(Z)-4-Benzyl­idene-3-methyl­isoxazol-5(4H)-one

Chandra; Srikantamurthy, N.; Jeyaseelan, S.; Umesha, K.B.; Palani, K.; Mahendra, M.

doi:10.1107/S1600536812041311

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3091

doi:10.1107/S1600536812041311

Open

access

(Z)-4-Benzylidene-3-methylisoxazol-5(4H)-one

Chandra,^a N. Srikantamurthy,^b S. Jeyaseelan,^c K. B. Umesha,^b K. Palani ^d 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, ^cDepartment of Physics, St Philomena's College, Mysore, India, and ^dSER-CAT, APS, Argonne National Laboratory, Argonne, IL-60439, USA
^*Correspondence e-mail: mahendra@physics.uni-mysore.ac.in

(Received 30 September 2012; accepted 2 October 2012; online 10 October 2012)

In the title compound C₁₁H₉NO₂, the phenyl and isoxazole rings are almost coplanar, making a dihedral angle of 1.14 (9)°. This planarity is also assisted by an intramolecular C—H⋯O hydrogen bond between the phenyl ring and the carbonyl O atom. In the crystal, weak C—H⋯O interactions generate a layered structure parallel to the ac plane.

Related literature

For the biological and therapeutic importance of isoxazoles, see: Kang et al. (2000 ); Conti et al. (1998 ); Changtam et al. (2010 ); Kwon et al., (1995 ); Abbiati et al. (2003 ). For bond-length and angle data in a related structure, see: Wolf et al. (1995 ).

Experimental

Crystal data

C₁₁H₉NO₂
M_r = 187.19
Monoclinic, P 2₁ /n
a = 12.144 (4) Å
b = 6.734 (2) Å
c = 12.333 (4) Å
β = 114.589 (5)°
V = 917.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
6722 measured reflections
1610 independent reflections
1352 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.111
S = 1.07
1610 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O1	0.93	2.21	3.042 (2)	149
C7—H7C⋯O6ⁱ	0.96	2.61	3.297 (2)	129
C8—H8⋯O1ⁱ	0.93	2.72	3.574 (2)	154
C14—H14⋯O1ⁱ	0.93	2.68	3.526 (2)	151
Symmetry code: (i) x, y+1, z.

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/S1600536812041311/sj5268sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812041311/sj5268Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812041311/sj5268Isup3.cml

checkCIF report

Comment top

Isoxazole and its derivatives represent one of the important classes of heterocyclic compounds. These derivatives are employed in the area of pharmaceuticals and demonstrate therapeutic properties such as anti-tumor (Kang et al., 2000), hypoglycemic (Conti et al., 1998), anti-mycobacterial (Changtam et al., 2010) and anti-inflammatory activity (Kwon et al., 1995). In addition, isoxazole derivatives serve as versatile building blocks in organic synthesis (Abbiati et al., 2003). With this extensive background of isoxazole derivatives, we have synthesized the title compound to study its crystal structure.

In the molecular structure of the title compound (Fig. 1), the dihedral angle between the phenyl ring (C9/C10/C11/C12/C13/C14) and isoxazole ring (C1/C3/C4/N5/O6) is 1.14 (9)°. The isoxazole moiety is in a syn-periplanar conformation with respect to the phenyl ring, as indicated by the torsion angle value of 0.5 (2)°. The bond lengths and angles agree with those reported for a related structure (Wolf et al., 1995). There are no classic hydrogen bonds. In the crystal structure weak C—H···O hydrogen bonds link molecules into sheets Table 1. The packing diagram viewed down the b axis shows a layered stacking feature (Fig. 2).

Related literature top

For the biological and therapeutic importance of isoxazoles, see: Kang et al. (2000); Conti et al. (1998); Changtam et al. (2010); Kwon et al., (1995); Abbiati et al. (2003). For bond-length and angle data in a related structure, see: Wolf et al. (1995).

Experimental top

A mixture of benzaldehyde oxime (1 mmol), ethyl acetoacetate (2 mmol) and anhydrous zinc chloride (0.1 mmol) were taken in a 10 ml round bottomed flask and contents were gradually heated to 120°C without any solvent for about one hour. After completion of the reaction (as indicated by TLC), the mixture was cooled to room temperature and methanol was added with stirring for about 30 min; the solids thus obtained were filtered and recrystallized from hot ethanol.

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 molecule with 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the molecule viewed down the b axis.

