2-Bromo-5-methyl­pyridine

Roy, M.; Golen, J.A.; Manke, D.R.

doi:10.1107/S2414314616000900

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 1| January 2016| x160090

doi:10.1107/S2414314616000900

Open

access

2-Bromo-5-methylpyridine

Mrittika Roy,^a James A. Golen ^a and David R. Manke ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 13 January 2016; accepted 15 January 2016; online 23 January 2016)

The title compound, C₆H₆BrN, has half of a molecule in the asymmetric unit, as it sits on a crystallographic plane of symmetry. In the crystal, weak C—H⋯N interactions link the molecules, forming chains along [100]. No π–π interactions are observed.

Keywords: crystal structure; pyridines; C—H⋯N interactions.

CCDC reference: 1447662

3D view (loading...)

Chemical scheme

Structure description

2-Bromopyridine and its derivatives are useful precursors for the formation of bipyridine and terpyridine ligands. Herein, we report the crystal structure of 2-bromo-5-methylpyridine, Fig. 1. The planar molecule lies on a crystallographic plane of symmetry, with a half molecule present in the asymmetric unit. The only intermolecular interactions observed are weak tip-to-tail C3—H3⋯N1 interactions that form infinite chains along [100]; see Table 1 and Fig. 2. Similar C—H⋯N interactions have been observed in other 5-substituted 2-bromopyridines (Al-Far & Ali, 2009 ; Bhasin et al., 2005 ; Ho & Pascal, 2014 ), though not in the closely related 2,6-dibromo-3,5-dimethylpyridine (Pugh, 2006 ). There are no other significant intermolecular interactions present.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N1ⁱ	0.95	2.46	3.409 (5)	179
Symmetry code: (i) x+1, y, z.

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

Figure 2
A view along the b axis of the crystal packing of the title compound.

Synthesis and crystallization

A commercial sample (Aldrich) of 2-bromo-5-methylpyridine was used for the crystallization. A sample suitable for single-crystal X-ray analysis was grown from the slow evaporation of an ethanol/water solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₆BrN
M_r	172.02
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	120
a, b, c (Å)	6.1889 (18), 6.614 (2), 7.835 (2)
β (°)	93.503 (9)
V (Å³)	320.12 (17)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	6.31
Crystal size (mm)	0.19 × 0.12 × 0.1

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.208, 0.259
No. of measured, independent and observed [I > 2σ(I)] reflections	4211, 639, 586
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.060, 1.10
No. of reflections	639
No. of parameters	53
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.50
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), olex2.refine (Bourhis et al., 2015 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1447662

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616000900/su4009sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616000900/su4009Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616000900/su4009Isup3.cml

checkCIF report

Experimental top

Structure description top

2-Bromopyridine and its derivatives are useful precursors for the formation of bipyridine and terpyridine ligands. Herein, we report the crystal structure of 2-bromo-5-methylpyridine, Fig. 1. The planar molecule lies on a crystallographic plane of symmetry, with a half molecule present in the asymmetric unit. The only intermolecular interactions observed are weak tip-to-tail C3—H3···N1 interactions that form infinite chains along [100]; see Table 1 and Fig. 2. Similar C—H···N interactions have been observed in other 5-substituted 2-bromopyridines (Al-Far & Ali, 2009; Bhasin et al., 2005; Ho & Pascal, 2014), though not in the closely related 2,6-dibromo-3,5-dimethylpyridine (Pugh, 2006). There are no other significant intermolecular interactions present.

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: olex2.refine (Bourhis et al. and 2015), SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.
	Fig. 2. A view along the b axis of the crystal packing of the title compound.

2-Bromo-5-methylpyridine top

Crystal data top

C₆H₆BrN	F(000) = 167.5322
M_r = 172.02	D_x = 1.785 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
a = 6.1889 (18) Å	Cell parameters from 2547 reflections
b = 6.614 (2) Å	θ = 3.3–25.4°
c = 7.835 (2) Å	µ = 6.31 mm⁻¹
β = 93.503 (9)°	T = 120 K
V = 320.12 (17) Å³	Block, colourless
Z = 2	0.19 × 0.12 × 0.1 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	586 reflections with I > 2σ(I)
TRIUMPH monochromator	R_int = 0.031
φ and ω scans	θ_max = 25.4°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −6→7
T_min = 0.208, T_max = 0.259	k = −7→7
4211 measured reflections	l = −9→9
639 independent reflections

Refinement top

Refinement on F²	7 restraints
Least-squares matrix: full	8 constraints
R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.0351P)² + 0.1977P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
639 reflections	Δρ_max = 0.53 e Å⁻³
53 parameters	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₆H₆BrN	V = 320.12 (17) Å³
M_r = 172.02	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 6.1889 (18) Å	µ = 6.31 mm⁻¹
b = 6.614 (2) Å	T = 120 K
c = 7.835 (2) Å	0.19 × 0.12 × 0.1 mm
β = 93.503 (9)°

