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Acta Cryst. (2007). E63, m2484    [ doi:10.1107/S1600536807043279 ]

Bromido[(1,2,5,6-[eta])-1,3,5,7-cyclooctatetraene]methylplatinum(II)

A.-R. Song, I.-C. Hwang and K. Ha

Abstract top

In the title complex, [PtBr(CH3)(C8H8)], the PtII centre lies in a square-planar environment defined by the Br and methyl C atoms and the midpoints of the two [pi]-coordinated double bonds of 1,3,5,7-cyclooctatetraene. Because of the different trans influences of the Br atom and the methyl group, the Pt-C bonds trans to the methyl group are longer than those trans to the Br atom.

Comment top

In the title complex, [Pt(CH3)Br(C8H8)], the central PtII ion lies in an essentially square-planar environment defined by the Br and methyl C atoms and by the two mid-points (M1, M2) of the π-coordinated double bonds of the 1,3,5,7-cyclooctatetraene (cot) ligand (M1 and M2 denote the mid-points of the olefinic bonds C1—C2 and C5—C6, respectively). The Pt, Br, C9 atoms and the mid-points lie in a coordination plane with the largest deviation of 0.031 Å (M2) from the least-squares plane, and with bond angles in the range 88.0°–92.9°.

Owing to the different trans influences of the Br atom and methyl group, the Pt—C bonds trans to C9 are on average 0.173 Å longer than those trans to Br (mean lengths: Pt—C1/C2 = 2.314 Å, Pt—C5/C6 = 2.141 Å). The distances between the Pt atom and the mid-points are 2.227 Å (M1) and 2.027 Å (M2). The cot ligand coordinates symmetrically to the Pt atom in the "tub" conformation. The four coordinating C atoms (C1, C2, C5 and C6) and the four non-coordinating C atoms (C3, C4, C7 and C8) lie on respective planes, with the torsion angles C1—C2—C5—C6 = 0.2 (16)° and C3—C4—C7—C8 = −0.7 (18)°. The Pt atom is displaced by 1.524 (9) Å from the plane C1/C2/C5/C6, and by 2.503 (9) Å from the plane C3/C4/C7/C8. In the complex, the cot ring angles lie in the range 118 (2)° − 126 (2)°.

Related literature top

For related literature, see: Song et al. (2007).

Experimental top

To a solution of cyclooctatetraenedimethylplatinum(II) (0.2035 g, 0.618 mmol) in CH2Cl2 (30 ml) was added hydrobromic acid (48%; 0.1120 g, 0.664 mmol), and stirred for 5 h at room temperature. The solvent was removed under vacuum, the residue was washed with pentane, dissolved in ether, and filtered through a plug of Al2O3 (1 cm x 2 cm). Evaporation of the solvent gave a yellow powder (0.0763 g). Large plates were obtained by slow evaporation from a CDCl3 solution.

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective carrier atoms, with C—H = 0.98, 0.93 or 0.96 Å and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 30% probability level for non-H atoms. Hydrogen atoms are shown as spheres of arbitrary radii.
[Figure 2] Fig. 2. View of the unit-cell contents of the title compound.
Bromido[(1,2,5,6-η)-1,3,5,7-cyclooctatetraene]methylplatinum(II) top
Crystal data top
[PtBr(CH3)(C8H8)]F000 = 712
Mr = 394.18Dx = 2.674 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1512 reflections
a = 8.3637 (12) Åθ = 2.8–24.2º
b = 10.1098 (15) ŵ = 18.35 mm−1
c = 11.6897 (17) ÅT = 293 (2) K
β = 97.928 (3)ºPlate, yellow
V = 979.0 (2) Å30.12 × 0.10 × 0.08 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer		2009 independent reflections
Radiation source: fine-focus sealed tube1435 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.045
T = 293(2) Kθmax = 26.4º
φ and ω scansθmin = 2.7º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −10→8
Tmin = 0.095, Tmax = 0.230k = −12→10
5568 measured reflectionsl = −14→14
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)] = 0.057H-atom parameters constrained
wR(F2) = 0.176  w = 1/[σ2(Fo2) + (0.1039P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2009 reflectionsΔρmax = 3.68 e Å−3
101 parametersΔρmin = −2.52 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[PtBr(CH3)(C8H8)]V = 979.0 (2) Å3
Mr = 394.18Z = 4
Monoclinic, P21/nMo Kα
a = 8.3637 (12) ŵ = 18.35 mm−1
b = 10.1098 (15) ÅT = 293 (2) K
c = 11.6897 (17) Å0.12 × 0.10 × 0.08 mm
β = 97.928 (3)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		2009 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1435 reflections with I > 2σ(I)
Tmin = 0.095, Tmax = 0.230Rint = 0.045
5568 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057101 parameters
wR(F2) = 0.176H-atom parameters constrained
S = 1.04Δρmax = 3.68 e Å−3
2009 reflectionsΔρmin = −2.52 e Å−3
Special details top

Experimental. The datum crystal was cut from a large plate of approximate dimensions 0.08 X 1.5 X 2.0 mm.

