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ISSN: 2056-9890

N-(2-Formamido­eth­yl)formamide

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[Yang, J. H., Yu, J. G., Feng, Y. & Ma, X. F. (2007). Carbohydr. Polym. pp. 197-203.]). For related structures, see: Goss et al. (1996[Goss, J. D., Folting, C. R., Santarsiero, K. B. D. & Hollingsworth, M. D. (1996). J. Am. Chem. Soc. pp. 9432-9433.]). For graph-set notation, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]); Etter et al. (1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]).

[Scheme 1]

Experimental

Crystal data
  • C4H8N2O2

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA.]) Tmin = 0.964, Tmax = 0.982

  • 2736 measured reflections

  • 467 independent reflections

  • 431 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.15 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]), ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97.

Supporting information


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)
Confocal monochromatorRint = 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
467 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
431 reflections with I > 2σ(I)
Tmin = 0.964, Tmax = 0.982Rint = 0.035
2736 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.073H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.21 e Å3
467 reflectionsΔρmin = 0.15 e Å3
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
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, º) 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 code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1ii0.844 (15)2.062 (16)2.8570 (13)156.9 (12)
Symmetry code: (ii) x+1/2, y+1, z1/2.

Experimental details

Crystal data
Chemical formulaC4H8N2O2
Mr116.12
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)113
a, b, c (Å)8.7138 (17), 6.6714 (13), 9.3162 (19)
V3)541.58 (19)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.32 × 0.26 × 0.16
Data collection
DiffractometerRigaku Saturn
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.964, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
2736, 467, 431
Rint0.035
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.073, 1.11
No. of reflections467
No. of parameters40
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1A···O1i0.844 (15)2.062 (16)2.8570 (13)156.9 (12)
Symmetry code: (i) x+1/2, y+1, z1/2.
 

References

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBurnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
First citationEtter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationGoss, J. D., Folting, C. R., Santarsiero, K. B. D. & Hollingsworth, M. D. (1996). J. Am. Chem. Soc. pp. 9432–9433.  Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationYang, J. H., Yu, J. G., Feng, Y. & Ma, X. F. (2007). Carbohydr. Polym. pp. 197–203.  CAS Google Scholar

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ISSN: 2056-9890
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