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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2943.
Published online 2010 October 23. doi:  10.1107/S1600536810042534
PMCID: PMC3009221

(E)-2,2-Dimethyl-5-(3-phenyl­allyl­idene)-1,3-dioxane-4,6-dione

Abstract

The title compound, C15H14O4, was prepared by the reaction of 2,2-dimethyl-1,3-dioxane-4,6-dione and (Z)-3-phenyl­acryl­aldehyde in ethanol. The dioxane ring is in a sofa conformation with the C atom bonded to the two methyl groups forming the flap. With the exception of the flap atom and the methyl group C atoms, all other non-H atoms are essentially planar, with an r.m.s. deviation of 0.067 (1) Å. The crystal structure is stabilized by weak inter­molecular C—H(...)O hydrogen bonds.

Related literature

For background to Meldrum’s acid, 2,2-dimethyl-1,3-dioxane-4,6-dione, see: Kuhn et al. (2003 [triangle]); Casadesus et al. (2006 [triangle]). For a related structure, see: Zeng & Jian (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2943-scheme1.jpg

Experimental

Crystal data

  • C15H14O4
  • M r = 258.26
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2943-efi1.jpg
  • a = 6.9171 (14) Å
  • b = 7.0961 (14) Å
  • c = 13.732 (3) Å
  • α = 94.79 (3)°
  • β = 90.79 (3)°
  • γ = 98.31 (3)°
  • V = 664.4 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.20 × 0.15 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • 6475 measured reflections
  • 3006 independent reflections
  • 2319 reflections with I > 2σ(I)
  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.170
  • S = 1.25
  • 3006 reflections
  • 172 parameters
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810042534/lh5147sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810042534/lh5147Isup2.hkl

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

supplementary crystallographic information

Comment

Starting with its discovery and correct structural assignment, Meldrum's acid has become a widely used reagent in organic synthesis (Kuhn et al., 2003; Casadesus et al., 2006) owing to the interesting conformational features of the products. We have recently reported the crystal structure of 5-(2-fluorobenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (Zeng et al. 2009). As part of our search for new Meldrum's acid, the title compound (I) has been synthesized and its structure is reported herein. The molecular structure of (I) is shown in Fig. 1. The dioxane ring is in a sofa conformation with the C atom bonded to the two methyl groups forming the flap. With the exception of the flap atom and the methyl group C atoms, all other non-hydrogen atoms are essentially planar with an rms deviation of 0.067 (1)Å. The deviation of atom C13 from the mean-plane formed by O1/O2/C11/C12/C10 is 0.270 (1)Å. The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1).

Experimental

The mixture of malonic acid (6.24 g, 0.06 mol) and acetic anhydride(9 ml) in strong sulfuric acid (0.25 ml) was stirred with water at 303K, After dissolving, propan-2-one (3.48 g, 0.06 mol) was added dropwise into solution for 1 h. The reaction was allowed to proceed for 2 h. The mixture was cooled and filtered, and then an ethanol solution of (Z)-3-phenylacrylaldehyde (7.92g,0.06 mol) was added. The solution was then filtered and concentrated. Single crystals were obtained by evaporation of an petroleum ether-ethylacetate (4:1 v/v) solution of (I) at room temperature over a period of several days.

Refinement

The H atoms were placed in calculated positions (C—H = 0.93 and 0.96 Å), and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I), drawn with 30% probability ellipsoids and spheres of arbritrary size for the H atoms.

Crystal data

C15H14O4Z = 2
Mr = 258.26F(000) = 272
Triclinic, P1Dx = 1.291 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9171 (14) ÅCell parameters from 2319 reflections
b = 7.0961 (14) Åθ = 3.2–27.5°
c = 13.732 (3) ŵ = 0.09 mm1
α = 94.79 (3)°T = 293 K
β = 90.79 (3)°Block, yellow
γ = 98.31 (3)°0.20 × 0.15 × 0.10 mm
V = 664.4 (2) Å3

Data collection

Bruker SMART CCD area-detector diffractometer2319 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
graphiteθmax = 27.5°, θmin = 3.2°
phi and ω scansh = −8→8
6475 measured reflectionsk = −9→9
3006 independent reflectionsl = −17→17

