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The OsII atom in the title compound, [OsCl2(C8H12)(C18H15P)2], is located on a crystallographic twofold axis and adopts a distorted octa­hedral coordination geometry. The two triphenyl­phosphine ligands are trans to each other, while the two chlorine ligands are cis-disposed. The coordination is completed by the cyclo­octa­diene (COD) ligand with bonding to the two olefin double bonds. The C=C bond has a length of 1.403 (6) Å, which is significntly longer than a free olefinic double bond (≃1.34 Å).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809037817/wm2258sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536809037817/wm2258Isup2.hkl
Contains datablock I

CCDC reference: 750568

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.008 Å
  • R factor = 0.022
  • wR factor = 0.044
  • Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT158_ALERT_4_C The Input Unitcell is NOT Standard/Reduced ..... ?
Alert level G REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 25.99 From the CIF: _reflns_number_total 2778 Count of symmetry unique reflns 1856 Completeness (_total/calc) 149.68% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 922 Fraction of Friedel pairs measured 0.497 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The ruthenium polymer [RuCl2(COD)]x (COD = cycloocta-1,5-diene), which can be readily prepared in 30–40% yield from RuCl3.3H2O and COD in boiling ethanol (Bennett & Wilkinson, 1959; Albers et al., 1989), has proved to be a useful precursor for a wide variety of ruthenium compounds (Cucullu et al., 1999; Coalter & Caulton, 2001; Alvarez et al., 2001). Although the analogous osmium polymer [OsCl2(COD)]x is also known, its utility as a starting material has remained relatively unexplored partially due to the difficuly in its preparation (Winkhaus et al., 1966; Schrock et al., 1974; Dickinson & Girolami, 2006). In our search for other potential precusors for the synthesis of osmium compounds, we have prepared [OsCl2(η4– COD)(PPh3)2] readily from the reaction of OsCl2(PPh3)3 with COD.

The title compound crystallizes in the non-centrosymmetric orthorhombic space group Fdd2. As shown in Fig.1, the structure possesses a crystallographic 2-fold axis passing through the osmium atom, thus the asymmetric unit contains half of a molecule. The OsII centre adopts a distorted octahedral geometry with the two triphenylphosphine ligands trans to each other (P(1)—Os(1)—P(1 A) 148.31 (6)°), while the two chlorine ligands are cis-disposed (Cl(1)—Os(1)—Cl(1 A) 103.69 (6)°) (symmetry code: -x + 1/2, -y + 1/2, z). The coordination is completed by the two olefin double bonds of the cyclooctadiene ligand. The Os(1)—C(1) and Os(1)—C(2) bond lengths (2.195 (5) and 2.168 (5) Å, respectively) are similar to the related Os—C bond lengths reported for other COD coordinated OsII complexes such as [H(EtOH)2[{OsCl(η4-COD)}2(µ-H)(µ-Cl)2] (2.129–2.152 Å) (Esteruelas et al., 2006) and TpOs(η4-COD)OMe (Tp = trispyrazolylborate) (2.141–2.198 Å) (Dickinson & Girolami, 2006). The C(1)—C(2) (1.403 (6) Å) bond length is significntly longer than a free olefinic double bond ( 1.34 Å) (Orpen et al., 1989) and is typical for a coordinated CC double bond, which is also close to the CC bond lengths found in [H(EtOH)2[{OsCl(η4-COD)}2(µ-H)(µ-Cl)2] (1.393–1.422 Å) and TpOs(η4-COD)OMe (1.396 (5) and 1.399 (5) Å).

Related literature top

For general background to RuII and OsII COD complexes, see: Bennett & Wilkinson (1959); Albers et al. (1989); Cucullu et al. (1999); Coalter & Caulton (2001); Alvarez et al. (2001); Winkhaus et al. (1966); Schrock et al. (1974); Dickinson & Girolami (2006). For CC bond lengths for free olefinic double bonds, see: Orpen et al. (1989). For related COD-coordinated OsII complexes, see: Esteruelas et al. (2006); Dickinson & Girolami (2006).

Experimental top

To a solution of OsCl2(PPh3)3 (0.52 g, 0.50 mmol) in toluene (10 ml) under nitrogen atmosphere was added cycloocta-1,5-diene (0.20 ml, 2.5 mmol). The reaction mixture was stirred at room temperature for 30 h to give the title compound as large amount of a yellow precipitate. The solid was collected by filtration, washed with toluene (2 × 5 ml) and diethyl ether (3 × 5 ml), and dried under vaccum. Yield: 0.38 g, 85%. Crystals suitable for X-ray analysis were obtained by layering a solution of the title compound with a solution of chloroform and hexane.

Refinement top

All non-hydrogen atoms were refined anisotropically. The hydrogen atoms were positioned geometrically (C—H =0.95, 1.00 or 0.99 Å for phenyl, tertiary or methylene H atoms, respectively) and were included in the refinement in the riding model approximation. The displacement parameters of H atoms were set to 1.2Ueq(C). In the final Fourier map the highest peak is 0.99 Å from atom Os1 and the deepest hole is 1.86 Å from atom C15.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); 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
[Figure 1] Fig. 1. The structure of [OsCl2(C8H12)(C18H15P) 2] showing 40% probability displacement ellipsoids. H atoms have been omitted for clarity. Atoms with symmetry code letter A are related by -x + 1/2, -y + 1/2, z.
Dichlorido(η4-cycloocta-1,5-diene)bis(triphenylphosphine)osmium(II) top
Crystal data top
[OsCl2(C8H12)(PC18H15)2]F(000) = 3568
Mr = 893.82Dx = 1.628 Mg m3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 5605 reflections
a = 39.6505 (15) Åθ = 2.3–32.5°
b = 10.4393 (5) ŵ = 3.76 mm1
c = 17.6248 (8) ÅT = 173 K
V = 7295.3 (6) Å3Block, light yellow
Z = 80.15 × 0.15 × 0.12 mm
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
2778 independent reflections
Radiation source: Enhance (Mo) X-ray Source2546 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 16.1930 pixels mm-1θmax = 26.0°, θmin = 2.3°
ω scansh = 4848
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
k = 1212
Tmin = 0.860, Tmax = 1.000l = 2116
6965 measured reflections
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)] = 0.022H-atom parameters constrained
wR(F2) = 0.044 w = 1/[σ2(Fo2) + (0.0184P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
2778 reflectionsΔρmax = 1.39 e Å3
222 parametersΔρmin = 0.74 e Å3
1 restraintAbsolute structure: Flack (1983), 937 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.009 (6)
Crystal data top
[OsCl2(C8H12)(PC18H15)2]V = 7295.3 (6) Å3
Mr = 893.82Z = 8
Orthorhombic, Fdd2Mo Kα radiation
a = 39.6505 (15) ŵ = 3.76 mm1
