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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): m48.
Published online 2009 December 12. doi:  10.1107/S1600536809052660
PMCID: PMC2980049

Bromido[(1,2,5,6-η)-cyclo­octa-1,5-diene]methyl­platinum(II)

Abstract

In the title complex, [PtBr(CH3)(C8H12)], the PtII ion is in a distorted square-planar environment defined by the Br and methyl C atoms and the mid-points of the two π-coordinated double bonds of cyclo­octa-1,5-diene. As a result of the different trans influences of the Br atom and the methyl group, the Pt—C bonds trans to the methyl group [2.262 (11) and 2.261 (10) Å] are longer than those trans to the Br atom [2.118 (8) and 2.138 (9) Å].

Related literature

For the crystal structure of [(cod)PtCl2] (cod = cyclo­octa-1,5-diene), see: Goel et al. (1982 [triangle]); Syed et al. (1984 [triangle]). For the crystal structures of [(cod)Pt(CH3)L] (L = OH, CH3 or Cl), see: Klein et al. (1999 [triangle]). For the crystal structure of [(cod)Pt(CH3)I], see: Nieger (2008 [triangle]). For related Pt–cot complexes, [(cot )PtX 2] (cot = cyclo­octa-1,3,5,7-tetra­ene; X = Br or I), see: Song et al. (2007a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-00m48-scheme1.jpg

Experimental

Crystal data

  • [PtBr(CH3)(C8H12)]
  • M r = 398.21
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-00m48-efi1.jpg
  • a = 7.1013 (15) Å
  • b = 11.184 (2) Å
  • c = 12.691 (3) Å
  • V = 1007.9 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 17.82 mm−1
  • T = 296 K
  • 0.25 × 0.22 × 0.12 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]) T min = 0.537, T max = 1.000
  • 7369 measured reflections
  • 2514 independent reflections
  • 1988 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.067
  • S = 1.04
  • 2514 reflections
  • 101 parameters
  • H-atom parameters constrained
  • Δρmax = 0.92 e Å−3
  • Δρmin = −1.27 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1023 Friedel pairs
  • Flack parameter: −0.02 (3)

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809052660/nk2017sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052660/nk2017Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by a Korea Research Foundation grant funded by the Korean Government (MOEHRD) (KRF-2007–412-J02001).

supplementary crystallographic information

Comment

In the title complex, [PtBr(CH3)(C8H12)], the central PtII ion lies in a distorted square-planar environment defined by the Br and methyl C atoms and the two mid-points (M1, M2) of the π-coordinated double bonds of cycloocta-1,5-diene (cod) ligand (M1 and M2 denote the mid-points of the olefinic bonds C1—C2 and C5—C6, respectively) (Fig. 1). The Pt, Br, C9 atoms and the mid-points lie in a coordination plane with the largest deviation of 0.018 Å (M2) from the least-squares plane, and with bond angles in the range of 85.4°–94.5°. Because of the different trans influences of the Br atom and the methyl group, the Pt—C bonds trans to C9 of the methyl group (2.261 (10)–2.262 (11) Å) are longer than those trans to the Br atom (2.118 (8)–2.138 (9) Å). The cod ligand coordinates to the Pt atom in the twist-boat conformation with the coordinated double-bond lengths of 1.334 (13) and 1.367 (14) Å, and the cod ring angles lie in the range of 115.1 (10)°–127.3 (9)°.

Experimental

To a solution of cyclooctadienedimethylplatinum(II) (0.1677 g, 0.503 mmol) in CH2Cl2/MeOH (15 ml/15 ml) was added acetyl bromide (0.0740 g, 0.602 mmol), and stirred for 5 h at room temperature. The solvent was removed under vacuum, the residue was washed with pentane and dried, to give a white powder (0.1611 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a methanol solution.

Refinement

H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.98 (CH), 0.97 (CH2) or 0.96 (CH3) Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C)]. The highest peak (0.92 e Å-3) and the deepest hole (-1.27 e Å-3) in the difference Fourier map are located 0.95 and 0.56 Å from the atoms Pt1 and Br1, respectively.

Figures

Fig. 1.
The structure of the title compound, with displacement ellipsoids drawn at the 30% probability level for non-H atoms.

Crystal data

[PtBr(CH3)(C8H12)]F(000) = 728
Mr = 398.21Dx = 2.624 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3683 reflections
a = 7.1013 (15) Åθ = 2.4–28.4°
b = 11.184 (2) ŵ = 17.82 mm1
c = 12.691 (3) ÅT = 296 K
V = 1007.9 (4) Å3Block, colourless
Z = 40.25 × 0.22 × 0.12 mm

