trans-Tetra­chloro­bis­(tri­phenyl­phosphine)­osmium(IV)

The structure of the title compound, [OsCl₄(C₁₈H₁₅P)₂], is centrosymmetric. The geometry of the Os^IV center is octahedral with the P atoms occupying mutually trans-positions.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.032
• wR factor = 0.078
• Data-to-parameter ratio = 19.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Osmium(IV) complexes of the type trans-[Os(PR₃)₂X₄] (X = Cl or Br) have been characterized spectroscopically (Salmon & Walton, 1978; Cipriano et al., 1990), but only the Os^IV(PMe₂Ph)₂Cl₄ species has been structurally characterized (Aslanov et al., 1970). In our preparation of OsCl₂(PPh₃)₃ from the reaction of K₂OsCl₆ with PPh₃ according to the literature method (Hoffmann & Caulton, 1975), the title compound, (I), was also formed and subsequently characterized crystallographically.

The structure of I (Fig. 1) is centrosymmetric. The geometry around the Os(IV) center is octahedral with two P atoms in mutually trans positions. The Os—Cl distances (mean 2.313 (6) Å) are experimentally equivalent to those reported for the Os^IV(PMe₂Ph)₂Cl₄ structure (mean 2.319 (3) Å, Aslanov et al., 1970), but significantly shorter than those for [Os^III(PEt₃)₂Cl₄]_- (mean 2.380 (2) Å, Kim et al., 1984), as expected.

S2. Experimental

The title compound was obtained as a by-product when Os(PPh₃)₃Cl₂ was prepared according to literature method (Hoffmann & Caulton, 1975). A mixture of K₂OsCl₆ and PPh₃ (1:7) in 2-propanol and H₂O (2:1) was refluxed for 4 h to give a green precipitate, which was collected and extracted with benzene. A small amount of benzene insoluble orange-red solid was collected by filtration and recrystallized from a CH₂Cl₂ solution layered with hexane to afford orange-red crystals suitable for X-ray structure analysis.

S3. Refinement

The C-bound H atoms were placed in their geometrically calculated positions and included in the final refinement in the riding model approximation.

Computing details

Data collection: Bruker SMART; cell refinement: Bruker SMART; data reduction: Bruker SHELXTL; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

Figures

Fig. 1. Molecular structure of (I) showing with displacement ellipsoids shown at the 30% probability level (Bruker, 1955). Symmetry operation for atoms labeled with 'A': -x, 1 - y, -z.

trans-Tetrachloro-bis(triphenylphosphine)osmium(IV)

Crystal data

C36H30Cl4OsP2	F(000) = 840
Mr = 856.54	Dx = 1.702 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.3364 (9) Å	Cell parameters from CCD reflections
b = 20.948 (2) Å	θ = 1.0–27.5°
c = 9.6251 (9) Å	µ = 4.26 mm^−1
β = 117.425 (2)°	T = 294 K
V = 1670.9 (3) Å^3	Prism, orange-red
Z = 2	0.20 × 0.16 × 0.10 mm

Data collection

Bruker CCD Area Detector diffractometer	3844 independent reflections
Radiation source: fine-focus sealed tube	2867 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
phi and ω scan	θmax = 27.6°, θmin = 1.9°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −6→12
Tmin = 0.483, Tmax = 0.676	k = −25→27
11100 measured reflections	l = −12→12

