3,3′-[(4-Nitro­phen­yl)methyl­ene]bis­(4-hy­droxy-2H-chromen-2-one)

N Ravikumar; G Gopikrishna; K Anand Solomon

doi:10.1107/S1600536811054778

. 2012 Jan 7;68(Pt 2):o265. doi: 10.1107/S1600536811054778

3,3′-[(4-Nitrophenyl)methylene]bis(4-hydroxy-2H-chromen-2-one)

N Ravikumar ^a, G Gopikrishna ^a, K Anand Solomon ^a,^*

PMCID: PMC3274964 PMID: 22346909

Abstract

The molecular conformation of the title compound, C₂₅H₁₅NO₈, is stabilized by strong intramolecular O—H⋯O hydrogen bonds, resulting in the formation of S ₁ ¹(7) ring motifs. In the crystal, π–π stacking interactions are observed between adjacent nitrobenzene and pyranone rings with a centroid–centroid distance of 3.513 (12) Å. The dihedral angles between the nitrobenzene ring and the coumarin ring systems are 65.61 (8) and 66.11 (8)° while the coumarin ring systems are inclined at 65.69 (8)°.

Related literature

For the synthesis of benzylidene-bis-(4-hydroxycoumarin) derivatives, see: Mehrabi & Abusaidi (2010 ▶); Završnik et al. (2011 ▶). For hydrogen bonds, see: Desiraju & Steiner (1999 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). For the biological activity of substituted benzylidene-bis-(4-hydroxycoumarin) derivatives, see: Borges et al. (2005 ▶); Nolan et al. (2009 ▶); Prakash et al. (2008 ▶); Zhao et al. (1997 ▶).

Experimental

Crystal data

C₂₅H₁₅NO₈
M _r = 457.38
Orthorhombic,
a = 14.0061 (6) Å
b = 14.1511 (6) Å
c = 10.4179 (4) Å
V = 2064.85 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.902, T _max = 0.973
15733 measured reflections
3316 independent reflections
2913 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.089
S = 1.04
3316 reflections
310 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811054778/rk2323sup1.cif

e-68-0o265-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811054778/rk2323Isup2.hkl

e-68-0o265-Isup2.hkl^{(162.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811054778/rk2323Isup3.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⋯O5	0.82	1.79	2.597 (2)	166
O6—H6A⋯O1	0.82	1.80	2.617 (2)	173

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Acknowledgments

The authors thank the Managing Trustee and the Founder Trustee of the Sankar Foundation for their financial support and encouragement. We also acknowledge, the Head, SAIF, IIT-Chennai, for the data collection.

supplementary crystallographic information

Comment

Sevaral methods were reported in the literature (Mehrabi et al. 2010) and (Završnik et al. 2011) for the synthesis of the title compound. Coumarin ring forms an important pharmacophore in several naturally occurring as well as synthetic molecules (Prakash et al. 2008). These coumarin derivaties showed numerous therapeutic applications such as anticoagulant and antibacterial agents (Borges et al. 2005). Several multifunctionalized coumarin derivatives were reported to exhibit anti-HIV properties (Zhao et al. 1997) and also as inhibitors of quinone oxidoreductase-1 (Nolan et al. 2009).

In title compound, C₂₅H₁₅NO₈, I, two 4-hydroxycoumarin moieties are linked through a methylene bridge on which one hydrogen atom has been replaced with a phenyl ring bearing p-nitro group (Fig. 1). The 4-hydroxycoumarin moieties are stabilized by intramolecular hydrogen bonding by forming S¹₁(7) ring motifs (Etter et al. 1990) and (Bernstein et al. 1995) between hydroxyl and carbonyl oxygen atoms. The crystal structure of I is stabilized by C–H···O and π–π interactions (Fig. 2). The range of H···O distances (Table 1) found in I agrees with those found for C–H···O hydrogen bonds (Desiraju & Steiner, 1999). The supramolecular chains were extended by π–π-interactions, where the distance between the two centroids namely (C1/O2/C2/C7-C9) and (C20-C25) of the two corresponding coplanar rings is 3.513 (12)Å.

Experimental

The 4-hydroxycoumarin (2 m.mol, 0.324 g) and 4-nitrobenzaldehyde (1 mmol, 0.151 g) were refluxed in ethanol (5 ml) at 333 K for 12 h. After completion of the reaction as monitored by TLC, the reaction mixture was cooled to room temperature. The obtained precipitate was collected by suction filtration and dried. The pure product was obtained by recrystallization from dichloromethane in 92% yield.