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Acta Cryst. (2007). E63, m1879    [ doi:10.1107/S1600536807028012 ]

[(1,2,5,6-[eta])-1,3,5,7-Cyclooctatetraene]iodido(methyl)platinum(II)

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

Abstract top

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

Comment top

In the title complex, [PtI(CH3)(C8H8)], the central PtII ion lies in an essentially square-planar environment defined by the I and methyl C atoms and by the two midpoints (M1, M2) of the π-coordinated double bonds of the 1,3,5,7-cyclooctatetraene (cot) ligand (M1 and M2 denote the midpoints of the olefinic bonds C1—C2 and C5—C6, respectively). The Pt, I, C9 atoms and the midpoints lie in a coordination plane with the largest deviation of 0.024 Å (M2) from the least-squares plane, and with bond angles in the range 85.9–94.5°.

Owing to the different trans influence of the I atom and methyl group, the Pt—C bondstrans to C9 are on average 0.142 Å longer than those trans to I (mean lengths: Pt—C1/C2 = 2.280 Å, Pt—C5/C6 = 2.138 Å). The distances between the Pt atom and the midpoints are 2.174 Å (M1) and 2.019 Å (M2). The cot ligand coordinates symmetrically to the Pt atom in the "tub" conformation, and displays some increase in the coordinated double-bond distances (1.376 (12) Å and 1.401 (13) Å) compared to the non-coordinated double bonds (1.325 (13) Å and 1.289 (15) Å). 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 = 0.8 (7)° and C3—C4—C7—C8 = −1.6 (8)°. The Pt atom is displaced by 1.532 (5) Å from the plane C1/C2/C5/C6, and by 2.501 (5) Å from the plane C3/C4/C7/C8. The dihedral angle between these least-squares planes is 0.4 (7)°. In the complex, the cot ring angles lie in the range 121.2 (8)–123.7 (8)°.

Related literature top

For a related structure, see: Song et al. (2006).

