3,5-Di­bromo-4-methyl­pyridine

Medjani, M.; Brihi, O.; Bouraoui, H.; Hamdouni, N.; Boudjada, A.; Meinnel, J.

doi:10.1107/S2414314616008592

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160859

doi:10.1107/S2414314616008592

Open

access

3,5-Dibromo-4-methylpyridine

Meriem Medjani,^a ^* Ouarda Brihi,^a Hazem Bouraoui,^a Noudjoud Hamdouni,^a Ali Boudjada ^a and Jean Meinnel ^b

^aLaboratory of Crystallography, Department of Physics, University of Mentouri Brothers Constantine, 25000 Constantine, Algeria, and ^bUMR 6226 CNRS University of Rennes 1, 'Chemical Sciences Rennes', Team Systems and Synthetic Condensed, Electroactive, 263 Avenue du General Leclerc, F-35042 Rennes, France
^*Correspondence e-mail: medjanimeriem@yahoo.fr

Edited by J. Simpson, University of Otago, New Zealand (Received 24 May 2016; accepted 27 May 2016; online 10 June 2016)

The title compound, C₆H₅Br₂N, lies on a mirror plane. In the crystal, molecules are linked by Br⋯N and Br⋯Br interactions, forming zigzag chains along [010]. The chains are linked by offset π–π interactions [intercentroid distance = 3.5451 (3) Å], forming a three-dimensional framework.

Keywords: crystal structure; pyridine; Br⋯N interactions; halogen bonds; offset π–π interactions; framework structure.

CCDC reference: 1482349

Structure description

Pyridine has been used very frequently as a proton acceptor in studies involving hydrogen-bonded complexes (Zeegers-Huyskens et al., 1981 ; Gur'yanova et al., 1976 ). Pyridine derivatives are used as non-linear optical materials (Tomaru et al., 1991 ) and photochemicals (Kaneko et al., 1966 ). The main use of 4-methylpyridine is in the production of the anti-tuberculosis agent, isoniazid (isonicotinic acid hydrazide). Another use of this substance is the production of 4-vinylpyridine used in the manufacture of polymers, especially in the production of anion exchangers (Shimizu et al., 2007 ).

The molecular structure of the title compound is shown in Fig. 1. The molecule is planar, with all atoms, except the methyl H atoms, lying in a mirror plane.

Figure 1
The molecular structure of the title compound, with atom labelling. Displacement ellipsoids drawn at the 50% probability level.

In the crystal, molecules are linked by Br⋯N interactions [Br3⋯N1ⁱ = 3.253 (7) Å; symmetry code: (i) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ], and Br⋯Br halogen bonds [Br3⋯Br5ⁱⁱ = 3.6579 (15) Å; symmetry code: (ii) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + $[{5\over 2}]$ ], forming zigzag chains along [010]. These chains are further interconnected by offset π–π interactions [Cg1⋯Cg1^iii/iv = 3.5451 (3) Å, Cg1 is the centroid of the pyridine ring N1/C2–C6, interplanar distance = 3.4594 Å, slippage = 0.775 Å, symmetry codes: (iii) −x + 2, y + $[{1\over 2}]$ , −z + 2; (iv) −x + 2, −y + 1, −z + 2], forming a three-dimensional framework (Fig. 2).

Figure 2
The crystal packing of the title compound, viewed along the b axis. The Br⋯N and Br⋯Br interactions are shown as dashed lines.

Synthesis and crystallization

The commercially available title compound (Sigma–Aldrich) was recrystallized from ethanol solution giving colourless prismatic crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₆H₅Br₂N
M_r	250.91
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	14.178 (3), 6.9187 (18), 7.6407 (12)
V (Å³)	749.5 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	10.72
Crystal size (mm)	0.11 × 0.10 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2013 $[Oxford Diffraction (2013). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ )
T_min, T_max	0.566, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3138, 1228, 650
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.756

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.125, 1.02
No. of reflections	1289
No. of parameters	55
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.83
Computer programs: CrysAlis PRO (Oxford Diffraction, 2013 $[Oxford Diffraction (2013). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ), SIR97 (Altomare et al., 1999 ), Mercury (Macrae et al., 2008 ), SHELXL2014 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1482349

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616008592/sj4042sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616008592/sj4042Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616008592/sj4042Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2013); cell refinement: CrysAlis PRO (Oxford Diffraction, 2013); data reduction: CrysAlis PRO (Oxford Diffraction, 2013); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

3,5-Dibromo-4-methylpyridine top

Crystal data top

C₆H₅Br₂N	D_x = 2.224 Mg m⁻³
M_r = 250.91	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 659 reflections
a = 14.178 (3) Å	θ = 4.1–31.1°
b = 6.9187 (18) Å	µ = 10.72 mm⁻¹
c = 7.6407 (12) Å	T = 293 K
V = 749.5 (3) Å³	Prism, colourless
Z = 4	0.11 × 0.10 × 0.08 mm
F(000) = 472

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1228 independent reflections
Radiation source: Enhance (Mo) X-ray Source	650 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 8.0226 pixels mm^-1	θ_max = 32.5°, θ_min = 3.0°
CCD rotation images, thin slices ω scans	h = −17→20
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2013)	k = −8→9
T_min = 0.566, T_max = 1.000	l = −11→11
3138 measured reflections

Refinement top

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0347P)² + 0.0979P] where P = (F_o² + 2F_c²)/3
1289 reflections	(Δ/σ)_max < 0.001
55 parameters	Δρ_max = 0.72 e Å⁻³
0 restraints	Δρ_min = −0.83 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br3	1.21026 (6)	0.25	0.84557 (11)	0.0563 (3)
Br5	0.91081 (6)	0.25	1.35326 (10)	0.0573 (3)
N1	0.9215 (5)	0.25	0.8206 (8)	0.0470 (16)
C4	1.0582 (5)	0.25	1.0898 (9)	0.0364 (15)
C41	1.1284 (5)	0.25	1.2406 (9)	0.0467 (18)
H41A	1.0949	0.25	1.3497	0.07*
H41B	1.1674	0.3633	1.2335	0.07*	0.5
H41C	1.1674	0.1367	1.2335	0.07*	0.5
C5	0.9601 (5)	0.25	1.1226 (9)	0.0369 (16)
C6	0.8968 (5)	0.25	0.9855 (11)	0.0476 (19)
H6	0.8327	0.25	1.0119	0.057*
C2	1.0145 (5)	0.25	0.7880 (9)	0.0411 (16)
H2	1.0344	0.25	0.6721	0.049*
C3	1.0811 (5)	0.25	0.9163 (9)	0.0345 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br3	0.0359 (5)	0.0897 (6)	0.0432 (5)	0	0.0061 (4)	0
Br5	0.0448 (5)	0.0912 (6)	0.0361 (4)	0	0.0069 (4)	0
N1	0.051 (4)	0.067 (4)	0.024 (3)	0	−0.006 (3)	0
C4	0.034 (4)	0.051 (4)	0.025 (3)	0	−0.005 (3)	0
C41	0.032 (4)	0.075 (5)	0.033 (3)	0	−0.011 (3)	0
C5	0.030 (4)	0.047 (4)	0.034 (3)	0	−0.003 (3)	0
C6	0.038 (4)	0.058 (4)	0.047 (4)	0	−0.017 (4)	0
C2	0.041 (4)	0.052 (4)	0.030 (3)	0	0.001 (3)	0
C3	0.026 (4)	0.044 (3)	0.033 (4)	0	0.009 (3)	0

Geometric parameters (Å, º) top

Br3—C3	1.909 (7)	C4—C5	1.414 (9)
Br5—C5	1.896 (7)	C4—C41	1.522 (9)
N1—C6	1.308 (9)	C5—C6	1.380 (9)
N1—C2	1.342 (9)	C2—C3	1.362 (10)
C4—C3	1.365 (8)

C6—N1—C2	116.2 (6)	C4—C5—Br5	121.9 (5)
C3—C4—C5	114.0 (6)	N1—C6—C5	123.9 (7)
C3—C4—C41	125.4 (7)	N1—C2—C3	123.3 (7)
C5—C4—C41	120.6 (7)	C2—C3—C4	122.3 (7)
C6—C5—C4	120.4 (7)	C2—C3—Br3	117.5 (6)
C6—C5—Br5	117.8 (6)	C4—C3—Br3	120.2 (6)

C6—N1—C2—C3	0.00	C2—C3—C4—C41	180.00
C2—N1—C6—C5	0.00	C3—C4—C5—Br5	180.00
N1—C2—C3—Br3	180.00	C3—C4—C5—C6	0.00
N1—C2—C3—C4	0.00	C41—C4—C5—Br5	0.00
Br3—C3—C4—C5	180.00	C41—C4—C5—C6	180.00
Br3—C3—C4—C41	0.00	Br5—C5—C6—N1	180.00
C2—C3—C4—C5	0.00	C4—C5—C6—N1	0.00

Acknowledgements

Thanks are due to MESRS and DG–RSDT (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique et la Direction Générale de la Recherche – Algérie) for financial support. We would also to thank Mr F. Saidi, Engineer at the Laboratory of Crystallography, University of Mentouri Brothers Constantine, for assistance in collecting data on the Xcalibur X-ray diffractometer.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gur'yanova, E. N., Gol'dshtein, I. P. & Perepelkova, T. I. (1976). Russ. Chem. Rev. 45, 792–806. Google Scholar
Kaneko, C., Yamada, S., Yokoe, I., Hata, N. & Ubukata, Y. (1966). Tetrahedron Lett. 7, 4729–4733. CrossRef Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2013). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shimizu, S., Watanabe, N., Kataoka, T., Shoji, T., Abe, N., Morishita, S. & Ichimura, H. (2007). Pyridine and Pyridine Derivatives, in Ullmann's Encyclopedia of Industrial Chemistry. New York: John Wiley & Sons. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tomaru, S., Matsumoto, S., Kurihara, T., Suzuki, H., Ooba, N. & Kaino, T. (1991). Appl. Phys. Lett. 58, 2583–2585. CrossRef CAS Web of Science Google Scholar
Zeegers-Huyskens, Th., Huyskens, O., Ratajczak, H. & Orville-Thomas, W. J. (1981). Editors. Molecular Interactions. Vol. 2, p. 1. Chichester: Wiley. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.