(Z)-2-Acetamido-3-(4-chloro­phen­yl)acrylic acid

Tian, Q.-J.; Ouyang, H.; Tian, C.-L.; Jiang, Y.-D.

doi:10.1107/S1600536809048041

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3110

doi:10.1107/S1600536809048041

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(Z)-2-Acetamido-3-(4-chlorophenyl)acrylic acid

Qi-Jian Tian,^a ^* Hui Ouyang,^a Chun-Lian Tian ^a and Yong-Dong Jiang ^a

^aKey Laboratory of Hunan Forest Products and, Chemical Industry Engineering, Jishou University, Jishou 416000, People's Republic of China
^*Correspondence e-mail: shenyangzhou@163.com

(Received 27 October 2009; accepted 12 November 2009; online 18 November 2009)

In the title compound, C₁₁H₁₀ClNO₃, the molecule consists of a benzene ring and an acetamidoacrylic acid unit on opposite sides of the C=C double bond. In the crystal, intermolecular O—H⋯O and N—H⋯O hydrogen bonds assemble the molecules into infinite two-dimensional ribbons. These ribbons are linked into a network by intermolecular C—H⋯π contacts.

Related literature

Derivatives of 2-acetamido-3-phenylacrylic acid are key intermates in the preparations of tanshinol (Wong et al. 1992 ; Xiao, et al. 2008a ), diaryl-3-hydroxy-2(5H)-furanones (Weber et al. 2002 ; Xiao et al. 2008b ) and benzylazauracil (Chen et al. 1993 ; Xiao, et al. 2008c ), which show anti-platelet aggregation, antifungal and antiviral activities, respectively.

Experimental

Crystal data

C₁₁H₁₀ClNO₃
M_r = 239.65
Monoclinic, P 2₁
a = 6.2440 (12) Å
b = 7.5450 (15) Å
c = 11.813 (2) Å
β = 100.47 (3)°
V = 547.26 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 298 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.935, T_max = 0.967
1160 measured reflections
1060 independent reflections
895 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.229
S = 1.01
1060 reflections
148 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.09	2.933 (7)	165
O2—H2A⋯O3ⁱⁱ	0.82	1.86	2.606 (7)	152
C3—H3⋯Cg1ⁱⁱⁱ	0.93	2.85	3.523 (8)	130
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+1]$ . Cg1 is the centroid of the C1–C6 ring.

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048041/bq2173sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048041/bq2173Isup2.hkl

checkCIF report

Comment top

Derivatives of 2-acetamido-3-phenylacrylic acid are key intermates for tanshinol (Wong et al. 1992; Xiao, et al. 2008a), diaryl-3-hydroxy-2(5H)-furanones (Weber et al. 2002; Xiao et al. 2008b) and benzylazauracil (Chen et al. 1993; Xiao, et al. 2008c), which show anti-platelet aggregation, antifungal and antiviral activities, respectively. In the course of our work on screening for anticancers, we synthesized the title compound and herein reported its crystal structure.

In the title compound (I), the plane of benzene ring (with mean dieviation deviation of 0.0053 Å) and the plane of hydroxy acrylic moiety (with mean deviation of 0.0049 Å) make a dihedral angle of 18.001 (97) Å. The benzene ring and the carboxy group occur on opposite side of the C8═C9 double bond with torsion angle of 179.8 (4) ° (Fig. 1). Intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) assemble the molecules into an infinite two-dimensional ribbon. This ribbons further form a network via C—H···pi contact (Fig. 2).

Related literature top

Experimental top

The mixture of alpha-acetoaminocinnamic acid (2.35 g, 10 mmol) in 0.5M HCl (60 mL) was refluxed for 3 h. The resulting mixture was allowed to cool to room temperature and the resulting precipitate was collected by filtration. The crude product was dissolved in EtOAc and twofold volume of petroleum was added carefully. Colorless blocks of (I) suitable for single-crystal structure determination was furnished after 2 d.

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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of (I), with the atom-numbering scheme and 30% probability displacement ellipsoids.
	Fig. 2. An infinite two-dimensional ribbon is formed through intermolecular O—H···O hydrogen bonds. Dashed lines indicate hydrogen bonds and solid dashed lines indicate C—H···π contacts.

(Z)-2-Acetamido-3-(4-chlorophenyl)acrylic acid top

Crystal data top

C₁₁H₁₀ClNO₃	F(000) = 248
M_r = 239.65	D_x = 1.454 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 775 reflections
a = 6.2440 (12) Å	θ = 1.9–24.7°
b = 7.5450 (15) Å	µ = 0.34 mm⁻¹
c = 11.813 (2) Å	T = 298 K
β = 100.47 (3)°	Block, colorless
V = 547.26 (19) Å³	0.20 × 0.10 × 0.10 mm
Z = 2

Data collection top

Bruker SMART APEX area-detector diffractometer	1060 independent reflections
Radiation source: fine-focus sealed tube	895 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 25.2°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = 0→7
T_min = 0.935, T_max = 0.967	k = 0→9
1160 measured reflections	l = −14→13

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.229	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.2P)²] where P = (F_o² + 2F_c²)/3
1060 reflections	(Δ/σ)_max = 0.001
148 parameters	Δρ_max = 0.32 e Å⁻³
1 restraint	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₁H₁₀ClNO₃	V = 547.26 (19) Å³
M_r = 239.65	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.2440 (12) Å	µ = 0.34 mm⁻¹
b = 7.5450 (15) Å	T = 298 K
c = 11.813 (2) Å	0.20 × 0.10 × 0.10 mm
β = 100.47 (3)°

Data collection top

Bruker SMART APEX area-detector diffractometer	1060 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	895 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.967	R_int = 0.036
1160 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	1 restraint
wR(F²) = 0.229	H-atom parameters constrained
S = 1.01	Δρ_max = 0.32 e Å⁻³
1060 reflections	Δρ_min = −0.35 e Å⁻³
148 parameters

Special details top

Experimental. We have re-refined our data by using 'MERG 1' instruction to avoid Friedel opposites being merged. The absolute structure parameter is still meaningless, though the data/parameter (985/148) is higher than the former (895/148).

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
Cl	−0.0425 (4)	0.7267 (4)	0.74675 (17)	0.0628 (8)
C1	0.3337 (10)	0.6719 (8)	0.4546 (5)	0.0297 (14)
N1	0.2032 (8)	0.7163 (9)	0.1907 (4)	0.0333 (13)
H1	0.0860	0.6715	0.2071	0.06 (3)*
O1	0.7621 (7)	0.6067 (9)	0.2131 (5)	0.0529 (16)
C2	0.1323 (11)	0.7587 (9)	0.4407 (6)	0.0360 (16)
H2	0.0726	0.8045	0.3688	0.043*
O2	0.4735 (8)	0.5437 (10)	0.0782 (5)	0.0579 (17)
H2A	0.5657	0.5193	0.0393	0.087*
C3	0.0201 (13)	0.7786 (10)	0.5294 (6)	0.0422 (18)
H3	−0.1134	0.8368	0.5177	0.051*
O3	0.3510 (8)	0.9179 (9)	0.0890 (4)	0.0496 (15)
C4	0.1089 (13)	0.7102 (11)	0.6378 (6)	0.0436 (18)
C5	0.3095 (13)	0.6317 (12)	0.6558 (6)	0.0480 (19)
H5	0.3701	0.5915	0.7291	0.058*
C6	0.4220 (11)	0.6116 (11)	0.5683 (6)	0.0424 (18)
H6	0.5582	0.5577	0.5825	0.051*
C7	0.4613 (10)	0.6378 (10)	0.3662 (6)	0.0337 (14)
H7	0.6012	0.5950	0.3924	0.040*
C8	0.4067 (10)	0.6591 (10)	0.2525 (6)	0.0352 (15)
C9	0.5701 (10)	0.6022 (10)	0.1796 (6)	0.0372 (16)
C10	0.1874 (11)	0.8392 (10)	0.1065 (5)	0.0363 (15)
C11	−0.0380 (12)	0.8731 (13)	0.0403 (6)	0.050 (2)
H11A	−0.0295	0.9462	−0.0252	0.075*
H11B	−0.1227	0.9323	0.0891	0.075*
H11C	−0.1059	0.7624	0.0149	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0756 (15)	0.0751 (15)	0.0438 (10)	−0.0037 (13)	0.0266 (10)	−0.0043 (11)
C1	0.028 (3)	0.032 (3)	0.026 (3)	−0.003 (3)	−0.001 (2)	0.002 (2)
N1	0.027 (3)	0.045 (3)	0.032 (2)	0.000 (3)	0.016 (2)	0.004 (3)
O1	0.025 (2)	0.077 (4)	0.057 (3)	0.003 (3)	0.005 (2)	0.000 (3)
C2	0.041 (4)	0.033 (4)	0.034 (3)	0.008 (3)	0.006 (3)	0.004 (3)
O2	0.033 (2)	0.084 (4)	0.058 (3)	−0.001 (3)	0.012 (2)	−0.034 (4)
C3	0.037 (4)	0.046 (4)	0.045 (4)	0.004 (3)	0.011 (3)	0.000 (3)
O3	0.047 (3)	0.063 (4)	0.041 (3)	−0.013 (3)	0.015 (2)	0.014 (3)
C4	0.051 (4)	0.038 (4)	0.040 (4)	−0.008 (4)	0.003 (3)	−0.002 (3)
C5	0.059 (5)	0.054 (5)	0.030 (3)	−0.005 (4)	0.005 (3)	0.006 (3)
C6	0.038 (4)	0.046 (4)	0.039 (4)	0.012 (3)	−0.004 (3)	0.008 (3)
C7	0.027 (3)	0.035 (3)	0.040 (3)	0.002 (3)	0.006 (2)	0.002 (3)
C8	0.029 (3)	0.034 (3)	0.045 (4)	0.000 (3)	0.014 (3)	0.003 (3)
C9	0.033 (3)	0.044 (4)	0.041 (4)	−0.004 (3)	0.022 (3)	−0.002 (3)
C10	0.040 (3)	0.044 (4)	0.029 (3)	0.005 (3)	0.016 (3)	−0.003 (3)
C11	0.054 (4)	0.057 (5)	0.034 (3)	0.011 (4)	−0.006 (3)	0.006 (4)

Geometric parameters (Å, º) top

Cl—C4	1.734 (8)	C3—H3	0.9300
C1—C2	1.401 (9)	O3—C10	1.231 (9)
C1—C6	1.430 (9)	C4—C5	1.367 (12)
C1—C7	1.446 (9)	C5—C6	1.360 (11)
N1—C10	1.350 (9)	C5—H5	0.9300
N1—C8	1.413 (9)	C6—H6	0.9300
N1—H1	0.8600	C7—C8	1.334 (11)
O1—C9	1.193 (8)	C7—H7	0.9300
C2—C3	1.370 (11)	C8—C9	1.512 (8)
C2—H2	0.9300	C10—C11	1.502 (10)
O2—C9	1.316 (9)	C11—H11A	0.9600
O2—H2A	0.8200	C11—H11B	0.9600
C3—C4	1.398 (11)	C11—H11C	0.9600

C2—C1—C6	116.3 (6)	C5—C6—H6	119.5
C2—C1—C7	126.8 (6)	C1—C6—H6	119.5
C6—C1—C7	116.9 (6)	C8—C7—C1	129.2 (6)
C10—N1—C8	121.9 (6)	C8—C7—H7	115.4
C10—N1—H1	119.0	C1—C7—H7	115.4
C8—N1—H1	119.0	C7—C8—N1	126.8 (6)
C3—C2—C1	122.3 (6)	C7—C8—C9	117.6 (6)
C3—C2—H2	118.8	N1—C8—C9	115.4 (6)
C1—C2—H2	118.8	O1—C9—O2	125.3 (6)
C9—O2—H2A	109.5	O1—C9—C8	123.0 (6)
C4—C3—C2	119.2 (7)	O2—C9—C8	111.7 (5)
C4—C3—H3	120.4	O3—C10—N1	120.2 (6)
C2—C3—H3	120.4	O3—C10—C11	123.9 (7)
C3—C4—C5	120.1 (7)	N1—C10—C11	115.9 (6)
C3—C4—Cl	118.3 (6)	C10—C11—H11A	109.5
C5—C4—Cl	121.6 (6)	C10—C11—H11B	109.5
C4—C5—C6	121.0 (7)	H11A—C11—H11B	109.5
C4—C5—H5	119.5	C10—C11—H11C	109.5
C6—C5—H5	119.5	H11A—C11—H11C	109.5
C5—C6—C1	121.0 (6)	H11B—C11—H11C	109.5

C6—C1—C2—C3	−2.8 (10)	C6—C1—C7—C8	170.8 (8)
C7—C1—C2—C3	177.5 (7)	C1—C7—C8—N1	−2.2 (13)
C1—C2—C3—C4	0.0 (11)	C1—C7—C8—C9	−176.5 (7)
C2—C3—C4—C5	2.9 (12)	C10—N1—C8—C7	134.8 (8)
C2—C3—C4—Cl	−176.7 (6)	C10—N1—C8—C9	−50.8 (9)
C3—C4—C5—C6	−2.9 (13)	C7—C8—C9—O1	−30.5 (11)
Cl—C4—C5—C6	176.6 (6)	N1—C8—C9—O1	154.6 (8)
C4—C5—C6—C1	0.0 (12)	C7—C8—C9—O2	147.7 (8)
C2—C1—C6—C5	2.8 (11)	N1—C8—C9—O2	−27.2 (10)
C7—C1—C6—C5	−177.5 (7)	C8—N1—C10—O3	−7.2 (11)
C2—C1—C7—C8	−9.5 (12)	C8—N1—C10—C11	174.0 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.09	2.933 (7)	165
O2—H2A···O3ⁱⁱ	0.82	1.86	2.606 (7)	152
C3—H3···Cg1ⁱⁱⁱ	0.93	2.85	3.523 (8)	130

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀ClNO₃
M_r	239.65
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	6.2440 (12), 7.5450 (15), 11.813 (2)
β (°)	100.47 (3)
V (Å³)	547.26 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.935, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	1160, 1060, 895
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.229, 1.01
No. of reflections	1060
No. of parameters	148
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.35

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), 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
N1—H1···O1ⁱ	0.86	2.09	2.933 (7)	165.0
O2—H2A···O3ⁱⁱ	0.82	1.86	2.606 (7)	151.7
C3—H3···Cg1ⁱⁱⁱ	0.93	2.85	3.523 (8)	130.0

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

Acknowledgements

This research was supported financially by the Key Laboratory of Hunan Forest Products and Chemical Industry Engineering of Hunan Province (grant No. JDZ200905).

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