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0409P)^2] where P = (Fo^2 + 2Fc^2)/3
3844 reflections	(Δ/σ)max < 0.001
194 parameters	Δρmax = 0.98 e Å^−3
0 restraints	Δρmin = −0.60 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	0.0000	0.5000	0.0000	0.02692 (8)
Cl1	−0.02973 (14)	0.52136 (6)	−0.24674 (13)	0.0406 (3)
Cl2	0.23832 (14)	0.55820 (6)	0.11330 (14)	0.0459 (3)
P1	0.16725 (13)	0.40280 (5)	0.02986 (12)	0.0292 (2)
C1	0.3804 (5)	0.4102 (2)	0.1714 (5)	0.0343 (9)
C2	0.5065 (6)	0.3981 (3)	0.1369 (6)	0.0509 (12)
H2A	0.4798	0.3867	0.0331	0.042*
C3	0.6625 (7)	0.4013 (3)	0.2523 (8)	0.0691 (17)
H3A	0.7317	0.3842	0.2281	0.062*
C4	0.6988 (6)	0.4155 (3)	0.4024 (7)	0.0661 (17)
H4A	0.8052	0.4218	0.4886	0.081*
C5	0.5765 (6)	0.4273 (3)	0.4389 (6)	0.0650 (16)
H5A	0.5996	0.4369	0.5414	0.078*
C6	0.4184 (6)	0.4251 (3)	0.3236 (6)	0.0555 (14)
H6A	0.3359	0.4339	0.3493	0.067*
C7	0.1138 (5)	0.32993 (19)	0.0984 (5)	0.0350 (10)
C8	−0.0207 (6)	0.3227 (2)	0.1166 (7)	0.0556 (14)
H8A	−0.0932	0.3564	0.0923	0.067*
C9	−0.0518 (8)	0.2658 (3)	0.1709 (8)	0.0722 (18)
H9A	−0.1450	0.2623	0.1826	0.087*
C10	0.0460 (7)	0.2166 (3)	0.2065 (8)	0.0685 (17)
H10A	0.0247	0.1792	0.2459	0.082*
C11	0.1791 (8)	0.2218 (3)	0.1842 (9)	0.0893 (19)
H11A	0.2588	0.1883	0.2088	0.105*
C12	0.2146 (7)	0.2783 (3)	0.1329 (8)	0.0730 (15)
H12A	0.3101	0.2831	0.1071	0.091*
C13	0.1654 (5)	0.3819 (2)	−0.1535 (5)	0.0331 (9)
C14	0.0885 (6)	0.3280 (2)	−0.2372 (6)	0.0487 (12)
H14A	0.0412	0.2996	−0.1963	0.058*
C15	0.0816 (7)	0.3160 (3)	−0.3819 (6)	0.0635 (15)
H15A	0.0293	0.2796	−0.4373	0.076*
C16	0.1505 (7)	0.3570 (3)	−0.4435 (6)	0.0644 (16)
H16A	0.1449	0.3486	−0.5408	0.077*
C17	0.2274 (8)	0.4103 (3)	−0.3629 (6)	0.0604 (16)
H17A	0.2790	0.4386	−0.3868	0.071*
C18	0.2355 (6)	0.4237 (2)	−0.2182 (6)	0.0483 (12)
H18A	0.2875	0.4605	−0.1644	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Os1	0.02432 (12)	0.02939 (13)	0.02396 (12)	−0.00038 (10)	0.00847 (9)	0.00007 (9)
Cl1	0.0425 (6)	0.0490 (6)	0.0307 (6)	0.0083 (5)	0.0172 (5)	0.0058 (5)
Cl2	0.0336 (6)	0.0444 (7)	0.0474 (7)	−0.0097 (5)	0.0081 (5)	−0.0006 (5)
P1	0.0265 (5)	0.0317 (6)	0.0287 (5)	0.0011 (4)	0.0121 (4)	0.0014 (4)
C1	0.025 (2)	0.036 (2)	0.038 (2)	−0.0007 (18)	0.0118 (19)	0.0014 (18)
C2	0.034 (3)	0.071 (3)	0.048 (3)	−0.004 (2)	0.018 (2)	−0.007 (2)
C3	0.035 (3)	0.094 (5)	0.080 (4)	0.006 (3)	0.027 (3)	−0.001 (4)
C4	0.031 (3)	0.074 (4)	0.069 (4)	0.005 (3)	0.001 (3)	−0.012 (3)
C5	0.044 (3)	0.097 (5)	0.036 (3)	0.013 (3)	0.003 (2)	−0.007 (3)
C6	0.032 (3)	0.086 (4)	0.038 (3)	0.015 (3)	0.007 (2)	0.002 (3)
C7	0.032 (2)	0.033 (2)	0.038 (2)	−0.0003 (19)	0.015 (2)	0.0032 (18)
C8	0.048 (3)	0.041 (3)	0.087 (4)	0.003 (2)	0.039 (3)	0.010 (3)
C9	0.065 (4)	0.051 (3)	0.118 (6)	−0.002 (3)	0.056 (4)	0.016 (3)
C10	0.056 (4)	0.051 (3)	0.097 (5)	−0.003 (3)	0.034 (4)	0.025 (3)
C11	0.065 (4)	0.074 (5)	0.107 (5)	0.010 (3)	0.021 (4)	0.049 (4)
C12	0.049 (3)	0.073 (4)	0.093 (3)	0.012 (3)	0.028 (3)	0.040 (3)
C13	0.030 (2)	0.040 (2)	0.028 (2)	0.0116 (18)	0.0121 (18)	0.0027 (18)
C14	0.041 (3)	0.056 (3)	0.049 (3)	0.004 (2)	0.021 (2)	−0.004 (2)
C15	0.055 (4)	0.075 (4)	0.050 (3)	0.007 (3)	0.015 (3)	−0.020 (3)
C16	0.069 (4)	0.090 (5)	0.035 (3)	0.024 (3)	0.025 (3)	0.004 (3)
C17	0.076 (4)	0.069 (4)	0.051 (3)	0.024 (3)	0.042 (3)	0.020 (3)
C18	0.062 (3)	0.045 (3)	0.046 (3)	0.015 (2)	0.033 (3)	0.008 (2)