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170H-atom parameters constrained
S = 1.25w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
3006 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = −0.30 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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 (Å2)

xyzUiso*/Ueq
O20.11039 (12)0.49034 (12)0.88464 (7)0.0556 (3)
O10.26632 (13)0.73340 (13)0.79292 (7)0.0576 (3)
C100.40643 (17)0.44465 (17)0.80181 (9)0.0489 (3)
C90.53406 (18)0.32290 (19)0.77683 (9)0.0533 (3)
H9A0.50870.20470.80240.064*
O40.52765 (15)0.70212 (16)0.70801 (9)0.0790 (4)
O30.21672 (17)0.21587 (14)0.89068 (9)0.0782 (4)
C110.24288 (19)0.37290 (18)0.86240 (9)0.0534 (3)
C80.70169 (18)0.3474 (2)0.71739 (10)0.0546 (3)
H8A0.73610.46170.68910.066*
C120.41250 (18)0.63399 (19)0.76415 (10)0.0537 (3)
C15−0.0208 (2)0.7761 (2)0.87670 (11)0.0621 (4)
H15A−0.09510.72130.81910.093*
H15B0.00820.91210.87450.093*
H15C−0.09530.74810.93350.093*
C70.80960 (19)0.2062 (2)0.70229 (9)0.0569 (3)
H7A0.76730.09440.73150.068*
C50.98573 (19)0.2077 (2)0.64538 (9)0.0553 (3)
C130.16573 (17)0.69346 (17)0.88135 (9)0.0503 (3)
C41.06834 (19)0.3651 (2)0.59900 (11)0.0648 (4)
H4A1.01240.47690.60490.078*
C61.0760 (2)0.0447 (2)0.63695 (11)0.0726 (4)
H6A1.0236−0.06200.66800.087*
C140.2935 (2)0.7718 (2)0.96872 (12)0.0717 (4)
H14A0.41060.71370.96730.108*
H14B0.22480.74431.02730.108*
H14C0.32710.90770.96750.108*
C31.2336 (2)0.3567 (3)0.54389 (13)0.0784 (5)
H3A1.28690.46240.51230.094*
C21.3187 (2)0.1942 (3)0.53569 (14)0.0887 (6)
H2A1.42860.18860.49790.106*
C11.2416 (3)0.0393 (3)0.58337 (14)0.0903 (6)
H1A1.3018−0.07000.57940.108*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O20.0584 (5)0.0430 (5)0.0644 (6)0.0006 (4)0.0176 (4)0.0074 (4)
O10.0619 (5)0.0547 (5)0.0613 (6)0.0155 (4)0.0176 (4)0.0212 (4)
C100.0530 (6)0.0473 (7)0.0473 (6)0.0056 (5)0.0066 (5)0.0115 (5)
C90.0593 (7)0.0520 (7)0.0500 (7)0.0098 (5)0.0023 (5)0.0097 (5)
O40.0782 (7)0.0716 (7)0.0972 (8)0.0208 (5)0.0424 (6)0.0429 (6)
O30.1022 (8)0.0478 (6)0.0891 (8)0.0118 (5)0.0430 (6)0.0245 (5)
C110.0652 (7)0.0439 (7)0.0509 (7)0.0035 (5)0.0112 (6)0.0082 (5)
C80.0546 (7)0.0582 (7)0.0525 (7)0.0106 (5)0.0027 (5)0.0086 (5)
C120.0531 (6)0.0531 (7)0.0577 (7)0.0087 (5)0.0127 (5)0.0180 (6)
C150.0607 (7)0.0590 (8)0.0679 (9)0.0116 (6)0.0127 (6)0.0063 (6)
C70.0603 (7)0.0609 (8)0.0519 (7)0.0148 (6)0.0021 (6)0.0098 (6)
C50.0556 (7)0.0672 (8)0.0463 (7)0.0197 (6)−0.0027 (5)0.0050 (6)
C130.0567 (6)0.0423 (6)0.0510 (7)0.0014 (5)0.0104 (5)0.0081 (5)
C40.0582 (7)0.0763 (10)0.0642 (8)0.0191 (7)0.0015 (6)0.0144 (7)
C60.0820 (9)0.0768 (10)0.0665 (9)0.0339 (8)0.0090 (8)0.0096 (8)
C140.0797 (9)0.0637 (9)0.0678 (9)0.0026 (7)−0.0088 (7)−0.0016 (7)
C30.0592 (8)0.1082 (14)0.0715 (10)0.0144 (8)0.0096 (7)0.0236 (9)
C20.0677 (9)0.1327 (18)0.0731 (10)0.0386 (10)0.0170 (8)0.0082 (11)
C10.0914 (12)0.1067 (14)0.0844 (12)0.0537 (11)0.0177 (10)0.0057 (10)

