Diethyl pyrazine-2,5-dicarboxyl­ate

Li, C.-H.; Wu, W.-S.; Huang, Y.-M.

doi:10.1107/S1600536812028164

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2236

https://doi.org/10.1107/S1600536812028164

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Diethyl pyrazine-2,5-dicarboxylate

Chuan-Hui Li,^a Wen-Shi Wu ^a ^* and Yu-Min Huang ^a

^aCollege of Materials Science and Engineering, Huaqiao University, Xiamen, Fujian 361021, People's Republic of China
^*Correspondence e-mail: wws@hqu.edu.cn

(Received 17 May 2012; accepted 21 June 2012; online 27 June 2012)

The molecule of the title compound, C₁₀H₁₂N₂O₄, is located around an inversion center. The carboxylate groups are twisted slightly with respect to the pyrazine ring, making a dihedral angle of 2.76 (19)°. In the crystal, molecules are stacked along the c axis via weak C—H⋯O hydrogen bonds.

Related literature

For the structures of related compounds, see: Zhang et al. (2010 ); Cockriel et al. (2008 ).

Experimental

Crystal data

C₁₀H₁₂N₂O₄
M_r = 224.22
Monoclinic, P 2₁ /c
a = 12.284 (6) Å
b = 5.640 (3) Å
c = 7.881 (4) Å
β = 108.713 (9)°
V = 517.2 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 173 K
0.7 × 0.3 × 0.05 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.960, T_max = 0.994
2994 measured reflections
1317 independent reflections
1055 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.131
S = 1.07
1317 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O2ⁱ	0.97	2.58	3.537 (3)	168
Symmetry code: (i) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812028164/is5143sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028164/is5143Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812028164/is5143Isup3.cml

checkCIF report

Comment top

The structure of the title compound is illustrated in Fig. 1. The molecule of title compound, C₁₀H₁₂N₂O₄, is essentially planar and the carboxylate groups are twisted slightly with respect to the pyrazine ring, making a dihedral angle of 2.76 (19)°. The carboxyl C—O and C═O bonds are normal, while the bond angle of C—N═C are slightly larger than those in diisopropyl pyrazine-2,5-dicarboxylate (Zhang et al., 2010). The angle C3—O1—C4 of 116.05° is larger compared to the value of 115.05° in pyrazine-2,5-dicarboxylic acid dimethyl ester (Cockriel et al., 2008). The crystal structure is stabilized via van der Waals forces and week C—H···O hydrogen bonds (Fig. 2 and Table 1).

Related literature top

For the structures of related compounds, see: Zhang et al. (2010); Cockriel et al. (2008).

Experimental top

The title compound was synthesized by dissolving 2,5-pyrazinedicarboxylic acid (2 g, 11.9 mmol) in 200 ml ethanol, while stirring 2 ml concentrated H₂SO₄ was added slowly. The solution was left to reflux for 12 h, then distillation under reduced pressure until no solution to outflow. The solution was made neutral with Na₂CO₃(aq), extracted with 30 ml ethyl acetate. Transparent crystals of the title compound were obtained by slow evaporation at room temperature for ten days.

Structure description top

For the structures of related compounds, see: Zhang et al. (2010); Cockriel et al. (2008).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure (at 30% probability) of the title compound. [Symmetry code: (A) 1 - x, -y, 1 - z].
	Fig. 2. Packing diagram of the title complex, showing hydrogen bonds as dashed lines. [Symmetry code: (A) x, -0.5 - y, 0.5 + z].

Diethyl pyrazine-2,5-dicarboxylate top

Crystal data top

C₁₀H₁₂N₂O₄	F(000) = 236.0
M_r = 224.22	D_x = 1.440 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2994 reflections
a = 12.284 (6) Å	θ = 4.0–28.5°
b = 5.640 (3) Å	µ = 0.11 mm⁻¹
c = 7.881 (4) Å	T = 173 K
β = 108.713 (9)°	Plate, colourless
V = 517.2 (5) Å³	0.7 × 0.3 × 0.05 mm
Z = 2

Data collection top

Bruker SMART diffractometer	1317 independent reflections
Radiation source: fine-focus sealed tube	1055 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 28.5°, θ_min = 4.0°
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	h = −16→14
T_min = 0.960, T_max = 0.994	k = −5→7
2994 measured reflections	l = −10→10

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0606P)² + 0.1472P] where P = (F_o² + 2F_c²)/3
1317 reflections	(Δ/σ)_max < 0.001
73 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₀H₁₂N₂O₄	V = 517.2 (5) Å³
M_r = 224.22	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.284 (6) Å	µ = 0.11 mm⁻¹
b = 5.640 (3) Å	T = 173 K
c = 7.881 (4) Å	0.7 × 0.3 × 0.05 mm
β = 108.713 (9)°

Data collection top

Bruker SMART diffractometer	1317 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	1055 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.994	R_int = 0.031
2994 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.07	Δρ_max = 0.21 e Å⁻³
1317 reflections	Δρ_min = −0.31 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
N1	0.46961 (11)	−0.2315 (2)	0.52651 (18)	0.0275 (3)
O1	0.26007 (9)	0.0921 (2)	0.64425 (16)	0.0308 (3)
O2	0.28072 (11)	−0.3005 (2)	0.63126 (19)	0.0401 (4)
C1	0.41208 (12)	−0.0450 (3)	0.55512 (19)	0.0241 (3)
C2	0.44174 (13)	0.1860 (3)	0.5289 (2)	0.0265 (4)
H2A	0.3986	0.3110	0.5507	0.032*
C3	0.31162 (13)	−0.1030 (3)	0.6147 (2)	0.0265 (4)
C4	0.16106 (15)	0.0568 (3)	0.7018 (3)	0.0359 (4)
H4A	0.1848	0.0010	0.8247	0.043*
H4B	0.1102	−0.0605	0.6266	0.043*
C5	0.10095 (15)	0.2883 (3)	0.6871 (2)	0.0377 (4)
H5A	0.0725	0.3356	0.5636	0.057*
H5B	0.1537	0.4058	0.7549	0.057*
H5C	0.0378	0.2732	0.7333	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0314 (7)	0.0174 (6)	0.0369 (7)	−0.0001 (5)	0.0154 (6)	0.0002 (5)
O1	0.0289 (6)	0.0234 (6)	0.0457 (7)	0.0012 (4)	0.0199 (5)	0.0006 (5)
O2	0.0450 (8)	0.0234 (7)	0.0617 (9)	−0.0062 (5)	0.0307 (6)	−0.0005 (6)
C1	0.0256 (7)	0.0211 (8)	0.0256 (7)	−0.0009 (6)	0.0080 (6)	−0.0005 (6)
C2	0.0304 (8)	0.0184 (7)	0.0328 (8)	0.0014 (6)	0.0132 (6)	0.0000 (6)
C3	0.0284 (8)	0.0212 (8)	0.0304 (8)	−0.0010 (6)	0.0104 (6)	0.0007 (6)
C4	0.0330 (9)	0.0337 (9)	0.0493 (10)	0.0000 (7)	0.0247 (8)	0.0048 (8)
C5	0.0330 (9)	0.0410 (11)	0.0450 (10)	0.0046 (7)	0.0208 (8)	0.0018 (8)

Geometric parameters (Å, º) top

N1—C2ⁱ	1.322 (2)	C2—H2A	0.9300
N1—C1	1.326 (2)	C4—C5	1.486 (3)
O1—C3	1.3270 (19)	C4—H4A	0.9700
O1—C4	1.442 (2)	C4—H4B	0.9700
O2—C3	1.197 (2)	C5—H5A	0.9600
C1—C2	1.386 (2)	C5—H5B	0.9600
C1—C3	1.490 (2)	C5—H5C	0.9600

C2ⁱ—N1—C1	116.31 (14)	O1—C4—H4A	110.2
C3—O1—C4	116.04 (13)	C5—C4—H4A	110.2
N1—C1—C2	122.69 (14)	O1—C4—H4B	110.2
N1—C1—C3	114.83 (14)	C5—C4—H4B	110.2
C2—C1—C3	122.47 (14)	H4A—C4—H4B	108.5
N1ⁱ—C2—C1	121.00 (15)	C4—C5—H5A	109.5
N1ⁱ—C2—H2A	119.5	C4—C5—H5B	109.5
C1—C2—H2A	119.5	H5A—C5—H5B	109.5
O2—C3—O1	124.49 (15)	C4—C5—H5C	109.5
O2—C3—C1	124.19 (15)	H5A—C5—H5C	109.5
O1—C3—C1	111.31 (13)	H5B—C5—H5C	109.5
O1—C4—C5	107.59 (14)

C2ⁱ—N1—C1—C2	0.1 (3)	N1—C1—C3—O2	−2.3 (2)
C2ⁱ—N1—C1—C3	179.07 (13)	C2—C1—C3—O2	176.70 (16)
N1—C1—C2—N1ⁱ	−0.1 (3)	N1—C1—C3—O1	178.63 (13)
C3—C1—C2—N1ⁱ	−178.99 (14)	C2—C1—C3—O1	−2.4 (2)
C4—O1—C3—O2	0.6 (2)	C3—O1—C4—C5	−167.24 (14)
C4—O1—C3—C1	179.71 (13)

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
C4—H4A···O2ⁱⁱ	0.97	2.58	3.537 (3)	168

Symmetry code: (ii) x, −y−1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₄
M_r	224.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	12.284 (6), 5.640 (3), 7.881 (4)
β (°)	108.713 (9)
V (Å³)	517.2 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.7 × 0.3 × 0.05

Data collection
Diffractometer	Bruker SMART
Absorption correction	Multi-scan (SADABS; Sheldrick,1996)
T_min, T_max	0.960, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	2994, 1317, 1055
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.131, 1.07
No. of reflections	1317
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.31

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), 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
C4—H4A···O2ⁱ	0.97	2.58	3.537 (3)	168

Symmetry code: (i) x, −y−1/2, z+1/2.

Acknowledgements

The authors are grateful for financial support from the National Science Foundation of Fujian Province of China (No. 2010 J01288) and the Fundamental Research Funds for the Central Universities (No. JB-JC1003).

References

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