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
Pt0.59256 (7)0.30579 (7)0.16610 (5)0.0429 (3)
Br0.36957 (17)0.13420 (17)0.12204 (16)0.0469 (5)
C10.668 (2)0.293 (2)−0.0165 (17)0.074 (7)
H10.58490.2611−0.07750.088*
C20.749 (2)0.2053 (18)0.0419 (16)0.050 (5)
H20.72310.11320.02070.060*
C30.923 (2)0.234 (2)0.106 (2)0.068 (6)
H31.00850.18820.08190.081*
C40.956 (2)0.320 (2)0.1956 (18)0.064 (6)
H41.06190.33570.22910.077*
C50.818 (2)0.3893 (18)0.2383 (17)0.057 (5)
H50.83020.40160.32220.069*
C60.730 (2)0.487 (2)0.176 (2)0.067 (6)
H60.68960.55720.22210.081*
C70.748 (3)0.523 (3)0.053 (2)0.081 (7)
H70.77970.60880.03690.097*
C80.722 (3)0.440 (3)−0.028 (2)0.084 (8)
H80.73520.4695−0.10190.100*
C90.484 (2)0.3641 (18)0.3157 (12)0.044 (4)
H9A0.46930.28750.36170.066*
H9B0.38080.40430.29100.066*
H9C0.55270.42630.36070.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt0.0398 (4)0.0485 (5)0.0418 (4)0.0024 (3)0.0102 (3)0.0010 (3)
Br0.0252 (7)0.0412 (10)0.0735 (11)−0.0053 (6)0.0036 (7)0.0021 (8)
C10.051 (12)0.13 (2)0.042 (11)−0.032 (12)0.010 (9)−0.001 (12)
C20.043 (9)0.060 (13)0.050 (10)0.022 (8)0.019 (8)0.010 (9)
C30.055 (11)0.059 (14)0.096 (17)0.014 (10)0.035 (11)0.040 (12)
C40.049 (11)0.082 (16)0.062 (13)−0.001 (10)0.014 (9)0.009 (11)
C50.053 (11)0.048 (12)0.068 (12)−0.005 (9)−0.002 (9)0.000 (9)
C60.047 (11)0.065 (14)0.091 (16)−0.020 (10)0.011 (10)−0.004 (11)
C70.082 (16)0.063 (16)0.101 (19)−0.004 (12)0.030 (15)0.041 (14)
C80.070 (14)0.14 (3)0.047 (13)0.002 (15)0.015 (11)0.040 (14)
C90.051 (9)0.053 (11)0.029 (8)0.008 (8)0.015 (7)0.010 (7)
Geometric parameters (Å, °) top
Pt—C52.129 (17)C4—C51.50 (3)
Pt—C62.152 (19)C4—H40.9300
Pt—C92.161 (15)C5—C61.38 (3)
Pt—C12.31 (2)C5—H50.9800
Pt—C22.318 (16)C6—C71.52 (3)
Pt—Br2.5472 (16)C6—H60.9800
C1—C21.26 (3)C7—C81.26 (3)
C1—C81.57 (3)C7—H70.9300
C1—H10.9800C8—H80.9300
C2—C31.57 (3)C9—H9A0.9600
C2—H20.9800C9—H9B0.9600
C3—C41.36 (3)C9—H9C0.9600
C3—H30.9300
C5—Pt—C637.5 (7)C2—C3—H3117.8
C5—Pt—C991.1 (7)C3—C4—C5118.0 (18)
C6—Pt—C990.3 (8)C3—C4—H4121.0
C5—Pt—C192.8 (8)C5—C4—H4121.0
C6—Pt—C183.4 (8)C6—C5—C4122.8 (19)
C9—Pt—C1164.0 (8)C6—C5—Pt72.1 (11)
C5—Pt—C283.0 (7)C4—C5—Pt111.4 (14)
