Bis{1,2-bis­[bis­(3-meth­oxy­prop­yl)phosphan­yl]ethane-κ2P,P′}dichlorido­osmium(II)

Szymczak, N.K.; Zakharov, L.N.; Tyler, D.R.

doi:10.1107/S1600536811048926

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page m1808

https://doi.org/10.1107/S1600536811048926

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Bis{1,2-bis[bis(3-methoxypropyl)phosphanyl]ethane-κ²P,P′}dichloridoosmium(II)

Nathaniel K. Szymczak,^a Lev N. Zakharov ^a and David R. Tyler ^a ^*

^aDepartment of Chemistry, 1253 University of Oregon, Eugene, Oregon 97403-1253, USA
^*Correspondence e-mail: dtyler@uoregon.edu

(Received 26 October 2011; accepted 16 November 2011; online 23 November 2011)

In the centrosymmetric title compound, [OsCl₂(C₁₈H₄₀O₄P₂)₂], the Os^II atom adopts a trans-OsCl₂P₄ geometry, arising from its coordination by two chelating diphosphane ligands and two chloride ions. One of the methoxy side chains of the ligand is disordered over two orientations in a 0.700 (6):0.300 (6) ratio.

Related literature

For background to transition-metal dihydride complexes, see: Egbert et al. (2007 ); Heinekey et al. (2004 ); Miller et al. (2002 ); Szymczak & Tyler (2007 ); Szymczak et al. (2006 ).

Experimental

Crystal data

[OsCl₂(C₁₈H₄₀O₄P₂)₂]
M_r = 1025.98
Monoclinic, P 2₁ /n
a = 12.667 (3) Å
b = 10.321 (2) Å
c = 18.754 (4) Å
β = 107.779 (3)°
V = 2335.0 (9) Å³
Z = 2
Mo Kα radiation
μ = 3.03 mm⁻¹
T = 173 K
0.14 × 0.10 × 0.04 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ) T_min = 0.677, T_max = 0.889
25950 measured reflections
5333 independent reflections
4423 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.058
S = 1.04
5333 reflections
251 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Selected bond lengths (Å)

Os1—P2	2.3383 (8)
Os1—P1	2.3434 (8)
Os1—Cl1	2.4515 (8)

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811048926/hb6479sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048926/hb6479Isup2.hkl

checkCIF report

Comment top

A consequence of the large d-orbitals in third-row transition metals is increased overlap to antibonding orbitals of ligands such as CO and H₂. Accordingly, when most third-row transition metal complexes are reacted with H₂, the product is often a dihydride complex (Egbert et al., 2007; Szymczak & Tyler, 2007). However, when the d-orbitals are not sufficiently electron rich to promote a complete oxidative-addition product, an arrested oxidative addition can result. The "arrested" intermediates belong to an unusual class of dihydrogen complexes with a bond distance between 1.1 Å and 1.5 Å (Heinekey et al., 2004). The H-H bond in these complexes sits in an unusually flat potential energy surface, and the H-H bond distance is consequently very sensitive to changes in the environment around the coordinated η²-H₂ ligand. We hypothesized that small changes to the environment around the H₂ ligand could potentially be correlated with small energetic fluctuations, such as those that are typical of weak intermolecular forces such as hydrogen bonding.

Several osmium dihydrogen complexes have previously been shown to have H-H bond distances in the elongated regime (1.1 - 1.5 Å). For our study of hydrogen bonding of water to the H₂ ligand, we sought therefore to study hydrogen bonding to the H₂ ligand in the water-soluble trans-Os(DMeOPrPE)₂(H₂)H⁺ complex. (DMeOPrPE is the water-soluble, bidentate phosphine ligand 1,2-bis(bis(methoxypropyl)phosphanyl)ethane.) In prior work, we synthesized trans-Fe(DMeOPrPE)₂(H₂)H⁺ and trans-Ru(DMeOPrPE)₂(H₂)H⁺ by reaction of the trans-M(DMeOPrPE)₂Cl₂ complexes with H₂ (Miller et al., 2002, Szymczak et al., 2006). In order to synthesize the analogous H₂ complex of Os, we synthesized the trans-Os(DMeOPrPE)₂Cl₂ complex reported here.