Geometric parameters (Å, º)

Os1—Cl1^i	2.3044 (11)	C5—C6	1.380 (7)
Os1—Cl1	2.3044 (11)	C7—C8	1.354 (6)
Os1—Cl2^i	2.3220 (11)	C7—C12	1.370 (7)
Os1—Cl2	2.3220 (11)	C8—C9	1.385 (7)
Os1—P1^i	2.5007 (11)	C9—C10	1.314 (8)
Os1—P1	2.5007 (11)	C10—C11	1.359 (8)
P1—C13	1.811 (4)	C11—C12	1.381 (8)
P1—C7	1.822 (4)	C13—C14	1.380 (6)
P1—C1	1.829 (4)	C13—C18	1.400 (6)
C1—C6	1.375 (6)	C14—C15	1.387 (7)
C1—C2	1.385 (6)	C15—C16	1.362 (8)
C2—C3	1.367 (7)	C16—C17	1.360 (8)
C3—C4	1.356 (8)	C17—C18	1.388 (7)
C4—C5	1.363 (7)
Cl1^i—Os1—Cl1	180.00 (6)	C2—C1—P1	124.0 (3)
Cl1^i—Os1—Cl2^i	90.95 (4)	C3—C2—C1	120.1 (5)
Cl1—Os1—Cl2^i	89.05 (4)	C4—C3—C2	121.7 (5)
Cl1^i—Os1—Cl2	89.05 (4)	C3—C4—C5	119.1 (5)
Cl1—Os1—Cl2	90.95 (4)	C4—C5—C6	120.0 (5)
Cl2^i—Os1—Cl2	180.00 (5)	C1—C6—C5	121.3 (5)
Cl1^i—Os1—P1^i	92.81 (4)	C8—C7—C12	117.1 (4)
Cl1—Os1—P1^i	87.19 (4)	C8—C7—P1	124.4 (3)
Cl2^i—Os1—P1^i	87.76 (4)	C12—C7—P1	118.5 (4)
Cl2—Os1—P1^i	92.24 (4)	C7—C8—C9	120.9 (5)
Cl1^i—Os1—P1	87.19 (4)	C10—C9—C8	122.2 (5)
Cl1—Os1—P1	92.81 (4)	C9—C10—C11	118.1 (5)
Cl2^i—Os1—P1	92.24 (4)	C10—C11—C12	120.9 (6)
Cl2—Os1—P1	87.76 (4)	C7—C12—C11	120.8 (5)
P1^i—Os1—P1	180.0	C14—C13—C18	118.4 (4)
C13—P1—C7	105.6 (2)	C14—C13—P1	122.3 (3)
C13—P1—C1	105.37 (19)	C18—C13—P1	119.1 (3)
C7—P1—C1	100.8 (2)	C13—C14—C15	120.4 (5)
C13—P1—Os1	111.06 (13)	C16—C15—C14	120.7 (5)
C7—P1—Os1	117.60 (14)	C17—C16—C15	120.0 (5)
C1—P1—Os1	115.10 (14)	C16—C17—C18	120.7 (5)
C6—C1—C2	117.8 (4)	C17—C18—C13	119.9 (5)
C6—C1—P1	118.1 (3)

Symmetry code: (i) −x, −y+1, −z.