3-(2,4-Difluoro­anilino)-9-nitro­dibenzo[b,e]oxepin-11(6H)-one

Benjamin Baur; Dieter Schollmeyer; Stefan Laufer

doi:10.1107/S1600536811002881

. 2011 Feb 2;67(Pt 3):o555. doi: 10.1107/S1600536811002881

3-(2,4-Difluoroanilino)-9-nitrodibenzo[b,e]oxepin-11(6H)-one

Benjamin Baur ^a, Dieter Schollmeyer ^b, Stefan Laufer ^a,^*

PMCID: PMC3052073 PMID: 21522320

Abstract

In the title compound, C₂₀H₁₂F₂N₂O₄, the two benzene rings of the tricyclic unit are oriented at a dihedral angle of 30.6 (1)°. The 2,4-difluoroanilino residue is oriented at a dihedral angle of 68.2 (1)° with respect to the phenoxy ring. In the crystal, N—H⋯O hydrogen bonds between the amino group and the carbonyl O atom of the oxepinone ring link the molecules into infinte chains along the c axis.

Related literature

For palladium-catalysed amination reactions of aryl halides with anilines, see: Jensen et al. (2004 ▶). For p38 MAP kinase inhibitors based on dibenzo[b,e]oxepin-11(6H)-one, see: Laufer et al. (2006 ▶).

Experimental

Crystal data

C₂₀H₁₂F₂N₂O₄
M _r = 382.32
Orthorhombic,
a = 27.0813 (15) Å
b = 13.0411 (8) Å
c = 4.5998 (2) Å
V = 1624.51 (15) Å³
Z = 4
Cu Kα radiation
μ = 1.08 mm⁻¹
T = 193 K
0.47 × 0.24 × 0.12 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: numerical (CORINC; Dräger & Gattow, 1971 ▶) T _min = 0.721, T _max = 0.882
3417 measured reflections
3010 independent reflections
2924 reflections with I > 2σ(I)
R _int = 0.051
3 standard reflections every 60 min intensity decay: 3%

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.127
S = 1.03
3010 reflections
253 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack, (1983 ▶), 1270 Friedel pairs
Flack parameter: −0.22 (18)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002881/im2261sup1.cif

e-67-0o555-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002881/im2261Isup2.hkl

e-67-0o555-Isup2.hkl^{(147.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N16—H16⋯O25ⁱ	0.95	2.32	3.236 (3)	162

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Based on dibenzo[b,e]oxepin-11(6H)-one (Laufer et al. 2006) as p38 MAP kinase inhibitors, our intent was to synthesize disubstituted oxepin derivatives. The title compound was synthesized in the course of an ongoing study to increase the solubility of the molecules. The structure of the title compound, at 193 K shows orthorhombic symmetry. The two phenyl rings of the tricyclic unit are oriented at a dihedral angle of 30.6 (1°). The 2,4-difluoroanilino residue is oriented at a dihedral angel of 68.2 (1°) towards the phenoxy ring. The crystal stucture is characterized by an intermolecular hydrogen bond N16–H···O25 (2.32 Å).

Experimental

For the preperation of the title compound a mixture of 200 mg (0.69 mmol) 3-chloro-9-nitrodibenzo[b,e]oxepin-11(6H)-one, 100 mg (0.77 mmol) 2–4-difluoroaniline, 1.00 g (3.07 mmol) Cs₂CO₃, 45 mg (0.10 mmol) 2-(dicyclohexylphosphino)-2`-4`-6`-triisopropylbiphenyl and 20 mg (0.09 mmol) Pd(OAc)₂ in 2 ml absolute tert-butanol and 10 ml absolute 2.4-dioxane was stirred for 1 h at 284 K under an argon atmosphere. The mixture was then filtered and evaporated under reduced pressure. The residue was purified by flash chromatography (SiO₂ n-hexane/ethyl acetate 2:1) to get 103 mg (0,27 mmol) of the product as a yellow solid (yield 39 %). Crystals of the title compound were obtained by slow evaporation of diethyl ether and hexane (1:1) at room temperature.