b = 10.4393 (5) ÅT = 173 K
c = 17.6248 (8) Å0.15 × 0.15 × 0.12 mm
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
2778 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
2546 reflections with I > 2σ(I)
Tmin = 0.860, Tmax = 1.000Rint = 0.033
6965 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.044Δρmax = 1.39 e Å3
S = 1.00Δρmin = 0.74 e Å3
2778 reflectionsAbsolute structure: Flack (1983), 937 Friedel pairs
222 parametersAbsolute structure parameter: 0.009 (6)
1 restraint
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
xyzUiso*/Ueq
Os10.25000.25000.134570 (16)0.01584 (6)
Cl10.27183 (3)0.08574 (11)0.22020 (7)0.0225 (3)
P10.19622 (3)0.14284 (12)0.17335 (8)0.0183 (3)
C10.25093 (11)0.1050 (4)0.0444 (3)0.0232 (10)
H1A0.24990.01450.06290.028*
C20.28281 (11)0.1625 (5)0.0509 (3)0.0203 (10)
H2A0.30050.10530.07280.024*
C30.29572 (11)0.2541 (5)0.0092 (3)0.0243 (10)
H3A0.29910.20670.05720.029*
H3B0.31790.28820.00690.029*
C40.27153 (12)0.3668 (5)0.0234 (3)0.0279 (12)
H4A0.28490.44420.03570.033*
H4B0.25720.34680.06780.033*
C110.19375 (10)0.0268 (4)0.1464 (3)0.0222 (11)
C120.18371 (11)0.0649 (5)0.0742 (3)0.0263 (12)
H12A0.17590.00210.03930.032*
C130.18481 (12)0.1911 (5)0.0520 (4)0.0342 (13)
H13A0.17790.21560.00240.041*
C140.19615 (15)0.2814 (6)0.1031 (5)0.0346 (18)
H14A0.19690.36890.08850.041*
C150.20651 (14)0.2471 (6)0.1754 (5)0.0349 (18)
H15A0.21420.31070.20990.042*
C160.20554 (11)0.1196 (4)0.1973 (3)0.0257 (12)
H16A0.21290.09520.24650.031*
C210.18731 (10)0.1237 (4)0.2762 (3)0.0204 (10)
C220.15626 (12)0.0737 (5)0.2961 (3)0.0270 (12)
H22A0.13950.06180.25820.032*
C230.14915 (12)0.0407 (5)0.3707 (4)0.0318 (14)
H23A0.12760.00770.38350.038*
C240.17309 (13)0.0556 (5)0.4255 (3)0.0317 (13)
H24A0.16850.03100.47640.038*
C250.20399 (12)0.1068 (5)0.4063 (3)0.0306 (13)
H25A0.22070.11820.44440.037*
C260.21088 (12)0.1414 (5)0.3332 (3)0.0259 (12)
H26A0.23220.17800.32130.031*
C310.15530 (10)0.2115 (4)0.1440 (3)0.0191 (12)
C320.14963 (12)0.3414 (5)0.1543 (3)0.0240 (12)
H32A0.16700.39300.17540.029*
C330.11927 (12)0.3978 (5)0.1344 (4)0.0305 (13)
H33A0.11610.48730.14140.037*
C340.09364 (12)0.3237 (6)0.1046 (3)0.0323 (14)
H34A0.07310.36220.08890.039*
C350.09823 (12)0.1943 (6)0.0978 (3)0.0304 (13)
H35A0.08020.14230.08000.037*
C360.12872 (12)0.1382 (5)0.1165 (3)0.0246 (14)
H36A0.13150.04840.11060.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Os10.01417 (9)0.01427 (10)0.01910 (11)0.00191 (17)0.0000.000
Cl10.0193 (5)0.0201 (6)0.0280 (7)0.0041 (4)0.0005 (5)0.0053 (6)
P10.0167 (5)0.0157 (6)0.0224 (7)0.0016 (5)0.0000 (5)0.0006 (6)
C10.027 (2)0.016 (2)0.027 (3)0.004 (2)0.007 (3)0.005 (2)
C20.022 (2)0.019 (3)0.019 (3)0.0009 (19)0.000 (2)0.005 (2)
C30.023 (2)0.027 (3)0.023 (2)0.001 (2)0.000 (2)0.003 (3)
C40.030 (2)0.026 (3)0.028 (3)0.002 (2)0.003 (2)0.003 (3)
C110.0164 (19)0.016 (2)0.034 (3)0.0028 (16)0.004 (2)0.007 (2)
C120.024 (2)0.023 (3)0.031 (3)0.001 (2)0.001 (2)0.003 (2)
C130.030 (3)0.031 (3)0.041 (3)0.004 (2)0.002 (3)0.014 (3)
C140.027 (3)0.017 (3)0.060 (5)0.004 (2)0.005 (3)0.011 (3)
C150.022 (3)0.027 (3)0.055 (5)0.008 (2)0.000 (3)0.007 (4)
C160.021 (2)0.020 (3)0.035 (3)0.0002 (19)0.003 (2)0.001 (2)
C210.021 (2)0.019 (2)0.022 (3)0.0058 (18)0.005 (2)0.005 (2)
C220.023 (2)0.028 (3)0.030 (3)0.000 (2)0.001 (2)0.005 (3)
C230.029 (2)0.031 (3)0.035 (4)0.0005 (18)0.005 (3)0.007 (3)
C240.043 (3)0.029 (3)0.024 (3)0.008 (2)0.004 (3)0.005 (3)
C250.030 (3)0.039 (3)0.023 (3)0.004 (2)0.002 (2)0.003 (3)
C260.025 (2)0.025 (3)0.028 (3)0.004 (2)0.004 (2)0.005 (2)
C310.0143 (18)0.021 (3)0.022 (4)0.0026 (15)0.000 (2)0.003 (3)
C320.022 (2)0.022 (3)0.028 (3)0.003 (2)0.001 (2)0.006 (2)
C330.028 (2)0.029 (3)0.035 (3)0.015 (2)0.007 (3)0.004 (3)
C340.016 (2)0.042 (4)0.039 (4)0.004 (2)0.000 (2)0.002 (3)
C350.017 (2)0.044 (3)0.030 (3)0.006 (2)0.001 (2)0.010 (3)
C360.020 (3)0.022 (3)0.032 (4)0.003 (2)0.001 (3)0.005 (3)
Geometric parameters (Å, º) top
Os1—C2i2.169 (5)C14—C151.386 (8)
Os1—C22.169 (5)C14—H14A0.9500
Os1—C12.195 (5)C15—C161.387 (7)
Os1—C1i2.195 (5)C15—H15A0.9500
Os1—Cl1i2.4429 (12)C16—H16A0.9500
Os1—Cl12.4429 (12)C21—C221.382 (6)
Os1—P12.5031 (12)C21—C261.384 (7)
Os1—P1i2.5031 (12)C22—C231.387 (8)
P1—C111.836 (4)C22—H22A0.9500
P1—C311.848 (4)C23—C241.364 (8)
P1—C211.858 (5)C23—H23A0.9500
C1—C21.404 (6)C24—C251.379 (7)
C1—C4i1.519 (7)C24—H24A0.9500
C1—H1A1.0000C25—C261.365 (7)
C2—C31.516 (7)C25—H25A0.9500
C2—H2A1.0000C26—H26A0.9500
C3—C41.538 (7)C31—C321.386 (7)
C3—H3A0.9900C31—C361.390 (7)
C3—H3B0.9900C32—C331.385 (7)
C4—C1i1.519 (7)C32—H32A0.9500
C4—H4A0.9900C33—C341.381 (7)
C4—H4B0.9900C33—H33A0.9500
C11—C121.392 (7)C34—C351.368 (7)
C11—C161.400 (7)C34—H34A0.9500
C12—C131.375 (7)C35—C361.383 (7)
C12—H12A0.9500C35—H35A0.9500
C13—C141.380 (9)C36—H36A0.9500
C13—H13A0.9500
C2i—Os1—C294.3 (3)C3—C4—H4B109.1
C2i—Os1—C178.95 (18)H4A—C4—H4B107.8
C2—Os1—C137.52 (16)C12—C11—C16118.9 (4)
C2i—Os1—C1i37.52 (16)C12—C11—P1121.8 (4)
C2—Os1—C1i78.95 (18)C16—C11—P1118.9 (4)
C1—Os1—C1i87.3 (3)C13—C12—C11121.7 (5)
C2i—Os1—Cl1i84.95 (14)C13—C12—H12A119.2
C2—Os1—Cl1i158.22 (12)C11—C12—H12A119.2
C1—Os1—Cl1i159.61 (12)C12—C13—C14118.6 (6)
C1i—Os1—Cl1i87.54 (13)C12—C13—H13A120.7
C2i—Os1—Cl1158.22 (12)C14—C13—H13A120.7
C2—Os1—Cl184.95 (14)C13—C14—C15121.4 (6)