C6—Pt—C293.7 (8)C6—C5—H5114.4
C9—Pt—C2164.4 (6)C4—C5—H5114.4
C1—Pt—C231.6 (7)Pt—C5—H5114.4
C5—Pt—Br158.9 (5)C5—C6—C7124 (2)
C6—Pt—Br163.5 (6)C5—C6—Pt70.4 (11)
C9—Pt—Br88.3 (5)C7—C6—Pt106.3 (15)
C1—Pt—Br93.5 (5)C5—C6—H6115.4
C2—Pt—Br92.0 (5)C7—C6—H6115.4
C2—C1—C8125.5 (19)Pt—C6—H6115.4
C2—C1—Pt74.5 (12)C8—C7—C6121 (2)
C8—C1—Pt98.5 (14)C8—C7—H7119.3
C2—C1—H1115.7C6—C7—H7119.3
C8—C1—H1115.7C7—C8—C1126 (2)
Pt—C1—H1115.7C7—C8—H8117.1
C1—C2—C3121.6 (18)C1—C8—H8117.1
C1—C2—Pt73.9 (12)Pt—C9—H9A109.5
C3—C2—Pt100.6 (13)Pt—C9—H9B109.5
C1—C2—H2116.8H9A—C9—H9B109.5
C3—C2—H2116.8Pt—C9—H9C109.5
Pt—C2—H2116.8H9A—C9—H9C109.5
C4—C3—C2124.4 (18)H9B—C9—H9C109.5
C4—C3—H3117.8
C5—Pt—C1—C271.8 (13)Br—Pt—C5—C6−177.3 (12)
C6—Pt—C1—C2108.1 (14)C6—Pt—C5—C4−119 (2)
C9—Pt—C1—C2176 (2)C9—Pt—C5—C4152.0 (14)
Br—Pt—C1—C2−88.1 (12)C1—Pt—C5—C4−43.6 (15)
C5—Pt—C1—C8−52.8 (14)C2—Pt—C5—C4−13.5 (14)
C6—Pt—C1—C8−16.4 (13)Br—Pt—C5—C464 (2)
C9—Pt—C1—C851 (3)C4—C5—C6—C78(3)
C2—Pt—C1—C8−124.6 (19)Pt—C5—C6—C7−97 (2)
Br—Pt—C1—C8147.3 (12)C4—C5—C6—Pt104.4 (18)
C8—C1—C2—C3−3(3)C9—Pt—C6—C591.5 (13)
Pt—C1—C2—C3−92.8 (18)C1—Pt—C6—C5−103.3 (14)
C8—C1—C2—Pt90 (2)C2—Pt—C6—C5−73.4 (13)
C5—Pt—C2—C1−107.1 (14)Br—Pt—C6—C5176.6 (16)
C6—Pt—C2—C1−71.1 (14)C5—Pt—C6—C7121 (2)
C9—Pt—C2—C1−175 (2)C9—Pt—C6—C7−147.5 (14)
Br—Pt—C2—C193.5 (12)C1—Pt—C6—C717.7 (14)
C5—Pt—C2—C313.0 (11)C2—Pt—C6—C747.6 (15)
C6—Pt—C2—C349.0 (12)Br—Pt—C6—C7−62 (3)
C9—Pt—C2—C3−55 (3)C5—C6—C7—C861 (3)
C1—Pt—C2—C3120.1 (18)Pt—C6—C7—C8−16 (3)
Br—Pt—C2—C3−146.5 (10)C6—C7—C8—C10(4)
C1—C2—C3—C465 (3)C2—C1—C8—C7−63 (4)
Pt—C2—C3—C4−12 (2)Pt—C1—C8—C715 (3)
C2—C3—C4—C52(3)C1—C2—C5—C60.2 (16)
C3—C4—C5—C6−71 (3)C3—C4—C7—C8−0.7 (18)
C3—C4—C5—Pt11 (2)C3—C2—C1—C8−3(3)
C9—Pt—C5—C6−89.0 (13)C4—C5—C6—C78(3)
C1—Pt—C5—C675.4 (14)C2—C3—C4—C52(3)
C2—Pt—C5—C6105.5 (13)C6—C7—C8—C10(4)
Acknowledgements top

This study was financially supported by Chonnam National University in 2006.

references
References top

Bruker (2000). SADABS (Version 2.03), SMART (Version 5.618) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Song, A.-R., Hwang, I.-C. & Ha, K. (2007). Acta Cryst. E63, m1879–?.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.