(Z)-3-(Benzyl­carbamo­yl)prop-2-enoic acid

Dong, S.-L.; Cheng, X.-C.

doi:10.1107/S160053681100609X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o689

doi:10.1107/S160053681100609X

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(Z)-3-(Benzylcarbamoyl)prop-2-enoic acid

Su-Lan Dong ^a ^* and Xiao-Chun Cheng ^b

^aHuaiyin Institute of Technology, Huaiyin 223003, Jiangsu, People's Republic of China, and ^bCollege of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaian, 223003, People's Republic of China
^*Correspondence e-mail: dsl710221@163.com

(Received 19 October 2010; accepted 17 February 2011; online 23 February 2011)

The title compound, C₁₁H₁₁NO₃, was synthesized by the reaction of maleic andydride and phenylmethanamine. The molecular conformation is stabilized by by an intramolecular O—H⋯O hydrogen bond. In the crystal, molecules are linked by intermolecular N—H⋯O and C—H⋯O hydrogen bonds, forming a chain along the b axis.

Related literature

For related structures, see Gowda et al. (2009a ,b ,c ); Prasad et al. (2002 ).

Experimental

Crystal data

C₁₁H₁₁NO₃
M_r = 205.21
Monoclinic, P 2₁ /c
a = 10.651 (2) Å
b = 12.601 (3) Å
c = 8.3130 (17) Å
β = 108.44 (3)°
V = 1058.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.972, T_max = 0.991
2018 measured reflections
1913 independent reflections
1013 reflections with I > 2σ(I)
R_int = 0.022
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.175
S = 1.00
1913 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O1	0.85	1.61	2.461 (3)	178
N—H0A⋯O2ⁱ	0.86	2.00	2.855 (3)	171
C9—H9A⋯O3ⁱ	0.93	2.48	3.413 (4)	177
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100609X/kj2163sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100609X/kj2163Isup2.hkl

checkCIF report

Comment top

The amide moiety is an important constituent of many biologically significant compounds. As a part of studying the effect of ring and side chain substitution on the crystal structures of this class compounds (Gowda et al., 2009a, 2009b, 2009c; Prasad et al., 2002), the crystal structure of (Z)-4-(benzylamino)-4-oxobut-2-enoic acid has been determined. The molecular conformation (Fig. 1) is stabilized by intramolecular O–H···O bonds. As can be seen from the packing diagram (Fig.2), molecules are linked by intermolecular N–H···O and C–H···O hydrogen bonds to form a chain along the b axis in which they may be effective in the stabilization of structure (Table 1).

Related literature top

For related structures, see Gowda et al. (2009a,b,c); Prasad et al. (2002).

Experimental top

A solution of maleic andydride (10 g, 0.1 mol) in dichloromethane (50 ml) was added dropwise to an ice-cold solution of phenylmethanamine (10.7 g,0.1 mol) in dichloromethane (50 ml). After the addition was complete (1.5 h), the resulting suspension was stirred at ambient temperature for 20 h. A white solid was collected and washed twice with ether to give the crude product. This crude soild was partitioned between a saturated NaHCO₃ solution and ether. The aqueous fraction was brought to pH = 1–2 with 5 N HCl in an ice bath then extracted with a (1:l) EtOAc-THF mixture. The combined organic layers were dried with Na₂SO₄, filtered and concentrated to give (Z)-4-(benzylamino)-4-oxobut-2-enoic acid as a white solid. The product was purified by repeated crystallization from methanol. Crystals of the title compound, suitable for X-ray diffraction, were obtained by slow evaporation from a solution in methanol.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Crystal packing of the title compound. Dashed lines indicate hydrogen bonds.

(Z)-3-(Benzylcarbamoyl)prop-2-enoic acid top

Crystal data top

C₁₁H₁₁NO₃	F(000) = 432
M_r = 205.21	D_x = 1.288 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.651 (2) Å	θ = 9–12°
b = 12.601 (3) Å	µ = 0.10 mm⁻¹
c = 8.3130 (17) Å	T = 298 K
β = 108.44 (3)°	Block, colorless
V = 1058.4 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1013 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 25.3°, θ_min = 2.0°
ω/2θ scans	h = −12→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
T_min = 0.972, T_max = 0.991	l = −9→9
2018 measured reflections	3 standard reflections every 200 reflections
1913 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.175	w = 1/[σ²(F_o²) + (0.078P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1913 reflections	Δρ_max = 0.17 e Å⁻³
137 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.030 (5)

Crystal data top

C₁₁H₁₁NO₃	V = 1058.4 (4) Å³
M_r = 205.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.651 (2) Å	µ = 0.10 mm⁻¹
b = 12.601 (3) Å	T = 298 K
c = 8.3130 (17) Å	0.30 × 0.20 × 0.10 mm
β = 108.44 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1013 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.022
T_min = 0.972, T_max = 0.991	3 standard reflections every 200 reflections
2018 measured reflections	intensity decay: 1%
1913 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.175	H-atom parameters constrained
S = 1.00	Δρ_max = 0.17 e Å⁻³
1913 reflections	Δρ_min = −0.16 e Å⁻³
137 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
N	0.6963 (2)	0.4593 (2)	0.1087 (3)	0.0537 (7)
H0A	0.6678	0.5211	0.1242	0.064*
O1	0.6741 (2)	0.28274 (17)	0.1283 (3)	0.0636 (7)
C1	1.0039 (4)	0.3602 (3)	0.2253 (6)	0.0904 (14)
H1A	0.9678	0.2962	0.1767	0.108*
O2	0.3695 (2)	0.17148 (18)	0.3280 (3)	0.0750 (8)
C2	1.1254 (4)	0.3611 (4)	0.3536 (7)	0.1015 (16)
H2A	1.1693	0.2975	0.3903	0.122*
O3	0.5270 (2)	0.15868 (18)	0.2112 (3)	0.0669 (7)
H3B	0.5786	0.2005	0.1821	0.100*
C3	1.1799 (4)	0.4531 (4)	0.4250 (6)	0.0853 (13)
H3A	1.2611	0.4532	0.5106	0.102*
C4	1.1149 (4)	0.5457 (4)	0.3707 (6)	0.0871 (13)
H4A	1.1519	0.6097	0.4188	0.104*
C5	0.9942 (4)	0.5450 (3)	0.2443 (5)	0.0754 (11)
H5A	0.9505	0.6088	0.2085	0.090*
C6	0.9377 (3)	0.4525 (3)	0.1707 (4)	0.0547 (9)
C7	0.8043 (3)	0.4522 (3)	0.0365 (4)	0.0621 (10)
H7A	0.7989	0.5117	−0.0394	0.074*
H7B	0.7946	0.3876	−0.0296	0.074*
C8	0.6403 (3)	0.3750 (2)	0.1514 (4)	0.0491 (8)
C9	0.5356 (3)	0.3986 (3)	0.2282 (4)	0.0500 (8)
H9A	0.5219	0.4702	0.2440	0.060*
C10	0.4586 (3)	0.3320 (3)	0.2777 (4)	0.0522 (8)
H10A	0.3995	0.3648	0.3235	0.063*
C11	0.4498 (4)	0.2143 (3)	0.2731 (4)	0.0556 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0488 (16)	0.0458 (15)	0.0658 (18)	0.0025 (13)	0.0169 (14)	0.0026 (13)
O1	0.0654 (15)	0.0463 (13)	0.0842 (17)	0.0078 (12)	0.0306 (13)	−0.0028 (12)
C1	0.064 (2)	0.062 (3)	0.134 (4)	0.000 (2)	0.016 (3)	−0.001 (2)
O2	0.0792 (17)	0.0585 (15)	0.094 (2)	−0.0142 (14)	0.0373 (16)	0.0101 (14)
C2	0.068 (3)	0.083 (3)	0.141 (4)	0.014 (2)	0.014 (3)	0.025 (3)
O3	0.0856 (18)	0.0436 (13)	0.0764 (16)	−0.0009 (12)	0.0326 (15)	0.0007 (12)
C3	0.066 (3)	0.109 (4)	0.078 (3)	0.001 (3)	0.020 (2)	−0.001 (3)
C4	0.077 (3)	0.086 (3)	0.097 (3)	−0.011 (3)	0.025 (3)	−0.027 (3)
C5	0.070 (2)	0.061 (3)	0.088 (3)	0.002 (2)	0.014 (2)	−0.003 (2)
C6	0.0485 (19)	0.055 (2)	0.065 (2)	−0.0001 (17)	0.0250 (17)	0.0034 (18)
C7	0.059 (2)	0.066 (2)	0.067 (2)	−0.0028 (18)	0.0293 (19)	0.0036 (18)
C8	0.0486 (19)	0.0436 (18)	0.0496 (19)	0.0012 (16)	0.0075 (15)	−0.0011 (15)
C9	0.055 (2)	0.0375 (17)	0.057 (2)	0.0008 (15)	0.0162 (17)	−0.0012 (15)
C10	0.058 (2)	0.0462 (18)	0.054 (2)	0.0006 (17)	0.0205 (17)	0.0011 (16)
C11	0.061 (2)	0.0463 (19)	0.053 (2)	−0.0039 (19)	0.0084 (17)	0.0024 (17)

Geometric parameters (Å, º) top

N—C8	1.320 (4)	C3—H3A	0.9300
N—C7	1.459 (4)	C4—C5	1.379 (5)
N—H0A	0.8600	C4—H4A	0.9300
O1—C8	1.250 (3)	C5—C6	1.365 (5)
C1—C6	1.361 (5)	C5—H5A	0.9300
C1—C2	1.392 (6)	C6—C7	1.503 (4)
C1—H1A	0.9300	C7—H7A	0.9700
O2—C11	1.216 (4)	C7—H7B	0.9700
C2—C3	1.347 (6)	C8—C9	1.480 (4)
C2—H2A	0.9300	C9—C10	1.327 (4)
O3—C11	1.304 (4)	C9—H9A	0.9300
O3—H3B	0.8501	C10—C11	1.485 (4)
C3—C4	1.360 (6)	C10—H10A	0.9300

C8—N—C7	122.9 (3)	C1—C6—C7	121.0 (3)
C8—N—H0A	118.5	C5—C6—C7	120.9 (3)
C7—N—H0A	118.5	N—C7—C6	112.2 (3)
C6—C1—C2	120.5 (4)	N—C7—H7A	109.2
C6—C1—H1A	119.8	C6—C7—H7A	109.2
C2—C1—H1A	119.8	N—C7—H7B	109.2
C3—C2—C1	120.7 (4)	C6—C7—H7B	109.2
C3—C2—H2A	119.6	H7A—C7—H7B	107.9
C1—C2—H2A	119.6	O1—C8—N	122.1 (3)
C11—O3—H3B	108.9	O1—C8—C9	123.1 (3)
C2—C3—C4	119.3 (4)	N—C8—C9	114.8 (3)
C2—C3—H3A	120.4	C10—C9—C8	129.1 (3)
C4—C3—H3A	120.4	C10—C9—H9A	115.5
C3—C4—C5	120.1 (4)	C8—C9—H9A	115.5
C3—C4—H4A	120.0	C9—C10—C11	131.6 (3)
C5—C4—H4A	120.0	C9—C10—H10A	114.2
C6—C5—C4	121.3 (4)	C11—C10—H10A	114.2
C6—C5—H5A	119.3	O2—C11—O3	121.0 (3)
C4—C5—H5A	119.3	O2—C11—C10	118.7 (3)
C1—C6—C5	118.1 (4)	O3—C11—C10	120.3 (3)

C6—C1—C2—C3	−0.4 (7)	C1—C6—C7—N	98.2 (4)
C1—C2—C3—C4	0.1 (7)	C5—C6—C7—N	−80.0 (4)
C2—C3—C4—C5	0.3 (7)	C7—N—C8—O1	−1.9 (5)
C3—C4—C5—C6	−0.3 (6)	C7—N—C8—C9	177.9 (3)
C2—C1—C6—C5	0.4 (6)	O1—C8—C9—C10	−3.0 (5)
C2—C1—C6—C7	−177.9 (4)	N—C8—C9—C10	177.2 (3)
C4—C5—C6—C1	−0.1 (6)	C8—C9—C10—C11	−0.3 (5)
C4—C5—C6—C7	178.2 (4)	C9—C10—C11—O2	179.7 (3)
C8—N—C7—C6	−89.9 (4)	C9—C10—C11—O3	−0.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O1	0.85	1.61	2.461 (3)	178
N—H0A···O2ⁱ	0.86	2.00	2.855 (3)	171
C9—H9A···O3ⁱ	0.93	2.48	3.413 (4)	177

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁NO₃
M_r	205.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.651 (2), 12.601 (3), 8.3130 (17)
β (°)	108.44 (3)
V (Å³)	1058.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.972, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2018, 1913, 1013
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.175, 1.00
No. of reflections	1913
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O1	0.85	1.61	2.461 (3)	178
N—H0A···O2ⁱ	0.86	2.00	2.855 (3)	171
C9—H9A···O3ⁱ	0.93	2.48	3.413 (4)	177

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support. They also thank the Natural Science Foundation of Jiangsu Province of China (BK2008195) and the Science Research Foundation of Huaiyin Institute of Technology (2517045).

References

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