6-Methyl­nicotinic acid

Abstract

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,

• a = 3.8788 (8) Å

• b = 13.634 (3) Å

• c = 6.1094 (12) Å

• β = 90.51 (3)°

• V = 323.07 (12) ų

• 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[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811031837/xu5270Isup3.cml

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	0.82	1.87	2.664 (4)	163
C4—H4A⋯O2ii	0.93	2.54	3.350 (4)	146

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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

Refinement

All H atoms were fixed geometrically and treated as riding with C—H (CH₃) = 0.96 Å or C—H (CH) = 0.93 Å and O—H = 0.82 Å with U_iso(H) =1.5 U_eq(C,O) for methyl and carboxyl H atoms and U_iso(H) = 1.2U_eq(C) for the others. Friedel pairs were merged as no significant anomalous scatterings.

Figures

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.

Crystal data

C7H7NO2	F(000) = 144
Mr = 137.14	Dx = 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

Rigaku SCXmini diffractometer	634 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.059
graphite	θmax = 27.5°, θmin = 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

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(Fo2) + (0.0712P)2 + 0.0005P] where P = (Fo2 + 2Fc2)/3
763 reflections	(Δ/σ)max < 0.001
92 parameters	Δρmax = 0.25 e Å−3
1 restraint	Δρmin = −0.16 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.