4-[(2-Methyl-5-oxo-4,5-dihydro-1,3-oxazol-4-yl­idene)meth­yl]phenyl acetate

Guo, P.; Wang, C.; Chen, J.; Mou, D.

doi:10.1107/S1600536809032243

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2215

doi:10.1107/S1600536809032243

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4-[(2-Methyl-5-oxo-4,5-dihydro-1,3-oxazol-4-ylidene)methyl]phenyl acetate

Pengran Guo,^a Chang Wang,^b Jianghan Chen ^b and Dehai Mou ^b ^*

^aSchool of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275, People's Republic of China, and ^bGuangdong Provincial Key Laboratory of Emergency Testing for Dangerous Chemicals, China National Analytical Center, Guangzhou 510070, People's Republic of China
^*Correspondence e-mail: guopengran@gmail.com

(Received 2 June 2009; accepted 14 August 2009; online 22 August 2009)

In the title compound, C₁₃H₁₁NO₄, an intramolecular C—H⋯N interaction helps to establish the conformation. In the crystal, two C—H⋯O contacts stack adjacent molecules into a one-dimensional double chain running in the a-axis direction.

Related literature

The title compound is an important medical intermediate, see: Baker (1951 ).

Experimental

Crystal data

C₁₃H₁₁NO₄
M_r = 245.23
Triclinic, $[P \overline 1]$
a = 5.5802 (15) Å
b = 7.446 (2) Å
c = 15.012 (4) Å
α = 94.322 (4)°
β = 93.156 (4)°
γ = 108.136 (4)°
V = 589.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.14 × 0.13 × 0.08 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2003 ) T_min = 0.985, T_max = 0.992
3324 measured reflections
2264 independent reflections
1707 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.164
S = 1.04
2264 reflections
153 parameters
H-atom parameters constrained
Δρ_max = 0.15 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
C4—H4⋯N1	0.93	2.45	3.098 (4)	127
C7—H7⋯O2ⁱ	0.93	2.53	3.417 (4)	160
C13—H13B⋯O4ⁱⁱ	0.96	2.50	3.382 (4)	152
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y, z.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S1600536809032243/kj2130sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032243/kj2130Isup2.hkl

checkCIF report

Comment top

The title compound is an important medical intermediate (Baker, 1951). Here we report the molecular and crystal structure of the title compound (Fig. 1). In the cystal structure,the five- and six-membered rings are nearly coplanar. The interplanar angle between the two rings is 1.392 (3)°. The crystal packing (Fig. 2) is stabilized by two types of intermolecular C—H···O interactions and one kind of intramolecular C—H···N interaction. Details are listed in Table 1. These interactions join the molecules into a double chain parallel to the a axis.

Related literature top

The title compound is an important medical intermediate, see: Baker (1951).

Experimental top

The title compund is synthesized according to previous reported literature (Baker, 1951). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in dichloromethane at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); 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. A view of the title compound with the atom-labeling scheme and 30% probability displacement ellipsoids.
	Fig. 2. Perspective view along the b-axis of the crystal packing of the title compound. Dashed lines indicate C-H···O and C-H···N contacts.

4-[(2-Methyl-5-oxo-4,5-dihydro-1,3-oxazol-4-ylidene)methyl]phenyl acetate top

Crystal data top

C₁₃H₁₁NO₄	Z = 2
M_r = 245.23	F(000) = 256
Triclinic, P1	D_x = 1.383 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.5802 (15) Å	Cell parameters from 2544 reflections
b = 7.446 (2) Å	θ = 3.0–25.4°
c = 15.012 (4) Å	µ = 0.10 mm⁻¹
α = 94.322 (4)°	T = 293 K
β = 93.156 (4)°	Block, colourless
γ = 108.136 (4)°	0.14 × 0.13 × 0.08 mm
V = 589.1 (3) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2264 independent reflections
Radiation source: fine-focus sealed tube	1707 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
Detector resolution: 15 pixels mm^-1	θ_max = 26.1°, θ_min = 2.7°
ϕ and ω scans	h = −6→3
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2003)	k = −9→9
T_min = 0.985, T_max = 0.992	l = −18→15
3324 measured reflections

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.164	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0685P)² + 0.3541P] where P = (F_o² + 2F_c²)/3
2264 reflections	(Δ/σ)_max < 0.001
153 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₃H₁₁NO₄	γ = 108.136 (4)°
M_r = 245.23	V = 589.1 (3) Å³
Triclinic, P1	Z = 2
a = 5.5802 (15) Å	Mo Kα radiation
b = 7.446 (2) Å	µ = 0.10 mm⁻¹
c = 15.012 (4) Å	T = 293 K
α = 94.322 (4)°	0.14 × 0.13 × 0.08 mm
β = 93.156 (4)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2264 independent reflections
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2003)	1707 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.992	R_int = 0.016
3324 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.164	H-atom parameters constrained
S = 1.04	Δρ_max = 0.15 e Å⁻³
2264 reflections	Δρ_min = −0.14 e Å⁻³
153 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	0.4700 (4)	0.9795 (3)	0.17606 (14)	0.0516 (6)
O1	1.3127 (3)	0.7316 (3)	0.44177 (12)	0.0565 (5)
O2	0.2844 (4)	0.6674 (3)	−0.02010 (13)	0.0725 (6)
O3	0.2123 (4)	0.9237 (3)	0.04884 (12)	0.0568 (5)
O4	1.0311 (4)	0.7157 (3)	0.54417 (13)	0.0631 (6)
C1	1.1357 (5)	0.7294 (4)	0.37105 (17)	0.0491 (6)
C2	1.1061 (5)	0.5959 (4)	0.29939 (17)	0.0540 (7)
H2	1.1950	0.5091	0.3002	0.065*
C3	0.9434 (5)	0.5922 (4)	0.22626 (17)	0.0518 (7)
H3	0.9229	0.5019	0.1778	0.062*
C4	0.8449 (5)	0.8561 (4)	0.29798 (17)	0.0529 (7)
H4	0.7574	0.9439	0.2980	0.064*
C5	1.0078 (5)	0.8603 (4)	0.37083 (17)	0.0552 (7)
H5	1.0312	0.9507	0.4195	0.066*
C6	0.8087 (5)	0.7219 (3)	0.22381 (16)	0.0460 (6)
C7	0.6402 (5)	0.7112 (4)	0.14512 (17)	0.0485 (6)
H7	0.6312	0.6140	0.1010	0.058*
C8	0.4950 (5)	0.8196 (3)	0.12586 (16)	0.0456 (6)
C9	0.3284 (5)	0.7834 (4)	0.04328 (18)	0.0517 (6)
C10	0.3096 (6)	1.0311 (4)	0.1294 (2)	0.0614 (5)
C11	0.2127 (6)	1.1906 (4)	0.1497 (2)	0.0614 (5)
H11A	0.2977	1.2619	0.2046	0.092*
H11B	0.0343	1.1427	0.1558	0.092*
H11C	0.2430	1.2715	0.1019	0.092*
C12	1.2360 (5)	0.7171 (4)	0.52634 (17)	0.0483 (6)
C13	1.4387 (6)	0.6997 (4)	0.5901 (2)	0.0614 (5)
H13A	1.4521	0.7817	0.6439	0.092*
H13B	1.5969	0.7353	0.5632	0.092*
H13C	1.3984	0.5707	0.6044	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0563 (13)	0.0520 (13)	0.0512 (12)	0.0260 (10)	−0.0003 (10)	−0.0015 (10)
O1	0.0468 (10)	0.0774 (13)	0.0507 (11)	0.0283 (9)	0.0027 (8)	0.0039 (9)
O2	0.0901 (16)	0.0779 (14)	0.0548 (12)	0.0428 (12)	−0.0140 (11)	−0.0167 (11)
O3	0.0637 (12)	0.0609 (12)	0.0513 (11)	0.0312 (10)	−0.0071 (9)	−0.0008 (9)
O4	0.0549 (12)	0.0869 (15)	0.0590 (12)	0.0379 (11)	0.0086 (9)	0.0100 (10)
C1	0.0461 (14)	0.0585 (15)	0.0465 (14)	0.0220 (12)	0.0049 (11)	0.0049 (12)
C2	0.0600 (16)	0.0603 (16)	0.0524 (15)	0.0355 (14)	0.0043 (13)	0.0020 (13)
C3	0.0634 (17)	0.0516 (15)	0.0470 (14)	0.0295 (13)	0.0039 (12)	−0.0020 (11)
C4	0.0654 (17)	0.0523 (15)	0.0507 (15)	0.0339 (13)	0.0019 (13)	0.0007 (12)
C5	0.0665 (17)	0.0570 (16)	0.0468 (14)	0.0299 (14)	−0.0005 (13)	−0.0061 (12)
C6	0.0512 (14)	0.0463 (13)	0.0450 (13)	0.0219 (11)	0.0058 (11)	0.0030 (11)
C7	0.0563 (15)	0.0482 (14)	0.0442 (13)	0.0220 (12)	0.0046 (11)	0.0001 (11)
C8	0.0502 (14)	0.0469 (13)	0.0429 (13)	0.0206 (11)	0.0040 (11)	0.0026 (10)
C9	0.0581 (16)	0.0522 (15)	0.0493 (14)	0.0249 (13)	0.0031 (12)	0.0025 (12)
C10	0.0603 (10)	0.0662 (11)	0.0616 (10)	0.0281 (8)	−0.0028 (8)	0.0013 (8)
C11	0.0603 (10)	0.0662 (11)	0.0616 (10)	0.0281 (8)	−0.0028 (8)	0.0013 (8)
C12	0.0472 (15)	0.0487 (14)	0.0487 (14)	0.0173 (12)	−0.0005 (11)	−0.0029 (11)
C13	0.0603 (10)	0.0662 (11)	0.0616 (10)	0.0281 (8)	−0.0028 (8)	0.0013 (8)

