Acta Cryst. (2008). E64, m1385 [ doi:10.1107/S160053680803208X ]
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.
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.
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.
Data collection: IPDS (Stoe & Cie, 1999); cell refinement: IPDS (Stoe & Cie, 1999); data reduction: IPDS (Stoe & Cie, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./rz2250fig1thm.gif)
| 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]. |
| [PtBr2(CH3)2(C5H5N)2] | F(000) = 1000 |
| Mr = 543.18 | Dx = 2.421 Mg m−3 |
| Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2n 2ab | Cell parameters from 8000 reflections |
| a = 13.297 (2) Å | θ = 2.2–25.9° |
| b = 8.2906 (15) Å | µ = 14.76 mm−1 |
| c = 13.516 (3) Å | T = 220 K |
| V = 1490.1 (5) Å3 | Block, orange |
| Z = 4 | 0.40 × 0.34 × 0.30 mm |
| Stoe IPDS diffractometer | 1453 independent reflections |
| Radiation source: fine-focus sealed tube | 1166 reflections with I > 2σ(I) |
| graphite | Rint = 0.144 |
| area detector scans | θmax = 26.0°, θmin = 2.9° |
| Absorption correction: numerical (IPDS; Stoe & Cie, 1999) | h = −16→16 |
| Tmin = 0.024, Tmax = 0.069 | k = −10→10 |
| 10568 measured reflections | l = −16→16 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0472P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max = 0.002 |
| 1453 reflections | Δρmax = 1.71 e Å−3 |
| 80 parameters | Δρmin = −1.68 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0012 (2) |
| [PtBr2(CH3)2(C5H5N)2] | V = 1490.1 (5) Å3 |
| Mr = 543.18 | Z = 4 |
| Orthorhombic, Pbcn | Mo Kα radiation |
| a = 13.297 (2) Å | µ = 14.76 mm−1 |
| b = 8.2906 (15) Å | T = 220 K |
| c = 13.516 (3) Å | 0.40 × 0.34 × 0.30 mm |
| Stoe IPDS diffractometer | 1453 independent reflections |
| Absorption correction: numerical (IPDS; Stoe & Cie, 1999) | 1166 reflections with I > 2σ(I) |
| Tmin = 0.024, Tmax = 0.069 | Rint = 0.144 |
| 10568 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.091 | Δρmax = 1.71 e Å−3 |
| S = 1.01 | Δρmin = −1.68 e Å−3 |
| 1453 reflections | Absolute structure: ? |
| 80 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.0667 (6) | −0.0872 (9) | 0.6693 (6) | 0.0487 (17) | |
| H3 | 0.1207 | −0.1336 | 0.7069 | 0.058* | |
| H1 | 0.0928 | −0.0434 | 0.6087 | 0.058* | |
| H2 | 0.0179 | −0.1690 | 0.6544 | 0.058* | |
| C2 | −0.1238 (5) | 0.4045 (8) | 0.7975 (5) | 0.0412 (15) | |
| H4 | −0.1268 | 0.4089 | 0.7288 | 0.049* | |
| C3 | −0.1703 (5) | 0.5237 (9) | 0.8514 (6) | 0.0479 (17) | |
| H5 | −0.2038 | 0.6070 | 0.8191 | 0.057* | |
| C4 | −0.1673 (5) | 0.5196 (10) | 0.9542 (6) | 0.0526 (19) | |
| H6 | −0.1976 | 0.6001 | 0.9918 | 0.063* | |
| C5 | −0.1182 (5) | 0.3930 (10) | 0.9987 (6) | 0.057 (2) | |
| H7 | −0.1161 | 0.3847 | 1.0673 | 0.068* | |
| C6 | −0.0716 (4) | 0.2771 (9) | 0.9396 (4) | 0.0423 (15) | |
| H8 | −0.0373 | 0.1928 | 0.9699 | 0.051* | |
| 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) | |
