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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2316.
Published online 2008 November 13. doi:  10.1107/S1600536808036209
PMCID: PMC2959978

(1R,2S)-N,N′-(1,2-Dihydroxy­ethyl­ene)diformamide

Abstract

The asymmetric unit of the title compound, C4H8N2O4, contains one half-mol­ecule which is completed via a crystallographic inversion centre. In the crystal structure, mol­ecules are arranged in undulating layers parallel to (001). Inter­molecular N—H(...)O and O—H(...)O hydrogen bonds consolidate this arrangement.

Related literature

The title compound has been synthesized as a by-product of a procedure described by Sidney et al. (1965 [triangle]) and Ferguson (1968a [triangle],b [triangle]). For related literature regarding the synthesis, see: Mitsch (1965 [triangle]). For the application of the inter­mediates, see: Ramakrishnan et al. (1990 [triangle]); Vedachalam et al. (1991 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-o2316-scheme1.jpg

Experimental

Crystal data

  • C4H8N2O4
  • M r = 148.12
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2316-efi1.jpg
  • a = 6.5065 (11) Å
  • b = 7.2634 (12) Å
  • c = 12.772 (2) Å
  • V = 603.59 (17) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.15 mm−1
  • T = 120 (2) K
  • 0.20 × 0.20 × 0.15 mm

Data collection

  • Bruker SMART 1000 CCD area-detector diffractometer
  • Absorption correction: none
  • 5931 measured reflections
  • 796 independent reflections
  • 662 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.107
  • S = 1.00
  • 796 reflections
  • 46 parameters
  • H-atom parameters constrained
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT-Plus (Bruker, 1998 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808036209/wm2200sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808036209/wm2200Isup2.hkl

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

supplementary crystallographic information

Comment

1,4-Diformyl-2,3,5,6-tetrahydroxypiperazine is an important intermediate (Mitsch, 1965) for the preparation of high energetic materials (Ramakrishnan et al. 1990; Vedachalam et al. 1991). The title compound, (I), was obtained as an unexpected by-product during synthesis of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine (Sidney et al., 1965; Ferguson, 1968a,b). In a modified procedure we have synthesized compound (I) in much better yield and present its crystal structure in this communication.

Formally, compound (I) is a derivative of ethane with two hydroxyl and two formyl groups as substitutes of the corresponding H atoms. The asymmetric unit of compound (I) contains one half of the molecule that is completed via an inversion centre, leading to a R,S conformation for the two C atoms (Fig. 1). The bond lengths (Allen et al., 1987) and angles in the molecule are within normal ranges.

In the crystal structure, molecules are arranged in undulated layers parallel to (001). Intermolecular N—H···O and O—H···O hydrogen bonds consolidate this arrangement (Fig. 2 and Table 1).

Experimental

76 mass parts of glyoxal monohydrate were stirred with 90 parts of formamide at room temperature. Then 6 mass parts of sodium bicarbonate were added. After 3 days, the crude crystalline product was washed with cold methanol and was dried, yielding 84.2 mass parts of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine (decomposition temperature 463 K). After filtering off the crystals, the aqueous mother liquor was kept at 273 K for 1 day and 2.2 mass parts of 1,2-dihydroxy-1,2-diformamidoethane were obtained (decomposition temperature 408 - 413 K). Crystals suitable for structure determination were grown by recrystallization from dimethyl sulfoxide (DMSO).

Refinement

H atoms were positioned geometrically, with N—H = 0.88 Å (for NH), O—H = 0.86 Å (for OH) and C—H = 0.95 Å (for the aldehyde group) and and C—H = 1.00 Å (for the aliphatic C atom), and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(N, O, C).

