(Z)-4-[4-(Dimethyl­amino)benzyl­idene]-3-methyl­isoxazol-5(4H)-one

Cheng, Q.; Wang, Q.; Liu, L.; Zhang, J.

doi:10.1107/S160053680904714X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3074

doi:10.1107/S160053680904714X

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(Z)-4-[4-(Dimethylamino)benzylidene]-3-methylisoxazol-5(4H)-one

Qingfang Cheng,^a ^* Qi-fa Wang,^a Li-sha Liu ^a and Jun-lei Zhang ^a

^aHuaihai Institute of Technology, Lianyungang 222005, People's Republic of China
^*Correspondence e-mail: cheng_qingfang@yahoo.com.cn

(Received 22 October 2009; accepted 8 November 2009; online 14 November 2009)

The title compound, C₁₃H₁₄N₂O₂, an isoxazol-5-one derivative, was synthesized by a one-pot, three-component condensation reaction of methyl acetoacetate, hydroxylamine hydrochloride and 4-(dimethylamino)benzaldehyde. All the non-H atoms are co-planar [r.m.s deviation = 0.0039 Å], with a Z configuration about the C=C bond. The dihedral angle between the phenyl ring and the isoxazole ring is 2.58 (19)°.

Related literature

For the biological activity of arylmethylene isoxazolone derivatives, see: Ishioka et al. (2002 ); Liu et al. (2005 ). For details of the synthesis of related compounds, see: Cocivera et al. (1976 ); Zhang et al. (2008 ); Villemin et al. (1993 ). For related structures, see: Kay et al. (2001 ); Wolf et al. (1995 ).

Experimental

Crystal data

C₁₃H₁₄N₂O₂
M_r = 230.26
Triclinic, $[P \overline 1]$
a = 6.4201 (10) Å
b = 7.8239 (12) Å
c = 12.1901 (15) Å
α = 100.272 (2)°
β = 97.319 (1)°
γ = 101.461 (2)°
V = 582.01 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.13 × 0.09 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.988, T_max = 0.993
2990 measured reflections
2020 independent reflections
943 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.178
S = 1.03
2020 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680904714X/su2156sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680904714X/su2156Isup2.hkl

checkCIF report

Comment top

Arylmethylene isoxazolone derivatives are effective anti-psychotics in the treatment of depression and schizophrenia. Studies on these compounds have mainly concentrated on their biological activities (Ishioka et al., 2002; Liu et al., 2005), and syntheses (Cocivera et al., 1976; Zhang et al., 2008; Villemin et al., 1993). However, structural studies have rarely been reported (Kay et al., 2001; Wolf et al., 1995). As part of our investigations on arylmethylene isoxazolone derivatives, we report herein on the structure of the title compound. It was synthesized by a three component condensation reaction of methyl acetoacetate, hydroxylamine with 4-dimethylaminobenzaldehyde, in aqueous media under ultrasonic irradiation.

The molecular structure of the title compound is illustrated in Fig. 1, and geometrical parameters are given in the archived CIF. The bond lengths and angles agree well with those reported for the related compound 4-(N-(2,4,6-Tri-t-butylphenyl)iminomethylene)-3-t-butylisoxazol-5(4H)-one (Wolf et al., 1995). The molecular structure adopts a planar conformation with Z-configuration about the C2═C5 double bond.

Related literature top

For the biological activity of arylmethylene isoxazolone derivatives, see: Ishioka et al. (2002); Liu et al. (2005). For details of the synthesis of related compounds, see: Cocivera et al. (1976); Zhang et al. (2008); Villemin et al. (1993). For related structures, see: Kay et al. (2001); Wolf et al. (1995).

Experimental top

A mixture of methyl acetoacetate (4 mol), hydroxylamine hydrochloride (4 mmol), and pyridine(4 mmol) in distilled water(10 ml) was irradiated in the water bath of an ultrasonic cleaner for 10 min, then 4-dimethylaminobenzaldehyde(4 mmol) was slowly added to the mixture. The resulting mixture was irradiated in the water bath of an ultrasonic cleaner for 0.5 h. The solution was kept at r.t. overnight, giving a turbid solution. It was filtered to give a solid that was washed with cold water and ethanol. The crude product was recrystallized from ethanol to afford the title compound as a yellow solid. Single crystals, suitable for X-ray analysis, were obtained by slow evaporation of an aqueous ethanol (95%) solution at ambient temperature after 4 d. Elemental analysis, calculated for C₁₃H₁₄N₂O₂: C 67.81, H 6.13, N 12.17%; found: C 67.87, H 6.19, N 12.11%.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXTL (Sheldrick, 2008).

Figures top

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

(Z)-4-[4-(Dimethylamino)benzylidene]-3-methylisoxazol-5(4H)-one top

Crystal data top

C₁₃H₁₄N₂O₂	Z = 2
M_r = 230.26	F(000) = 244
Triclinic, P1	D_x = 1.314 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4201 (10) Å	Cell parameters from 607 reflections
b = 7.8239 (12) Å	θ = 2.9–25.1°
c = 12.1901 (15) Å	µ = 0.09 mm⁻¹
α = 100.272 (2)°	T = 298 K
β = 97.319 (1)°	Needle, red
γ = 101.461 (2)°	0.13 × 0.09 × 0.08 mm
V = 582.01 (15) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2020 independent reflections
Radiation source: fine-focus sealed tube	943 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.988, T_max = 0.993	k = −9→6
2990 measured reflections	l = −13→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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.069P)² + ] where P = (F_o² + 2F_c²)/3
2020 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₃H₁₄N₂O₂	γ = 101.461 (2)°
M_r = 230.26	V = 582.01 (15) Å³
Triclinic, P1	Z = 2
a = 6.4201 (10) Å	Mo Kα radiation
b = 7.8239 (12) Å	µ = 0.09 mm⁻¹
c = 12.1901 (15) Å	T = 298 K
α = 100.272 (2)°	0.13 × 0.09 × 0.08 mm
β = 97.319 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2020 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	943 reflections with I > 2σ(I)
T_min = 0.988, T_max = 0.993	R_int = 0.039
2990 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.03	Δρ_max = 0.23 e Å⁻³
2020 reflections	Δρ_min = −0.29 e Å⁻³
157 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	0.7351 (5)	0.6599 (4)	0.8929 (3)	0.0671 (10)
N2	0.3808 (5)	0.8488 (4)	0.1943 (3)	0.0604 (9)
O1	0.9130 (4)	0.7385 (4)	0.8421 (2)	0.0746 (9)
O2	0.9643 (4)	0.8104 (4)	0.6764 (2)	0.0797 (9)
C1	0.8347 (6)	0.7524 (5)	0.7333 (4)	0.0626 (11)
C2	0.6035 (5)	0.6855 (5)	0.7140 (3)	0.0492 (9)
C3	0.5624 (5)	0.6321 (4)	0.8187 (3)	0.0503 (9)
C4	0.3517 (5)	0.5490 (5)	0.8451 (3)	0.0634 (11)
H4A	0.3722	0.5237	0.9195	0.095*
H4B	0.2895	0.4400	0.7907	0.095*
H4C	0.2568	0.6293	0.8423	0.095*
C5	0.4464 (5)	0.6758 (4)	0.6248 (3)	0.0506 (9)
H5	0.3094	0.6266	0.6373	0.061*
C6	0.4428 (5)	0.7234 (4)	0.5171 (3)	0.0458 (9)
C7	0.2412 (5)	0.6921 (5)	0.4469 (3)	0.0546 (10)
H7	0.1181	0.6420	0.4730	0.066*
C8	0.2192 (5)	0.7323 (5)	0.3417 (3)	0.0563 (10)
H8	0.0829	0.7086	0.2980	0.068*
C9	0.4013 (5)	0.8091 (4)	0.2993 (3)	0.0496 (9)
C10	0.6035 (5)	0.8435 (5)	0.3700 (3)	0.0526 (10)
H10	0.7264	0.8965	0.3448	0.063*
C11	0.6244 (5)	0.8012 (4)	0.4750 (3)	0.0507 (9)
H11	0.7605	0.8244	0.5187	0.061*
C12	0.5668 (6)	0.9262 (5)	0.1481 (3)	0.0691 (12)
H12A	0.6721	1.0058	0.2079	0.104*
H12B	0.5224	0.9911	0.0929	0.104*
H12C	0.6287	0.8329	0.1129	0.104*
C13	0.1725 (6)	0.8003 (6)	0.1198 (3)	0.0751 (12)
H13A	0.1191	0.6734	0.1050	0.113*
H13B	0.1886	0.8376	0.0499	0.113*
H13C	0.0725	0.8581	0.1555	0.113*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0601 (19)	0.091 (3)	0.058 (2)	0.0251 (18)	0.0110 (18)	0.027 (2)
N2	0.057 (2)	0.066 (2)	0.057 (2)	0.0083 (16)	0.0014 (17)	0.0214 (18)
O1	0.0534 (16)	0.105 (2)	0.0670 (19)	0.0177 (15)	0.0012 (14)	0.0282 (17)
O2	0.0470 (15)	0.116 (2)	0.075 (2)	0.0066 (15)	0.0082 (14)	0.0298 (18)
C1	0.053 (2)	0.076 (3)	0.058 (3)	0.018 (2)	0.003 (2)	0.012 (2)
C2	0.0429 (19)	0.056 (2)	0.050 (2)	0.0151 (16)	0.0067 (17)	0.0117 (19)
C3	0.051 (2)	0.059 (2)	0.045 (2)	0.0233 (18)	0.0035 (18)	0.0117 (19)
C4	0.067 (2)	0.077 (3)	0.055 (3)	0.020 (2)	0.013 (2)	0.027 (2)
C5	0.0423 (18)	0.049 (2)	0.063 (3)	0.0112 (16)	0.0113 (18)	0.016 (2)
C6	0.046 (2)	0.046 (2)	0.048 (2)	0.0124 (16)	0.0067 (17)	0.0134 (18)
C7	0.044 (2)	0.061 (3)	0.060 (3)	0.0079 (17)	0.0069 (18)	0.021 (2)
C8	0.046 (2)	0.058 (2)	0.062 (3)	0.0066 (18)	0.0001 (18)	0.016 (2)
C9	0.051 (2)	0.047 (2)	0.052 (2)	0.0118 (17)	0.0030 (18)	0.0161 (19)
C10	0.0437 (19)	0.059 (2)	0.055 (2)	0.0097 (17)	0.0045 (18)	0.016 (2)
C11	0.0435 (19)	0.055 (2)	0.054 (2)	0.0119 (17)	0.0021 (17)	0.0155 (19)
C12	0.075 (3)	0.077 (3)	0.060 (3)	0.016 (2)	0.015 (2)	0.027 (2)
C13	0.071 (3)	0.096 (3)	0.059 (3)	0.018 (2)	−0.002 (2)	0.029 (2)

Geometric parameters (Å, º) top

N1—C3	1.294 (4)	C6—C11	1.405 (4)
N1—O1	1.451 (3)	C6—C7	1.409 (5)
N2—C9	1.367 (4)	C7—C8	1.371 (5)
N2—C12	1.455 (4)	C7—H7	0.9300
N2—C13	1.457 (4)	C8—C9	1.407 (4)
O1—C1	1.388 (4)	C8—H8	0.9300
O2—C1	1.220 (4)	C9—C10	1.412 (5)
C1—C2	1.446 (5)	C10—C11	1.375 (4)
C2—C5	1.365 (5)	C10—H10	0.9300
C2—C3	1.451 (4)	C11—H11	0.9300
C3—C4	1.481 (4)	C12—H12A	0.9600
C4—H4A	0.9600	C12—H12B	0.9600
C4—H4B	0.9600	C12—H12C	0.9600
C4—H4C	0.9600	C13—H13A	0.9600
C5—C6	1.426 (4)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600

C3—N1—O1	106.5 (3)	C8—C7—H7	118.7
C9—N2—C12	121.9 (3)	C6—C7—H7	118.7
C9—N2—C13	120.9 (3)	C7—C8—C9	120.4 (3)
C12—N2—C13	117.0 (3)	C7—C8—H8	119.8
C1—O1—N1	109.2 (3)	C9—C8—H8	119.8
O2—C1—O1	118.0 (3)	N2—C9—C8	120.8 (3)
O2—C1—C2	134.7 (4)	N2—C9—C10	122.0 (3)
O1—C1—C2	107.3 (3)	C8—C9—C10	117.2 (3)
C5—C2—C1	132.2 (3)	C11—C10—C9	122.0 (3)
C5—C2—C3	124.2 (3)	C11—C10—H10	119.0
C1—C2—C3	103.6 (3)	C9—C10—H10	119.0
N1—C3—C2	113.3 (3)	C10—C11—C6	120.9 (3)
N1—C3—C4	119.5 (3)	C10—C11—H11	119.5
C2—C3—C4	127.1 (3)	C6—C11—H11	119.5
C3—C4—H4A	109.5	N2—C12—H12A	109.5
C3—C4—H4B	109.5	N2—C12—H12B	109.5
H4A—C4—H4B	109.5	H12A—C12—H12B	109.5
C3—C4—H4C	109.5	N2—C12—H12C	109.5
H4A—C4—H4C	109.5	H12A—C12—H12C	109.5
H4B—C4—H4C	109.5	H12B—C12—H12C	109.5
C2—C5—C6	135.0 (3)	N2—C13—H13A	109.5
C2—C5—H5	112.5	N2—C13—H13B	109.5
C6—C5—H5	112.5	H13A—C13—H13B	109.5
C11—C6—C7	116.8 (3)	N2—C13—H13C	109.5
C11—C6—C5	125.4 (3)	H13A—C13—H13C	109.5
C7—C6—C5	117.8 (3)	H13B—C13—H13C	109.5
C8—C7—C6	122.7 (3)

C3—N1—O1—C1	−0.9 (4)	C2—C5—C6—C7	−179.7 (4)
N1—O1—C1—O2	−177.5 (3)	C11—C6—C7—C8	0.8 (5)
N1—O1—C1—C2	1.1 (4)	C5—C6—C7—C8	−179.8 (3)
O2—C1—C2—C5	−5.2 (8)	C6—C7—C8—C9	−0.4 (5)
O1—C1—C2—C5	176.5 (4)	C12—N2—C9—C8	−179.2 (3)
O2—C1—C2—C3	177.5 (4)	C13—N2—C9—C8	−4.7 (5)
O1—C1—C2—C3	−0.9 (4)	C12—N2—C9—C10	1.1 (5)
O1—N1—C3—C2	0.4 (4)	C13—N2—C9—C10	175.6 (3)
O1—N1—C3—C4	178.9 (3)	C7—C8—C9—N2	179.7 (3)
C5—C2—C3—N1	−177.3 (3)	C7—C8—C9—C10	−0.6 (5)
C1—C2—C3—N1	0.3 (4)	N2—C9—C10—C11	−179.0 (3)
C5—C2—C3—C4	4.2 (6)	C8—C9—C10—C11	1.3 (5)
C1—C2—C3—C4	−178.2 (3)	C9—C10—C11—C6	−0.9 (5)
C1—C2—C5—C6	0.8 (7)	C7—C6—C11—C10	−0.1 (5)
C3—C2—C5—C6	177.6 (3)	C5—C6—C11—C10	−179.5 (3)
C2—C5—C6—C11	−0.4 (6)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂O₂
M_r	230.26
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.4201 (10), 7.8239 (12), 12.1901 (15)
α, β, γ (°)	100.272 (2), 97.319 (1), 101.461 (2)
V (Å³)	582.01 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.13 × 0.09 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.988, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	2990, 2020, 943
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.178, 1.03
No. of reflections	2020
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.29

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We are grateful for financial support from the the Foundation of Jiangsu Key Laboratory of Marine Biotechnology (grant No. 2009HS04).

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