C1—Os1—Cl187.54 (13)C13—C14—H14A119.3
C1i—Os1—Cl1159.61 (12)C15—C14—H14A119.3
Cl1i—Os1—Cl1103.69 (6)C14—C15—C16119.7 (6)
C2i—Os1—P182.14 (12)C14—C15—H15A120.2
C2—Os1—P1120.55 (12)C16—C15—H15A120.2
C1—Os1—P184.48 (13)C15—C16—C11119.7 (6)
C1i—Os1—P1119.44 (12)C15—C16—H16A120.1
Cl1i—Os1—P180.97 (4)C11—C16—H16A120.1
Cl1—Os1—P179.60 (4)C22—C21—C26117.9 (5)
C2i—Os1—P1i120.55 (12)C22—C21—P1117.2 (4)
C2—Os1—P1i82.14 (12)C26—C21—P1124.4 (3)
C1—Os1—P1i119.44 (12)C21—C22—C23121.0 (5)
C1i—Os1—P1i84.48 (13)C21—C22—H22A119.5
Cl1i—Os1—P1i79.60 (4)C23—C22—H22A119.5
Cl1—Os1—P1i80.97 (4)C24—C23—C22120.1 (5)
P1—Os1—P1i148.31 (6)C24—C23—H23A120.0
C11—P1—C31104.8 (2)C22—C23—H23A120.0
C11—P1—C2198.0 (2)C23—C24—C25119.3 (5)
C31—P1—C2198.5 (2)C23—C24—H24A120.4
C11—P1—Os1113.95 (14)C25—C24—H24A120.4
C31—P1—Os1119.87 (15)C26—C25—C24120.8 (5)
C21—P1—Os1118.45 (15)C26—C25—H25A119.6
C2—C1—C4i120.5 (4)C24—C25—H25A119.6
C2—C1—Os170.2 (3)C25—C26—C21120.9 (4)
C4i—C1—Os1115.2 (3)C25—C26—H26A119.5
C2—C1—H1A114.5C21—C26—H26A119.5
C4i—C1—H1A114.5C32—C31—C36117.5 (4)
Os1—C1—H1A114.5C32—C31—P1119.0 (4)
C1—C2—C3121.2 (4)C36—C31—P1123.3 (4)
C1—C2—Os172.3 (3)C31—C32—C33121.6 (5)
C3—C2—Os1114.3 (3)C31—C32—H32A119.2
C1—C2—H2A114.2C33—C32—H32A119.2
C3—C2—H2A114.2C34—C33—C32119.8 (5)
Os1—C2—H2A114.2C34—C33—H33A120.1
C2—C3—C4112.7 (4)C32—C33—H33A120.1
C2—C3—H3A109.1C35—C34—C33119.2 (5)
C4—C3—H3A109.1C35—C34—H34A120.4
C2—C3—H3B109.1C33—C34—H34A120.4
C4—C3—H3B109.1C34—C35—C36120.9 (5)
H3A—C3—H3B107.8C34—C35—H35A119.5
C1i—C4—C3112.7 (4)C36—C35—H35A119.5
C1i—C4—H4A109.1C35—C36—C31120.8 (5)
C3—C4—H4A109.1C35—C36—H36A119.6
C1i—C4—H4B109.1C31—C36—H36A119.6
Symmetry code: (i) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula[OsCl2(C8H12)(PC18H15)2]
Mr893.82
Crystal system, space groupOrthorhombic, Fdd2
Temperature (K)173
a, b, c (Å)39.6505 (15), 10.4393 (5), 17.6248 (8)
V3)7295.3 (6)
Z8
Radiation typeMo Kα
µ (mm1)3.76
Crystal size (mm)0.15 × 0.15 × 0.12
Data collection
DiffractometerOxford Diffraction Gemini S Ultra
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2008)
Tmin, Tmax0.860, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
6965, 2778, 2546
Rint0.033
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.044, 1.00
No. of reflections2778
No. of parameters222
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.39, 0.74
Absolute structureFlack (1983), 937 Friedel pairs
Absolute structure parameter0.009 (6)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
Os1—C22.169 (5)Os1—Cl12.4429 (12)
Os1—C12.195 (5)Os1—P12.5031 (12)
 

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