Isopropyl 3-phenyl­isoxazole-5-carboxyl­ate

Wang, L.; Liu, X.-Y.; Li, Z.-W.; Zhang, S.-Y.

doi:10.1107/S1600536813009392

organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Page o733

https://doi.org/10.1107/S1600536813009392

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Isopropyl 3-phenylisoxazole-5-carboxylate

Li Wang,^a,^b Xue-Ying Liu,^c Zheng-Wei Li ^b and Sheng-Yong Zhang ^c ^*

^aDepartment of Chemistry, School of Preclinical Medicine, Shanxi Medical University, 56 Xinjian South Road, 030001 Tai Yuan, People's Republic of China, ^bAffiliated Hospital of Xi'an Medical College, 48 Fenggao West Road, 710077 Xi-An, People's Republic of China, and ^cDepartment of Chemistry, School of Pharmacy, Fourth Military Medical University, Changle West Road 17, 710032 Xi-An, People's Republic of China
^*Correspondence e-mail: syzhang@fmmu.edu.cn

(Received 30 March 2013; accepted 7 April 2013; online 13 April 2013)

In the title compound, C₁₃H₁₃NO₃, the isoxazole ring is approximately coplanar with the phenyl ring, the dihedral angle between their planes being 7.37 (19)°. In the crystal, centrosymmetrically related molecules are linked into dimers by pairs of C—H⋯O hydrogen bonds, generating a ring of graph-set motif R₂²(10).

Related literature

For the biological activity of isoxazole derivatives, see: Angibaud et al. (2003 ). For the structure of a related compound, see: Yao & Deng (2008 ). For the synthesis of 3-phenylisoxazole-5-carboxylic acid, see: Liu et al. (2006 ).

Experimental

Crystal data

C₁₃H₁₃NO₃
M_r = 231.24
Monoclinic, P 2₁ /n
a = 4.6311 (10) Å
b = 16.596 (4) Å
c = 15.897 (3) Å
β = 98.321 (4)°
V = 1208.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.36 × 0.28 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.968, T_max = 0.984
6039 measured reflections
2169 independent reflections
1511 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.126
S = 1.03
2169 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O2ⁱ	0.93	2.37	3.277 (2)	166
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); 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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813009392/rz5055sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813009392/rz5055Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813009392/rz5055Isup3.cml

checkCIF report

Comment top

Isoxazole derivatives, as useful intermediates in organic synthesis, show widespread biological activities, and are employed as antiviral drugs, antibacteria reagents, fungicide, anti-inflammatory agents, analgesics, antidepressants, anticonvulsants and pesticides (Angibaud et al., 2003). In the molecule of the title compound (Fig. 1), the dihedral angle between the phenyl and the isoxazole rings is 7.37 (19)°. The bond lengths within the isoxazole ring [C7—N1 = 1.306 (2) Å, N1—O1 = 1.402 (18) Å, O1—C9 = 1.345 (2) Å, C9—C8 = 1.327 (2) Å and C8—C7 = 1.409 (2) Å] are in agreement with those reported by Yao & Deng (2008) for 5-amino-3-(4-pyridyl)isoxazole [C7—N1 = 1.316 (18) Å, N1—O1 = 1.429 (14) Å, O1—C9 = 1.353 (17) Å, C9—C8 = 1.368 (19) Å and C8—C7 = 1.400 (19) Å]. In the crystal, centrosymmetrically related molecules are linked into dimers by C—H···O hydrogen bonds (Table 1), generating a ring of graph-set motif < i>R²₂(10).

Related literature top

For the biological activity of isoxazole derivatives, see: Angibaud et al. (2003). For the structure of a related compound, see: Yao & Deng (2008). For the synthesis of 3-phenylisoxazole-5-carboxylic acid, see: Liu et al. (2006).

