3-(4-Nitro­benz­yl)-4H-chromen-4-one

Kaalin Gopaul; Neil Anthony Koorbanally; Mahidansha M Shaikh; Deresh Ramjugernath; Hong Su

doi:10.1107/S1600536813006119

. 2013 Mar 9;69(Pt 4):o513. doi: 10.1107/S1600536813006119

3-(4-Nitrobenzyl)-4H-chromen-4-one

Kaalin Gopaul ^a, Neil Anthony Koorbanally ^a,^*, Mahidansha M Shaikh ^a, Deresh Ramjugernath ^b, Hong Su ^c

PMCID: PMC3629541 PMID: 23634059

Abstract

In the title compound, C₁₆H₁₁NO₄, the dihedral angle between the ten-membered chromen-4-one ring system (r.m.s. deviation = 0.0095 Å) and the benzene ring is 86.16 (5)°. In the crystal, molecules are linked into a three-dimensional network by weak C—H⋯O hydrogen bonds. The crystal studied was a non-merohedral twin, with the minor twin component refining to 0.093 (1).

Related literature

For the preparation, see: Desideri et al. (2011 ▶); Valkonen et al. (2012 ▶). For related structures, see: Valkonen et al. (2012 ▶); Gopaul et al. (2013 ▶). For the biological activity of homoisoflavonoids, see: Abegaz et al. (2007 ▶).

Experimental

Crystal data

C₁₆H₁₁NO₄
M _r = 281.26
Monoclinic,
a = 4.9246 (9) Å
b = 10.0160 (19) Å
c = 25.907 (5) Å
β = 92.845 (4)°
V = 1276.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 173 K
0.35 × 0.09 × 0.08 mm

Data collection

Bruker Kappa DUO APEXII diffractometer
Absorption correction: multi-scan (TWINABS; Sheldrick, 1997 ▶) T _min = 0.964, T _max = 0.992
87638 measured reflections
3303 independent reflections
2887 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.154
S = 1.09
3303 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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: SHELXL97.

Supplementary Material

Click here for additional data file.^{(22.5KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813006119/fj2618sup1.cif

e-69-0o513-sup1.cif^{(22.5KB, cif)}

Click here for additional data file.^{(162KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006119/fj2618Isup2.hkl

e-69-0o513-Isup2.hkl^{(162KB, hkl)}

Click here for additional data file.^{(5.1KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813006119/fj2618Isup3.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
C2—H2⋯O2ⁱ	0.95	2.38	3.322 (3)	170
C7—H7⋯O3ⁱⁱ	0.95	2.56	3.491 (3)	166
C9—H9⋯O4ⁱⁱⁱ	0.95	2.42	3.355 (3)	167
C13—H13⋯O3^iv	0.95	2.53	3.382 (3)	149
C16—H16⋯O2^v	0.95	2.46	3.378 (3)	163

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

We thank the University of KwaZulu-Natal and the South Africa Research Chairs initiative of the Department of Science and Technology for financial support and the National Research Foundation of South Africa for a bursary for KG.

supplementary crystallographic information

Comment

Homoisoflavonoids are a group of naturally occurring oxygen heterocyclic compounds, related to the flavonoids, which consists of a chromone skeleton with a benzyl or benzylidene group at C-3. In the 3-benzyl-4-chromonanone class of homoisoflavonoid, an extra methylene group exists between the phenyl group and the chromone skeleton. They are commonly synthesized by either the acid or base catalysed condensation of an aromatic aldehyde with chromanone (Desideri et al., 2011, Valkonen et al., 2012). Naturally occurring homoisoflavonoids are normally oxygenated and have shown a wide range of biological activities (Abegaz et al., 2007).

The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between the 10-membered co-planar chromone ring and the nitrated phenyl ring is 86.16 (5)°. In the crystal, the inter-moclecular weak hydrogen bonds C—H···O link the molecules into a three dimentional network, as shown in Fig.2. The details of the hydrogen bonds are shown in Table 1.

Experimental

A mixture of chroman-4-one (1.02 g, 6.749 mmol), 4-nitrobenzaldehyde (1.22 g, 8.099 mmol) and 10–15 drops of piperidine was heated at 80°C for 12 hrs. The reaction mixture was monitored for completion by thin layer chromatography. Upon completion, the reaction mixture was cooled, diluted with water and neutralized using 10% HCl. To the viscous reaction mixture, 20 ml of ethyl acetate was added. Upon the addition of hexane to the reaction mixture, the homoisoflavonoid precipitated out. The powdered product was filtered, washed with hexane and dried under vacuum. Upon slow evaporation of chloroform, the crystals of the homoisoflavonoid were obtained. (m.p. of 179–180 °C).

¹H NMR (400 MHz, CDCl₃) δ: 3.87 (2H, s, H-9), 7.38 (1H, t, J=7.54 Hz, H-6), 7.41 (1H, d, J=8.60 Hz, H-8), 7.45 (1H, d, J=8.48 Hz, H-2'/6'), 7.65 (1H, td, J=8.32, 1.10 Hz, H-7), 7.79 (1H, s, H-2), 8.12 (1H, d, J=8.56 Hz, H-3'/5'), 8.18 (1H, dd, J=7.98, 0.66 Hz, H-5).

¹³C NMR (100 MHz, CDCl₃) δ: 31.89 (C-9), 118.15 (C-8), 123.06 (C-3/1'), 123.79 (C-3'/5'), 123.83 (C-4a), 125.32 (C-6), 125.92 (C-5), 129.65 (C-2'/6'), 133.84 (C-7), 146.76 (C-4'), 153.14 (C-2), 156.52 (C-8a), 177.18 (C-4).