(Z)-3-(1-Hy­droxy-3-oxobut-1-en­yl)-6-nitro-2H-chromen-2-one

Nishith Saurav Topno; Venkataswamy Tangeti; H Surya Prakash Rao; R Krishna

doi:10.1107/S1600536812051872

. 2013 Jan 23;69(Pt 2):o284. doi: 10.1107/S1600536812051872

(Z)-3-(1-Hydroxy-3-oxobut-1-enyl)-6-nitro-2H-chromen-2-one

Nishith Saurav Topno ^a, Venkataswamy Tangeti ^b, H Surya Prakash Rao ^b,^‡, R Krishna ^a,^*

PMCID: PMC3569810 PMID: 23424556

Abstract

In the title compound, C₁₃H₉NO₆, the coumarin system has the benzene ring aligned at 0.61 (18)° with respect to the pyrone ring. An intramolecular O—H⋯O hydrogen bond stabilizes the molecular conformation and a C—H⋯O contact also occurs. In the crystal, weak C—H⋯O interactions link the molecules, forming inversion dimers.

Related literature

For the biological importance of flavinoids and coumarins, see: Murry et al. (1982 ▶); Andersen et al. (2006 ▶); Murakami et al. (2001 ▶); Wu et al. (2003 ▶). For their use as fluorescent probes and triplet sensitisers, see: Wagner (2009 ▶); Takadate et al. (1995 ▶). For a related structure, see: Da & Quan (2010 ▶). graphic file with name e-69-0o284-scheme1.jpg

Experimental

Crystal data

C₁₃H₉NO₆
M _r = 275.21
Triclinic,
a = 7.4591 (13) Å
b = 8.2178 (19) Å
c = 10.0087 (18) Å
α = 85.202 (17)°
β = 77.346 (15)°
γ = 89.278 (17)°
V = 596.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.4 × 0.32 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.917, T _max = 1.000
4789 measured reflections
2093 independent reflections
1395 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.170
S = 0.93
2093 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(22.9KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812051872/sj5289sup1.cif

e-69-0o284-sup1.cif^{(22.9KB, cif)}

Click here for additional data file.^{(102.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051872/sj5289Isup2.hkl

e-69-0o284-Isup2.hkl^{(102.9KB, hkl)}

Click here for additional data file.^{(4.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812051872/sj5289Isup3.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
O3—H3A⋯O4	0.82	1.78	2.510 (2)	147
C11—H11⋯O2	0.93	2.24	2.870 (3)	125
C3—H3⋯O5ⁱ	0.93	2.58	3.308 (3)	136
C7—H7⋯O4ⁱⁱ	0.93	2.39	3.304 (3)	166

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

Acknowledgments

RK thanks the Department of Biotechnology and the Department of Information Technology, Government of India, New Delhi, for their financial support of the Centre for Bioinformatics, Pondicherry University, Puducherry. NST [No. F. 14–2(ST)/2010 (SA-III)] thanks the UGC for a Rajiv Gandhi National Fellowship to pursue his PhD degree. HSPR and VT thank the Council for Scientific and Industrial Research (CSIR), New Delhi, for financial support.

supplementary crystallographic information

Comment

Coumarins are heterocyclic compounds belonging to the benzopyrone chemical class, well known to exhibit varied biological activities (Murry et al., 1982; Andersen et al., 2006). In the technological and medicinal fields, coumarins and flavones, independently, find extensive use (Murakami et al., 2001) (Wu et al., 2003), with activities reported for anti-HIV, anti-tumor, anti-cancer, anti-hypertension, anti-arrhythmia, anti-inflammatory, anti-osteoporosis, antiseptic, and analgesic uses. They are also known to be used as fluorescent probes and as triplet sensitizers, especially those having electronic push-pull characteristics (Wagner, 2009; Takadate et al., 1995). Considering the importance of coumarin derivatives, we report here the structure of the title compound. A structure related to the title compound has also been reported (Da & Quan, 2010).

The molecular structure of the title compound is shown in Fig.1. The pyrone ring and the benzene ring are essentially co-planar with a dihedral angle of 0.61 (18)° between them. The benzene ring orients in a (-)-anti-periplanar conformation with respect to the pyrone ring. The crystal packing is stabilized by intermolecular C₃—H₃···O₅, C₃—H₃···O₅ and C₇—H₇···O₄ bonds as shown in Fig.2 and Fig.3.

Experimental

A solution of 4-hydroxy-6-methyl-3-(2-(methylamino)-3,6-dinitro-4H-chromen-4-yl)-2H-pyran-2-one (0.010 g, 0.266 mmol) in ethanol (15 ml) was heated to reflux for 25 min by which time the reaction was complete (TLC; hexanes: EtOAc, 6:4). The compound was crystallized and separated by filtration with the help of cold ethanol (5 ml) to yield 93% of the product, a yellow crystalline solid, mp 121.6 °C; IR (KBr) υ_max cm^-1; ¹H NMR (400 MHz, DMSO-D₆) δ 15.71 (s, 1H), 8.70 (s, 1H), 8.58 (s, 1H), 8.49 (d, J = 9.0 Hz, 1H), 7.51 (d, J = 9.12 Hz, 1H), 6.98 (s, 1H), 2.29 (s, 3H) p.p.m.; ¹³C NMR (100 MHz, DMSO-D₆) δ 200.2, 171.1, 157.5, 153.3, 144.0, 136.6, 131.6, 121.8, 120.1, 118.4, 117.6, 102.0, 27.8 p.p.m..