Data collection top

Bruker D8 Venture CMOS diffractometer	639 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	586 reflections with I > 2σ(I)
T_min = 0.208, T_max = 0.259	R_int = 0.031
4211 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	7 restraints
wR(F²) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.53 e Å⁻³
639 reflections	Δρ_min = −0.50 e Å⁻³
53 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.28961 (6)	0.25	0.03206 (4)	0.03579 (17)
N1	0.3705 (5)	0.25	0.3819 (4)	0.0249 (6)
C1	0.4724 (6)	0.25	0.2391 (4)	0.0241 (7)
C2	0.6941 (6)	0.25	0.2276 (5)	0.0292 (8)
H2	0.7573 (6)	0.25	0.1201 (5)	0.0350 (9)*
C3	0.8195 (6)	0.25	0.3790 (5)	0.0276 (8)
H3	0.9729 (6)	0.25	0.3775 (5)	0.0331 (9)*
C4	0.7211 (6)	0.25	0.5348 (5)	0.0240 (7)
C5	0.4962 (6)	0.25	0.5274 (4)	0.0252 (7)
H5	0.4270 (6)	0.25	0.6323 (4)	0.0303 (9)*
C6	0.8515 (7)	0.25	0.7021 (5)	0.0341 (9)
H6a	0.751 (5)	0.25	0.794 (3)	0.0409 (11)*
H6b	0.944 (4)	0.130 (3)	0.714 (3)	0.0409 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0341 (3)	0.0495 (3)	0.0228 (2)	−0.000000	−0.00615 (15)	0.000000
N1	0.0209 (16)	0.0293 (15)	0.0245 (15)	−0.000000	0.0022 (12)	0.000000
C1	0.0244 (19)	0.0262 (18)	0.0215 (16)	−0.000000	−0.0001 (13)	0.000000
C2	0.028 (2)	0.036 (2)	0.0236 (18)	−0.000000	0.0062 (14)	0.000000
C3	0.0206 (18)	0.0278 (18)	0.0345 (19)	−0.000000	0.0030 (14)	0.000000
C4	0.0262 (19)	0.0198 (16)	0.0257 (18)	−0.000000	−0.0020 (13)	0.000000
C5	0.0269 (19)	0.0286 (18)	0.0207 (17)	−0.000000	0.0057 (14)	0.000000
C6	0.036 (2)	0.038 (2)	0.028 (2)	−0.000000	−0.0056 (16)	0.000000

Geometric parameters (Å, º) top

Br1—C1	1.920 (4)	C3—C4	1.397 (5)
N1—C1	1.317 (5)	C4—C5	1.390 (5)
N1—C5	1.340 (5)	C4—C6	1.496 (5)
C1—C2	1.380 (5)	C5—H5	0.9500
C2—H2	0.9500	C6—H6a	0.979 (5)
C2—C3	1.378 (5)	C6—H6bⁱ	0.979 (5)
C3—H3	0.9500	C6—H6b	0.979 (5)

C5—N1—C1	116.1 (3)	C6—C4—C3	121.6 (3)
N1—C1—Br1	115.5 (3)	C6—C4—C5	121.5 (3)
C2—C1—Br1	118.8 (3)	C4—C5—N1	124.3 (3)
C2—C1—N1	125.8 (3)	H5—C5—N1	117.85 (19)
H2—C2—C1	121.5 (2)	H5—C5—C4	117.8 (2)
C3—C2—C1	117.0 (3)	H6a—C6—C4	108 (2)
C3—C2—H2	121.5 (2)	H6b—C6—C4	111.3 (17)
H3—C3—C2	120.0 (2)	H6bⁱ—C6—C4	111.3 (17)
C4—C3—C2	120.0 (3)	H6b—C6—H6a	109.1 (5)
C4—C3—H3	120.0 (2)	H6bⁱ—C6—H6a	109.1 (5)
C5—C4—C3	116.9 (3)	H6bⁱ—C6—H6b	108 (3)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱⁱ	0.95	2.46	3.409 (5)	179

Symmetry code: (ii) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.95	2.46	3.409 (5)	179

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₆H₆BrN
M_r	172.02
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	120
a, b, c (Å)	6.1889 (18), 6.614 (2), 7.835 (2)
β (°)	93.503 (9)
V (Å³)	320.12 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.31
Crystal size (mm)	0.19 × 0.12 × 0.1

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014)
T_min, T_max	0.208, 0.259
No. of measured, independent and observed [I > 2σ(I)] reflections	4211, 639, 586
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.060, 1.10
No. of reflections	639
No. of parameters	53
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.50

Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008), olex2.refine (Bourhis et al. and 2015), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Acknowledgements

We greatly acknowledge support from the National Science Foundation (grant No. CHE-1429086).

References

Al-Far, R. H. & Ali, B. F. (2009). Acta Cryst. E65, o843. CSD CrossRef IUCr Journals Google Scholar
Bhasin, K. K., Arora, V., Sharma, S. K. & Venugopalan, P. (2005). Appl. Organomet. Chem. 19, 161–166. CSD CrossRef CAS Google Scholar
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. Web of Science CrossRef IUCr Journals Google Scholar
Bruker (2014). APEX2, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ho, D. M. & Pascal, R. A. Jr (2014). Private communication (deposition number CCDC 989200). CCDC, Cambridge, England. Google Scholar
Pugh, D. (2006). Acta Cryst. C62, o590–o592. CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals 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.