the PHCy₂ group, which is pseudo-trans to the bridged Os—Os bond and is attached to Os2. The Os2—P bond length of 2.345 (2) Å is equal to that for (I) [2.342 (3) Å] and the coordination geometry of (II) is almost the same as for (I), with torsion angles C5—Os2—Os3—C7 0.1 (4), C6—Os2—Os3—C8 1.3 (4) and P1—Os2—Os3—C9 9.9 (4)°.

The dihedral angle between planes Os₂µ-H and Os₂µ-S is 47.3 (1)° and the dihedral angles between the Os₃ ring and Os₂µ-S and Os₂µ-H planes are 77.1 (1) and 124.4 (1)°, respectively. The Os—S bond lengths of 2.423 (2) and 2.434 (2) Å differ only slightly and S—C_naphthyl is 1.798 (8) Å. However, the Os₃ ring geometry has changed, obviously due to the different substitution pattern of the metal atoms. In (II) there are two nearly equal but short bond lengths, Os1—Os3 2.8544 (6) and Os2—Os3 2.8585 (5) Å, and one long Os1—Os2 edge of 2.8928 (5) Å. This latter edge is now cis to the PHCy₂ ligand at Os2.

The µ-H atoms of (I) and (II) have been located from difference Fourier maps and refined. Both lie above the Os₃ planes if the µ-S atoms are considered to lie below these planes. The mean Os—H bond lengths are 1.86 (8) for (I) and 1.70 (12) Å for (II).

The coordination geometry of (II) is just the same as for Os₃(µ-H)(µ-SPh)(CO)₉PEt₃, (III) (Ditzel et al., 1987) but in this complex there are two long [2.883 (1) and 2.901 (1) Å] and one short [2.862 (1) Å] Os—Os edges. The short edge is between the two Os atoms which are not coordinated by the phosphine group and this ligand is pseudo-trans to the bridged Os—Os edge. The same order of long and short Os—Os edges [2.873 (1), 2.880 (1) and 2.855 (1) Å] is valid for the compound Os₃(µ-H)(µ-SCH₂CH=CH₂)(CO)₉PPh₃, (IV) (Adams & Pompeo, 1992), but here the phosphine ligand is cis to the µ-H-µ-S bridged Os—Os edge.

In summary, these four phosphine-substituted cluster complexes each have in common two equal and one significantly different Os—Os edge. The accompanying bond length differences range from 0.015 for (IV) to 0.032 Å for (II), taking the reported s.u.s into account. There is, however, no clear conjunction between the substitution pattern and the sequence of the Os—Os bonds. Related unsubstituted Os₃ carbonyl compounds exhibit almost equal bond lengths for all three Os—Os edges: Os₃(µ-H)(µ-SC(H)N-p- C₆H₄F)(CO)₁₀ (Adams & Dawoodi, 1981) with a bond difference, Δ, of 0.003 Å, Os₃(µ-H)(µ-SC=NCH₂CH₂S)(CO)₁₀ (Δ = 0.002 Å; Brodie et al., 1983), Os₃(µ-H)(µ-SC(CH₃)₃)(CO)₁₀ (Δ = 0.004 Å; Monari et al., 1996), and Os₃(µ-H)(µ-SC(HPh₂))(CO)₁₀ (Δ = 0.008 Å; Holden et al., 1983).

S2. Experimental

In an argon atmosphere Os₃(µ-H)(µ-SPh)(CO)₁₀ (90 mg, 0.094 mmol) or Os₃(µ-H)(µ-S(2-naphthyl))(CO)₁₀ (95 mg, 0.094 mmol) were dissolved in a mixture of dichloromethane (15 ml) and acetonitrile (1 ml). Trimethylamine-N-oxide (9 mg) was then added. After 1 h the solvent was removed under reduced pressure and the crude material was purified by thin-layer chromatography (eluent: dichloromethane-n-hexane, 1:10). The resulting product fractions contained a mixture of four isomers of Os₃(µ-H)(µ-SR)(CO)₉(PHCy₂) (R = Ph or naphthyl). Upon crystallization from n-pentane in both cases, single crystals of (I) and (II) were obtained.

S3. Refinement

For both structures, the phosphine H atoms as well as the bridging H atoms were located from difference Fourier maps. Their positional parameters were refined; the isotropic displacement parameters were held fixed. Phenyl, cyclohexyl and naphpthyl H atoms were fixed at idealized positions. Refinement used a riding model and U_iso(H) = 1.2U_iso(C). The maximum residual electron density peak in (I) was 1.2 Å from H36, while that in (II) was 1.0 Å from Os1.

Computing details

For both compounds, data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL/NT (Siemens, 1995); program(s) used to refine structure: SHELXTL/NT; molecular graphics: SHELXTL/NT; software used to prepare material for publication: SHELXTL/NT.

Figures

	Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids. Phenyl and cyclohexyl H atoms have been omitted for clarity.
	Fig. 2. The molecular structure of (II) showing 50% probability displacement ellipsoids. Naphthyl and cyclohexyl H atoms have been omitted for clarity.

