6-Phenyl­oxane-2,4-dione

Abstract

The title compound, C₁₁H₁₀O₃, is a phenyl-subsituted dihydro­pyran­dione in which the heterocycle adopts a boat conformation with the phenyl substituent canted 72.14 (5)° relative to the mean plane of the heterocycle.

Related literature  

For the crystal structure of methyl 4-methyl-3,5-dioxo-1-phenyl-2-oxaspiro­[5.5]-4-carboxyl­ate, see: Kirillov et al. (2010 ▶) and of trans-5,6-diphenyl­perhydro­pyran-2,4-dione, see: de Souza et al. (2009 ▶). For the synthesis, see: Andersh et al. (2008 ▶). For the biological activity of the title compound and its derivatives, see: Aguiar Amaral et al. (2005 ▶); Souza et al. (2004 ▶); Tait et al. (1997 ▶); Wang et al. (1999 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). A geometry check was performed using Mogul, see: Bruno et al. (2004 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental  

Crystal data  

• C₁₁H₁₀O₃

• M _r = 190.19

• Orthorhombic,

• a = 16.9888 (6) Å

• b = 5.4501 (2) Å

• c = 19.7350 (8) Å

• V = 1827.28 (12) ų

• Z = 8

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 100 K

• 0.17 × 0.14 × 0.03 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.662, T _max = 0.746

• 17960 measured reflections

• 1804 independent reflections

• 1322 reflections with I > 2σ(I)

• R _int = 0.071

Refinement  

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.114

• S = 1.06

• 1804 reflections

• 127 parameters

• H-atom parameters constrained

• Δρ_max = 0.29 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: APEX2 and SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The title compound has a diverse array of biological effects, including reducing sensitivity to pain (Aguiar Amaral et al., 2005) and killing mollusks (Souza et al., 2004). Derivatives of this compound have anti-fungal properties (Wang et al., 1999) and are effective HIV protease inhibitors (Tait et al., 1997).

The molecular structure (Fig. 1.) is the singular moiety in the asymmetric unit. A Mogul (Bruno et al., 2004) geometry check showed all non-H bond angles and distances to be normal. Ring puckering analysis of the dihydropyrandione ring using PLATON (Spek, 2009; Cremer & Pople, 1975) indicates Φ = 297.5 (2)° and θ = 84.76 (18)° for the O3—C1—C2—C3—C4—C5 ring. These parameters are consistent with a formal conformational assignment close to an idealized B_C2,C5 boat with C2 at the bow and C5 at the stern. The plane of the phenyl ring attached to C5 may be described as a rudder canted 72.14 (5)° relative to the mean plane of the six core atoms of the heterocycle. The 106.6 (2)° C6—C5—O3 bond angle compared to the 112.8 (2)° C6—C5—C4 bond angle indicates a small steer to said rudder; however, whether it is to port or starboard depends upon which enantiomer is considered.

Based upon a CSD search (Allen, 2002), two structures containing similar lactone ring motifs have been reported in the crystallographic literature. These include the spiro compound methyl 4-methyl-3,5-dioxo-1-phenyl-2-oxaspiro[5.5]-4-carboxylate with CSD refcode IRITIN (Kirillov et al., 2010) and trans-5,6-diphenylperhydropyran-2,4-dione with CSD refcode PONVAQ (de Souza et al., 2009). In all three cases the pyran rings adopt the boat conformation.

Experimental

The title compound 6-(phenyl)-dihydro-2H-pyran-2,4-(3H)-dione, (also named 5-phenyl-3-oxo-delta-lactone), was prepared by the literature method (Andersh et al., 2008). Benzaldehyde (2 mmol), ethanol (2 ml), ethylacetoacetate (2 mmol), and potassium carbonate (4 mmol) were heated overnight under nitrogen at 318 K. The solution was diluted with ethylacetate, treated with 1 M HCl, and the combined organic layer extracts were dried, filtered, concentrated, and purified by flash chromatography.

Crystals suitable for X-Ray analysis were grown by vapor diffusion of pentane into a concentrated solution of the lactone in dichloromethane.

Refinement

All non-H atoms were refined anisotropically. All H atoms were included in the refinement in the riding-model approximation (C–H = 0.95, 0.99, and 1.00 Å for Ar–H, CH₂, and CH; U_iso(H) = 1.2Ueq(C).

