N-(3-Bromo-1,4-dioxo-1,4-dihydro-2-naphth­yl)-4-fluoro-N-(4-fluoro­benzo­yl)benzamide

Emmanuel S Akinboye; Ray J Butcher; Dwayne A Wright; Yakini Brandy; Oladapo Bakare

doi:10.1107/S1600536809000117

. 2009 Jan 10;65(Pt 2):o277. doi: 10.1107/S1600536809000117

N-(3-Bromo-1,4-dioxo-1,4-dihydro-2-naphthyl)-4-fluoro-N-(4-fluorobenzoyl)benzamide

Emmanuel S Akinboye ^a, Ray J Butcher ^a,^*, Dwayne A Wright ^a, Yakini Brandy ^a, Oladapo Bakare ^a

PMCID: PMC2968378 PMID: 21581890

Abstract

In the title compound, C₂₄H₁₂BrF₂NO₄, synthesized from 2-amino-3-bromo-1,4-naphthoquinone and 4-fluorobenzoyl chloride, the two p-fluorophenyl rings are inclined at 73.9 (1) and 73.6 (1)° to the naphthoquinone ring system. The two imido carbonyl O atoms are anti to each other, while the fluorophenyl rings are located opposite each other, connected to the imide group in a funnel-like arrangement. This conformation allows the fluorine groups be oriented slightly away from each other. An examination of the packing shows a close intermolecular F⋯O contact of 2.982 (5) Å and a Br⋯O contact of 2.977 (4) Å. In addition, the molecules are linked by weak intermolecular C—H⋯O and C—H⋯F interactions.

Related literature

For similar structures, see: Lien et al. (1997 ▶); Huang et al. (2005 ▶); Bakare et al. (2003 ▶); Akinboye et al. (2009 ▶); Win et al. (2005 ▶); Rubin-Preminger et al. (2004 ▶). For general background, see: Berhe et al. (2008 ▶).

Experimental

Crystal data

C₂₄H₁₂BrF₂NO₄
M _r = 496.26
Monoclinic,
a = 14.5931 (3) Å
b = 6.6471 (1) Å
c = 20.6324 (4) Å
β = 98.407 (2)°
V = 1979.88 (6) Å³
Z = 4
Cu Kα radiation
μ = 3.30 mm⁻¹
T = 200 (2) K
0.53 × 0.48 × 0.32 mm

Data collection

Oxford Diffraction Gemini R diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.230, T _max = 0.348
7835 measured reflections
3802 independent reflections
3362 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.158
S = 1.14
3802 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 1.29 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: CrysAlisPro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlisPro; data reduction: CrysAlisPro; 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000117/bq2117sup1.cif

e-65-0o277-sup1.cif^{(21.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000117/bq2117Isup2.hkl

e-65-0o277-Isup2.hkl^{(186.4KB, 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
C5—H5A⋯O1Bⁱ	0.95	2.56	3.297 (6)	135
C4—H4A⋯F1Aⁱⁱ	0.95	2.40	3.266 (6)	151

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

We have developed some imido-substituted 2-chloro-1,4-naphthoquinones with cytotoxic activities on some cancer cell lines (Bakare et al., 2003; Berhe et al., 2008); and have recently reported on the crystal structure of N-(3-bromo-1,4-dioxo- 1,4-dihydro-naphthalen-2-yl)-2-chloro-N-(2-chloro-benzoyl)-benzamide (Akinboye et al., 2009). In continuation of our work, the title compound C₂₄H₁₂BrF₂NO₄, (I), was synthesized as a potential anticancer agent.

The crystal structure shows that the two p-fluorophenyl rings are inclined at 73.9 (1) and 73.6 (1)° to the naphthoquinone ring. The two imido carbonyl oxygen atoms are anti-to each other, while fluorophenyl rings are placed facing each other and connected to the imide moiety in a funnel-like arrangement. This conformation allowed the fluorine groups in the para position of each fluorophenyl ring to be oriented slightly away from each other. An examination of the packing shows a close contact between F1A and O2 at (1/2 - x, 1/2 + y, 1/2 - z) (2.982 (5)Å) and between C2 and O1B at (1/2 - x, -1/2 + y, 1/2 - z) (2.977 (4)Å). In addition, the molecules are linked by weak intermolecular C—H···O and C—H···F interactions (Table 1).

Experimental

To a solution 2-amino-3-bromo-1,4-naphthoquinone (300 mg, 1.19 mmol) in dry THF was added NaH (68.64 mg 2.86 mmol) and the mixture was stirred for 15 minutes. 4-Fluoro-benzoylchloride (0.35 ml, 2.86 mmol) was added thereafter and this mixture was stirred at room temperature for 16–24 hr under argon. The solvent was removed in vacuo and the solid residue was dissolved in dichloromethane (40 ml). The resultant solution was washed with water (3 x 15 ml), saturated NaCl solution (2 x 15 ml) and dried over anhydrous magnesium sulfate. The solvent was removed in vacuo and the residue recrystallized from ethyl acetate to obtain a yellow solid (391.0 g m). Further recrystallization was carried out in ethanol to furnish the title imide (340.2 mg, 57%).