Methyl pyrazine-2-carboxyl­ate

Zhang, C.-H.; Tan, X.-J.; Xing, D.-X.

doi:10.1107/S1600536809043451

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2902

https://doi.org/10.1107/S1600536809043451

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Methyl pyrazine-2-carboxylate

Chang-Hua Zhang,^a Xue-Jie Tan ^b ^* and Dian-Xiang Xing ^b

^aDepartment of Chemistry and Chemical Industry, Binzhou University, Binzhou, Shandong Province 256600, People's Republic of China, and ^bDepartment of Chemical Industry, Shandong Institute of Light Industry, Jinan 250353, People's Republic of China
^*Correspondence e-mail: tanxuejie@163.com

(Received 7 October 2009; accepted 21 October 2009; online 28 October 2009)

The title compound, C₆H₆N₂O₂, is approximately planar [r.m.s. deviation = 0.0488 (3) Å]. In the crystal, weak intermolecular C—H⋯O and C—H⋯N interactions join the molecules into an infinite three-dimensional network.

Related literature

For the synthetic procedure, see: Kim et al. (2004 ). For reduction of heteroaromatic esters, see: Boechat et al. (2005 ). For a description of weak hydrogen bonds, see: Desiraju & Steiner (1999 ).

Experimental

Crystal data

C₆H₆N₂O₂
M_r = 138.13
Orthorhombic, P 2₁ 2₁ 2₁
a = 3.865 (2) Å
b = 6.690 (4) Å
c = 24.92 (2) Å
V = 644.4 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.32 × 0.12 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.980, T_max = 0.994
3378 measured reflections
757 independent reflections
505 reflections with I > 2σ(I)
R_int = 0.080

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.153
S = 1.05
757 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H2⋯O2ⁱ	0.93	2.35	3.205 (3)	153
C6—H4⋯N1ⁱⁱ	0.96	2.62	3.582 (3)	177
Symmetry codes: (i) x+1, y-1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809043451/im2150sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043451/im2150Isup2.hkl

checkCIF report

Comment top

Heteroaromatic esters are more easily reduced than the corresponding free acids (Boechat et al. 2005). The title compound, (I) (Fig. 1), [C₆H₆N₂O₂], was obtained as an intermediate in the synthesis of another pyrazine-based compound.

All non-hydrogen atoms of (I) are coplanar. The maximum deviation from the mean plane is 0.1249 (4) Å for O2 and the mean deviation is only 0.0488 (3) Å. The almost perfect planarity of the molecule reflects its efficient π-conjugation.

There are no classical hydrogen bonds present in the crystal structure (Spek, 2009). Nevertheless, there are weak C—H···O and C—H···N hydrogen bonds (Table 1, Desiraju & Steiner, 1999) linking the molecules into an infinite three-dimensional network [Fig. 2].

Related literature top

For the synthetic procedure, see: Kim et al. (2004). For reduction of heteroaromatic esters, see: Boechat et al. (2005). For a description of weak hydrogen bonds, see: Desiraju & Steiner (1999).

Experimental top

Compound (I) was prepared following a procedure published by Kim et al. (2004), but the product is not "pale brown" but colorless. Elemental analysis Calcd: C 52.17, H 4.38, N 20.28%. Found: C 51.87, H 4.02, N 20.14%.

Structure description top

For the synthetic procedure, see: Kim et al. (2004). For reduction of heteroaromatic esters, see: Boechat et al. (2005). For a description of weak hydrogen bonds, see: Desiraju & Steiner (1999).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of (I), viewed down the a axis, showing one layer of molecules connected by C—H···O and C—H···N hydrogen bonds (dashed lines).

Methyl pyrazine-2-carboxylate top

Crystal data top

C₆H₆N₂O₂	F(000) = 288
M_r = 138.13	D_x = 1.424 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 378 reflections
a = 3.865 (2) Å	θ = 1.6–25.5°
b = 6.690 (4) Å	µ = 0.11 mm⁻¹
c = 24.92 (2) Å	T = 298 K
V = 644.4 (7) Å³	Needle, colourless
Z = 4	0.32 × 0.12 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	757 independent reflections
Radiation source: fine-focus sealed tube	505 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
π and ω scans	θ_max = 25.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −4→4
T_min = 0.980, T_max = 0.994	k = −7→8
3378 measured reflections	l = −30→22

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0698P)²] where P = (F_o² + 2F_c²)/3
757 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₆H₆N₂O₂	V = 644.4 (7) Å³
M_r = 138.13	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 3.865 (2) Å	µ = 0.11 mm⁻¹
b = 6.690 (4) Å	T = 298 K
c = 24.92 (2) Å	0.32 × 0.12 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	757 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	505 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.994	R_int = 0.080
3378 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.05	Δρ_max = 0.18 e Å⁻³
757 reflections	Δρ_min = −0.17 e Å⁻³
91 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
C1	0.2013 (5)	0.6623 (3)	0.93604 (7)	0.0546 (6)
H1	0.0959	0.7714	0.9524	0.065*
C2	0.2602 (4)	0.6690 (2)	0.88246 (6)	0.0371 (5)
C3	0.5035 (6)	0.3674 (2)	0.88599 (7)	0.0561 (6)
H2	0.6133	0.2594	0.8698	0.067*
C4	0.4367 (6)	0.3607 (3)	0.93986 (7)	0.0604 (6)
H3	0.4999	0.2470	0.9589	0.072*
C5	0.1459 (4)	0.8493 (2)	0.85163 (6)	0.0395 (5)
C6	0.1405 (5)	1.0165 (2)	0.76991 (8)	0.0642 (7)
H4	0.2569	1.0139	0.7359	0.096*
H5	0.1955	1.1385	0.7883	0.096*
H6	−0.1049	1.0089	0.7643	0.096*
N1	0.4157 (4)	0.52391 (19)	0.85628 (6)	0.0479 (5)
N2	0.2869 (5)	0.5082 (2)	0.96584 (6)	0.0665 (6)
O1	0.2516 (3)	0.84861 (17)	0.80180 (4)	0.0514 (4)
O2	−0.0298 (4)	0.97530 (17)	0.87108 (5)	0.0690 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0681 (13)	0.0448 (11)	0.0508 (10)	0.0017 (11)	0.0019 (11)	0.0020 (10)
C2	0.0335 (8)	0.0284 (8)	0.0494 (10)	0.0006 (8)	0.0029 (9)	0.0011 (8)
C3	0.0621 (12)	0.0330 (9)	0.0733 (12)	0.0112 (11)	−0.0098 (11)	0.0040 (10)
C4	0.0677 (13)	0.0406 (10)	0.0728 (12)	0.0014 (11)	−0.0187 (12)	0.0199 (10)
C5	0.0409 (10)	0.0302 (8)	0.0475 (10)	−0.0001 (9)	0.0019 (9)	0.0023 (9)
C6	0.0719 (15)	0.0541 (11)	0.0666 (13)	0.0086 (12)	−0.0045 (11)	0.0180 (11)
N1	0.0535 (9)	0.0344 (7)	0.0559 (9)	0.0089 (8)	−0.0002 (8)	−0.0017 (8)
N2	0.0891 (12)	0.0549 (10)	0.0554 (10)	0.0024 (11)	−0.0065 (10)	0.0083 (9)
O1	0.0664 (8)	0.0412 (6)	0.0465 (7)	0.0105 (7)	0.0004 (7)	0.0083 (6)
O2	0.0935 (10)	0.0428 (7)	0.0705 (9)	0.0264 (8)	0.0187 (8)	−0.0033 (7)

Geometric parameters (Å, º) top

C1—N2	1.312 (2)	C4—N2	1.315 (3)
C1—C2	1.355 (2)	C4—H3	0.9300
C1—H1	0.9300	C5—O2	1.186 (2)
C2—N1	1.315 (2)	C5—O1	1.307 (2)
C2—C5	1.497 (2)	C6—O1	1.441 (2)
C3—N1	1.327 (2)	C6—H4	0.9600
C3—C4	1.368 (3)	C6—H5	0.9600
C3—H2	0.9300	C6—H6	0.9600

N2—C1—C2	122.76 (17)	O2—C5—O1	124.72 (15)
N2—C1—H1	118.6	O2—C5—C2	122.14 (15)
C2—C1—H1	118.6	O1—C5—C2	113.11 (14)
N1—C2—C1	122.77 (15)	O1—C6—H4	109.5
N1—C2—C5	118.36 (15)	O1—C6—H5	109.5
C1—C2—C5	118.87 (15)	H4—C6—H5	109.5
N1—C3—C4	121.68 (17)	O1—C6—H6	109.5
N1—C3—H2	119.2	H4—C6—H6	109.5
C4—C3—H2	119.2	H5—C6—H6	109.5
N2—C4—C3	122.83 (17)	C2—N1—C3	114.99 (15)
N2—C4—H3	118.6	C1—N2—C4	114.94 (16)
C3—C4—H3	118.6	C5—O1—C6	115.33 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H2···O2ⁱ	0.93	2.35	3.205 (3)	153
C6—H4···N1ⁱⁱ	0.96	2.62	3.582 (3)	177

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

Experimental details

Crystal data
Chemical formula	C₆H₆N₂O₂
M_r	138.13
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	3.865 (2), 6.690 (4), 24.92 (2)
V (Å³)	644.4 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.32 × 0.12 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.980, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	3378, 757, 505
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.153, 1.05
No. of reflections	757
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H2···O2ⁱ	0.93	2.35	3.205 (3)	152.9
C6—H4···N1ⁱⁱ	0.96	2.62	3.582 (3)	177.4

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

Acknowledgements

The authors thank the Shandong Distinguished Middle-Aged and Young Scientist Encouragement and the Reward Fund (No. 2006BS04006) for financial support.

References

Boechat, N., Costa, J. C. S., Mendonca, J. S., Paes, K. C., Fernandes, E. L., Oliveira, P. S. M., Vasconcelos, T. R. A. & Souza, M. V. N. (2005). Synth. Commun. 35, 3187–3190. Web of Science CrossRef CAS Google Scholar
Bruker (2000). SMART), SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond. Oxford University Press. Google Scholar
Kim, J. W., Choi, K. D., Lim, J. W., Lee, K. H. & Lee, S. H. (2004). PCT Int. Appl. WO 2004048369. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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