N-Acryloyl glycinamide

Jan Seuring; Seema Agarwal; Klaus Harms

doi:10.1107/S1600536811029758

. 2011 Jul 30;67(Pt 8):o2170. doi: 10.1107/S1600536811029758

N-Acryloyl glycinamide

Jan Seuring ^a, Seema Agarwal ^a,^*, Klaus Harms ^a,^*

PMCID: PMC3213605 PMID: 22091182

Abstract

The molecule of the title compound [systematic name: N-(carbamoylmethyl)prop-2-enamide], C₅H₈N₂O₂, which can be radically polymerized to polymers with thermoresponsive behavior in aqueous solution, consists of linked essentially planar acrylamide and amide segments [maximum deviations = 0.054 (1) and 0.009 (1) Å] with an angle of 81.36 (7)° between their mean planes. In the crystal, N—H⋯O hydrogen bonding leads to an infinite two-dimensional network along (100).

Related literature

For the first preparation of the title compound, see: Haas & Schuler (1964 ▶). For the properties of polymers of the title compound in aquous solution, see: Haas et al. (1967 ▶, 1970a ▶,b ▶,c ▶,d ▶); Marstokk et al. (1998 ▶); Nagaoka et al. (2007 ▶); Ohnishi et al. (2007 ▶); Seuring & Agarwal (2010 ▶); Glatzel et al. (2010 ▶). For the structure of the related compound, 2-(2-acrylamidoacetamido)acetic acid monohydrate, see Gao et al. (2007 ▶).

Experimental

Crystal data

C₅H₈N₂O₂
M _r = 128.13
Monoclinic,
a = 15.938 (2) Å
b = 4.8055 (4) Å
c = 8.4920 (12) Å
β = 98.109 (11)°
V = 643.91 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.23 × 0.19 × 0.09 mm

Data collection

Stoe IPDS 2T diffractometer
Absorption correction: integration (X-RED; Stoe & Cie, 2006 ▶) T _min = 0.991, T _max = 0.997
6001 measured reflections
1362 independent reflections
1065 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.085
S = 0.97
1362 reflections
115 parameters
All H-atom parameters refined
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2006 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2007 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶), PLATON (Spek, 2009 ▶) and WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811029758/sj5179sup1.cif

e-67-o2170-sup1.cif^{(14.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811029758/sj5179Isup2.hkl

e-67-o2170-Isup2.hkl^{(65.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811029758/sj5179Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯O4ⁱ	0.850 (19)	2.062 (19)	2.8946 (14)	166.3 (15)
N8—H8B⋯O9ⁱⁱ	0.881 (17)	2.081 (17)	2.9494 (14)	168.2 (15)
N8—H8A⋯O9ⁱⁱⁱ	0.927 (18)	1.971 (18)	2.8855 (14)	168.6 (16)

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We acknowledge financial support from Philipps-Universität Marburg, Germany.

supplementary crystallographic information

Comment

N-acryloyl glycinamide was first synthesized by Haas and Schuler (1964). It can be polymerized radically to obtain polymers that exhibit thermoresponsive behavior in aqueous solution. The polymers show gelatin-like thermoreversible gelation (Haas & Schuler, 1964; Haas et al., 1967, 1970a, 1970b, 1970c, 1970d; Marstokk et al., 1998; Seuring & Agarwal, 2010; Glatzel et al., 2010) and an upper critical solution temperature (Seuring & Agarwal, 2010; Ohnishi et al., 2007; Nagaoka et al., 2007) in water. These phenomena rely on intermolecular hydrogen bonding. Therefore, investigating the intermolecular hydrogen bonding between monomer units in the crystal may contribute to the understanding of interpolymer interactions.

The molecular structure of the title compound shows two planar parts with C1, C2, C3, O4, N5, C6 and C6, C7, N8, O9 in plane. The angle between these mean planes is 81.36 (7)°. In the packing the molecule forms three hydrogen bonds to three different neighbouring molecules. For details see Table 1. The intermolecular N5—H5···O4ⁱ contacts form an infinite chain in the (0 1 0) direction. Two of these chains are linked via N8—H8A···O9ⁱⁱⁱ and N8—H8B···O9ⁱⁱ interactions, respectively (symmetry codes: (i) x, y + 1, z; (ii) -x + 1, y - 1/2, -z + 3/2; (iii) x, -y + 1/2, z + 1/2). Herein the N8—H8A···O9ⁱⁱⁱ hydrogen bonds form a second chain with direction (0 0 1), and hydrogen bonded rings are generated. In conclusion, a two dimensional hydrogen bond network has been formed with the hydrophobic tails of the molecules as border planes.

For the crystal structure of a related compound, 2-(2-acrylamidoacetamido)acetic acid monohydrate, see Gao et al. (2007).

Experimental

N-acryloyl glycinamide has been prepared according to the route of Haas and Schuler (1964). However, reagent ratios, workup and purification have been modified as follows.

In a 1 l three-necked round-bottom flask equipped with a mechanical stirrer glycinamide hydrochloride (23.11 g, 209 mmol) and potassium carbonate (56.7 g, 410 mmol) were dissolved in 125 ml of water. The solution was cooled in an ice bath and acryloyl chloride (16.65 ml, 205 mmol) dissolved in 250 ml of diethylether was added dropwise over 30 min with fast stirring (300 rpm). The suspension was further stirred at RT for 2 h. The diethylether was removed by rotary evaporation at 35 °C. The remaining aqueous phase was freeze dried. The crude brittle solid was extracted with acetone (6 times, 500 ml acetone, 40 °C, stirring for at least 15 min). Insoluble potassium salts were filtered off and the acetone was removed by rotary evaporation at 35 °C. 22.7 g (85%) of crude product were obtained. The crude product was dissolved in an eluent mixture of methanol and dichloromethane (v/v = 1/4, 600 ml) by heating to reflux once. The solution was filtered to remove polymeric impurities and purified by column chromatography (d = 9 cm, 900 g silica, porosity 60 Å, 0.063–0.2 mm mesh size, TLC: R_f(N-acryloyl glycinamide) = 0.40) to obtain 21.3 g (80%) of product which was recrystallized from 240 ml of a mixture of methanol and acetone (v/v = 1/2) to yield 15.3 g (57%) of colorless needle-like crystals.

For obtaining crystals that are suitable for X-ray analysis a small fraction of purified N-acryloyl glycinamide was again recrystallized from a dilute solution in 2-propanol.