2-(2-Chloro­pyridin-3-yl)-N-ethyl-4-methyl-1,3-oxazole-5-carboxamide

Yang, G.; Liang, J.; Yu, H.; Li, B.

doi:10.1107/S1600536810045885

organic compounds

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Volume 66| Part 12| December 2010| Page o3154

https://doi.org/10.1107/S1600536810045885

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2-(2-Chloropyridin-3-yl)-N-ethyl-4-methyl-1,3-oxazole-5-carboxamide

Guiqiu Yang,^a ^* Jiakuang Liang,^a Haibo Yu ^b and Bin Li ^b

^aShenyang Universtity of Chemical Technology, Shenyang 110142, People's Republic of China, and ^bAgrochemicals Division, Shenyang Research Institute of Chemical Industry, Shenyang 110021, People's Republic of China
^*Correspondence e-mail: yangguiqiu@gmail.com

(Received 20 October 2010; accepted 8 November 2010; online 13 November 2010)

In the title compound, C₁₂H₁₂ClN₃O₂, the dihedral angle between the aromatic rings is 8.42 (10)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, generating C(4) chains propagating in [001].

Related literature

For background to derivatives of oxazolyl carboxylic acids, see: Takechi et al. (2000 ); Lechel et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₂ClN₃O₂
M_r = 265.70
Monoclinic, P 2₁ /c
a = 8.2143 (12) Å
b = 14.545 (2) Å
c = 10.4360 (16) Å
β = 97.425 (3)°
V = 1236.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.32 × 0.28 × 0.22 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.908, T_max = 0.936
6234 measured reflections
2183 independent reflections
1736 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.109
S = 1.07
2183 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O2ⁱ	0.86	2.29	3.115 (2)	161
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810045885/hb5697sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810045885/hb5697Isup2.hkl

checkCIF report

Comment top

Derivatives of oxazolyl carboxylic acid are important heterocyclic compounds. They display a broad range of biological, medical and pharmacological properties (Takechi et al., 2000; Lechel et al., 2009). We report the crystal structure of the title compound (I) to determine the structure of the main product in the preparation of derivatives ofoxazolyl carboxylic acid. The molecular structure of (I) (Fig. 1) contains no crystallographically imposed symmetry. The pyridine and oxazole rings in each of the ligands are not coplanar, the dihedral angle formed by the least-squares planes of the benzene and pyrazole rings being equal to 8.8°. Analysis of the crystal packing of (I) shows the existence of N3—H3···O2 interactions, as shown in Fig. 2.

Related literature top

For background to derivatives of oxazolyl carboxylic acids, see: Takechi et al. (2000); Lechel et al. (2009).

Experimental top

The title compound was synthesized by 2-(2-chloropyridin-3-yl) -4-methyloxazole-5-carbonyl chloride with ethanamine in toluene. The crude products were purified by silica-gel column chromatography and then grown from dichloromethane to afford colorless blocks of (I). To a 100 ml flask ethanamine (0.24 g, 5.40 mmol),triethylamine (0.68 g, 6.75 mmol), 2-(2-chloropyridin-3-yl)-4-methyloxazole-5-carbonyl chloride (1.16 g, 4.50 mmol) and 45 ml toluene were added sequentially. The reaction mixture was reacted for 2 h. After separation through silica gel column chromatography (fluent: ethyl acetate/petroleum ether=1/5), The title compound was gained as a yellow solid (0.42 g, 58%).

Anal. Calcd for C₁₂H₁₂N₃: C, 54.25; H, 4.55; N, 15.82. Found: C, 54.33; H, 4.54; N, 15.75. ¹H NMR(CDCl₃): 1.27 (t,3H, CH₃), 2.61 (s,3H, Ar—CH₃), 3.50 (m, 2H, CH₂), 6.29 (br s, 1H, NH), 7.40 (dd, 1H, py—H), 8.42 (dd, 1H, py—H), 8.53 (dd, 1H, py—H).

Structure description top

For background to derivatives of oxazolyl carboxylic acids, see: Takechi et al. (2000); Lechel et al. (2009).

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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids.
	Fig. 2. Crystal packing of (I).

2-(2-Chloropyridin-3-yl)-N-ethyl-4-methyl-1,3-oxazole-5-carboxamide top

Crystal data top

C₁₂H₁₂ClN₃O₂	F(000) = 552
M_r = 265.70	D_x = 1.427 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.2143 (12) Å	Cell parameters from 2185 reflections
b = 14.545 (2) Å	θ = 2.4–25.4°
c = 10.4360 (16) Å	µ = 0.31 mm⁻¹
β = 97.425 (3)°	T = 296 K
V = 1236.4 (3) Å³	Block, colorless
Z = 4	0.32 × 0.28 × 0.22 mm

Data collection top

Bruker SMART CCD diffractometer	2183 independent reflections
Radiation source: fine-focus sealed tube	1736 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.908, T_max = 0.936	k = −17→17
6234 measured reflections	l = −12→8

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0583P)² + 0.2339P] where P = (F_o² + 2F_c²)/3
2183 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₂H₁₂ClN₃O₂	V = 1236.4 (3) Å³
M_r = 265.70	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.2143 (12) Å	µ = 0.31 mm⁻¹
b = 14.545 (2) Å	T = 296 K
c = 10.4360 (16) Å	0.32 × 0.28 × 0.22 mm
β = 97.425 (3)°

Data collection top

Bruker SMART CCD diffractometer	2183 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1736 reflections with I > 2σ(I)
T_min = 0.908, T_max = 0.936	R_int = 0.027
6234 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	Δρ_max = 0.23 e Å⁻³
2183 reflections	Δρ_min = −0.23 e Å⁻³
165 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 > 2sigma(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
Cl1	0.52313 (8)	1.15459 (4)	0.30039 (6)	0.0650 (2)
O1	0.81459 (15)	0.89027 (8)	0.35667 (12)	0.0424 (3)
O2	0.91578 (18)	0.72507 (9)	0.12724 (13)	0.0542 (4)
N1	0.6093 (2)	1.15962 (11)	0.54565 (19)	0.0582 (5)
N2	0.6424 (2)	0.96872 (10)	0.21507 (15)	0.0449 (4)
N3	0.9699 (2)	0.72633 (10)	0.34513 (15)	0.0476 (4)
H3	0.9523	0.7530	0.4156	0.057*
C1	0.6202 (2)	1.10823 (12)	0.4431 (2)	0.0457 (5)
C2	0.6806 (3)	1.12864 (15)	0.6593 (2)	0.0625 (6)
H2	0.6733	1.1642	0.7324	0.075*
C3	0.7641 (3)	1.04702 (15)	0.6739 (2)	0.0636 (6)
H3A	0.8122	1.0278	0.7551	0.076*
C4	0.7752 (3)	0.99428 (13)	0.56647 (19)	0.0525 (5)
H4	0.8320	0.9388	0.5744	0.063*
C5	0.7019 (2)	1.02335 (12)	0.44587 (18)	0.0420 (4)
C6	0.7133 (2)	0.96435 (12)	0.33294 (18)	0.0399 (4)
C7	0.8032 (2)	0.84506 (11)	0.23930 (18)	0.0402 (4)
C8	0.6982 (2)	0.89204 (12)	0.15339 (18)	0.0416 (4)
C9	0.6388 (3)	0.87207 (15)	0.0153 (2)	0.0567 (6)
H9A	0.7179	0.8936	−0.0378	0.085*
H9B	0.5359	0.9027	−0.0091	0.085*
H9C	0.6242	0.8070	0.0038	0.085*
C10	0.9008 (2)	0.76014 (12)	0.23233 (18)	0.0412 (4)
C11	1.0747 (3)	0.64501 (15)	0.3517 (2)	0.0627 (6)
H11A	1.0109	0.5931	0.3149	0.075*
H11B	1.1631	0.6554	0.3001	0.075*
C12	1.1446 (4)	0.6227 (2)	0.4837 (3)	0.0857 (9)
H12A	1.2037	0.6749	0.5220	0.129*
H12B	1.2181	0.5715	0.4827	0.129*
H12C	1.0580	0.6070	0.5333	0.129*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0845 (4)	0.0471 (3)	0.0613 (4)	0.0194 (3)	0.0012 (3)	0.0078 (2)
O1	0.0535 (8)	0.0366 (7)	0.0360 (7)	0.0063 (6)	0.0015 (6)	−0.0004 (5)
O2	0.0808 (10)	0.0446 (8)	0.0379 (8)	0.0047 (7)	0.0104 (7)	−0.0043 (6)
N1	0.0718 (12)	0.0405 (9)	0.0626 (12)	0.0066 (8)	0.0098 (10)	−0.0062 (8)
N2	0.0531 (10)	0.0376 (8)	0.0428 (9)	0.0036 (7)	0.0016 (8)	0.0025 (7)
N3	0.0633 (10)	0.0408 (9)	0.0387 (9)	0.0139 (7)	0.0071 (8)	0.0002 (7)
C1	0.0502 (11)	0.0347 (10)	0.0524 (12)	0.0005 (8)	0.0078 (9)	0.0015 (8)
C2	0.0843 (16)	0.0496 (12)	0.0541 (14)	0.0016 (12)	0.0106 (12)	−0.0126 (11)
C3	0.0910 (17)	0.0517 (13)	0.0461 (13)	0.0102 (12)	0.0011 (12)	−0.0032 (10)
C4	0.0688 (14)	0.0396 (10)	0.0481 (12)	0.0090 (9)	0.0034 (10)	−0.0018 (9)
C5	0.0474 (11)	0.0339 (9)	0.0453 (11)	−0.0019 (8)	0.0080 (9)	0.0023 (8)
C6	0.0454 (10)	0.0308 (9)	0.0431 (11)	0.0008 (7)	0.0048 (9)	0.0039 (7)
C7	0.0502 (11)	0.0345 (9)	0.0353 (10)	−0.0022 (8)	0.0029 (8)	−0.0011 (7)
C8	0.0479 (11)	0.0375 (10)	0.0387 (10)	−0.0033 (8)	0.0031 (8)	0.0016 (8)
C9	0.0672 (14)	0.0549 (12)	0.0442 (12)	0.0043 (11)	−0.0069 (10)	−0.0020 (10)
C10	0.0500 (11)	0.0348 (9)	0.0392 (10)	−0.0035 (8)	0.0072 (9)	−0.0006 (8)
C11	0.0796 (16)	0.0500 (13)	0.0578 (14)	0.0237 (11)	0.0068 (12)	0.0004 (10)
C12	0.103 (2)	0.0863 (18)	0.0661 (17)	0.0496 (16)	0.0029 (15)	0.0079 (14)

Geometric parameters (Å, º) top

Cl1—C1	1.733 (2)	C4—C5	1.389 (3)
O1—C6	1.364 (2)	C4—H4	0.9300
O1—C7	1.383 (2)	C5—C6	1.471 (3)
O2—C10	1.230 (2)	C7—C8	1.347 (2)
N1—C1	1.318 (3)	C7—C10	1.479 (3)
N1—C2	1.332 (3)	C8—C9	1.489 (3)
N2—C6	1.293 (2)	C9—H9A	0.9600
N2—C8	1.395 (2)	C9—H9B	0.9600
N3—C10	1.333 (2)	C9—H9C	0.9600
N3—C11	1.459 (2)	C11—C12	1.459 (3)
N3—H3	0.8600	C11—H11A	0.9700
C1—C5	1.404 (3)	C11—H11B	0.9700
C2—C3	1.370 (3)	C12—H12A	0.9600
C2—H2	0.9300	C12—H12B	0.9600
C3—C4	1.372 (3)	C12—H12C	0.9600
C3—H3A	0.9300

C6—O1—C7	104.17 (14)	O1—C7—C10	117.74 (15)
C1—N1—C2	117.59 (18)	C7—C8—N2	108.60 (16)
C6—N2—C8	105.37 (15)	C7—C8—C9	130.30 (18)
C10—N3—C11	121.45 (17)	N2—C8—C9	121.08 (17)
C10—N3—H3	119.3	C8—C9—H9A	109.5
C11—N3—H3	119.3	C8—C9—H9B	109.5
N1—C1—C5	124.39 (19)	H9A—C9—H9B	109.5
N1—C1—Cl1	113.91 (15)	C8—C9—H9C	109.5
C5—C1—Cl1	121.70 (15)	H9A—C9—H9C	109.5
N1—C2—C3	123.3 (2)	H9B—C9—H9C	109.5
N1—C2—H2	118.4	O2—C10—N3	123.63 (17)
C3—C2—H2	118.4	O2—C10—C7	120.50 (17)
C2—C3—C4	118.6 (2)	N3—C10—C7	115.86 (16)
C2—C3—H3A	120.7	C12—C11—N3	112.48 (19)
C4—C3—H3A	120.7	C12—C11—H11A	109.1
C3—C4—C5	120.25 (19)	N3—C11—H11A	109.1
C3—C4—H4	119.9	C12—C11—H11B	109.1
C5—C4—H4	119.9	N3—C11—H11B	109.1
C4—C5—C1	115.87 (18)	H11A—C11—H11B	107.8
C4—C5—C6	118.92 (16)	C11—C12—H12A	109.5
C1—C5—C6	125.21 (17)	C11—C12—H12B	109.5
N2—C6—O1	113.63 (16)	H12A—C12—H12B	109.5
N2—C6—C5	131.78 (17)	C11—C12—H12C	109.5
O1—C6—C5	114.57 (16)	H12A—C12—H12C	109.5
C8—C7—O1	108.22 (15)	H12B—C12—H12C	109.5
C8—C7—C10	134.03 (17)

C2—N1—C1—C5	−0.1 (3)	C4—C5—C6—O1	−7.8 (3)
C2—N1—C1—Cl1	179.87 (17)	C1—C5—C6—O1	172.89 (16)
C1—N1—C2—C3	0.3 (4)	C6—O1—C7—C8	−0.41 (19)
N1—C2—C3—C4	0.0 (4)	C6—O1—C7—C10	179.86 (15)
C2—C3—C4—C5	−0.5 (4)	O1—C7—C8—N2	0.6 (2)
C3—C4—C5—C1	0.6 (3)	C10—C7—C8—N2	−179.76 (19)
C3—C4—C5—C6	−178.8 (2)	O1—C7—C8—C9	−178.03 (19)
N1—C1—C5—C4	−0.3 (3)	C10—C7—C8—C9	1.6 (4)
Cl1—C1—C5—C4	179.72 (15)	C6—N2—C8—C7	−0.5 (2)
N1—C1—C5—C6	179.00 (19)	C6—N2—C8—C9	178.25 (18)
Cl1—C1—C5—C6	−1.0 (3)	C11—N3—C10—O2	1.9 (3)
C8—N2—C6—O1	0.2 (2)	C11—N3—C10—C7	−177.52 (18)
C8—N2—C6—C5	−178.29 (19)	C8—C7—C10—O2	11.7 (3)
C7—O1—C6—N2	0.1 (2)	O1—C7—C10—O2	−168.64 (17)
C7—O1—C6—C5	178.89 (15)	C8—C7—C10—N3	−168.8 (2)
C4—C5—C6—N2	170.7 (2)	O1—C7—C10—N3	10.8 (2)
C1—C5—C6—N2	−8.6 (3)	C10—N3—C11—C12	176.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2ⁱ	0.86	2.29	3.115 (2)	161

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂ClN₃O₂
M_r	265.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.2143 (12), 14.545 (2), 10.4360 (16)
β (°)	97.425 (3)
V (Å³)	1236.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.32 × 0.28 × 0.22

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.908, 0.936
No. of measured, independent and observed [I > 2σ(I)] reflections	6234, 2183, 1736
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.109, 1.07
No. of reflections	2183
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2ⁱ	0.86	2.29	3.115 (2)	161

Symmetry code: (i) x, −y+3/2, z+1/2.

References

Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lechel, T., Lentz, D. & Reissig, H. U. (2009). Chem. Eur. J. 15, 5432–5435. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Takechi, H., Oda, Y., Nishizono, N., Oda, K. & Machida, M. (2000). Chem. Pharm. Bull. 48, 1702–1710. Web of Science CrossRef PubMed CAS Google Scholar

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