The structure shows an octahedral coordination environment around osmium with trans-chloride ligands (Fig. 1). Crystallization of the osmium congener allowed a direct comparison of trans-M(DMeOPrPE)₂Cl₂ complexes down the group 8 triad (Table 1). The M-L bonds were found to increase substantially from iron to ruthenium with minimal elongation from ruthenium to osmium. This minimal change in going from ruthenium to osmium is consistent with a lanthanide contraction of the atomic radius.

Related literature top

For background to transition-metal dihydride complexes, see: Egbert et al. (2007); Heinekey et al. (2004); Miller et al. (2002); Szymczak et al. (2006, 2007).

Experimental top

To a flask containing [OsCl₆][NEt₄]₂ (0.9114 g, 1.374 mmol) and NaBPh₄ (1.890 g, 5.523 mmol) was added a solution of DMeOPrPE (2.11 g, 5.524 mmol) in methanol (300 ml) followed by ethanol (365 ml). After heating to reflux for 16 h, the solution was deep purple with a white precipitate, and the solution was kept at reflux. After 4 days, the solution was clear yellow with a white solid on the flask walls. The solvent was removed and the residue was extracted with hot hexanes (3 x 30 ml) and diethyl ether (3 x 30 ml), leaving a yellow oil. Upon letting the oil stand for 24 h, yellow crystals of trans-[Os(DMeOPrPE)₂Cl₂] developed. Yield: 0.862 g (61%); {¹H} ³¹P NMR: d 8.6.

Structure description top

For background to transition-metal dihydride complexes, see: Egbert et al. (2007); Heinekey et al. (2004); Miller et al. (2002); Szymczak et al. (2006, 2007).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of (I) with 50% probability displacement ellipsoids [Symmetry code (A): -x,-y,-z]. Only one position of the disordered C17/O4/C18 group is shown for clarity.

Bis{1,2-bis[bis(3-methoxypropyl)phosphanyl]ethane-κ²P,P'}dichloridoosmium(II) top

Crystal data top

[OsCl₂(C₁₈H₄₀O₄P₂)₂]	F(000) = 1060
M_r = 1025.98	D_x = 1.459 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8415 reflections
a = 12.667 (3) Å	θ = 2.3–26.7°
b = 10.321 (2) Å	µ = 3.03 mm⁻¹
c = 18.754 (4) Å	T = 173 K
β = 107.779 (3)°	Plate, yellow
V = 2335.0 (9) Å³	0.14 × 0.10 × 0.04 mm
Z = 2

Data collection top

Bruker APEX CCD diffractometer	5333 independent reflections
Radiation source: fine-focus sealed tube	4423 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
phi and ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	h = −16→16
T_min = 0.677, T_max = 0.889	k = −13→13
25950 measured reflections	l = −23→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.028P)² + 0.9782P] where P = (F_o² + 2F_c²)/3
5333 reflections	(Δ/σ)_max < 0.001
251 parameters	Δρ_max = 0.87 e Å⁻³
5 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

[OsCl₂(C₁₈H₄₀O₄P₂)₂]	V = 2335.0 (9) Å³
M_r = 1025.98	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.667 (3) Å	µ = 3.03 mm⁻¹
b = 10.321 (2) Å	T = 173 K
c = 18.754 (4) Å	0.14 × 0.10 × 0.04 mm
β = 107.779 (3)°

Data collection top

Bruker APEX CCD diffractometer	5333 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	4423 reflections with I > 2σ(I)
T_min = 0.677, T_max = 0.889	R_int = 0.032
25950 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	5 restraints
wR(F²) = 0.058	H-atom parameters constrained
S = 1.04	Δρ_max = 0.87 e Å⁻³
5333 reflections	Δρ_min = −0.51 e Å⁻³
251 parameters

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 > 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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Os1	0.5000	0.5000	0.0000	0.02110 (5)
Cl1	0.31396 (6)	0.41077 (7)	−0.05728 (4)	0.03191 (16)
P1	0.57375 (6)	0.32518 (7)	−0.04887 (4)	0.02556 (15)
P2	0.53170 (6)	0.36384 (7)	0.10408 (4)	0.02567 (15)
O1	0.9493 (2)	0.2799 (3)	−0.02252 (14)	0.0575 (7)
O2	0.5043 (2)	0.1314 (3)	−0.27322 (14)	0.0666 (8)
O3	0.5690 (2)	0.4496 (3)	0.35068 (13)	0.0512 (6)
C1	0.5965 (3)	0.1882 (3)	0.01729 (16)	0.0354 (7)
H1A	0.5270	0.1384	0.0089	0.043*
H1B	0.6539	0.1295	0.0096	0.043*
C2	0.6341 (3)	0.2421 (3)	0.09683 (16)	0.0352 (7)
H2A	0.7082	0.2823	0.1076	0.042*
H2B	0.6386	0.1715	0.1334	0.042*
C3	0.7111 (2)	0.3487 (3)	−0.05918 (18)	0.0355 (7)
H3A	0.7085	0.4293	−0.0883	0.043*
H3B	0.7632	0.3645	−0.0086	0.043*
C4	0.7620 (3)	0.2440 (3)	−0.09552 (18)	0.0397 (7)
H4A	0.7657	0.1617	−0.0677	0.048*
H4B	0.7141	0.2298	−0.1475	0.048*
C5	0.8773 (3)	0.2810 (4)	−0.09625 (19)	0.0457 (8)
H5A	0.9035	0.2188	−0.1273	0.055*
H5B	0.8759	0.3685	−0.1182	0.055*
C6	1.0568 (3)	0.3250 (5)	−0.0175 (2)	0.0691 (12)
H6A	1.1037	0.3219	0.0348	0.104*
H6B	1.0521	0.4144	−0.0358	0.104*
H6C	1.0889	0.2699	−0.0481	0.104*
C7	0.4913 (3)	0.2555 (3)	−0.13885 (17)	0.0336 (7)
H7A	0.4127	0.2782	−0.1465	0.040*
H7B	0.5140	0.2990	−0.1789	0.040*
C8	0.4975 (3)	0.1093 (3)	−0.15003 (18)	0.0410 (8)
H8A	0.5761	0.0816	−0.1339	0.049*
H8B	0.4593	0.0638	−0.1185	0.049*
C9	0.4444 (3)	0.0725 (3)	−0.23097 (19)	0.0455 (8)
H9A	0.4455	−0.0228	−0.2367	0.055*
H9B	0.3664	0.1021	−0.2481	0.055*
C10	0.4635 (4)	0.1030 (6)	−0.3488 (2)	0.0944 (18)
H10A	0.5089	0.1464	−0.3755	0.142*
H10B	0.3867	0.1333	−0.3683	0.142*
H10C	0.4659	0.0091	−0.3560	0.142*
C11	0.5917 (2)	0.4287 (3)	0.19857 (16)	0.0303 (6)
H11A	0.6554	0.4842	0.1984	0.036*
H11B	0.5356	0.4853	0.2097	0.036*
C12	0.6318 (3)	0.3317 (3)	0.26298 (17)	0.0381 (7)
H12A	0.5718	0.2690	0.2608	0.046*
H12B	0.6959	0.2829	0.2571	0.046*
C13	0.6655 (3)	0.3987 (3)	0.33861 (18)	0.0437 (8)
H13A	0.7016	0.3361	0.3786	0.052*
H13B	0.7187	0.4693	0.3393	0.052*
C14	0.5931 (5)	0.5225 (4)	0.4180 (3)	0.0833 (16)
H14A	0.5240	0.5559	0.4241	0.125*
H14B	0.6419	0.5950	0.4157	0.125*
H14C	0.6301	0.4667	0.4606	0.125*
C15	0.4218 (3)	0.2540 (3)	0.11326 (17)	0.0374 (7)
H15A	0.3810	0.2211	0.0628	0.045*
H15B	0.4577	0.1787	0.1438	0.045*
C16	0.3385 (3)	0.3093 (3)	0.1475 (2)	0.0509 (9)
H16A	0.2935	0.3763	0.1140	0.061*
H16B	0.3777	0.3508	0.1960	0.061*
C17	0.2609 (4)	0.2002 (6)	0.1602 (3)	0.0890 (18)	0.700 (6)
H17A	0.1975	0.2396	0.1727	0.107*	0.700 (6)
H17B	0.2313	0.1495	0.1136	0.107*	0.700 (6)
O4	0.3138 (3)	0.1245 (3)	0.2135 (2)	0.0515 (12)	0.700 (6)
C18	0.2400 (6)	0.0305 (5)	0.2282 (4)	0.0579 (17)	0.700 (6)
H18A	0.2813	−0.0264	0.2690	0.087*	0.700 (6)
H18B	0.2072	−0.0213	0.1830	0.087*	0.700 (6)
H18C	0.1812	0.0747	0.2426	0.087*	0.700 (6)
C17A	0.2609 (4)	0.2002 (6)	0.1602 (3)	0.0890 (18)	0.300 (6)
H17C	0.2140	0.1721	0.1101	0.107*	0.300 (6)
H17D	0.3090	0.1257	0.1825	0.107*	0.300 (6)
O4A	0.2061 (9)	0.2156 (9)	0.1940 (6)	0.072 (4)	0.300 (6)
C18A	0.1540 (15)	0.0978 (17)	0.2088 (10)	0.098 (7)	0.300 (6)
H18D	0.1048	0.1184	0.2387	0.146*	0.300 (6)
H18E	0.2112	0.0368	0.2364	0.146*	0.300 (6)
H18F	0.1106	0.0586	0.1612	0.146*	0.300 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Os1	0.02079 (8)	0.01550 (8)	0.02816 (8)	−0.00026 (6)	0.00918 (6)	0.00023 (6)
Cl1	0.0249 (3)	0.0302 (4)	0.0410 (4)	−0.0056 (3)	0.0105 (3)	−0.0045 (3)
P1	0.0281 (4)	0.0187 (3)	0.0315 (4)	0.0028 (3)	0.0115 (3)	0.0000 (3)
P2	0.0300 (4)	0.0183 (3)	0.0300 (4)	0.0004 (3)	0.0112 (3)	0.0013 (3)
O1	0.0332 (13)	0.091 (2)	0.0499 (15)	0.0038 (14)	0.0149 (11)	0.0043 (14)
O2	0.080 (2)	0.078 (2)	0.0400 (14)	−0.0198 (16)	0.0150 (14)	−0.0137 (14)
O3	0.0617 (17)	0.0534 (14)	0.0407 (14)	−0.0105 (13)	0.0189 (12)	−0.0129 (12)
C1	0.0489 (19)	0.0217 (15)	0.0398 (17)	0.0087 (13)	0.0196 (15)	0.0028 (13)
C2	0.0464 (18)	0.0263 (15)	0.0345 (16)	0.0116 (13)	0.0146 (14)	0.0071 (12)
C3	0.0338 (16)	0.0309 (16)	0.0464 (18)	0.0029 (13)	0.0188 (14)	−0.0018 (14)
C4	0.0377 (18)	0.0457 (19)	0.0392 (18)	0.0094 (15)	0.0169 (15)	−0.0033 (15)
C5	0.0375 (18)	0.060 (2)	0.047 (2)	0.0101 (16)	0.0230 (16)	−0.0002 (17)
C6	0.036 (2)	0.097 (4)	0.074 (3)	0.004 (2)	0.016 (2)	−0.002 (3)
C7	0.0354 (17)	0.0254 (15)	0.0382 (17)	0.0027 (12)	0.0088 (14)	−0.0059 (13)
C8	0.057 (2)	0.0219 (16)	0.0427 (18)	−0.0017 (14)	0.0134 (16)	−0.0029 (13)
C9	0.051 (2)	0.0304 (18)	0.050 (2)	−0.0037 (15)	0.0078 (17)	−0.0116 (15)
C10	0.074 (3)	0.160 (6)	0.044 (3)	0.007 (3)	0.011 (2)	−0.018 (3)
C11	0.0334 (16)	0.0243 (16)	0.0323 (15)	0.0008 (12)	0.0086 (13)	0.0014 (12)
C12	0.0465 (19)	0.0299 (17)	0.0347 (16)	0.0052 (14)	0.0074 (14)	0.0044 (13)
C13	0.051 (2)	0.0391 (19)	0.0338 (17)	−0.0034 (16)	0.0019 (15)	0.0051 (14)
C14	0.115 (5)	0.076 (3)	0.061 (3)	−0.019 (3)	0.031 (3)	−0.033 (2)
C15	0.0468 (19)	0.0304 (17)	0.0363 (17)	−0.0084 (14)	0.0148 (15)	0.0023 (13)
C16	0.046 (2)	0.048 (2)	0.065 (2)	−0.0052 (17)	0.0256 (18)	0.0135 (18)
C17	0.080 (3)	0.128 (5)	0.076 (3)	0.005 (3)	0.048 (3)	0.044 (3)
O4	0.041 (2)	0.058 (2)	0.056 (2)	−0.0074 (17)	0.0166 (17)	0.0144 (18)
C18	0.059 (4)	0.047 (3)	0.080 (4)	−0.018 (3)	0.042 (4)	0.005 (3)
C17A	0.080 (3)	0.128 (5)	0.076 (3)	0.005 (3)	0.048 (3)	0.044 (3)
O4A	0.077 (7)	0.062 (6)	0.077 (7)	−0.007 (5)	0.024 (6)	0.012 (5)
C18A	0.076 (12)	0.099 (14)	0.105 (13)	−0.061 (11)	0.009 (10)	0.042 (11)

Geometric parameters (Å, º) top

Os1—P2	2.3383 (8)	C8—C9	1.509 (4)
Os1—P2ⁱ	2.3383 (8)	C8—H8A	0.9900
Os1—P1ⁱ	2.3434 (8)	C8—H8B	0.9900
Os1—P1	2.3434 (8)	C9—H9A	0.9900
Os1—Cl1	2.4515 (8)	C9—H9B	0.9900
Os1—Cl1ⁱ	2.4515 (8)	C10—H10A	0.9800
P1—C3	1.825 (3)	C10—H10B	0.9800
P1—C7	1.838 (3)	C10—H10C	0.9800
P1—C1	1.845 (3)	C11—C12	1.531 (4)
P2—C11	1.829 (3)	C11—H11A	0.9900
P2—C2	1.840 (3)	C11—H11B	0.9900
P2—C15	1.844 (3)	C12—C13	1.517 (4)
O1—C5	1.405 (4)	C12—H12A	0.9900
O1—C6	1.414 (4)	C12—H12B	0.9900
O2—C10	1.384 (5)	C13—H13A	0.9900
O2—C9	1.392 (4)	C13—H13B	0.9900
O3—C13	1.412 (4)	C14—H14A	0.9800
O3—C14	1.420 (5)	C14—H14B	0.9800
C1—C2	1.525 (4)	C14—H14C	0.9800
C1—H1A	0.9900	C15—C16	1.506 (5)
C1—H1B	0.9900	C15—H15A	0.9900
C2—H2A	0.9900	C15—H15B	0.9900
C2—H2B	0.9900	C16—C17	1.560 (6)
C3—C4	1.521 (4)	C16—H16A	0.9900
C3—H3A	0.9900	C16—H16B	0.9900
C3—H3B	0.9900	C17—O4	1.283 (5)
C4—C5	1.514 (4)	C17—H17A	0.9900
C4—H4A	0.9900	C17—H17B	0.9900
C4—H4B	0.9900	O4—C18	1.431 (6)
C5—H5A	0.9900	C18—H18A	0.9800
C5—H5B	0.9900	C18—H18B	0.9800
C6—H6A	0.9800	C18—H18C	0.9800
C6—H6B	0.9800	O4A—C18A	1.451 (13)
C6—H6C	0.9800	C18A—H18D	0.9800
C7—C8	1.528 (4)	C18A—H18E	0.9800
C7—H7A	0.9900	C18A—H18F	0.9800
C7—H7B	0.9900

P2—Os1—P2ⁱ	180.00 (4)	C9—C8—H8A	109.4
P2—Os1—P1ⁱ	97.10 (3)	C7—C8—H8A	109.4
P2ⁱ—Os1—P1ⁱ	82.90 (3)	C9—C8—H8B	109.4
P2—Os1—P1	82.90 (3)	C7—C8—H8B	109.4
P2ⁱ—Os1—P1	97.10 (3)	H8A—C8—H8B	108.0
P1ⁱ—Os1—P1	180.00 (3)	O2—C9—C8	108.1 (3)
P2—Os1—Cl1	92.13 (3)	O2—C9—H9A	110.1
P2ⁱ—Os1—Cl1	87.87 (3)	C8—C9—H9A	110.1
P1ⁱ—Os1—Cl1	90.91 (3)	O2—C9—H9B	110.1
P1—Os1—Cl1	89.09 (3)	C8—C9—H9B	110.1
P2—Os1—Cl1ⁱ	87.87 (3)	H9A—C9—H9B	108.4
P2ⁱ—Os1—Cl1ⁱ	92.13 (3)	O2—C10—H10A	109.5
P1ⁱ—Os1—Cl1ⁱ	89.09 (3)	O2—C10—H10B	109.5
P1—Os1—Cl1ⁱ	90.91 (3)	H10A—C10—H10B	109.5
Cl1—Os1—Cl1ⁱ	180.0	O2—C10—H10C	109.5
C3—P1—C7	104.32 (15)	H10A—C10—H10C	109.5
C3—P1—C1	102.40 (15)	H10B—C10—H10C	109.5
C7—P1—C1	104.24 (14)	C12—C11—P2	117.7 (2)
C3—P1—Os1	116.50 (10)	C12—C11—H11A	107.9
C7—P1—Os1	118.55 (10)	P2—C11—H11A	107.9
C1—P1—Os1	109.03 (10)	C12—C11—H11B	107.9
C11—P2—C2	103.16 (14)	P2—C11—H11B	107.9
C11—P2—C15	103.69 (14)	H11A—C11—H11B	107.2
C2—P2—C15	98.98 (15)	C13—C12—C11	111.8 (2)
C11—P2—Os1	120.25 (10)	C13—C12—H12A	109.3
C2—P2—Os1	107.11 (10)	C11—C12—H12A	109.3
C15—P2—Os1	120.36 (11)	C13—C12—H12B	109.3
C5—O1—C6	112.7 (3)	C11—C12—H12B	109.3
C10—O2—C9	113.1 (3)	H12A—C12—H12B	107.9
C13—O3—C14	112.2 (3)	O3—C13—C12	108.0 (3)
C2—C1—P1	108.5 (2)	O3—C13—H13A	110.1
C2—C1—H1A	110.0	C12—C13—H13A	110.1
P1—C1—H1A	110.0	O3—C13—H13B	110.1
C2—C1—H1B	110.0	C12—C13—H13B	110.1
P1—C1—H1B	110.0	H13A—C13—H13B	108.4
H1A—C1—H1B	108.4	O3—C14—H14A	109.5
C1—C2—P2	107.7 (2)	O3—C14—H14B	109.5
C1—C2—H2A	110.2	H14A—C14—H14B	109.5
P2—C2—H2A	110.2	O3—C14—H14C	109.5
C1—C2—H2B	110.2	H14A—C14—H14C	109.5
P2—C2—H2B	110.2	H14B—C14—H14C	109.5
H2A—C2—H2B	108.5	C16—C15—P2	117.0 (2)
C4—C3—P1	120.1 (2)	C16—C15—H15A	108.0
C4—C3—H3A	107.3	P2—C15—H15A	108.0
P1—C3—H3A	107.3	C16—C15—H15B	108.0
C4—C3—H3B	107.3	P2—C15—H15B	108.0
P1—C3—H3B	107.3	H15A—C15—H15B	107.3
H3A—C3—H3B	106.9	C15—C16—C17	110.3 (3)
C5—C4—C3	111.5 (3)	C15—C16—H16A	109.6
C5—C4—H4A	109.3	C17—C16—H16A	109.6
C3—C4—H4A	109.3	C15—C16—H16B	109.6
C5—C4—H4B	109.3	C17—C16—H16B	109.6
C3—C4—H4B	109.3	H16A—C16—H16B	108.1
H4A—C4—H4B	108.0	O4—C17—C16	110.8 (4)
O1—C5—C4	109.1 (3)	O4—C17—H17A	109.5
O1—C5—H5A	109.9	C16—C17—H17A	109.5
C4—C5—H5A	109.9	O4—C17—H17B	109.5
O1—C5—H5B	109.9	C16—C17—H17B	109.5
C4—C5—H5B	109.9	H17A—C17—H17B	108.1
H5A—C5—H5B	108.3	C17—O4—C18	110.3 (4)
O1—C6—H6A	109.5	O4—C18—H18A	109.5
O1—C6—H6B	109.5	O4—C18—H18B	109.5
H6A—C6—H6B	109.5	H18A—C18—H18B	109.5
O1—C6—H6C	109.5	O4—C18—H18C	109.5
H6A—C6—H6C	109.5	H18A—C18—H18C	109.5
H6B—C6—H6C	109.5	H18B—C18—H18C	109.5
C8—C7—P1	118.3 (2)	O4A—C18A—H18D	109.5
C8—C7—H7A	107.7	O4A—C18A—H18E	109.5
P1—C7—H7A	107.7	H18D—C18A—H18E	109.5
C8—C7—H7B	107.7	O4A—C18A—H18F	109.5
P1—C7—H7B	107.7	H18D—C18A—H18F	109.5
H7A—C7—H7B	107.1	H18E—C18A—H18F	109.5
C9—C8—C7	111.2 (3)

