N-Acryloylphenyl­alanine

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.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.063
• wR factor = 0.161
• Data-to-parameter ratio = 7.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.50
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O3     --  C10     ..       5.78 su
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Labels ..........          1

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.18
           From the CIF: _reflns_number_total               1088
           Count of symmetry unique reflns         1095
           Completeness (_total/calc)             99.36%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT791_ALERT_4_G Confirm the Absolute Configuration of C8     ...          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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).

S3. Refinement

H atoms were positioned geometrically, with O-H = 0.82 Å (for OH), N-H = 0.86 Å (for NH) and C-H = 0.93, 0.98 and 0.97 Å for aromatic, methine and methylene H, respectively, and constrained to ride on their parent atoms with U_iso(H) = xU_eq(C,N,O), where x = 1.5 for OH H and x = 1.2 for all other H atoms.

Computing details

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

	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

Crystal data

C12H13NO3	F(000) = 232
Mr = 219.23	Dx = 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) Å^3	Block, colorless
Z = 2	0.30 × 0.10 × 0.10 mm

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.062	H-atom parameters constrained
wR(F^2) = 0.161	w = 1/[σ^2(Fo^2) + (0.06P)^2 + 0.62P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
1088 reflections	Δρmax = 0.19 e Å^−3
145 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O2^i	0.86	2.30	3.036 (6)	144
O1—H1B···O3^ii	0.82	1.84	2.614 (6)	156
C12—H12B···O1^iii	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.