Experimental top

An aqueous solution of HI (57%; 0.1337 g, 0.596 mmol) was added to a solution of cyclooctatetraenedimethylplatinum(II) (0.2120 g, 0.644 mmol) in CH2Cl2 (20 ml) and MeOH (10 ml), and stirred for 10 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 × 2 cm). Evaporation of the solvent gave a yellow powder (0.0171 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH2Cl2 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; 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.
[Figure 2] Fig. 2. View of the unit-cell contents of the title compound.
[(1,2,5,6-η4)-1,3,5,7-Cyclooctatetraene]iodo(methyl)platinum(II) top
Crystal data top
[Pt(CH3)I(C8H8)]F000 = 784
Mr = 441.17Dx = 2.941 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3200 reflections
a = 8.447 (2) Åθ = 2.7–26.4º
b = 10.181 (2) ŵ = 17.12 mm−1
c = 13.504 (2) ÅT = 293 (2) K
β = 120.901 (3)ºPlate, yellow
V = 996.5 (3) Å30.18 × 0.17 × 0.10 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer		2034 independent reflections
Radiation source: fine-focus sealed tube1824 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.031
T = 293(2) Kθmax = 26.4º
φ and ω scansθmin = 2.7º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −5→10
Tmin = 0.063, Tmax = 0.181k = −12→12
5241 measured reflectionsl = −16→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)] = 0.035H-atom parameters constrained
wR(F2) = 0.095  w = 1/[σ2(Fo2) + (0.0652P)2 + 0.318P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2034 reflectionsΔρmax = 2.04 e Å−3
101 parametersΔρmin = −1.64 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Pt(CH3)I(C8H8)]V = 996.5 (3) Å3
Mr = 441.17Z = 4
Monoclinic, P21/cMo Kα
a = 8.447 (2) ŵ = 17.12 mm−1
b = 10.181 (2) ÅT = 293 (2) K
c = 13.504 (2) Å0.18 × 0.17 × 0.10 mm
β = 120.901 (3)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		2034 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1824 reflections with I > 2σ(I)
Tmin = 0.063, Tmax = 0.181Rint = 0.031
5241 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035101 parameters
wR(F2) = 0.095H-atom parameters constrained
S = 1.04Δρmax = 2.04 e Å−3
2034 reflectionsΔρmin = −1.64 e Å−3
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
Pt−0.07706 (4)0.19134 (3)0.33127 (2)0.03353 (14)
I−0.25885 (8)0.36453 (6)0.37576 (6)0.0554 (2)
C10.1744 (12)0.1904 (9)0.5146 (7)0.048 (2)
H10.15470.22150.57610.058*
C20.2011 (11)0.2851 (9)0.4519 (8)0.0438 (19)
H20.19650.37600.47430.053*
C30.3096 (11)0.2642 (9)0.3965 (7)0.0456 (19)
H30.41960.30970.42330.055*
C40.2537 (12)0.1815 (9)0.3090 (8)0.050 (2)
H40.32630.16940.27630.060*
C50.0784 (12)0.1079 (9)0.2621 (7)0.048 (2)
H50.01010.09500.17830.057*
C60.0489 (13)0.0121 (8)0.3254 (8)0.052 (2)
H6−0.0371−0.05800.27930.063*
C70.1911 (14)−0.0256 (10)0.4420 (10)0.061 (2)
H70.2403−0.10990.45500.073*
C80.2505 (14)0.0547 (11)0.5277 (9)0.066 (3)
H80.34380.02720.60020.079*
C9−0.3222 (14)0.1393 (12)0.1861 (8)0.064 (3)
H9A−0.30100.06830.14760.096*
H9B−0.37110.21330.13500.096*
H9C−0.40880.11220.20800.096*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt0.0312 (2)0.0354 (2)0.0346 (2)−0.00195 (10)0.01736 (15)−0.00058 (11)
I0.0558 (4)0.0487 (4)0.0810 (4)0.0069 (3)0.0489 (3)0.0041 (3)
C10.036 (4)0.074 (7)0.029 (4)−0.008 (4)0.013 (3)−0.005 (4)
C20.037 (4)0.051 (5)0.045 (4)−0.009 (3)0.022 (4)−0.015 (4)
C30.027 (4)0.050 (5)0.052 (5)−0.003 (4)0.015 (3)0.010 (4)
C40.045 (5)0.062 (6)0.057 (5)0.014 (4)0.036 (4)0.016 (4)
C50.052 (5)0.052 (5)0.048 (4)0.004 (4)0.032 (4)−0.007 (4)
C60.063 (6)0.028 (4)0.067 (6)−0.003 (4)0.034 (5)−0.007 (4)
C70.064 (6)0.041 (5)0.082 (7)0.012 (4)0.041 (5)0.020 (5)
C80.053 (6)0.076 (7)0.062 (6)0.013 (5)0.025 (5)0.041 (6)
C90.048 (5)0.081 (7)0.046 (5)−0.014 (5)0.012 (4)−0.009 (5)
Geometric parameters (Å, °) top
Pt—C92.060 (9)C4—C51.481 (13)
Pt—C62.135 (8)C4—H40.930
Pt—C52.140 (8)C5—C61.401 (13)
Pt—C22.270 (8)C5—H50.980
Pt—C12.289 (8)C6—C71.459 (14)
Pt—I2.6029 (7)C6—H60.980
C1—C21.376 (12)C7—C81.289 (15)
C1—C81.495 (14)C7—H70.930
C1—H10.980C8—H80.930
C2—C31.466 (12)C9—H9A0.960
C2—H20.980C9—H9B0.960
C3—C41.325 (13)C9—H9C0.960
C3—H30.930
C9—Pt—C691.2 (4)C2—C3—H3119.4
C9—Pt—C591.4 (4)C3—C4—C5121.6 (8)
C6—Pt—C538.3 (3)C3—C4—H4119.2
C9—Pt—C2162.8 (4)C5—C4—H4119.2
C6—Pt—C292.0 (3)C6—C5—C4122.9 (8)
C5—Pt—C280.8 (3)C6—C5—Pt70.7 (5)
C9—Pt—C1161.7 (4)C4—C5—Pt108.4 (6)
C6—Pt—C180.4 (3)C6—C5—H5115.4
C5—Pt—C191.9 (3)C4—C5—H5115.4
C2—Pt—C135.1 (3)Pt—C5—H5115.4
C9—Pt—I88.3 (3)C5—C6—C7122.4 (8)
C6—Pt—I162.2 (3)C5—C6—Pt71.1 (5)
C5—Pt—I159.5 (2)C7—C6—Pt109.5 (7)
C2—Pt—I93.7 (2)C5—C6—H6115.2
C1—Pt—I94.8 (2)C7—C6—H6115.2
C2—C1—C8121.6 (8)Pt—C6—H6115.2
C2—C1—Pt71.7 (5)C8—C7—C6121.8 (9)
C8—C1—Pt103.6 (6)C8—C7—H7119.1
C2—C1—H1116.6C6—C7—H7119.1
C8—C1—H1116.6C7—C8—C1122.3 (9)
Pt—C1—H1116.6C7—C8—H8118.8
C1—C2—C3123.7 (8)C1—C8—H8118.8
C1—C2—Pt73.2 (5)Pt—C9—H9A109.5
C3—C2—Pt105.1 (5)Pt—C9—H9B109.5
C1—C2—H2115.3H9A—C9—H9B109.5
C3—C2—H2115.3Pt—C9—H9C109.5
Pt—C2—H2115.3H9A—C9—H9C109.5
C4—C3—C2121.2 (8)H9B—C9—H9C109.5
C4—C3—H3119.4
C9—Pt—C1—C2171.3 (12)I—Pt—C5—C6−179.1 (5)
C6—Pt—C1—C2107.5 (6)C9—Pt—C5—C4150.5 (7)
C5—Pt—C1—C270.9 (6)C6—Pt—C5—C4−119.3 (8)
I—Pt—C1—C2−89.7 (5)C2—Pt—C5—C4−14.1 (6)
C9—Pt—C1—C852.1 (15)C1—Pt—C5—C4−47.6 (6)
C6—Pt—C1—C8−11.7 (6)I—Pt—C5—C461.6 (10)
C5—Pt—C1—C8−48.3 (6)C4—C5—C6—C7−1.8 (14)
C2—Pt—C1—C8−119.2 (9)Pt—C5—C6—C7−101.6 (9)
I—Pt—C1—C8151.1 (6)C4—C5—C6—Pt99.8 (8)
C8—C1—C2—C3−2.2 (13)C9—Pt—C6—C590.7 (6)
Pt—C1—C2—C3−97.2 (8)C2—Pt—C6—C5−72.4 (5)
C8—C1—C2—Pt95.0 (8)C1—Pt—C6—C5−105.7 (6)
C9—Pt—C2—C1−170.8 (13)I—Pt—C6—C5178.9 (6)
C6—Pt—C2—C1−70.2 (6)C9—Pt—C6—C7−150.6 (7)
C5—Pt—C2—C1−106.9 (6)C5—Pt—C6—C7118.7 (9)
I—Pt—C2—C193.0 (5)C2—Pt—C6—C746.3 (7)
C9—Pt—C2—C3−49.5 (16)C1—Pt—C6—C713.0 (6)
C6—Pt—C2—C351.1 (6)I—Pt—C6—C7−62.4 (11)
C5—Pt—C2—C314.3 (6)C5—C6—C7—C866.5 (14)
C1—Pt—C2—C3121.2 (9)Pt—C6—C7—C8−13.0 (12)
I—Pt—C2—C3−145.8 (6)C6—C7—C8—C11.9 (16)
C1—C2—C3—C466.9 (12)C2—C1—C8—C7−67.4 (13)
Pt—C2—C3—C4−12.8 (10)Pt—C1—C8—C79.3 (12)
C2—C3—C4—C50.9 (13)C1—C2—C5—C60.8 (7)
C3—C4—C5—C6−65.9 (12)C3—C4—C7—C8−1.6 (8)
C3—C4—C5—Pt12.6 (10)C3—C2—C1—C8−2.2 (13)
C9—Pt—C5—C6−90.2 (6)C4—C5—C6—C7−1.8 (14)
C2—Pt—C5—C6105.2 (6)C2—C3—C4—C50.9 (13)
C1—Pt—C5—C671.8 (5)C6—C7—C8—C11.9 (16)
Acknowledgements top

This study received financial support from Chonnam National University in 2006.

references
References top

Bruker (2000). SADABS (Version 2.03 AU OK?), 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). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Song, A.-R., Hwang, I.-C. & Ha, K. (2006). Z. Kristallogr. New Cryst. Struct. 221, 465–467.

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