10-Phenyl-6b,7,8,9,9a,10-hexa­hydro-6H-cyclo­penta­[4,5]pyrano[3,2-c]chromen-6,9-dione

Zhen Qiao; Li Liu; Dong Wang

doi:10.1107/S1600536811006192

. 2011 Mar 12;67(Pt 4):o855. doi: 10.1107/S1600536811006192

10-Phenyl-6b,7,8,9,9a,10-hexahydro-6H-cyclopenta[4,5]pyrano[3,2-c]chromen-6,9-dione

Zhen Qiao ^a, Li Liu ^a,^*, Dong Wang ^a

PMCID: PMC3099813 PMID: 21754136

Abstract

In the title compound, C₂₁H₁₆O₄, the dihedral angle between the phenyl ring and the 2H-chromene ring system is 59.8 (2)°. The crystal packing is stabilized by weak π–π stacking interactions [centroid–centroid distances = 3.667 (2) Å] and intermolecular C—H⋯O hydrogen-bonding interactions.

Related literature

For applications of coumarin, see: Vu et al. (2008 ▶); Maresca et al. (2009 ▶); Maresca et al. (2010 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₁H₁₆O₄
M _r = 332.34
Monoclinic,
a = 9.1672 (14) Å
b = 8.6538 (14) Å
c = 19.899 (3) Å
β = 91.295 (3)°
V = 1578.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 K
0.50 × 0.50 × 0.41 mm

Data collection

Rigaku Saturn724+ CCD diffractometer
Absorption correction: numerical (CrystalClear; Rigaku, 2007 ▶) T _min = 0.953, T _max = 0.961
13128 measured reflections
3608 independent reflections
3469 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.144
S = 1.10
3608 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811006192/hg2800sup1.cif

e-67-0o855-sup1.cif^{(21KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006192/hg2800Isup2.hkl

e-67-0o855-Isup2.hkl^{(176.9KB, hkl)}

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
C8—H8A⋯O3ⁱ	1.00	2.45	3.4042 (19)	160
C17—H17A⋯O2ⁱⁱ	0.95	2.54	3.322 (2)	140

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

supplementary crystallographic information

Comment

Coumarins constitute a ubiquitous class of heterocycles found in numerous natural products, food industry, marketed drugs, and drug candidates [Vu et al., 2008; Maresca et al., 2009; Maresca et al., 2010]. Alkylations of electron-rich arenes such as 4-hydroxycoumarin are of great importance for the synthesis of many natural products and pharmaceuticals. Therefore, multiple approaches have been undertaken to develop catalytic enantioselective additions of 4-hydroxycoumarin to α,β-unsaturated carbonyl compounds. In this context the use of cyclic Morita Baylis Hillman alcohol is of particular interest since they not only exhibit regioselectivity but also can be cyclized readily followed by reaction of the resultant allylic cation with a suitable O nucleophile. In continuation of our work in this direction, we report here the crystal structure of the title compound.

In title compound, all bond lengths in the molecular are normal (Allen et al., 1987). The dihedral angle between benzene (C16—C21) and 2H-chromene (C1—C7/C14/C15/O1) rings is 59.8 (2) °. π—π interactions are indicated by the short distance (Cg1···Cg2 distance of 3.667 (2) Å, symmetry code: 1 - x,1 - y,z) between the centroids of the 2H-pyran ring (C1/C6/C7/C14/C15/O2) (Cg1) and benzene ring C1—C6 (Cg2) (Table 1). There are weaker C—H···O intermolecular interactions, which stabilized the structure (Table 1).

Experimental

A mixture of 9-amino-9-deoxyepiquinine QA (20 mol %) in the combination with TFA (40 mol %) exhibited high catalytic activity for the Michael addition followed by cycloaddition of 4-hydroxycoumarin to cyclopent-2-enone-derived MBH alcohol in acetone at 60 °C for 72 h, yield 61%. Single crystals suitable for X-ray measurements were obtained by recrystallization from acetonitrile at room temperature.