organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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2-Bromo-3-hy­dr­oxy-6-methyl­pyridine

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.

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[Tetsu, A., Berhane, T., Robert, F. T. & John, E. C. (1990). J. Agric. Food Chem. 38, 1712-1715.]). For the synthesis, see: Kjell et al. (1969[Kjell, U., Vegard, N. & Knut, T. (1969). Acta Chem. Scand. 23, 1704-1714.]).

[Scheme 1]

Experimental

Crystal data
  • C6H6BrNO

  • Mr = 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[Bruker (2001). SMART, SAINT and SADABS . Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.255, Tmax = 0.539

  • 12822 measured reflections

  • 1335 independent reflections

  • 1115 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.36 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2001). SMART, SAINT and SADABS . Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART, SAINT and SADABS . Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL and X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]).

Supporting information


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
[Figure 1] Fig. 1. A view of the molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 35% probability level.
[Figure 2] 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
C6H6BrNOF(000) = 736
Mr = 188.03Dx = 1.814 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4373 reflections
a = 11.4484 (19) Åθ = 3.1–25.7°
b = 9.0914 (15) ŵ = 5.88 mm1
c = 13.230 (2) ÅT = 298 K
V = 1377.1 (4) Å3Needle, colorless
Z = 80.32 × 0.22 × 0.12 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1335 independent reflections
Radiation source: fine-focus sealed tube1115 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
phi and ω scansθmax = 25.9°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1414
Tmin = 0.255, Tmax = 0.539k = 1111
12822 measured reflectionsl = 1616
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H 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 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
C6H6BrNOV = 1377.1 (4) Å3
Mr = 188.03Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 11.4484 (19) ŵ = 5.88 mm1
b = 9.0914 (15) ÅT = 298 K
c = 13.230 (2) Å0.32 × 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)
Tmin = 0.255, Tmax = 0.539Rint = 0.032
12822 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.066H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.22 e Å3
1335 reflectionsΔρmin = 0.36 e Å3
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
xyzUiso*/Ueq
Br10.71386 (2)1.06988 (3)0.63569 (2)0.0542 (1)
O10.95756 (15)0.9896 (2)0.69349 (15)0.0603 (7)
N10.68110 (16)0.8898 (2)0.79970 (15)0.0419 (6)
C10.76362 (18)0.9477 (2)0.74339 (17)0.0380 (6)
C20.88204 (18)0.9217 (2)0.75492 (19)0.0422 (7)
C30.9120 (2)0.8254 (3)0.83193 (19)0.0498 (8)
C40.8269 (2)0.7633 (3)0.89095 (18)0.0506 (8)
C50.7110 (2)0.7963 (3)0.87433 (17)0.0466 (8)
C60.6136 (2)0.7345 (4)0.9362 (2)0.0664 (10)
H11.023 (3)0.961 (3)0.700 (2)0.075 (10)*
H30.990100.802900.843600.0600*
H40.847400.698600.942400.0610*
H6A0.578400.811700.975200.1000*
H6B0.643700.660400.980900.1000*
H6C0.556100.691600.892400.1000*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0429 (2)0.0644 (2)0.0552 (2)0.0084 (1)0.0049 (1)0.0091 (1)
O10.0266 (9)0.0798 (13)0.0746 (13)0.0023 (8)0.0044 (8)0.0172 (11)
N10.0281 (8)0.0498 (10)0.0479 (11)0.0018 (8)0.0013 (8)0.0035 (9)
C10.0286 (10)0.0420 (12)0.0434 (11)0.0032 (9)0.0032 (9)0.0038 (9)
C20.0252 (10)0.0493 (13)0.0520 (13)0.0004 (9)0.0013 (9)0.0039 (10)
C30.0304 (11)0.0610 (15)0.0580 (14)0.0062 (11)0.0076 (10)0.0011 (12)
C40.0447 (13)0.0576 (15)0.0496 (13)0.0047 (12)0.0095 (10)0.0038 (12)
C50.0395 (13)0.0516 (14)0.0486 (14)0.0036 (10)0.0007 (10)0.0032 (10)
C60.0535 (15)0.0822 (19)0.0634 (17)0.0139 (14)0.0056 (13)0.0121 (15)
Geometric parameters (Å, º) top
Br1—C11.894 (2)C4—C51.378 (3)
O1—C21.338 (3)C5—C61.493 (4)
O1—H10.80 (3)C3—H30.9300
N1—C51.347 (3)C4—H40.9300
N1—C11.313 (3)C6—H6A0.9600
C1—C21.385 (3)C6—H6B0.9600
C2—C31.386 (3)C6—H6C0.9600
C3—C41.370 (3)
C2—O1—H1113 (2)N1—C5—C4119.9 (2)
C1—N1—C5119.07 (19)C2—C3—H3120.00
Br1—C1—N1116.45 (15)C4—C3—H3120.00
N1—C1—C2125.0 (2)C3—C4—H4120.00
Br1—C1—C2118.52 (16)C5—C4—H4120.00
O1—C2—C1119.2 (2)C5—C6—H6A109.00
C1—C2—C3115.5 (2)C5—C6—H6B109.00
O1—C2—C3125.3 (2)C5—C6—H6C110.00
C2—C3—C4120.2 (2)H6A—C6—H6B109.00
C3—C4—C5120.3 (2)H6A—C6—H6C109.00
N1—C5—C6116.7 (2)H6B—C6—H6C109.00
C4—C5—C6123.4 (2)
C5—N1—C1—Br1176.80 (17)N1—C1—C2—O1178.9 (2)
C5—N1—C1—C20.8 (3)C1—C2—C3—C40.2 (3)
C1—N1—C5—C6179.7 (2)O1—C2—C3—C4179.3 (2)
C1—N1—C5—C40.3 (3)C2—C3—C4—C50.1 (4)
Br1—C1—C2—C3176.81 (17)C3—C4—C5—C6179.2 (3)
Br1—C1—C2—O13.6 (3)C3—C4—C5—N10.1 (4)
N1—C1—C2—C30.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N1i0.80 (3)1.92 (3)2.717 (3)174 (3)
C6—H6B···Br1ii0.963.043.993 (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···AD—HH···AD···AD—H···A
O1—H1···N1i0.80 (3)1.92 (3)2.717 (3)174 (3)
C6—H6B···Br1ii0.963.0373.993 (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

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS
First citationBruker (2001). SMART, SAINT and SADABS . Bruker AXS Inc., Madison, Wisconsin, USA.
First citationKjell, U., Vegard, N. & Knut, T. (1969). Acta Chem. Scand. 23, 1704–1714.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationTetsu, A., Berhane, T., Robert, F. T. & John, E. C. (1990). J. Agric. Food Chem. 38, 1712–1715.

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ISSN: 2056-9890
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