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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3315.
Published online 2010 November 27. doi:  10.1107/S1600536810048075
PMCID: PMC3011555

Piperazine-2,3,5,6-tetra­one

Abstract

The mol­ecule of the title compound, C4H2N2O4, is located around an inversion center and the four O atoms are in the 2,3,5,6-positions of the piperazine ring. In the crystal, bifurcated N—H(...)O hydrogen bonds link the mol­ecules into a corrugated layer parallel to (101).

Related literature

For the synthesis of tetra­one, see: Norcross et al. (2008 [triangle]). For related structures, see Sletten et al. (1970 [triangle], 1980 [triangle]); Sarangarajan et al. (2005 [triangle]); Norcross et al. (2008 [triangle]); Jin et al. (1998 [triangle]); Sanner et al. (1992 [triangle]); Ongania et al. (1985 [triangle]).

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Object name is e-66-o3315-scheme1.jpg

Experimental

Crystal data

  • C4H2N2O4
  • M r = 142.08
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3315-efi7.jpg
  • a = 5.163 (1) Å
  • b = 8.6220 (17) Å
  • c = 5.6540 (11) Å
  • β = 105.25 (3)°
  • V = 242.83 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.18 mm−1
  • T = 293 K
  • 0.42 × 0.32 × 0.12 mm

Data collection

  • Siemens P4 diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.930, T max = 0.978
  • 1357 measured reflections
  • 438 independent reflections
  • 383 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.092
  • S = 1.23
  • 438 reflections
  • 46 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: XSCANS (Siemens, 1994 [triangle]); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 [triangle]), ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810048075/dn2617sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048075/dn2617Isup2.hkl

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

Acknowledgments

This work was funded by the Guangxi Science Foundation, Guangxi Zhuang Autonomous Region of the People’s Republic of China (grant No. 2010GXNSFD013017).

supplementary crystallographic information

Comment

The synthesis and antitumor activity of some tetraone compounds have been widely studied (Jin et al., 1998; Sanner et al., 1992). Most tetraone compounds were found from a naturally occurring alkaloid in a variety of leguminous plant and tree species, including broom, lupin, gorse, and laburnum(Norcross et al., 2008). As part of our interest in the synthesis of tetraone derivatives, we report here the structure of the title compound.

The molecule of the title compound is located around inversion center and the four O atoms are in the 2,3,5,6 position on the piperazine ring (Fig. 1). The molecule is planar with rms deviation of 0.013Å. The bond distances and angles are similar to those found in related piperazine derivatives (Sletten et al., 1970; Sarangarajan et al., 2005; Sletten et al., 1980; Ongania et al., 1985).

The N—H donor and the C—O acceptor groups participate in the hydrogen bonding forming corrugated layers parallel to the (1 0 1) plane through bifurcated N-H···O hydrogen bonds (Table 1, Fig. 2).

Experimental

For the preparation of the title compound,the 2-mercaptopyrazine (10 mmol,1.1200 g) was dissolved in ethanol (50 ml) at 358 K and a solution of 30% H202 (10 ml) was added. The resulting solution was stirred at 358 K for 4 h, then concentrating at 388 K,until 3 ml solution remained. Colourless-block crystal suitable for X-ray diffraction were obtained by slow evaporation at room temperature after several days in 55% yield.

Refinement

H atom attached to N atom was positioned geometrically and treated as riding on the parent atom with N-H= 0.86 Å and Uiso(H)=1.2Ueq(N).

Figures

Fig. 1.
Molecular view of compound I with the atom labeling scheme. Ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. [Symmetry code: (i) -x+1, -y+1, -z+1]
Fig. 2.
Partial packing view showing the corrugated layer parallel to the (1 0 1) plane. H bonds are shown as dashed lines. [Symmetry codes: (ii) -x+1/2, y-1/2, -z+3/2; (iii) x-1/2, -y+1/2, z+1/2]

Crystal data

C4H2N2O4F(000) = 144
Mr = 142.08Dx = 1.943 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 438 reflections
a = 5.163 (1) Åθ = 4.4–25.3°
b = 8.6220 (17) ŵ = 0.18 mm1
c = 5.6540 (11) ÅT = 293 K
β = 105.25 (3)°Block, colourless
V = 242.83 (8) Å30.42 × 0.32 × 0.12 mm
Z = 2

Data collection

Siemens P4 diffractometer438 independent reflections
Radiation source: fine-focus sealed tube383 reflections with I > 2σ(I)
graphiteRint = 0.024
ω scansθmax = 25.3°, θmin = 4.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −6→6
Tmin = 0.930, Tmax = 0.978k = −10→10
1357 measured reflectionsl = −6→6

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 1.23w = 1/[σ2(Fo2) + (0.0355P)2 + 0.1147P] where P = (Fo2 + 2Fc2)/3
438 reflections(Δ/σ)max < 0.001
46 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = −0.21 e Å3

Special details

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)

xyzUiso*/Ueq
O10.1613 (3)0.55814 (19)0.7646 (3)0.0343 (5)
O20.8069 (3)0.25100 (19)0.6060 (3)0.0342 (5)
N10.4775 (4)0.3995 (2)0.6856 (3)0.0261 (5)
H10.46030.33620.79810.031*
C10.6621 (5)0.3635 (2)0.5614 (4)0.0233 (5)
C20.3169 (4)0.5281 (2)0.6461 (4)0.0233 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0357 (10)0.0355 (10)0.0373 (10)0.0010 (8)0.0197 (9)−0.0034 (8)
O20.0348 (10)0.0268 (9)0.0402 (10)0.0099 (8)0.0086 (8)0.0048 (7)
N10.0330 (11)0.0229 (10)0.0248 (11)0.0004 (9)0.0120 (9)0.0053 (8)
C10.0221 (12)0.0205 (11)0.0256 (12)−0.0019 (10)0.0034 (10)−0.0017 (9)
C20.0224 (12)0.0225 (11)0.0239 (12)−0.0027 (10)0.0042 (10)−0.0038 (9)

Geometric parameters (Å, °)

O1—C21.202 (3)N1—C21.368 (3)
O2—C11.210 (3)N1—H10.8600
N1—C11.360 (3)C1—C2i1.526 (3)
C1—N1—C2125.31 (19)N1—C1—C2i117.28 (19)
C1—N1—H1117.3O1—C2—N1123.3 (2)
C2—N1—H1117.3O1—C2—C1i119.3 (2)
O2—C1—N1123.6 (2)N1—C2—C1i117.35 (18)
O2—C1—C2i119.10 (19)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1ii0.862.483.060 (2)125
N1—H1···O2iii0.862.233.035 (2)157

Symmetry codes: (ii) −x+1/2, y−1/2, −z+3/2; (iii) x−1/2, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2617).

References

  • Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Jin, G. Z., Kim, Y., Chung, J. H., Sok, D. E. & Ahn, B. Z. (1998). Arch. Pharm. (Weinheim), 331, 380–4. [PubMed]
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  • Sanner, M. A., Weigelt, C., Stansberry, M., Killeen, K., Michne, W. F., Kessler, D. W. & Kullnig, R. K. (1992). J. Org. Chem.57, 5264–5268.
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