| Pt | 0.0000 | 0.09312 (4) | 0.7500 | 0.03167 (18) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.055 (4) | 0.047 (4) | 0.044 (4) | −0.004 (3) | 0.007 (3) | −0.012 (3) |
| C2 | 0.039 (3) | 0.045 (4) | 0.039 (4) | 0.002 (3) | −0.001 (3) | 0.003 (3) |
| C3 | 0.036 (3) | 0.044 (4) | 0.064 (5) | 0.000 (3) | 0.004 (3) | 0.003 (4) |
| C4 | 0.035 (3) | 0.062 (5) | 0.061 (5) | −0.001 (3) | 0.010 (3) | −0.023 (4) |
| C5 | 0.045 (4) | 0.087 (7) | 0.038 (4) | 0.002 (3) | 0.006 (3) | −0.010 (4) |
| C6 | 0.034 (3) | 0.063 (4) | 0.030 (3) | 0.007 (3) | −0.002 (2) | −0.004 (3) |
| N | 0.029 (2) | 0.047 (3) | 0.030 (3) | 0.000 (2) | 0.0029 (19) | 0.003 (2) |
| Br | 0.0385 (3) | 0.0661 (5) | 0.0347 (4) | −0.0103 (3) | −0.0087 (3) | 0.0010 (3) |
| Pt | 0.0312 (2) | 0.0397 (2) | 0.0242 (3) | 0.000 | −0.00189 (11) | 0.000 |
| C1—Pt | 2.053 (7) | C4—H6 | 0.9300 |
| C1—H3 | 0.9600 | C5—C6 | 1.394 (10) |
| C1—H1 | 0.9600 | C5—H7 | 0.9300 |
| C1—H2 | 0.9600 | C6—N | 1.347 (7) |
| C2—N | 1.329 (8) | C6—H8 | 0.9300 |
| C2—C3 | 1.375 (10) | N—Pt | 2.226 (5) |
| C2—H4 | 0.9300 | Br—Pt | 2.4605 (7) |
| C3—C4 | 1.391 (10) | Pt—C1i | 2.053 (7) |
| C3—H5 | 0.9300 | Pt—Ni | 2.226 (5) |
| C4—C5 | 1.375 (11) | Pt—Bri | 2.4605 (7) |
| Pt—C1—H3 | 109.5 | C5—C6—H8 | 118.9 |
| Pt—C1—H1 | 109.5 | C2—N—C6 | 118.4 (6) |
| H3—C1—H1 | 109.5 | C2—N—Pt | 121.2 (4) |
| Pt—C1—H2 | 109.5 | C6—N—Pt | 120.4 (5) |
| H3—C1—H2 | 109.5 | C1—Pt—C1i | 86.5 (4) |
| H1—C1—H2 | 109.5 | C1—Pt—N | 178.4 (2) |
| N—C2—C3 | 122.4 (7) | C1i—Pt—N | 91.9 (3) |
| N—C2—H4 | 118.8 | C1—Pt—Ni | 91.9 (3) |
| C3—C2—H4 | 118.8 | C1i—Pt—Ni | 178.4 (2) |
| C2—C3—C4 | 119.9 (7) | N—Pt—Ni | 89.8 (3) |
| C2—C3—H5 | 120.0 | C1—Pt—Bri | 89.2 (2) |
| C4—C3—H5 | 120.0 | C1i—Pt—Bri | 88.8 (2) |
| C5—C4—C3 | 117.9 (7) | N—Pt—Bri | 90.80 (12) |
| C5—C4—H6 | 121.0 | Ni—Pt—Bri | 91.11 (12) |
| C3—C4—H6 | 121.0 | C1—Pt—Br | 88.8 (2) |
| C4—C5—C6 | 119.1 (7) | C1i—Pt—Br | 89.2 (2) |
| C4—C5—H7 | 120.4 | N—Pt—Br | 91.11 (12) |
| C6—C5—H7 | 120.4 | Ni—Pt—Br | 90.80 (12) |
| N—C6—C5 | 122.2 (7) | Bri—Pt—Br | 177.31 (4) |
| N—C6—H8 | 118.9 | ||
| N—C2—C3—C4 | −0.3 (10) | C5—C6—N—Pt | −179.4 (5) |
| C2—C3—C4—C5 | −0.9 (11) | C2—N—Pt—Ni | 49.9 (4) |
| C3—C4—C5—C6 | 1.6 (11) | C6—N—Pt—Ni | −130.6 (6) |
| C4—C5—C6—N | −1.3 (11) | C2—N—Pt—Bri | 141.0 (4) |
| C3—C2—N—C6 | 0.7 (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—C2 | 0.1 (10) | C6—N—Pt—Br | 138.6 (5) |
| Symmetry codes: (i) −x, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H8···Bri | 0.93 | 2.92 | 3.412 (6) | 115 |
| Symmetry codes: (i) −x, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H8···Bri | 0.93 | 2.92 | 3.412 (6) | 115 |
| Symmetry codes: (i) −x, y, −z+3/2. |
The authors acknowledge the Deutsche Forschungsgemeinschaft for financial support and Merck for gifts of chemicals.
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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).