Geometric parameters (Å, º) top

N1—C10	1.275 (3)	C4—C6	1.400 (3)
N1—C8	1.409 (3)	C4—H4	0.9300
O1—C12	1.363 (3)	C5—H5	0.9300
O1—C1	1.405 (3)	C6—C7	1.450 (3)
O2—C9	1.196 (3)	C7—C8	1.345 (4)
O3—C10	1.381 (3)	C7—H7	0.9300
O3—C9	1.390 (3)	C8—C9	1.463 (4)
O4—C12	1.185 (3)	C10—C11	1.469 (4)
C1—C2	1.374 (4)	C11—H11A	0.9600
C1—C5	1.376 (4)	C11—H11B	0.9600
C2—C3	1.379 (4)	C11—H11C	0.9600
C2—H2	0.9300	C12—C13	1.484 (4)
C3—C6	1.398 (3)	C13—H13A	0.9600
C3—H3	0.9300	C13—H13B	0.9600
C4—C5	1.375 (4)	C13—H13C	0.9600

C10—N1—C8	105.4 (2)	C7—C8—N1	129.4 (2)
C12—O1—C1	118.8 (2)	C7—C8—C9	122.6 (2)
C10—O3—C9	105.4 (2)	N1—C8—C9	108.0 (2)
C2—C1—C5	121.3 (2)	O2—C9—O3	121.5 (2)
C2—C1—O1	116.6 (2)	O2—C9—C8	133.5 (2)
C5—C1—O1	122.0 (2)	O3—C9—C8	105.0 (2)
C1—C2—C3	119.3 (2)	N1—C10—O3	116.3 (2)
C1—C2—H2	120.3	N1—C10—C11	128.7 (3)
C3—C2—H2	120.3	O3—C10—C11	115.1 (2)
C2—C3—C6	121.1 (2)	C10—C11—H11A	109.5
C2—C3—H3	119.5	C10—C11—H11B	109.5
C6—C3—H3	119.5	H11A—C11—H11B	109.5
C5—C4—C6	121.1 (2)	C10—C11—H11C	109.5
C5—C4—H4	119.4	H11A—C11—H11C	109.5
C6—C4—H4	119.4	H11B—C11—H11C	109.5
C4—C5—C1	119.4 (2)	O4—C12—O1	123.0 (2)
C4—C5—H5	120.3	O4—C12—C13	125.9 (3)
C1—C5—H5	120.3	O1—C12—C13	111.1 (2)
C3—C6—C4	117.8 (2)	C12—C13—H13A	109.5
C3—C6—C7	118.6 (2)	C12—C13—H13B	109.5
C4—C6—C7	123.6 (2)	H13A—C13—H13B	109.5
C8—C7—C6	130.1 (2)	C12—C13—H13C	109.5
C8—C7—H7	114.9	H13A—C13—H13C	109.5
C6—C7—H7	114.9	H13B—C13—H13C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N1	0.93	2.45	3.098 (4)	127
C7—H7···O2ⁱ	0.93	2.53	3.417 (4)	160
C13—H13B···O4ⁱⁱ	0.96	2.50	3.382 (4)	152

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁NO₄
M_r	245.23
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.5802 (15), 7.446 (2), 15.012 (4)
α, β, γ (°)	94.322 (4), 93.156 (4), 108.136 (4)
V (Å³)	589.1 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.14 × 0.13 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SAINT-Plus; Bruker, 2003)
T_min, T_max	0.985, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	3324, 2264, 1707
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.164, 1.04
No. of reflections	2264
No. of parameters	153
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.14

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N1	0.93	2.45	3.098 (4)	127
C7—H7···O2ⁱ	0.93	2.53	3.417 (4)	160
C13—H13B···O4ⁱⁱ	0.96	2.50	3.382 (4)	152

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z.

Acknowledgements

This work was supported by Guangdong Provincial Key Laboratory of Emergency Testing for Dangerous Chemicals, China National Analytical Center (Guangzhou), People's Republic of China.

References

Baker, L. E. (1951). J. Biol. Chem. 193, 809–819. PubMed CAS Web of Science Google Scholar
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsion, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar