3-[2-(Triphenyl­phosphanyl­idene)acet­yl]-2H-chromen-2-one

Muhammad Taha; Nor Hadiani Ismail; Ahmad Nazif Aziza; Syed Adnan Ali Shah; Sammer Yousuf

doi:10.1107/S160053681300127X

. 2013 Jan 19;69(Pt 2):o245. doi: 10.1107/S160053681300127X

3-[2-(Triphenylphosphanylidene)acetyl]-2H-chromen-2-one

Muhammad Taha ^a, Nor Hadiani Ismail ^b,^c, Ahmad Nazif Aziza ^d, Syed Adnan Ali Shah ^a,^e, Sammer Yousuf ^f,^*

PMCID: PMC3569778 PMID: 23424524

Abstract

In the title compound, C₂₉H₂₁O₃P, a coumarin-substitued ylid, the P atom is linked to three benzene rings and a planar coumarin moiety via a methylenecarbonyl group. The bond lengths in the P=C–C=O fragment clearly indicate a delocalized system involving the olefinic and carbonyl bonds. The molecular structure is stabilized by an intramolecular C—H⋯O interaction that results in an S7 graph-set ring motif. In the crystal, molecules are linked into a three-dimensional framework by C—H⋯O hydrogen bonds.

Related literature

For applications and biological activity of coumarin, see: Kabak et al. (1999 ▶); El-Ansary et al. (1992 ▶); Czerpack & Skolska (1982 ▶); Reddy & Somayojulu (1981 ▶); Jund et al. (1971 ▶). For the crystal structure of a related compound, see: Schobert et al. (2000 ▶).

Experimental

Crystal data

C₂₉H₂₁O₃P
M _r = 448.43
Triclinic,
a = 9.7837 (12) Å
b = 10.3917 (14) Å
c = 12.2925 (17) Å
α = 108.669 (4)°
β = 104.484 (4)°
γ = 99.746 (4)°
V = 1103.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 100 K
0.46 × 0.41 × 0.34 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.932, T _max = 0.949
36693 measured reflections
4102 independent reflections
3716 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.093
S = 1.07
4102 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; 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.

Supplementary Material

Click here for additional data file.^{(24.2KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681300127X/pv2616sup1.cif

e-69-0o245-sup1.cif^{(24.2KB, cif)}

Click here for additional data file.^{(201KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300127X/pv2616Isup2.hkl

e-69-0o245-Isup2.hkl^{(201KB, hkl)}

Click here for additional data file.^{(8.2KB, cml)}

Supplementary material file. DOI: 10.1107/S160053681300127X/pv2616Isup3.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—H2A⋯O2ⁱ	0.95	2.45	3.378 (2)	166
C7—H7A⋯O3ⁱⁱ	0.95	2.28	3.171 (2)	156
C22—H22A⋯O2ⁱⁱⁱ	0.95	2.48	3.398 (2)	163
C25—H25A⋯O3	0.95	2.31	3.168 (2)	150
C28—H28A⋯O1^iv	0.95	2.54	3.281 (2)	135

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

supplementary crystallographic information

Comment

The chromone chemistry continues to draw considerable interest of synthetic organic and medicinal chemists (Kabak et al., 1999). Chromones are more widely distributed in nature, especially in the plant kingdom, and exhibit low toxicity along with a wide spectrum of useful biological activities including antifungal, antiviral, antitublin, anti-inflammatory antiulcer and antihypertensive and immune-stimulating properties (El-Ansary et al., 1992; Czerpack & Skolska, 1982; Reddy & Somayojulu, 1981; Jund et al., 1971). The title compound is a coumarin substitued ylid synthesized as a part of our ongoing resaerch to study biological activities of this medicinally important class of compounds.

The bond distances and angles in the title compound (Fig. 1) agree very well with the corresponding bond distances and angles reported in a closely related compound (Schobert et al., 2000). In the title molecule, the central phosphorus atom adopts a tetrahedral geometry and is linked to three benzene rings and a planner coumarin moiety (maximum deviation of 0.005 (2) Å for C1 atom) via methylene carbonyl group. The bond lengths P1–C11 (1.7237 (14) Å) and C10–C11 (1.395 (2) Å), deviating from typical P═C (1.67 Å) and C–C (1.50 Å) support the congugation of double bond with that of carbonyl group via keto enol tautomerization. The geomatry of the molecule is stablizied by an intramolecular C25—H25A···O3 hydrogen bonding interaction. The crystal structure is stabilized by intermolecular C2—H2A···O2, C7—H7A···O3, C22—H22A···O2 and C28—H28A···O1 interactions forming a three-dimensional network (Table 1 and Fig. 2).

Experimental

The title compound was synthesized in two steps. In the first step, 3-((triphenylphosphinyl) acetyl)coumarin bromide was synthesized by treating 3-(bromoacetyl)coumarin (2 mmol, 0.534 g) in 10 ml of CH₂Cl₂ and triphenylphosphine (2 mmol, 0.524 g). The mixture was stirred for 3 hrs at room temperature. The solvent was evaporated and washed with diethyl ether, to obtain a yellow crystalline solid (96% yield, 1.14 g). In the next step 3-((triphenylphosphinyl) acetyl)coumarin bromide (1 mmol, 0.528 g) was dissolved in ethanol (10 ml), treated dropwise with potassium carbonate (1 mmol, 0.1 g) in 5 ml of H₂O, stirred for 1.5 h at room temperature, diluted with 40 ml of H₂O, and extracted with 4 × 10 ml of EtOAc. The combined organic phases were dried over MgSO₄, filtered, and evaporated under reduced pressure to give the title compound as a yellow crystalline solid (90% yield, 0.403 g). Mp: 388–390 K.