Acta Cryst. (2008). E64, o2418 [ doi:10.1107/S1600536808038488 ]
The complete molecule of the title compound, C4H8N2O2, is generated by a crystallographic inversion center. The occurence of N-H
O hydrogen bonds results in the formation of a two-dimensional infinite network parallel to the (010) plane. In this plane, the hydrogen bonds define graph-set motif R44(22) in a centrosymmetric array by the association of four molecules.
Methyl formate (500 ml) was placed in a 1000 ml flask cooled by ice-bath and ethylenediamine (250 ml) was slowly added. Subsequently, ice-bath was removed and the mixture was refluxed for 10 h. After standing overnight, the product was isolated by filtration. The solids obtained by filtration were recrystallized from anhydrous ethyl alcohol in 95% yield. Colorless crystals of N-(2-Formylaminoethyl)formamide were obtained by slow evaporation of a solution of anhydrous methyl alcohol at 278 k(m.p. 381 k).
The N-bound H atoms were located in a difference map and freely refined with Uiso(H) = 1.2 Ueq(N)], H atoms attached to carbon were positioned geometrically and treated as riding on their parent atoms [C—H distances are 0.93 Å for CH and 0.97 Å for CH2 groups, both with Uiso(H) = 1.2 Ueq(C)].
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./dn2396fig1thm.gif)
| Fig. 1. A view of the molecular structure of (I) with the atom-labeling scheme. Displacement ellopsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code:(i) 1-x, 1-y, 1-z ] |
![[Figure 2]](./dn2396fig2thm.gif)
| Fig. 2. Partial packing view showing the formation of the two dimensional network through N-H···O hydrogen bonds which are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry code: (i) -x+1/2, -y+1, z-1/2] |
| C4H8N2O2 | F(000) = 248 |
| Mr = 116.12 | Dx = 1.424 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 1513 reflections |
| a = 8.7138 (17) Å | θ = 3.1–27.8° |
| b = 6.6714 (13) Å | µ = 0.12 mm−1 |
| c = 9.3162 (19) Å | T = 113 K |
| V = 541.58 (19) Å3 | Block, colorless |
| Z = 4 | 0.32 × 0.26 × 0.16 mm |
| Rigaku Saturn diffractometer | 467 independent reflections |
| Radiation source: rotating anode | 431 reflections with I > 2σ(I) |
| confocal | Rint = 0.035 |
| ω scans | θmax = 25.0°, θmin = 4.4° |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | h = −10→7 |
| Tmin = 0.964, Tmax = 0.982 | k = −7→7 |
| 2736 measured reflections | l = −9→11 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.11 | w = 1/[σ2(Fo2) + (0.0378P)2 + 0.1199P] where P = (Fo2 + 2Fc2)/3 |
| 467 reflections | (Δ/σ)max < 0.001 |
| 40 parameters | Δρmax = 0.21 e Å−3 |
| 0 restraints | Δρmin = −0.15 e Å−3 |
| C4H8N2O2 | V = 541.58 (19) Å3 |
| Mr = 116.12 | Z = 4 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 8.7138 (17) Å | µ = 0.12 mm−1 |
| b = 6.6714 (13) Å | T = 113 K |
| c = 9.3162 (19) Å | 0.32 × 0.26 × 0.16 mm |
| Rigaku Saturn diffractometer | 431 reflections with I > 2σ(I) |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | Rint = 0.035 |
| Tmin = 0.964, Tmax = 0.982 | θmax = 25.0° |
| 2736 measured reflections | Standard reflections: 0 |
| 467 independent reflections |
| R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.073 | Δρmax = 0.21 e Å−3 |
| S = 1.11 | Δρmin = −0.15 e Å−3 |
| 467 reflections | Absolute structure: ? |
| 40 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.26367 (12) | 0.50564 (15) | 0.69236 (11) | 0.0165 (3) | |
| H1 | 0.1616 | 0.4744 | 0.7110 | 0.020* | |
| C2 | 0.45751 (11) | 0.59669 (16) | 0.51762 (12) | 0.0158 (3) | |
| H2A | 0.5102 | 0.6659 | 0.5948 | 0.019* | |
| H2B | 0.4575 | 0.6835 | 0.4341 | 0.019* | |
| N1 | 0.30073 (10) | 0.55554 (13) | 0.56027 (10) | 0.0160 (3) | |
| H1A | 0.2325 (15) | 0.5444 (19) | 0.4965 (17) | 0.019* | |
| O1 | 0.35499 (8) | 0.49743 (11) | 0.79307 (8) | 0.0209 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0155 (5) | 0.0165 (6) | 0.0175 (6) | 0.0003 (4) | 0.0024 (5) | −0.0025 (4) |
| C2 | 0.0170 (6) | 0.0170 (6) | 0.0133 (6) | −0.0011 (4) | 0.0004 (4) | 0.0009 (4) |
| N1 | 0.0140 (5) | 0.0196 (5) | 0.0143 (5) | 0.0010 (4) | −0.0027 (3) | −0.0015 (4) |
| O1 | 0.0200 (4) | 0.0288 (5) | 0.0139 (5) | −0.0006 (3) | −0.0002 (3) | 0.0012 (3) |
| C1—O1 | 1.2314 (13) | C2—C2i | 1.523 (2) |
| C1—N1 | 1.3151 (14) | C2—H2A | 0.9700 |
| C1—H1 | 0.9300 | C2—H2B | 0.9700 |
| C2—N1 | 1.4490 (15) | N1—H1A | 0.844 (15) |
| O1—C1—N1 | 124.44 (10) | N1—C2—H2B | 109.5 |
| O1—C1—H1 | 117.8 | C2i—C2—H2B | 109.5 |
| N1—C1—H1 | 117.8 | H2A—C2—H2B | 108.0 |
| N1—C2—C2i | 110.91 (11) | C1—N1—C2 | 122.41 (9) |
| N1—C2—H2A | 109.5 | C1—N1—H1A | 117.6 (9) |
| C2i—C2—H2A | 109.5 | C2—N1—H1A | 119.2 (9) |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1ii | 0.844 (15) | 2.062 (16) | 2.8570 (13) | 156.9 (12) |
| Symmetry codes: (ii) −x+1/2, −y+1, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1i | 0.844 (15) | 2.062 (16) | 2.8570 (13) | 156.9 (12) |
| Symmetry codes: (i) −x+1/2, −y+1, z−1/2. |
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N-(2-Formylaminoethyl)formamide is a plasticizer to prepare thermoplastic starch. The mechanical properties of N-(2-Formylaminoethyl)formamide plasticized starch were enhanced compared with the conventional glycerol plasticized one (Yang,et al., 2007).
The molecule of (I) has a center of symmetry at the mid-point of the central C2—C2i bond (Fig. 1).
Intermolecular N—H···O hydrogen bonds link the molecule to form a two dimensionnal network parallel to the (0 1 0) plane. In this plane, the hydrogen bonds define rings by associating 4 molécules displaying graph set motif R44(21) (Etter et al., 1990; Bernstein et al., 1995).
Therefore, the OH group of the starch can also form intermolecular O—H···O hydrogen bonds with the N-(2-Formylaminoethyl)formamide, the mechanical properties of the plasticized starch is then enhanced.