2-Chloro-3-[(2-oxo-2H-chromen-6-yl)amino]­naphthalene-1,4-dione

Mikaelly O B Sousa; Gleiciani Q Silveira; Javier A G Gomez

doi:10.1107/S1600536813019922

. 2013 Jul 27;69(Pt 8):o1317. doi: 10.1107/S1600536813019922

2-Chloro-3-[(2-oxo-2H-chromen-6-yl)amino]naphthalene-1,4-dione

Mikaelly O B Sousa ^a, Gleiciani Q Silveira ^a, Javier A G Gomez ^a,^*

PMCID: PMC3793804 PMID: 24109391

Abstract

In the title compound, C₁₉H₁₀ClNO₄, the dihedral angle between the naphthoquinone and coumarin rings is 48.99 (6)°. In the crystal, molecules are linked by strong N—H⋯O hydrogen bonds into chains with graph-set motif C(6) along [101]. The packing also features π–π stacking interactions between naphthoquinone and coumarin rings [centroid-to-centroid distances = 3.7679 (12) and 3.6180 (13) Å].

Related literature

For related compounds see: Rózsa et al. (1989 ▶); Ito et al. (1993 ▶); Ishikawa et al. (1995 ▶); Padwal et al. (2011 ▶). For reference structural data, see: Ibis & Deniz (2012 ▶); Resende & Gomez (2012 ▶). For graph-set notation of hydrogen bonds, see: Bernstein et al. (1995 ▶). graphic file with name e-69-o1317-scheme1.jpg

Experimental

Crystal data

C₁₉H₁₀ClNO₄
M _r = 351.73
Monoclinic,
a = 10.9371 (5) Å
b = 10.4462 (5) Å
c = 13.5104 (7) Å
β = 108.533 (5)°
V = 1463.53 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 150 K
0.23 × 0.13 × 0.07 mm

Data collection

Oxford Xcalibur Gemini Ultra diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.947, T _max = 1
15281 measured reflections
3527 independent reflections
2714 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.065
S = 0.91
3527 reflections
226 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ▶), 1217 Friedel pairs
Absolute structure parameter: −0.07 (5)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813019922/bx2446sup1.cif

e-69-o1317-sup1.cif^{(19KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813019922/bx2446Isup2.hkl

e-69-o1317-Isup2.hkl^{(173KB, hkl)}

Click here for additional data file.^{(5.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813019922/bx2446Isup3.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
N1—H1⋯O2ⁱ	0.86	2.21	3.015 (2)	157

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Brazilian agencies Proppi–UFF, FAPERJ, Scholarship Postgraduate Students Agreement Program – PEC-PG, CAPES/CNPq – Brazil and CAPES. The authors thank the X-ray diffraction laboratory LabCri-UFMG for the data collection, Professor Jackson A. L. C. Resende (IQ-UFF), and Professor M. D. Vargas (IQ-UFF) for her help and encouragement.

supplementary crystallographic information

Comment

There are very few examples in the literature of coumarin–naphthoquinone conjugates, most of them (direct C—C bond) are from natural sources (Rózsa et al., 1989; Ito et al., 1993; Ishikawa et al., 1995; Padwal et al., 2011) and only one synthetic, the coumarin–naphthoquinone hybrid linked through sulfur spacer attached at 7-position of the coumarin ring and 2-position of the naphthoquinone [2-(7-sulphanyl-4-methyl-coumarinyl)-3-(1-ethoxy)-1,4-naphthoquinone; Ibis & Deniz, 2012]. The title compound (I) is the product of the reaction of 2,3-dicloro-1,4-naphtoquionone with 6-aminocoumarin. The average C—C, C—O, C═O and C—N bond distances are in agreement with those observed in tert-butyl N-{3-[(3-chloro-1,4-dioxo-1,4-dihydronaphthalen2-yl)amino]propyl}carbamate (Resende & Gomez, 2012). The angle between the naphthoquinone and coumarin planes is 48.99 (6)°. The molecular structure is stabilized by one intramolecular N—H···O hydrogen bond. In the crystal, molecules are linked by strong N—H···O hydrogen bonds into chains with graph-set notation C(6) along [101] (Bernstein et al., 1995). The packing also features π–π stacking interactions between naphthoquinone and coumarin rings [centroid–centroid distances = 3.7679 (12) and 3.6180 (13) Å]. The dihedral angle between naphthoquinone and coumarin rings is 48.99 (6)°.

Experimental

2,3-Dichloro-1,4-naphthoquinone (681 mg, 3 mmol) was added to a solution of 6-aminocoumarin (579.6 mg, 3.6 mmol) in DMF (10 ml). The mixture was stirred at 60–70°C for 72 h. The solvent was evaporated under reduced pressure and the crude product was purified through recrystallization in hexane, resulting in a red solid. Yield: 833.8 mg, 79%. Single crystals suitable for a study of X-ray diffraction of compound (I) were obtained at 4°C by slow evaporation of an acetonitrile–dichloromethane (1:1) solution. m.p. 301°C. Found: C, 64.12; H, 2.91; N, 4.14. Calc. for C₁₉H₁₀ClNO₄: C, 64.51; H, 3.42; N, 3.96%. 1H NMR (300 MHz, d6-DMSO): δ 8.16 (d, J = 7.5 Hz, 2H), 8.13 (d, J = 9.6 Hz, 1H), 8.00 (t, J = 7.5 Hz, 1H), 7.94 (t, J = 7.5 Hz, 1H), 7.58–7.52 (m, 2H), 7.48 (d, J = 8.7 Hz, 1H), 6.62 (d, J = 9.6 Hz, 1H). 13 C NMR - APT (d6-DMSO, 75 MHz): δ 180.0, 176.8, 160.0, 150.4, 144.0, 143.3, 135.5, 134.8, 133.4, 131.9, 130.3, 128.0, 126.7, 126.2, 122.7, 118.2, 116.7, 116.0, 114.7. IR (KBr): νC═O (quin.) = 1672, νC═O (ester) = 1720, νC—O (ester) = 1568, 1290, νN—H = 3294, νC—H (arom.) = 3080. UV–Vis [CH₃CN; λ/nm (log ε)]: 277 (4.10), 333 (3.28), 469 (3.10).