2-Bromo-5-methyl­pyridine

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.

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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⋯N1^i	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
Mr	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 (Å^3)	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)
Tmin, Tmax	0.208, 0.259
No. of measured, independent and observed [I > 2σ(I)] reflections	4211, 639, 586
Rint	0.031
(sin θ/λ)max (Å^−1)	0.603
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), 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
Δρmax, Δρmin (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

S1. Experimental

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.

S2. Refinement

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

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.

Computing details

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

	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

Crystal data

C6H6BrN	F(000) = 167.5322
Mr = 172.02	Dx = 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) Å^3	Block, colourless
Z = 2	0.19 × 0.12 × 0.1 mm

Data collection

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

Refinement

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—H6b^i	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)	H6b^i—C6—C4	111.3 (17)
C4—C3—C2	120.0 (3)	H6b—C6—H6a	109.1 (5)
C4—C3—H3	120.0 (2)	H6b^i—C6—H6a	109.1 (5)
C5—C4—C3	116.9 (3)	H6b^i—C6—H6b	108 (3)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1^ii	0.95	2.46	3.409 (5)	179

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