Ethyl 5-methyl-3-phenyl­isoxazole-4-carboxyl­ate

Chandra; Raghu, K.; Jeyaseelan, S.; Umesha, K.B.; Mahendra, M.

doi:10.1107/S160053681301427X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o987

doi:10.1107/S160053681301427X

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Ethyl 5-methyl-3-phenylisoxazole-4-carboxylate

Chandra,^a K. Raghu,^b S. Jeyaseelan,^c K. B. Umesha ^b and M. Mahendra ^a ^*

^aDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore 570 006, India, ^bDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysore 570 005, India, and ^cDepartment of Physics, St Philomena's College, Mysore, India
^*Correspondence e-mail: mahendra@physics.uni-mysore.ac.in

(Received 5 April 2013; accepted 23 May 2013; online 31 May 2013)

In the title compound, C₁₃H₁₃NO₃, the dihedral angle between the phenyl and isoxazole rings is 43.40 (13)°. The ethoxycarbonyl group is rotated out of the plane of the isoxazole ring by 16.2 (13)°.

Related literature

For the biological and pharmacological importance of isoxazoles, see: Lin et al. (1997 ). For the synthesis of isoxazole derivatives and a related structure, see: Chandra et al. (2013 ).

Experimental

Crystal data

C₁₃H₁₃NO₃
M_r = 231.24
Monoclinic, P 2₁ /c
a = 9.750 (8) Å
b = 14.589 (13) Å
c = 9.397 (8) Å
β = 116.872 (13)°
V = 1192.3 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 273 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
10036 measured reflections
2060 independent reflections
1340 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.186
S = 0.99
2060 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681301427X/nc2309sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681301427X/nc2309Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681301427X/nc2309Isup3.cml

checkCIF report

Comment top

Isoxazole and its derivatives are of well known heterocyclic compounds, which have a variety of biologically activities; such as anti-convulsant, antibacterial, antiasthmatic, and other pharmacological activities (Lin et al., 1997). In view of their importance we have special interest in the synthesis and structural studies of isoxazole derivatives (Chandra et al., 2013). Within this project, the title compound was prepared and characterized by single-crystal X-ray diffraction.

In the molecular structure of the title compound (Fig. 1), the dihedral angle between the phenyl ring (C1/C2/C3/C4/C5/C6) and the isoxazole ring (C7/N8/O9/C10/C12) amount to 43.40 (13)°. The ethoxycarbonyl unit is not in same plane with the isoxazole ring, as indicated by the torsion angle of 16.2 (13)°.

Related literature top

For the biological and pharmacological importance of isoxazoles, see: Lin et al. (1997). For the synthesis of isoxazole derivatives and a related structure, see: Chandra et al. (2013).

Experimental top

A mixture of benzaldehyde oxime (1 g, 8.33 mmol), chloramine-T (2.33 g, 8.33 mmol) and freshly distilled ethyl acetoacetate (2.16 g, 16.6 mmol) in ethyl alcohol (20 ml) were stirred at 10°C about 6 h. The progress of the reaction was monitored by TLC. After the completion of the reaction the solvent was evaporated in vacuum. The solids thus obtained were recrystalized from hot ethanol to get single crystals of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Perspective diagram of the title molecule with labeling and displacement ellipsoids drawn at the 50% probability level.

Ethyl 5-methyl-3-phenylisoxazole-4-carboxylate top

Crystal data top

C₁₃H₁₃NO₃	F(000) = 488
M_r = 231.24	D_x = 1.288 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2060 reflections
a = 9.750 (8) Å	θ = 2.3–25.0°
b = 14.589 (13) Å	µ = 0.09 mm⁻¹
c = 9.397 (8) Å	T = 273 K
β = 116.872 (13)°	Block, yellow
V = 1192.3 (18) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	R_int = 0.039
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.3°
10036 measured reflections	h = −11→11
2060 independent reflections	k = −17→17
1340 reflections with I > 2σ(I)	l = −11→11

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.1145P)²] where P = (F_o² + 2F_c²)/3
2060 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₃H₁₃NO₃	V = 1192.3 (18) Å³
M_r = 231.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.750 (8) Å	µ = 0.09 mm⁻¹
b = 14.589 (13) Å	T = 273 K
c = 9.397 (8) Å	0.30 × 0.25 × 0.20 mm
β = 116.872 (13)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1340 reflections with I > 2σ(I)
10036 measured reflections	R_int = 0.039
2060 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.186	H-atom parameters constrained
S = 0.99	Δρ_max = 0.16 e Å⁻³
2060 reflections	Δρ_min = −0.17 e Å⁻³
156 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 e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
O9	0.6154 (2)	0.13026 (13)	−0.1802 (3)	0.0780 (8)
O14	0.6825 (2)	0.12137 (19)	0.2907 (3)	0.1153 (12)
O15	0.4317 (2)	0.09643 (11)	0.17563 (19)	0.0667 (6)
N8	0.4554 (3)	0.14345 (15)	−0.2522 (3)	0.0747 (9)
C1	0.1443 (3)	0.10417 (18)	−0.3147 (3)	0.0721 (10)
C2	−0.0093 (3)	0.1141 (2)	−0.3603 (4)	0.0840 (11)
C3	−0.0594 (3)	0.1676 (2)	−0.2736 (4)	0.0861 (11)
C4	0.0469 (3)	0.21272 (19)	−0.1411 (4)	0.0798 (11)
C5	0.2008 (3)	0.20332 (16)	−0.0937 (3)	0.0649 (9)
C6	0.2520 (3)	0.14949 (15)	−0.1799 (3)	0.0571 (8)
C7	0.4161 (3)	0.13941 (14)	−0.1372 (3)	0.0577 (8)
C10	0.6666 (3)	0.11924 (16)	−0.0234 (3)	0.0646 (9)
C11	0.8327 (3)	0.0997 (2)	0.0691 (4)	0.0865 (11)
C12	0.5479 (3)	0.12501 (14)	0.0123 (3)	0.0592 (8)
C13	0.5628 (3)	0.11456 (17)	0.1739 (3)	0.0654 (9)
C16	0.4341 (4)	0.0912 (2)	0.3301 (3)	0.0824 (11)
C17	0.2752 (4)	0.0730 (2)	0.3043 (4)	0.0957 (14)
H1	0.17710	0.06700	−0.37380	0.0870*
H2	−0.08040	0.08420	−0.45110	0.1010*
H3	−0.16400	0.17340	−0.30390	0.1030*
H4	0.01350	0.25020	−0.08290	0.0950*
H5	0.27120	0.23350	−0.00280	0.0780*
H11A	0.85120	0.03600	0.05850	0.1300*
H11B	0.86540	0.11380	0.17950	0.1300*
H11C	0.88940	0.13650	0.02920	0.1300*
H16A	0.47100	0.14850	0.38720	0.0990*
H16B	0.50210	0.04240	0.39260	0.0990*
H17A	0.20880	0.12140	0.24150	0.1430*
H17B	0.27330	0.06990	0.40550	0.1430*
H17C	0.24040	0.01570	0.24930	0.1430*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O9	0.0756 (13)	0.0937 (13)	0.0679 (14)	0.0024 (9)	0.0352 (11)	0.0109 (10)
O14	0.0684 (14)	0.196 (3)	0.0521 (14)	−0.0009 (13)	0.0015 (11)	−0.0013 (13)
O15	0.0746 (12)	0.0772 (11)	0.0415 (10)	−0.0015 (8)	0.0203 (9)	0.0048 (7)
N8	0.0768 (16)	0.0898 (15)	0.0555 (15)	0.0044 (11)	0.0281 (12)	0.0099 (11)
C1	0.0728 (18)	0.0765 (16)	0.0501 (16)	−0.0049 (12)	0.0129 (13)	−0.0015 (12)
C2	0.072 (2)	0.091 (2)	0.0633 (19)	−0.0137 (15)	0.0079 (16)	0.0049 (15)
C3	0.0632 (18)	0.091 (2)	0.092 (2)	0.0039 (15)	0.0245 (18)	0.0233 (18)
C4	0.081 (2)	0.0796 (17)	0.076 (2)	0.0125 (14)	0.0329 (16)	0.0104 (15)
C5	0.0744 (17)	0.0609 (14)	0.0497 (15)	0.0009 (11)	0.0195 (13)	0.0038 (11)
C6	0.0634 (15)	0.0558 (12)	0.0411 (14)	−0.0012 (10)	0.0139 (12)	0.0063 (10)
C7	0.0676 (16)	0.0533 (13)	0.0445 (15)	−0.0043 (10)	0.0186 (12)	0.0011 (10)
C10	0.0661 (16)	0.0592 (13)	0.0621 (18)	−0.0047 (11)	0.0234 (14)	0.0014 (11)
C11	0.0643 (18)	0.096 (2)	0.091 (2)	−0.0043 (14)	0.0279 (16)	0.0033 (16)
C12	0.0619 (15)	0.0555 (12)	0.0494 (15)	−0.0033 (10)	0.0157 (12)	0.0027 (10)
C13	0.0633 (17)	0.0723 (15)	0.0466 (16)	0.0026 (12)	0.0126 (13)	0.0014 (11)
C16	0.110 (2)	0.090 (2)	0.0457 (16)	0.0163 (16)	0.0338 (16)	0.0099 (13)
C17	0.121 (3)	0.098 (2)	0.090 (2)	0.0003 (18)	0.067 (2)	−0.0064 (18)

