2-(4-Fluoro­phen­yl)quinoxaline

Wang, C.-P.; Ma, S.; Yu, J.-L.; Yan, J.-B.; Zhang, Z.-Q.

doi:10.1107/S1600536812017771

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1779

doi:10.1107/S1600536812017771

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2-(4-Fluorophenyl)quinoxaline

Cui-Ping Wang,^a Saiyong Ma,^a Jiang-Long Yu,^a Jing-Bo Yan ^a and Zhi-Qiang Zhang ^a ^*

^aSchool of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, People's Republic of China
^*Correspondence e-mail: zhangzhiqiang@ustl.edu.cn

(Received 31 March 2012; accepted 21 April 2012; online 19 May 2012)

In the title compound, C₁₄H₉FN₂, the dihedral angle between the benzene ring and the quinoxaline ring system is 22.2 (3)°. Any aromatic π–π stacking in the crystal must be very weak, with a minimum centroid–centroid separation of 3.995 (2) Å.

Related literature

For background to the applications of quinoxaline derivatives, see: Lindsley et al. (2005 ); Dailey et al. (2001 ).

Experimental

Crystal data

C₁₄H₉FN₂
M_r = 224.23
Monoclinic, C 2/c
a = 24.249 (13) Å
b = 3.7925 (19) Å
c = 22.609 (13) Å
β = 91.866 (9)°
V = 2078.2 (19) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.10 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.981, T_max = 0.990
9711 measured reflections
2454 independent reflections
1797 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.109
S = 1.01
2454 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812017771/hb6725sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017771/hb6725Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812017771/hb6725Isup3.cml

checkCIF report

Comment top

Quinoxaline and its derivatives are an important class of nitrogen-containing heterocycles displaying both biologial activities (Lindsley et al., 2005) and technological applications (Dailey et al., 2001). Here, we report the synthesis and crystal structure of the title compound (Fig. 1).

In the title compound, C₁₄H₉FN₂, the dihedral angle between the benzene ring and the quinoxaline ring is 22.2 (3)°.

Related literature top

For background to the applications of quinoxaline derivatives, see: Lindsley et al. (2005); Dailey et al. (2001).

Experimental top

A solution of benzene-1,2-diamine (1.5 mmol) and 2-(4-fluorophenyl)-2-oxoacetaldehyde monohydrate (1.5 mmol) in EtOH (10 ml) was stirred at room temperature for 0.5 h. After completion of the reaction (monitored by TLC or HPLC), the precipitated solid was collected by filtration and dried to afford the pure product. Or after completion of the reaction, water was added to the reaction mixture and filtered to afford the product. When necessary, the product was recrystallized from ethanol/water. Colourless prisms were grown by slow evaporation of a solution in chloroform/ethanol (1:1).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids for the non-hydrogen atoms.

2-(4-Fluorophenyl)quinoxaline top

Crystal data top

C₁₄H₉FN₂	F(000) = 928
M_r = 224.23	D_x = 1.433 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.249 (13) Å	Cell parameters from 3509 reflections
b = 3.7925 (19) Å	θ = 1.7–27.9°
c = 22.609 (13) Å	µ = 0.10 mm⁻¹
β = 91.866 (9)°	T = 113 K
V = 2078.2 (19) Å³	Prism, colorless
Z = 8	0.20 × 0.18 × 0.10 mm

Data collection top

Rigaku Saturn724 CCD diffractometer	2454 independent reflections
Radiation source: rotating anode	1797 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.032
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.9°, θ_min = 1.7°
ω and ϕ scans	h = −31→31
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	k = −4→4
T_min = 0.981, T_max = 0.990	l = −29→29
9711 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0692P)²] where P = (F_o² + 2F_c²)/3
2454 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₄H₉FN₂	V = 2078.2 (19) Å³
M_r = 224.23	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 24.249 (13) Å	µ = 0.10 mm⁻¹
b = 3.7925 (19) Å	T = 113 K
c = 22.609 (13) Å	0.20 × 0.18 × 0.10 mm
β = 91.866 (9)°

Data collection top

Rigaku Saturn724 CCD diffractometer	2454 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	1797 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.990	R_int = 0.032
9711 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.01	Δρ_max = 0.25 e Å⁻³
2454 reflections	Δρ_min = −0.22 e Å⁻³
154 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
F1	0.46580 (3)	0.67692 (19)	1.18737 (3)	0.0321 (2)
N1	0.39311 (3)	0.1470 (2)	0.93164 (4)	0.0184 (2)
N2	0.28374 (3)	−0.1127 (2)	0.93193 (4)	0.0213 (2)
C1	0.36818 (4)	0.0119 (3)	0.88147 (4)	0.0182 (2)
C2	0.39774 (4)	−0.0011 (3)	0.82863 (5)	0.0216 (3)
H2	0.4347	0.0813	0.8283	0.026*
C3	0.37306 (5)	−0.1322 (3)	0.77801 (5)	0.0238 (3)
H3	0.3931	−0.1408	0.7426	0.029*
C4	0.31805 (5)	−0.2552 (3)	0.77785 (5)	0.0246 (3)
H4	0.3013	−0.3434	0.7423	0.030*
C5	0.28877 (4)	−0.2481 (3)	0.82842 (5)	0.0226 (3)
H5	0.2519	−0.3332	0.8280	0.027*
C6	0.31319 (4)	−0.1147 (3)	0.88123 (5)	0.0189 (2)
C7	0.30886 (4)	0.0153 (3)	0.97928 (5)	0.0205 (2)
H7	0.2895	0.0180	1.0152	0.025*
C8	0.36398 (4)	0.1514 (3)	0.97994 (5)	0.0175 (2)
C9	0.38994 (4)	0.2927 (3)	1.03511 (4)	0.0173 (2)
C10	0.35866 (4)	0.4178 (3)	1.08148 (5)	0.0204 (3)
H10	0.3195	0.4132	1.0779	0.025*
C11	0.38416 (5)	0.5485 (3)	1.13269 (5)	0.0217 (3)
H11	0.3630	0.6352	1.1642	0.026*
C12	0.44101 (5)	0.5499 (3)	1.13683 (5)	0.0217 (3)
C13	0.47352 (4)	0.4309 (3)	1.09221 (5)	0.0220 (3)
H13	0.5126	0.4356	1.0963	0.026*
C14	0.44741 (4)	0.3042 (3)	1.04120 (5)	0.0193 (2)
H14	0.4690	0.2235	1.0096	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0308 (4)	0.0440 (5)	0.0213 (4)	−0.0068 (3)	−0.0033 (3)	−0.0063 (3)
N1	0.0176 (4)	0.0186 (5)	0.0190 (4)	−0.0001 (4)	0.0009 (3)	0.0012 (4)
N2	0.0164 (4)	0.0220 (5)	0.0256 (5)	−0.0004 (4)	0.0011 (4)	0.0017 (4)
C1	0.0184 (5)	0.0157 (5)	0.0204 (5)	0.0005 (4)	−0.0014 (4)	0.0015 (4)
C2	0.0208 (5)	0.0212 (6)	0.0228 (6)	−0.0016 (4)	0.0017 (4)	0.0009 (4)
C3	0.0282 (6)	0.0227 (6)	0.0206 (5)	0.0005 (5)	0.0023 (4)	0.0004 (5)
C4	0.0279 (6)	0.0225 (6)	0.0229 (6)	0.0010 (5)	−0.0066 (4)	−0.0017 (5)
C5	0.0183 (5)	0.0208 (6)	0.0284 (6)	0.0000 (4)	−0.0045 (5)	−0.0002 (5)
C6	0.0180 (5)	0.0152 (5)	0.0233 (5)	0.0018 (4)	−0.0011 (4)	0.0023 (4)
C7	0.0164 (5)	0.0225 (6)	0.0226 (5)	−0.0002 (4)	0.0021 (4)	0.0026 (4)
C8	0.0156 (5)	0.0161 (6)	0.0207 (5)	0.0020 (4)	0.0002 (4)	0.0031 (4)
C9	0.0177 (5)	0.0159 (5)	0.0182 (5)	−0.0010 (4)	0.0007 (4)	0.0034 (4)
C10	0.0163 (5)	0.0224 (6)	0.0227 (5)	0.0008 (4)	0.0022 (4)	0.0032 (4)
C11	0.0245 (5)	0.0228 (6)	0.0183 (5)	0.0011 (5)	0.0050 (4)	0.0013 (4)
C12	0.0260 (5)	0.0221 (6)	0.0169 (5)	−0.0035 (4)	−0.0024 (4)	0.0007 (4)
C13	0.0176 (5)	0.0247 (6)	0.0235 (5)	−0.0008 (4)	−0.0010 (4)	0.0018 (5)
C14	0.0176 (5)	0.0196 (6)	0.0208 (5)	0.0007 (4)	0.0027 (4)	0.0012 (4)

Geometric parameters (Å, º) top

F1—C12	1.3617 (13)	C5—H5	0.9500
N1—C8	1.3198 (14)	C7—C8	1.4325 (15)
N1—C1	1.3676 (14)	C7—H7	0.9500
N2—C7	1.3078 (15)	C8—C9	1.4792 (16)
N2—C6	1.3703 (14)	C9—C14	1.3966 (15)
C1—C2	1.4138 (16)	C9—C10	1.3969 (15)
C1—C6	1.4171 (16)	C10—C11	1.3864 (16)
C2—C3	1.3676 (16)	C10—H10	0.9500
C2—H2	0.9500	C11—C12	1.3787 (17)
C3—C4	1.4131 (17)	C11—H11	0.9500
C3—H3	0.9500	C12—C13	1.3764 (16)
C4—C5	1.3656 (16)	C13—C14	1.3835 (15)
C4—H4	0.9500	C13—H13	0.9500
C5—C6	1.4095 (16)	C14—H14	0.9500

C8—N1—C1	117.21 (9)	C8—C7—H7	118.3
C7—N2—C6	116.44 (10)	N1—C8—C7	120.74 (10)
N1—C1—C2	119.44 (10)	N1—C8—C9	118.54 (10)
N1—C1—C6	121.36 (10)	C7—C8—C9	120.71 (9)
C2—C1—C6	119.20 (10)	C14—C9—C10	118.67 (10)
C3—C2—C1	119.98 (11)	C14—C9—C8	119.37 (9)
C3—C2—H2	120.0	C10—C9—C8	121.96 (10)
C1—C2—H2	120.0	C11—C10—C9	120.66 (10)
C2—C3—C4	120.63 (10)	C11—C10—H10	119.7
C2—C3—H3	119.7	C9—C10—H10	119.7
C4—C3—H3	119.7	C12—C11—C10	118.41 (10)
C5—C4—C3	120.52 (10)	C12—C11—H11	120.8
C5—C4—H4	119.7	C10—C11—H11	120.8
C3—C4—H4	119.7	F1—C12—C13	118.89 (10)
C4—C5—C6	120.05 (10)	F1—C12—C11	118.13 (10)
C4—C5—H5	120.0	C13—C12—C11	122.98 (10)
C6—C5—H5	120.0	C12—C13—C14	117.86 (10)
N2—C6—C5	119.65 (10)	C12—C13—H13	121.1
N2—C6—C1	120.73 (10)	C14—C13—H13	121.1
C5—C6—C1	119.61 (10)	C13—C14—C9	121.40 (10)
N2—C7—C8	123.50 (10)	C13—C14—H14	119.3
N2—C7—H7	118.3	C9—C14—H14	119.3

C8—N1—C1—C2	−179.57 (9)	C1—N1—C8—C9	179.40 (9)
C8—N1—C1—C6	0.65 (15)	N2—C7—C8—N1	−1.44 (17)
N1—C1—C2—C3	−179.32 (10)	N2—C7—C8—C9	179.95 (10)
C6—C1—C2—C3	0.47 (16)	N1—C8—C9—C14	−21.66 (15)
C1—C2—C3—C4	0.10 (17)	C7—C8—C9—C14	156.99 (10)
C2—C3—C4—C5	−0.63 (17)	N1—C8—C9—C10	157.91 (10)
C3—C4—C5—C6	0.56 (17)	C7—C8—C9—C10	−23.44 (16)
C7—N2—C6—C5	−179.90 (10)	C14—C9—C10—C11	−0.46 (16)
C7—N2—C6—C1	0.90 (15)	C8—C9—C10—C11	179.97 (10)
C4—C5—C6—N2	−179.19 (10)	C9—C10—C11—C12	−0.40 (16)
C4—C5—C6—C1	0.02 (16)	C10—C11—C12—F1	−179.66 (10)
N1—C1—C6—N2	−1.55 (16)	C10—C11—C12—C13	0.72 (17)
C2—C1—C6—N2	178.67 (9)	F1—C12—C13—C14	−179.76 (9)
N1—C1—C6—C5	179.25 (9)	C11—C12—C13—C14	−0.15 (18)
C2—C1—C6—C5	−0.53 (15)	C12—C13—C14—C9	−0.76 (16)
C6—N2—C7—C8	0.53 (16)	C10—C9—C14—C13	1.06 (16)
C1—N1—C8—C7	0.76 (15)	C8—C9—C14—C13	−179.36 (9)

Experimental details

Crystal data
Chemical formula	C₁₄H₉FN₂
M_r	224.23
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	113
a, b, c (Å)	24.249 (13), 3.7925 (19), 22.609 (13)
β (°)	91.866 (9)
V (Å³)	2078.2 (19)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.18 × 0.10

Data collection
Diffractometer	Rigaku Saturn724 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.981, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	9711, 2454, 1797
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.109, 1.01
No. of reflections	2454
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.22

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Open Fund of the Functional Material Laboratory–Key Laboratory of Liaoning Education Department (USTLKL-2011–10). The authors are indebted to Beijing Amber Tech Co. Ltd for the offer of some reagents.

References

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