2-Chloro-3-(4-chloro­benzamido)-1,4-naphthoquinone

Yakini Brandy; Ray J Butcher; Tolulope A Adesiyun; Solomon Berhe; Oladapo Bakare

doi:10.1107/S1600536808040993

. 2008 Dec 10;65(Pt 1):o64. doi: 10.1107/S1600536808040993

2-Chloro-3-(4-chlorobenzamido)-1,4-naphthoquinone

Yakini Brandy ^a, Ray J Butcher ^a,^*, Tolulope A Adesiyun ^a, Solomon Berhe ^a, Oladapo Bakare ^a

PMCID: PMC2967976 PMID: 21581704

Abstract

The naphthoquinone ring is almost perpendicular [dihedral angle 71.02 (3)°] to the phenyl group of the title compound, C₁₇H₉Cl₂NO₃, while the dihedral angle between the amide group and the 4-chlorophenyl ring is 21.9 (2)°. The conformation of the N—H and C=O bonds are anti to each other. N—H⋯Cl hydrogen bonds link the molecules into chains in the a-axis direction. In addition, these chains are linked by weak intermolecular C—H⋯O interactions.

Related literature

For similar structures see: Lien et al. (1997 ▶); Huang et al. (2005 ▶); Bakare et al. (2003 ▶); Copeland et al. (2007 ▶); Win et al. (2005 ▶); Rubin-Preminger et al. (2004 ▶). For related literature, see: Gowda, Kožíšek et al. (2008 ▶); Gowda, Tokarčík et al. (2008 ▶); van Oosten et al. (2008 ▶); Shen et al. (2008 ▶).

Experimental

Crystal data

C₁₇H₉Cl₂NO₃
M _r = 346.15
Monoclinic,
a = 5.6011 (2) Å
b = 8.7237 (3) Å
c = 29.7957 (9) Å
β = 93.504 (3)°
V = 1453.16 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 200 (2) K
0.49 × 0.41 × 0.12 mm

Data collection

Oxford Diffraction Gemini R diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.887, T _max = 1.000 (expected range = 0.839–0.946)
13882 measured reflections
4842 independent reflections
2832 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.086
S = 0.93
4842 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; 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/S1600536808040993/at2690sup1.cif

e-65-00o64-sup1.cif^{(18.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040993/at2690Isup2.hkl

e-65-00o64-Isup2.hkl^{(237.2KB, 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
N—H0A⋯Cl1ⁱ	0.88	2.89	3.6491 (12)	145
C14—H14A⋯O2ⁱⁱ	0.95	2.40	3.2517 (19)	149

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

Acknowledgments

RJB acknowledges the Laboratory for the Structure of Matter at the Naval Research Laboratory for access to their diffractometers.

supplementary crystallographic information

Comment

The amido and imido derivatives of 3-chloro-1,4-naphthoquinone are well known for their anti-inflammatory, antiplatelet, antiallergic and anticancer activities (Lien et al., 1997; Huang et al., 2005; Bakare et al., 2003; Copeland et al., 2007). The title compound, 2-chloro-3-(p-chlorobenzamido)-1,4-naphthoquinone was obtained as an intermediate in the synthesis of some oxazolo-1,4-naphthoquinone and imido-substituted-1,4-naphthoquinone analogs.

The naphthoquinone ring is almost perpendicular to the phenyl group of the title compound C₁₇H₉Cl₂NO₃, while the dihedral angle betwen the amide group and the 4-chlorophenyl ring is 21.9 (2)° (Fig. 1). The conformation of the N—H and C=O bonds are anti to each other (Gowda, Kožíšek et al., 2008; Gowda, Tokarčík et al., 2008). N—H···Cl hydrogen bonds link the molecules into chains in the a direction. In addition, these chains are linked by weak intermolecular Ar—H···O interactions (Fig. 2, Table 1).

Experimental

A mixture of 2-amino-3-chloro-1,4-naphthoquinone (213 mg, 1.03 mmol) and 4-chloro-benzoylchloride (2 ml) was refluxed for 2 1/2 h (powerstat setting at 70). The reaction mixture was cooled to room temperature. The precipitate was isolated by vacuum filtration and the yellow-grey solid was washed with diethyl ether. The crude was recrystallized from ethanol (20 ml) to obtain a yellow solid (67 mg, 18.8%). Crystals for x-ray study were obtained by recrystallization from methanol.