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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].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809052660/nk2017sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536809052660/nk2017Isup2.hkl
Contains datablock I

CCDC reference: 766669

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.016 Å
  • R factor = 0.032
  • wR factor = 0.067
  • Data-to-parameter ratio = 24.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Pt1 -- Br1 .. 8.75 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C3 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C8 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Pt1 PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 16 PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C3 - C4 ... 1.41 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C1 - C2 ... 1.33 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C5 - C6 ... 1.37 Ang. PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 4 PLAT234_ALERT_4_C Large Hirshfeld Difference C6 -- C7 .. 0.17 Ang. PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 6
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.49 From the CIF: _reflns_number_total 2514 Count of symmetry unique reflns 1491 Completeness (_total/calc) 168.61% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1023 Fraction of Friedel pairs measured 0.686 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 11 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 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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)°.

Related literature top

For the crystal structure of [(cod)PtCl2] (cod = cycloocta-1,5-diene), see: Goel et al. (1982); Syed et al. (1984). For the crystal structures of [(cod)Pt(CH3)L] (L = OH, CH3 or Cl), see: Klein et al. (1999). For the crystal structure of [(cod)Pt(CH3)I], see: Nieger (2008). For related Pt–cot complexes, [(cot)PtX2] (cot = cycloocta-1,3,5,7-tetraene; X = Br or I), see: Song et al. (2007a,b).

Experimental top

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 top

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.

Computing details top

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

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.
Bromido[(1,2,5,6-η)-cycloocta-1,5-diene]methylplatinum(II) top
Crystal data top
[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 top
Bruker SMART 1000 CCD
diffractometer
2514 independent reflections
Radiation source: fine-focus sealed tube1988 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ω scansθmax = 28.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 89
Tmin = 0.537, Tmax = 1.000k = 158
7369 measured reflectionsl = 1516
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)] = 0.032H-atom parameters constrained
wR(F2) = 0.067 w = 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 methodsAbsolute structure parameter: 0.02 (3)
Crystal data top
[PtBr(CH3)(C8H12)]V = 1007.9 (4) Å3
Mr = 398.21Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.1013 (15) ŵ = 17.82 mm1
b = 11.184 (2) ÅT = 296 K
c = 12.691 (3) Å0.25 × 0.22 × 0.12 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
2514 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
1988 reflections with I > 2σ(I)
Tmin = 0.537, Tmax = 1.000Rint = 0.041
7369 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.067Δρmax = 0.92 e Å3
S = 1.04Δρmin = 1.27 e Å3
2514 reflectionsAbsolute structure: Flack (1983), 1023 Friedel pairs
101 parametersAbsolute structure parameter: 0.02 (3)
0 restraints
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
Pt10.14514 (4)0.09470 (4)0.38595 (2)0.03996 (10)
Br10.13276 (14)0.10500 (13)0.27310 (7)0.0679 (3)
C10.0998 (13)0.1007 (10)0.4243 (7)0.052 (2)
H10.01120.14080.37680.063*
C20.0164 (14)0.0373 (11)0.5001 (7)0.059 (3)
H20.12150.04030.50060.071*
C30.109 (2)0.0160 (13)0.6061 (8)0.091 (4)
H3A0.00920.00390.65750.110*
H3B0.17420.08870.62580.110*
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)
H7A0.48500.09290.52790.098*
H7B0.55620.09850.41160.098*
C80.2914 (17)0.1587 (11)0.4282 (9)0.083 (4)
H8A0.28790.22290.47950.099*
H8B0.31710.19430.36000.099*
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) top
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, º) top
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—C692.0 (7)
C6—Pt1—C1—C2103.7 (6)C2—Pt1—C5—C6102.8 (7)
C9—Pt1—C1—C2179.9 (9)C1—Pt1—C5—C670.7 (7)
Br1—Pt1—C1—C293.3 (5)Br1—Pt1—C5—C6179.4 (7)
C5—Pt1—C1—C856.6 (7)C6—Pt1—C5—C4123.3 (13)
C6—Pt1—C1—C821.0 (7)C9—Pt1—C5—C4144.7 (9)
C9—Pt1—C1—C855.4 (13)C2—Pt1—C5—C420.6 (9)
C2—Pt1—C1—C8124.7 (9)C1—Pt1—C5—C452.6 (9)
Br1—Pt1—C1—C8142.0 (7)Br1—Pt1—C5—C456.1 (15)
C8—C1—C2—C30.9 (18)C4—C5—C6—C70.5 (16)
Pt1—C1—C2—C399.6 (10)Pt1—C5—C6—C7104.2 (10)
C8—C1—C2—Pt198.8 (11)C4—C5—C6—Pt1103.7 (9)
C5—Pt1—C2—C1110.0 (6)C9—Pt1—C6—C590.8 (7)
C6—Pt1—C2—C173.7 (6)C2—Pt1—C6—C574.1 (7)
C9—Pt1—C2—C1179.9 (11)C1—Pt1—C6—C5107.3 (8)
Br1—Pt1—C2—C189.1 (5)Br1—Pt1—C6—C5179.4 (8)
C5—Pt1—C2—C39.2 (8)C5—Pt1—C6—C7120.0 (12)
C6—Pt1—C2—C345.6 (8)C9—Pt1—C6—C7149.1 (9)
C9—Pt1—C2—C360.9 (16)C2—Pt1—C6—C745.9 (9)
C1—Pt1—C2—C3119.2 (10)C1—Pt1—C6—C712.7 (9)
Br1—Pt1—C2—C3151.7 (8)Br1—Pt1—C6—C759.4 (15)
C1—C2—C3—C484.4 (16)C5—C6—C7—C879.3 (14)
Pt1—C2—C3—C44.3 (14)Pt1—C6—C7—C81.6 (14)
C2—C3—C4—C522.8 (17)C6—C7—C8—C117.9 (16)
C3—C4—C5—C653.1 (15)C2—C1—C8—C754.7 (15)
C3—C4—C5—Pt130.0 (14)Pt1—C1—C8—C726.4 (12)

Experimental details

Crystal data
Chemical formula[PtBr(CH3)(C8H12)]
Mr398.21
Crystal system, space groupOrthorhombic, P212121
Temperature (K)296
a, b, c (Å)7.1013 (15), 11.184 (2), 12.691 (3)
V3)1007.9 (4)
Z4
Radiation typeMo Kα
µ (mm1)17.82
Crystal size (mm)0.25 × 0.22 × 0.12
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.537, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
7369, 2514, 1988
Rint0.041
(sin θ/λ)max1)0.671
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.067, 1.04
No. of reflections2514
No. of parameters101
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.92, 1.27
Absolute structureFlack (1983), 1023 Friedel pairs
Absolute structure parameter0.02 (3)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected bond lengths (Å) top
Pt1—C52.118 (8)Pt1—C22.261 (10)
Pt1—C62.138 (9)Pt1—C12.262 (11)
 

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