2-Methyl­pyrazine 1,4-dioxide

Gratton, J.L.; Knaust, J.M.

doi:10.1107/S1600536809046534

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3040

doi:10.1107/S1600536809046534

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2-Methylpyrazine 1,4-dioxide

Jessica L. Gratton ^a and Jacqueline M. Knaust ^a ^*

^aAllegheny College, Chemistry Department, 520 North Main St., Meadville, PA 16335, USA
^*Correspondence e-mail: jknaust@allegheny.edu

(Received 2 November 2009; accepted 4 November 2009; online 7 November 2009)

The title compound, C₅H₆N₂O₂, was prepared from 2-methylpyrazine, acetic acid and hydrogen peroxide. In the crystal, π–π stacking interactions between neighboring molecules are observed, with a centroid–centroid distance of 3.7370 Å, an interplanar distance of 3.167 Å, and a slippage of 1.984 Å. Each molecule is linked to four neighbors through C—H⋯O hydrogen-bonding interactions, forming one-dimensional ribbons.

Related literature

For the synthesis of 2,2′-bipyridine N,N'-dioxide, see: Simpson et al. (1963 ). For the synthesis of lanthanide coordination networks with pyrazine N,N'-dioxide, see: Cardoso et al. (2001 ); Sun et al. (2004 ). For the use of 2-methylpyrazine 1,4-dioxide in the synthesis of a cadmium (II) coordination network, see: Shi et al. (2006 ). For the use of 2-methylpyrazine 1,4-dioxide in the synthesis of several molecular complexes, see: Sun et al. (2005 ); Xu et al. (2005a ,b ).

Experimental

Crystal data

C₅H₆N₂O₂
M_r = 126.12
Orthorhombic, P b c a
a = 6.3953 (9) Å
b = 12.2472 (18) Å
c = 13.6613 (19) Å
V = 1070.0 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 173 K
0.53 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.763, T_max = 1.000
5556 measured reflections
1708 independent reflections
1407 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.122
S = 1.07
1708 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.45 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
C1—H1⋯O2ⁱ	0.93	2.31	3.2224 (16)	165
C2—H2⋯O2ⁱⁱ	0.93	2.23	3.1405 (17)	167
C3—H3⋯O1ⁱⁱⁱ	0.93	2.29	3.2090 (15)	168
Symmetry codes: (i) x-1, y, z; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (iii) x+1, y, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: X-SEED.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809046534/zl2250sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046534/zl2250Isup2.hkl

checkCIF report

Comment top

The use of pyrazine N,N'-dioxide in the synthesis of lanthanide coordination networks has been of recent interest (Cardoso et al. (2001), Sun et al. (2004)). Shi et al. (2006) recently reported the use 2-methylpyrazine 1,4-dioxide in the synthesis of a cadmium (II) coordination network, and Sun et al. (2005), Xu et al. (2005a), and Xu et al. (2005b) report its use in the synthesis of several molecular complexes. The title compound was prepared using the reaction the conditions described by Simpson et al. (1963) to prepare 2,2'-bipyridine N,N'-dioxide.

The asymmetric unit of the title compound contains one 2-methylpyrazine 1,4-dioxide molecule (Figure 1). π-π stacking interactions with a centroid to centroid distance of 3.7370 Å, an interplanar distance of 3.167 Å, and a slippage of 1.984 Å. are observed between neighboring N-oxide molecules [symmetry code: -x + 1, -y + 1, -z + 1] (Figure 2). The title compound forms six C—H···O hydrogen bonds with four neighboring N-oxide molecules, and these hydrogen bonding interactions result in the formation of one-dimensional ribbons that propagate parallel to the a axis (Figure 4). As seen in the packing diagram, each one-dimensional ribbon is surrounded by six similar ribbons. (Figure 5)

Related literature top

For the synthesis of 2,2'-bipyridine N,N'-dioxide, see: Simpson et al. (1963). For the synthesis of lanthanide coordination networks with pyrazine N,N'-dioxide, see: Cardoso et al. (2001); Sun et al. (2004). For the use of 2-methylpyrazine 1,4-dioxide in the synthesis of a cadmium (II) coordination network, see: Shi et al. (2006). For the use of 2-methylpyrazine 1,4-dioxide in the synthesis of several molecular complexes, see: Sun et al. (2005); Xu et al. (2005a,b).

