Methyl 6-chloro­nicotinate

Abstract

The mol­ecule of the title compound, C₇H₆ClNO₂, is almost planar, with a dihedral angle of 3.34 (14)° between the COOMe group and the aromatic ring. In the crystal, the mol­ecules are arranged into (12) layers by C—H⋯N hydrogen bonds and there are π–π stacking inter­actions between the aromatic rings in adjacent layers [centroid–centroid distance 3.8721 (4) Å]

Related literature

For background to the synthesis of methyl 6-chloro­nicotinate, see: González et al. (2009 ▶); Rekha et al. (2009 ▶). For a related structure, see: Ma & Liu (2008 ▶).

Experimental

Crystal data

• C₇H₆ClNO₂

• M _r = 171.58

• Triclinic,

• a = 3.8721 (4) Å

• b = 5.8068 (6) Å

• c = 17.3721 (18) Å

• α = 95.563 (9)°

• β = 94.918 (8)°

• γ = 104.657 (9)°

• V = 373.64 (7) ų

• Z = 2

• Mo Kα radiation

• μ = 0.45 mm⁻¹

• T = 293 K

• 0.30 × 0.30 × 0.12 mm

Data collection

• Oxford Diffraction Xcalibur E diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.037, T _max = 1.000

• 3068 measured reflections

• 1527 independent reflections

• 855 reflections with I > 2σ(I)

• R _int = 0.029

Refinement

• R[F ² > 2σ(F ²)] = 0.055

• wR(F ²) = 0.119

• S = 0.99

• 1527 reflections

• 101 parameters

• H-atom parameters constrained

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.18 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811053517/gk2439Isup3.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
C3—H3⋯N1i	0.93	2.59	3.440 (4)	151

Symmetry code: (i) .

supplementary crystallographic information

Comment

The title compound is one of the key intermediates in our synthetic investigations of GPCR(G-protein coupled receptor) modulators. We have synthesized the title compound and here we report its crystal structure.

As shown in Fig.1, the molecule is nearly planar, the dihedral angle formed by the pyridine ring and the ester group (C6/C7/O1/O2) being 3.34 (14)°. Weak C—H···O and C—H···N hydrogen bonds are present in the crystal structure linking molecules into (1 -1 2) layers. There are also π-π stacking interactions between the aromatic rings in adjacent layers [centroid-centroid distance 3.8721 (4) Å].

Experimental

The title compound was prepared by the following method. A mixture of 6-chloronicotinic acid (5.67 g, 0.036 mol), dimethyl carbonate (10.95 mL, 0.131 mol) and concentrated H₂SO₄ (2.72 mL, 0.049 mol) was refluxed for 17 h. Then aqueous NaHCO₃ solution (8.6 g in 86 mL water) was added, extracted with dichloromethane (150 mL), dried (Na₂SO₄), filtered and evaporated under reduced pressure to afford the title compound. Crystals suitable for X-ray analysis were obtained by slow evaporation from dichloromethane solution at room temperature over a period of one week.

Refinement

H atoms were positioned geometrically and refined using a riding model approximation, with d(C—H) = 0.93 - 0.96 Å, and U_iso(H) =1.2U_eq(C) or 1.5U_eq(methyl C).

Figures

Fig. 1.

The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

Fig. 2.

A packing diagram of the title compound. Intermolecular interactions are shown as dashed lines in blue.

Crystal data

C7H6ClNO2	Z = 2
Mr = 171.58	F(000) = 176
Triclinic, P1	Dx = 1.525 Mg m−3
a = 3.8721 (4) Å	Mo Kα radiation, λ = 0.7107 Å
b = 5.8068 (6) Å	Cell parameters from 741 reflections
c = 17.3721 (18) Å	θ = 3.6–26.3°
α = 95.563 (9)°	µ = 0.45 mm−1
β = 94.918 (8)°	T = 293 K
γ = 104.657 (9)°	Block, colourless
V = 373.64 (7) Å3	0.30 × 0.30 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur E diffractometer	1527 independent reflections
Radiation source: Enhance (Mo) X-ray Source	855 reflections with I > 2σ(I)
graphite	Rint = 0.029
Detector resolution: 16.0874 pixels mm-1	θmax = 26.4°, θmin = 3.6°
ω scans	h = −4→4
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −7→7
Tmin = 0.037, Tmax = 1.000	l = −21→21
3068 measured 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.041P)2] where P = (Fo2 + 2Fc2)/3
1527 reflections	(Δ/σ)max < 0.001
101 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
Cl1	0.3480 (2)	1.23478 (16)	0.44450 (4)	0.0710 (4)
O1	0.4875 (6)	0.7116 (4)	0.10003 (12)	0.0728 (8)
O2	0.1351 (5)	0.3994 (4)	0.14496 (10)	0.0521 (6)
N1	0.5039 (6)	1.1467 (5)	0.30475 (15)	0.0529 (7)
C1	0.3350 (8)	1.0448 (6)	0.36075 (16)	0.0452 (8)
C2	0.1561 (7)	0.8050 (6)	0.35567 (17)	0.0480 (8)
H2	0.0435	0.7421	0.3971	0.058*
C3	0.1498 (7)	0.6630 (6)	0.28773 (15)	0.0443 (8)
H3	0.0331	0.5003	0.2823	0.053*
C4	0.3182 (7)	0.7630 (5)	0.22726 (15)	0.0399 (7)
C5	0.4935 (7)	1.0035 (5)	0.23934 (17)	0.0484 (8)
H5	0.6125	1.0704	0.1993	0.058*
C6	0.3266 (8)	0.6273 (6)	0.15097 (18)	0.0464 (8)
C7	0.1289 (8)	0.2550 (6)	0.07211 (16)	0.0618 (10)
H7A	−0.0050	0.3080	0.0315	0.093*
H7B	0.0171	0.0899	0.0765	0.093*
H7C	0.3703	0.2710	0.0599	0.093*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0898 (7)	0.0583 (7)	0.0610 (6)	0.0171 (5)	0.0109 (5)	−0.0070 (5)
O1	0.0875 (17)	0.0632 (18)	0.0575 (14)	−0.0044 (13)	0.0288 (13)	0.0043 (13)
O2	0.0669 (14)	0.0379 (14)	0.0472 (12)	0.0064 (11)	0.0127 (10)	−0.0011 (10)
N1	0.0611 (17)	0.0362 (17)	0.0564 (16)	0.0033 (13)	0.0081 (13)	0.0050 (14)
C1	0.0451 (18)	0.043 (2)	0.0472 (17)	0.0109 (16)	0.0029 (14)	0.0064 (16)
C2	0.0517 (19)	0.044 (2)	0.0505 (18)	0.0091 (16)	0.0165 (15)	0.0146 (16)
C3	0.0457 (17)	0.0346 (19)	0.0485 (17)	0.0021 (14)	0.0071 (14)	0.0060 (15)
C4	0.0394 (17)	0.042 (2)	0.0400 (16)	0.0105 (15)	0.0059 (13)	0.0138 (14)
C5	0.0509 (19)	0.042 (2)	0.0496 (17)	0.0048 (16)	0.0110 (14)	0.0112 (16)
C6	0.0450 (18)	0.046 (2)	0.0489 (18)	0.0112 (16)	0.0075 (15)	0.0093 (17)
C7	0.071 (2)	0.054 (2)	0.0551 (19)	0.0092 (18)	0.0116 (17)	−0.0019 (18)

Geometric parameters (Å, °)

Cl1—C1	1.728 (3)	C3—H3	0.9300
O1—C6	1.198 (4)	C3—C4	1.382 (4)
O2—C6	1.333 (4)	C4—C5	1.376 (4)
O2—C7	1.444 (3)	C4—C6	1.482 (4)
N1—C1	1.322 (4)	C5—H5	0.9300
N1—C5	1.333 (3)	C7—H7A	0.9600
C1—C2	1.380 (4)	C7—H7B	0.9600
C2—H2	0.9300	C7—H7C	0.9600
C2—C3	1.367 (4)
C6—O2—C7	116.0 (2)	C5—C4—C6	118.1 (3)
C1—N1—C5	116.2 (3)	N1—C5—C4	124.2 (3)
N1—C1—Cl1	115.3 (2)	N1—C5—H5	117.9
N1—C1—C2	124.6 (3)	C4—C5—H5	117.9
C2—C1—Cl1	120.1 (2)	O1—C6—O2	123.3 (3)
C1—C2—H2	121.1	O1—C6—C4	124.1 (3)
C3—C2—C1	117.8 (3)	O2—C6—C4	112.6 (3)
C3—C2—H2	121.1	O2—C7—H7A	109.5
C2—C3—H3	120.2	O2—C7—H7B	109.5
C2—C3—C4	119.5 (3)	O2—C7—H7C	109.5
C4—C3—H3	120.2	H7A—C7—H7B	109.5
C3—C4—C6	124.3 (3)	H7A—C7—H7C	109.5
C5—C4—C3	117.7 (3)	H7B—C7—H7C	109.5

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1i	0.93	2.59	3.440 (4)	151
C5—H5···O1	0.93	2.49	2.812 (3)	101

Symmetry codes: (i) x−1, y−1, z.