Experimental top

3-Phenylisoxazole-5-carboxylic acid (10 mmol, 1.95 g; Liu et al., 2006) was dissolved in 100 ml dichloromethane, then thionyl chloride(12 mmol, 1.43 g)was dropped into the solution and stirred for 20 minutes in ice bath. The solvent was removed under reduced pressure and the mixture was used for the next step without further purification. 2-Propanol (20 mmol, 1.5 ml) was added subsequently and the mixture stirred for 6 h at room temperature. The resulting residue was purified as a white solid (1.96 g, 85% yield). Recrystallization in ethyl acetate gave fine colourless crystals suitable for X-ray study. All chemicals were purchased by Sigma Aldrich Germany.

Structure description top

For the biological activity of isoxazole derivatives, see: Angibaud et al. (2003). For the structure of a related compound, see: Yao & Deng (2008). For the synthesis of 3-phenylisoxazole-5-carboxylic acid, see: Liu et al. (2006).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The formation of the title compound.

Isopropyl 3-phenylisoxazole-5-carboxylate top

Crystal data top

C₁₃H₁₃NO₃	F(000) = 488
M_r = 231.24	D_x = 1.271 Mg m⁻³ D_m = 1.270 Mg m⁻³ D_m measured by not measured
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1178 reflections
a = 4.6311 (10) Å	θ = 2.5–21.2°
b = 16.596 (4) Å	µ = 0.09 mm⁻¹
c = 15.897 (3) Å	T = 296 K
β = 98.321 (4)°	Block, colourless
V = 1208.9 (5) Å³	0.36 × 0.28 × 0.17 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2169 independent reflections
Radiation source: fine-focus sealed tube	1511 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
φ and ω scans	θ_max = 25.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −4→5
T_min = 0.968, T_max = 0.984	k = −19→19
6039 measured reflections	l = −18→17

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0611P)² + 0.0883P] where P = (F_o² + 2F_c²)/3
2169 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.11 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₃H₁₃NO₃	V = 1208.9 (5) Å³
M_r = 231.24	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.6311 (10) Å	µ = 0.09 mm⁻¹
b = 16.596 (4) Å	T = 296 K
c = 15.897 (3) Å	0.36 × 0.28 × 0.17 mm
β = 98.321 (4)°

