meso-3,6-Dioxopiperazine-2,5-diacet­amide

Li, P.; Zhang, C.; Xu, W.

doi:10.1107/S1600536811043376

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3041

doi:10.1107/S1600536811043376

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meso-3,6-Dioxopiperazine-2,5-diacetamide

Ping Li,^a Chun Zhang ^a and Wei Xu ^a ^*

^aCenter of Applied Solid State Chemistry Research, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
^*Correspondence e-mail: xuwei@nbu.edu.cn

(Received 7 September 2011; accepted 19 October 2011; online 29 October 2011)

The title compound, C₈H₁₂N₄O₄, was obtained by cyclization of the two L-asparagine molecules and reveals a crystallographic inversion symmetry, and accordingly the two stereogenic centres are of opposite chirality. Thus, an asymmetric unit comprises a half of a molecule. The molecules are assembled into a three-dimensional hydrogen-bonding network by N—H⋯O hydrogen bonds.

Related literature

For general background to coordination polymers, see: Anitha et al. (2005 ); Aarthy et al. (2005 ); Guenifa et al. (2009 ); Moussa Slimane et al. (2009 ). For related structures, see: Howes et al. (1983 ).

Experimental

Crystal data

C₈H₁₂N₄O₄
M_r = 228.22
Monoclinic, P 2₁ /c
a = 5.0409 (10) Å
b = 8.3178 (17) Å
c = 12.900 (3) Å
β = 109.76 (3)°
V = 509.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.10 × 0.10 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.988, T_max = 0.988
4836 measured reflections
1166 independent reflections
889 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.098
S = 1.07
1166 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	2.12	2.9185 (19)	154
N1—H1B⋯O2ⁱⁱ	0.86	2.03	2.8795 (18)	167
N2—H2C⋯O1ⁱⁱⁱ	0.86	2.06	2.8509 (17)	152
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x+1, y, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811043376/kp2350sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043376/kp2350Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811043376/kp2350Isup3.cml

checkCIF report

Comment top

The past decade has witnessed enormous expansion of research on non-centrosymmetric coordination polymers. For such purpose, rational design and synthesis have been focused on choices of metal cations with non-centrosymmetric organic ligands. Asparagine (Anitha et al., (2005); Aarthy et al., (2005); Guenifa et al., (2009); Moussa Slimane et al., (2009)) is a chiral molecule and one of the common neutral amino acids with carboxamide as the side-chain functional group. However, condensation led to a centrosyymmetric compound and we report its crystal structure.

In (I) (Fig. 1), two L–asparagine molecules engage in the dehydration condensation between each carboxyl and the adjacent amino groups. The resulting product reveals the molecular symmetry C_i (crystallographic inversion symmetry). In (I) a piperazinedione-2,5 unit is close to be planar (the mean value of intracyclic torsion angles is 2.65 °) and it is different to those reported by (Howes et al., (1983)). The molecules are connected through N1–H1A···O2ⁱ, N1–H1B···O2ⁱⁱ, and N2–H2C···O1ⁱⁱⁱ hydrogen bonds generating a 3D-network (Table 1, Figs. 2 and 3.

Related literature top

For general background to coordination polymers, see: Anitha et al. (2005); Aarthy et al. (2005); Guenifa et al. (2009); Moussa Slimane et al. (2009). For related structures, see: Howes et al. (1983).

Experimental top

Dropwise addition of 1 M NaOH (1.0 mL) to a stirred aqueous solution of (0.1438 g, 0.5 mmol) ZnSO₄.7H₂O in 5.0 mL H₂O produced pale-white Zn(OH)₂.xH₂O precipitate, which was separated by centrifugation and washed with distilled water for several times. Subsequently, the 0.1501 g (1.0 mmol) L–asparagine was dissolved completely with 10.0 mL H₂O, and then the precipitate was added. The resulting mixture was further stirred at 323 K for 1 h and then filtered. The white filtrate was allowed to stand at room temperature. Slow evaporation for several days afforded colourless needle-like crystals.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of the title compound. The dispalcement ellipsoids are drawn at 45% probability dispalcement ellipsoids. [Symmetry codes: (i)–x+1, -y, –z+1.]
	Fig. 2. Packing diagram of the title crystal structure viewed down along [010] direction with N2-H2C···O1 hydrogen bond motif.
	Fig. 3. Packing diagram of the title crystal viewed down the a axis shows 3D-hydrogen bond network. N–H···O hydrogen bonds are shown as dashed lines.

3,6-Dioxopiperazine-2,5-diacetamide top

Crystal data top

C₈H₁₂N₄O₄	F(000) = 240
M_r = 228.22	D_x = 1.489 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3368 reflections
a = 5.0409 (10) Å	θ = 3.4–27.4°
b = 8.3178 (17) Å	µ = 0.12 mm⁻¹
c = 12.900 (3) Å	T = 293 K
β = 109.76 (3)°	Needle, colourless
V = 509.0 (2) Å³	0.10 × 0.10 × 0.10 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	1166 independent reflections
Radiation source: fine-focus sealed tube	889 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
ω scans	h = −6→5
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
T_min = 0.988, T_max = 0.988	l = −16→16
4836 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0415P)² + 0.146P] where P = (F_o² + 2F_c²)/3
1166 reflections	(Δ/σ)_max < 0.001
73 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₈H₁₂N₄O₄	V = 509.0 (2) Å³
M_r = 228.22	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.0409 (10) Å	µ = 0.12 mm⁻¹
b = 8.3178 (17) Å	T = 293 K
c = 12.900 (3) Å	0.10 × 0.10 × 0.10 mm
β = 109.76 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1166 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	889 reflections with I > 2σ(I)
T_min = 0.988, T_max = 0.988	R_int = 0.028
4836 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.07	Δρ_max = 0.24 e Å⁻³
1166 reflections	Δρ_min = −0.16 e Å⁻³
73 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