Data collection

Bruker SMART 1000 CCD diffractometer2514 independent reflections
Radiation source: fine-focus sealed tube1988 reflections with I > 2σ(I)
graphiteRint = 0.041
ω scansθmax = 28.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −8→9
Tmin = 0.537, Tmax = 1.000k = −15→8
7369 measured reflectionsl = −15→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.067w = 1/[σ2(Fo2) + (0.0196P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2514 reflectionsΔρmax = 0.92 e Å3
101 parametersΔρmin = −1.27 e Å3
0 restraintsAbsolute structure: Flack (1983), 1023 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.02 (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 (Å2)

xyzUiso*/Ueq
Pt10.14514 (4)0.09470 (4)0.38595 (2)0.03996 (10)
Br1−0.13276 (14)0.10500 (13)0.27310 (7)0.0679 (3)
C10.0998 (13)−0.1007 (10)0.4243 (7)0.052 (2)
H10.0112−0.14080.37680.063*
C20.0164 (14)−0.0373 (11)0.5001 (7)0.059 (3)
H2−0.1215−0.04030.50060.071*
C30.109 (2)−0.0160 (13)0.6061 (8)0.091 (4)
H3A0.0092−0.00390.65750.110*
H3B0.1742−0.08870.62580.110*
C40.2370 (16)0.0801 (14)0.6157 (9)0.091 (4)
H4A0.33610.05630.66400.109*
H4B0.17150.14720.64740.109*
C50.3254 (13)0.1214 (11)0.5168 (7)0.066 (3)
H50.37420.20320.52130.079*
C60.4194 (13)0.0527 (11)0.4448 (9)0.060 (3)
H60.52180.09470.40860.072*
C70.4495 (15)−0.0771 (15)0.4554 (9)0.082 (4)
H7A0.4850−0.09290.52790.098*
H7B0.5562−0.09850.41160.098*
C80.2914 (17)−0.1587 (11)0.4282 (9)0.083 (4)
H8A0.2879−0.22290.47950.099*
H8B0.3171−0.19430.36000.099*
C90.2351 (11)0.2549 (9)0.3069 (7)0.043 (2)
H9A0.37020.25690.30410.064*
H9B0.19000.32350.34470.064*
H9C0.18540.25580.23650.064*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pt10.03947 (15)0.03876 (19)0.04166 (15)−0.0015 (2)−0.00064 (15)0.00082 (18)
Br10.0593 (5)0.0812 (9)0.0631 (5)0.0112 (9)−0.0145 (5)0.0043 (6)
C10.062 (6)0.030 (5)0.065 (6)−0.018 (6)−0.020 (4)0.009 (5)
C20.055 (6)0.064 (8)0.059 (6)−0.017 (6)0.006 (5)0.012 (6)
C30.130 (11)0.100 (11)0.045 (6)0.011 (10)0.012 (7)0.012 (7)
C40.079 (7)0.128 (14)0.066 (7)0.002 (10)−0.021 (6)−0.017 (11)
C50.057 (6)0.078 (10)0.063 (6)−0.004 (7)−0.025 (5)−0.024 (6)
C60.035 (5)0.059 (8)0.086 (7)−0.008 (5)−0.013 (5)0.009 (6)
C70.060 (6)0.095 (12)0.089 (8)0.020 (9)−0.017 (6)−0.003 (9)
C80.106 (10)0.045 (8)0.097 (9)0.009 (8)−0.006 (7)0.006 (7)
C90.038 (4)0.029 (6)0.061 (5)−0.008 (5)0.004 (4)0.007 (5)

Geometric parameters (Å, °)

Pt1—C52.118 (8)C4—H4A0.9700
Pt1—C62.138 (9)C4—H4B0.9700
Pt1—C92.151 (9)C5—C61.367 (14)
Pt1—C22.261 (10)C5—H50.9800
Pt1—C12.262 (11)C6—C71.473 (18)
Pt1—Br12.4410 (11)C6—H60.9800
C1—C21.334 (13)C7—C81.488 (17)
C1—C81.508 (14)C7—H7A0.9700
C1—H10.9800C7—H7B0.9700
C2—C31.515 (13)C8—H8A0.9700
C2—H20.9800C8—H8B0.9700
C3—C41.415 (17)C9—H9A0.9600
C3—H3A0.9700C9—H9B0.9600
C3—H3B0.9700C9—H9C0.9600
C4—C51.478 (14)
C5—Pt1—C637.5 (4)C5—C4—H4A108.3
C5—Pt1—C993.9 (4)C3—C4—H4B108.3
C6—Pt1—C994.3 (4)C5—C4—H4B108.3
C5—Pt1—C280.5 (4)H4A—C4—H4B107.4
C6—Pt1—C290.1 (4)C6—C5—C4126.8 (12)
C9—Pt1—C2164.3 (4)C6—C5—Pt172.1 (5)
C5—Pt1—C193.1 (4)C4—C5—Pt1111.4 (7)
C6—Pt1—C180.9 (4)C6—C5—H5113.1
C9—Pt1—C1161.4 (4)C4—C5—H5113.1
C2—Pt1—C134.3 (3)Pt1—C5—H5113.1
C5—Pt1—Br1160.4 (3)C5—C6—C7124.3 (11)
C6—Pt1—Br1162.1 (3)C5—C6—Pt170.4 (5)
C9—Pt1—Br185.8 (2)C7—C6—Pt1112.3 (7)
C2—Pt1—Br194.6 (2)C5—C6—H6114.0
C1—Pt1—Br193.3 (2)C7—C6—H6114.0
C2—C1—C8127.3 (9)Pt1—C6—H6114.0
C2—C1—Pt172.8 (7)C6—C7—C8118.3 (10)
C8—C1—Pt1107.1 (7)C6—C7—H7A107.7
C2—C1—H1113.7C8—C7—H7A107.7
C8—C1—H1113.7C6—C7—H7B107.7
Pt1—C1—H1113.7C8—C7—H7B107.7
C1—C2—C3122.1 (10)H7A—C7—H7B107.1
C1—C2—Pt172.9 (6)C7—C8—C1115.1 (10)
C3—C2—Pt1107.0 (8)C7—C8—H8A108.5
C1—C2—H2115.5C1—C8—H8A108.5
C3—C2—H2115.5C7—C8—H8B108.5
Pt1—C2—H2115.5C1—C8—H8B108.5
C4—C3—C2118.3 (10)H8A—C8—H8B107.5
C4—C3—H3A107.7Pt1—C9—H9A109.5
C2—C3—H3A107.7Pt1—C9—H9B109.5
C4—C3—H3B107.7H9A—C9—H9B109.5
C2—C3—H3B107.7Pt1—C9—H9C109.5
H3A—C3—H3B107.1H9A—C9—H9C109.5
C3—C4—C5116.0 (10)H9B—C9—H9C109.5
C3—C4—H4A108.3
C5—Pt1—C1—C268.1 (6)C9—Pt1—C5—C6−92.0 (7)
C6—Pt1—C1—C2103.7 (6)C2—Pt1—C5—C6102.8 (7)
C9—Pt1—C1—C2−179.9 (9)C1—Pt1—C5—C670.7 (7)
Br1—Pt1—C1—C2−93.3 (5)Br1—Pt1—C5—C6179.4 (7)
C5—Pt1—C1—C8−56.6 (7)C6—Pt1—C5—C4−123.3 (13)
C6—Pt1—C1—C8−21.0 (7)C9—Pt1—C5—C4144.7 (9)
C9—Pt1—C1—C855.4 (13)C2—Pt1—C5—C4−20.6 (9)
C2—Pt1—C1—C8−124.7 (9)C1—Pt1—C5—C4−52.6 (9)
Br1—Pt1—C1—C8142.0 (7)Br1—Pt1—C5—C456.1 (15)
C8—C1—C2—C3−0.9 (18)C4—C5—C6—C7−0.5 (16)
Pt1—C1—C2—C3−99.6 (10)Pt1—C5—C6—C7−104.2 (10)
C8—C1—C2—Pt198.8 (11)C4—C5—C6—Pt1103.7 (9)
C5—Pt1—C2—C1−110.0 (6)C9—Pt1—C6—C590.8 (7)
C6—Pt1—C2—C1−73.7 (6)C2—Pt1—C6—C5−74.1 (7)
C9—Pt1—C2—C1179.9 (11)C1—Pt1—C6—C5−107.3 (8)
Br1—Pt1—C2—C189.1 (5)Br1—Pt1—C6—C5−179.4 (8)
C5—Pt1—C2—C39.2 (8)C5—Pt1—C6—C7120.0 (12)
C6—Pt1—C2—C345.6 (8)C9—Pt1—C6—C7−149.1 (9)
C9—Pt1—C2—C3−60.9 (16)C2—Pt1—C6—C745.9 (9)
C1—Pt1—C2—C3119.2 (10)C1—Pt1—C6—C712.7 (9)
Br1—Pt1—C2—C3−151.7 (8)Br1—Pt1—C6—C7−59.4 (15)
C1—C2—C3—C484.4 (16)C5—C6—C7—C879.3 (14)
Pt1—C2—C3—C44.3 (14)Pt1—C6—C7—C8−1.6 (14)
C2—C3—C4—C5−22.8 (17)C6—C7—C8—C1−17.9 (16)
C3—C4—C5—C6−53.1 (15)C2—C1—C8—C7−54.7 (15)
C3—C4—C5—Pt130.0 (14)Pt1—C1—C8—C726.4 (12)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NK2017).

References

  • Bruker (2007). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Goel, A. B., Goel, S. & van der Veer, D. (1982). Inorg. Chim. Acta, 65, L205–L206.
  • Klein, A., Klinkhammer, K.-W. & Scheiring, T. (1999). J. Organomet. Chem.592, 128–135.
  • Nieger, M. (2008). Private communication (CCDC No. 677297). CCDC, Cambridge, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Song, A.-R., Hwang, I.-C. & Ha, K. (2007a). Acta Cryst. E63, m2484.
  • Song, A.-R., Hwang, I.-C. & Ha, K. (2007b). Acta Cryst. E63, m1879.
  • Syed, A., Stevens, E. D. & Cruz, S. G. (1984). Inorg. Chem.23, 3673–3674.

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