2-Isopropyl-3-methyl­quinoxaline 1,4-dioxide

Li, J.-Y.; Sun, T.; Hao, A.-Y.; Qiao, H.; Xin, F.

doi:10.1107/S1600536810023706

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o1906

https://doi.org/10.1107/S1600536810023706

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2-Isopropyl-3-methylquinoxaline 1,4-dioxide

Jian-Ye Li,^a Tao Sun,^a Ai-You Hao,^a ^* Hongwei Qiao ^b and Feifei Xin ^a

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China, and ^bShandong Shengquan Chemical Co. Ltd, Jinan 250204, People's Republic of China
^*Correspondence e-mail: haoay@sdu.edu.cn

(Received 26 May 2010; accepted 18 June 2010; online 3 July 2010)

In the title compound, C₁₂H₁₄N₂O₂, the quinoxaline ring system and the C atoms of the methylene and methyl substituents lie on a mirror plane. The crystal packing is stabilized by weak π–π interactions [centroid–centroid distance = 3.680 (7) Å].

Related literature

For the preparation, see: Issidorides & Haddadin (1966 ). For the biological activity of quinoxaline di-N-oxide compounds, see: Amin et al. (2006 ); Edwards et al. (1975 ); Glazer & Chappel (1982 ).

Experimental

Crystal data

C₁₂H₁₄N₂O₂
M_r = 218.25
Orthorhombic, P n m a
a = 13.3879 (10) Å
b = 6.8462 (6) Å
c = 11.8861 (9) Å
V = 1089.44 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.29 × 0.27 × 0.26 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.651, T_max = 0.745
10376 measured reflections
1446 independent reflections
1062 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.203
S = 1.17
1446 reflections
96 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810023706/jh2164sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810023706/jh2164Isup2.hkl

checkCIF report

Comment top

In recent years, the compounds of quinoxaline di-N-oxide have been used as important and widely-used drugs for sterilization and growth-promoting of animals. Quinoxaline di-N-oxide also has pharmacological properties usable as intermediates for producing plant protection agents. The research in the crystal of quinoxaline di-N-oxide has great meaning to pharmacology. The title compound 2-isopropyl-3-methylquinoxaline 1,4-dioxide was obtained by Beirut Reaction: benzofurazan-N-oxides reacted with cyclohexanone catalysed by triethylamine without any other solvent.

Related literature top

For the preparation, see: Issidorides & Haddadin (1966). For the biological activity of quinoxaline di-N-oxide compounds, see: Amin et al. (2006); Edwards et al. (1975); Glazer & Chappel (1982).

Experimental top

Yellow crystals were obtained by slow evaporation of the solvents from solutions of the title compound in methanol. ¹H NMR (400 MHz, DMSO-d6): δ 8.43 (2H, d, J = 3.5 Hz, Ar—H), 7.88 (2H, d, J = 3.2 Hz, Ar—H), 2.93 (4H, s, CH₂), 1.83 (4H, s, CH₂); IRνmax (KBr, cm^-1): 3455, 3125, 2943, 2866, 1987, 1953, 1737, 1605, 1516, 1441, 1422, 1400, 1357, 1315, 1277, 1246, 1125, 1089, 1016, 979, 933, 904, 842, 824, 776, 694, 668, 640, 613, 557, 528, 436; Calcd for C₁₂H₁₂N₂O₂: C, 66.65; H, 5.59; N, 12.96. Found: C, 66.34; H, 5.32; N, 12.90; ESIMS calcd for C₁₂H₁₂N₂O₂H⁺ m/z 217.24, found m/z 217.20.

Structure description top

For the preparation, see: Issidorides & Haddadin (1966). For the biological activity of quinoxaline di-N-oxide compounds, see: Amin et al. (2006); Edwards et al. (1975); Glazer & Chappel (1982).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Ellipsoid plot.
	Fig. 2. Packing diagram.

2-Isopropyl-3-methylquinoxaline 1,4-dioxide top

Crystal data top

C₁₂H₁₄N₂O₂	D_x = 1.331 Mg m⁻³
M_r = 218.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 4638 reflections
a = 13.3879 (10) Å	θ = 3.0–27.9°
b = 6.8462 (6) Å	µ = 0.09 mm⁻¹
c = 11.8861 (9) Å	T = 296 K
V = 1089.44 (15) Å³	Block, colourless
Z = 4	0.29 × 0.27 × 0.26 mm
F(000) = 464

Data collection top

Bruker APEXII CCD area-detector diffractometer	1446 independent reflections
Radiation source: fine-focus sealed tube	1062 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
φ and ω scans	θ_max = 28.6°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −18→17
T_min = 0.651, T_max = 0.745	k = −9→9
10376 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.203	w = 1/[σ²(F_o²) + (0.0863P)² + 0.4481P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max < 0.001
1446 reflections	Δρ_max = 0.38 e Å⁻³
96 parameters	Δρ_min = −0.35 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (4)

Crystal data top

C₁₂H₁₄N₂O₂	V = 1089.44 (15) Å³
M_r = 218.25	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 13.3879 (10) Å	µ = 0.09 mm⁻¹
b = 6.8462 (6) Å	T = 296 K
c = 11.8861 (9) Å	0.29 × 0.27 × 0.26 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1446 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1062 reflections with I > 2σ(I)
T_min = 0.651, T_max = 0.745	R_int = 0.019
10376 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	1 restraint
wR(F²) = 0.203	H-atom parameters constrained
S = 1.17	Δρ_max = 0.38 e Å⁻³
1446 reflections	Δρ_min = −0.35 e Å⁻³
96 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 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.

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

	x	y	z	U_iso*/U_eq
C1	0.9509 (2)	0.2500	1.1853 (3)	0.0603 (8)
H11	0.9026	0.2500	1.2416	0.072*
C2	1.0499 (3)	0.2500	1.2128 (4)	0.0731 (10)
H2	1.0689	0.2500	1.2880	0.088*
C3	1.1212 (2)	0.2500	1.1306 (4)	0.0723 (11)
H3	1.1883	0.2500	1.1510	0.087*
C4	1.0962 (2)	0.2500	1.0186 (4)	0.0641 (9)
H4	1.1454	0.2500	0.9633	0.077*
C5	0.99369 (19)	0.2500	0.9893 (2)	0.0449 (6)
C6	0.92245 (18)	0.2500	1.0730 (2)	0.0440 (6)
C7	0.79331 (18)	0.2500	0.9352 (2)	0.0427 (6)
C8	0.8664 (2)	0.2500	0.8500 (2)	0.0481 (6)
C9	0.8419 (3)	0.2500	0.7287 (3)	0.0705 (9)
H9A	0.9023	0.2500	0.6845	0.080*
H9B	0.8034	0.1355	0.7099	0.080*
C10	0.6836 (2)	0.2500	0.9063 (3)	0.0551 (7)
H10	0.6798	0.2500	0.8240	0.066*
C11	0.63084 (17)	0.0655 (4)	0.9452 (2)	0.0777 (8)
H11A	0.6657	−0.0468	0.9169	0.117*
H11B	0.5636	0.0652	0.9173	0.117*
H11C	0.6299	0.0615	1.0259	0.117*
N1	0.82094 (15)	0.2500	1.04424 (19)	0.0445 (6)
N2	0.96482 (17)	0.2500	0.8772 (2)	0.0513 (6)
O1	0.75580 (15)	0.2500	1.12490 (18)	0.0681 (7)
O2	1.03357 (18)	0.2500	0.8002 (2)	0.0809 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0617 (17)	0.0652 (18)	0.0539 (18)	0.000	−0.0125 (14)	0.000
C2	0.067 (2)	0.066 (2)	0.085 (3)	0.000	−0.0309 (19)	0.000
C3	0.0494 (16)	0.0531 (16)	0.114 (3)	0.000	−0.0284 (19)	0.000
C4	0.0403 (13)	0.0433 (14)	0.109 (3)	0.000	0.0089 (16)	0.000
C5	0.0405 (12)	0.0326 (11)	0.0616 (17)	0.000	0.0047 (11)	0.000
C6	0.0389 (12)	0.0377 (12)	0.0553 (15)	0.000	−0.0038 (11)	0.000
C7	0.0408 (12)	0.0438 (12)	0.0434 (14)	0.000	−0.0006 (10)	0.000
C8	0.0557 (14)	0.0409 (12)	0.0477 (15)	0.000	0.0076 (12)	0.000
C9	0.084 (2)	0.081 (2)	0.0466 (17)	0.000	0.0075 (16)	0.000
C10	0.0409 (13)	0.0706 (18)	0.0537 (17)	0.000	−0.0040 (12)	0.000
C11	0.0525 (11)	0.0818 (17)	0.099 (2)	−0.0170 (11)	−0.0097 (12)	0.0027 (15)
N1	0.0368 (10)	0.0509 (12)	0.0457 (12)	0.000	0.0050 (9)	0.000
N2	0.0485 (12)	0.0406 (11)	0.0648 (15)	0.000	0.0196 (11)	0.000
O1	0.0461 (10)	0.1067 (18)	0.0516 (12)	0.000	0.0126 (9)	0.000
O2	0.0716 (15)	0.0876 (17)	0.0836 (18)	0.000	0.0422 (13)	0.000

Geometric parameters (Å, º) top

C1—C2	1.365 (4)	C7—C10	1.508 (4)
C1—C6	1.389 (4)	C8—N2	1.357 (4)
C1—H11	0.9300	C8—C9	1.479 (4)
C2—C3	1.366 (6)	C9—H9A	0.964 (4)
C2—H2	0.9300	C9—H9B	0.964 (2)
C3—C4	1.373 (5)	C10—C11ⁱ	1.519 (3)
C3—H3	0.9300	C10—C11	1.519 (3)
C4—C5	1.416 (4)	C10—H10	0.9800
C4—H4	0.9300	C11—H11A	0.9600
C5—C6	1.378 (4)	C11—H11B	0.9600
C5—N2	1.387 (4)	C11—H11C	0.9600
C6—N1	1.401 (3)	N1—O1	1.296 (3)
C7—N1	1.348 (3)	N2—O2	1.298 (3)
C7—C8	1.409 (4)

C2—C1—C6	119.7 (3)	C7—C8—C9	123.1 (3)
C2—C1—H11	120.1	C8—C9—H9A	110.2 (3)
C6—C1—H11	120.1	C8—C9—H9B	110.1 (2)
C1—C2—C3	120.5 (3)	H9A—C9—H9B	108.8 (2)
C1—C2—H2	119.7	C7—C10—C11ⁱ	112.56 (16)
C3—C2—H2	119.7	C7—C10—C11	112.56 (16)
C2—C3—C4	121.5 (3)	C11ⁱ—C10—C11	112.5 (3)
C2—C3—H3	119.2	C7—C10—H10	106.2
C4—C3—H3	119.2	C11ⁱ—C10—H10	106.2
C3—C4—C5	118.4 (3)	C11—C10—H10	106.2
C3—C4—H4	120.8	C10—C11—H11A	109.5
C5—C4—H4	120.8	C10—C11—H11B	109.5
C6—C5—N2	120.0 (2)	H11A—C11—H11B	109.5
C6—C5—C4	119.6 (3)	C10—C11—H11C	109.5
N2—C5—C4	120.4 (3)	H11A—C11—H11C	109.5
C5—C6—C1	120.3 (3)	H11B—C11—H11C	109.5
C5—C6—N1	119.7 (3)	O1—N1—C7	121.8 (2)
C1—C6—N1	120.0 (3)	O1—N1—C6	118.2 (2)
N1—C7—C8	120.0 (2)	C7—N1—C6	120.0 (2)
N1—C7—C10	119.1 (2)	O2—N2—C8	121.4 (3)
C8—C7—C10	120.9 (3)	O2—N2—C5	118.7 (2)
N2—C8—C7	120.2 (3)	C8—N2—C5	120.0 (2)
N2—C8—C9	116.6 (3)

C6—C1—C2—C3	0.000 (2)	C8—C7—C10—C11	115.8 (2)
C1—C2—C3—C4	0.000 (2)	C8—C7—N1—O1	180.0
C2—C3—C4—C5	0.000 (1)	C10—C7—N1—O1	0.0
C3—C4—C5—C6	0.000 (1)	C8—C7—N1—C6	0.0
C3—C4—C5—N2	180.000 (1)	C10—C7—N1—C6	180.0
N2—C5—C6—C1	180.0	C5—C6—N1—O1	180.0
C4—C5—C6—C1	0.000 (1)	C1—C6—N1—O1	0.0
N2—C5—C6—N1	0.0	C5—C6—N1—C7	0.0
C4—C5—C6—N1	180.0	C1—C6—N1—C7	180.0
C2—C1—C6—C5	0.000 (1)	C7—C8—N2—O2	180.0
C2—C1—C6—N1	180.0	C9—C8—N2—O2	0.0
N1—C7—C8—N2	0.0	C7—C8—N2—C5	0.0
C10—C7—C8—N2	180.0	C9—C8—N2—C5	180.0
N1—C7—C8—C9	180.0	C6—C5—N2—O2	180.0
C10—C7—C8—C9	0.0	C4—C5—N2—O2	0.0
N1—C7—C10—C11ⁱ	64.2 (2)	C6—C5—N2—C8	0.0
C8—C7—C10—C11ⁱ	−115.8 (2)	C4—C5—N2—C8	180.0
N1—C7—C10—C11	−64.2 (2)

Symmetry code: (i) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂O₂
M_r	218.25
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	296
a, b, c (Å)	13.3879 (10), 6.8462 (6), 11.8861 (9)
V (Å³)	1089.44 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.29 × 0.27 × 0.26

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.651, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	10376, 1446, 1062
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.203, 1.17
No. of reflections	1446
No. of parameters	96
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.35

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Acknowledgements

This work was supported by the NSFC (grant No. 20625307), the National Basic Research Program of China (973 Program, 2009CB930103) and the Graduate Independent Innovation Foundation of Shandong University (GIIFSDU).

References

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