organic compounds
(Z)-4-Benzylidene-3-methylisoxazol-5(4H)-one
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
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
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S1600536812041311/sj5268sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812041311/sj5268Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812041311/sj5268Isup3.cml
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.
H atoms were placed at idealized positions and allowed to ride on their parent atoms with C–H distances in the range of 0.93 to 0.96 Å; Uiso(H) = 1.2-1.5Ueq(carrier atom) for all H atoms.
Data collection: APEX2 (Bruker, 2009); cell
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).Fig. 1. Perspective diagram of the molecule with 50% probability displacement ellipsoids. | |
Fig. 2. Packing diagram of the molecule viewed down the b axis. |
C11H9NO2 | F(000) = 392 |
Mr = 187.19 | Dx = 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 |
Bruker APEXII CCD area-detector diffractometer | Rint = 0.016 |
ω and ϕ scans | θmax = 25.0°, θmin = 2.0° |
6722 measured reflections | h = −14→14 |
1610 independent reflections | k = −7→7 |
1352 reflections with I > 2σ(I) | l = −14→14 |
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(Fo2) + (0.0548P)2 + 0.1944P] where P = (Fo2 + 2Fc2)/3 |
1610 reflections | (Δ/σ)max < 0.001 |
128 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
C11H9NO2 | V = 917.1 (5) Å3 |
Mr = 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)° |
Bruker APEXII CCD area-detector diffractometer | 1352 reflections with I > 2σ(I) |
6722 measured reflections | Rint = 0.016 |
1610 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.19 e Å−3 |
1610 reflections | Δρmin = −0.14 e Å−3 |
128 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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···C2vi | 3.364 (3) |
O6···C7i | 3.297 (3) | C13···C3vi | 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···H7Biv | 3.0300 |
C2···C10 | 3.380 (3) | C11···H7Ciii | 3.0500 |
C2···C14iii | 3.582 (3) | H7A···H13vii | 2.4400 |
C2···C13iv | 3.364 (3) | H7B···C11vi | 3.0300 |
C2···C13iii | 3.434 (3) | H7C···O6v | 2.6100 |
C3···C13iii | 3.493 (3) | H7C···C8 | 3.0200 |
C3···C13iv | 3.471 (3) | H7C···H8 | 2.4600 |
C3···C12iii | 3.562 (3) | H7C···C11iii | 3.0500 |
C4···C12iii | 3.408 (3) | H8···O1v | 2.7200 |
C7···O6v | 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···O6viii | 2.9100 |
C10···O1 | 3.042 (2) | H12···N5viii | 2.7600 |
C12···C4iii | 3.408 (3) | H13···H7Aix | 2.4400 |
C12···C3iii | 3.562 (3) | H14···O1v | 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. |
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···O6v | 0.96 | 2.61 | 3.297 (2) | 129 |
C8—H8···O1v | 0.93 | 2.72 | 3.574 (2) | 154 |
C14—H14···O1v | 0.93 | 2.68 | 3.526 (2) | 151 |
Symmetry code: (v) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C11H9NO2 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.19, −0.14 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
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
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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).