2-Bromo-3-hy­droxy-6-methyl­pyridine

Abstract

In the title compound, C₆H₆BrNO, the Br atom is displaced from the pyridine ring mean plane by 0.0948 (3) Å, while the hydroxyl O atom and the methyl C atom are displaced by 0.0173 (19) and 0.015 (3) Å, respectively. In the crystal, mol­ecules are linked via O—H⋯N hydrogen bonds, forming chains propagating along the a-axis direction. These chains are linked by C—H⋯Br hydrogen bonds, forming corrugated two-dimensional networks lying parallel to the ac plane.

Related literature  

3-Hy­droxy­pyridine, the core skeleton of the title compound is an integral part of Nikkomycin Z (a potent fungicide), see: Tetsu et al. (1990 ▶). For the synthesis, see: Kjell et al. (1969 ▶).

Experimental  

Crystal data  

• C₆H₆BrNO

• M _r = 188.03

• Orthorhombic,

• a = 11.4484 (19) Å

• b = 9.0914 (15) Å

• c = 13.230 (2) Å

• V = 1377.1 (4) ų

• Z = 8

• Mo Kα radiation

• μ = 5.88 mm⁻¹

• T = 298 K

• 0.32 × 0.22 × 0.12 mm

Data collection  

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.255, T _max = 0.539

• 12822 measured reflections

• 1335 independent reflections

• 1115 reflections with I > 2σ(I)

• R _int = 0.032

Refinement  

• R[F ² > 2σ(F ²)] = 0.025

• wR(F ²) = 0.066

• S = 1.06

• 1335 reflections

• 87 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.22 e Å⁻³

• Δρ_min = −0.36 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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 and X-SEED (Barbour, 2001 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1i	0.80 (3)	1.92 (3)	2.717 (3)	174 (3)
C6—H6B⋯Br1ii	0.96	3.04	3.993 (3)	174

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

1. Comment

3-Hydroxypyridine is an integral part of Nikkomycin Z (NZ), a potent fungicide, insecticide, miticide, and inhibitor of fungal and insect chitin synthetase (Tetsu et al., 1990). Various biaryl derivative compounds, derived originally from 3-hydroxypyridine, are PDE4 inhibitors useful for the treatment and prevention of strokes, myocardial infarction and cardiovascular inflammatory diseases and disorders. Herein we describe the crystal structure of the 2-bromo derivative of 3-hydroxy-6-methylpyridine, previously synthesized by (Kjell et al., 1969).

The molecular structure of the title molecule is illustrated in Fig. 1. The bond lengths and angles are normal.

In the crystal, molecules are linked via O-H···N hydrogen bonds forming chains propagating along the a axis direction (Fig. 2 and Table 1). These chains are linked by weak C-H···Br hydrogen bonds forming corrugated two-dimensional networks lying parallel to the ac plane (Fig. 2 and Table 1).

2. Experimental

The title compound was synthesized following the published procedure (Kjell et al., 1969). Colourless crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution of the title compound in ethanol [m.p. = 460–462 K].

Figures

Fig. 1.

A view of the molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 35% probability level.

Fig. 2.

A view normal to the ac plane of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 for details; a axis vertical; c axis horizontal).

Crystal data

C6H6BrNO	F(000) = 736
Mr = 188.03	Dx = 1.814 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4373 reflections
a = 11.4484 (19) Å	θ = 3.1–25.7°
b = 9.0914 (15) Å	µ = 5.88 mm−1
c = 13.230 (2) Å	T = 298 K
V = 1377.1 (4) Å3	Needle, colorless
Z = 8	0.32 × 0.22 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1335 independent reflections
Radiation source: fine-focus sealed tube	1115 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
phi and ω scans	θmax = 25.9°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→14
Tmin = 0.255, Tmax = 0.539	k = −11→11
12822 measured reflections	l = −16→16

Refinement

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0376P)2 + 0.3754P] where P = (Fo2 + 2Fc2)/3
1335 reflections	(Δ/σ)max = 0.001
87 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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.