Data collection top

Bruker APEXII CCD diffractometer	2169 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1511 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.984	R_int = 0.037
6039 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.03	Δρ_max = 0.11 e Å⁻³
2169 reflections	Δρ_min = −0.20 e Å⁻³
156 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
N1	1.1576 (4)	0.66232 (10)	0.15016 (9)	0.0630 (5)
O1	1.0131 (3)	0.60739 (8)	0.19660 (7)	0.0607 (4)
O2	0.4550 (3)	0.46825 (8)	0.12822 (8)	0.0746 (5)
O3	0.6627 (3)	0.50549 (7)	0.25802 (7)	0.0576 (4)
C1	0.9997 (5)	0.69977 (13)	−0.07802 (12)	0.0712 (6)
H1	0.8549	0.6615	−0.0930	0.085*
C2	1.0757 (6)	0.75230 (15)	−0.13884 (14)	0.0828 (7)
H2	0.9802	0.7496	−0.1944	0.099*
C3	1.2896 (6)	0.80792 (14)	−0.11749 (17)	0.0844 (7)
H3	1.3391	0.8433	−0.1584	0.101*
C4	1.4315 (5)	0.81193 (13)	−0.03635 (16)	0.0845 (7)
H4	1.5793	0.8496	−0.0222	0.101*
C5	1.3566 (5)	0.76046 (12)	0.02457 (14)	0.0681 (6)
H5	1.4541	0.7636	0.0799	0.082*
C6	1.1380 (4)	0.70408 (10)	0.00457 (11)	0.0521 (5)
C7	1.0454 (4)	0.65230 (10)	0.07063 (10)	0.0491 (4)
C8	0.8306 (4)	0.59153 (11)	0.06221 (10)	0.0530 (5)
H8	0.7213	0.5728	0.0124	0.064*
C9	0.8187 (4)	0.56698 (10)	0.14107 (10)	0.0492 (5)
C10	0.6272 (4)	0.50799 (11)	0.17418 (11)	0.0525 (5)
C11	0.4715 (5)	0.45151 (12)	0.29747 (12)	0.0629 (5)
H11	0.2788	0.4501	0.2627	0.075*
C12	0.4454 (7)	0.48786 (17)	0.38172 (15)	0.1041 (10)
H12A	0.6342	0.4896	0.4158	0.156*
H12B	0.3159	0.4558	0.4099	0.156*
H12C	0.3692	0.5416	0.3738	0.156*
C13	0.6001 (6)	0.36909 (14)	0.30211 (16)	0.0981 (8)
H13A	0.6165	0.3505	0.2458	0.147*
H13B	0.4765	0.3331	0.3280	0.147*
H13C	0.7901	0.3705	0.3355	0.147*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0788 (12)	0.0650 (10)	0.0460 (9)	−0.0149 (9)	0.0112 (8)	0.0018 (7)
O1	0.0757 (9)	0.0651 (8)	0.0408 (7)	−0.0141 (7)	0.0070 (6)	0.0003 (6)
O2	0.0940 (11)	0.0756 (9)	0.0512 (8)	−0.0266 (8)	0.0007 (8)	−0.0020 (7)
O3	0.0695 (9)	0.0626 (8)	0.0410 (7)	−0.0099 (7)	0.0085 (6)	0.0042 (6)
C1	0.0870 (16)	0.0752 (14)	0.0524 (12)	−0.0040 (12)	0.0136 (11)	0.0074 (11)
C2	0.1036 (19)	0.0902 (17)	0.0575 (13)	0.0099 (15)	0.0219 (13)	0.0172 (12)
C3	0.111 (2)	0.0674 (15)	0.0847 (18)	0.0077 (14)	0.0463 (16)	0.0227 (13)
C4	0.1026 (19)	0.0696 (15)	0.0871 (17)	−0.0156 (13)	0.0332 (15)	0.0076 (13)
C5	0.0797 (15)	0.0618 (12)	0.0650 (13)	−0.0042 (11)	0.0182 (11)	0.0010 (10)
C6	0.0606 (12)	0.0479 (10)	0.0505 (11)	0.0045 (9)	0.0171 (9)	0.0010 (8)
C7	0.0570 (11)	0.0483 (10)	0.0427 (10)	0.0027 (9)	0.0095 (8)	−0.0019 (8)
C8	0.0630 (12)	0.0541 (11)	0.0409 (10)	−0.0005 (9)	0.0043 (9)	−0.0014 (8)
C9	0.0592 (11)	0.0474 (10)	0.0402 (10)	0.0009 (9)	0.0047 (8)	−0.0036 (8)
C10	0.0662 (12)	0.0493 (10)	0.0417 (10)	0.0033 (9)	0.0068 (9)	0.0004 (8)
C11	0.0712 (13)	0.0637 (13)	0.0550 (11)	−0.0105 (10)	0.0132 (10)	0.0104 (9)
C12	0.147 (3)	0.107 (2)	0.0693 (16)	−0.0330 (18)	0.0530 (17)	−0.0100 (14)
C13	0.122 (2)	0.0687 (15)	0.107 (2)	0.0054 (15)	0.0270 (17)	0.0262 (14)

Geometric parameters (Å, º) top

N1—C7	1.306 (2)	C5—H5	0.9300
N1—O1	1.4022 (18)	C6—C7	1.468 (2)
O1—C9	1.345 (2)	C7—C8	1.409 (2)
O2—C10	1.198 (2)	C8—C9	1.327 (2)
O3—C10	1.3197 (19)	C8—H8	0.9300
O3—C11	1.463 (2)	C9—C10	1.469 (3)
C1—C6	1.377 (3)	C11—C13	1.489 (3)
C1—C2	1.384 (3)	C11—C12	1.490 (3)
C1—H1	0.9300	C11—H11	0.9800
C2—C3	1.361 (3)	C12—H12A	0.9600
C2—H2	0.9300	C12—H12B	0.9600
C3—C4	1.362 (3)	C12—H12C	0.9600
C3—H3	0.9300	C13—H13A	0.9600
C4—C5	1.373 (3)	C13—H13B	0.9600
C4—H4	0.9300	C13—H13C	0.9600
C5—C6	1.381 (3)

C7—N1—O1	105.89 (14)	C7—C8—H8	127.6
C9—O1—N1	107.68 (12)	C8—C9—O1	110.58 (16)
C10—O3—C11	117.22 (15)	C8—C9—C10	130.77 (17)
C6—C1—C2	120.2 (2)	O1—C9—C10	118.60 (15)
C6—C1—H1	119.9	O2—C10—O3	124.97 (18)
C2—C1—H1	119.9	O2—C10—C9	122.10 (16)
C3—C2—C1	120.1 (2)	O3—C10—C9	112.92 (16)
C3—C2—H2	119.9	O3—C11—C13	108.73 (18)
C1—C2—H2	119.9	O3—C11—C12	105.69 (16)
C2—C3—C4	120.2 (2)	C13—C11—C12	114.28 (19)
C2—C3—H3	119.9	O3—C11—H11	109.3
C4—C3—H3	119.9	C13—C11—H11	109.3
C3—C4—C5	120.1 (2)	C12—C11—H11	109.3
C3—C4—H4	120.0	C11—C12—H12A	109.5
C5—C4—H4	120.0	C11—C12—H12B	109.5
C4—C5—C6	120.7 (2)	H12A—C12—H12B	109.5
C4—C5—H5	119.6	C11—C12—H12C	109.5
C6—C5—H5	119.6	H12A—C12—H12C	109.5
C1—C6—C5	118.61 (18)	H12B—C12—H12C	109.5
C1—C6—C7	120.53 (18)	C11—C13—H13A	109.5
C5—C6—C7	120.80 (17)	C11—C13—H13B	109.5
N1—C7—C8	111.06 (15)	H13A—C13—H13B	109.5
N1—C7—C6	120.10 (16)	C11—C13—H13C	109.5
C8—C7—C6	128.77 (16)	H13A—C13—H13C	109.5
C9—C8—C7	104.79 (16)	H13B—C13—H13C	109.5
C9—C8—H8	127.6

C7—N1—O1—C9	−0.11 (18)	N1—C7—C8—C9	0.9 (2)
C6—C1—C2—C3	0.7 (3)	C6—C7—C8—C9	−176.01 (17)
C1—C2—C3—C4	0.4 (4)	C7—C8—C9—O1	−0.9 (2)
C2—C3—C4—C5	−0.8 (4)	C7—C8—C9—C10	176.46 (18)
C3—C4—C5—C6	0.1 (3)	N1—O1—C9—C8	0.68 (19)
C2—C1—C6—C5	−1.4 (3)	N1—O1—C9—C10	−177.06 (15)
C2—C1—C6—C7	175.88 (18)	C11—O3—C10—O2	−1.7 (3)
C4—C5—C6—C1	0.9 (3)	C11—O3—C10—C9	176.98 (15)
C4—C5—C6—C7	−176.28 (18)	C8—C9—C10—O2	5.0 (3)
O1—N1—C7—C8	−0.5 (2)	O1—C9—C10—O2	−177.82 (17)
O1—N1—C7—C6	176.73 (14)	C8—C9—C10—O3	−173.73 (18)
C1—C6—C7—N1	−173.13 (18)	O1—C9—C10—O3	3.5 (2)
C5—C6—C7—N1	4.0 (3)	C10—O3—C11—C13	84.7 (2)
C1—C6—C7—C8	3.5 (3)	C10—O3—C11—C12	−152.16 (19)
C5—C6—C7—C8	−179.33 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2ⁱ	0.93	2.37	3.277 (2)	166

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃NO₃
M_r	231.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	4.6311 (10), 16.596 (4), 15.897 (3)
β (°)	98.321 (4)
V (Å³)	1208.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.36 × 0.28 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.968, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	6039, 2169, 1511
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.126, 1.03
No. of reflections	2169
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.20

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2ⁱ	0.93	2.37	3.277 (2)	166.4

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (21172262).

References

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