N-(2-Formamido­eth­yl)formamide

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

doi:10.1107/S1600536808038488

organic compounds

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Volume 64| Part 12| December 2008| Page o2418

doi:10.1107/S1600536808038488

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N-(2-Formamidoethyl)formamide

Jin-hui Yang,^a Yan-xue Chen,^b ^* Shao-hui Wang ^a and Jian-lei Wang ^a

^aSchool of Materials Science and Engineering, Shijiazhuang Railway Institute, Shijiazhuang 050043, People's Republic of China, and ^bSchool of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, People's Republic of China
^*Correspondence e-mail: chenyanxue8010@yahoo.com.cn

(Received 22 October 2008; accepted 18 November 2008; online 22 November 2008)

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.

Related literature

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

Crystal data

C₄H₈N₂O₂
M_r = 116.12
Orthorhombic, P b c a
a = 8.7138 (17) Å
b = 6.6714 (13) Å
c = 9.3162 (19) Å
V = 541.58 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 113 (2) K
0.32 × 0.26 × 0.16 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.964, T_max = 0.982
2736 measured reflections
467 independent reflections
431 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.073
S = 1.11
467 reflections
40 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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 code: (i) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038488/dn2396sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038488/dn2396Isup2.hkl

checkCIF report

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).

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

	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 ]
	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

C₄H₈N₂O₂	F(000) = 248
M_r = 116.12	D_x = 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

Data collection top

Rigaku Saturn diffractometer	467 independent reflections
Radiation source: rotating anode	431 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.035
ω scans	θ_max = 25.0°, θ_min = 4.4°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −10→7
T_min = 0.964, T_max = 0.982	k = −7→7
2736 measured reflections	l = −9→11

Refinement top

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(F_o²) + (0.0378P)² + 0.1199P] where P = (F_o² + 2F_c²)/3
467 reflections	(Δ/σ)_max < 0.001
40 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₄H₈N₂O₂	V = 541.58 (19) Å³
M_r = 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

Data collection top

Rigaku Saturn diffractometer	467 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	431 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.982	R_int = 0.035
2736 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.21 e Å⁻³
467 reflections	Δρ_min = −0.15 e Å⁻³
40 parameters

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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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 code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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 code: (ii) −x+1/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₄H₈N₂O₂
M_r	116.12
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	113
a, b, c (Å)	8.7138 (17), 6.6714 (13), 9.3162 (19)
V (Å³)	541.58 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.32 × 0.26 × 0.16

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.964, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	2736, 467, 431
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.11
No. of reflections	467
No. of parameters	40
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.15

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

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 code: (i) −x+1/2, −y+1, z−1/2.

References

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

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2418

doi:10.1107/S1600536808038488

Open

access