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

	x	y	z	Uiso*/Ueq
Br1	0.71386 (2)	1.06988 (3)	0.63569 (2)	0.0542 (1)
O1	0.95756 (15)	0.9896 (2)	0.69349 (15)	0.0603 (7)
N1	0.68110 (16)	0.8898 (2)	0.79970 (15)	0.0419 (6)
C1	0.76362 (18)	0.9477 (2)	0.74339 (17)	0.0380 (6)
C2	0.88204 (18)	0.9217 (2)	0.75492 (19)	0.0422 (7)
C3	0.9120 (2)	0.8254 (3)	0.83193 (19)	0.0498 (8)
C4	0.8269 (2)	0.7633 (3)	0.89095 (18)	0.0506 (8)
C5	0.7110 (2)	0.7963 (3)	0.87433 (17)	0.0466 (8)
C6	0.6136 (2)	0.7345 (4)	0.9362 (2)	0.0664 (10)
H1	1.023 (3)	0.961 (3)	0.700 (2)	0.075 (10)*
H3	0.99010	0.80290	0.84360	0.0600*
H4	0.84740	0.69860	0.94240	0.0610*
H6A	0.57840	0.81170	0.97520	0.1000*
H6B	0.64370	0.66040	0.98090	0.1000*
H6C	0.55610	0.69160	0.89240	0.1000*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0429 (2)	0.0644 (2)	0.0552 (2)	0.0084 (1)	−0.0049 (1)	0.0091 (1)
O1	0.0266 (9)	0.0798 (13)	0.0746 (13)	0.0023 (8)	0.0044 (8)	0.0172 (11)
N1	0.0281 (8)	0.0498 (10)	0.0479 (11)	−0.0018 (8)	−0.0013 (8)	−0.0035 (9)
C1	0.0286 (10)	0.0420 (12)	0.0434 (11)	0.0032 (9)	−0.0032 (9)	−0.0038 (9)
C2	0.0252 (10)	0.0493 (13)	0.0520 (13)	−0.0004 (9)	−0.0013 (9)	−0.0039 (10)
C3	0.0304 (11)	0.0610 (15)	0.0580 (14)	0.0062 (11)	−0.0076 (10)	−0.0011 (12)
C4	0.0447 (13)	0.0576 (15)	0.0496 (13)	0.0047 (12)	−0.0095 (10)	0.0038 (12)
C5	0.0395 (13)	0.0516 (14)	0.0486 (14)	−0.0036 (10)	0.0007 (10)	−0.0032 (10)
C6	0.0535 (15)	0.0822 (19)	0.0634 (17)	−0.0139 (14)	0.0056 (13)	0.0121 (15)

Geometric parameters (Å, º)

Br1—C1	1.894 (2)	C4—C5	1.378 (3)
O1—C2	1.338 (3)	C5—C6	1.493 (4)
O1—H1	0.80 (3)	C3—H3	0.9300
N1—C5	1.347 (3)	C4—H4	0.9300
N1—C1	1.313 (3)	C6—H6A	0.9600
C1—C2	1.385 (3)	C6—H6B	0.9600
C2—C3	1.386 (3)	C6—H6C	0.9600
C3—C4	1.370 (3)
C2—O1—H1	113 (2)	N1—C5—C4	119.9 (2)
C1—N1—C5	119.07 (19)	C2—C3—H3	120.00
Br1—C1—N1	116.45 (15)	C4—C3—H3	120.00
N1—C1—C2	125.0 (2)	C3—C4—H4	120.00
Br1—C1—C2	118.52 (16)	C5—C4—H4	120.00
O1—C2—C1	119.2 (2)	C5—C6—H6A	109.00
C1—C2—C3	115.5 (2)	C5—C6—H6B	109.00
O1—C2—C3	125.3 (2)	C5—C6—H6C	110.00
C2—C3—C4	120.2 (2)	H6A—C6—H6B	109.00
C3—C4—C5	120.3 (2)	H6A—C6—H6C	109.00
N1—C5—C6	116.7 (2)	H6B—C6—H6C	109.00
C4—C5—C6	123.4 (2)
C5—N1—C1—Br1	176.80 (17)	N1—C1—C2—O1	−178.9 (2)
C5—N1—C1—C2	−0.8 (3)	C1—C2—C3—C4	−0.2 (3)
C1—N1—C5—C6	179.7 (2)	O1—C2—C3—C4	179.3 (2)
C1—N1—C5—C4	0.3 (3)	C2—C3—C4—C5	−0.1 (4)
Br1—C1—C2—C3	−176.81 (17)	C3—C4—C5—C6	−179.2 (3)
Br1—C1—C2—O1	3.6 (3)	C3—C4—C5—N1	0.1 (4)
N1—C1—C2—C3	0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1i	0.80 (3)	1.92 (3)	2.717 (3)	174 (3)
C6—H6B···Br1ii	0.96	3.04	3.993 (3)	174

Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) x, −y+3/2, z+1/2.