2-Acetamido-3-(4-hydr­oxy-3-methoxy­phen­yl)acrylic acid

Lan, X.-B.; Nan, Y.-F.; Chen, L.; Wang, S.-X.; Zheng, X.-H.

doi:10.1107/S1600536808001347

organic compounds

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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page o566

doi:10.1107/S1600536808001347

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2-Acetamido-3-(4-hydroxy-3-methoxyphenyl)acrylic acid

Xiao-Bing Lan,^a,^b Ye-Fei Nan,^b Lin Chen,^a Shi-Xiang Wang ^b and Xiao-Hui Zheng ^a,^b ^*

^aSchool of Chemistry and Biotechnology, Yunnan Nationalities University, Kunming 650031, People's Republic of China, and ^bEngineering and Research Center of Chinese Herb Modernization, Northwest University, Xi'an 710069, People's Republic of China
^*Correspondence e-mail: zhengxh@nwu.edu.cn

(Received 1 December 2007; accepted 14 January 2008; online 6 February 2008)

In the title compound, C₁₂H₁₃NO₅, the azlactone of vanillin, the acrylic acid side chain has a trans extended conformation. There are intermolecular N—H⋯O and O—H⋯O hydrogen bonds in the crystal structure.

Related literature

For a related structure, see: Haasbroek et al. (1998 ). For information on the synthesis, see: Wong et al. (1992 ).

Experimental

Crystal data

C₁₂H₁₃NO₅
M_r = 251.23
Orthorhombic, P b c a
a = 12.7573 (14) Å
b = 12.7518 (14) Å
c = 14.7290 (17) Å
V = 2396.1 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 (2) K
0.37 × 0.30 × 0.26 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
11011 measured reflections
2122 independent reflections
1788 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.122
S = 1.01
2122 reflections
167 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O3ⁱ	0.82	1.79	2.6044 (15)	171
O1—H1B⋯O5ⁱⁱ	0.82	1.84	2.6582 (13)	177
N1—H1⋯O1ⁱⁱⁱ	0.86	2.13	2.9501 (14)	159
Symmetry codes: (i) -x, -y+2, -z; (ii) -x, -y+2, -z+1; (iii) $[-x+{\script{1\over 2}}, -y+2, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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/S1600536808001347/cf2176sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808001347/cf2176Isup2.hkl

checkCIF report

Comment top

The molecular structure of the title compound is illustrated in Fig. 1. There are three intermolecular hydrogen bonds. One is formed between the NH group and the phenolic hydroxyl O atom of another molecule, the others between the carbonyl O atom and OH group.

A similar structure has been reported for a related compound (Haasbroek et al., 1998).

Related literature top

For a related structure, see: Haasbroek et al. (1998). For information on the synthesis, see: Wong et al. (1992).

Experimental top

The azlactone (Wong et al., 1992) of vanillin (2.0 g, 7.3 mmol) was heated at 353 K with stirring in a sodium hydroxide solution (20 ml, 20%). A dark wine-red solution formed. After 3 h, the mixture was cooled and acidified with hydrochloric acid (6 M) to a pH of 1.35. The mixture was stirred well and allowed to cool to 273 K. The crystals that formed were filtered off and dried under vacuum at 318 K (1.45 g, 5.7 mmol). Recrystallization from ethanol/water gave pale-yellow crystals of (I) with a melting point of 481 K. Yellow single crystals suitable for X-ray analysis were obtained by slow evaporation of a solution in methanol–water at room temperature for two weeks. Spectroscopic analysis: IR (KBr, cm^-1): 3256, 2952, 1678, 1656; ¹H NMR (DMSO, δ, p.p.m.): 12.389 (s, 1 H), 9.492 (s, 1 H), 9.316 (s, 1 H), 7.286–7.282 (d, 1 H), 7.196 (s, 1 H), 7.088–7.068 (m, 1 H), 6.797–6.781 (d, 1 H), 3.771 (s, 3 H), 1.985 (s, 3 H).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. H atoms have been omitted.
	Fig. 2. The packing of (I), viewed down the c axis. Molecules are connected by O—H···O and N—H···O hydrogen bonds shown as dashed lines.

2-Acetamido-3-(4-hydroxy-3-methoxyphenyl)acrylic acid top

Crystal data top

C₁₂H₁₃NO₅	D_x = 1.393 Mg m⁻³
M_r = 251.23	Melting point: 481 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 12.7573 (14) Å	Cell parameters from 4984 reflections
b = 12.7518 (14) Å	θ = 2.7–28.1°
c = 14.7290 (17) Å	µ = 0.11 mm⁻¹
V = 2396.1 (5) Å³	T = 296 K
Z = 8	Block, yellow
F(000) = 1056	0.37 × 0.30 × 0.26 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1788 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 25.1°, θ_min = 2.7°
ϕ and ω scans	h = −15→13
11011 measured reflections	k = −15→15
2122 independent reflections	l = −14→17

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 0.0344P] where P = (F_o² + 2F_c²)/3
2122 reflections	(Δ/σ)_max < 0.001
167 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₂H₁₃NO₅	V = 2396.1 (5) Å³
M_r = 251.23	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.7573 (14) Å	µ = 0.11 mm⁻¹
b = 12.7518 (14) Å	T = 296 K
c = 14.7290 (17) Å	0.37 × 0.30 × 0.26 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1788 reflections with I > 2σ(I)
11011 measured reflections	R_int = 0.021
2122 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.01	Δρ_max = 0.20 e Å⁻³
2122 reflections	Δρ_min = −0.31 e Å⁻³
167 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	0.16380 (8)	0.89736 (8)	0.23064 (7)	0.0337 (3)
H1	0.2301	0.9037	0.2218	0.040*
O1	0.12427 (7)	1.09483 (8)	0.65078 (6)	0.0426 (3)
H1B	0.0745	1.1269	0.6725	0.064*
O2	0.22102 (8)	0.94162 (8)	0.56758 (7)	0.0473 (3)
O3	−0.00149 (10)	1.06674 (9)	0.09716 (8)	0.0604 (4)
O4	0.07449 (9)	0.91314 (8)	0.06704 (7)	0.0521 (3)
H4	0.0520	0.9262	0.0161	0.078*
O5	0.03350 (7)	0.79383 (7)	0.28136 (8)	0.0465 (3)
C1	0.11343 (9)	1.08974 (10)	0.55890 (9)	0.0330 (3)
C2	0.05408 (9)	1.16043 (10)	0.50975 (9)	0.0363 (3)
H2	0.0209	1.2156	0.5394	0.044*
C3	0.04374 (10)	1.14964 (10)	0.41675 (9)	0.0361 (3)
H3	0.0033	1.1977	0.3846	0.043*
C4	0.09273 (9)	1.06807 (9)	0.37029 (9)	0.0320 (3)
C5	0.15561 (10)	0.99846 (10)	0.42060 (9)	0.0353 (3)
H5	0.1912	0.9449	0.3908	0.042*
C6	0.16531 (9)	1.00837 (10)	0.51307 (9)	0.0342 (3)
C7	0.26213 (15)	0.85003 (13)	0.52600 (12)	0.0631 (5)
H7A	0.2063	0.8115	0.4979	0.095*
H7B	0.2952	0.8070	0.5712	0.095*
H7C	0.3127	0.8696	0.4808	0.095*
C8	0.07026 (10)	1.05762 (10)	0.27390 (9)	0.0339 (3)
H8	0.0296	1.1117	0.2503	0.041*
C9	0.09724 (9)	0.98457 (10)	0.21286 (9)	0.0326 (3)
C10	0.05389 (11)	0.98977 (10)	0.12025 (9)	0.0383 (3)
C11	0.12612 (9)	0.80575 (10)	0.26066 (9)	0.0344 (3)
C12	0.20317 (13)	0.71764 (12)	0.27005 (12)	0.0547 (4)
H12A	0.1975	0.6877	0.3296	0.082*
H12B	0.2729	0.7439	0.2612	0.082*
H12C	0.1884	0.6649	0.2253	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0316 (6)	0.0389 (6)	0.0306 (6)	0.0028 (4)	0.0014 (4)	−0.0005 (4)
O1	0.0364 (5)	0.0617 (7)	0.0295 (6)	0.0091 (4)	−0.0031 (4)	−0.0095 (4)
O2	0.0569 (6)	0.0501 (6)	0.0349 (6)	0.0194 (5)	−0.0089 (4)	−0.0023 (4)
O3	0.0912 (8)	0.0506 (7)	0.0393 (7)	0.0255 (6)	−0.0191 (6)	−0.0037 (5)
O4	0.0774 (8)	0.0472 (6)	0.0317 (6)	0.0116 (5)	−0.0112 (5)	−0.0069 (4)
O5	0.0448 (6)	0.0363 (6)	0.0583 (7)	−0.0007 (4)	0.0118 (5)	−0.0027 (4)
C1	0.0288 (6)	0.0413 (7)	0.0289 (7)	−0.0045 (5)	−0.0015 (5)	−0.0042 (5)
C2	0.0366 (6)	0.0353 (7)	0.0370 (8)	0.0011 (5)	0.0012 (5)	−0.0052 (6)
C3	0.0394 (7)	0.0332 (7)	0.0357 (8)	0.0009 (5)	−0.0019 (5)	0.0020 (5)
C4	0.0343 (6)	0.0315 (6)	0.0301 (7)	−0.0032 (5)	−0.0001 (5)	0.0011 (5)
C5	0.0373 (7)	0.0352 (7)	0.0333 (8)	0.0019 (5)	−0.0006 (5)	−0.0038 (5)
C6	0.0318 (6)	0.0368 (7)	0.0339 (8)	0.0006 (5)	−0.0040 (5)	−0.0001 (5)
C7	0.0809 (11)	0.0573 (10)	0.0512 (10)	0.0334 (9)	−0.0081 (9)	−0.0042 (8)
C8	0.0386 (6)	0.0314 (7)	0.0319 (8)	0.0002 (5)	−0.0011 (5)	0.0030 (5)
C9	0.0366 (7)	0.0326 (7)	0.0286 (7)	−0.0009 (5)	−0.0006 (5)	0.0036 (5)
C10	0.0490 (8)	0.0349 (7)	0.0310 (8)	0.0019 (5)	−0.0018 (6)	0.0001 (5)
C11	0.0404 (7)	0.0354 (7)	0.0275 (7)	0.0044 (5)	0.0010 (5)	−0.0042 (5)
C12	0.0614 (9)	0.0458 (9)	0.0570 (11)	0.0191 (7)	0.0032 (7)	0.0022 (7)

Geometric parameters (Å, º) top

N1—C11	1.3383 (17)	C3—H3	0.930
N1—C9	1.4236 (16)	C4—C5	1.4074 (18)
N1—H1	0.860	C4—C8	1.4544 (19)
O1—C1	1.3619 (17)	C5—C6	1.3734 (19)
O1—H1B	0.820	C5—H5	0.930
O2—C6	1.3690 (15)	C7—H7A	0.960
O2—C7	1.4192 (18)	C7—H7B	0.960
O3—C10	1.2563 (17)	C7—H7C	0.960
O4—C10	1.2798 (17)	C8—C9	1.3396 (19)
O4—H4	0.820	C8—H8	0.930
O5—C11	1.2298 (15)	C9—C10	1.4733 (19)
C1—C2	1.3819 (18)	C11—C12	1.4992 (19)
C1—C6	1.4037 (18)	C12—H12A	0.960
C2—C3	1.3831 (19)	C12—H12B	0.960
C2—H2	0.930	C12—H12C	0.960
C3—C4	1.3931 (18)

C11—N1—C9	121.90 (10)	O2—C7—H7A	109.5
C11—N1—H1	119.0	O2—C7—H7B	109.5
C9—N1—H1	119.0	H7A—C7—H7B	109.5
C1—O1—H1B	109.5	O2—C7—H7C	109.5
C6—O2—C7	116.78 (11)	H7A—C7—H7C	109.5
C10—O4—H4	109.5	H7B—C7—H7C	109.5
O1—C1—C2	123.03 (11)	C9—C8—C4	131.93 (12)
O1—C1—C6	117.72 (11)	C9—C8—H8	114.0
C2—C1—C6	119.25 (12)	C4—C8—H8	114.0
C1—C2—C3	120.41 (12)	C8—C9—N1	124.96 (12)
C1—C2—H2	119.8	C8—C9—C10	119.58 (12)
C3—C2—H2	119.8	N1—C9—C10	115.43 (11)
C2—C3—C4	121.20 (12)	O3—C10—O4	123.11 (13)
C2—C3—H3	119.4	O3—C10—C9	119.79 (12)
C4—C3—H3	119.4	O4—C10—C9	117.10 (12)
C3—C4—C5	117.90 (12)	O5—C11—N1	122.34 (11)
C3—C4—C8	117.35 (11)	O5—C11—C12	120.96 (12)
C5—C4—C8	124.65 (11)	N1—C11—C12	116.69 (12)
C6—C5—C4	121.03 (12)	C11—C12—H12A	109.5
C6—C5—H5	119.5	C11—C12—H12B	109.5
C4—C5—H5	119.5	H12A—C12—H12B	109.5
O2—C6—C5	124.83 (12)	C11—C12—H12C	109.5
O2—C6—C1	114.99 (12)	H12A—C12—H12C	109.5
C5—C6—C1	120.16 (12)	H12B—C12—H12C	109.5

O1—C1—C2—C3	−178.29 (11)	C2—C1—C6—C5	−1.02 (18)
C6—C1—C2—C3	1.61 (18)	C3—C4—C8—C9	−173.93 (14)
C1—C2—C3—C4	−0.21 (19)	C5—C4—C8—C9	2.4 (2)
C2—C3—C4—C5	−1.73 (18)	C4—C8—C9—N1	−3.7 (2)
C2—C3—C4—C8	174.86 (11)	C4—C8—C9—C10	174.16 (13)
C3—C4—C5—C6	2.31 (18)	C11—N1—C9—C8	89.19 (16)
C8—C4—C5—C6	−174.01 (12)	C11—N1—C9—C10	−88.76 (15)
C7—O2—C6—C5	−6.86 (19)	C8—C9—C10—O3	5.4 (2)
C7—O2—C6—C1	171.24 (13)	N1—C9—C10—O3	−176.52 (13)
C4—C5—C6—O2	177.05 (11)	C8—C9—C10—O4	−173.86 (13)
C4—C5—C6—C1	−0.96 (19)	N1—C9—C10—O4	4.20 (18)
O1—C1—C6—O2	0.68 (16)	C9—N1—C11—O5	−5.8 (2)
C2—C1—C6—O2	−179.22 (11)	C9—N1—C11—C12	175.51 (12)
O1—C1—C6—C5	178.88 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ⁱ	0.82	1.79	2.6044 (15)	171
O1—H1B···O5ⁱⁱ	0.82	1.84	2.6582 (13)	177
N1—H1···O1ⁱⁱⁱ	0.86	2.13	2.9501 (14)	159

Symmetry codes: (i) −x, −y+2, −z; (ii) −x, −y+2, −z+1; (iii) −x+1/2, −y+2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃NO₅
M_r	251.23
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	12.7573 (14), 12.7518 (14), 14.7290 (17)
V (Å³)	2396.1 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.37 × 0.30 × 0.26

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11011, 2122, 1788
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.122, 1.01
No. of reflections	2122
No. of parameters	167
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.31

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ⁱ	0.82	1.79	2.6044 (15)	171.2
O1—H1B···O5ⁱⁱ	0.82	1.84	2.6582 (13)	176.5
N1—H1···O1ⁱⁱⁱ	0.86	2.13	2.9501 (14)	158.8

Symmetry codes: (i) −x, −y+2, −z; (ii) −x, −y+2, −z+1; (iii) −x+1/2, −y+2, z−1/2.

Acknowledgements

The authors thank the Ministry of Science and Technology of Shaanxi Province and the Ministry of Education of the People's Republic of China for financial support (grant Nos. 2006kz10-G5, 2007ZDKG-70 and 207151).

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Haasbroek, P. P., Oliver, D. W. & Carpy, A. J. M. (1998). J. Chem. Crystallogr. 28, 193–196. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wong, H. N. C., Xu, Z. L., Chang, H. M. & Lee, C. M. (1992). Synthesis, pp. 793–797. CrossRef Web of Science Google Scholar