Experimental top

2-Methylpyrazine (5.871 ml, 64.0 mmol), acetic acid (75 ml), and 30% hydrogen peroxide (13 ml) were heated at 343–353 K for 3 h. Additional hydrogen peroxide (9 ml) was added, and heating was continued. After an additional 19 h of heating the solution was cooled to room temperature. Crystals formed upon the addition of acetone (1L) and cooling to 273 K, and were recrystallized from hot water by addition of excess acetone and cooling to 273 K.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED (Barbour, 2001).

Figures top

	Fig. 1. The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. π-π interactions between neighboring 2-methylpyrazine 1,4-dioxide molecules.
	Fig. 3. C—H···O hydrogen bonding interactions between neighboring 2-methylpyrazine 1,4-dioxide molecules. Hydrogen bonds are shown as dashed lines. Symmetry codes: (i) x - 1, y, z; (ii) x - 1/2, y, -z + 3/2; (iii) x + 1, y, z; (iv) x + 1/2, y, -z + 3/2.
	Fig. 4. Packing of the title compound viewed down the a axis. Color scheme indicates individual C—H···O hydrogen bonded ribbons. Hydrogen bonds are shown as dashed lines

2-Methylpyrazine 1,4-dioxide top

Crystal data top

C₅H₆N₂O₂	F(000) = 528
M_r = 126.12	D_x = 1.566 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1890 reflections
a = 6.3953 (9) Å	θ = 3.0–31.5°
b = 12.2472 (18) Å	µ = 0.12 mm⁻¹
c = 13.6613 (19) Å	T = 173 K
V = 1070.0 (3) Å³	Rod, colorless
Z = 8	0.53 × 0.20 × 0.15 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1708 independent reflections
Radiation source: fine-focus sealed tube	1407 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 31.8°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→8
T_min = 0.763, T_max = 1.000	k = −17→8
5556 measured reflections	l = −11→19

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0537P)² + 0.6359P] where P = (F_o² + 2F_c²)/3
1708 reflections	(Δ/σ)_max < 0.001
83 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₅H₆N₂O₂	V = 1070.0 (3) Å³
M_r = 126.12	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 6.3953 (9) Å	µ = 0.12 mm⁻¹
b = 12.2472 (18) Å	T = 173 K
c = 13.6613 (19) Å	0.53 × 0.20 × 0.15 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1708 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1407 reflections with I > 2σ(I)
T_min = 0.763, T_max = 1.000	R_int = 0.025
5556 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.07	Δρ_max = 0.45 e Å⁻³
1708 reflections	Δρ_min = −0.31 e Å⁻³
83 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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	0.33101 (13)	0.64269 (8)	0.41676 (7)	0.0164 (2)
O2	0.99921 (14)	0.59296 (8)	0.64921 (7)	0.0183 (2)
N1	0.49403 (15)	0.63273 (8)	0.47271 (8)	0.0122 (2)
N2	0.83721 (15)	0.60672 (9)	0.59294 (8)	0.0128 (2)
C1	0.47150 (19)	0.62449 (10)	0.57203 (9)	0.0136 (2)
H1	0.3386	0.6279	0.5995	0.016*
C2	0.64141 (19)	0.61132 (10)	0.63137 (9)	0.0142 (2)
H2	0.6230	0.6055	0.6987	0.017*
C3	0.86033 (18)	0.61629 (10)	0.49464 (9)	0.0126 (2)
H3	0.9940	0.6141	0.4679	0.015*
C4	0.69092 (18)	0.62919 (10)	0.43327 (9)	0.0125 (2)
C5	0.7106 (2)	0.63969 (11)	0.32565 (9)	0.0165 (2)
H5A	0.6439	0.7059	0.3046	0.025*
H5B	0.6448	0.5783	0.2946	0.025*
H5C	0.8559	0.6417	0.3080	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0092 (4)	0.0223 (5)	0.0177 (4)	0.0005 (3)	−0.0044 (3)	0.0008 (3)
O2	0.0112 (4)	0.0298 (5)	0.0140 (4)	0.0004 (3)	−0.0053 (3)	0.0002 (4)
N1	0.0090 (4)	0.0139 (4)	0.0138 (5)	0.0001 (3)	−0.0009 (4)	−0.0004 (3)
N2	0.0103 (4)	0.0169 (5)	0.0113 (5)	−0.0005 (3)	−0.0013 (4)	−0.0003 (4)
C1	0.0118 (5)	0.0155 (5)	0.0136 (5)	0.0000 (4)	0.0027 (4)	0.0001 (4)
C2	0.0137 (5)	0.0167 (5)	0.0122 (5)	−0.0006 (4)	0.0026 (4)	−0.0006 (4)
C3	0.0097 (4)	0.0160 (5)	0.0120 (5)	−0.0007 (4)	0.0013 (4)	−0.0006 (4)
C4	0.0104 (5)	0.0143 (5)	0.0126 (5)	0.0000 (4)	0.0008 (4)	−0.0004 (4)
C5	0.0142 (5)	0.0242 (6)	0.0112 (5)	0.0008 (4)	0.0007 (4)	0.0015 (5)

Geometric parameters (Å, º) top

O1—N1	1.2985 (13)	C2—H2	0.9300
O2—N2	1.3011 (13)	C3—C4	1.3789 (16)
N1—C1	1.3681 (16)	C3—H3	0.9300
N1—C4	1.3703 (15)	C4—C5	1.4813 (18)
N2—C3	1.3561 (16)	C5—H5A	0.9600
N2—C2	1.3590 (15)	C5—H5B	0.9600
C1—C2	1.3653 (17)	C5—H5C	0.9600
C1—H1	0.9300

O1—N1—C1	120.41 (10)	N2—C3—C4	121.75 (11)
O1—N1—C4	120.62 (10)	N2—C3—H3	119.1
C1—N1—C4	118.97 (10)	C4—C3—H3	119.1
O2—N2—C3	120.63 (10)	N1—C4—C3	119.11 (11)
O2—N2—C2	120.72 (10)	N1—C4—C5	117.75 (11)
C3—N2—C2	118.65 (10)	C3—C4—C5	123.14 (11)
C2—C1—N1	120.92 (11)	C4—C5—H5A	109.5
C2—C1—H1	119.5	C4—C5—H5B	109.5
N1—C1—H1	119.5	H5A—C5—H5B	109.5
N2—C2—C1	120.59 (11)	C4—C5—H5C	109.5
N2—C2—H2	119.7	H5A—C5—H5C	109.5
C1—C2—H2	119.7	H5B—C5—H5C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱ	0.93	2.31	3.2224 (16)	165
C2—H2···O2ⁱⁱ	0.93	2.23	3.1405 (17)	167
C3—H3···O1ⁱⁱⁱ	0.93	2.29	3.2090 (15)	168

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

Experimental details

Crystal data
Chemical formula	C₅H₆N₂O₂
M_r	126.12
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	6.3953 (9), 12.2472 (18), 13.6613 (19)
V (Å³)	1070.0 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.53 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.763, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5556, 1708, 1407
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.742

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.122, 1.07
No. of reflections	1708
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.31

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱ	0.93	2.31	3.2224 (16)	165.3
C2—H2···O2ⁱⁱ	0.93	2.23	3.1405 (17)	166.5
C3—H3···O1ⁱⁱⁱ	0.93	2.29	3.2090 (15)	168.4

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

Acknowledgements

The authors are thankful to Allegheny College for providing funding in support of this research. The diffractometer was funded by the NSF (grant No. 0087210), the Ohio Board of Regents (grant No. CAP-491) and by Youngstown State University. The authors would also like to acknowledge the STaRBURSTT CyberInstrumentation Consortium for assistance with the crystallography.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191. CrossRef CAS Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cardoso, M. C. C., Zinner, L. B., Zukerman-Scheptor, J., Araújo Melo, D. M. & Vincentini, G. J. (2001). J. Alloys Compd, 323–324, 22–25. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, J. M., Zhang, F. X., Zhang, X., Xu, H. Y., Lui, L. D. & Ma, J. P. (2006). Chin. J. Struct. Chem. 20, 1238–1242. Google Scholar
Simpson, P. G., Vinciguerra, A. & Quagliano, J. V. (1963). Inorg. Chem. 2, 282–286. CrossRef CAS Web of Science Google Scholar
Sun, H. L., Gao, S., Ma, B. Q., Chang, F. & Fu, W. F. (2004). Microporous Mesoporous Mater. 73, 89–95. Web of Science CSD CrossRef CAS Google Scholar
Sun, Y.-M., Shi, J.-M. & Zhang, X. (2005). Acta Cryst. E61, m1501–m1502. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, W., Shi, J. M. & Zhang, X. (2005a). Acta Cryst. E61, m854–m855. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, W., Shi, J.-M. & Zhang, X. (2005b). Acta Cryst. E61, m2194–m2195. Web of Science CSD CrossRef IUCr Journals Google Scholar