2-Chloro-3-(4-methyl­anilino)naph­tha­lene-1,4-dione

Li-Jiu Gao; Yun Liu

doi:10.1107/S1600536812045229

. 2012 Nov 17;68(Pt 12):o3378. doi: 10.1107/S1600536812045229

2-Chloro-3-(4-methylanilino)naphthalene-1,4-dione

Li-Jiu Gao ^a, Yun Liu ^a,^*

PMCID: PMC3588974 PMID: 23476210

Abstract

In the title compound, C₁₇H₁₂ClNO₂, the naphthoquinone system is essentially planar [maximum deviation = 0.078 (2) Å] and makes a dihedral angle of 52.38 (7)° with the benzene ring. The crystal structure features N—H⋯O interactions.

Related literature

For the properties of substituted naphthoquinones, see: Batton et al. (2000 ▶); Monks et al. (1992 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For the structure of 2-hydroxyquinoxaline, see: Stępień et al. (1976 ▶).

Experimental

Crystal data

C₁₇H₁₂ClNO₂
M _r = 297.73
Orthorhombic,
a = 12.1614 (10) Å
b = 22.4915 (18) Å
c = 5.0444 (4) Å
V = 1379.79 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 296 K
0.2 × 0.2 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995 ▶) T _min = 0.946, T _max = 0.972
15471 measured reflections
2479 independent reflections
2420 reflections with I > 2σ(I)
R _int = 0.036
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.119
S = 1.27
2479 reflections
195 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(16.3KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812045229/ds2213sup1.cif

e-68-o3378-sup1.cif^{(16.3KB, cif)}

Click here for additional data file.^{(121.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812045229/ds2213Isup2.hkl

e-68-o3378-Isup2.hkl^{(121.8KB, hkl)}

Click here for additional data file.^{(5.3KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812045229/ds2213Isup3.cml

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—H⋯O2	0.70 (2)	2.23 (3)	2.611 (3)	116 (2)

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Acknowledgments

The authors acknowledge the financial support of Xuzhou City (XZZD1213).

supplementary crystallographic information

Comment

The substituted naphthoquinone have a diversity of biological activity and are playing an increasingly important role in developing new pharmaceuticals [Batton et al., 2000; Monks et al., 1992]. In our ongoing research work on the syntheses of amino-substituted naphthoquinones, we have prepared the title compound, (I), as one of the products. As part of this study, we have undertaken an X-ray crystallographic analysis of (I) in order to confirm its structure.

In the title compound, the bond lengths and angles of the title molecule (Fig. 1) are within normal ranges (Allen et al., 1987). The naphthoquinone ring[C1—C10] is essentially planar. The naphthoquinone ring makes the dihedral angle 52.38 (0.07) with the benzene ring [C11—C16]. Although atoms C9 and C11 attached to atom N are all of sp^2^ hybridization, their different environments cause slight differences in the N—C9, N—C11 bond lengths, and in the C9—N—H, C11—N—H angles (Table 1). The molecular packing is stabilized by intermolecular N—H···O hydrogen bonds (Table 2).

Experimental

To a stirred solution of naphthoquinone (1.0 eq) in 10 ml of acetonitrile, potassium carbonate (3.0 eq) was added. The mixture was stirred at room temperature for 5 min, followed by the addition of aniline (1.0 eq) and silver nitrate (0.1 mmol). The reaction mixture was refluxed for 10 h until complete consumption of starting material was observed on TLC. The reaction mixture was purified over silica gel (EtOAc/hexane)to afford the product in 96% yield.