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organic compounds
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access2,3,6-Trichloro-5-(trichloromethyl)pyridine
aCollege of Chemical and Biological Engineering, Yancheng Institute of Technology, Yinbing Road No. 9 Yancheng, Yancheng 224051, People's Republic of China, and bInstitute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key and Open Laboratory on Forest Chemical Engineering, SFA, Nanjing 210042, Jiangsu Province, People's Republic of China
*Correspondence e-mail: jsyc_czs@163.com
The title compound, C6HCl6N, lies on a mirror plane, the conataining a half-molecule. Weak intramolecular C—H⋯Cl contacts are observed.
Related literature
For biological background, see: Okorley & Dietsche (1988![[Okorley, J. A. & Dietsche, T. J. (1988). Patent Int. Appl. No. PCT/US1998/4723019.]](../../../../../../logos/arrows/e_arr.gif "Okorley, J. A. & Dietsche, T. J. (1988). Patent Int. Appl. No. PCT/US1998/4723019.")
). For the synthetic procedure, see: Allphin et al. (1993); For a related structure, see: Fun et al. (2011).
![[Scheme 1]](pv2577scheme1.gif)
Experimental
Crystal data
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Refinement
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Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536812035404/pv2577sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536812035404/pv2577Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812035404/pv2577Isup3.cml
The title compound was synthesized by the chlorination of 2-chloro-5-chloromethyl pyridine using chlorine gas as a chlorinating agent in the presence of ultraviolet radiation and in the presence of WCl6 for 6.0 h by following a reported synthetic procedure (Allphin et al., 1993). The crystals of the title compound were obtained from a solution of 1,2-dichloroethane by evaporating the solvent slowly at room temperature in about 5 d.
The only H atom was positioned geometrically and constrained to ride on C1 with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
| Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atom ise presented as small spheres of arbitrary radius. [Symmetry code A: x, y, 1/2-z] Fig. 2. A packing diagram for the title compound showing C—H···Cl intra-molecular hydrogen bonds (dashed lines). |
| C6HCl6N | F(000) = 584 |
| Mr = 299.78 | Dx = 1.925 Mg m−3 |
| Orthorhombic, Pbcm | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2c 2b | Cell parameters from 25 reflections |
| a = 8.3100 (17) Å | θ = 10–13° |
| b = 17.018 (3) Å | µ = 1.61 mm−1 |
| c = 7.3160 (15) Å | T = 293 K |
| V = 1034.6 (4) Å3 | Block, colorless |
| Z = 4 | 0.30 × 0.20 × 0.20 mm |
| Enraf–Nonius CAD-4 diffractometer | 779 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.063 |
| Graphite monochromator | θmax = 25.4°, θmin = 2.4° |
| ω/2θ scans | h = −10→10 |
| Absorption correction: ψ scan (North et al., 1968) | k = −20→0 |
| Tmin = 0.644, Tmax = 0.739 | l = −8→0 |
| 1985 measured reflections | 3 standard reflections every 200 reflections |
| 1033 independent reflections | intensity decay: 1% |