	x	y	z	U_iso*/U_eq
O1	0.0282 (2)	−0.01262 (16)	0.31172 (9)	0.0483 (4)
O2	0.2805 (3)	0.29340 (13)	0.49666 (9)	0.0482 (3)
N1	0.0676 (4)	0.0393 (2)	0.14760 (11)	0.0580 (5)
H1A	−0.0736	−0.0213	0.1141	0.070*
H1B	0.1561	0.0889	0.1107	0.070*
N2	0.6588 (2)	−0.04206 (14)	0.43619 (9)	0.0316 (3)
H2C	0.7546	−0.0678	0.3948	0.038*
C1	0.1482 (3)	0.05588 (18)	0.25545 (11)	0.0320 (3)
C2	0.3991 (3)	0.16430 (17)	0.30689 (11)	0.0300 (3)
H2A	0.3353	0.2749	0.3022	0.036*
H2B	0.5274	0.1554	0.2656	0.036*
C3	0.5568 (3)	0.12212 (17)	0.42763 (11)	0.0289 (3)
H3A	0.7224	0.1923	0.4531	0.035*
C4	0.3792 (3)	0.15646 (18)	0.49910 (11)	0.0307 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0425 (6)	0.0752 (9)	0.0326 (6)	−0.0194 (6)	0.0199 (5)	−0.0009 (5)
O2	0.0730 (8)	0.0412 (6)	0.0366 (6)	0.0250 (6)	0.0267 (6)	0.0066 (5)
N1	0.0743 (11)	0.0739 (11)	0.0270 (7)	−0.0402 (9)	0.0185 (7)	−0.0063 (7)
N2	0.0336 (6)	0.0399 (7)	0.0266 (6)	0.0094 (5)	0.0172 (5)	0.0028 (5)
C1	0.0331 (7)	0.0392 (8)	0.0267 (7)	0.0000 (6)	0.0140 (6)	0.0016 (6)
C2	0.0347 (7)	0.0327 (7)	0.0261 (7)	−0.0005 (6)	0.0150 (6)	0.0024 (6)
C3	0.0292 (7)	0.0322 (7)	0.0268 (7)	−0.0005 (6)	0.0116 (6)	−0.0003 (6)
C4	0.0329 (7)	0.0364 (7)	0.0227 (7)	0.0067 (6)	0.0093 (6)	0.0003 (6)

Geometric parameters (Å, º) top

O1—C1	1.2304 (17)	C1—C2	1.512 (2)
O2—C4	1.2392 (17)	C2—C3	1.5309 (19)
N1—C1	1.3182 (19)	C2—H2A	0.9700
N1—H1A	0.8599	C2—H2B	0.9700
N1—H1B	0.8599	C3—C4	1.5135 (19)
N2—C4ⁱ	1.3219 (18)	C3—H3A	0.9800
N2—C3	1.4502 (18)	C4—N2ⁱ	1.3219 (18)
N2—H2C	0.8599

C1—N1—H1A	119.9	C1—C2—H2B	109.1
C1—N1—H1B	120.1	C3—C2—H2B	109.1
H1A—N1—H1B	120.0	H2A—C2—H2B	107.9
C4ⁱ—N2—C3	127.05 (12)	N2—C3—C4	113.51 (11)
C4ⁱ—N2—H2C	116.4	N2—C3—C2	110.01 (11)
C3—N2—H2C	116.5	C4—C3—C2	111.46 (11)
O1—C1—N1	122.47 (14)	N2—C3—H3A	107.2
O1—C1—C2	121.49 (13)	C4—C3—H3A	107.2
N1—C1—C2	116.05 (13)	C2—C3—H3A	107.2
C1—C2—C3	112.30 (12)	O2—C4—N2ⁱ	122.34 (13)
C1—C2—H2A	109.1	O2—C4—C3	118.24 (13)
C3—C2—H2A	109.1	N2ⁱ—C4—C3	119.39 (12)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱ	0.86	2.12	2.9185 (19)	154
N1—H1B···O2ⁱⁱⁱ	0.86	2.03	2.8795 (18)	167
N2—H2C···O1^iv	0.86	2.06	2.8509 (17)	152

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N₄O₄
M_r	228.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.0409 (10), 8.3178 (17), 12.900 (3)
β (°)	109.76 (3)
V (Å³)	509.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.988, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	4836, 1166, 889
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.098, 1.07
No. of reflections	1166
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.16

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.12	2.9185 (19)	154.0
N1—H1B···O2ⁱⁱ	0.86	2.03	2.8795 (18)	167.3
N2—H2C···O1ⁱⁱⁱ	0.86	2.06	2.8509 (17)	151.8

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

Acknowledgements

This project was supported by the Scientific Reaearch Fund of Zhejiang Provincial Education Department (grant No. Y201017782). Thanks are also extended to the K. C. Wong Magna Fund of Ningbo University.

References

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