Acta Cryst. (2008). E64, o1483 [ doi:10.1107/S1600536808020849 ]
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-HO and C-HO hydrogen bonds link the molecules into a three-dimensional network.
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).
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 Uiso(H) = xUeq(C,N,O), where x = 1.5 for OH H and x = 1.2 for all other H atoms.
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).
![[Figure 1]](./hk2488fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./hk2488fig2thm.gif)
| Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. |
| C12H13NO3 | F000 = 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 = 10–14º |
| c = 12.512 (3) Å | µ = 0.09 mm−1 |
| β = 98.58 (3)º | T = 291 (2) K |
| V = 563.3 (2) Å3 | Block, colorless |
| Z = 2 | 0.30 × 0.10 × 0.10 mm |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.015 |
| Radiation source: fine-focus sealed tube | θmax = 25.2º |
| Monochromator: graphite | θmin = 1.7º |
| T = 291(2) K | h = −7→7 |
| ω/2θ scans | k = 0→9 |
| Absorption correction: ψ scan (North et al., 1968) | l = 0→14 |
| Tmin = 0.973, Tmax = 0.991 | 3 standard reflections |
| 1195 measured reflections | every 120 min |
| 1088 independent reflections | intensity decay: none |
| 940 reflections with I > 2σ(I) |
| 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(Fo2) + (0.06P)2 + 0.62P] where P = (Fo2 + 2Fc2)/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) |
| C12H13NO3 | V = 563.3 (2) Å3 |
| Mr = 219.23 | Z = 2 |
| Monoclinic, P21 | Mo Kα |
| a = 6.0050 (12) Å | µ = 0.09 mm−1 |
| b = 7.5820 (15) Å | T = 291 (2) K |
| c = 12.512 (3) Å | 0.30 × 0.10 × 0.10 mm |
| β = 98.58 (3)º |
| Enraf–Nonius CAD-4 diffractometer | 940 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.015 |
| Tmin = 0.973, Tmax = 0.991 | 3 standard reflections |
| 1195 measured reflections | every 120 min |
| 1088 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.062 | H-atom parameters constrained |
| wR(F2) = 0.161 | Δρmax = 0.19 e Å−3 |
| S = 1.01 | Δρmin = −0.19 e Å−3 |
| 1088 reflections | Absolute structure: ? |
| 145 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
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. |
| 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* |
| 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) |
| 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) |
| 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. |
| 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. |
The authors thank the Center of Testing and Analysis, Nanjing University, for support.
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.
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
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.