| 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)] = 0.040 | H-atom parameters constrained |
| wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.078P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.00 | (Δ/σ)max = 0.001 |
| 1033 reflections | Δρmax = 0.26 e Å−3 |
| 77 parameters | Δρmin = −0.38 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: 0.077 (6) |
| C6HCl6N | V = 1034.6 (4) Å3 |
| Mr = 299.78 | Z = 4 |
| Orthorhombic, Pbcm | Mo Kα radiation |
| a = 8.3100 (17) Å | µ = 1.61 mm−1 |
| b = 17.018 (3) Å | T = 293 K |
| c = 7.3160 (15) Å | 0.30 × 0.20 × 0.20 mm |
| Enraf–Nonius CAD-4 diffractometer | 779 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.063 |
| Tmin = 0.644, Tmax = 0.739 | 3 standard reflections every 200 reflections |
| 1985 measured reflections | intensity decay: 1% |
| 1033 independent reflections |
| R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
| wR(F2) = 0.123 | H-atom parameters constrained |
| S = 1.00 | Δρmax = 0.26 e Å−3 |
| 1033 reflections | Δρmin = −0.38 e Å−3 |
| 77 parameters |
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 | ||
| N | 0.5025 (5) | 0.4324 (2) | 0.2500 | 0.0467 (9) | |
| Cl1 | 0.8417 (2) | 0.26884 (8) | 0.2500 | 0.0806 (6) | |
| C1 | 0.8339 (6) | 0.4268 (3) | 0.2500 | 0.0478 (11) | |
| H1A | 0.9457 | 0.4241 | 0.2500 | 0.057* | |
| Cl2 | 0.45826 (19) | 0.28195 (8) | 0.2500 | 0.0753 (5) | |
| C2 | 0.7445 (7) | 0.3584 (3) | 0.2500 | 0.0537 (12) | |
| Cl3 | 0.47402 (13) | 0.58193 (7) | 0.2500 | 0.0569 (4) | |
| C3 | 0.5783 (6) | 0.3642 (3) | 0.2500 | 0.0486 (11) | |
| Cl4 | 0.81252 (10) | 0.63147 (5) | 0.05227 (15) | 0.0619 (4) | |
| C4 | 0.5902 (5) | 0.4969 (2) | 0.2500 | 0.0399 (10) | |
| Cl5 | 1.06686 (13) | 0.55710 (8) | 0.2500 | 0.0672 (5) | |
| C5 | 0.7586 (5) | 0.4991 (2) | 0.2500 | 0.0418 (10) | |
| C6 | 0.8554 (5) | 0.5748 (2) | 0.2500 | 0.0451 (11) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N | 0.0472 (18) | 0.042 (2) | 0.051 (2) | −0.0058 (15) | 0.000 | 0.000 |
| Cl1 | 0.1128 (13) | 0.0423 (7) | 0.0867 (11) | 0.0263 (7) | 0.000 | 0.000 |
| C1 | 0.051 (3) | 0.042 (2) | 0.051 (3) | 0.0113 (19) | 0.000 | 0.000 |
| Cl2 | 0.0977 (11) | 0.0433 (7) | 0.0849 (10) | −0.0220 (6) | 0.000 | 0.000 |
| C2 | 0.075 (3) | 0.042 (2) | 0.044 (2) | 0.014 (2) | 0.000 | 0.000 |
| Cl3 | 0.0372 (6) | 0.0463 (7) | 0.0872 (10) | 0.0073 (4) | 0.000 | 0.000 |
| C3 | 0.061 (3) | 0.043 (2) | 0.042 (2) | −0.009 (2) | 0.000 | 0.000 |
| Cl4 | 0.0572 (5) | 0.0552 (6) | 0.0734 (7) | 0.0006 (3) | 0.0064 (5) | 0.0182 (4) |
| C4 | 0.039 (2) | 0.034 (2) | 0.046 (2) | 0.0056 (17) | 0.000 | 0.000 |
| Cl5 | 0.0334 (6) | 0.0666 (8) | 0.1018 (12) | 0.0007 (5) | 0.000 | 0.000 |
| C5 | 0.041 (2) | 0.040 (2) | 0.044 (2) | −0.0008 (18) | 0.000 | 0.000 |
| C6 | 0.036 (2) | 0.039 (2) | 0.061 (3) | 0.0008 (17) | 0.000 | 0.000 |
| N—C4 | 1.318 (6) | C2—C3 | 1.385 (8) |
| N—C3 | 1.321 (6) | Cl3—C4 | 1.739 (4) |
| Cl1—C2 | 1.724 (5) | Cl4—C6 | 1.774 (3) |
| C1—C2 | 1.381 (7) | C4—C5 | 1.400 (6) |
| C1—C5 | 1.381 (6) | Cl5—C6 | 1.783 (5) |
| C1—H1A | 0.9300 | C5—C6 | 1.519 (6) |
| Cl2—C3 | 1.719 (4) | C6—Cl4i | 1.774 (3) |
| C4—N—C3 | 118.0 (4) | N—C4—Cl3 | 112.7 (3) |
