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

Zeng, W.-L.

doi:10.1107/S1600536810042534

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2943

https://doi.org/10.1107/S1600536810042534

Open

access

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

Wu-Lan Zeng ^a ^*

^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 ); Casadesus et al. (2006 ). For a related structure, see: Zeng & Jian (2009 ).

Experimental

Crystal data

C₁₅H₁₄O₄
M_r = 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)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.170
S = 1.25
3006 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 1997); 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.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042534/lh5147Isup2.hkl

checkCIF report

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.

Structure description 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).

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

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

C₁₅H₁₄O₄	Z = 2
M_r = 258.26	F(000) = 272
Triclinic, P1	D_x = 1.291 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9171 (14) Å	Cell parameters from 2319 reflections
b = 7.0961 (14) Å	θ = 3.2–27.5°
c = 13.732 (3) Å	µ = 0.09 mm⁻¹
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 tube	R_int = 0.045
Graphite monochromator	θ_max = 27.5°, θ_min = 3.2°
phi and ω scans	h = −8→8
6475 measured reflections	k = −9→9
3006 independent reflections	l = −17→17

Refinement top

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H-atom parameters constrained
S = 1.25	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
3006 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₅H₁₄O₄	γ = 98.31 (3)°
M_r = 258.26	V = 664.4 (2) Å³
Triclinic, P1	Z = 2
a = 6.9171 (14) Å	Mo Kα radiation
b = 7.0961 (14) Å	µ = 0.09 mm⁻¹
c = 13.732 (3) Å	T = 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 reflections	R_int = 0.045
3006 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.25	Δρ_max = 0.33 e Å⁻³
3006 reflections	Δρ_min = −0.30 e Å⁻³
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

	x	y	z	U_iso*/U_eq
O2	0.11039 (12)	0.49034 (12)	0.88464 (7)	0.0556 (3)
O1	0.26632 (13)	0.73340 (13)	0.79292 (7)	0.0576 (3)
C10	0.40643 (17)	0.44465 (17)	0.80181 (9)	0.0489 (3)
C9	0.53406 (18)	0.32290 (19)	0.77683 (9)	0.0533 (3)
H9A	0.5087	0.2047	0.8024	0.064*
O4	0.52765 (15)	0.70212 (16)	0.70801 (9)	0.0790 (4)
O3	0.21672 (17)	0.21587 (14)	0.89068 (9)	0.0782 (4)
C11	0.24288 (19)	0.37290 (18)	0.86240 (9)	0.0534 (3)
C8	0.70169 (18)	0.3474 (2)	0.71739 (10)	0.0546 (3)
H8A	0.7361	0.4617	0.6891	0.066*
C12	0.41250 (18)	0.63399 (19)	0.76415 (10)	0.0537 (3)
C15	−0.0208 (2)	0.7761 (2)	0.87670 (11)	0.0621 (4)
H15A	−0.0951	0.7213	0.8191	0.093*
H15B	0.0082	0.9121	0.8745	0.093*
H15C	−0.0953	0.7481	0.9335	0.093*
C7	0.80960 (19)	0.2062 (2)	0.70229 (9)	0.0569 (3)
H7A	0.7673	0.0944	0.7315	0.068*
C5	0.98573 (19)	0.2077 (2)	0.64538 (9)	0.0553 (3)
C13	0.16573 (17)	0.69346 (17)	0.88135 (9)	0.0503 (3)
C4	1.06834 (19)	0.3651 (2)	0.59900 (11)	0.0648 (4)
H4A	1.0124	0.4769	0.6049	0.078*
C6	1.0760 (2)	0.0447 (2)	0.63695 (11)	0.0726 (4)
H6A	1.0236	−0.0620	0.6680	0.087*
C14	0.2935 (2)	0.7718 (2)	0.96872 (12)	0.0717 (4)
H14A	0.4106	0.7137	0.9673	0.108*
H14B	0.2248	0.7443	1.0273	0.108*
H14C	0.3271	0.9077	0.9675	0.108*
C3	1.2336 (2)	0.3567 (3)	0.54389 (13)	0.0784 (5)
H3A	1.2869	0.4624	0.5123	0.094*
C2	1.3187 (2)	0.1942 (3)	0.53569 (14)	0.0887 (6)
H2A	1.4286	0.1886	0.4979	0.106*
C1	1.2416 (3)	0.0393 (3)	0.58337 (14)	0.0903 (6)
H1A	1.3018	−0.0700	0.5794	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0584 (5)	0.0430 (5)	0.0644 (6)	0.0006 (4)	0.0176 (4)	0.0074 (4)
O1	0.0619 (5)	0.0547 (5)	0.0613 (6)	0.0155 (4)	0.0176 (4)	0.0212 (4)
C10	0.0530 (6)	0.0473 (7)	0.0473 (6)	0.0056 (5)	0.0066 (5)	0.0115 (5)
C9	0.0593 (7)	0.0520 (7)	0.0500 (7)	0.0098 (5)	0.0023 (5)	0.0097 (5)
O4	0.0782 (7)	0.0716 (7)	0.0972 (8)	0.0208 (5)	0.0424 (6)	0.0429 (6)
O3	0.1022 (8)	0.0478 (6)	0.0891 (8)	0.0118 (5)	0.0430 (6)	0.0245 (5)
C11	0.0652 (7)	0.0439 (7)	0.0509 (7)	0.0035 (5)	0.0112 (6)	0.0082 (5)
C8	0.0546 (7)	0.0582 (7)	0.0525 (7)	0.0106 (5)	0.0027 (5)	0.0086 (5)
C12	0.0531 (6)	0.0531 (7)	0.0577 (7)	0.0087 (5)	0.0127 (5)	0.0180 (6)
C15	0.0607 (7)	0.0590 (8)	0.0679 (9)	0.0116 (6)	0.0127 (6)	0.0063 (6)
C7	0.0603 (7)	0.0609 (8)	0.0519 (7)	0.0148 (6)	0.0021 (6)	0.0098 (6)
C5	0.0556 (7)	0.0672 (8)	0.0463 (7)	0.0197 (6)	−0.0027 (5)	0.0050 (6)
C13	0.0567 (6)	0.0423 (6)	0.0510 (7)	0.0014 (5)	0.0104 (5)	0.0081 (5)
C4	0.0582 (7)	0.0763 (10)	0.0642 (8)	0.0191 (7)	0.0015 (6)	0.0144 (7)
C6	0.0820 (9)	0.0768 (10)	0.0665 (9)	0.0339 (8)	0.0090 (8)	0.0096 (8)
C14	0.0797 (9)	0.0637 (9)	0.0678 (9)	0.0026 (7)	−0.0088 (7)	−0.0016 (7)
C3	0.0592 (8)	0.1082 (14)	0.0715 (10)	0.0144 (8)	0.0096 (7)	0.0236 (9)
C2	0.0677 (9)	0.1327 (18)	0.0731 (10)	0.0386 (10)	0.0170 (8)	0.0082 (11)
C1	0.0914 (12)	0.1067 (14)	0.0844 (12)	0.0537 (11)	0.0177 (10)	0.0057 (10)

Geometric parameters (Å, º) top

O2—C11	1.3468 (15)	C7—C5	1.456 (2)
O2—C13	1.4415 (14)	C7—H7A	0.9300
O1—C12	1.3590 (15)	C5—C4	1.387 (2)
O1—C13	1.4362 (15)	C5—C6	1.389 (2)
C10—C9	1.3501 (17)	C13—C14	1.4992 (19)
C10—C11	1.4702 (18)	C4—C3	1.385 (2)
C10—C12	1.4746 (17)	C4—H4A	0.9300
C9—C8	1.4256 (19)	C6—C1	1.374 (2)
C9—H9A	0.9300	C6—H6A	0.9300
O4—C12	1.1959 (16)	C14—H14A	0.9600
O3—C11	1.2004 (15)	C14—H14B	0.9600
C8—C7	1.3375 (18)	C14—H14C	0.9600
C8—H8A	0.9300	C3—C2	1.366 (2)
C15—C13	1.4955 (17)	C3—H3A	0.9300
C15—H15A	0.9600	C2—C1	1.372 (3)
C15—H15B	0.9600	C2—H2A	0.9300
C15—H15C	0.9600	C1—H1A	0.9300

C11—O2—C13	119.15 (10)	C6—C5—C7	118.85 (14)
C12—O1—C13	119.85 (9)	O1—C13—O2	110.44 (10)
C9—C10—C11	116.66 (11)	O1—C13—C15	106.78 (10)
C9—C10—C12	123.71 (12)	O2—C13—C15	106.17 (10)
C11—C10—C12	119.36 (11)	O1—C13—C14	110.25 (11)
C10—C9—C8	130.02 (12)	O2—C13—C14	109.54 (10)
C10—C9—H9A	115.0	C15—C13—C14	113.55 (13)
C8—C9—H9A	115.0	C3—C4—C5	120.42 (15)
O3—C11—O2	118.16 (12)	C3—C4—H4A	119.8
O3—C11—C10	124.58 (13)	C5—C4—H4A	119.8
O2—C11—C10	117.22 (10)	C1—C6—C5	120.81 (17)
C7—C8—C9	120.10 (13)	C1—C6—H6A	119.6
C7—C8—H8A	119.9	C5—C6—H6A	119.6
C9—C8—H8A	119.9	C13—C14—H14A	109.5
O4—C12—O1	118.08 (11)	C13—C14—H14B	109.5
O4—C12—C10	126.04 (12)	H14A—C14—H14B	109.5
O1—C12—C10	115.79 (11)	C13—C14—H14C	109.5
C13—C15—H15A	109.5	H14A—C14—H14C	109.5
C13—C15—H15B	109.5	H14B—C14—H14C	109.5
H15A—C15—H15B	109.5	C2—C3—C4	120.37 (17)
C13—C15—H15C	109.5	C2—C3—H3A	119.8
H15A—C15—H15C	109.5	C4—C3—H3A	119.8
H15B—C15—H15C	109.5	C3—C2—C1	119.80 (16)
C8—C7—C5	127.42 (13)	C3—C2—H2A	120.1
C8—C7—H7A	116.3	C1—C2—H2A	120.1
C5—C7—H7A	116.3	C2—C1—C6	120.36 (16)
C4—C5—C6	118.21 (13)	C2—C1—H1A	119.8
C4—C5—C7	122.93 (13)	C6—C1—H1A	119.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄O₄
M_r	258.26
Crystal system, space group	Triclinic, 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)
V (Å³)	664.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6475, 3006, 2319
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.170, 1.25
No. of reflections	3006
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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.

References

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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2943

https://doi.org/10.1107/S1600536810042534

Open

access