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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.

Supporting information


Crystallographic Information File (CIF)
Contains datablocks I, global


Structure factor file (CIF format)
Contains datablock I

CCDC reference: 712424

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.042
  • wR factor = 0.107
  • Data-to-parameter ratio = 17.3

checkCIF/PLATON results

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Alert level G PLAT793_ALERT_4_G The Model has Chirality at C1 (Verify) .... R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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).

Related literature top

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

Experimental top

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 top

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).

Computing details top

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

Figures top
[Figure 1] 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.
[Figure 2] Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
(1R,2S)-1,2-Dihydroxy-1,2-diformamidoethane top
Crystal data top
C4H8N2O4F(000) = 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 = 3–30°
b = 7.2634 (12) ŵ = 0.15 mm1
c = 12.772 (2) ÅT = 120 K
V = 603.59 (17) Å3Prism, colourless
Z = 40.20 × 0.20 × 0.15 mm
Data collection top
Bruker SMART 1000 CCD area-detector
662 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
Graphite monochromatorθmax = 29.0°, θmin = 3.2°
ϕ and ω scansh = 88
5931 measured reflectionsk = 99
796 independent reflectionsl = 1717
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)] = 0.042Hydrogen site location: mixed
wR(F2) = 0.107H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0499P)2 + 0.531P]
where P = (Fo2 + 2Fc2)/3
796 reflections(Δ/σ)max < 0.001
46 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C4H8N2O4V = 603.59 (17) Å3
Mr = 148.12Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 6.5065 (11) ŵ = 0.15 mm1
b = 7.2634 (12) ÅT = 120 K
c = 12.772 (2) Å0.20 × 0.20 × 0.15 mm
Data collection top
Bruker SMART 1000 CCD area-detector
662 reflections with I > 2σ(I)
5931 measured reflectionsRint = 0.031
796 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.00Δρmax = 0.41 e Å3
796 reflectionsΔρmin = 0.24 e Å3
46 parameters
Special details top

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) top
N10.07678 (19)0.16658 (16)0.39820 (9)0.0180 (3)
O10.25095 (15)0.06643 (13)0.45643 (7)0.0193 (3)
O20.07384 (16)0.05127 (14)0.23276 (7)0.0207 (3)
C10.0424 (2)0.01985 (18)0.44519 (10)0.0164 (3)
C20.1269 (2)0.16978 (19)0.29690 (10)0.0178 (3)
Atomic displacement parameters (Å2) top
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, º) top
N1—C21.3344 (17)O2—C21.2374 (17)
N1—C11.4483 (17)C1—C1i1.532 (3)
O1—C11.4056 (16)C2—H2A0.9500
C2—N1—C1123.06 (11)O1—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—O199.08 (15)C1—N1—C2—O21.6 (2)
C2—N1—C1—C1i141.93 (15)
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
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) x1/2, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC4H8N2O4
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)120
a, b, c (Å)6.5065 (11), 7.2634 (12), 12.772 (2)
V3)603.59 (17)
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.20 × 0.20 × 0.15
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5931, 796, 662
(sin θ/λ)max1)0.682
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.107, 1.00
No. of reflections796
No. of parameters46
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.41, 0.24

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldricr, 2008).

Hydrogen-bond geometry (Å, º) top
N1—H1N···O1i0.882.042.9093 (16)170
O1—H1O···O2ii0.861.812.6740 (14)175
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x1/2, y, z+1/2.

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