Methyl rac-(2R,11S,12R)-12-(2-chloro­phen­yl)-22-oxo-9,13,21-trioxapenta­cyclo­[12.8.0.02,11.03,8.015,20]docosa-1(14),3,5,7,15(20),16,18-hepta­ene-11-carboxyl­ate

K Swaminathan; K Sethusankar; G Sivakumar; M Bakthadoss

doi:10.1107/S1600536811037196

. 2011 Sep 17;67(Pt 10):o2673. doi: 10.1107/S1600536811037196

Methyl rac-(2R,11S,12R)-12-(2-chlorophenyl)-22-oxo-9,13,21-trioxapentacyclo[12.8.0.0^2,11.0^3,8.0^15,20]docosa-1(14),3,5,7,15(20),16,18-heptaene-11-carboxylate

K Swaminathan ^a, K Sethusankar ^a,^*, G Sivakumar ^b, M Bakthadoss ^b

PMCID: PMC3201225 PMID: 22065629

Abstract

In the title compound C₂₇H₁₉ClO₆, the coumarin ring system is not exactly planar, with a dihedral angle of 4.12 (7)° between its benzene and lactone rings. The cis-fused pyran rings adopt half-chair conformations. The carbomethoxy and chlorophenyl groups are in a trans configuration. The crystal packing is stabilized by intermolecular C—H⋯O interactions, which produce a centrosymmetric R ₂ ²(14) dimer and two centrosymmetric R ₂ ²(18) dimers connecting the molecules in a two-dimensional fashion.

Related literature

For uses of coumarins, see: Kayser & Kolodziej (1997 ▶); Fan et al. (2001 ▶); Wang et al. (2002 ▶). For related structures, see: Kanchanadevi et al. (2011 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₇H₁₉ClO₆
M _r = 474.87
Triclinic,
a = 8.4441 (3) Å
b = 9.7556 (3) Å
c = 13.8546 (5) Å
α = 73.831 (2)°
β = 82.858 (2)°
γ = 87.962 (2)°
V = 1087.65 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
26685 measured reflections
6336 independent reflections
4968 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.143
S = 1.01
6336 reflections
308 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037196/ld2025sup1.cif

e-67-o2673-sup1.cif^{(24KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037196/ld2025Isup2.hkl

e-67-o2673-Isup2.hkl^{(310.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037196/ld2025Isup3.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⋯O5ⁱ	0.93	2.59	3.271 (2)	130
C12—H12⋯O4ⁱⁱ	0.98	2.53	3.3316 (16)	139
C23—H23⋯O5ⁱⁱⁱ	0.93	2.47	3.355 (3)	159

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

Acknowledgments

K. Swaminathan and K. Sethusankar thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the X-ray intensity data collection and Dr V. Murugan, Head of the Department of Physics, RKM Vivekananda College, Chennai, India, for providing facilities in the department to carry out this work.

supplementary crystallographic information

Comment

The title compound C₂₇H₁₉Cl O₆ was synthesized using domino Knoevenagel intramolecular hetero-Diels-Alder reaction, used extensively in the synthesis of heterocyclic and polycyclic compounds. Coumarin derivatives find applications as active components in pesticides and additives in the manufacture of pharmaceuticals and cosmetics. They are also known to posses antibacterial (Kayser & Kolodziej, 1997), anticancer (Wang et al., 2002) and steroid 5a-reductase inhibitory (Fan et al., 2001) activities.

The title compound C₂₇H₁₉ClO₆ comprises a chromene ring and a coumarin ring fused to alternate sides of a pyran ring. A chlorobenzene ring and a carboxylate group are also trans-attached to the same pyran ring in adjacent positions. The X-ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig.1.

The chlorine atom Cl1 deviates from the least square plane of the phenyl ring (C20-C25) by 0.0568 Å and the deviation of atom O4 from the least square plane of the coumarin ring (O3,C10,C11,C13-C19) is 0.3315 (12) Å. Also, the dihedral angle between the least square planes of the pyran ring (O2,C8-C12) and the carboxylate side chain is 56.47 (6)°. The title compound exhibits sturctural similarities with a reported structure (Kanchanadevi et al., 2011).

The crystal packing is stabilized by C—H..O intermolecular ineractions, which include a R₂²(14) dimer and two R₂²(18) dimers formed through a bifurcated hydrogen bond between a carboxylate O atom and two C atoms, one each from the nearby chromene and chlorobenzene rings, respectively (Bernstein et al.. 1995). (Table 1). The symmetry codes are: (i) 1 - x,1 - y,1 - z; (ii) 1 - x,1 - y,-z and (iii) -x,-y,1 - z. The packing arrangement of the title compound is shown in Fig.2.

Experimental

A mixture of (E)-methyl 2-((2-formylphenoxy)methyl)-3-(2-chlorophenyl) acrylate (0.330 g, 1 mmol) and 4-hydroxy-2H-chromen-2-one (0.162 g, 1 mmol) was placed in a round bottom flask and melted at 180°C for 1 h. After completion of the reaction as indicated by TLC, the crude product was washed with 5 ml of ethylacetate:hexane mixture (1:49 ratio) which successfully provided the pure product, methyl rac-(2R,11S,12R)- 12-(2-chlorophenyl)-22-oxo-9,13,21-trioxapentacyclo [12.8.0.0^2,11.0^3,8.0^15,20]docosa-1(14),3,5,7,15 (20),16,18- heptaene-11-carboxylate, as colourless solid in 92% yield.