| C2—C1—C5 | 120.5 (4) | C5—C4—Cl3 | 122.2 (3) |
| C2—C1—H1A | 119.7 | C1—C5—C4 | 115.4 (4) |
| C5—C1—H1A | 119.7 | C1—C5—C6 | 121.1 (4) |
| C1—C2—C3 | 118.4 (4) | C4—C5—C6 | 123.5 (4) |
| C1—C2—Cl1 | 119.6 (4) | C5—C6—Cl4 | 110.77 (18) |
| C3—C2—Cl1 | 122.0 (4) | C5—C6—Cl4i | 110.77 (18) |
| N—C3—C2 | 122.6 (4) | Cl4—C6—Cl4i | 109.2 (2) |
| N—C3—Cl2 | 116.0 (4) | C5—C6—Cl5 | 112.2 (3) |
| C2—C3—Cl2 | 121.4 (4) | Cl4—C6—Cl5 | 106.84 (17) |
| N—C4—C5 | 125.1 (4) | Cl4i—C6—Cl5 | 106.84 (17) |
| C5—C1—C2—C3 | 0.0 | C2—C1—C5—C6 | 180.0 |
| C5—C1—C2—Cl1 | 180.0 | N—C4—C5—C1 | 0.0 |
| C4—N—C3—C2 | 0.0 | Cl3—C4—C5—C1 | 180.0 |
| C4—N—C3—Cl2 | 180.0 | N—C4—C5—C6 | 180.0 |
| C1—C2—C3—N | 0.0 | Cl3—C4—C5—C6 | 0.0 |
| Cl1—C2—C3—N | 180.0 | C1—C5—C6—Cl4 | 119.32 (19) |
| C1—C2—C3—Cl2 | 180.0 | C4—C5—C6—Cl4 | −60.68 (19) |
| Cl1—C2—C3—Cl2 | 0.0 | C1—C5—C6—Cl4i | −119.32 (19) |
| C3—N—C4—C5 | 0.0 | C4—C5—C6—Cl4i | 60.68 (19) |
| C3—N—C4—Cl3 | 180.0 | C1—C5—C6—Cl5 | 0.0 |
| C2—C1—C5—C4 | 0.0 | C4—C5—C6—Cl5 | 180.0 |
| Symmetry code: (i) x, y, −z+1/2. |
Experimental details
| Crystal data | |
| Chemical formula | C6HCl6N |
| Mr | 299.78 |
| Crystal system, space group | Orthorhombic, Pbcm |
| Temperature (K) | 293 |
| a, b, c (Å) | 8.3100 (17), 17.018 (3), 7.3160 (15) |
| V (Å3) | 1034.6 (4) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 1.61 |
| Crystal size (mm) | 0.30 × 0.20 × 0.20 |
| Data collection | |
| Diffractometer | Enraf–Nonius CAD-4 diffractometer |
| Absorption correction | ψ scan (North et al., 1968) |
| Tmin, Tmax | 0.644, 0.739 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 1985, 1033, 779 |
| Rint | 0.063 |
| (sin θ/λ)max (Å−1) | 0.603 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.123, 1.00 |
| No. of reflections | 1033 |
| No. of parameters | 77 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.26, −0.38 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1A···Cl5 | 0.9300 | 2.4800 | 2.944 (5) | 111.00 |
Acknowledgements
We gratefully acknowledged the support of the National Natural Science Foundation of P. R. China (No. 31170543) and the Foundation of the Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province (No. AE 201155). We also gratefully acknowledge the support of China Pharmaceutical University and Changzhou University in the analysis.
References
Allphin, C. P., DesJardin, M. A. & Harley, A. D. (1993). Patent Int. Appl. No. PCT /EP1993/544267. Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Fun, H.-K., Arshad, S., Chandrakantha, B., Isloor, A. M. & Shetty, P. (2011). Acta Cryst. E67, o1785. Web of Science CSD CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Okorley, J. A. & Dietsche, T. J. (1988). Patent Int. Appl. No. PCT/US1998/4723019. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Polychloropyridines derivatives are useful as intermediates for production of biological compounds (Okorley & Dietsche, (1988). Herein, we report the crystal structure of the title compound (Fig. 1). The bond distances and angles in the title compound agree very well with the corresponding bond distances and angles reported in a closely related compound (Fun et al., 2011).