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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3052.
Published online 2009 November 11. doi:  10.1107/S1600536809046741
PMCID: PMC2971924

2,5-Dimethyl­pyrazine 1,4-dioxide

Abstract

The title compound, C6H8N2O2, was prepared from 2,5-dimethyl­pyrazine, acetic acid, and hydrogen peroxide. The 2,5-dimethyl­pyrazine 1,4-dioxide mol­ecule is located on an inversion center. π–π inter­actions between neighboring 2,5-dimethyl­pyrazine 1,4-dioxide mol­ecules are observed with an inter­planar distance of 3.191 Å. Each 2,5-dimethyl­pyrazine 1,4-dioxide mol­ecule is linked to four neighboring N-oxide mol­ecules through C—H(...)O hydrogen-bonding inter­actions, forming two-dimensional layers.

Related literature

For the synthesis of 2,2′-bipyridine N,N′-dioxide, see: Simpson et al. (1963 [triangle]). For the synthesis of lanthanide coordination networks with pyrazine N,N′-dioxide, see: Cardoso et al. (2001 [triangle]); Sun et al. (2004 [triangle]). For the use of 2,5-dimethyl­pyrazine 1,4-dioxide in the synthesis of transition metal coordination networks, see: Shi, Sun et al. (2006 [triangle]); Shi, Zhang et al. (2006 [triangle]); Shi et al. (2007 [triangle]); Sun, Gao et al. (2005 [triangle]); Sun, Wang et al. (2005 [triangle]). For related structures, see: Näther et al. (2002 [triangle]); Gratton & Knaust (2009 [triangle]).

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Object name is e-65-o3052-scheme1.jpg

Experimental

Crystal data

  • C6H8N2O2
  • M r = 140.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3052-efi2.jpg
  • a = 3.9971 (8) Å
  • b = 8.9176 (17) Å
  • c = 8.9249 (17) Å
  • β = 102.205 (3)°
  • V = 310.93 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 173 K
  • 0.45 × 0.12 × 0.11 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.623, T max = 0.746
  • 2388 measured reflections
  • 965 independent reflections
  • 811 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.144
  • S = 1.07
  • 965 reflections
  • 47 parameters
  • H-atom parameters constrained
  • Δρmax = 0.62 e Å−3
  • Δρmin = −0.34 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809046741/zl2251sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809046741/zl2251Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors are grateful 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.

supplementary crystallographic information

Comment

The use of pyrazine N,N'-dioxide in the synthesis of lanthanide coordination networks has been of recent interest (Cardoso et al. (2001), and Sun et al. (2004)). Shi, Sun et al. (2006), Shi, Zhang et al. (2006), Shi et al. (2007), Sun, Gao et al. (2005), and Sun, Wang et al. (2005) recently reported the use 2,5-dimethylpyrazine 1,4-dioxide in the synthesis of a transition metal coordination networks. The title compound was prepared using the reaction conditions described by Simpson et al. (1963) to prepare 2,2'-bipyridine N,N'-dioxide.

The asymmetric unit of the title compound contains half of a 2,5-dimethylpyrazine 1,4-dioxide molecule (Figure 1) and the N-oxide molecule lies on an inversion center. π-Cloud interactions between neighboring 2,5-dimethylpyrazine 1,4-dioxide molecules are observed with an interplanar distance of 3.191 Å (Figure 2); there is a slippage of 2.408 Å such that N1iii on the neighboring N-oxide molecule lies directly over the centroid of the C3—N1i bond [symmetry codes: (i) -x + 1, -y, -z + 1; (iii) x + 1, y, z] (Figure 3). The title compound forms eight C—H···O hydrogen bonds with four neighboring N-oxide molecules, and these hydrogen bonding interactions result in the formation of two-dimensional layers (Figure 5); whereas in the related structures of 2-methylpyrazine 1,4-dioxide and pyrazine N,N'-dioxide, the N-oxide molecules form hydrogen bonded ribbons and a three-dimensional network, respectively (Gratton et al. (2009), Näther et al. (2002)). A packing diagram of the title compound is given in Figure 5.

Experimental

2,5-Dimethylpyrazine (6.99 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.

Refinement

All H atoms were positioned geometrically and refined using a riding model with C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids for non-H atoms. Atoms not labeled are generated by the symmetry operator (i) -x + 1,-y, -z + 1.
Fig. 2.
Space filling representation of the π-cloud interactions between neighboring 2,5-dimethylpyrazine 1,4-dioxide molecules.
Fig. 3.
Ball and stick representation of the π-cloud interactions between neighboring 2,5-diethylpyrazine 1,4-dioxide molecules. symmetry codes: (i) -x + 1, -y, -z + 1; (iii) x + 1, y, z; (iv) -x + 2, -y, -z + 1
Fig. 4.
C—H···O hydrogen bonding interactions between neighboring 2,5-dimethylpyrazine 1,4-dioxide molecules. Hydrogen bonds are shown as dashed lines. Symmetry code: (ii) x + 1, -y + 1/2, z +1 /2.
Fig. 5.
Packing of the title compound viewed down the b axis. Hydrogen bonds are shown as dashed red lines, and π-cloud interactions are shown as dashed blue lines.

Crystal data

C6H8N2O2F(000) = 148
Mr = 140.14Dx = 1.497 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 958 reflections
a = 3.9971 (8) Åθ = 3.3–31.5°
b = 8.9176 (17) ŵ = 0.12 mm1
c = 8.9249 (17) ÅT = 173 K
β = 102.205 (3)°Rod, colorless
V = 310.93 (10) Å30.45 × 0.12 × 0.11 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer965 independent reflections
Radiation source: fine-focus sealed tube811 reflections with I > 2σ(I)
graphiteRint = 0.023
ω scansθmax = 31.5°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −5→5
Tmin = 0.623, Tmax = 0.746k = −12→9
2388 measured reflectionsl = −12→8

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0934P)2 + 0.0493P] where P = (Fo2 + 2Fc2)/3
965 reflections(Δ/σ)max < 0.001
47 parametersΔρmax = 0.62 e Å3
0 restraintsΔρmin = −0.34 e Å3

Special details

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.Highest peak 0.62 at 0.4105 0.2353 0.4867 [0.74 A from C1] Deepest hole -0.34 at 0.1454 0.0185 0.3480 [0.59 A from N1]

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O1−0.0014 (2)0.11342 (10)0.28187 (10)0.0190 (3)
N10.2436 (2)0.05941 (11)0.38743 (11)0.0141 (3)
C10.3636 (3)0.31533 (12)0.48341 (15)0.0182 (3)
H1A0.12860.33380.49480.027*
H1B0.39100.35220.38320.027*
H1C0.52380.36800.56470.027*
C20.4355 (3)0.15172 (13)0.49468 (13)0.0145 (3)
C30.6882 (3)0.09028 (12)0.60638 (14)0.0146 (3)
H30.81940.15430.68160.017*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0183 (4)0.0186 (5)0.0151 (5)0.0029 (3)−0.0081 (3)0.0031 (3)
N10.0137 (4)0.0150 (5)0.0112 (5)0.0004 (3)−0.0028 (4)0.0019 (4)
C10.0204 (5)0.0122 (5)0.0191 (6)0.0012 (4)−0.0022 (4)0.0010 (4)
C20.0155 (5)0.0136 (5)0.0130 (5)−0.0012 (4)−0.0002 (4)−0.0002 (4)
C30.0157 (5)0.0134 (5)0.0126 (5)−0.0006 (4)−0.0012 (4)−0.0001 (4)

Geometric parameters (Å, °)

O1—N11.2996 (12)C1—H1B0.9800
N1—C3i1.3611 (14)C1—H1C0.9800
N1—C21.3681 (15)C2—C31.3744 (15)
C1—C21.4863 (15)C3—H30.9500
C1—H1A0.9800
O1—N1—C3i120.44 (10)H1B—C1—H1C109.5
O1—N1—C2120.62 (10)N1—C2—C3119.01 (10)
C3i—N1—C2118.94 (10)N1—C2—C1118.14 (10)
C2—C1—H1A109.5C3—C2—C1122.85 (10)
C2—C1—H1B109.5N1i—C3—C2122.05 (10)
H1A—C1—H1B109.5N1i—C3—H3119.0
C2—C1—H1C109.5C2—C3—H3119.0
H1A—C1—H1C109.5

Symmetry codes: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1C···O1ii0.982.413.3290 (15)155
C3—H3···O1ii0.952.313.1863 (15)153

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2251).

References

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