(I) nonacarbonyl-1κ³C,2κ³C,3κ³C-dicyclohexylphosphine-3κP-µ-hydrido- 1:2κ²H-µ-phenylthio-1:2κ²S-triangulo-triosmium

Crystal data

[Os3(CO)9H(C6H5S)(C12H23P)]	F(000) = 4176
Mr = 1131.13	Dx = 2.390 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.893 (3) Å	Cell parameters from 23 reflections
b = 9.010 (2) Å	θ = 14.5–38.0°
c = 33.399 (5) Å	µ = 12.26 mm^−1
β = 91.04 (1)°	T = 203 K
V = 6286.2 (19) Å^3	Block, yellow
Z = 8	0.27 × 0.14 × 0.08 mm

Data collection

Siemens P4 diffractometer	4147 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
Graphite monochromator	θmax = 27.5°, θmin = 2.3°
ω scans	h = −27→1
Absorption correction: ψ-scan (North et al., 1968)	k = −1→11
Tmin = 0.146, Tmax = 0.375	l = −43→43
8816 measured reflections	3 standard reflections every 397 reflections
7221 independent reflections	intensity decay: 5%

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	w = 1/[σ^2(Fo^2) + (0.0145P)^2] where P = (Fo^2 + 2Fc^2)/3
7221 reflections	(Δ/σ)max = 0.001
376 parameters	Δρmax = 0.91 e Å^−3
4 restraints	Δρmin = −0.98 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Os1	0.33880 (2)	0.14011 (5)	0.127082 (13)	0.03545 (11)
Os2	0.28893 (2)	0.01966 (5)	0.054454 (13)	0.03882 (12)
Os3	0.20756 (2)	0.19213 (6)	0.104673 (13)	0.03985 (13)
S1	0.20468 (13)	−0.0736 (3)	0.09604 (8)	0.0408 (7)
P1	0.34617 (14)	0.2789 (3)	0.18630 (9)	0.0384 (7)
H1	0.285 (4)	0.372 (12)	0.191 (3)	0.080*
O1	0.2950 (4)	−0.1323 (9)	0.1743 (2)	0.056 (2)
C1	0.3092 (5)	−0.0341 (14)	0.1555 (3)	0.043 (3)
O2	0.3739 (4)	0.4109 (10)	0.0749 (2)	0.063 (3)
C2	0.3603 (5)	0.3090 (14)	0.0940 (3)	0.042 (3)
O3	0.4739 (4)	0.0192 (10)	0.1255 (3)	0.066 (3)
C3	0.4230 (5)	0.0695 (12)	0.1267 (3)	0.040 (3)
O4	0.3882 (4)	0.1860 (10)	0.0076 (2)	0.071 (3)
C4	0.3506 (6)	0.1229 (14)	0.0258 (3)	0.050 (3)
O5	0.2383 (4)	−0.0967 (10)	−0.0254 (2)	0.063 (3)
C5	0.2537 (5)	−0.0513 (15)	0.0045 (4)	0.053 (3)
O6	0.3768 (4)	−0.2394 (11)	0.0742 (3)	0.072 (3)
C6	0.3444 (6)	−0.1396 (15)	0.0665 (3)	0.050 (3)
O7	0.0708 (4)	0.2593 (10)	0.0770 (2)	0.065 (3)
C7	0.1216 (5)	0.2278 (13)	0.0853 (3)	0.045 (3)
O8	0.1788 (4)	0.1624 (10)	0.1933 (2)	0.060 (2)
C8	0.1903 (5)	0.1791 (14)	0.1602 (4)	0.048 (3)
O9	0.2439 (4)	0.5187 (11)	0.1125 (3)	0.066 (3)
C9	0.2295 (5)	0.3977 (15)	0.1090 (3)	0.044 (3)
C11	0.4102 (5)	0.4190 (13)	0.1927 (3)	0.045 (3)
H11	0.4201	0.4223	0.2215	0.054*
C12	0.4718 (5)	0.3752 (12)	0.1727 (3)	0.050 (3)
H12A	0.4634	0.3594	0.1444	0.060*
H12B	0.4870	0.2822	0.1840	0.060*
C13	0.5243 (6)	0.4939 (15)	0.1779 (4)	0.070 (4)
H13A	0.5380	0.4974	0.2058	0.084*
H13B	0.5610	0.4662	0.1621	0.084*
C14	0.5018 (6)	0.6444 (15)	0.1652 (4)	0.070 (4)
H14A	0.4941	0.6450	0.1365	0.084*
H14B	0.5349	0.7168	0.1713	0.084*
C15	0.4415 (5)	0.6879 (13)	0.1859 (4)	0.054 (3)
H15A	0.4263	0.7814	0.1749	0.065*
H15B	0.4510	0.7029	0.2141	0.065*
C16	0.3890 (5)	0.5728 (14)	0.1814 (4)	0.063 (4)
H16A	0.3535	0.6010	0.1981	0.075*
H16B	0.3737	0.5721	0.1539	0.075*
C21	0.3462 (5)	0.1668 (13)	0.2324 (3)	0.045 (3)
H21	0.3137	0.0896	0.2284	0.054*
C22	0.3280 (5)	0.2510 (14)	0.2696 (3)	0.060 (4)
H22A	0.2868	0.2985	0.2654	0.072*
H22B	0.3595	0.3276	0.2753	0.072*
C23	0.3247 (5)	0.1435 (14)	0.3051 (3)	0.055 (3)
H23A	0.3152	0.1993	0.3291	0.066*
H23B	0.2898	0.0743	0.3003	0.066*
C24	0.3865 (5)	0.0561 (15)	0.3121 (3)	0.061 (4)
H24A	0.4200	0.1227	0.3215	0.073*
H24B	0.3799	−0.0182	0.3327	0.073*
C25	0.4068 (6)	−0.0177 (15)	0.2747 (3)	0.064 (4)
H25A	0.3771	−0.0976	0.2684	0.077*
H25B	0.4487	−0.0614	0.2791	0.077*
C26	0.4096 (5)	0.0869 (13)	0.2388 (3)	0.045 (3)
H26A	0.4434	0.1592	0.2432	0.054*
H26B	0.4196	0.0306	0.2149	0.054*
C31	0.1385 (4)	−0.1348 (13)	0.0648 (3)	0.040 (3)
C32	0.1132 (5)	−0.2716 (14)	0.0747 (3)	0.056 (4)
H32	0.1285	−0.3220	0.0972	0.067*
C33	0.0651 (5)	−0.3330 (16)	0.0511 (4)	0.069 (4)
H33	0.0474	−0.4242	0.0579	0.083*
C34	0.0437 (6)	−0.2579 (18)	0.0176 (4)	0.075 (5)
H34	0.0123	−0.3011	0.0013	0.091*
C35	0.0676 (6)	−0.1194 (17)	0.0074 (4)	0.062 (4)
H35	0.0514	−0.0680	−0.0147	0.075*
C36	0.1156 (5)	−0.0609 (15)	0.0309 (3)	0.054 (3)
H36	0.1333	0.0301	0.0240	0.065*
H2	0.235 (4)	0.185 (9)	0.052 (2)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Os1	0.0388 (2)	0.0348 (3)	0.0327 (2)	−0.0015 (2)	0.00199 (19)	0.0010 (2)
Os2	0.0407 (2)	0.0420 (3)	0.0339 (2)	0.0005 (2)	0.00148 (19)	−0.0016 (2)
Os3	0.0409 (3)	0.0428 (3)	0.0360 (2)	0.0037 (2)	0.0030 (2)	0.0008 (2)
S1	0.0430 (16)	0.0406 (17)	0.0387 (16)	−0.0042 (15)	−0.0023 (13)	0.0045 (14)
P1	0.0407 (16)	0.0362 (19)	0.0383 (16)	0.0023 (14)	0.0019 (13)	−0.0015 (15)
O1	0.054 (5)	0.046 (6)	0.067 (6)	−0.007 (5)	−0.010 (4)	0.016 (5)
C1	0.032 (6)	0.059 (9)	0.036 (6)	0.009 (6)	−0.009 (5)	−0.011 (7)
O2	0.073 (6)	0.058 (6)	0.058 (6)	−0.011 (5)	0.012 (5)	0.010 (5)
C2	0.047 (7)	0.049 (8)	0.031 (6)	−0.010 (6)	0.004 (5)	−0.004 (6)
O3	0.050 (5)	0.065 (7)	0.082 (7)	0.018 (5)	0.018 (5)	0.001 (6)
C3	0.053 (7)	0.031 (7)	0.037 (6)	−0.003 (6)	0.005 (6)	0.011 (6)
O4	0.073 (6)	0.085 (8)	0.053 (6)	−0.031 (6)	0.009 (5)	0.008 (6)
C4	0.063 (8)	0.049 (8)	0.038 (7)	−0.004 (7)	0.012 (6)	0.002 (6)
O5	0.075 (6)	0.074 (7)	0.039 (5)	−0.003 (5)	−0.005 (5)	−0.014 (5)
C5	0.045 (7)	0.059 (9)	0.054 (8)	−0.015 (7)	−0.010 (6)	0.013 (7)
O6	0.074 (7)	0.070 (7)	0.071 (7)	0.021 (6)	−0.007 (5)	−0.022 (6)
C6	0.052 (8)	0.056 (9)	0.041 (7)	−0.010 (7)	0.004 (6)	−0.002 (7)
O7	0.040 (5)	0.089 (8)	0.065 (6)	0.006 (5)	0.000 (4)	0.016 (6)
C7	0.037 (7)	0.049 (8)	0.049 (7)	−0.001 (6)	0.004 (6)	0.011 (6)
O8	0.068 (6)	0.067 (7)	0.045 (5)	0.007 (5)	0.014 (4)	0.004 (5)
C8	0.045 (7)	0.050 (8)	0.050 (7)	0.004 (6)	−0.009 (6)	−0.003 (7)
O9	0.076 (6)	0.063 (7)	0.060 (6)	0.001 (6)	0.007 (5)	−0.004 (6)
C9	0.042 (7)	0.055 (9)	0.036 (7)	0.009 (7)	0.001 (5)	−0.002 (7)
C11	0.038 (6)	0.042 (7)	0.055 (8)	−0.006 (6)	0.001 (6)	0.003 (6)
C12	0.051 (7)	0.030 (7)	0.068 (8)	−0.019 (6)	0.006 (6)	0.007 (7)
C13	0.056 (8)	0.065 (10)	0.088 (11)	−0.008 (8)	0.000 (7)	−0.008 (9)
C14	0.053 (8)	0.055 (10)	0.103 (12)	−0.014 (8)	0.003 (8)	0.008 (9)
C15	0.054 (8)	0.034 (7)	0.074 (9)	−0.005 (7)	0.009 (7)	0.002 (7)
C16	0.053 (8)	0.042 (8)	0.093 (11)	−0.008 (7)	0.011 (7)	0.019 (8)
C21	0.059 (7)	0.039 (8)	0.038 (6)	0.004 (6)	0.005 (6)	−0.008 (6)
C22	0.054 (8)	0.069 (10)	0.057 (8)	0.025 (7)	0.008 (7)	−0.001 (8)
C23	0.072 (8)	0.057 (9)	0.037 (7)	−0.003 (8)	0.016 (6)	0.000 (7)
C24	0.067 (8)	0.071 (10)	0.046 (7)	0.016 (8)	0.007 (6)	0.021 (8)
C25	0.072 (9)	0.065 (10)	0.055 (8)	0.015 (8)	0.009 (7)	−0.004 (8)
C26	0.056 (7)	0.039 (7)	0.041 (7)	0.006 (6)	0.012 (6)	0.018 (6)
C31	0.028 (6)	0.048 (7)	0.043 (7)	0.000 (6)	−0.004 (5)	0.000 (6)
C32	0.060 (8)	0.062 (10)	0.045 (7)	−0.009 (7)	−0.002 (6)	0.012 (7)
C33	0.052 (8)	0.074 (11)	0.081 (10)	−0.025 (8)	0.005 (7)	0.004 (9)
C34	0.044 (8)	0.111 (14)	0.072 (10)	−0.032 (9)	−0.004 (7)	−0.005 (10)
C35	0.053 (8)	0.081 (11)	0.053 (8)	0.016 (8)	0.003 (7)	−0.014 (8)
C36	0.050 (7)	0.058 (9)	0.055 (8)	0.002 (7)	0.001 (6)	0.001 (7)