Geometric parameters (Å, °)

O2—C111.3468 (15)C7—C51.456 (2)
O2—C131.4415 (14)C7—H7A0.9300
O1—C121.3590 (15)C5—C41.387 (2)
O1—C131.4362 (15)C5—C61.389 (2)
C10—C91.3501 (17)C13—C141.4992 (19)
C10—C111.4702 (18)C4—C31.385 (2)
C10—C121.4746 (17)C4—H4A0.9300
C9—C81.4256 (19)C6—C11.374 (2)
C9—H9A0.9300C6—H6A0.9300
O4—C121.1959 (16)C14—H14A0.9600
O3—C111.2004 (15)C14—H14B0.9600
C8—C71.3375 (18)C14—H14C0.9600
C8—H8A0.9300C3—C21.366 (2)
C15—C131.4955 (17)C3—H3A0.9300
C15—H15A0.9600C2—C11.372 (3)
C15—H15B0.9600C2—H2A0.9300
C15—H15C0.9600C1—H1A0.9300
C11—O2—C13119.15 (10)C6—C5—C7118.85 (14)
C12—O1—C13119.85 (9)O1—C13—O2110.44 (10)
C9—C10—C11116.66 (11)O1—C13—C15106.78 (10)
C9—C10—C12123.71 (12)O2—C13—C15106.17 (10)
C11—C10—C12119.36 (11)O1—C13—C14110.25 (11)
C10—C9—C8130.02 (12)O2—C13—C14109.54 (10)
C10—C9—H9A115.0C15—C13—C14113.55 (13)
C8—C9—H9A115.0C3—C4—C5120.42 (15)
O3—C11—O2118.16 (12)C3—C4—H4A119.8
O3—C11—C10124.58 (13)C5—C4—H4A119.8
O2—C11—C10117.22 (10)C1—C6—C5120.81 (17)
C7—C8—C9120.10 (13)C1—C6—H6A119.6
C7—C8—H8A119.9C5—C6—H6A119.6
C9—C8—H8A119.9C13—C14—H14A109.5
O4—C12—O1118.08 (11)C13—C14—H14B109.5
O4—C12—C10126.04 (12)H14A—C14—H14B109.5
O1—C12—C10115.79 (11)C13—C14—H14C109.5
C13—C15—H15A109.5H14A—C14—H14C109.5
C13—C15—H15B109.5H14B—C14—H14C109.5
H15A—C15—H15B109.5C2—C3—C4120.37 (17)
C13—C15—H15C109.5C2—C3—H3A119.8
H15A—C15—H15C109.5C4—C3—H3A119.8
H15B—C15—H15C109.5C3—C2—C1119.80 (16)
C8—C7—C5127.42 (13)C3—C2—H2A120.1
C8—C7—H7A116.3C1—C2—H2A120.1
C5—C7—H7A116.3C2—C1—C6120.36 (16)
C4—C5—C6118.21 (13)C2—C1—H1A119.8
C4—C5—C7122.93 (13)C6—C1—H1A119.8

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C15—H15B···O3i0.962.413.2991 (19)155
C15—H15C···O3ii0.962.573.486 (2)159

Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5147).

References

  • Bruker (1997). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Casadesus, M., Coogan, M. P. & Ooi, L. L. (2006). Org. Biomol. Chem. 58, 3822–3830. [PubMed]
  • Kuhn, N., Al-Sheikh, A. & Steimann, M. (2003). Z. Naturforsch 58, 381–384.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zeng, W.-L. & Jian, F.-F. (2009). Acta Cryst. E65, o2587. [PMC free article] [PubMed]

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