Piperazine-2,3,5,6-tetra­one

Jia, J.-J.; Meng, X.-J.; Liang, S.-Z.; Zhang, S.-H.; Jiang, Y.-M.

doi:10.1107/S1600536810048075

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3315

https://doi.org/10.1107/S1600536810048075

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ADDENDA AND ERRATA

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Piperazine-2,3,5,6-tetraone

Jing-Jing Jia,^a ^* Xiu-Jin Meng,^a Shi-Zhang Liang,^a Shu-Hua Zhang ^b and Yi-Min Jiang ^a

^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 ). 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

Crystal data

C₄H₂N₂O₄
M_r = 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 ) 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[F² > 2σ(F²)] = 0.048
wR(F²) = 0.092
S = 1.23
438 reflections
46 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: XSCANS; data reduction: XSCANS; 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).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810048075/dn2617Isup2.hkl

checkCIF report

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.

Structure description 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) .

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

	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]

Piperazine-2,3,5,6-tetraone top

Crystal data top

C₄H₂N₂O₄	F(000) = 144
M_r = 142.08	D_x = 1.943 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 438 reflections
a = 5.163 (1) Å	θ = 4.4–25.3°
b = 8.6220 (17) Å	µ = 0.18 mm⁻¹
c = 5.6540 (11) Å	T = 293 K
β = 105.25 (3)°	Block, colourless
V = 242.83 (8) Å³	0.42 × 0.32 × 0.12 mm
Z = 2

Data collection top

Siemens P4 diffractometer	438 independent reflections
Radiation source: fine-focus sealed tube	383 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 25.3°, θ_min = 4.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.930, T_max = 0.978	k = −10→10
1357 measured reflections	l = −6→6

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.23	w = 1/[σ²(F_o²) + (0.0355P)² + 0.1147P] where P = (F_o² + 2F_c²)/3
438 reflections	(Δ/σ)_max < 0.001
46 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₄H₂N₂O₄	V = 242.83 (8) Å³
M_r = 142.08	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.163 (1) Å	µ = 0.18 mm⁻¹
b = 8.6220 (17) Å	T = 293 K
c = 5.6540 (11) Å	0.42 × 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)
T_min = 0.930, T_max = 0.978	R_int = 0.024
1357 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.23	Δρ_max = 0.20 e Å⁻³
438 reflections	Δρ_min = −0.21 e Å⁻³
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

	x	y	z	U_iso*/U_eq
O1	0.1613 (3)	0.55814 (19)	0.7646 (3)	0.0343 (5)
O2	0.8069 (3)	0.25100 (19)	0.6060 (3)	0.0342 (5)
N1	0.4775 (4)	0.3995 (2)	0.6856 (3)	0.0261 (5)
H1	0.4603	0.3362	0.7981	0.031*
C1	0.6621 (5)	0.3635 (2)	0.5614 (4)	0.0233 (5)
C2	0.3169 (4)	0.5281 (2)	0.6461 (4)	0.0233 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0357 (10)	0.0355 (10)	0.0373 (10)	0.0010 (8)	0.0197 (9)	−0.0034 (8)
O2	0.0348 (10)	0.0268 (9)	0.0402 (10)	0.0099 (8)	0.0086 (8)	0.0048 (7)
N1	0.0330 (11)	0.0229 (10)	0.0248 (11)	0.0004 (9)	0.0120 (9)	0.0053 (8)
C1	0.0221 (12)	0.0205 (11)	0.0256 (12)	−0.0019 (10)	0.0034 (10)	−0.0017 (9)
C2	0.0224 (12)	0.0225 (11)	0.0239 (12)	−0.0027 (10)	0.0042 (10)	−0.0038 (9)

Geometric parameters (Å, º) top

O1—C2	1.202 (3)	N1—C2	1.368 (3)
O2—C1	1.210 (3)	N1—H1	0.8600
N1—C1	1.360 (3)	C1—C2ⁱ	1.526 (3)

C1—N1—C2	125.31 (19)	N1—C1—C2ⁱ	117.28 (19)
C1—N1—H1	117.3	O1—C2—N1	123.3 (2)
C2—N1—H1	117.3	O1—C2—C1ⁱ	119.3 (2)
O2—C1—N1	123.6 (2)	N1—C2—C1ⁱ	117.35 (18)
O2—C1—C2ⁱ	119.10 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.86	2.48	3.060 (2)	125
N1—H1···O2ⁱⁱⁱ	0.86	2.23	3.035 (2)	157

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

Experimental details

Crystal data
Chemical formula	C₄H₂N₂O₄
M_r	142.08
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	5.163 (1), 8.6220 (17), 5.6540 (11)
β (°)	105.25 (3)
V (Å³)	242.83 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.42 × 0.32 × 0.12

Data collection
Diffractometer	Siemens P4
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.930, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	1357, 438, 383
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.092, 1.23
No. of reflections	438
No. of parameters	46
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.48	3.060 (2)	125.4
N1—H1···O2ⁱⁱ	0.86	2.23	3.035 (2)	157.0

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

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