Figures

Fig. 1.

The molecular structure of the compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C11H10O3	F(000) = 800
Mr = 190.19	Dx = 1.383 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2535 reflections
a = 16.9888 (6) Å	θ = 2.4–23.5°
b = 5.4501 (2) Å	µ = 0.10 mm−1
c = 19.7350 (8) Å	T = 100 K
V = 1827.28 (12) Å3	Prism, colourless
Z = 8	0.17 × 0.14 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer	1322 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
φ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −20→20
Tmin = 0.662, Tmax = 0.746	k = −6→6
17960 measured reflections	l = −24→24
1804 independent reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.039P)2 + 1.8272P] where P = (Fo2 + 2Fc2)/3
1804 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.15992 (11)	0.2655 (4)	0.22819 (11)	0.0198 (5)
C2	0.13487 (12)	0.0646 (4)	0.27556 (11)	0.0208 (5)
H2A	0.1203	0.1376	0.3198	0.025*
H2B	0.1799	−0.0474	0.2833	0.025*
C3	0.06630 (12)	−0.0808 (4)	0.24883 (12)	0.0200 (5)
C4	0.06699 (12)	−0.1241 (4)	0.17377 (11)	0.0203 (5)
H4A	0.0222	−0.0357	0.1529	0.024*
H4B	0.0598	−0.3015	0.1649	0.024*
C5	0.14301 (12)	−0.0391 (4)	0.14093 (11)	0.0197 (5)
H5	0.1869	−0.1489	0.1557	0.024*
C6	0.13875 (12)	−0.0384 (4)	0.06490 (11)	0.0196 (5)
C7	0.17318 (12)	−0.2284 (4)	0.02863 (12)	0.0240 (5)
H7	0.2002	−0.3554	0.052	0.029*
C8	0.16830 (13)	−0.2336 (4)	−0.04141 (12)	0.0289 (6)
H8	0.1921	−0.364	−0.0659	0.035*
C9	0.12897 (13)	−0.0501 (4)	−0.07580 (12)	0.0283 (5)
H9	0.1257	−0.0542	−0.1238	0.034*
C10	0.09416 (13)	0.1406 (4)	−0.03986 (12)	0.0284 (6)
H10	0.0672	0.2673	−0.0634	0.034*
C11	0.09869 (12)	0.1464 (4)	0.03021 (11)	0.0242 (5)
H11	0.0745	0.2763	0.0546	0.029*
O1	0.17979 (9)	0.4702 (3)	0.24675 (8)	0.0240 (4)
O2	0.01417 (8)	−0.1540 (3)	0.28609 (8)	0.0237 (4)
O3	0.16073 (8)	0.2144 (3)	0.16170 (7)	0.0211 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0139 (10)	0.0164 (11)	0.0290 (13)	0.0004 (8)	−0.0010 (9)	−0.0005 (10)
C2	0.0213 (10)	0.0181 (11)	0.0230 (11)	0.0013 (8)	0.0009 (9)	−0.0004 (9)
C3	0.0190 (10)	0.0102 (9)	0.0307 (12)	0.0038 (8)	0.0010 (10)	0.0024 (9)
C4	0.0183 (10)	0.0147 (10)	0.0279 (12)	−0.0013 (9)	0.0001 (9)	−0.0002 (9)
C5	0.0193 (10)	0.0125 (10)	0.0274 (12)	0.0011 (8)	−0.0004 (9)	−0.0019 (9)
C6	0.0151 (10)	0.0168 (10)	0.0269 (12)	−0.0038 (8)	0.0001 (9)	−0.0007 (10)
C7	0.0221 (11)	0.0184 (11)	0.0314 (13)	−0.0003 (9)	0.0002 (9)	−0.0002 (10)
C8	0.0305 (12)	0.0234 (12)	0.0327 (14)	−0.0010 (10)	0.0030 (10)	−0.0079 (11)
C9	0.0332 (13)	0.0285 (13)	0.0232 (12)	−0.0066 (10)	−0.0002 (10)	−0.0006 (11)
C10	0.0315 (13)	0.0210 (12)	0.0326 (14)	−0.0021 (10)	−0.0039 (10)	0.0030 (11)
C11	0.0258 (11)	0.0179 (11)	0.0289 (13)	−0.0008 (9)	0.0017 (10)	−0.0029 (10)
O1	0.0257 (8)	0.0159 (7)	0.0303 (9)	−0.0028 (6)	−0.0007 (7)	−0.0015 (7)
O2	0.0230 (8)	0.0158 (7)	0.0324 (9)	−0.0014 (6)	0.0062 (7)	0.0014 (7)
O3	0.0229 (7)	0.0152 (7)	0.0253 (9)	−0.0048 (6)	−0.0002 (6)	0.0004 (7)

Geometric parameters (Å, º)

C1—O1	1.222 (3)	C5—H5	1
C1—O3	1.342 (2)	C6—C7	1.388 (3)
C1—C2	1.501 (3)	C6—C11	1.395 (3)
C2—C3	1.505 (3)	C7—C8	1.385 (3)
C2—H2A	0.99	C7—H7	0.95
C2—H2B	0.99	C8—C9	1.381 (3)
C3—O2	1.218 (2)	C8—H8	0.95
C3—C4	1.500 (3)	C9—C10	1.391 (3)
C4—C5	1.517 (3)	C9—H9	0.95
C4—H4A	0.99	C10—C11	1.385 (3)
C4—H4B	0.99	C10—H10	0.95
C5—O3	1.472 (2)	C11—H11	0.95
C5—C6	1.502 (3)
O1—C1—O3	118.69 (19)	C6—C5—H5	109.2
O1—C1—C2	123.9 (2)	C4—C5—H5	109.2
O3—C1—C2	117.43 (18)	C7—C6—C11	119.4 (2)
C1—C2—C3	112.66 (18)	C7—C6—C5	119.53 (19)
C1—C2—H2A	109.1	C11—C6—C5	121.03 (19)
C3—C2—H2A	109.1	C8—C7—C6	120.3 (2)
C1—C2—H2B	109.1	C8—C7—H7	119.8
C3—C2—H2B	109.1	C6—C7—H7	119.8
H2A—C2—H2B	107.8	C9—C8—C7	120.3 (2)
O2—C3—C4	123.38 (19)	C9—C8—H8	119.9
O2—C3—C2	121.6 (2)	C7—C8—H8	119.9
C4—C3—C2	115.03 (18)	C8—C9—C10	119.8 (2)
C3—C4—C5	112.35 (17)	C8—C9—H9	120.1
C3—C4—H4A	109.1	C10—C9—H9	120.1
C5—C4—H4A	109.1	C11—C10—C9	120.2 (2)
C3—C4—H4B	109.1	C11—C10—H10	119.9
C5—C4—H4B	109.1	C9—C10—H10	119.9
H4A—C4—H4B	107.9	C10—C11—C6	120.0 (2)
O3—C5—C6	106.59 (17)	C10—C11—H11	120
O3—C5—C4	109.98 (16)	C6—C11—H11	120
C6—C5—C4	112.73 (17)	C1—O3—C5	117.72 (16)
O3—C5—H5	109.2
O1—C1—C2—C3	139.8 (2)	C11—C6—C7—C8	0.4 (3)
O3—C1—C2—C3	−40.6 (3)	C5—C6—C7—C8	178.5 (2)
C1—C2—C3—O2	−141.94 (19)	C6—C7—C8—C9	−0.1 (3)
C1—C2—C3—C4	37.3 (2)	C7—C8—C9—C10	0.0 (3)
O2—C3—C4—C5	−173.43 (19)	C8—C9—C10—C11	−0.2 (3)
C2—C3—C4—C5	7.4 (2)	C9—C10—C11—C6	0.5 (3)
C3—C4—C5—O3	−50.7 (2)	C7—C6—C11—C10	−0.6 (3)
C3—C4—C5—C6	−169.46 (17)	C5—C6—C11—C10	−178.68 (19)
O3—C5—C6—C7	137.70 (18)	O1—C1—O3—C5	174.97 (17)
C4—C5—C6—C7	−101.5 (2)	C2—C1—O3—C5	−4.6 (3)
O3—C5—C6—C11	−44.2 (2)	C6—C5—O3—C1	173.64 (17)
C4—C5—C6—C11	76.5 (2)	C4—C5—O3—C1	51.1 (2)