Geometric parameters (Å, º)

Os1—C3	1.872 (11)	O7—C7	1.129 (11)
Os1—C2	1.939 (12)	O8—C8	1.145 (12)
Os1—C1	1.941 (13)	O9—C9	1.137 (14)
Os1—P1	2.342 (3)	C11—C16	1.500 (15)
Os1—Os2	2.8382 (7)	C11—C12	1.513 (13)
Os1—Os3	2.8678 (7)	C12—C13	1.540 (14)
Os2—C4	1.866 (12)	C13—C14	1.494 (16)
Os2—C6	1.883 (13)	C14—C15	1.499 (14)
Os2—C5	1.919 (12)	C15—C16	1.515 (14)
Os2—S1	2.413 (3)	C21—C22	1.510 (14)
Os2—Os3	2.8674 (7)	C21—C26	1.519 (13)
Os3—C8	1.899 (12)	C22—C23	1.533 (14)
Os3—C9	1.913 (14)	C23—C24	1.527 (14)
Os3—C7	1.925 (11)	C24—C25	1.485 (14)
Os3—S1	2.412 (3)	C25—C26	1.527 (14)
S1—C31	1.803 (10)	C31—C32	1.384 (15)
P1—C21	1.843 (11)	C31—C36	1.392 (14)
P1—C11	1.849 (11)	C32—C33	1.381 (15)
O1—C1	1.128 (13)	C33—C34	1.377 (17)
O2—C2	1.155 (12)	C34—C35	1.388 (18)
O3—C3	1.157 (11)	C35—C36	1.367 (15)
O4—C4	1.154 (12)	Os2—H2	1.86 (8)
O5—C5	1.121 (12)	Os3—H2	1.85 (8)
O6—C6	1.152 (13)	P1—H1	1.54 (10)
C3—Os1—C2	92.0 (4)	C7—Os3—Os1	175.4 (3)
C3—Os1—C1	92.1 (4)	S1—Os3—Os1	83.72 (7)
C2—Os1—C1	173.1 (4)	Os2—Os3—Os1	59.324 (17)
C3—Os1—P1	98.1 (3)	C31—S1—Os3	112.9 (4)
C2—Os1—P1	92.9 (3)	C31—S1—Os2	109.4 (4)
C1—Os1—P1	92.0 (3)	Os3—S1—Os2	72.92 (8)
C3—Os1—Os2	101.2 (3)	C21—P1—C11	106.7 (5)
C2—Os1—Os2	84.1 (3)	C21—P1—Os1	114.4 (4)
C1—Os1—Os2	89.6 (3)	C11—P1—Os1	119.9 (4)
P1—Os1—Os2	160.59 (7)	O1—C1—Os1	174.9 (10)
C3—Os1—Os3	161.5 (3)	O2—C2—Os1	178.5 (10)
C2—Os1—Os3	87.3 (3)	O3—C3—Os1	176.5 (11)
C1—Os1—Os3	87.0 (3)	O4—C4—Os2	179.0 (11)
P1—Os1—Os3	100.43 (7)	O5—C5—Os2	174.0 (11)
Os2—Os1—Os3	60.332 (18)	O6—C6—Os2	177.9 (12)
C4—Os2—C6	93.5 (5)	O7—C7—Os3	172.8 (11)
C4—Os2—C5	88.8 (5)	O8—C8—Os3	175.8 (12)
C6—Os2—C5	99.0 (5)	O9—C9—Os3	177.9 (12)
C4—Os2—S1	170.4 (4)	C16—C11—C12	112.3 (10)
C6—Os2—S1	93.7 (4)	C16—C11—P1	113.1 (8)
C5—Os2—S1	96.4 (3)	C12—C11—P1	113.0 (8)
C4—Os2—Os1	90.1 (3)	C11—C12—C13	112.3 (10)
C6—Os2—Os1	83.9 (4)	C14—C13—C12	112.2 (10)
C5—Os2—Os1	176.9 (4)	C13—C14—C15	111.7 (11)
S1—Os2—Os1	84.34 (7)	C14—C15—C16	112.8 (11)
C4—Os2—Os3	116.8 (4)	C11—C16—C15	113.4 (10)
C6—Os2—Os3	131.1 (4)	C22—C21—C26	110.8 (9)
C5—Os2—Os3	117.8 (4)	C22—C21—P1	114.6 (8)
S1—Os2—Os3	53.52 (7)	C26—C21—P1	111.3 (7)
Os1—Os2—Os3	60.344 (18)	C21—C22—C23	109.5 (10)
C8—Os3—C9	92.0 (5)	C24—C23—C22	113.3 (9)
C8—Os3—C7	98.4 (5)	C25—C24—C23	110.7 (10)
C9—Os3—C7	94.9 (5)	C24—C25—C26	113.6 (11)
C8—Os3—S1	92.9 (4)	C21—C26—C25	110.8 (9)
C9—Os3—S1	167.3 (3)	C32—C31—C36	119.5 (11)
C7—Os3—S1	96.0 (4)	C32—C31—S1	115.2 (9)
C8—Os3—Os2	131.5 (4)	C36—C31—S1	125.0 (10)
C9—Os3—Os2	115.2 (3)	C33—C32—C31	119.9 (12)
C7—Os3—Os2	116.9 (3)	C34—C33—C32	119.3 (13)
S1—Os3—Os2	53.56 (7)	C33—C34—C35	121.9 (13)
C8—Os3—Os1	86.1 (3)	C36—C35—C34	118.0 (13)
C9—Os3—Os1	84.9 (3)	C35—C36—C31	121.4 (13)

(II) nonacarbonyl-1κ³C,2κ²C,3κ⁴C-dicyclohexylphosphine-2κP-µ-hydrido- 1:2κ²H-µ-(2-naphthylthio)-1:2κ²S-triangulo-triosmium

Crystal data

[Os3(CO)9H(C10H7S)(C12H23P)]	Z = 2
Mr = 1181.19	F(000) = 1096
Triclinic, P1	Dx = 2.265 Mg m^−3
a = 10.214 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.997 (2) Å	Cell parameters from 29 reflections
c = 14.409 (1) Å	θ = 14.6–34.9°
α = 69.16 (1)°	µ = 11.13 mm^−1
β = 80.58 (1)°	T = 203 K
γ = 76.62 (1)°	Block, yellow
V = 1732.2 (4) Å^3	0.50 × 0.15 × 0.13 mm

Data collection

Siemens P4 diffractometer	6138 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 27.5°, θmin = 3.0°
ω scans	h = −1→13
Absorption correction: ψ-scan (North et al., 1968)	k = −15→15
Tmin = 0.126, Tmax = 0.235	l = −18→18
9107 measured reflections	3 standard reflections every 397 reflections
7794 independent reflections	intensity decay: 4%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0618P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.003
7794 reflections	Δρmax = 0.99 e Å^−3
413 parameters	Δρmin = −0.91 e Å^−3
14 restraints	Extinction correction: SHELXTL/NT (Siemens, 1995), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00020 (14)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Os1	−0.23656 (3)	0.70810 (3)	0.03218 (2)	0.02584 (10)
Os2	−0.21307 (3)	0.79033 (2)	−0.18349 (2)	0.02282 (10)
Os3	−0.14439 (3)	0.91348 (2)	−0.07477 (2)	0.02251 (10)
S1	−0.3504 (2)	0.95826 (16)	−0.15536 (15)	0.0250 (4)
P1	−0.3944 (2)	0.71616 (18)	−0.19791 (17)	0.0291 (5)
H1	−0.451 (12)	0.643 (10)	−0.099 (9)	0.080*
O1	−0.5341 (7)	0.8303 (6)	0.0401 (5)	0.0498 (18)
C1	−0.4238 (9)	0.7904 (7)	0.0328 (6)	0.032 (2)
O2	0.0609 (6)	0.5985 (5)	0.0031 (5)	0.0387 (15)
C2	−0.0514 (10)	0.6385 (7)	0.0128 (6)	0.0306 (19)
O3	−0.2044 (9)	0.6870 (7)	0.2463 (5)	0.065 (2)
C3	−0.2155 (10)	0.6957 (8)	0.1666 (7)	0.040 (2)
O4	−0.3434 (8)	0.4966 (6)	0.0673 (7)	0.067 (2)
C4	−0.3013 (10)	0.5739 (8)	0.0547 (8)	0.042 (2)
O5	0.0027 (7)	0.5891 (5)	−0.1917 (5)	0.0423 (16)
C5	−0.0832 (9)	0.6627 (7)	−0.1853 (6)	0.0292 (18)
O6	−0.1546 (7)	0.8904 (6)	−0.4081 (5)	0.0459 (17)
C6	−0.1819 (9)	0.8548 (7)	−0.3226 (6)	0.0317 (19)
O7	0.1288 (7)	0.8063 (6)	0.0088 (5)	0.0441 (17)
C7	0.0259 (10)	0.8457 (7)	−0.0202 (7)	0.0313 (19)
O8	−0.0333 (8)	1.1267 (6)	−0.1954 (5)	0.0482 (18)
C8	−0.0782 (9)	1.0491 (7)	−0.1541 (6)	0.0276 (18)
O9	−0.2683 (8)	0.9848 (6)	0.1054 (5)	0.0454 (17)
C9	−0.2232 (8)	0.9604 (7)	0.0372 (6)	0.0284 (18)
C11	−0.5451 (8)	0.8208 (7)	−0.2457 (6)	0.0295 (18)
H11	−0.5689	0.8684	−0.2027	0.035*
C12	−0.6673 (9)	0.7664 (8)	−0.2342 (8)	0.044 (2)
H12A	−0.6482	0.7175	−0.2751	0.052*
H12B	−0.6831	0.7200	−0.1645	0.052*
C13	−0.7933 (9)	0.8540 (9)	−0.2658 (8)	0.047 (3)
H13A	−0.8677	0.8164	−0.2623	0.056*
H13B	−0.8191	0.8965	−0.2193	0.056*
C14	−0.7723 (11)	0.9328 (10)	−0.3687 (8)	0.054 (3)
H14A	−0.8534	0.9911	−0.3841	0.065*
H14B	−0.7583	0.8920	−0.4162	0.065*
C15	−0.6503 (10)	0.9876 (9)	−0.3805 (8)	0.052 (3)
H15A	−0.6364	1.0358	−0.4499	0.062*
H15B	−0.6682	1.0348	−0.3381	0.062*
C16	−0.5225 (9)	0.8997 (8)	−0.3520 (7)	0.040 (2)
H16A	−0.4470	0.9367	−0.3569	0.048*
H16B	−0.4995	0.8567	−0.3982	0.048*
C21	−0.3600 (11)	0.6110 (8)	−0.2625 (8)	0.045 (3)
H21	−0.4472	0.6096	−0.2831	0.054*
C22	−0.2629 (12)	0.6376 (9)	−0.3564 (9)	0.054 (3)
H22A	−0.1794	0.6495	−0.3400	0.064*
H22B	−0.3035	0.7074	−0.4055	0.064*
C23	−0.2280 (14)	0.5429 (11)	−0.4032 (11)	0.077 (4)
H23A	−0.3086	0.5391	−0.4297	0.092*
H23B	−0.1584	0.5605	−0.4590	0.092*
C24	−0.1793 (17)	0.4337 (12)	−0.3303 (14)	0.104 (7)
H24A	−0.0920	0.4346	−0.3111	0.125*
H24B	−0.1651	0.3758	−0.3616	0.125*
C25	−0.2762 (16)	0.4033 (10)	−0.2373 (13)	0.084 (5)
H25A	−0.2353	0.3327	−0.1894	0.101*
H25B	−0.3594	0.3922	−0.2548	0.101*
C26	−0.3104 (12)	0.4935 (8)	−0.1894 (10)	0.061 (3)
H26A	−0.2300	0.4949	−0.1612	0.073*
H26B	−0.3806	0.4746	−0.1344	0.073*
C31	−0.3510 (8)	1.0789 (6)	−0.2664 (6)	0.0258 (17)
C32	−0.2390 (8)	1.1028 (6)	−0.3307 (6)	0.0261 (17)
H32	−0.1553	1.0542	−0.3174	0.031*
C33	−0.2473 (9)	1.1998 (6)	−0.4170 (6)	0.0289 (18)
C34	−0.1318 (11)	1.2264 (8)	−0.4829 (7)	0.041 (2)
H34	−0.0473	1.1789	−0.4705	0.050*
C35	−0.1431 (12)	1.3210 (9)	−0.5646 (7)	0.049 (3)
H35	−0.0655	1.3385	−0.6074	0.058*
C36	−0.2660 (13)	1.3918 (9)	−0.5859 (8)	0.054 (3)
H36	−0.2708	1.4554	−0.6436	0.064*
C37	−0.3807 (12)	1.3707 (8)	−0.5244 (8)	0.050 (3)
H37	−0.4637	1.4200	−0.5390	0.059*
C38	−0.3727 (10)	1.2715 (7)	−0.4362 (6)	0.033 (2)
C39	−0.4856 (9)	1.2467 (8)	−0.3707 (7)	0.039 (2)
H39	−0.5695	1.2949	−0.3839	0.046*
C40	−0.4771 (8)	1.1529 (7)	−0.2867 (7)	0.0309 (19)
H40	−0.5546	1.1378	−0.2429	0.037*
H2	−0.092 (12)	0.853 (8)	−0.166 (8)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Os1	0.02409 (18)	0.02190 (16)	0.02724 (17)	−0.00312 (13)	0.00059 (13)	−0.00500 (12)
Os2	0.02102 (17)	0.02188 (16)	0.02611 (17)	−0.00272 (12)	−0.00206 (13)	−0.00946 (12)
Os3	0.02165 (17)	0.02190 (16)	0.02495 (17)	−0.00516 (12)	−0.00030 (13)	−0.00901 (12)
S1	0.0215 (10)	0.0235 (9)	0.0284 (10)	−0.0038 (8)	−0.0008 (8)	−0.0076 (8)
P1	0.0272 (12)	0.0263 (10)	0.0360 (12)	−0.0068 (9)	−0.0038 (10)	−0.0113 (9)
O1	0.033 (4)	0.046 (4)	0.054 (4)	0.004 (3)	0.007 (3)	−0.008 (3)
C1	0.032 (5)	0.029 (4)	0.032 (5)	−0.012 (4)	0.004 (4)	−0.006 (4)
O2	0.029 (4)	0.033 (3)	0.051 (4)	0.004 (3)	−0.006 (3)	−0.014 (3)
C2	0.039 (5)	0.022 (4)	0.030 (4)	−0.005 (4)	−0.011 (4)	−0.006 (3)
O3	0.066 (6)	0.088 (6)	0.027 (4)	0.001 (5)	−0.004 (4)	−0.011 (4)
C3	0.039 (6)	0.040 (5)	0.033 (5)	−0.003 (4)	0.002 (4)	−0.010 (4)
O4	0.050 (5)	0.040 (4)	0.102 (7)	−0.019 (4)	0.014 (5)	−0.017 (4)
C4	0.029 (5)	0.031 (5)	0.056 (6)	−0.003 (4)	0.000 (5)	−0.006 (4)
O5	0.046 (4)	0.036 (3)	0.038 (4)	0.004 (3)	0.003 (3)	−0.014 (3)
C5	0.030 (5)	0.026 (4)	0.033 (4)	0.000 (4)	−0.006 (4)	−0.014 (3)
O6	0.053 (5)	0.045 (4)	0.031 (4)	0.001 (3)	−0.002 (3)	−0.010 (3)
C6	0.033 (5)	0.037 (5)	0.026 (4)	0.000 (4)	0.000 (4)	−0.017 (4)
O7	0.034 (4)	0.045 (4)	0.057 (4)	−0.002 (3)	−0.017 (3)	−0.021 (3)
C7	0.034 (5)	0.025 (4)	0.037 (5)	−0.005 (4)	0.000 (4)	−0.015 (4)
O8	0.062 (5)	0.042 (4)	0.043 (4)	−0.029 (4)	−0.007 (4)	−0.005 (3)
C8	0.030 (5)	0.028 (4)	0.026 (4)	−0.007 (4)	−0.003 (4)	−0.009 (3)
O9	0.054 (5)	0.049 (4)	0.035 (4)	−0.009 (3)	0.009 (3)	−0.023 (3)
C9	0.023 (4)	0.025 (4)	0.038 (5)	0.003 (3)	−0.011 (4)	−0.011 (4)
C11	0.022 (4)	0.030 (4)	0.037 (5)	−0.005 (3)	−0.001 (4)	−0.013 (4)
C12	0.028 (5)	0.034 (5)	0.061 (7)	−0.001 (4)	−0.009 (5)	−0.006 (5)
C13	0.020 (5)	0.061 (7)	0.055 (6)	−0.013 (5)	0.005 (5)	−0.014 (5)
C14	0.043 (7)	0.066 (7)	0.045 (6)	0.001 (6)	−0.001 (5)	−0.017 (5)
C15	0.038 (6)	0.055 (6)	0.047 (6)	−0.005 (5)	−0.016 (5)	0.005 (5)
C16	0.025 (5)	0.049 (6)	0.039 (5)	−0.010 (4)	−0.005 (4)	−0.004 (4)
C21	0.039 (6)	0.045 (6)	0.066 (7)	−0.002 (5)	−0.013 (5)	−0.036 (5)
C22	0.050 (7)	0.057 (7)	0.069 (7)	0.006 (5)	−0.020 (6)	−0.043 (6)
C23	0.058 (8)	0.095 (10)	0.113 (11)	0.015 (7)	−0.026 (8)	−0.088 (10)
C24	0.096 (12)	0.086 (10)	0.165 (17)	0.054 (9)	−0.066 (12)	−0.104 (12)
C25	0.080 (10)	0.040 (7)	0.154 (15)	0.002 (7)	−0.034 (11)	−0.055 (9)
C26	0.055 (7)	0.030 (5)	0.109 (10)	−0.001 (5)	−0.035 (7)	−0.028 (6)
C31	0.022 (4)	0.024 (4)	0.032 (4)	−0.006 (3)	−0.004 (4)	−0.009 (3)
C32	0.021 (4)	0.031 (4)	0.027 (4)	−0.002 (3)	−0.005 (3)	−0.011 (3)
C33	0.036 (5)	0.027 (4)	0.026 (4)	−0.005 (4)	−0.004 (4)	−0.011 (3)
C34	0.045 (6)	0.048 (6)	0.032 (5)	−0.011 (5)	0.003 (4)	−0.015 (4)
C35	0.054 (7)	0.053 (6)	0.034 (5)	−0.021 (5)	0.014 (5)	−0.009 (5)
C36	0.082 (9)	0.043 (6)	0.033 (5)	−0.030 (6)	−0.005 (6)	0.002 (4)
C37	0.060 (7)	0.033 (5)	0.046 (6)	−0.003 (5)	−0.012 (6)	−0.003 (4)
C38	0.036 (5)	0.028 (4)	0.032 (5)	−0.007 (4)	−0.003 (4)	−0.005 (4)
C39	0.023 (5)	0.038 (5)	0.045 (5)	0.006 (4)	−0.009 (4)	−0.007 (4)
C40	0.016 (4)	0.034 (4)	0.037 (5)	0.001 (3)	−0.005 (4)	−0.007 (4)

Geometric parameters (Å, º)

Os1—C4	1.909 (10)	C11—C12	1.530 (12)
Os1—C2	1.920 (9)	C11—C16	1.526 (12)
Os1—C3	1.929 (10)	C12—C13	1.518 (13)
Os1—C1	1.964 (9)	C13—C14	1.487 (14)
Os1—Os3	2.8544 (6)	C14—C15	1.531 (15)
Os1—Os2	2.8928 (5)	C15—C16	1.526 (13)
Os2—C5	1.874 (8)	C21—C22	1.524 (15)
Os2—C6	1.882 (8)	C21—C26	1.540 (14)
Os2—P1	2.345 (2)	C22—C23	1.552 (13)
Os2—S1	2.434 (2)	C23—C24	1.47 (2)
Os2—Os3	2.8585 (5)	C24—C25	1.52 (2)
Os3—C9	1.916 (9)	C25—C26	1.509 (15)
Os3—C7	1.914 (10)	C31—C32	1.370 (11)
Os3—C8	1.933 (8)	C31—C40	1.421 (11)
Os3—S1	2.423 (2)	C32—C33	1.419 (11)
S1—C31	1.798 (8)	C33—C38	1.402 (12)
P1—C11	1.845 (9)	C33—C34	1.415 (13)
P1—C21	1.853 (9)	C34—C35	1.364 (13)
O1—C1	1.131 (11)	C35—C36	1.380 (16)
O2—C2	1.153 (10)	C36—C37	1.367 (15)
O3—C3	1.135 (11)	C37—C38	1.451 (12)
O4—C4	1.128 (11)	C38—C39	1.386 (13)
O5—C5	1.158 (10)	C39—C40	1.376 (12)
O6—C6	1.162 (10)	P1—H1	1.42 (10)
O7—C7	1.133 (11)	Os2—H2	1.70 (11)
O8—C8	1.131 (10)	Os3—H2	1.70 (12)
O9—C9	1.133 (10)
C4—Os1—C2	93.0 (4)	C31—S1—Os2	111.8 (3)
C4—Os1—C3	101.2 (4)	Os3—S1—Os2	72.12 (6)
C2—Os1—C3	91.9 (4)	C11—P1—C21	108.4 (4)
C4—Os1—C1	89.6 (4)	C11—P1—Os2	115.2 (3)
C2—Os1—C1	172.4 (4)	C21—P1—Os2	118.3 (3)
C3—Os1—C1	94.7 (4)	O1—C1—Os1	174.1 (8)
C4—Os1—Os3	158.9 (3)	O2—C2—Os1	177.7 (8)
C2—Os1—Os3	85.0 (2)	O3—C3—Os1	178.8 (10)
C3—Os1—Os3	99.9 (3)	O4—C4—Os1	177.8 (9)
C1—Os1—Os3	90.0 (2)	O5—C5—Os2	174.9 (8)
C4—Os1—Os2	99.3 (3)	O6—C6—Os2	175.6 (8)
C2—Os1—Os2	82.8 (2)	O7—C7—Os3	177.6 (8)
C3—Os1—Os2	159.1 (3)	O8—C8—Os3	175.0 (8)
C1—Os1—Os2	89.6 (3)	O9—C9—Os3	177.8 (8)
Os3—Os1—Os2	59.650 (14)	C12—C11—C16	111.0 (8)
C5—Os2—C6	90.7 (4)	C12—C11—P1	112.0 (6)
C5—Os2—P1	94.5 (3)	C16—C11—P1	114.5 (6)
C6—Os2—P1	92.4 (3)	C13—C12—C11	111.4 (8)
C5—Os2—S1	167.3 (3)	C14—C13—C12	112.0 (8)
C6—Os2—S1	96.2 (3)	C13—C14—C15	111.5 (9)
P1—Os2—S1	95.91 (7)	C16—C15—C14	111.3 (9)
C5—Os2—Os3	113.6 (3)	C15—C16—C11	109.8 (8)
C6—Os2—Os3	113.5 (3)	C22—C21—C26	110.9 (9)
P1—Os2—Os3	140.40 (6)	C22—C21—P1	114.3 (7)
S1—Os2—Os3	53.76 (5)	C26—C21—P1	110.0 (7)
C5—Os2—Os1	90.1 (3)	C21—C22—C23	112.5 (10)
C6—Os2—Os1	172.5 (3)	C24—C23—C22	111.8 (11)
P1—Os2—Os1	94.91 (6)	C23—C24—C25	113.1 (12)
S1—Os2—Os1	81.68 (5)	C24—C25—C26	111.6 (11)
Os3—Os2—Os1	59.509 (14)	C25—C26—C21	113.3 (11)
C9—Os3—C7	93.7 (3)	C32—C31—C40	119.2 (8)
C9—Os3—C8	97.1 (3)	C32—C31—S1	124.2 (6)
C7—Os3—C8	91.4 (4)	C40—C31—S1	116.6 (6)
C9—Os3—S1	96.8 (2)	C31—C32—C33	121.1 (8)
C7—Os3—S1	165.9 (2)	C38—C33—C34	119.5 (8)
C8—Os3—S1	96.6 (3)	C38—C33—C32	118.9 (8)
C9—Os3—Os1	86.5 (3)	C34—C33—C32	121.5 (8)
C7—Os3—Os1	88.6 (3)	C35—C34—C33	120.0 (10)
C8—Os3—Os1	176.4 (2)	C34—C35—C36	121.5 (10)
S1—Os3—Os1	82.68 (5)	C37—C36—C35	121.1 (9)
C9—Os3—Os2	136.6 (3)	C36—C37—C38	119.2 (10)
C7—Os3—Os2	111.8 (2)	C39—C38—C33	119.7 (8)
C8—Os3—Os2	115.9 (2)	C39—C38—C37	121.6 (9)
S1—Os3—Os2	54.12 (5)	C33—C38—C37	118.8 (9)
Os1—Os3—Os2	60.842 (14)	C40—C39—C38	121.3 (8)
C31—S1—Os3	111.4 (3)	C39—C40—C31	119.9 (8)