6-Methyl­nicotinic acid

Pan, M.-L.; Luo, Y.-H.; Mao, S.-L.

doi:10.1107/S1600536811031837

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2345

doi:10.1107/S1600536811031837

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6-Methylnicotinic acid

Mei-Ling Pan,^a ^* Yang-Hui Luo ^a and Shu-Lin Mao ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chmsunbw@seu.edu.cn

(Received 13 July 2011; accepted 6 August 2011; online 17 August 2011)

All non-H atoms of the title compound, C₇H₇NO₂, are nearly coplaner, the r.m.s. deviation being 0.0087 Å. In the crystal, the partially overlapped arrangement and the face-to-face distance of 3.466 (17) Å between parallel pyridine rings of neighboring molecules indicates the existence of π–π stacking. Intermolecular O—H⋯N hydrogen bonding and weak C—H⋯O hydrogen bonding are present in the crystal structure.

Related literature

The title compound is an intermediate of the drug etoricoxib (systematic name: 5-chloro-6′-methyl-3-[4-(methylsulfonyl)phenyl]- 2,3′-bipyridine). For the structure of etoricoxibium picrate, see: Jasinski et al. (2011 ).

Experimental

Crystal data

C₇H₇NO₂
M_r = 137.14
Monoclinic, P 2₁
a = 3.8788 (8) Å
b = 13.634 (3) Å
c = 6.1094 (12) Å
β = 90.51 (3)°
V = 323.07 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
3358 measured reflections
763 independent reflections
634 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.126
S = 1.05
763 reflections
92 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	1.87	2.664 (4)	163
C4—H4A⋯O2ⁱⁱ	0.93	2.54	3.350 (4)	146
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+2]$ ; (ii) x+1, y, z-1.

Data collection: CrystalClear (Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811031837/xu5270sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811031837/xu5270Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811031837/xu5270Isup3.cml

checkCIF report

Comment top

The title compound is the drug intermediate of etoricoxib (a non- steroidal anti-inflammatory drug for the treatment of arthritis and osteoarthritis) (Jasinski et al., 2011). As part of our interest in the intermediate, we report here the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. All the non-H atoms are almost located in one plane as the atoms O1 and O2 are shifted 0.0377 and 0.0236 Å out of the pyridine ring plane, respectively.

The crystal structure is stabilized by intermolecular O—H···N and C—H···O hydrogen bonds (Table 1). π···π stacking is present between pyridine rings of the neighboring molecules.

Related literature top

The title compound is an intermediate of the drug etoricoxib (systematic name: 5-chloro-6'-methyl-3-[4-(methylsulfonyl)phenyl]- 2,3'-bipyridine). For the structure of etoricoxibium picrate, see: Jasinski et al. (2011).

Experimental top

6-Methyl-nicotinic acid was purchased commercially. Crystals suitable for X-ray diffraction were obtained by slow evaporation of a methanol solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Packing diagram.

6-Methylnicotinic acid top

Crystal data top

C₇H₇NO₂	F(000) = 144
M_r = 137.14	D_x = 1.410 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 764 reflections
a = 3.8788 (8) Å	θ = 3.3–27.5°
b = 13.634 (3) Å	µ = 0.11 mm⁻¹
c = 6.1094 (12) Å	T = 293 K
β = 90.51 (3)°	Prism, colorless
V = 323.07 (12) Å³	0.20 × 0.20 × 0.20 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	634 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.059
Graphite monochromator	θ_max = 27.5°, θ_min = 3.3°
Detector resolution: 13.6612 pixels mm^-1	h = −5→4
CCD_Profile_fitting scans	k = −17→17
3358 measured reflections	l = −7→7
763 independent reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0712P)² + 0.0005P] where P = (F_o² + 2F_c²)/3
763 reflections	(Δ/σ)_max < 0.001
92 parameters	Δρ_max = 0.25 e Å⁻³
1 restraint	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₇H₇NO₂	V = 323.07 (12) Å³
M_r = 137.14	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 3.8788 (8) Å	µ = 0.11 mm⁻¹
b = 13.634 (3) Å	T = 293 K
c = 6.1094 (12) Å	0.20 × 0.20 × 0.20 mm
β = 90.51 (3)°

Data collection top

Rigaku SCXmini diffractometer	634 reflections with I > 2σ(I)
3358 measured reflections	R_int = 0.059
763 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	1 restraint
wR(F²) = 0.126	H-atom parameters constrained
S = 1.05	Δρ_max = 0.25 e Å⁻³
763 reflections	Δρ_min = −0.16 e Å⁻³
92 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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
O1	0.0195 (8)	0.40438 (18)	0.9514 (4)	0.0631 (8)
H1	−0.0573	0.3629	1.0349	0.095*
O2	−0.1535 (7)	0.50696 (18)	1.2089 (4)	0.0675 (8)
C1	−0.0216 (7)	0.4918 (2)	1.0367 (5)	0.0440 (7)
C2	0.4505 (10)	0.8121 (3)	0.5202 (7)	0.0574 (9)
H2A	0.5640	0.8578	0.6162	0.086*
H2B	0.2546	0.8431	0.4526	0.086*
H2C	0.6080	0.7911	0.4092	0.086*
C3	0.2600 (8)	0.5539 (3)	0.6920 (6)	0.0465 (8)
H3A	0.2823	0.4902	0.6394	0.056*
C4	0.3724 (8)	0.6311 (3)	0.5713 (5)	0.0482 (8)
H4A	0.4753	0.6202	0.4366	0.058*
C5	0.3345 (9)	0.7257 (3)	0.6479 (5)	0.0423 (7)
C6	0.0802 (8)	0.6670 (2)	0.9593 (5)	0.0439 (8)
H6A	−0.0207	0.6796	1.0940	0.053*
N1	0.1857 (8)	0.74310 (17)	0.8408 (4)	0.0453 (7)
C7	0.1119 (9)	0.5709 (2)	0.8942 (5)	0.0395 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1000 (19)	0.0295 (13)	0.0602 (16)	−0.0059 (12)	0.0191 (14)	0.0014 (11)
O2	0.107 (2)	0.0408 (16)	0.0551 (13)	−0.0023 (14)	0.0297 (14)	−0.0016 (11)
C1	0.0556 (18)	0.0312 (16)	0.0452 (16)	−0.0007 (15)	0.0018 (14)	0.0039 (14)
C2	0.063 (2)	0.048 (2)	0.0615 (19)	−0.0032 (17)	0.0127 (17)	0.0114 (17)
C3	0.054 (2)	0.0369 (18)	0.0483 (15)	0.0028 (14)	0.0021 (14)	−0.0069 (14)
C4	0.0549 (17)	0.047 (2)	0.0432 (16)	0.0036 (15)	0.0089 (13)	−0.0069 (15)
C5	0.0446 (16)	0.0364 (17)	0.0460 (16)	0.0002 (14)	0.0013 (13)	0.0022 (14)
C6	0.0542 (19)	0.0347 (18)	0.0431 (16)	0.0006 (14)	0.0076 (15)	0.0002 (13)
N1	0.0578 (16)	0.0310 (16)	0.0472 (14)	0.0019 (12)	0.0085 (13)	−0.0009 (10)
C7	0.0437 (16)	0.0338 (17)	0.0409 (15)	0.0005 (11)	−0.0005 (13)	0.0026 (11)

Geometric parameters (Å, º) top

O1—C1	1.311 (4)	C3—C7	1.387 (4)
O1—H1	0.8200	C3—H3A	0.9300
O2—C1	1.192 (3)	C4—C5	1.380 (5)
C1—C7	1.482 (4)	C4—H4A	0.9300
C2—C5	1.485 (5)	C5—N1	1.337 (4)
C2—H2A	0.9600	C6—N1	1.332 (4)
C2—H2B	0.9600	C6—C7	1.375 (5)
C2—H2C	0.9600	C6—H6A	0.9300
C3—C4	1.359 (5)

C1—O1—H1	109.5	C3—C4—C5	120.3 (3)
O2—C1—O1	124.3 (3)	C3—C4—H4A	119.9
O2—C1—C7	123.2 (3)	C5—C4—H4A	119.9
O1—C1—C7	112.6 (2)	N1—C5—C4	120.8 (3)
C5—C2—H2A	109.5	N1—C5—C2	117.2 (3)
C5—C2—H2B	109.5	C4—C5—C2	121.9 (3)
H2A—C2—H2B	109.5	N1—C6—C7	123.8 (3)
C5—C2—H2C	109.5	N1—C6—H6A	118.1
H2A—C2—H2C	109.5	C7—C6—H6A	118.1
H2B—C2—H2C	109.5	C6—N1—C5	118.6 (3)
C4—C3—C7	119.4 (3)	C6—C7—C3	117.1 (3)
C4—C3—H3A	120.3	C6—C7—C1	119.4 (3)
C7—C3—H3A	120.3	C3—C7—C1	123.5 (3)

C7—C3—C4—C5	−1.0 (4)	N1—C6—C7—C1	−178.6 (3)
C3—C4—C5—N1	−0.3 (5)	C4—C3—C7—C6	1.4 (4)
C3—C4—C5—C2	−179.4 (4)	C4—C3—C7—C1	179.3 (3)
C7—C6—N1—C5	−0.7 (5)	O2—C1—C7—C6	−1.0 (5)
C4—C5—N1—C6	1.2 (5)	O1—C1—C7—C6	178.6 (3)
C2—C5—N1—C6	−179.7 (4)	O2—C1—C7—C3	−178.8 (3)
N1—C6—C7—C3	−0.6 (5)	O1—C1—C7—C3	0.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.87	2.664 (4)	163
C4—H4A···O2ⁱⁱ	0.93	2.54	3.350 (4)	146

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

Experimental details

Crystal data
Chemical formula	C₇H₇NO₂
M_r	137.14
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	3.8788 (8), 13.634 (3), 6.1094 (12)
β (°)	90.51 (3)
V (Å³)	323.07 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3358, 763, 634
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.126, 1.05
No. of reflections	763
No. of parameters	92
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.16

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.87	2.664 (4)	163
C4—H4A···O2ⁱⁱ	0.93	2.54	3.350 (4)	146

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Ppoject 20671019)

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Jasinski, J. P., Butcher, R. J., Siddegowda, M. S., Yathirajan, H. S. & Ramesha, A. R. (2011). Acta Cryst. E67, o107–o108. Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar