PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): o28.
Published online 2009 December 4. doi:  10.1107/S1600536809051289
PMCID: PMC2980041

Quinoxaline-2-carbonitrile

Abstract

In the title compound, C9H5N3, the quinoxaline ring is essentially planar, with a maximum deviation of 0.012 (1) Å. Short inter­molecular distances between the centroids of the 2,3-dihydro­pyrazine and benzene rings [3.6490 (5) Å] indicate the existence of π(...)π inter­actions. In the crystal packing, the mol­ecules are linked via two pairs of inter­molecular C—H(...)N inter­actions, forming R 2 2 (8) and R 2 2 (10) ring motifs; these mol­ecules are further linked into a two-dimensional network parallel to (1 0 2) via another C–H(...)N inter­action.

Related literature

For the synthesis of cyano N-heterocyclic compounds, see: Goswami et al. (2007 [triangle], 2009 [triangle]). For reference bond lengths, see: Allen et al. (1987 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-00o28-scheme1.jpg

Experimental

Crystal data

  • C9H5N3
  • M r = 155.16
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-00o28-efi1.jpg
  • a = 3.8055 (1) Å
  • b = 19.0466 (4) Å
  • c = 10.1845 (2) Å
  • β = 93.466 (1)°
  • V = 736.84 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 100 K
  • 0.39 × 0.28 × 0.25 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.966, T max = 0.978
  • 11604 measured reflections
  • 2716 independent reflections
  • 2183 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.135
  • S = 1.08
  • 2716 reflections
  • 129 parameters
  • All H-atom parameters refined
  • Δρmax = 0.53 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809051289/sj2699sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809051289/sj2699Isup2.hkl

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

Acknowledgments

HKF and CKQ thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PFIZIK/811012). CKQ thanks USM for a Research Fellowship.

supplementary crystallographic information

Comment

Heterocyclic molecules containing a cyano group are useful as drug intermediates. The development of new pathways leading to efficient synthesis of heterocycles with diversity in skeleton and functional groups is an important field of research in both synthetic and medicinal chemistry. Recently, we have synthesized a number of cyano N-heterocyclic compounds using triselenium dicyanide (TSD) (Goswami et al., 2007, 2009). Herein we report the synthesis of 2-cyanoquinoxaline from quinoxaline under microwave irradiation and its molecular structure.

The bond lengths (Allen et al., 1987) and angles in the title compound (Fig. 1) are within normal ranges. The quinoxaline ring (N1/N2/C1-C8) is essentially planar, with the maximum deviation of 0.012 (1) Å for atom C5. Short intermolecular distances between the centroids of the pyrazine (N1/N2/C1/C6-C8) and benzene rings (C1-C6) [3.6490 (5) Å] indicate the existence of π···π interactions.

In the crystal packing (Fig. 2), the molecules are linked via pairs of intermolecular C2—H2···N1 and C7—H7···N3 interactions, forming R22 (8) and R22 (10) ring motifs (Bernstein et al., 1995) and these molecules are further linked into two-dimensional networks parallel to plane (1 0 2) via C4–H4···N2 interactions.

Experimental

A thoroughly ground mixture of selenium dioxide (1.32 g, 12 mmol) and malononitrile (0.26 g, 4 mmol) in 4-5 drops of DMSO was kept stirring in an open-mouth conical flask. The mixture became reddish-brown after 7 min. An exothermic reaction began in the next 10 minutes when triselenium dicyanide was formed. The heterocyclic substrate quinoxaline (0.39 g, 3 mmol) was added to the mixture after the termination of the exothermic reaction. The conical flask was placed in a domestic microwave oven at 240 W for 20 min. The progress of the reaction was monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with chloroform. The organic layer was washed with saturated brine and dried over MgSO4 and followed by evaporation with a rotary evaporator under low pressure to afford a light yellow substance. This was purified on silica gel (60-120 mesh) column chromatography eluting with petroleum ether (boiling point, 60-80° C) to give the compound (0.34 g, 74 %) as a crystalline solid.

Refinement

All H atoms were located in a difference Fourier map and refined freely.

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme.
Fig. 2.
The crystal structure of the title compound viewed along the a axis. Intermolecular interactions are shown in dashed lines.

Crystal data

C9H5N3F(000) = 320
Mr = 155.16Dx = 1.399 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4710 reflections
a = 3.8055 (1) Åθ = 2.9–32.7°
b = 19.0466 (4) ŵ = 0.09 mm1
c = 10.1845 (2) ÅT = 100 K
β = 93.466 (1)°Block, yellow
V = 736.84 (3) Å30.39 × 0.28 × 0.25 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer2716 independent reflections
Radiation source: fine-focus sealed tube2183 reflections with I > 2σ(I)
graphiteRint = 0.023
[var phi] and ω scansθmax = 32.8°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −5→5
Tmin = 0.966, Tmax = 0.978k = −29→21
11604 measured reflectionsl = −15→14

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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135All H-atom parameters refined
S = 1.08w = 1/[σ2(Fo2) + (0.0782P)2 + 0.0918P] where P = (Fo2 + 2Fc2)/3
2716 reflections(Δ/σ)max = 0.001
129 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = −0.23 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/Ueq
N10.12156 (18)0.46098 (4)0.84114 (7)0.01481 (16)
N2−0.12366 (19)0.33470 (4)0.71846 (8)0.01659 (17)
N3−0.2187 (2)0.57757 (5)0.60971 (9)0.0269 (2)
C10.1884 (2)0.39728 (4)0.89844 (8)0.01344 (17)
C20.3822 (2)0.39456 (5)1.02181 (9)0.01744 (18)
C30.4514 (2)0.33059 (5)1.07937 (10)0.02033 (19)
C40.3352 (2)0.26756 (5)1.01678 (10)0.0210 (2)
C50.1474 (2)0.26871 (5)0.89805 (9)0.01857 (19)
C60.0674 (2)0.33382 (4)0.83638 (9)0.01441 (17)
C7−0.1868 (2)0.39663 (4)0.66474 (9)0.01675 (18)
C8−0.0633 (2)0.45941 (4)0.72702 (8)0.01496 (17)
C9−0.1450 (2)0.52598 (5)0.66332 (9)0.01913 (19)
H20.471 (4)0.4375 (7)1.0662 (14)0.030 (3)*
H30.591 (4)0.3282 (7)1.1650 (16)0.038 (4)*
H40.396 (3)0.2229 (7)1.0622 (13)0.028 (3)*
H50.057 (4)0.2262 (7)0.8533 (14)0.032 (3)*
H7−0.328 (4)0.4008 (7)0.5793 (14)0.028 (3)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0154 (3)0.0145 (3)0.0146 (3)0.0003 (2)0.0014 (2)0.0010 (2)
N20.0168 (3)0.0173 (3)0.0157 (4)−0.0006 (2)0.0014 (3)−0.0016 (3)
N30.0328 (4)0.0235 (4)0.0241 (5)0.0028 (3)−0.0002 (3)0.0057 (3)
C10.0128 (3)0.0147 (3)0.0130 (4)0.0002 (2)0.0019 (3)0.0004 (3)
C20.0157 (4)0.0218 (4)0.0147 (4)−0.0004 (3)−0.0002 (3)0.0005 (3)
C30.0164 (4)0.0275 (4)0.0170 (4)0.0019 (3)0.0003 (3)0.0055 (3)
C40.0176 (4)0.0208 (4)0.0248 (5)0.0030 (3)0.0042 (3)0.0088 (3)
C50.0179 (4)0.0147 (4)0.0235 (5)0.0007 (3)0.0036 (3)0.0029 (3)
C60.0131 (3)0.0152 (3)0.0151 (4)0.0000 (2)0.0027 (3)0.0000 (3)
C70.0164 (4)0.0195 (4)0.0142 (4)−0.0003 (3)0.0000 (3)−0.0004 (3)
C80.0145 (3)0.0168 (4)0.0137 (4)0.0005 (3)0.0019 (3)0.0015 (3)
C90.0204 (4)0.0202 (4)0.0167 (4)0.0005 (3)0.0005 (3)0.0015 (3)

Geometric parameters (Å, °)

N1—C81.3220 (11)C3—C41.4175 (14)
N1—C11.3636 (10)C3—H30.995 (16)
N2—C71.3161 (11)C4—C51.3670 (13)
N2—C61.3659 (11)C4—H40.988 (13)
N3—C91.1506 (12)C5—C61.4150 (11)
C1—C21.4190 (12)C5—H50.980 (14)
C1—C61.4273 (11)C7—C81.4202 (12)
C2—C31.3706 (12)C7—H70.997 (14)
C2—H20.985 (14)C8—C91.4495 (12)
C8—N1—C1115.57 (7)C4—C5—C6119.57 (8)
C7—N2—C6116.78 (7)C4—C5—H5123.2 (8)
N1—C1—C2119.01 (7)C6—C5—H5117.2 (8)
N1—C1—C6121.14 (8)N2—C6—C5119.33 (7)
C2—C1—C6119.85 (7)N2—C6—C1121.28 (7)
C3—C2—C1119.16 (8)C5—C6—C1119.38 (8)
C3—C2—H2119.4 (8)N2—C7—C8121.44 (8)
C1—C2—H2121.5 (8)N2—C7—H7120.7 (7)
C2—C3—C4120.92 (9)C8—C7—H7117.9 (7)
C2—C3—H3119.6 (8)N1—C8—C7123.77 (7)
C4—C3—H3119.4 (8)N1—C8—C9117.52 (7)
C5—C4—C3121.10 (8)C7—C8—C9118.71 (8)
C5—C4—H4121.5 (8)N3—C9—C8177.49 (10)
C3—C4—H4117.4 (8)
C8—N1—C1—C2−179.34 (7)C4—C5—C6—C10.84 (13)
C8—N1—C1—C60.75 (12)N1—C1—C6—N2−0.95 (13)
N1—C1—C2—C3−179.68 (8)C2—C1—C6—N2179.14 (7)
C6—C1—C2—C30.24 (13)N1—C1—C6—C5178.94 (7)
C1—C2—C3—C40.62 (13)C2—C1—C6—C5−0.97 (12)
C2—C3—C4—C5−0.75 (14)C6—N2—C7—C8−0.32 (13)
C3—C4—C5—C60.00 (14)C1—N1—C8—C7−0.38 (12)
C7—N2—C6—C5−179.20 (7)C1—N1—C8—C9179.15 (7)
C7—N2—C6—C10.69 (12)N2—C7—C8—N10.18 (14)
C4—C5—C6—N2−179.26 (7)N2—C7—C8—C9−179.36 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···N1i0.984 (14)2.619 (14)3.5730 (12)163.4 (12)
C4—H4···N2ii0.988 (13)2.593 (13)3.4268 (12)142.0 (10)
C7—H7···N3iii0.998 (14)2.540 (15)3.5225 (12)168.3 (12)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2699).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, S1–19.
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chamg, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst.19, 105–107.
  • Goswami, S. P., Maity, A. C., Das, N. K., Sen, D. & Maity, S. P. (2009). Synth. Commun.39, 407–415.
  • Goswami, S., Maity, A. C., García-Granda, S. & Torre-Fernández, L. (2007). Acta Cryst. E63, o1741–o1742.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography