organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Quinoxaline-2-carbo­nitrile

aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and bDepartment of Chemistry, Bengal Engineering and Science University, Shibpur, Howrah 711 103, India
*Correspondence e-mail: hkfun@usm.my

(Received 26 November 2009; accepted 28 November 2009; online 4 December 2009)

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 ππ inter­actions. In the crystal packing, the mol­ecules are linked via two pairs of inter­molecular C—H⋯N inter­actions, forming R22 (8) and R22 (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[Goswami, S., Maity, A. C., García-Granda, S. & Torre-Fernández, L. (2007). Acta Cryst. E63, o1741-o1742.], 2009[Goswami, S. P., Maity, A. C., Das, N. K., Sen, D. & Maity, S. P. (2009). Synth. Commun. 39, 407-415.]). For reference bond lengths, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, S1-19.]). For hydrogen-bond motifs, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chamg, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986[Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105-107.]).

[Scheme 1]

Experimental

Crystal data
  • C9H5N3

  • Mr = 155.16

  • Monoclinic, P 21 /c

  • 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[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.966, Tmax = 0.978

  • 11604 measured reflections

  • 2716 independent reflections

  • 2183 reflections with I > 2σ(I)

  • Rint = 0.023

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2⋯N1i 0.984 (14) 2.619 (14) 3.5730 (12) 163.4 (12)
C4—H4⋯N2ii 0.988 (13) 2.593 (13) 3.4268 (12) 142.0 (10)
C7—H7⋯N3iii 0.998 (14) 2.540 (15) 3.5225 (12) 168.3 (12)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) [x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (iii) -x-1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

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.

Related literature top

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

Experimental top

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 top

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

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal structure of the title compound viewed along the a axis. Intermolecular interactions are shown in dashed lines.
Quinoxaline-2-carbonitrile top
Crystal data top
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 top
Bruker SMART APEXII CCD area-detector
diffractometer
2716 independent reflections
Radiation source: fine-focus sealed tube2183 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ϕ and ω scansθmax = 32.8°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 55
Tmin = 0.966, Tmax = 0.978k = 2921
11604 measured reflectionsl = 1514
Refinement top
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 = 1.08 w = 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
Crystal data top
C9H5N3V = 736.84 (3) Å3
Mr = 155.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 3.8055 (1) ŵ = 0.09 mm1
b = 19.0466 (4) ÅT = 100 K
c = 10.1845 (2) Å0.39 × 0.28 × 0.25 mm
β = 93.466 (1)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
2716 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
2183 reflections with I > 2σ(I)
Tmin = 0.966, Tmax = 0.978Rint = 0.023
11604 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.135All H-atom parameters refined
S = 1.08Δρmax = 0.53 e Å3
2716 reflectionsΔρmin = 0.23 e Å3
129 parameters
Special details top

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) top
xyzUiso*/Ueq
N10.12156 (18)0.46098 (4)0.84114 (7)0.01481 (16)
N20.12366 (19)0.33470 (4)0.71846 (8)0.01659 (17)
N30.2187 (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)
C70.1868 (2)0.39663 (4)0.66474 (9)0.01675 (18)
C80.0633 (2)0.45941 (4)0.72702 (8)0.01496 (17)
C90.1450 (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)*
H70.328 (4)0.4008 (7)0.5793 (14)0.028 (3)*
Atomic displacement parameters (Å2) top
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, º) top
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—C2179.34 (7)C4—C5—C6—C10.84 (13)
C8—N1—C1—C60.75 (12)N1—C1—C6—N20.95 (13)
N1—C1—C2—C3179.68 (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—C50.97 (12)
C2—C3—C4—C50.75 (14)C6—N2—C7—C80.32 (13)
C3—C4—C5—C60.00 (14)C1—N1—C8—C70.38 (12)
C7—N2—C6—C5179.20 (7)C1—N1—C8—C9179.15 (7)
C7—N2—C6—C10.69 (12)N2—C7—C8—N10.18 (14)
C4—C5—C6—N2179.26 (7)N2—C7—C8—C9179.36 (8)
Hydrogen-bond geometry (Å, º) top
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) x1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC9H5N3
Mr155.16
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)3.8055 (1), 19.0466 (4), 10.1845 (2)
β (°) 93.466 (1)
V3)736.84 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.39 × 0.28 × 0.25
Data collection
DiffractometerBruker SMART APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.966, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
11604, 2716, 2183
Rint0.023
(sin θ/λ)max1)0.763
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.135, 1.08
No. of reflections2716
No. of parameters129
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.53, 0.23

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
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) x1, y+1, z+1.
 

Footnotes

Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

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.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, S1–19.  CrossRef Google Scholar
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chamg, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationGoswami, S. P., Maity, A. C., Das, N. K., Sen, D. & Maity, S. P. (2009). Synth. Commun. 39, 407–415.  Web of Science CrossRef CAS Google Scholar
First citationGoswami, S., Maity, A. C., García-Granda, S. & Torre-Fernández, L. (2007). Acta Cryst. E63, o1741–o1742.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds