1-(Prop-2-en-1-yl)-3-[(prop-2-en-1-yl)­oxy]quin­oxalin-2(1H)-one

El Bourakadi, K.; El Bakri, Y.; Sebhaoui, J.; Rayni, I.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314617006563

organic compounds

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ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170656

https://doi.org/10.1107/S2414314617006563

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1-(Prop-2-en-1-yl)-3-[(prop-2-en-1-yl)oxy]quinoxalin-2(1H)-one

Khadija El Bourakadi,^a ^* Youness El Bakri,^a Jihad Sebhaoui,^a Ibtissam Rayni,^a El Mokhtar Essassi ^a and Joel T. Mague ^b

^aLaboratoire de Chimie Organique Hétérocyclique, URAC 21, Pôle de Compétence Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Mohammed V University, Rabat, Morocco, and ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: elbourakadi25@gmail.com

Edited by J. Simpson, University of Otago, New Zealand (Received 25 April 2017; accepted 2 May 2017; online 16 May 2017)

In the title compound, C₁₄H₁₄N₂O₂, the dihydroquinoxaline moiety deviates slightly from planarity. In the crystal, zigzag chains are formed by inversion-related C—H⋯O hydrogen bonds. Adjacent chains are associated through pairwise C—H⋯π(ring) and π-stacking interactions.

Keywords: crystal structure; dihydroquinoxalinone; hydrogen bonds; π-stacking.

CCDC reference: 1547344

Structure description

Nitrogen-containing heterocyclic compounds are indispensable structural units for medicinal chemists. Among the various heterocyclic compounds, quinoxaline derivatives display important biological activities including anticonvulsant (Ghadage & Shirote, 2011a ), antitubercular and antimicrobial activities (Ramalingam et al., 2010 ; Ghadage & Shirote, 2011b ). They are also used as NMDA receptor antagonists (Lin, 1996 ). These compounds also have applications in organic synthesis and as ligands in new coordination complexes (Nassar et al., 2013 ; Attia et al., 2013 ).

In the title compound (Fig. 1), the C1–C6 ring is planar to within 0.0094 (9) Å (r.m.s. deviation = 0.0065) while the C1/C6/N1/C7/C8/N2 ring deviates by 0.0192 (8) Å from planarity (r.m.s. deviation = 0.0125 Å). The dihedral angle between the mean planes of the two rings is 1.36 (6)°. The N1/C9–C11 unit is planar with an r.m.s. deviation of 0.0041 and subtends an angle of 84.77 (6)° to the dihydroquinoxalinone ring system. The propenyloxy substituent is far from planar, as indicated by the O2—C12—C13—C14 torsion angle of −128.4 (1)°. The plane of the C12–C14 segment subtends an angle of 51.00 (9)° to the dihydroquinoxalinone ring system.

Figure 1
The structure of title molecule, showing the atom-labelling scheme, with ellipsoids drawn at the 50% probability level.

In the crystal, atom O1 acts as a bifurcated acceptor, forming inversion-related C10—H10⋯O1ⁱ and C13—H13⋯O1ⁱⁱ hydrogen bonds that enclose R₂²(12) and R₂²(14) rings respectively. These contacts link the molecules into zigzag chains parallel to (10 $[\overline{1}]$ ) (Table 1 and Fig. 2). Inversion-related C12—H12B⋯Cg2ⁱⁱⁱ interactions (Table 1 and Fig. 2) bind two neighboring chains together and these paired chains are further associated through offset π-stacking interactions between head-to-tail pairs of dihydroquinoxaline units [Cg1⋯Cg2 = 3.8484 (8) Å, dihedral angle = 1.38 (6)°; Cg1 and Cg2 are the centroids of the N1/N2/C1/C6–C8 and C1–C6 rings respectively] (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O1ⁱ	0.97 (2)	2.54 (2)	3.4353 (16)	152.4 (15)
C12—H12B⋯Cg2ⁱⁱ	0.984 (17)	2.74 (2)	3.544 (1)	139 (1)
C13—H13⋯O1ⁱⁱⁱ	0.967 (18)	2.491 (18)	3.2604 (16)	136.4 (14)
Symmetry codes: (i) -x, -y, -z; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y, -z+1.

Figure 2
The packing viewed along the c-axis direction. C—H⋯O hydrogen bonds are shown as black dashed lines, while C—H⋯π(ring) interactions are shown as purple dashed lines. The π-stacking interactions are shown as orange dashed lines. Cg1 and Cg2 are the centroids of the C1–C6 and C1/C6/N1/C7/C8/N2 rings, respectively. [Symmetry codes (i), (ii) and (iii) are defined in Table 1

, while (iv) is −x, −y + 1, −z + 1.]

Synthesis and crystallization

A mixture of quinoxain-2,3-dione (1 g; 6,17 mmol),K₂CO₃ (1,7 g; 12,33 mmol), allylbromide (1,6 ml; 18,60 mmol) and tetra-n-butylammonium bromide as a catalyst in N,N-dimethylformamide (60 ml) was stirred at room temperature for 48 h. Solvent was removed under reduced pressure and the residue chromatographed on a silica-gel column using hexane and ethyl acetate (80/20) as eluent. Recrystallization of the solid product from ethanol afforded the title compound as colourless crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₂O₂
M_r	242.27
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	8.4015 (6), 9.0041 (6), 9.1465 (7)
α, β, γ (°)	114.214 (3), 101.275 (4), 90.978 (3)
V (Å³)	615.19 (8)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	0.72
Crystal size (mm)	0.19 × 0.17 × 0.05

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.84, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	4854, 2344, 2090
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.112, 1.06
No. of reflections	2344
No. of parameters	219
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.27
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1547344

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617006563/sj4106sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617006563/sj4106Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617006563/sj4106Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617006563/sj4106Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

1-(Prop-2-en-1-yl)-3-[(prop-2-en-1-yl)oxy]quinoxalin-2(1H)-one top

Crystal data top

C₁₄H₁₄N₂O₂	Z = 2
M_r = 242.27	F(000) = 256
Triclinic, P1	D_x = 1.308 Mg m⁻³
a = 8.4015 (6) Å	Cu Kα radiation, λ = 1.54178 Å
b = 9.0041 (6) Å	Cell parameters from 4058 reflections
c = 9.1465 (7) Å	θ = 5.4–74.5°
α = 114.214 (3)°	µ = 0.72 mm⁻¹
β = 101.275 (4)°	T = 150 K
γ = 90.978 (3)°	Plate, colourless
V = 615.19 (8) Å³	0.19 × 0.17 × 0.05 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2344 independent reflections
Radiation source: INCOATEC IµS micro-focus source	2090 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.024
Detector resolution: 10.4167 pixels mm^-1	θ_max = 74.5°, θ_min = 5.4°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −11→10
T_min = 0.84, T_max = 0.97	l = −10→10
4854 measured reflections

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)] = 0.041	Hydrogen site location: difference Fourier map
wR(F²) = 0.112	All H-atom parameters refined
S = 1.06	w = 1/[σ²(F_o²) + (0.058P)² + 0.1639P] where P = (F_o² + 2F_c²)/3
2344 reflections	(Δ/σ)_max < 0.001
219 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Special details top

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
O1	0.17021 (12)	0.09718 (10)	0.33041 (12)	0.0308 (2)
O2	0.38667 (11)	0.24075 (10)	0.61136 (11)	0.0257 (2)
N1	0.11292 (12)	0.34249 (12)	0.32610 (13)	0.0215 (2)
N2	0.35558 (12)	0.49626 (12)	0.61668 (13)	0.0227 (2)
C1	0.27145 (15)	0.58701 (14)	0.54019 (15)	0.0221 (3)
C2	0.31123 (16)	0.75694 (15)	0.61000 (16)	0.0265 (3)
H2	0.397 (2)	0.804 (2)	0.709 (2)	0.036 (4)*
C3	0.22833 (18)	0.85253 (16)	0.54246 (17)	0.0297 (3)
H3	0.260 (2)	0.971 (2)	0.592 (2)	0.033 (4)*
C4	0.10465 (17)	0.77887 (16)	0.40083 (17)	0.0282 (3)
H4	0.047 (2)	0.844 (2)	0.355 (2)	0.045 (5)*
C5	0.06517 (16)	0.61093 (16)	0.32696 (16)	0.0261 (3)
H5	−0.015 (2)	0.561 (2)	0.225 (2)	0.036 (4)*
C6	0.14787 (14)	0.51286 (14)	0.39596 (15)	0.0215 (3)
C7	0.19495 (15)	0.24637 (15)	0.39248 (15)	0.0225 (3)
C8	0.31766 (14)	0.34077 (15)	0.54840 (15)	0.0218 (3)
C9	−0.01289 (15)	0.25660 (15)	0.17450 (15)	0.0238 (3)
H9A	−0.106 (2)	0.3235 (19)	0.1812 (19)	0.028 (4)*
H9B	−0.0541 (19)	0.1501 (19)	0.1772 (19)	0.028 (4)*
C10	0.04657 (16)	0.22011 (17)	0.02069 (16)	0.0303 (3)
H10	−0.037 (2)	0.162 (2)	−0.079 (2)	0.046 (5)*
C11	0.19630 (19)	0.2551 (2)	0.01212 (19)	0.0403 (4)
H11A	0.284 (2)	0.313 (2)	0.111 (2)	0.043 (5)*
H11B	0.227 (3)	0.227 (2)	−0.096 (3)	0.055 (5)*
C12	0.51603 (15)	0.31527 (15)	0.75823 (16)	0.0263 (3)
H12A	0.4707 (19)	0.3934 (19)	0.8475 (19)	0.026 (4)*
H12B	0.601 (2)	0.376 (2)	0.737 (2)	0.032 (4)*
C13	0.58081 (15)	0.17844 (16)	0.79496 (17)	0.0267 (3)
H13	0.613 (2)	0.092 (2)	0.704 (2)	0.036 (4)*
C14	0.59740 (16)	0.17503 (19)	0.93963 (19)	0.0333 (3)
H14A	0.566 (2)	0.265 (2)	1.034 (2)	0.038 (4)*
H14B	0.641 (2)	0.083 (2)	0.958 (2)	0.037 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0343 (5)	0.0177 (4)	0.0329 (5)	0.0004 (4)	−0.0022 (4)	0.0078 (4)
O2	0.0274 (5)	0.0214 (4)	0.0261 (5)	0.0008 (3)	−0.0026 (4)	0.0117 (4)
N1	0.0213 (5)	0.0202 (5)	0.0216 (5)	0.0008 (4)	0.0027 (4)	0.0085 (4)
N2	0.0251 (5)	0.0212 (5)	0.0221 (5)	0.0004 (4)	0.0041 (4)	0.0100 (4)
C1	0.0255 (6)	0.0226 (6)	0.0214 (6)	0.0021 (5)	0.0076 (5)	0.0113 (5)
C2	0.0323 (7)	0.0219 (6)	0.0241 (6)	−0.0002 (5)	0.0063 (5)	0.0085 (5)
C3	0.0398 (7)	0.0202 (6)	0.0316 (7)	0.0028 (5)	0.0119 (6)	0.0117 (5)
C4	0.0340 (7)	0.0266 (7)	0.0321 (7)	0.0082 (5)	0.0112 (5)	0.0185 (5)
C5	0.0264 (6)	0.0271 (7)	0.0272 (7)	0.0046 (5)	0.0061 (5)	0.0139 (5)
C6	0.0224 (6)	0.0208 (6)	0.0230 (6)	0.0021 (4)	0.0079 (5)	0.0097 (5)
C7	0.0232 (6)	0.0208 (6)	0.0231 (6)	0.0022 (4)	0.0042 (5)	0.0093 (5)
C8	0.0228 (6)	0.0207 (6)	0.0228 (6)	0.0026 (4)	0.0045 (5)	0.0103 (5)
C9	0.0205 (6)	0.0243 (6)	0.0240 (6)	−0.0012 (5)	0.0010 (5)	0.0096 (5)
C10	0.0292 (7)	0.0329 (7)	0.0234 (7)	0.0007 (5)	0.0019 (5)	0.0084 (5)
C11	0.0344 (8)	0.0514 (9)	0.0291 (8)	−0.0005 (7)	0.0104 (6)	0.0097 (7)
C12	0.0251 (6)	0.0252 (6)	0.0248 (7)	−0.0007 (5)	−0.0008 (5)	0.0098 (5)
C13	0.0216 (6)	0.0284 (6)	0.0295 (7)	0.0022 (5)	0.0020 (5)	0.0132 (5)
C14	0.0260 (6)	0.0405 (8)	0.0363 (8)	0.0031 (6)	0.0000 (5)	0.0221 (7)

Geometric parameters (Å, º) top

O1—C7	1.2202 (15)	C5—H5	0.962 (18)
O2—C8	1.3385 (15)	C7—C8	1.4900 (17)
O2—C12	1.4494 (15)	C9—C10	1.4960 (19)
N1—C7	1.3713 (16)	C9—H9A	0.993 (16)
N1—C6	1.3982 (15)	C9—H9B	1.026 (16)
N1—C9	1.4688 (15)	C10—C11	1.317 (2)
N2—C8	1.2812 (16)	C10—H10	0.97 (2)
N2—C1	1.3971 (16)	C11—H11A	0.986 (19)
C1—C2	1.3993 (17)	C11—H11B	1.00 (2)
C1—C6	1.4080 (17)	C12—C13	1.4892 (17)
C2—C3	1.3769 (19)	C12—H12A	0.983 (16)
C2—H2	0.970 (18)	C12—H12B	0.984 (17)
C3—C4	1.394 (2)	C13—C14	1.316 (2)
C3—H3	0.981 (17)	C13—H13	0.967 (18)
C4—C5	1.3821 (18)	C14—H14A	1.000 (18)
C4—H4	0.943 (19)	C14—H14B	0.972 (18)
C5—C6	1.4026 (17)

C8—O2—C12	116.73 (9)	N2—C8—C7	126.24 (11)
C7—N1—C6	122.40 (10)	O2—C8—C7	110.83 (10)
C7—N1—C9	116.37 (10)	N1—C9—C10	113.87 (10)
C6—N1—C9	121.22 (10)	N1—C9—H9A	107.6 (9)
C8—N2—C1	117.14 (10)	C10—C9—H9A	111.8 (9)
N2—C1—C2	118.74 (11)	N1—C9—H9B	106.4 (9)
N2—C1—C6	122.05 (11)	C10—C9—H9B	110.4 (9)
C2—C1—C6	119.20 (11)	H9A—C9—H9B	106.4 (13)
C3—C2—C1	121.01 (12)	C11—C10—C9	126.25 (13)
C3—C2—H2	121.9 (10)	C11—C10—H10	120.2 (11)
C1—C2—H2	117.0 (10)	C9—C10—H10	113.5 (11)
C2—C3—C4	119.59 (12)	C10—C11—H11A	122.6 (11)
C2—C3—H3	119.8 (10)	C10—C11—H11B	121.9 (12)
C4—C3—H3	120.5 (10)	H11A—C11—H11B	115.5 (16)
C5—C4—C3	120.71 (12)	O2—C12—C13	106.27 (10)
C5—C4—H4	119.4 (12)	O2—C12—H12A	108.9 (9)
C3—C4—H4	119.9 (12)	C13—C12—H12A	112.5 (9)
C4—C5—C6	120.05 (12)	O2—C12—H12B	109.2 (10)
C4—C5—H5	119.7 (10)	C13—C12—H12B	111.7 (10)
C6—C5—H5	120.2 (10)	H12A—C12—H12B	108.2 (14)
N1—C6—C5	122.36 (11)	C14—C13—C12	123.59 (13)
N1—C6—C1	118.22 (11)	C14—C13—H13	121.8 (10)
C5—C6—C1	119.41 (11)	C12—C13—H13	114.6 (10)
O1—C7—N1	123.43 (11)	C13—C14—H14A	122.2 (10)
O1—C7—C8	122.73 (11)	C13—C14—H14B	120.4 (10)
N1—C7—C8	113.85 (10)	H14A—C14—H14B	117.4 (14)
N2—C8—O2	122.93 (11)

C8—N2—C1—C2	−179.10 (11)	C6—N1—C7—O1	−177.41 (11)
C8—N2—C1—C6	1.18 (18)	C9—N1—C7—O1	1.48 (18)
N2—C1—C2—C3	−177.86 (11)	C6—N1—C7—C8	2.70 (17)
C6—C1—C2—C3	1.87 (19)	C9—N1—C7—C8	−178.41 (10)
C1—C2—C3—C4	−1.1 (2)	C1—N2—C8—O2	−178.49 (10)
C2—C3—C4—C5	−0.4 (2)	C1—N2—C8—C7	1.61 (19)
C3—C4—C5—C6	1.1 (2)	C12—O2—C8—N2	−3.60 (18)
C7—N1—C6—C5	179.27 (11)	C12—O2—C8—C7	176.30 (10)
C9—N1—C6—C5	0.43 (18)	O1—C7—C8—N2	176.57 (12)
C7—N1—C6—C1	−0.35 (18)	N1—C7—C8—N2	−3.54 (19)
C9—N1—C6—C1	−179.18 (10)	O1—C7—C8—O2	−3.33 (18)
C4—C5—C6—N1	−179.89 (11)	N1—C7—C8—O2	176.56 (10)
C4—C5—C6—C1	−0.28 (19)	C7—N1—C9—C10	−94.54 (13)
N2—C1—C6—N1	−1.83 (18)	C6—N1—C9—C10	84.37 (14)
C2—C1—C6—N1	178.45 (11)	N1—C9—C10—C11	1.2 (2)
N2—C1—C6—C5	178.54 (11)	C8—O2—C12—C13	−175.46 (10)
C2—C1—C6—C5	−1.18 (18)	O2—C12—C13—C14	−128.35 (13)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1ⁱ	0.97 (2)	2.54 (2)	3.4353 (16)	152.4 (15)
C12—H12B···Cg2ⁱⁱ	0.984 (17)	2.74 (2)	3.544 (1)	139 (1)
C13—H13···O1ⁱⁱⁱ	0.967 (18)	2.491 (18)	3.2604 (16)	136.4 (14)

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

Acknowledgements

The support of NSF–MRI Grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

References

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