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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): m1385.
Published online 2008 October 11. doi:  10.1107/S160053680803208X
PMCID: PMC2959558

Dibromidodimethyl­dipyridine­platinum(IV)

Abstract

In the title complex, [PtBr2(CH3)2(C5H5N)2], the PtIV metal centre lies on a twofold rotation axis and adopts a slightly distorted octa­hedral coordination geometry. The structure displays weak intra­molecular C—H(...)Br hydrogen-bonding inter­actions.

Related literature

For the crystal structures of related compounds, see: Brammer et al. (2001 [triangle]); Burton et al. (1983 [triangle]); Canty et al. (1990 [triangle]); Clark et al. (1983 [triangle]); Contreras et al. (2001 [triangle]); Hall & Swile (1971 [triangle]); Hindmarch et al. (1997 [triangle]); Hughes et al. (2001 [triangle]); Kaluderović et al. (2007 [triangle]); Kelly, Gómez-Ruiz, Kluge et al. (2008 [triangle]); Kelly, Gómez-Ruiz, Schmidt et al. (2008 [triangle]); Kelly, Dietrich et al. (2008 [triangle]); Klingler et al. (1982 [triangle]). For bond-length data, see: Allen (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1385-scheme1.jpg

Experimental

Crystal data

  • [PtBr2(CH3)2(C5H5N)2]
  • M r = 543.18
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1385-efi2.jpg
  • a = 13.297 (2) Å
  • b = 8.2906 (15) Å
  • c = 13.516 (3) Å
  • V = 1490.1 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 14.76 mm−1
  • T = 220 (2) K
  • 0.40 × 0.34 × 0.30 mm

Data collection

  • Stoe IPDS diffractometer
  • Absorption correction: numerical (IPDS; Stoe & Cie, 1999 [triangle]) T min = 0.024, T max = 0.069
  • 10568 measured reflections
  • 1453 independent reflections
  • 1166 reflections with I > 2σ(I)
  • R int = 0.144

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.091
  • S = 1.01
  • 1453 reflections
  • 80 parameters
  • H-atom parameters constrained
  • Δρmax = 1.71 e Å−3
  • Δρmin = −1.68 e Å−3

Data collection: IPDS Software (Stoe & Cie, 1999 [triangle]); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680803208X/rz2250sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680803208X/rz2250Isup2.hkl

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

Acknowledgments

The authors acknowledge the Deutsche Forschungsgemeinschaft for financial support and Merck for gifts of chemicals.

supplementary crystallographic information

Comment

The structure of the title compound is one of a relatively small number of structures with the PtBr2Me2 moiety (Contreras et al., 2001; Kaluderović et al., 2007; Kelly, Gómez-Ruiz, Kluge et al., 2008; Kelly, Gómez-Ruiz, Schmidt et al., 2008; Kelly, Dietrich et al., 2008). The compound crystallizes in the orthorhombic space group Pbcn and half the molecule is generated by a twofold crystallographic axis bisecting the C—Pt—N axis as illustrated in Fig. 1. The ligating atoms have an approximate octahedral arrangement around the platinum atom. The Pt—N bond length (2.226 (5) Å) is slightly longer than expected for a platinum(IV)—N bond trans-configured to a ligating carbon atom (median: 2.156 Å; lower/upper quartile: 2.135/2.194 Å for 402 entries in the Cambridge Structural Database; CSD, Version 5.28, August 2007; Allen, 2002). The Pt—Br bond length (2.461 (1) Å) and the Pt—C bond length (2.053 (7) Å) are typical for bonds of these types (Clark et al., 1983; Klingler et al., 1982; Burton et al., 1983; Hughes et al., 2001; Canty et al., 1990; Hindmarch et al., 1997; Kelly, Gómez-Ruiz, Kluge et al., 2008; Kelly, Gómez-Ruiz, Schmidt et al., 2008; Kelly, Dietrich et al., 2008). A short intramolecular distance between the C6 carbon atom of the pyridine ligand and a bromo ligand of the same molecule is found, indicating the presence of weak C—H···Br interactions (Brammer et al., 2001).

Experimental

The title compound was prepared by dissolving [(PtBr2Me2)n] in an excess of pyridine (Hall & Swile, 1971). Single crystals suitable for X-ray analysis were obtained by slow evaporation of a chloroform solution.

Refinement

H atoms were positioned geometrically and treated as riding, with C—H bonding lengths constrained to 0.93–0.96 Å and with Uiso(H) = 1.2Ueq(C). The poor quality of the crystal may account for the rather high Rint value.

Figures

Fig. 1.
A view of the title complex with displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x, y, -z + 3/2z].

Crystal data

[PtBr2(CH3)2(C5H5N)2]F(000) = 1000
Mr = 543.18Dx = 2.421 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 8000 reflections
a = 13.297 (2) Åθ = 2.2–25.9°
b = 8.2906 (15) ŵ = 14.76 mm1
c = 13.516 (3) ÅT = 220 K
V = 1490.1 (5) Å3Block, orange
Z = 40.40 × 0.34 × 0.30 mm

Data collection

Stoe IPDS diffractometer1453 independent reflections
Radiation source: fine-focus sealed tube1166 reflections with I > 2σ(I)
graphiteRint = 0.144
area detector scansθmax = 26.0°, θmin = 2.9°
Absorption correction: numerical (IPDS; Stoe & Cie, 1999)h = −16→16
Tmin = 0.024, Tmax = 0.069k = −10→10
10568 measured reflectionsl = −16→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)] = 0.037H-atom parameters constrained
wR(F2) = 0.091w = 1/[σ2(Fo2) + (0.0472P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.002
1453 reflectionsΔρmax = 1.71 e Å3
80 parametersΔρmin = −1.68 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0012 (2)

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
C10.0667 (6)−0.0872 (9)0.6693 (6)0.0487 (17)
H30.1207−0.13360.70690.058*
H10.0928−0.04340.60870.058*
H20.0179−0.16900.65440.058*
C2−0.1238 (5)0.4045 (8)0.7975 (5)0.0412 (15)
H4−0.12680.40890.72880.049*
C3−0.1703 (5)0.5237 (9)0.8514 (6)0.0479 (17)
H5−0.20380.60700.81910.057*
C4−0.1673 (5)0.5196 (10)0.9542 (6)0.0526 (19)
H6−0.19760.60010.99180.063*
C5−0.1182 (5)0.3930 (10)0.9987 (6)0.057 (2)
H7−0.11610.38471.06730.068*
C6−0.0716 (4)0.2771 (9)0.9396 (4)0.0423 (15)
H8−0.03730.19280.96990.051*
N−0.0747 (3)0.2833 (7)0.8400 (3)0.0355 (11)
Br−0.14288 (5)0.08616 (9)0.63441 (5)0.0465 (2)
Pt0.00000.09312 (4)0.75000.03167 (18)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.055 (4)0.047 (4)0.044 (4)−0.004 (3)0.007 (3)−0.012 (3)
C20.039 (3)0.045 (4)0.039 (4)0.002 (3)−0.001 (3)0.003 (3)
C30.036 (3)0.044 (4)0.064 (5)0.000 (3)0.004 (3)0.003 (4)
C40.035 (3)0.062 (5)0.061 (5)−0.001 (3)0.010 (3)−0.023 (4)
C50.045 (4)0.087 (7)0.038 (4)0.002 (3)0.006 (3)−0.010 (4)
C60.034 (3)0.063 (4)0.030 (3)0.007 (3)−0.002 (2)−0.004 (3)
N0.029 (2)0.047 (3)0.030 (3)0.000 (2)0.0029 (19)0.003 (2)
Br0.0385 (3)0.0661 (5)0.0347 (4)−0.0103 (3)−0.0087 (3)0.0010 (3)
Pt0.0312 (2)0.0397 (2)0.0242 (3)0.000−0.00189 (11)0.000

Geometric parameters (Å, °)

C1—Pt2.053 (7)C4—H60.9300
C1—H30.9600C5—C61.394 (10)
C1—H10.9600C5—H70.9300
C1—H20.9600C6—N1.347 (7)
C2—N1.329 (8)C6—H80.9300
C2—C31.375 (10)N—Pt2.226 (5)
C2—H40.9300Br—Pt2.4605 (7)
C3—C41.391 (10)Pt—C1i2.053 (7)
C3—H50.9300Pt—Ni2.226 (5)
C4—C51.375 (11)Pt—Bri2.4605 (7)
Pt—C1—H3109.5C5—C6—H8118.9
Pt—C1—H1109.5C2—N—C6118.4 (6)
H3—C1—H1109.5C2—N—Pt121.2 (4)
Pt—C1—H2109.5C6—N—Pt120.4 (5)
H3—C1—H2109.5C1—Pt—C1i86.5 (4)
H1—C1—H2109.5C1—Pt—N178.4 (2)
N—C2—C3122.4 (7)C1i—Pt—N91.9 (3)
N—C2—H4118.8C1—Pt—Ni91.9 (3)
C3—C2—H4118.8C1i—Pt—Ni178.4 (2)
C2—C3—C4119.9 (7)N—Pt—Ni89.8 (3)
C2—C3—H5120.0C1—Pt—Bri89.2 (2)
C4—C3—H5120.0C1i—Pt—Bri88.8 (2)
C5—C4—C3117.9 (7)N—Pt—Bri90.80 (12)
C5—C4—H6121.0Ni—Pt—Bri91.11 (12)
C3—C4—H6121.0C1—Pt—Br88.8 (2)
C4—C5—C6119.1 (7)C1i—Pt—Br89.2 (2)
C4—C5—H7120.4N—Pt—Br91.11 (12)
C6—C5—H7120.4Ni—Pt—Br90.80 (12)
N—C6—C5122.2 (7)Bri—Pt—Br177.31 (4)
N—C6—H8118.9
N—C2—C3—C4−0.3 (10)C5—C6—N—Pt−179.4 (5)
C2—C3—C4—C5−0.9 (11)C2—N—Pt—Ni49.9 (4)
C3—C4—C5—C61.6 (11)C6—N—Pt—Ni−130.6 (6)
C4—C5—C6—N−1.3 (11)C2—N—Pt—Bri141.0 (4)
C3—C2—N—C60.7 (9)C6—N—Pt—Bri−39.5 (5)
C3—C2—N—Pt−179.8 (5)C2—N—Pt—Br−40.9 (4)
C5—C6—N—C20.1 (10)C6—N—Pt—Br138.6 (5)

Symmetry codes: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H8···Bri0.932.923.412 (6)115

Symmetry codes: (i) −x, y, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2250).

References

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