(E)-7-(4-Chloro­phen­yl)-5,7-dihydro-4H-pyrano[3,4-c]isoxazole-3-carbaldehyde oxime

Lim, H.S.; Kim, H.J.; Otgonbaatar, E.; Kwak, C.-H.

doi:10.1107/S1600536811005575

organic compounds

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doi:10.1107/S1600536811005575

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(E)-7-(4-Chlorophenyl)-5,7-dihydro-4H-pyrano[3,4-c]isoxazole-3-carbaldehyde oxime

Hyun Sub Lim,^a Hyung Jin Kim,^a ^* Enkhzul Otgonbaatar ^b and Chee-Hun Kwak ^b ^*

^aSchool of Applied Chemical Engineering, Chonnam National University, Gwangju 500-757, Republic of Korea, and ^bDepartment of Chemistry, Sunchon National University, Sunchon 540-742, Republic of Korea
^*Correspondence e-mail: hyungkim@chonnam.ac.kr, chkwak@sunchon.ac.kr

(Received 28 January 2011; accepted 15 February 2011; online 19 February 2011)

In the title compound, C₁₃H₁₁ClN₂O₃, the nine-membered bicycle includes an oxime group having the C=N group in an E configuration. The isoxazole ring is almost planar [r.m.s. deviation = 0.0056 Å]; the dihedral angle between the isoxazole and 4-chlorophenyl ring is 75.60 (5)°. In the crystal, intermolecular O—H⋯N_isoxazole hydrogen bonds give rise to chains running along the b axis.

Related literature

For the synthesis, see: Kim & Lee (1994 ).

Experimental

Crystal data

C₁₃H₁₁ClN₂O₃
M_r = 278.69
Monoclinic, C 2/c
a = 32.748 (2) Å
b = 8.8501 (5) Å
c = 8.6366 (5) Å
β = 90.478 (2)°
V = 2503.0 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 293 K
0.8 × 0.6 × 0.4 mm

Data collection

Rigaku R-AXIS RAPID II-S diffractometer
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2008 ) T_min = 0.800, T_max = 0.833
11943 measured reflections
2860 independent reflections
2467 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.101
S = 1.04
2860 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N1ⁱ	0.82	2.07	2.7920 (15)	147
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 2008); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005575/ng5111sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005575/ng5111Isup2.hkl

checkCIF report

Comment top

Fused bicyclic isoxazoles, such as dihydrofuro- and dihydropyrano[3,4-c]isoxazole,particularly have fungicidal activities against some plant pathogens. To find a new lead compound as plant fungicide and to study the structure-activity relationship (SAR), we are interested in the solid-state structures of the fused bicyclic isoxazoles.The title compound, C₁₃H₁₁ClN₂O₃, forms bicycle adjointed 5-membered isoxazole ring and 6-membered oxane ring in C8 and C9 position and it adopts E conformation (Fig.1). Isoxazole ring is a plane with the largest deviation of 0.0081 (8)Å from the least suare plane.The C7 and C10 atoms lie in the isoxazole ring plane with the largest deviation of 0.00157 (7)Å (C7) from the least-squares plane of the isoxazole ring. The dihedral angle between isoxazole and 4-chlorophenyl ring is 75.60 (5)°.The compound displays intermolecular hydrogen boning between oxyen(O3) of oxime and nitrogen(symmetric code:O3 and H3 = x,y,z+1,N3 = -x+1/2, y+1/2, -z+/2)isoxazole with a distance between O3 and N1 of 2.79 (2)Å )(Fig. 2 and Table 1). This intermolecular hydrogen bonding forms 1-D zig-zag chain of of titled compound in crystalline solid.

Related literature top

For the synthesis, see: Kim & Lee (1994).

Experimental top

A mixture of 7-(4-chlorophenyl)-5,7-dihydro-4H-pyrano[3,4-c]isoxazole-3-carbaldehyde (1.50 g, 5.69 mmol), HONH₂.HCl (593 mg, 8.53 mmol) and NaOAc (700 mg, 8.53 mmol) in EtOH (30 ml) was stirred for 3 h at 25 °C. After filtration of the reaction mixture, the filtrate was concentrated under vacuum to give crude product, which was chromatographed on SiO₂ eluting with n-hexane/EtOAc (2:1) solution to afford an isomeric mixture mixture (E:Z = 9:2). Single crystals of the (E)-isomer suitable for X-ray analysis were obtained by slow evaporation from an n-hexane/EtOAc solution at room temperature.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2008); cell refinement: RAPID-AUTO (Rigaku, 2008); data reduction: RAPID-AUTO (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level for non-H atoms.
	Fig. 2. A packing diagram of the title compound. Dashed bonds represent hydrogen bonds.

(E)-7-(4-Chlorophenyl)-5,7-dihydro-4H- pyrano[3,4-c]isoxazole-3-carbaldehyde oxime top

Crystal data top

C₁₃H₁₁ClN₂O₃	Z = 8
M_r = 278.69	D_x = 1.479 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 32.748 (2) Å	Cell parameters from 12348 reflections
b = 8.8501 (5) Å	θ = 27.5–3.4°
c = 8.6366 (5) Å	µ = 0.31 mm⁻¹
β = 90.478 (2)°	T = 293 K
V = 2503.0 (3) Å³	Block, colorless
Z = 8	0.8 × 0.6 × 0.4 mm
F(000) = 1152

Data collection top

Rigaku R-AXIS RAPID II-S diffractometer	2860 independent reflections
Radiation source: fine-focus sealed tube	2467 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2008)	h = −42→42
T_min = 0.800, T_max = 0.833	k = −10→11
11943 measured reflections	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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0482P)² + 1.5098P] where P = (F_o² + 2F_c²)/3
2860 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₃H₁₁ClN₂O₃	V = 2503.0 (3) Å³
M_r = 278.69	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 32.748 (2) Å	µ = 0.31 mm⁻¹
b = 8.8501 (5) Å	T = 293 K
c = 8.6366 (5) Å	0.8 × 0.6 × 0.4 mm
β = 90.478 (2)°

Data collection top

Rigaku R-AXIS RAPID II-S diffractometer	2860 independent reflections
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2008)	2467 reflections with I > 2σ(I)
T_min = 0.800, T_max = 0.833	R_int = 0.050
11943 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.04	Δρ_max = 0.38 e Å⁻³
2860 reflections	Δρ_min = −0.25 e Å⁻³
172 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
Cl1	0.011720 (14)	0.77709 (6)	0.05872 (5)	0.05107 (15)
O3	0.30644 (3)	1.11893 (12)	−0.46915 (11)	0.0345 (2)
H3	0.3206	1.1478	−0.3961	0.052*
O2	0.21571 (3)	0.83333 (11)	−0.33603 (10)	0.0274 (2)
C13	0.25192 (4)	0.98089 (15)	−0.52385 (14)	0.0257 (3)
H13	0.2577	1.0035	−0.6265	0.031*
O1	0.10481 (3)	0.75465 (11)	−0.63146 (11)	0.0305 (2)
N2	0.27422 (3)	1.03185 (13)	−0.41410 (12)	0.0281 (3)
C7	0.12022 (4)	0.68615 (15)	−0.49215 (15)	0.0261 (3)
H7	0.1238	0.5776	−0.5095	0.031*
N1	0.17910 (3)	0.75114 (13)	−0.31966 (13)	0.0277 (3)
C1	0.04117 (4)	0.75176 (18)	−0.10681 (16)	0.0330 (3)
C4	0.09035 (4)	0.70947 (15)	−0.36207 (15)	0.0257 (3)
C12	0.21739 (4)	0.88671 (15)	−0.48414 (14)	0.0246 (3)
C8	0.16124 (4)	0.75648 (14)	−0.45511 (15)	0.0241 (3)
C9	0.18390 (4)	0.83945 (15)	−0.56547 (14)	0.0248 (3)
C3	0.08107 (4)	0.85489 (16)	−0.31074 (17)	0.0328 (3)
H3A	0.0915	0.9380	−0.3630	0.039*
C5	0.07352 (4)	0.58664 (15)	−0.28589 (16)	0.0288 (3)
H5	0.0788	0.4894	−0.3212	0.035*
C6	0.04879 (4)	0.60687 (17)	−0.15740 (17)	0.0331 (3)
H6	0.0376	0.5242	−0.1066	0.040*
C10	0.16899 (4)	0.85873 (17)	−0.72871 (15)	0.0317 (3)
H10A	0.1909	0.8387	−0.8007	0.038*
H10B	0.1595	0.9613	−0.7450	0.038*
C11	0.13411 (5)	0.74717 (18)	−0.75476 (16)	0.0336 (3)
H11A	0.1206	0.7696	−0.8524	0.040*
H11B	0.1451	0.6455	−0.7609	0.040*
C2	0.05646 (4)	0.87708 (17)	−0.18291 (18)	0.0353 (3)
H2	0.0503	0.9741	−0.1490	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0505 (3)	0.0642 (3)	0.0388 (2)	0.0056 (2)	0.01860 (18)	−0.00215 (17)
O3	0.0336 (5)	0.0442 (6)	0.0257 (5)	−0.0137 (4)	0.0038 (4)	−0.0043 (4)
O2	0.0245 (4)	0.0339 (5)	0.0239 (5)	0.0006 (4)	0.0016 (3)	0.0031 (4)
C13	0.0275 (6)	0.0295 (7)	0.0201 (6)	0.0010 (5)	0.0023 (5)	−0.0011 (5)
O1	0.0294 (5)	0.0361 (5)	0.0260 (5)	−0.0023 (4)	−0.0017 (4)	0.0030 (4)
N2	0.0280 (5)	0.0322 (6)	0.0241 (5)	−0.0040 (5)	0.0045 (4)	−0.0013 (4)
C7	0.0275 (6)	0.0241 (6)	0.0268 (6)	−0.0003 (5)	0.0020 (5)	0.0010 (5)
N1	0.0245 (5)	0.0311 (6)	0.0277 (6)	0.0011 (4)	0.0031 (4)	0.0041 (4)
C1	0.0253 (6)	0.0453 (9)	0.0283 (7)	0.0026 (6)	0.0029 (5)	−0.0005 (6)
C4	0.0228 (6)	0.0265 (7)	0.0277 (7)	0.0003 (5)	0.0002 (5)	0.0010 (5)
C12	0.0276 (6)	0.0255 (6)	0.0207 (6)	0.0033 (5)	0.0025 (5)	−0.0009 (4)
C8	0.0253 (6)	0.0232 (6)	0.0238 (6)	0.0038 (5)	0.0022 (5)	0.0003 (4)
C9	0.0271 (6)	0.0235 (6)	0.0240 (6)	0.0006 (5)	0.0035 (5)	−0.0002 (5)
C3	0.0336 (7)	0.0261 (7)	0.0387 (8)	−0.0009 (6)	0.0061 (6)	0.0016 (5)
C5	0.0285 (6)	0.0251 (7)	0.0329 (7)	0.0009 (5)	0.0007 (5)	0.0027 (5)
C6	0.0313 (7)	0.0352 (8)	0.0327 (7)	−0.0025 (6)	0.0024 (5)	0.0081 (6)
C10	0.0363 (7)	0.0370 (8)	0.0219 (6)	−0.0085 (6)	−0.0013 (5)	0.0026 (5)
C11	0.0381 (8)	0.0406 (8)	0.0221 (7)	−0.0093 (6)	0.0007 (6)	−0.0014 (5)
C2	0.0344 (7)	0.0313 (8)	0.0401 (8)	0.0033 (6)	0.0040 (6)	−0.0053 (6)

Geometric parameters (Å, º) top

Cl1—C1	1.7456 (14)	C4—C5	1.3872 (18)
O3—N2	1.3934 (14)	C4—C3	1.3955 (19)
O3—H3	0.8200	C12—C9	1.3633 (18)
O2—C12	1.3651 (15)	C8—C9	1.4178 (17)
O2—N1	1.4105 (14)	C9—C10	1.4978 (18)
C13—N2	1.2742 (17)	C3—C2	1.386 (2)
C13—C12	1.4482 (18)	C3—H3A	0.9300
C13—H13	0.9300	C5—C6	1.3907 (19)
O1—C7	1.4351 (16)	C5—H5	0.9300
O1—C11	1.4409 (17)	C6—H6	0.9300
C7—C4	1.5099 (17)	C10—C11	1.525 (2)
C7—C8	1.5123 (18)	C10—H10A	0.9700
C7—H7	0.9800	C10—H10B	0.9700
N1—C8	1.3043 (18)	C11—H11A	0.9700
C1—C6	1.378 (2)	C11—H11B	0.9700
C1—C2	1.385 (2)	C2—H2	0.9300

N2—O3—H3	109.5	C12—C9—C10	134.78 (12)
C12—O2—N1	108.26 (9)	C8—C9—C10	121.57 (12)
N2—C13—C12	118.12 (11)	C2—C3—C4	120.87 (13)
N2—C13—H13	120.9	C2—C3—H3A	119.6
C12—C13—H13	120.9	C4—C3—H3A	119.6
C7—O1—C11	111.63 (10)	C4—C5—C6	120.92 (13)
C13—N2—O3	111.89 (10)	C4—C5—H5	119.5
O1—C7—C4	109.92 (11)	C6—C5—H5	119.5
O1—C7—C8	107.99 (10)	C1—C6—C5	118.75 (13)
C4—C7—C8	111.48 (11)	C1—C6—H6	120.6
O1—C7—H7	109.1	C5—C6—H6	120.6
C4—C7—H7	109.1	C9—C10—C11	107.63 (11)
C8—C7—H7	109.1	C9—C10—H10A	110.2
C8—N1—O2	105.46 (10)	C11—C10—H10A	110.2
C6—C1—C2	121.84 (13)	C9—C10—H10B	110.2
C6—C1—Cl1	118.81 (11)	C11—C10—H10B	110.2
C2—C1—Cl1	119.35 (12)	H10A—C10—H10B	108.5
C5—C4—C3	118.92 (12)	O1—C11—C10	111.33 (11)
C5—C4—C7	120.54 (12)	O1—C11—H11A	109.4
C3—C4—C7	120.44 (12)	C10—C11—H11A	109.4
C9—C12—O2	109.75 (11)	O1—C11—H11B	109.4
C9—C12—C13	132.92 (12)	C10—C11—H11B	109.4
O2—C12—C13	117.31 (11)	H11A—C11—H11B	108.0
N1—C8—C9	112.85 (12)	C1—C2—C3	118.65 (13)
N1—C8—C7	124.45 (11)	C1—C2—H2	120.7
C9—C8—C7	122.68 (12)	C3—C2—H2	120.7
C12—C9—C8	103.65 (11)

C12—C13—N2—O3	179.32 (11)	O2—C12—C9—C10	−179.11 (14)
C11—O1—C7—C4	174.62 (11)	C13—C12—C9—C10	2.5 (3)
C11—O1—C7—C8	52.81 (13)	N1—C8—C9—C12	−0.76 (15)
C12—O2—N1—C8	0.96 (13)	C7—C8—C9—C12	177.73 (11)
O1—C7—C4—C5	121.01 (13)	N1—C8—C9—C10	179.62 (12)
C8—C7—C4—C5	−119.28 (13)	C7—C8—C9—C10	−1.90 (19)
O1—C7—C4—C3	−62.69 (16)	C5—C4—C3—C2	1.9 (2)
C8—C7—C4—C3	57.02 (16)	C7—C4—C3—C2	−174.40 (13)
N1—O2—C12—C9	−1.48 (14)	C3—C4—C5—C6	−2.0 (2)
N1—O2—C12—C13	177.20 (10)	C7—C4—C5—C6	174.35 (12)
N2—C13—C12—C9	165.24 (14)	C2—C1—C6—C5	1.9 (2)
N2—C13—C12—O2	−13.06 (18)	Cl1—C1—C6—C5	−177.63 (11)
O2—N1—C8—C9	−0.11 (14)	C4—C5—C6—C1	0.1 (2)
O2—N1—C8—C7	−178.57 (11)	C12—C9—C10—C11	167.22 (15)
O1—C7—C8—N1	161.63 (12)	C8—C9—C10—C11	−13.29 (18)
C4—C7—C8—N1	40.79 (17)	C7—O1—C11—C10	−73.78 (15)
O1—C7—C8—C9	−16.68 (16)	C9—C10—C11—O1	48.62 (16)
C4—C7—C8—C9	−137.52 (12)	C6—C1—C2—C3	−1.9 (2)
O2—C12—C9—C8	1.34 (14)	Cl1—C1—C2—C3	177.59 (11)
C13—C12—C9—C8	−177.05 (13)	C4—C3—C2—C1	0.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N1ⁱ	0.82	2.07	2.7920 (15)	147

Symmetry code: (i) −x+1/2, y+1/2, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁ClN₂O₃
M_r	278.69
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	32.748 (2), 8.8501 (5), 8.6366 (5)
β (°)	90.478 (2)
V (Å³)	2503.0 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.8 × 0.6 × 0.4

Data collection
Diffractometer	Rigaku R-AXIS RAPID II-S diffractometer
Absorption correction	Multi-scan (RAPID-AUTO; Rigaku, 2008)
T_min, T_max	0.800, 0.833
No. of measured, independent and observed [I > 2σ(I)] reflections	11943, 2860, 2467
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.101, 1.04
No. of reflections	2860
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.25

Computer programs: RAPID-AUTO (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N1ⁱ	0.82	2.07	2.7920 (15)	147

Symmetry code: (i) −x+1/2, y+1/2, −z−1/2.

Acknowledgements

This study was supported financially by Chonnam National University. CHK thanks the RIC, Sunchon National University, for financial support.

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kim, H. J. & Lee, J. H. (1994). Heterocycles, 38, 1383–1391. CAS Google Scholar
Rigaku (2008). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(E)-7-(4-Chloro­phen­yl)-5,7-di­hydro-4H-pyrano[3,4-c]isoxazole-3-carbaldehyde oxime

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(E)-7-(4-Chlorophenyl)-5,7-dihydro-4H-pyrano[3,4-c]isoxazole-3-carbaldehyde oxime