P2—Os1—P1—C3	−109.55 (12)	C7—P1—C1—C2	−163.7 (2)
P2ⁱ—Os1—P1—C3	70.45 (12)	Os1—P1—C1—C2	−36.2 (2)
P1ⁱ—Os1—P1—C3	5 (47)	P1—C1—C2—P2	53.3 (2)
Cl1—Os1—P1—C3	158.19 (12)	C11—P2—C2—C1	−175.8 (2)
Cl1ⁱ—Os1—P1—C3	−21.81 (12)	C15—P2—C2—C1	77.8 (2)
P2—Os1—P1—C7	124.59 (12)	Os1—P2—C2—C1	−47.9 (2)
P2ⁱ—Os1—P1—C7	−55.41 (12)	C7—P1—C3—C4	−43.0 (3)
P1ⁱ—Os1—P1—C7	−121 (47)	C1—P1—C3—C4	65.5 (3)
Cl1—Os1—P1—C7	32.34 (12)	Os1—P1—C3—C4	−175.7 (2)
Cl1ⁱ—Os1—P1—C7	−147.66 (12)	P1—C3—C4—C5	−178.2 (2)
P2—Os1—P1—C1	5.65 (11)	C6—O1—C5—C4	−174.6 (3)
P2ⁱ—Os1—P1—C1	−174.35 (11)	C3—C4—C5—O1	68.8 (4)
P1ⁱ—Os1—P1—C1	120 (47)	C3—P1—C7—C8	83.9 (3)
Cl1—Os1—P1—C1	−86.61 (11)	C1—P1—C7—C8	−23.2 (3)
Cl1ⁱ—Os1—P1—C1	93.39 (11)	Os1—P1—C7—C8	−144.6 (2)
P2ⁱ—Os1—P2—C11	88 (100)	P1—C7—C8—C9	−168.4 (2)
P1ⁱ—Os1—P2—C11	−43.13 (12)	C10—O2—C9—C8	179.3 (4)
P1—Os1—P2—C11	136.87 (12)	C7—C8—C9—O2	62.8 (4)
Cl1—Os1—P2—C11	−134.31 (12)	C2—P2—C11—C12	−49.0 (3)
Cl1ⁱ—Os1—P2—C11	45.69 (12)	C15—P2—C11—C12	53.8 (3)
P2ⁱ—Os1—P2—C2	−29 (100)	Os1—P2—C11—C12	−168.09 (19)
P1ⁱ—Os1—P2—C2	−160.21 (11)	P2—C11—C12—C13	−172.6 (2)
P1—Os1—P2—C2	19.79 (11)	C14—O3—C13—C12	−175.8 (3)
Cl1—Os1—P2—C2	108.61 (11)	C11—C12—C13—O3	68.3 (3)
Cl1ⁱ—Os1—P2—C2	−71.39 (11)	C11—P2—C15—C16	52.9 (3)
P2ⁱ—Os1—P2—C15	−141 (100)	C2—P2—C15—C16	158.9 (3)
P1ⁱ—Os1—P2—C15	88.10 (12)	Os1—P2—C15—C16	−85.1 (3)
P1—Os1—P2—C15	−91.90 (12)	P2—C15—C16—C17	−173.0 (3)
Cl1—Os1—P2—C15	−3.08 (12)	C15—C16—C17—O4	70.8 (5)
Cl1ⁱ—Os1—P2—C15	176.92 (12)	C16—C17—O4—C18	175.9 (4)
C3—P1—C1—C2	87.8 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[OsCl₂(C₁₈H₄₀O₄P₂)₂]
M_r	1025.98
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	12.667 (3), 10.321 (2), 18.754 (4)
β (°)	107.779 (3)
V (Å³)	2335.0 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.03
Crystal size (mm)	0.14 × 0.10 × 0.04

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1995)
T_min, T_max	0.677, 0.889
No. of measured, independent and observed [I > 2σ(I)] reflections	25950, 5333, 4423
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.058, 1.04
No. of reflections	5333
No. of parameters	251
No. of restraints	5
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.51

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Os1—P2	2.3383 (8)	Os1—Cl1	2.4515 (8)
Os1—P1	2.3434 (8)

Acknowledgements

We thank the NSF for funding.

References

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