(Z)-4-Benzylidene-3-methylisoxazol-5(4H)-one top

Crystal data top

C₁₁H₉NO₂	F(000) = 392
M_r = 187.19	D_x = 1.356 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1610 reflections
a = 12.144 (4) Å	θ = 2.0–25.0°
b = 6.734 (2) Å	µ = 0.10 mm⁻¹
c = 12.333 (4) Å	T = 293 K
β = 114.589 (5)°	Block, yellow
V = 917.1 (5) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	R_int = 0.016
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.0°
6722 measured reflections	h = −14→14
1610 independent reflections	k = −7→7
1352 reflections with I > 2σ(I)	l = −14→14

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0548P)² + 0.1944P] where P = (F_o² + 2F_c²)/3
1610 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₁H₉NO₂	V = 917.1 (5) Å³
M_r = 187.19	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.144 (4) Å	µ = 0.10 mm⁻¹
b = 6.734 (2) Å	T = 293 K
c = 12.333 (4) Å	0.30 × 0.25 × 0.20 mm
β = 114.589 (5)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1352 reflections with I > 2σ(I)
6722 measured reflections	R_int = 0.016
1610 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.07	Δρ_max = 0.19 e Å⁻³
1610 reflections	Δρ_min = −0.14 e Å⁻³
128 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
O1	0.33893 (13)	0.04132 (18)	0.47425 (13)	0.0680 (5)
O6	0.23528 (13)	0.11975 (18)	0.58010 (12)	0.0703 (5)
N5	0.18345 (15)	0.2949 (2)	0.60829 (15)	0.0632 (6)
C2	0.29158 (16)	0.1691 (2)	0.50821 (15)	0.0505 (6)
C3	0.27739 (13)	0.3852 (2)	0.48985 (13)	0.0387 (5)
C4	0.20890 (14)	0.4425 (2)	0.55692 (14)	0.0450 (5)
C7	0.16786 (17)	0.6440 (3)	0.57095 (17)	0.0594 (7)
C8	0.31588 (13)	0.5159 (2)	0.42957 (13)	0.0392 (5)
C9	0.38358 (13)	0.4957 (2)	0.35687 (13)	0.0391 (5)
C10	0.42882 (16)	0.3176 (2)	0.33333 (15)	0.0514 (6)
C11	0.49210 (17)	0.3185 (3)	0.26289 (17)	0.0593 (7)
C12	0.51257 (17)	0.4919 (3)	0.21543 (16)	0.0556 (6)
C13	0.47001 (15)	0.6689 (3)	0.23875 (15)	0.0522 (6)
C14	0.40617 (14)	0.6711 (2)	0.30883 (14)	0.0452 (5)
H7A	0.13330	0.64020	0.62820	0.0890*
H7B	0.10800	0.68910	0.49560	0.0890*
H7C	0.23560	0.73320	0.59810	0.0890*
H8	0.29440	0.64640	0.43610	0.0470*
H10	0.41620	0.19900	0.36510	0.0620*
H11	0.52150	0.19940	0.24720	0.0710*
H12	0.55500	0.48960	0.16770	0.0670*
H13	0.48420	0.78670	0.20740	0.0630*
H14	0.37770	0.79120	0.32430	0.0540*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0942 (10)	0.0354 (7)	0.0893 (10)	0.0065 (6)	0.0529 (8)	0.0014 (6)
O6	0.1040 (11)	0.0394 (7)	0.0916 (10)	−0.0073 (7)	0.0646 (9)	0.0076 (6)
N5	0.0818 (11)	0.0514 (9)	0.0777 (11)	−0.0065 (8)	0.0544 (9)	0.0020 (8)
C2	0.0602 (10)	0.0383 (9)	0.0576 (10)	−0.0049 (8)	0.0291 (9)	0.0003 (7)
C3	0.0401 (8)	0.0349 (8)	0.0435 (8)	−0.0026 (6)	0.0197 (7)	−0.0019 (6)
C4	0.0466 (9)	0.0452 (9)	0.0490 (9)	−0.0065 (7)	0.0258 (8)	−0.0008 (7)
C7	0.0701 (12)	0.0539 (11)	0.0733 (12)	0.0062 (9)	0.0488 (10)	−0.0012 (9)
C8	0.0415 (8)	0.0343 (8)	0.0443 (8)	0.0008 (6)	0.0203 (7)	−0.0021 (6)
C9	0.0387 (8)	0.0401 (8)	0.0400 (8)	−0.0011 (6)	0.0178 (7)	−0.0026 (6)
C10	0.0615 (11)	0.0394 (9)	0.0615 (10)	−0.0027 (8)	0.0339 (9)	−0.0073 (7)
C11	0.0681 (12)	0.0532 (11)	0.0706 (12)	0.0000 (9)	0.0427 (10)	−0.0172 (9)
C12	0.0555 (10)	0.0707 (12)	0.0503 (10)	−0.0019 (9)	0.0317 (8)	−0.0070 (8)
C13	0.0547 (10)	0.0566 (11)	0.0531 (10)	0.0014 (8)	0.0303 (8)	0.0088 (8)
C14	0.0480 (9)	0.0438 (9)	0.0498 (9)	0.0057 (7)	0.0263 (8)	0.0036 (7)

Geometric parameters (Å, º) top

O1—C2	1.203 (2)	C11—C12	1.374 (3)
O6—N5	1.446 (2)	C12—C13	1.376 (3)
O6—C2	1.367 (3)	C13—C14	1.381 (3)
N5—C4	1.284 (2)	C7—H7A	0.9600
C2—C3	1.472 (2)	C7—H7B	0.9600
C3—C4	1.448 (2)	C7—H7C	0.9600
C3—C8	1.355 (2)	C8—H8	0.9300
C4—C7	1.480 (3)	C10—H10	0.9300
C8—C9	1.453 (2)	C11—H11	0.9300
C9—C10	1.399 (2)	C12—H12	0.9300
C9—C14	1.399 (2)	C13—H13	0.9300
C10—C11	1.379 (3)	C14—H14	0.9300

O1···C10	3.042 (2)	C13···C2^vi	3.364 (3)
O6···C7ⁱ	3.297 (3)	C13···C3^vi	3.471 (3)
O1···H10	2.2100	C14···C2ⁱⁱⁱ	3.582 (3)
O1···H14ⁱ	2.6800	C2···H10	2.7700
O1···H8ⁱ	2.7200	C3···H10	2.9900
O6···H7Cⁱ	2.6100	C7···H8	2.6900
O6···H12ⁱⁱ	2.9100	C8···H7C	3.0200
N5···H12ⁱⁱ	2.7600	C11···H7B^iv	3.0300
C2···C10	3.380 (3)	C11···H7Cⁱⁱⁱ	3.0500
C2···C14ⁱⁱⁱ	3.582 (3)	H7A···H13^vii	2.4400
C2···C13^iv	3.364 (3)	H7B···C11^vi	3.0300
C2···C13ⁱⁱⁱ	3.434 (3)	H7C···O6^v	2.6100
C3···C13ⁱⁱⁱ	3.493 (3)	H7C···C8	3.0200
C3···C13^iv	3.471 (3)	H7C···H8	2.4600
C3···C12ⁱⁱⁱ	3.562 (3)	H7C···C11ⁱⁱⁱ	3.0500
C4···C12ⁱⁱⁱ	3.408 (3)	H8···O1^v	2.7200
C7···O6^v	3.297 (3)	H8···C7	2.6900
C8···C10ⁱⁱⁱ	3.446 (3)	H8···H7C	2.4600
C8···C9ⁱⁱⁱ	3.502 (3)	H8···H14	2.2400
C9···C9ⁱⁱⁱ	3.486 (2)	H10···O1	2.2100
C9···C8ⁱⁱⁱ	3.502 (3)	H10···C2	2.7700
C10···C8ⁱⁱⁱ	3.446 (3)	H10···C3	2.9900
C10···C2	3.380 (3)	H12···O6^viii	2.9100
C10···O1	3.042 (2)	H12···N5^viii	2.7600
C12···C4ⁱⁱⁱ	3.408 (3)	H13···H7A^ix	2.4400
C12···C3ⁱⁱⁱ	3.562 (3)	H14···O1^v	2.6800
C13···C3ⁱⁱⁱ	3.493 (3)	H14···H8	2.2400
C13···C2ⁱⁱⁱ	3.434 (3)

N5—O6—C2	110.06 (12)	C9—C14—C13	121.09 (15)
O6—N5—C4	107.14 (16)	C4—C7—H7A	109.00
O1—C2—O6	119.51 (14)	C4—C7—H7B	109.00
O1—C2—C3	134.11 (18)	C4—C7—H7C	109.00
O6—C2—C3	106.38 (14)	H7A—C7—H7B	109.00
C2—C3—C4	103.52 (13)	H7A—C7—H7C	109.00
C2—C3—C8	132.98 (16)	H7B—C7—H7C	109.00
C4—C3—C8	123.48 (13)	C3—C8—H8	113.00
N5—C4—C3	112.89 (14)	C9—C8—H8	113.00
N5—C4—C7	119.35 (17)	C9—C10—H10	120.00
C3—C4—C7	127.76 (15)	C11—C10—H10	120.00
C3—C8—C9	133.69 (13)	C10—C11—H11	119.00
C8—C9—C10	125.46 (14)	C12—C11—H11	119.00
C8—C9—C14	116.32 (13)	C11—C12—H12	120.00
C10—C9—C14	118.22 (15)	C13—C12—H12	120.00
C9—C10—C11	119.80 (15)	C12—C13—H13	120.00
C10—C11—C12	121.27 (18)	C14—C13—H13	120.00
C11—C12—C13	119.77 (19)	C9—C14—H14	119.00
C12—C13—C14	119.85 (17)	C13—C14—H14	119.00

C2—O6—N5—C4	−0.8 (2)	C8—C3—C4—C7	0.9 (3)
N5—O6—C2—O1	−179.11 (17)	C2—C3—C4—N5	−0.07 (19)
N5—O6—C2—C3	0.72 (19)	C3—C8—C9—C10	−1.0 (3)
O6—N5—C4—C3	0.5 (2)	C3—C8—C9—C14	−179.86 (17)
O6—N5—C4—C7	−179.50 (15)	C8—C9—C10—C11	−179.85 (17)
O6—C2—C3—C4	−0.41 (18)	C14—C9—C10—C11	−1.0 (3)
O1—C2—C3—C4	179.4 (2)	C8—C9—C14—C13	179.80 (15)
O1—C2—C3—C8	−1.8 (4)	C10—C9—C14—C13	0.8 (2)
O6—C2—C3—C8	178.46 (17)	C9—C10—C11—C12	0.4 (3)
C2—C3—C4—C7	179.93 (17)	C10—C11—C12—C13	0.4 (3)
C8—C3—C4—N5	−179.08 (16)	C11—C12—C13—C14	−0.5 (3)
C2—C3—C8—C9	1.8 (3)	C12—C13—C14—C9	−0.1 (3)
C4—C3—C8—C9	−179.54 (16)

Symmetry codes: (i) x, y−1, z; (ii) x−1/2, −y+1/2, z+1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+1/2, y−1/2, −z+1/2; (v) x, y+1, z; (vi) −x+1/2, y+1/2, −z+1/2; (vii) x−1/2, −y+3/2, z+1/2; (viii) x+1/2, −y+1/2, z−1/2; (ix) x+1/2, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1	0.93	2.21	3.042 (2)	149
C7—H7C···O6^v	0.96	2.61	3.297 (2)	129
C8—H8···O1^v	0.93	2.72	3.574 (2)	154
C14—H14···O1^v	0.93	2.68	3.526 (2)	151

Symmetry code: (v) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₉NO₂
M_r	187.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	12.144 (4), 6.734 (2), 12.333 (4)
β (°)	114.589 (5)
V (Å³)	917.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
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	6722, 1610, 1352
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 1.07
No. of reflections	1610
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.14

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1	0.9300	2.2100	3.042 (2)	149
C7—H7C···O6ⁱ	0.9600	2.6120	3.297 (2)	129
C8—H8···O1ⁱ	0.9300	2.7160	3.574 (2)	154
C14—H14···O1ⁱ	0.9300	2.6840	3.526 (2)	151

Symmetry code: (i) x, y+1, z.

Acknowledgements

MM would like to thank the University of Mysore for the award of project DV3/136/2007–2008/24.09.09.

References

Abbiati, G., Beccalli, E. M., Broggini, G. & Zoni, C. (2003). Tetrahedron, 59, 9887–9893. Web of Science CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Changtam, C., Hongmanee, P. & Suksamrarn, A. (2010). Eur. J. Med. Chem. 45, 4446–4457. Web of Science CrossRef CAS PubMed Google Scholar
Conti, P., Dallanoce, C., Amici, M. D., Micheli, C. D. & Klotz, K. N. (1998). Bioorg. Med. Chem. 6, 401–408. Web of Science CrossRef CAS PubMed Google Scholar
Kang, Y. Y., Shin, K. L., Yoo, K. H., Seo, K. J., Hong, C. Y., Lee, C. S., Park, S. Y., Kim, D. J. & Park, S. W. (2000). Bioorg. Med. Chem. Lett. 10, 95–99. Web of Science CrossRef PubMed CAS Google Scholar
Kwon, T., Heimann, A. S., Oriaku, E. T., Yoon, K. & Lee, H. J. (1995). J. Med. Chem. 38, 1048–1051. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wolf, R., Wong, M. W., Kennard, C. H. L. & Wentrup, C. (1995). J. Am. Chem. Soc. 117, 6789–6790. CSD CrossRef CAS Web of Science Google Scholar