organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

aMicroScale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
*Correspondence e-mail: wulanzeng@163.com

(Received 9 October 2010; accepted 20 October 2010; online 23 October 2010)

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[Kuhn, N., Al-Sheikh, A. & Steimann, M. (2003). Z. Naturforsch. 58, 381-384.]); Casadesus et al. (2006[Casadesus, M., Coogan, M. P. & Ooi, L. L. (2006). Org. Biomol. Chem.. 58, 3822-3830.]). For a related structure, see: Zeng & Jian (2009[Zeng, W.-L. & Jian, F.-F. (2009). Acta Cryst. E65, o2587.]).

[Scheme 1]

Experimental

Crystal data
  • C15H14O4

  • Mr = 258.26

  • Triclinic, [P \overline 1]

  • 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)

  • Rint = 0.045

Refinement
  • R[F2 > 2σ(F2)] = 0.055

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C15—H15B⋯O3i 0.96 2.41 3.2991 (19) 155
C15—H15C⋯O3ii 0.96 2.57 3.486 (2) 159
Symmetry codes: (i) x, y+1, z; (ii) -x, -y+1, -z+2.

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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).

Related literature top

For background to Meldrum's acid, see: Kuhn et al. (2003); Casadesus et al. (2006). For a related structure, see: Zeng et al. (2009).

Experimental top

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 top

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).

Structure description top

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).

For background to Meldrum's acid, see: Kuhn et al. (2003); Casadesus et al. (2006). For a related structure, see: Zeng et al. (2009).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids and spheres of arbritrary size for the H atoms.
(E)-2,2-Dimethyl-5-(3-phenylallylidene)-1,3-dioxane-4,6-dione top
Crystal data top
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 top
Bruker SMART CCD area-detector
diffractometer
2319 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
Graphite monochromatorθmax = 27.5°, θmin = 3.2°
phi and ω scansh = 88
6475 measured reflectionsk = 99
3006 independent reflectionsl = 1717
Refinement top
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 = 1.25 w = 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
Crystal data top
C15H14O4γ = 98.31 (3)°
Mr = 258.26V = 664.4 (2) Å3
Triclinic, P1Z = 2
a = 6.9171 (14) ÅMo Kα radiation
b = 7.0961 (14) ŵ = 0.09 mm1
c = 13.732 (3) ÅT = 293 K
α = 94.79 (3)°0.20 × 0.15 × 0.10 mm
β = 90.79 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2319 reflections with I > 2σ(I)
6475 measured reflectionsRint = 0.045
3006 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.170H-atom parameters constrained
S = 1.25Δρmax = 0.33 e Å3
3006 reflectionsΔρmin = 0.30 e Å3
172 parameters
Special details top

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) top
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)
C150.0208 (2)0.7761 (2)0.87670 (11)0.0621 (4)
H15A0.09510.72130.81910.093*
H15B0.00820.91210.87450.093*
H15C0.09530.74810.93350.093*
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)
H6A1.02360.06200.66800.087*
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)
H1A1.30180.07000.57940.108*
Atomic displacement parameters (Å2) top
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, º) top
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, º) top
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.

Experimental details

Crystal data
Chemical formulaC15H14O4
Mr258.26
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)6.9171 (14), 7.0961 (14), 13.732 (3)
α, β, γ (°)94.79 (3), 90.79 (3), 98.31 (3)
V3)664.4 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.20 × 0.15 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6475, 3006, 2319
Rint0.045
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.170, 1.25
No. of reflections3006
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.30

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
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.
 

References

First citationBruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCasadesus, M., Coogan, M. P. & Ooi, L. L. (2006). Org. Biomol. Chem.. 58, 3822–3830.  Web of Science CSD CrossRef Google Scholar
First citationKuhn, N., Al-Sheikh, A. & Steimann, M. (2003). Z. Naturforsch. 58, 381–384.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZeng, W.-L. & Jian, F.-F. (2009). Acta Cryst. E65, o2587.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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ISSN: 2056-9890
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