Quinoxaline-2-carbonitrile

Fun, H.-K.; Quah, C.K.; Maity, A.C.; Das, N.K.; Goswami, S.

doi:10.1107/S1600536809051289

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o28

doi:10.1107/S1600536809051289

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Quinoxaline-2-carbonitrile

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Annada C. Maity,^b Nirmal Kumar Das ^b and Shyamaprosad Goswami ^b

^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 π⋯π 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 , 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

Crystal data

C₉H₅N₃
M_r = 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 ) 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[F² > 2σ(F²)] = 0.047
wR(F²) = 0.135
S = 1.08
2716 reflections
129 parameters
All H-atom parameters refined
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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

Supporting information

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

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

checkCIF report

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.

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

	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.

Quinoxaline-2-carbonitrile top

Crystal data top

C₉H₅N₃	F(000) = 320
M_r = 155.16	D_x = 1.399 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4710 reflections
a = 3.8055 (1) Å	θ = 2.9–32.7°
b = 19.0466 (4) Å	µ = 0.09 mm⁻¹
c = 10.1845 (2) Å	T = 100 K
β = 93.466 (1)°	Block, yellow
V = 736.84 (3) Å³	0.39 × 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 tube	2183 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 32.8°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −5→5
T_min = 0.966, T_max = 0.978	k = −29→21
11604 measured reflections	l = −15→14

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	All H-atom parameters refined
S = 1.08	w = 1/[σ²(F_o²) + (0.0782P)² + 0.0918P] where P = (F_o² + 2F_c²)/3
2716 reflections	(Δ/σ)_max = 0.001
129 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₅N₃	V = 736.84 (3) Å³
M_r = 155.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.8055 (1) Å	µ = 0.09 mm⁻¹
b = 19.0466 (4) Å	T = 100 K
c = 10.1845 (2) Å	0.39 × 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)
T_min = 0.966, T_max = 0.978	R_int = 0.023
11604 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.135	All H-atom parameters refined
S = 1.08	Δρ_max = 0.53 e Å⁻³
2716 reflections	Δρ_min = −0.23 e Å⁻³
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

	x	y	z	U_iso*/U_eq
N1	0.12156 (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)
C1	0.1884 (2)	0.39728 (4)	0.89844 (8)	0.01344 (17)
C2	0.3822 (2)	0.39456 (5)	1.02181 (9)	0.01744 (18)
C3	0.4514 (2)	0.33059 (5)	1.07937 (10)	0.02033 (19)
C4	0.3352 (2)	0.26756 (5)	1.01678 (10)	0.0210 (2)
C5	0.1474 (2)	0.26871 (5)	0.89805 (9)	0.01857 (19)
C6	0.0674 (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)
H2	0.471 (4)	0.4375 (7)	1.0662 (14)	0.030 (3)*
H3	0.591 (4)	0.3282 (7)	1.1650 (16)	0.038 (4)*
H4	0.396 (3)	0.2229 (7)	1.0622 (13)	0.028 (3)*
H5	0.057 (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) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0154 (3)	0.0145 (3)	0.0146 (3)	0.0003 (2)	0.0014 (2)	0.0010 (2)
N2	0.0168 (3)	0.0173 (3)	0.0157 (4)	−0.0006 (2)	0.0014 (3)	−0.0016 (3)
N3	0.0328 (4)	0.0235 (4)	0.0241 (5)	0.0028 (3)	−0.0002 (3)	0.0057 (3)
C1	0.0128 (3)	0.0147 (3)	0.0130 (4)	0.0002 (2)	0.0019 (3)	0.0004 (3)
C2	0.0157 (4)	0.0218 (4)	0.0147 (4)	−0.0004 (3)	−0.0002 (3)	0.0005 (3)
C3	0.0164 (4)	0.0275 (4)	0.0170 (4)	0.0019 (3)	0.0003 (3)	0.0055 (3)
C4	0.0176 (4)	0.0208 (4)	0.0248 (5)	0.0030 (3)	0.0042 (3)	0.0088 (3)
C5	0.0179 (4)	0.0147 (4)	0.0235 (5)	0.0007 (3)	0.0036 (3)	0.0029 (3)
C6	0.0131 (3)	0.0152 (3)	0.0151 (4)	0.0000 (2)	0.0027 (3)	0.0000 (3)
C7	0.0164 (4)	0.0195 (4)	0.0142 (4)	−0.0003 (3)	0.0000 (3)	−0.0004 (3)
C8	0.0145 (3)	0.0168 (4)	0.0137 (4)	0.0005 (3)	0.0019 (3)	0.0015 (3)
C9	0.0204 (4)	0.0202 (4)	0.0167 (4)	0.0005 (3)	0.0005 (3)	0.0015 (3)

Geometric parameters (Å, º) top

N1—C8	1.3220 (11)	C3—C4	1.4175 (14)
N1—C1	1.3636 (10)	C3—H3	0.995 (16)
N2—C7	1.3161 (11)	C4—C5	1.3670 (13)
N2—C6	1.3659 (11)	C4—H4	0.988 (13)
N3—C9	1.1506 (12)	C5—C6	1.4150 (11)
C1—C2	1.4190 (12)	C5—H5	0.980 (14)
C1—C6	1.4273 (11)	C7—C8	1.4202 (12)
C2—C3	1.3706 (12)	C7—H7	0.997 (14)
C2—H2	0.985 (14)	C8—C9	1.4495 (12)

C8—N1—C1	115.57 (7)	C4—C5—C6	119.57 (8)
C7—N2—C6	116.78 (7)	C4—C5—H5	123.2 (8)
N1—C1—C2	119.01 (7)	C6—C5—H5	117.2 (8)
N1—C1—C6	121.14 (8)	N2—C6—C5	119.33 (7)
C2—C1—C6	119.85 (7)	N2—C6—C1	121.28 (7)
C3—C2—C1	119.16 (8)	C5—C6—C1	119.38 (8)
C3—C2—H2	119.4 (8)	N2—C7—C8	121.44 (8)
C1—C2—H2	121.5 (8)	N2—C7—H7	120.7 (7)
C2—C3—C4	120.92 (9)	C8—C7—H7	117.9 (7)
C2—C3—H3	119.6 (8)	N1—C8—C7	123.77 (7)
C4—C3—H3	119.4 (8)	N1—C8—C9	117.52 (7)
C5—C4—C3	121.10 (8)	C7—C8—C9	118.71 (8)
C5—C4—H4	121.5 (8)	N3—C9—C8	177.49 (10)
C3—C4—H4	117.4 (8)

C8—N1—C1—C2	−179.34 (7)	C4—C5—C6—C1	0.84 (13)
C8—N1—C1—C6	0.75 (12)	N1—C1—C6—N2	−0.95 (13)
N1—C1—C2—C3	−179.68 (8)	C2—C1—C6—N2	179.14 (7)
C6—C1—C2—C3	0.24 (13)	N1—C1—C6—C5	178.94 (7)
C1—C2—C3—C4	0.62 (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—C6	0.00 (14)	C1—N1—C8—C7	−0.38 (12)
C7—N2—C6—C5	−179.20 (7)	C1—N1—C8—C9	179.15 (7)
C7—N2—C6—C1	0.69 (12)	N2—C7—C8—N1	0.18 (14)
C4—C5—C6—N2	−179.26 (7)	N2—C7—C8—C9	−179.36 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, z+1/2; (iii) −x−1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₅N₃
M_r	155.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	3.8055 (1), 19.0466 (4), 10.1845 (2)
β (°)	93.466 (1)
V (Å³)	736.84 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.39 × 0.28 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.966, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	11604, 2716, 2183
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.763

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.135, 1.08
No. of reflections	2716
No. of parameters	129
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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+1/2, z+1/2; (iii) −x−1, −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

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