2-Bromo-3-hy­droxy-6-methyl­pyridine

Singh, G.P.; Rajesh Goud, N.; Jeevan Kumar, P.; Sundaresan, C.N.; Nageswara Rao, G.

doi:10.1107/S1600536813029498

organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page o1729

doi:10.1107/S1600536813029498

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2-Bromo-3-hydroxy-6-methylpyridine

Govind Pratap Singh,^a N. Rajesh Goud,^b P. Jeevan Kumar,^a C. N. Sundaresan ^c and G. Nageswara Rao ^a ^*

^aDepartment of Chemistry, Sri Sathya Sai Institute of Higher Learning, Prasanthinilayam, Ananthapur, Andhra Pradesh, 515 134, India, ^bSchool of Chemistry, University of Hyderabad, Gachibowli, Hyderabad, 500 046, India, and ^cDepartment of Chemistry, Sri Sathya Sai Institute of Higher Learning, Brindavan Campus, Whitefield, Bangalore, India
^*Correspondence e-mail: gnageswararao@sssihl.edu.in

(Received 14 October 2013; accepted 25 October 2013; online 6 November 2013)

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.

CCDC reference: 968763

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, P b c a
a = 11.4484 (19) Å
b = 9.0914 (15) Å
c = 13.230 (2) Å
V = 1377.1 (4) Å³
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[F² > 2σ(F²)] = 0.025
wR(F²) = 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

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) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

CCDC reference: 968763

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813029498/su2659sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813029498/su2659Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813029498/su2659Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536813029498/su2659Isup4.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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].

Computing details top

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

Figures top

	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).

2-Bromo-3-hydroxy-6-methylpyridine top

Crystal data top

C₆H₆BrNO	F(000) = 736
M_r = 188.03	D_x = 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 top

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

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)] = 0.025	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(F_o²) + (0.0376P)² + 0.3754P] where P = (F_o² + 2F_c²)/3
1335 reflections	(Δ/σ)_max = 0.001
87 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₆H₆BrNO	V = 1377.1 (4) Å³
M_r = 188.03	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.4484 (19) Å	µ = 5.88 mm⁻¹
b = 9.0914 (15) Å	T = 298 K
c = 13.230 (2) Å	0.32 × 0.22 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1335 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1115 reflections with I > 2σ(I)
T_min = 0.255, T_max = 0.539	R_int = 0.032
12822 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.22 e Å⁻³
1335 reflections	Δρ_min = −0.36 e Å⁻³
87 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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.

Hydrogen-bond geometry (Å, º) top

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	3.037	3.993 (3)	174

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

Acknowledgements

The authors thank Bhagavan Sri Sathya Sai Baba for constant guidance and motivation. We would like to thank Professor Ashwini Nangia, University of Hyderabad, for his help with the single-crystal X-ray diffraction facility. GNR acknowledges financial support from the Council of Scientific and Industrial Research (CSIR), 01 (2286)/08/EMR-II, India. NRG thanks the CSIR for a fellowship.

References

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Tetsu, A., Berhane, T., Robert, F. T. & John, E. C. (1990). J. Agric. Food Chem. 38, 1712–1715. Google Scholar