Figures

Fig. 1.
The molecular structure of the title compound, drawn with displacement ellipsoids at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
Fig. 2.
A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C4H8N2O4F000 = 312
Mr = 148.12Dx = 1.630 Mg m3
Orthorhombic, PbcaMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 854 reflections
a = 6.5065 (11) Åθ = 3–30º
b = 7.2634 (12) ŵ = 0.15 mm1
c = 12.772 (2) ÅT = 120 (2) K
V = 603.59 (17) Å3Prism, colourless
Z = 40.20 × 0.20 × 0.15 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer662 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
Monochromator: graphiteθmax = 29.0º
T = 120(2) Kθmin = 3.2º
[var phi] and ω scansh = −8→8
Absorption correction: nonek = −9→9
5931 measured reflectionsl = −17→17
796 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.107  w = 1/[σ2(Fo2) + (0.0499P)2 + 0.531P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
796 reflectionsΔρmax = 0.41 e Å3
46 parametersΔρmin = −0.24 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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)

xyzUiso*/Ueq
N10.07678 (19)0.16658 (16)0.39820 (9)0.0180 (3)
H1N0.11700.25620.43970.022*
O1−0.25095 (15)0.06643 (13)0.45643 (7)0.0193 (3)
H1O−0.31450.06280.39700.023*
O20.07384 (16)0.05127 (14)0.23276 (7)0.0207 (3)
C1−0.0424 (2)0.01985 (18)0.44519 (10)0.0164 (3)
H1A−0.0304−0.09350.40120.020*
C20.1269 (2)0.16978 (19)0.29690 (10)0.0178 (3)
H2A0.20850.26940.27250.021*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0226 (6)0.0168 (5)0.0147 (5)−0.0028 (4)−0.0004 (4)−0.0002 (4)
O10.0165 (5)0.0254 (5)0.0160 (4)0.0025 (4)−0.0025 (4)−0.0020 (4)
O20.0203 (5)0.0258 (5)0.0160 (5)−0.0010 (4)0.0020 (4)−0.0012 (4)
C10.0164 (6)0.0182 (6)0.0146 (6)−0.0005 (5)−0.0003 (5)0.0004 (5)
C20.0168 (6)0.0196 (6)0.0170 (6)0.0025 (5)0.0007 (5)0.0035 (5)

Geometric parameters (Å, °)

N1—C21.3344 (17)O2—C21.2374 (17)
N1—C11.4483 (17)C1—C1i1.532 (3)
N1—H1N0.88C1—H1A1.0000
O1—C11.4056 (16)C2—H2A0.9500
O1—H1O0.86
C2—N1—C1123.06 (11)O1—C1—H1A109.3
C2—N1—H1N119.9N1—C1—H1A109.3
C1—N1—H1N117.0C1i—C1—H1A109.3
C1—O1—H1O111.4O2—C2—N1124.17 (13)
O1—C1—N1112.47 (11)O2—C2—H2A117.9
O1—C1—C1i107.45 (13)N1—C2—H2A117.9
N1—C1—C1i108.91 (13)
C2—N1—C1—O1−99.08 (15)C1—N1—C2—O21.6 (2)
C2—N1—C1—C1i141.93 (15)

Symmetry codes: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O1ii0.882.042.9093 (16)170
O1—H1O···O2iii0.861.812.6740 (14)175

Symmetry codes: (ii) x+1/2, −y+1/2, −z+1; (iii) x−1/2, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2200).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (1998). SMART and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ferguson, A. N. (1968a). US Patent 3 369 020.
  • Ferguson, A. N. (1968b). US Patent 3 365 454.
  • Mitsch, R. A. (1965). J. Am. Chem. Soc.87, 328–333.
  • Ramakrishnan, V. T., Vedachalam, M. & Boyer, J. H. (1990). Heterocycles, 31, 479-480.
  • Sheldrick, G. M. (2008). Acta Cryst A64, 112–122. [PubMed]
  • Sidney, V., Clifford, M. & Barker, R. (1965). J. Org. Chem 30, 1195-1199.
  • Vedachalam, M., Ramakrishnan, V. T., Boyer, H., Dagley, I. J., Nelson, K. A. & Adolph, H. G. (1991). J. Org. Chem.56, 3413–3419.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography