N-Acryloylphenyl­alanine

Wu, C.-R.; Gao, X.-F.; Wang, H.-B.; Jin, D.; Wang, J.-T.

doi:10.1107/S1600536808020849

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1483

doi:10.1107/S1600536808020849

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N-Acryloylphenylalanine

Cong-Ren Wu,^a Xiao-Feng Gao,^a Hai-Bo Wang,^a ^* Dong Jin ^b and Jin-Tang Wang ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: wjt@njut.edu.cn

(Received 3 July 2008; accepted 6 July 2008; online 12 July 2008)

The title compound, C₁₂H₁₃NO₃, was prepared by the nucleophilic substitution reaction of acryloyl chloride with glycylglycine. In the crystal structure, intermolecular N—H⋯O, O–H⋯O and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₃NO₃
M_r = 219.23
Monoclinic, P 2₁
a = 6.0050 (12) Å
b = 7.5820 (15) Å
c = 12.512 (3) Å
β = 98.58 (3)°
V = 563.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 291 (2) K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.973, T_max = 0.991
1195 measured reflections
1088 independent reflections
940 reflections with I > 2σ(I)
R_int = 0.015
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.161
S = 1.00
1088 reflections
145 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯O2ⁱ	0.86	2.30	3.036 (6)	144
O1—H1B⋯O3ⁱⁱ	0.82	1.84	2.614 (6)	156
C12—H12B⋯O1ⁱⁱⁱ	0.93	2.60	3.178 (8)	121
Symmetry codes: (i) x+1, y, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+1]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808020849/hk2488sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020849/hk2488Isup2.hkl

checkCIF report

Comment top

N-Acryloylphenylalanie is one of the useful synthetic intermediates and free radical addition monomers. The crystal structure determination of the title compound has been carried out in order to elucidate the molecular conformation. We report herein its synthesis and crystal structure.

In the molecule of the title compound (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987).

In the crystal structure, intermolecular N-H···O, O-H···O and C-H···O hydrogen bonds (Table 1) link the molecules into a three dimensional network (Fig. 2), in which they may be effective in stabilization of the structure.

Related literature top

For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, to a well stirred solutions of phenylalanie (2.5 g) in H₂O (30 ml) and sodium hydroxide (0.66 g) in H₂O (5 ml), acryloyl chloride (1.34 ml) containing diphenylpicrylhydrazyl polymerization inhibitor (0.01%) and sodium hydroxide solution (0.66 g) in H₂O (5 ml) were added dropwise simultaneously over a 30 min period and the stirring was continued for another 1 h. The reaction mixture was kept at 273 K in an ice-water bath. The solution was acidified to pH = 2 with HCl (6 N). The resulting solid was filtered off, and crystallized from ethanol (95%) (yield; 61%, m.p.401-403 K).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

N-Acryloylphenylalanine top

Crystal data top

C₁₂H₁₃NO₃	F(000) = 232
M_r = 219.23	D_x = 1.293 Mg m⁻³
Monoclinic, P2₁	Melting point: 402 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.0050 (12) Å	Cell parameters from 25 reflections
b = 7.5820 (15) Å	θ = 10–14°
c = 12.512 (3) Å	µ = 0.09 mm⁻¹
β = 98.58 (3)°	T = 291 K
V = 563.3 (2) Å³	Block, colorless
Z = 2	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	940 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.015
Graphite monochromator	θ_max = 25.2°, θ_min = 1.7°
ω/2θ scans	h = −7→7
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.973, T_max = 0.991	l = 0→14
1195 measured reflections	3 standard reflections every 120 min
1088 independent reflections	intensity decay: none

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)] = 0.062	H-atom parameters constrained
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.06P)² + 0.62P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1088 reflections	Δρ_max = 0.19 e Å⁻³
145 parameters	Δρ_min = −0.19 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.028 (5)

Crystal data top

C₁₂H₁₃NO₃	V = 563.3 (2) Å³
M_r = 219.23	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.0050 (12) Å	µ = 0.09 mm⁻¹
b = 7.5820 (15) Å	T = 291 K
c = 12.512 (3) Å	0.30 × 0.10 × 0.10 mm
β = 98.58 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	940 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.015
T_min = 0.973, T_max = 0.991	3 standard reflections every 120 min
1195 measured reflections	intensity decay: none
1088 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	1 restraint
wR(F²) = 0.161	H-atom parameters constrained
S = 1.01	Δρ_max = 0.19 e Å⁻³
1088 reflections	Δρ_min = −0.19 e Å⁻³
145 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 > 2sigma(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	0.7481 (7)	0.7059 (7)	0.2952 (3)	0.0555 (11)
H0A	0.8730	0.7469	0.2798	0.067*
O1	0.5602 (6)	0.8820 (8)	0.4513 (3)	0.0843 (15)
H1B	0.4871	0.9128	0.4985	0.126*
C1	0.8147 (14)	0.9763 (11)	−0.0922 (6)	0.086 (2)
H1A	0.8611	0.9777	−0.1599	0.103*
O2	0.2165 (6)	0.8618 (7)	0.3516 (3)	0.0700 (11)
C2	0.9519 (13)	1.0469 (10)	−0.0068 (7)	0.084 (2)
H2A	1.0883	1.0979	−0.0164	0.101*
O3	0.5572 (6)	0.4855 (7)	0.3658 (3)	0.0632 (11)
C3	0.8883 (9)	1.0423 (9)	0.0922 (5)	0.0699 (16)
H3A	0.9839	1.0857	0.1517	0.084*
C4	0.6681 (9)	0.9687 (8)	0.1060 (4)	0.0592 (13)
C5	0.5445 (10)	0.8933 (9)	0.0224 (4)	0.0670 (15)
H5A	0.4140	0.8336	0.0325	0.080*
C6	0.6059 (12)	0.9014 (10)	−0.0818 (5)	0.0801 (19)
H6A	0.5110	0.8584	−0.1417	0.096*
C7	0.5920 (12)	0.9795 (10)	0.2154 (5)	0.0743 (17)
H7A	0.4576	1.0520	0.2085	0.089*
H7B	0.7079	1.0400	0.2642	0.089*
C8	0.5411 (10)	0.8052 (8)	0.2676 (4)	0.0608 (15)
H8A	0.4362	0.7369	0.2159	0.073*
C9	0.4281 (9)	0.8489 (9)	0.3655 (4)	0.0634 (15)
C10	0.7431 (9)	0.5410 (8)	0.3477 (3)	0.0566 (14)
C11	0.9502 (11)	0.4520 (10)	0.3691 (4)	0.0701 (18)
H11A	1.0794	0.5112	0.3564	0.084*
C12	0.9710 (12)	0.2919 (10)	0.4055 (6)	0.083 (2)
H12A	0.8446	0.2297	0.4189	0.099*
H12B	1.1124	0.2392	0.4183	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.055 (2)	0.065 (3)	0.049 (2)	−0.007 (2)	0.0183 (18)	−0.002 (2)
O1	0.076 (3)	0.118 (4)	0.066 (2)	−0.021 (3)	0.033 (2)	−0.036 (3)
C1	0.118 (5)	0.070 (4)	0.076 (4)	0.005 (5)	0.036 (4)	0.008 (4)
O2	0.0515 (19)	0.084 (3)	0.078 (2)	0.001 (2)	0.0231 (17)	0.001 (3)
C2	0.093 (5)	0.074 (5)	0.090 (4)	0.000 (4)	0.029 (4)	0.023 (4)
O3	0.0551 (19)	0.090 (3)	0.0452 (18)	−0.009 (2)	0.0088 (14)	0.010 (2)
C3	0.062 (3)	0.074 (4)	0.078 (4)	−0.003 (3)	0.026 (3)	0.000 (3)
C4	0.077 (3)	0.052 (3)	0.052 (3)	0.004 (3)	0.020 (2)	0.005 (3)
C5	0.081 (4)	0.063 (4)	0.059 (3)	−0.003 (3)	0.019 (3)	0.004 (3)
C6	0.116 (5)	0.077 (5)	0.048 (3)	0.001 (4)	0.017 (3)	−0.004 (3)
C7	0.099 (4)	0.066 (4)	0.064 (3)	−0.017 (4)	0.032 (3)	0.002 (3)
C8	0.072 (3)	0.064 (4)	0.048 (3)	−0.012 (3)	0.016 (2)	−0.006 (3)
C9	0.068 (3)	0.068 (4)	0.055 (3)	−0.006 (3)	0.011 (2)	0.010 (3)
C10	0.073 (3)	0.069 (4)	0.030 (2)	0.003 (3)	0.011 (2)	−0.006 (2)
C11	0.083 (4)	0.080 (5)	0.053 (3)	−0.010 (4)	0.031 (3)	−0.014 (3)
C12	0.067 (4)	0.063 (4)	0.115 (6)	0.003 (3)	0.003 (4)	−0.014 (4)

