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Piperazine-2,3,5,6-tetra­one

aCollege of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin, Guangxi 541004, People's Republic of China, and bCollege of Chemistry and Bioengineering, Guilin University of Technology, Guilin, Guangxi 541004, People's Republic of China
*Correspondence e-mail: 19768069@qq.com

(Received 2 November 2010; accepted 18 November 2010; online 27 November 2010)

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[Norcross, N. R., Melbardis, J. P., Solera, M. F., Sephton, M. A., Kilner, C., Zakharov, L. N., Astles, P. C., Warriner, S. L. & Blakemore, P. R. (2008). J. Org. Chem. 73, 7939-7951.]). For related structures, see Sletten et al. (1970[Sletten, E. (1970). J. Am. Chem. Soc. 92, 172-177.], 1980[Sletten, J. (1980). Acta Chem. Scand. Ser. A, 34, 593-595.]); Sarangarajan et al. (2005[Sarangarajan, T. R., Panchanatheswaran, K., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o118-o121.]); Norcross et al. (2008[Norcross, N. R., Melbardis, J. P., Solera, M. F., Sephton, M. A., Kilner, C., Zakharov, L. N., Astles, P. C., Warriner, S. L. & Blakemore, P. R. (2008). J. Org. Chem. 73, 7939-7951.]); Jin et al. (1998[Jin, G. Z., Kim, Y., Chung, J. H., Sok, D. E. & Ahn, B. Z. (1998). Arch. Pharm. (Weinheim), 331, 380-4.]); Sanner et al. (1992[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.]); Ongania et al. (1985[Ongania, K. H., Granozzi, G., Busetti, V., Casarin, M. & Ajò, D. (1985). Tetrahedron, 41, 2015-2018.]).

[Scheme 1]

Experimental

Crystal data
  • C4H2N2O4

  • Mr = 142.08

  • Monoclinic, P 21 /n

  • 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.930, Tmax = 0.978

  • 1357 measured reflections

  • 438 independent reflections

  • 383 reflections with I > 2σ(I)

  • Rint = 0.024

Refinement
  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 0.86 2.48 3.060 (2) 125
N1—H1⋯O2ii 0.86 2.23 3.035 (2) 157
Symmetry codes: (i) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: XSCANS (Siemens, 1994[Siemens (1994). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: XSCANS; data reduction: XSCANS; 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, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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).

Structure description top

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).

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

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS (Siemens, 1994); data reduction: XSCANS (Siemens, 1994); 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, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] 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]
[Figure 2] 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]
Piperazine-2,3,5,6-tetraone top
Crystal data top
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 top
Siemens P4
diffractometer
438 independent reflections
Radiation source: fine-focus sealed tube383 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω scansθmax = 25.3°, θmin = 4.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 66
Tmin = 0.930, Tmax = 0.978k = 1010
1357 measured reflectionsl = 66
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 1.23 w = 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
Crystal data top
C4H2N2O4V = 242.83 (8) Å3
Mr = 142.08Z = 2
Monoclinic, P21/nMo Kα radiation
a = 5.163 (1) ŵ = 0.18 mm1
b = 8.6220 (17) ÅT = 293 K
c = 5.6540 (11) Å0.42 × 0.32 × 0.12 mm
β = 105.25 (3)°
Data collection top
Siemens P4
diffractometer
438 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
383 reflections with I > 2σ(I)
Tmin = 0.930, Tmax = 0.978Rint = 0.024
1357 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 1.23Δρmax = 0.20 e Å3
438 reflectionsΔρmin = 0.21 e Å3
46 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
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) top
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, º) top
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 code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
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, y1/2, z+3/2; (iii) x1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC4H2N2O4
Mr142.08
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)5.163 (1), 8.6220 (17), 5.6540 (11)
β (°) 105.25 (3)
V3)242.83 (8)
Z2
Radiation typeMo Kα
µ (mm1)0.18
Crystal size (mm)0.42 × 0.32 × 0.12
Data collection
DiffractometerSiemens P4
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.930, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
1357, 438, 383
Rint0.024
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.092, 1.23
No. of reflections438
No. of parameters46
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.21

Computer programs: XSCANS (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.483.060 (2)125.4
N1—H1···O2ii0.862.233.035 (2)157.0
Symmetry codes: (i) x+1/2, y1/2, z+3/2; (ii) x1/2, y+1/2, z+1/2.
 

Acknowledgements

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

References

First citationBurnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
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First citationSanner, M. A., Weigelt, C., Stansberry, M., Killeen, K., Michne, W. F., Kessler, D. W. & Kullnig, R. K. (1992). J. Org. Chem. 57, 5264–5268.  CSD CrossRef CAS Web of Science Google Scholar
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First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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