Geometric parameters (Å, º) top

O9—N8	1.405 (4)	C12—C13	1.467 (4)
O9—C10	1.335 (4)	C16—C17	1.480 (6)
O14—C13	1.191 (4)	C1—H1	0.9300
O15—C13	1.313 (4)	C2—H2	0.9300
O15—C16	1.443 (4)	C3—H3	0.9300
N8—C7	1.301 (4)	C4—H4	0.9300
C1—C2	1.367 (5)	C5—H5	0.9300
C1—C6	1.394 (4)	C11—H11A	0.9600
C2—C3	1.368 (5)	C11—H11B	0.9600
C3—C4	1.375 (5)	C11—H11C	0.9600
C4—C5	1.366 (5)	C16—H16A	0.9700
C5—C6	1.374 (4)	C16—H16B	0.9700
C6—C7	1.470 (5)	C17—H17A	0.9600
C7—C12	1.427 (4)	C17—H17B	0.9600
C10—C11	1.479 (5)	C17—H17C	0.9600
C10—C12	1.345 (5)

O14···C2ⁱ	3.300 (5)	C5···H17Aⁱⁱⁱ	3.0100
O14···C11	3.056 (5)	C12···H5	3.0800
O15···C5	2.959 (4)	C13···H11B	2.9300
O15···C10ⁱⁱ	3.410 (4)	C13···H5	3.1000
O15···C6	3.089 (4)	C16···H16B^vii	3.0800
O9···H17Cⁱⁱ	2.7900	H1···N8	2.6700
O14···H16B	2.6200	H2···O14^iv	2.5400
O14···H11B	2.4400	H4···H11C^vi	2.5500
O14···H16A	2.6300	H4···C1^v	3.1000
O14···H2ⁱ	2.5400	H4···C2^v	2.9600
O15···H5	2.6200	H5···O15	2.6200
N8···H1	2.6700	H5···C12	3.0800
N8···H5ⁱⁱⁱ	2.8600	H5···C13	3.1000
C2···O14^iv	3.300 (5)	H5···N8^v	2.8600
C5···C17ⁱⁱⁱ	3.567 (5)	H11B···O14	2.4400
C5···C13	3.526 (5)	H11B···C13	2.9300
C5···O15	2.959 (4)	H11C···C4^viii	2.8900
C6···O15	3.089 (4)	H11C···H4^viii	2.5500
C10···O15ⁱⁱ	3.410 (4)	H16A···O14	2.6300
C11···O14	3.056 (5)	H16B···O14	2.6200
C13···C5	3.526 (5)	H16B···C16^vii	3.0800
C17···C5^v	3.567 (5)	H16B···H16B^vii	2.3800
C1···H4ⁱⁱⁱ	3.1000	H17A···C5^v	3.0100
C2···H4ⁱⁱⁱ	2.9600	H17C···O9ⁱⁱ	2.7900
C4···H11C^vi	2.8900

N8—O9—C10	109.1 (2)	C1—C2—H2	120.00
C13—O15—C16	116.7 (2)	C3—C2—H2	120.00
O9—N8—C7	105.9 (2)	C2—C3—H3	120.00
C2—C1—C6	120.2 (3)	C4—C3—H3	120.00
C1—C2—C3	120.6 (3)	C3—C4—H4	120.00
C2—C3—C4	119.1 (3)	C5—C4—H4	119.00
C3—C4—C5	121.0 (3)	C4—C5—H5	120.00
C4—C5—C6	120.2 (3)	C6—C5—H5	120.00
C1—C6—C5	118.8 (3)	C10—C11—H11A	109.00
C1—C6—C7	118.7 (2)	C10—C11—H11B	110.00
C5—C6—C7	122.5 (2)	C10—C11—H11C	109.00
N8—C7—C6	117.5 (2)	H11A—C11—H11B	109.00
N8—C7—C12	110.6 (3)	H11A—C11—H11C	109.00
C6—C7—C12	131.9 (3)	H11B—C11—H11C	109.00
O9—C10—C11	115.8 (3)	O15—C16—H16A	110.00
O9—C10—C12	109.5 (3)	O15—C16—H16B	110.00
C11—C10—C12	134.6 (3)	C17—C16—H16A	110.00
C7—C12—C10	104.9 (2)	C17—C16—H16B	110.00
C7—C12—C13	131.2 (3)	H16A—C16—H16B	108.00
C10—C12—C13	123.9 (3)	C16—C17—H17A	110.00
O14—C13—O15	124.0 (3)	C16—C17—H17B	109.00
O14—C13—C12	122.9 (3)	C16—C17—H17C	109.00
O15—C13—C12	113.1 (2)	H17A—C17—H17B	110.00
O15—C16—C17	107.8 (2)	H17A—C17—H17C	109.00
C2—C1—H1	120.00	H17B—C17—H17C	109.00
C6—C1—H1	120.00

C10—O9—N8—C7	−0.4 (3)	C1—C6—C7—N8	42.7 (3)
N8—O9—C10—C11	176.9 (2)	C1—C6—C7—C12	−137.0 (3)
N8—O9—C10—C12	−0.3 (3)	C5—C6—C7—N8	−136.0 (3)
C16—O15—C13—O14	4.6 (4)	C5—C6—C7—C12	44.3 (4)
C16—O15—C13—C12	−175.9 (2)	N8—C7—C12—C10	−1.1 (3)
C13—O15—C16—C17	178.4 (2)	N8—C7—C12—C13	−179.1 (2)
O9—N8—C7—C6	−178.90 (18)	C6—C7—C12—C10	178.7 (2)
O9—N8—C7—C12	0.9 (2)	C6—C7—C12—C13	0.7 (4)
C6—C1—C2—C3	−0.8 (4)	O9—C10—C12—C7	0.8 (3)
C2—C1—C6—C5	0.6 (4)	O9—C10—C12—C13	179.0 (2)
C2—C1—C6—C7	−178.2 (2)	C11—C10—C12—C7	−175.7 (3)
C1—C2—C3—C4	1.1 (5)	C11—C10—C12—C13	2.4 (4)
C2—C3—C4—C5	−1.3 (5)	C7—C12—C13—O14	−164.3 (3)
C3—C4—C5—C6	1.1 (4)	C7—C12—C13—O15	16.2 (3)
C4—C5—C6—C1	−0.7 (4)	C10—C12—C13—O14	18.0 (4)
C4—C5—C6—C7	178.0 (2)	C10—C12—C13—O15	−161.5 (2)

Symmetry codes: (i) x+1, y, z+1; (ii) −x+1, −y, −z; (iii) x, −y+1/2, z−1/2; (iv) x−1, y, z−1; (v) x, −y+1/2, z+1/2; (vi) x−1, y, z; (vii) −x+1, −y, −z+1; (viii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃NO₃
M_r	231.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	9.750 (8), 14.589 (13), 9.397 (8)
β (°)	116.872 (13)
V (Å³)	1192.3 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10036, 2060, 1340
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.186, 0.99
No. of reflections	2060
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

Chandra would like to thank the University of Mysore for awarding an RFSMS fellowship under the head DV5/Physics/389/RFSMS/2009–2010/10.07.2012.

References

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