Geometric parameters (Å, º) top

N—C10	1.414 (8)	C4—C7	1.509 (7)
N—C8	1.451 (7)	C5—C6	1.408 (8)
N—H0A	0.8600	C5—H5A	0.9300
O1—C9	1.261 (6)	C6—H6A	0.9300
O1—H1B	0.8200	C7—C8	1.525 (9)
C1—C2	1.358 (11)	C7—H7A	0.9700
C1—C6	1.400 (10)	C7—H7B	0.9700
C1—H1A	0.9300	C8—C9	1.523 (7)
O2—C9	1.261 (6)	C8—H8A	0.9800
C2—C3	1.350 (10)	C10—C11	1.405 (9)
C2—H2A	0.9300	C11—C12	1.296 (10)
O3—C10	1.245 (6)	C11—H11A	0.9300
C3—C4	1.468 (8)	C12—H12A	0.9300
C3—H3A	0.9300	C12—H12B	0.9300
C4—C5	1.319 (8)

C10—N—C8	119.5 (4)	C4—C7—H7A	108.1
C10—N—H0A	120.2	C8—C7—H7A	108.1
C8—N—H0A	120.2	C4—C7—H7B	108.1
C9—O1—H1B	109.5	C8—C7—H7B	108.1
C2—C1—C6	122.2 (6)	H7A—C7—H7B	107.3
C2—C1—H1A	118.9	N—C8—C9	112.9 (5)
C6—C1—H1A	118.9	N—C8—C7	109.4 (5)
C3—C2—C1	119.4 (7)	C9—C8—C7	107.3 (5)
C3—C2—H2A	120.3	N—C8—H8A	109.0
C1—C2—H2A	120.3	C9—C8—H8A	109.0
C2—C3—C4	120.0 (6)	C7—C8—H8A	109.0
C2—C3—H3A	120.0	O2—C9—O1	126.5 (5)
C4—C3—H3A	120.0	O2—C9—C8	117.8 (5)
C5—C4—C3	118.8 (5)	O1—C9—C8	115.4 (5)
C5—C4—C7	122.2 (5)	O3—C10—C11	126.5 (6)
C3—C4—C7	119.0 (5)	O3—C10—N	117.7 (5)
C4—C5—C6	121.4 (6)	C11—C10—N	115.7 (5)
C4—C5—H5A	119.3	C12—C11—C10	123.6 (7)
C6—C5—H5A	119.3	C12—C11—H11A	118.2
C1—C6—C5	117.7 (6)	C10—C11—H11A	118.2
C1—C6—H6A	121.1	C11—C12—H12A	120.0
C5—C6—H6A	121.1	C11—C12—H12B	120.0
C4—C7—C8	116.7 (6)	H12A—C12—H12B	120.0

C6—C1—C2—C3	1.3 (12)	C10—N—C8—C7	178.2 (4)
C1—C2—C3—C4	−2.8 (11)	C4—C7—C8—N	67.3 (7)
C2—C3—C4—C5	6.2 (10)	C4—C7—C8—C9	−169.9 (5)
C2—C3—C4—C7	−174.7 (7)	N—C8—C9—O2	−149.5 (6)
C3—C4—C5—C6	−8.0 (10)	C7—C8—C9—O2	89.9 (7)
C7—C4—C5—C6	172.9 (7)	N—C8—C9—O1	35.8 (8)
C2—C1—C6—C5	−2.9 (12)	C7—C8—C9—O1	−84.9 (7)
C4—C5—C6—C1	6.5 (10)	C8—N—C10—O3	1.8 (6)
C5—C4—C7—C8	58.1 (9)	C8—N—C10—C11	178.5 (4)
C3—C4—C7—C8	−121.1 (7)	O3—C10—C11—C12	4.3 (9)
C10—N—C8—C9	58.7 (6)	N—C10—C11—C12	−172.1 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O2ⁱ	0.86	2.30	3.036 (6)	144
O1—H1B···O3ⁱⁱ	0.82	1.84	2.614 (6)	156
C12—H12B···O1ⁱⁱⁱ	0.93	2.60	3.178 (8)	121

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃NO₃
M_r	219.23
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	291
a, b, c (Å)	6.0050 (12), 7.5820 (15), 12.512 (3)
β (°)	98.58 (3)
V (Å³)	563.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	1195, 1088, 940
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.161, 1.01
No. of reflections	1088
No. of parameters	145
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.19

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), 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
N—H0A···O2ⁱ	0.86	2.30	3.036 (6)	144
O1—H1B···O3ⁱⁱ	0.82	1.84	2.614 (6)	156
C12—H12B···O1ⁱⁱⁱ	0.93	2.60	3.178 (8)	121

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar