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. 2026 Sep 3;11(Pt 9):x260892. doi: 10.1107/S2414314626008928

6,7-Di­chloro-2-methyl-3-phenyl­quinoxaline

Myron W Jones a, Katelyn M Aldridge b, Guy Crundwell b,*
Editor: M Zellerc
PMCID: PMC13640444  PMID: 42840957

The title compound was synthesized using the acid catalyst NH4HF2 in a water/methanol solution. The extended structure features offset stacked quinoxalines along the [100] direction.

Keywords: crystal structure, quinoxaline

Abstract

The title compound, C15H10Cl2N2, was synthesized using the acid catalyst NH4HF2 in a water/methanol solution. The dihedral angle between the phenyl ring and the quinoxaline unit is 39.80 (5)°. There is an inter­molecular hydrogen-bonding-like inter­action with a neighboring chlorine atom at a distance of 2.76 Å. The extended structure features offset-stacked quinoxaline units along the [100] direction.graphic file with name x-11-x260892-scheme1-3D1.webp

Structure description

In general, quinoxalines are of inter­est as potential anti­bacterial (Parhi et al., 2013 ▸), anti­microbial (Singh et al., 2010 ▸), and anti­fungal medicines (Tang et al., 2022 ▸) and therefore exploring their synthesis and structures are of inter­est. The title compound was synthesized via a condensation reaction of a di­amine and diketone using a water/methanol solution containing the NH4HF2 catalyst (Lassagne et al., 2015 ▸).

The mol­ecular structure is shown in Fig. 1 ▸. The quinoxaline ring system is essentially planar. The r.m.s. deviation of the di­chloro­quinoxaline unit (using atoms C1–C9, N1, N2, Cl1, and Cl2) is only 0.0604 Å. The quinoxaline moiety makes an angle of 39.80 (5)° with respect to the phenyl ring. There is a hydrogen-bonding-like inter­action between a carbon hydrogen and a neighboring chlorine atom (Table 1 ▸). Mol­ecules stack along the [100] direction of the unit cell (Fig. 2 ▸). Analysis of ring inter­actions using PLATON (Spek, 2009 ▸) indicats that the quinoxaline ring system (C1–C6,C8,C9,N1,N2) exhibits π⋯π stacking with inter­planar spacings of 3.5039 (7) Å [for neighbor at (1 − x, −y, z)], 3.4022 (7) Å [for neighbor at (Inline graphic − x, y, −Inline graphic + z)], and 3.3845 (7) Å [for neighbor at (Inline graphic − x, y, 1/2 + z)] with slippages of 1.515, 3.582, and 3.565Å, respectively..

Figure 1.

Figure 1

A view of the title molecule. Hydrogen atoms are omitted and displacement ellipsoids are drawn at the 50% probability level.

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C2—H2⋯Cl2i 0.95 2.76 3.704 (3) 175

Symmetry code: (i) Inline graphic.

Figure 2.

Figure 2

A view of the unit-cell packing along the [100] direction.

Synthesis and crystallization

In a 50 mL Erlenmeyer flask, 1.49 g of 1-phenyl-1,2-propane­dione (10.0 mmol) were added to 2 mL of H2O and 20 mL of a 2.5 x 10−3M methanol solution of NH4HF2 (Lassagne et al., 2015 ▸). To this mixture 1.78 g of 4,5-di­chloro-1,2-phenyl­enedi­amine (10.0 mmol) were added. The solution was stirred for 24 h during which the product precipitated as a pale light-tan product. 2.65 g of crude product were isolated and recrysallized from methanol solution yielding 1.92 g of purified product (66%). Crystals for the diffraction study were isolated by the slow evaporation of 50/50 hexa­ne/ethyl acetate solutions. M.p: 426 K; 1H NMR (CDCl3, 300 MHz): δ = 2.78 (s, 3H), 7.55 (m, 3H), 7.64 (m, 2H), 8.17 (s, 1H), 8.22 (s, 1H); 13C NMR (CDCl3, 300 MHz): δ = 24.51, 128.85, 128.91, 129.16, 129.43, 129.84, 133.65, 134.12, 138.31, 139.77, 139.86, 153.98, 155.89.

Refinement

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

Table 2. Experimental details.

Crystal data
Chemical formula C15H10Cl2N2
M r 289.15
Crystal system, space group Orthorhombic, Aea2
Temperature (K) 150
a, b, c (Å) 13.7569 (4), 26.2508 (8), 7.1470 (2)
V (Å3) 2580.99 (13)
Z 8
Radiation type Cu Kα
μ (mm−1) 4.40
Crystal size (mm) 0.21 × 0.11 × 0.06
 
Data collection
Diffractometer Bruker AXS D8 Quest
Absorption correction Multi-scan (SADABS; Krause et al., 2015 ▸)
Tmin, Tmax 0.500, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections 35150, 2788, 2646
R int 0.064
(sin θ/λ)max (Å−1) 0.640
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.078, 1.11
No. of reflections 2788
No. of parameters 173
No. of restraints 1
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.23, −0.28
Absolute structure Flack x determined using 1146 quotients [(I+)−(I−)]/[(I+)+(I−)] (Parsons et al., 2013 ▸)
Absolute structure parameter 0.004 (7)

Computer programs: APEX6 and SAINT (Bruker, 2026 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2025/1 (Sheldrick, 2015b ▸), OLEX2 (Dolomanov et al., 2009 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2020 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2414314626008928/zl4103sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2414314626008928/zl4103Isup2.hkl

x-11-x260892-Isup2.hkl (223.4KB, hkl)
x-11-x260892-Isup3.cml (4.9KB, cml)

Supporting information file. DOI: 10.1107/S2414314626008928/zl4103Isup3.cml

CCDC reference: 2583897

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by a CCSU-AAUP grant. All data were collected at Purdue University by Dr Matthias Zeller as part of the American Crystallographic Association Summer Course (2026). Dr Zeller also assisted with the refinement.

full crystallographic data

6,7-Dichloro-2-methyl-3-phenylquinoxaline. Crystal data

C15H10Cl2N2 Dx = 1.488 Mg m−3
Mr = 289.15 Melting point: 426 K
Orthorhombic, Aea2 Cu Kα radiation, λ = 1.54178 Å
a = 13.7569 (4) Å Cell parameters from 9889 reflections
b = 26.2508 (8) Å θ = 3.4–80.1°
c = 7.1470 (2) Å µ = 4.40 mm−1
V = 2580.99 (13) Å3 T = 150 K
Z = 8 Plate, clear colourless
F(000) = 1184 0.21 × 0.11 × 0.06 mm

6,7-Dichloro-2-methyl-3-phenylquinoxaline. Data collection

Bruker AXS D8 Quest diffractometer 2788 independent reflections
Radiation source: I-mu-S 3.0 microsource X-ray tube 2646 reflections with I > 2σ(I)
HELIOS multilayer Montel optics monochromator Rint = 0.064
Detector resolution: 7.4074 pixels mm-1 θmax = 80.6°, θmin = 3.4°
ω and phi scans h = −17→17
Absorption correction: multi-scan (SADABS; Krause et al., 2015) k = −33→33
Tmin = 0.500, Tmax = 0.754 l = −8→9
35150 measured reflections

6,7-Dichloro-2-methyl-3-phenylquinoxaline. Refinement

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)] = 0.029 H-atom parameters constrained
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.0438P)2 + 0.4866P] where P = (Fo2 + 2Fc2)/3
S = 1.11 (Δ/σ)max = 0.001
2788 reflections Δρmax = 0.23 e Å−3
173 parameters Δρmin = −0.28 e Å−3
1 restraint Absolute structure: Flack x determined using 1146 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: dual Absolute structure parameter: 0.004 (7)

6,7-Dichloro-2-methyl-3-phenylquinoxaline. Special details

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. Hydrogen atoms on sp2 and sp3 carbons were placed at calculated positions with a C-H distance of 0.95 Å and 0.98 Å and were included in the refinement in riding motion approximation with Uiso = 1.2Ueq or 1.5Ueq of the carrier atom, respectively.

6,7-Dichloro-2-methyl-3-phenylquinoxaline. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
C1 0.37186 (15) 0.47901 (10) 0.6000 (4) 0.0262 (5)
C3 0.37034 (16) 0.56404 (10) 0.4771 (4) 0.0284 (5)
C10 0.37433 (14) 0.32221 (9) 0.4945 (4) 0.0242 (5)
C15 0.42966 (17) 0.30390 (9) 0.3437 (3) 0.0258 (5)
H15 0.466810 0.327048 0.270755 0.031*
N1 0.37599 (15) 0.44750 (9) 0.7518 (3) 0.0280 (5)
Cl1 0.36731 (4) 0.62940 (2) 0.51359 (11) 0.03628 (18)
C13 0.37601 (17) 0.21837 (10) 0.4054 (4) 0.0303 (5)
H13 0.377408 0.183049 0.376637 0.036*
C6 0.37267 (16) 0.45912 (9) 0.4161 (4) 0.0242 (5)
C12 0.31946 (17) 0.23595 (9) 0.5524 (3) 0.0306 (5)
H12 0.281249 0.212716 0.622943 0.037*
Cl2 0.37977 (5) 0.58627 (2) 0.10644 (10) 0.03599 (18)
C4 0.37379 (16) 0.54433 (10) 0.2935 (4) 0.0275 (5)
C5 0.37397 (16) 0.49310 (10) 0.2613 (4) 0.0267 (5)
H5 0.374956 0.480307 0.136961 0.032*
C8 0.37819 (16) 0.39822 (10) 0.7220 (4) 0.0250 (5)
C14 0.43071 (17) 0.25251 (10) 0.3002 (4) 0.0291 (5)
H14 0.468808 0.240553 0.198416 0.035*
N2 0.37302 (13) 0.40786 (8) 0.3852 (3) 0.0259 (5)
C2 0.36965 (16) 0.53235 (11) 0.6280 (4) 0.0294 (5)
H2 0.367700 0.545967 0.751059 0.035*
C9 0.37394 (14) 0.37773 (10) 0.5335 (4) 0.0232 (5)
C11 0.31853 (16) 0.28751 (8) 0.5968 (4) 0.0276 (4)
H11 0.279563 0.299277 0.697663 0.033*
C7 0.38880 (19) 0.36530 (10) 0.8927 (4) 0.0299 (5)
H7A 0.325163 0.351482 0.927622 0.045*
H7B 0.414578 0.385727 0.996143 0.045*
H7C 0.433567 0.337216 0.865550 0.045*

6,7-Dichloro-2-methyl-3-phenylquinoxaline. Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
C1 0.0260 (11) 0.0266 (13) 0.0260 (11) 0.0011 (8) 0.0006 (10) −0.0021 (11)
C3 0.0277 (11) 0.0226 (13) 0.0350 (14) −0.0003 (8) 0.0032 (9) −0.0036 (10)
C10 0.0257 (10) 0.0242 (11) 0.0228 (12) 0.0017 (7) −0.0034 (8) −0.0012 (10)
C15 0.0287 (10) 0.0266 (11) 0.0221 (10) 0.0002 (9) −0.0007 (8) 0.0006 (8)
N1 0.0320 (10) 0.0285 (11) 0.0235 (10) 0.0005 (8) 0.0006 (7) −0.0029 (9)
Cl1 0.0454 (3) 0.0214 (3) 0.0421 (4) −0.0014 (2) 0.0073 (3) −0.0051 (2)
C13 0.0405 (13) 0.0215 (13) 0.0289 (13) 0.0001 (9) −0.0036 (11) −0.0014 (10)
C6 0.0256 (11) 0.0218 (12) 0.0252 (11) 0.0012 (8) −0.0003 (8) −0.0007 (10)
C12 0.0354 (12) 0.0287 (12) 0.0278 (13) −0.0049 (9) 0.0008 (8) 0.0018 (8)
Cl2 0.0506 (3) 0.0257 (3) 0.0316 (3) −0.0025 (2) −0.0014 (3) 0.0041 (2)
C4 0.0281 (11) 0.0266 (13) 0.0278 (13) −0.0002 (9) −0.0006 (9) 0.0014 (10)
C5 0.0303 (12) 0.0256 (12) 0.0241 (13) −0.0006 (9) −0.0005 (8) 0.0000 (10)
C8 0.0249 (11) 0.0268 (12) 0.0234 (12) 0.0001 (8) 0.0003 (8) −0.0026 (10)
C14 0.0332 (11) 0.0294 (11) 0.0246 (10) 0.0028 (10) 0.0008 (9) −0.0028 (9)
N2 0.0281 (10) 0.0256 (12) 0.0240 (11) 0.0018 (7) −0.0002 (8) −0.0016 (8)
C2 0.0346 (12) 0.0270 (13) 0.0267 (14) 0.0006 (8) 0.0027 (9) −0.0056 (10)
C9 0.0225 (9) 0.0252 (12) 0.0220 (11) 0.0005 (7) 0.0005 (8) 0.0001 (9)
C11 0.0292 (10) 0.0281 (11) 0.0257 (10) 0.0000 (8) 0.0019 (9) −0.0018 (9)
C7 0.0374 (12) 0.0296 (14) 0.0226 (12) 0.0005 (10) −0.0029 (10) −0.0008 (10)

6,7-Dichloro-2-methyl-3-phenylquinoxaline. Geometric parameters (Å, º)

C1—N1 1.365 (4) C6—N2 1.364 (3)
C1—C6 1.415 (4) C12—H12 0.9500
C1—C2 1.415 (4) C12—C11 1.390 (3)
C3—Cl1 1.736 (3) Cl2—C4 1.734 (3)
C3—C4 1.411 (4) C4—C5 1.364 (4)
C3—C2 1.362 (4) C5—H5 0.9500
C10—C15 1.404 (3) C8—C9 1.451 (4)
C10—C9 1.484 (3) C8—C7 1.502 (4)
C10—C11 1.397 (3) C14—H14 0.9500
C15—H15 0.9500 N2—C9 1.323 (4)
C15—C14 1.385 (3) C2—H2 0.9500
N1—C8 1.311 (3) C11—H11 0.9500
C13—H13 0.9500 C7—H7A 0.9800
C13—C12 1.386 (4) C7—H7B 0.9800
C13—C14 1.391 (4) C7—H7C 0.9800
C6—C5 1.421 (3)
N1—C1—C6 121.0 (2) C6—C5—H5 120.4
N1—C1—C2 119.2 (3) C4—C5—C6 119.2 (2)
C6—C1—C2 119.8 (3) C4—C5—H5 120.4
C4—C3—Cl1 120.2 (2) N1—C8—C9 121.0 (2)
C2—C3—Cl1 119.0 (2) N1—C8—C7 116.0 (2)
C2—C3—C4 120.8 (2) C9—C8—C7 123.0 (2)
C15—C10—C9 118.8 (2) C15—C14—C13 120.0 (2)
C11—C10—C15 118.4 (2) C15—C14—H14 120.0
C11—C10—C9 122.7 (2) C13—C14—H14 120.0
C10—C15—H15 119.6 C9—N2—C6 117.4 (2)
C14—C15—C10 120.8 (2) C1—C2—H2 120.2
C14—C15—H15 119.6 C3—C2—C1 119.5 (2)
C8—N1—C1 118.0 (2) C3—C2—H2 120.2
C12—C13—H13 120.0 C8—C9—C10 122.6 (2)
C12—C13—C14 119.9 (2) N2—C9—C10 115.9 (2)
C14—C13—H13 120.0 N2—C9—C8 121.5 (2)
C1—C6—C5 119.5 (2) C10—C11—H11 119.7
N2—C6—C1 121.0 (2) C12—C11—C10 120.7 (2)
N2—C6—C5 119.6 (2) C12—C11—H11 119.7
C13—C12—H12 119.9 C8—C7—H7A 109.5
C13—C12—C11 120.1 (2) C8—C7—H7B 109.5
C11—C12—H12 119.9 C8—C7—H7C 109.5
C3—C4—Cl2 119.1 (2) H7A—C7—H7B 109.5
C5—C4—C3 121.2 (2) H7A—C7—H7C 109.5
C5—C4—Cl2 119.7 (2) H7B—C7—H7C 109.5
C1—N1—C8—C9 −1.5 (3) C6—N2—C9—C10 −179.98 (18)
C1—N1—C8—C7 176.4 (2) C6—N2—C9—C8 −2.3 (3)
C1—C6—C5—C4 −0.4 (3) C12—C13—C14—C15 0.8 (4)
C1—C6—N2—C9 −0.9 (3) Cl2—C4—C5—C6 177.70 (17)
C3—C4—C5—C6 −1.3 (3) C4—C3—C2—C1 −0.4 (4)
C10—C15—C14—C13 0.5 (3) C5—C6—N2—C9 178.54 (19)
C15—C10—C9—C8 −139.0 (2) C14—C13—C12—C11 −1.1 (4)
C15—C10—C9—N2 38.6 (3) N2—C6—C5—C4 −179.9 (2)
C15—C10—C11—C12 1.3 (3) C2—C1—N1—C8 −179.85 (19)
N1—C1—C6—C5 −176.4 (2) C2—C1—C6—C5 1.7 (3)
N1—C1—C6—N2 3.1 (3) C2—C1—C6—N2 −178.80 (19)
N1—C1—C2—C3 176.8 (2) C2—C3—C4—Cl2 −177.28 (18)
N1—C8—C9—C10 −178.79 (18) C2—C3—C4—C5 1.7 (4)
N1—C8—C9—N2 3.7 (3) C9—C10—C15—C14 −178.8 (2)
Cl1—C3—C4—Cl2 2.5 (3) C9—C10—C11—C12 178.5 (2)
Cl1—C3—C4—C5 −178.48 (17) C11—C10—C15—C14 −1.5 (3)
Cl1—C3—C2—C1 179.85 (16) C11—C10—C9—C8 43.8 (3)
C13—C12—C11—C10 0.0 (4) C11—C10—C9—N2 −138.6 (2)
C6—C1—N1—C8 −1.7 (3) C7—C8—C9—C10 3.4 (3)
C6—C1—C2—C3 −1.3 (3) C7—C8—C9—N2 −174.1 (2)

6,7-Dichloro-2-methyl-3-phenylquinoxaline. Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A
C2—H2···Cl2i 0.95 2.76 3.704 (3) 175

Symmetry code: (i) x, y, z+1.

References

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2414314626008928/zl4103sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2414314626008928/zl4103Isup2.hkl

x-11-x260892-Isup2.hkl (223.4KB, hkl)
x-11-x260892-Isup3.cml (4.9KB, cml)

Supporting information file. DOI: 10.1107/S2414314626008928/zl4103Isup3.cml

CCDC reference: 2583897

Additional supporting information: crystallographic information; 3D view; checkCIF report


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