Acta Cryst. (2009). E65, m60 [ doi:10.1107/S1600536808041597 ]
In the title compound, trans-[PtCl2(C7H9N)2], the PtII atom is located on an inversion center and is coordinated by two 3,4-dimethylpyridine ligands and two chloride ligands, resulting in a typical slightly distorted square-planar geometry. The crystallographic inversion centre forces the value of the C-N-N-C torsion angle to be linear and the 3,4-dimethyl-pyridine ligands to be coplanar.
3,4-dimethylpyridine (1 ml) was added to the powder of K2[PtCl4] (0.2 g) and the resulting mixture was heated to 150°C until the complete evaporation of the 3,4-dimethylpyridine. The resulting complex was recrystallized from CHCl3 (yield 92%). Crystals were obtained by slow evaporation of CHCl3 solution. Anal. calc. for C14H18N2Cl2Pt:C, 35.01; H, 3.78; N, 5.83%. Found: C, 35.30; H, 3.96; N, 5.54%.
Hydrogen atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.95–0.98 Å, and Uĩso~ = 1.2–1.5 U~eq~(parent atom). The highest peak is located 0.87 Å from atom Pt1 and the deepest hole is located 0.83 Å from atom Pt1.
Data collection: COLLECT (Bruker, 2004); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./kj2108fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
| [PtCl2(C7H9N)2] | F(000) = 456 |
| Mr = 480.29 | Dx = 2.127 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2339 reflections |
| a = 7.9763 (5) Å | θ = 1.0–20.0° |
| b = 7.1102 (3) Å | µ = 9.70 mm−1 |
| c = 13.3586 (7) Å | T = 120 K |
| β = 98.247 (5)° | Block, pale yellow |
| V = 749.77 (7) Å3 | 0.21 × 0.20 × 0.10 mm |
| Z = 2 |
| Nonius KappaCCD diffractometer | 2177 independent reflections |
| Radiation source: fine-focus sealed tube | 1705 reflections with I > 2σ(I) |
| horizontally mounted graphite crystal | Rint = 0.033 |
| Detector resolution: 9 pixels mm-1 pixels mm-1 | θmax = 30.0°, θmin = 2.8° |
| φ scans and ω scans with κ offset | h = −11→10 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −10→9 |
| Tmin = 0.201, Tmax = 0.381 | l = −18→18 |
| 17165 measured reflections |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.015 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.030 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.0064P)2 + 0.7739P] where P = (Fo2 + 2Fc2)/3 |
| 2177 reflections | (Δ/σ)max < 0.001 |
| 90 parameters | Δρmax = 0.67 e Å−3 |
| 0 restraints | Δρmin = −0.78 e Å−3 |
| [PtCl2(C7H9N)2] | V = 749.77 (7) Å3 |
| Mr = 480.29 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 7.9763 (5) Å | µ = 9.70 mm−1 |
| b = 7.1102 (3) Å | T = 120 K |
| c = 13.3586 (7) Å | 0.21 × 0.20 × 0.10 mm |
| β = 98.247 (5)° |
| Nonius KappaCCD diffractometer | 2177 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1705 reflections with I > 2σ(I) |
| Tmin = 0.201, Tmax = 0.381 | Rint = 0.033 |
| 17165 measured reflections | θmax = 30.0° |
| R[F2 > 2σ(F2)] = 0.015 | H-atom parameters constrained |
| wR(F2) = 0.030 | Δρmax = 0.67 e Å−3 |
| S = 1.08 | Δρmin = −0.78 e Å−3 |
| 2177 reflections | Absolute structure: ? |
| 90 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 | ||
| Pt1 | 0.0000 | 0.0000 | 0.0000 | 0.01078 (3) | |
| Cl1 | −0.12594 (8) | −0.27477 (8) | 0.03883 (4) | 0.01897 (11) | |
| N1 | 0.0259 (2) | 0.0765 (3) | 0.14663 (13) | 0.0127 (4) | |
| C1 | −0.0247 (3) | 0.2464 (3) | 0.17546 (16) | 0.0143 (4) | |
| H1 | −0.0716 | 0.3324 | 0.1246 | 0.017* | |
| C2 | −0.0115 (3) | 0.3015 (3) | 0.27567 (16) | 0.0141 (4) | |
| C3 | −0.0729 (3) | 0.4918 (3) | 0.30137 (17) | 0.0227 (5) | |
| H3A | −0.1179 | 0.5582 | 0.2390 | 0.034* | |
| H3B | 0.0215 | 0.5637 | 0.3379 | 0.034* | |
| H3C | −0.1623 | 0.4781 | 0.3440 | 0.034* | |
| C4 | 0.0634 (3) | 0.1776 (3) | 0.35029 (16) | 0.0138 (4) | |
| C5 | 0.0883 (3) | 0.2318 (4) | 0.45953 (16) | 0.0188 (5) | |
| H5A | 0.1668 | 0.3383 | 0.4702 | 0.028* | |
| H5B | 0.1353 | 0.1249 | 0.5006 | 0.028* | |
| H5C | −0.0209 | 0.2676 | 0.4795 | 0.028* | |
| C6 | 0.1162 (3) | 0.0044 (4) | 0.31969 (15) | 0.0161 (4) | |
| H6 | 0.1677 | −0.0824 | 0.3688 | 0.019* | |
| C7 | 0.0948 (3) | −0.0435 (3) | 0.21858 (17) | 0.0163 (5) | |
| H7 | 0.1297 | −0.1645 | 0.1994 | 0.020* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Pt1 | 0.01278 (5) | 0.01094 (5) | 0.00822 (5) | 0.00154 (6) | 0.00017 (3) | −0.00158 (5) |
| Cl1 | 0.0265 (3) | 0.0165 (2) | 0.0140 (2) | −0.0048 (2) | 0.0032 (2) | −0.0015 (2) |
| N1 | 0.0139 (9) | 0.0141 (8) | 0.0096 (8) | 0.0001 (8) | 0.0003 (7) | −0.0017 (7) |
| C1 | 0.0145 (10) | 0.0156 (11) | 0.0126 (9) | −0.0004 (9) | 0.0014 (8) | 0.0006 (8) |
| C2 | 0.0168 (11) | 0.0133 (11) | 0.0132 (10) | −0.0030 (9) | 0.0050 (8) | −0.0033 (8) |
| C3 | 0.0370 (13) | 0.0158 (10) | 0.0165 (10) | 0.0026 (13) | 0.0077 (9) | −0.0002 (11) |
| C4 | 0.0122 (10) | 0.0181 (11) | 0.0111 (10) | −0.0041 (9) | 0.0019 (8) | −0.0013 (8) |
| C5 | 0.0222 (12) | 0.0232 (12) | 0.0109 (10) | −0.0042 (10) | 0.0018 (9) | −0.0026 (9) |
| C6 | 0.0168 (9) | 0.0174 (10) | 0.0131 (9) | 0.0019 (11) | −0.0013 (7) | 0.0011 (11) |
| C7 | 0.0166 (11) | 0.0173 (12) | 0.0147 (10) | 0.0027 (8) | 0.0008 (8) | −0.0010 (8) |
| Pt1—N1i | 2.0148 (18) | C3—H3B | 0.9800 |
| Pt1—N1 | 2.0148 (18) | C3—H3C | 0.9800 |
| Pt1—Cl1i | 2.2901 (6) | C4—C6 | 1.382 (3) |
| Pt1—Cl1 | 2.2901 (6) | C4—C5 | 1.495 (3) |
| N1—C7 | 1.343 (3) | C5—H5A | 0.9800 |
| N1—C1 | 1.347 (3) | C5—H5B | 0.9800 |
| C1—C2 | 1.384 (3) | C5—H5C | 0.9800 |
| C1—H1 | 0.9500 | C6—C7 | 1.380 (3) |
| C2—C4 | 1.398 (3) | C6—H6 | 0.9500 |
| C2—C3 | 1.495 (3) | C7—H7 | 0.9500 |
| C3—H3A | 0.9800 | ||
| N1i—Pt1—N1 | 180.0 | C2—C3—H3C | 109.5 |
| N1i—Pt1—Cl1i | 89.85 (6) | H3A—C3—H3C | 109.5 |
| N1—Pt1—Cl1i | 90.15 (6) | H3B—C3—H3C | 109.5 |
| N1i—Pt1—Cl1 | 90.15 (6) | C6—C4—C2 | 117.88 (19) |
| N1—Pt1—Cl1 | 89.85 (6) | C6—C4—C5 | 121.0 (2) |
| Cl1i—Pt1—Cl1 | 180.0 | C2—C4—C5 | 121.1 (2) |
| C7—N1—C1 | 118.30 (19) | C4—C5—H5A | 109.5 |
| C7—N1—Pt1 | 119.91 (15) | C4—C5—H5B | 109.5 |
| C1—N1—Pt1 | 121.79 (15) | H5A—C5—H5B | 109.5 |
| N1—C1—C2 | 123.1 (2) | C4—C5—H5C | 109.5 |
| N1—C1—H1 | 118.5 | H5A—C5—H5C | 109.5 |
| C2—C1—H1 | 118.5 | H5B—C5—H5C | 109.5 |
| C1—C2—C4 | 118.5 (2) | C7—C6—C4 | 120.6 (2) |
| C1—C2—C3 | 119.8 (2) | C7—C6—H6 | 119.7 |
| C4—C2—C3 | 121.78 (19) | C4—C6—H6 | 119.7 |
| C2—C3—H3A | 109.5 | N1—C7—C6 | 121.6 (2) |
| C2—C3—H3B | 109.5 | N1—C7—H7 | 119.2 |
| H3A—C3—H3B | 109.5 | C6—C7—H7 | 119.2 |
| Symmetry codes: (i) −x, −y, −z. |
| Pt1—N1 | 2.0148 (18) | Pt1—Cl1 | 2.2901 (6) |
| N1—Pt1—Cl1 | 89.85 (6) |
| L | Pt—N | Pt—Cl | N—Pt—Cl |
| 4-picoline [1] | 2.024 (5) | 2.3046 (18) | 90.16 (12) |
| N-nitroxyethylnicotinamide [2] | 2.019 (8) | 2.311 (3) | 90.8 (2) |
| 4-vinylpyridine [3] | 2.021 (3) | 2.3000 (9) | 89.9 (8) |
| 3-fluoropyridine [4] | 2.0177 (20) | 2.3013 (12) | 89.86 (9) |
| 3-chloropyridine [4] | 2.015 (3) | 2.3001 (8) | 90.55 (8) |
| 3-bromopyridine [4] | 1.992 (6) | 2.3106 (16) | 90.40 (19) |
| 3-iodopyridine [4] | 2.019 (5) | 2.303 (3) | 89.7 (2) |
| 2,6-bis(hydroxymethyl)pyridine [5] | 2.040 (7) | 2.306 (3) | 90m |
| pyridine [6] | 1.977 (2) | 2.308 (3) | 88.01 (6) |
| In all structures Pt atom is located on an inversion centre. m = Pt is on a mirror plane. [1] Tessier & Rochon (1999); [2] Eremenko et al. (1997); [3] Shaver et al. (2000); [4] Zordan et al. (2005); [5] Rochon et al. (1996); [6] Colamarino & Orioli (1975). |
This work was supported by the Russian Fund for Basic Research (grant 08–03-00247 and 08–03-00631).
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The complex trans-[PtCl2(C7H9N)2] has an inversion symmetry and the PtII atom is situated at an inversion center and it is coordinated by two 3,4-dimethylpyridine ligands and two chloro ligands and exhibit trans configuration. Such arrangement of ligands leads to the square planar geometry. In the coordination polyhedron, all angles are very close to the ideal value of 90°. The crystallographic inversion centre forces the value of the torsion angle C1—N1—N1i—Ci (symmetry operation i: -x, -y, -z) to be 180° and the the 3,4-dimethyl-pyridine ligands to be coplanar.
The geometry of 3,4-dimethylpyridine ligands resembles the geometry of the uncoordinated 3,4-dimethylpyridine, i.e. the C—C and C—N bond distances and angles in the coordinated 3,4-dimethylpyridine agree well with the expected value (Bond, Davies, 2002). The bond distance Pt–N (2.0148 (18) Å) is similar to the Pt—N bond lengths in other related compounds (Orpen et al., 1989). The Pt—Cl bond lengths agree well with the reported values (See Table 2).
All trans-[PtCl2L2] complexes given in Table 2 have the same coordination environment as in the title compound. Indeed, they are square-planar and their pyridine rings lie in the same plane. The N—Pt—N and Cl—Pt—Cl angles in all observed compounds are equal to 180°, the angles N—Pt—Cl are very close to 90°.