supplementary materials


Acta Cryst. (2008). E64, o2418    [ doi:10.1107/S1600536808038488 ]

N-(2-Formamidoethyl)formamide

J. Yang, Y. Chen, S. Wang and J. Wang

Abstract top

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.

Comment top

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.

Related literature top

For general background, see: Yang et al. (2007). For related structures, see: Goss et al. (1996). For graph-set notation, see: Bernstein et al. (1995); Etter et al. (1990).

Experimental top

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).

Refinement top

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)].

Computing details top

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).

Figures top
[Figure 1] 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] 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]
N-(2-Formamidoethyl)formamide top
Crystal data top
C4H8N2O2F(000) = 248
Mr = 116.12Dx = 1.424 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1513 reflections
a = 8.7138 (17) Åθ = 3.1–27.8°
b = 6.6714 (13) ŵ = 0.12 mm1
c = 9.3162 (19) ÅT = 113 K
V = 541.58 (19) Å3Block, colorless
Z = 40.32 × 0.26 × 0.16 mm
Data collection top
Rigaku Saturn
diffractometer
467 independent reflections
Radiation source: rotating anode431 reflections with I > 2σ(I)
confocalRint = 0.035
ω scansθmax = 25.0°, θmin = 4.4°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
h = 107
Tmin = 0.964, Tmax = 0.982k = 77
2736 measured reflectionsl = 911
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H 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 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C4H8N2O2V = 541.58 (19) Å3
Mr = 116.12Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 8.7138 (17) ŵ = 0.12 mm1
b = 6.6714 (13) ÅT = 113 K
c = 9.3162 (19) Å0.32 × 0.26 × 0.16 mm
Data collection top
Rigaku Saturn
diffractometer
431 reflections with I > 2σ(I)
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
Rint = 0.035
Tmin = 0.964, Tmax = 0.982θmax = 25.0°
2736 measured reflectionsStandard reflections: 0
467 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073Δρmax = 0.21 e Å3
S = 1.11Δρmin = 0.15 e Å3
467 reflectionsAbsolute structure: ?
40 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.26367 (12)0.50564 (15)0.69236 (11)0.0165 (3)
H10.16160.47440.71100.020*
C20.45751 (11)0.59669 (16)0.51762 (12)0.0158 (3)
H2A0.51020.66590.59480.019*
H2B0.45750.68350.43410.019*
N10.30073 (10)0.55554 (13)0.56027 (10)0.0160 (3)
H1A0.2325 (15)0.5444 (19)0.4965 (17)0.019*
O10.35499 (8)0.49743 (11)0.79307 (8)0.0209 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0155 (5)0.0165 (6)0.0175 (6)0.0003 (4)0.0024 (5)0.0025 (4)
C20.0170 (6)0.0170 (6)0.0133 (6)0.0011 (4)0.0004 (4)0.0009 (4)
N10.0140 (5)0.0196 (5)0.0143 (5)0.0010 (4)0.0027 (3)0.0015 (4)
O10.0200 (4)0.0288 (5)0.0139 (5)0.0006 (3)0.0002 (3)0.0012 (3)
Geometric parameters (Å, °) top
C1—O11.2314 (13)C2—C2i1.523 (2)
C1—N11.3151 (14)C2—H2A0.9700
C1—H10.9300C2—H2B0.9700
C2—N11.4490 (15)N1—H1A0.844 (15)
O1—C1—N1124.44 (10)N1—C2—H2B109.5
O1—C1—H1117.8C2i—C2—H2B109.5
N1—C1—H1117.8H2A—C2—H2B108.0
N1—C2—C2i110.91 (11)C1—N1—C2122.41 (9)
N1—C2—H2A109.5C1—N1—H1A117.6 (9)
C2i—C2—H2A109.5C2—N1—H1A119.2 (9)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1ii0.844 (15)2.062 (16)2.8570 (13)156.9 (12)
Symmetry codes: (ii) −x+1/2, −y+1, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.844 (15)2.062 (16)2.8570 (13)156.9 (12)
Symmetry codes: (i) −x+1/2, −y+1, z−1/2.
Acknowledgements top

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references
References top

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.

Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Goss, J. D., Folting, C. R., Santarsiero, K. B. D. & Hollingsworth, M. D. (1996). J. Am. Chem. Soc. pp. 9432–9433.

Rigaku (2005). CrystalClear and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. CrystalStructureis not mentioned anywhere else in CIF; omit it here?

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Yang, J. H., Yu, J. G., Feng, Y. & Ma, X. F. (2007). Carbohydr. Polym. pp. 197–203.