5-(3,4-Dimethyl­benzyl­idene)-2,2-dimethyl-1,3-dioxane-4,6-dione

Zeng, W.-L.

doi:10.1107/S1600536811016497

organic compounds

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Volume 67| Part 6| June 2011| Page o1351

doi:10.1107/S1600536811016497

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5-(3,4-Dimethylbenzylidene)-2,2-dimethyl-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 18 April 2011; accepted 2 May 2011; online 7 May 2011)

The title compound, C₁₅H₁₆O₄, was prepared by the reaction of 2,2-dimethyl-1,3-dioxane-4,6-dione and 3,4-dimethylbenzaldehyde in ethanol. The 1,3-dioxane ring exhibits an envelope conformation. In the crystal, molecules are linked by weak intermolecular C—H⋯O hydrogen bonds, forming chains parallel to the b axis.

Related literature

For related structures, see: Zeng (2010 , 2011 ).

Experimental

Crystal data

C₁₅H₁₆O₄
M_r = 260.28
Monoclinic, P 2₁ /c
a = 16.8249 (15) Å
b = 7.1390 (6) Å
c = 11.7101 (11) Å
β = 108.612 (1)°
V = 1333.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.45 × 0.32 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.959, T_max = 0.972
6611 measured reflections
2341 independent reflections
1330 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.201
S = 1.09
2341 reflections
176 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6C⋯O4ⁱ	0.96	2.58	3.447 (4)	151
Symmetry code: (i) x, y+1, z.

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: 10.1107/S1600536811016497/rz2588sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016497/rz2588Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811016497/rz2588Isup3.cml

checkCIF report

Comment top

In previous papers, the crystal structure of 5-(4-hydroxybenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (Zeng, 2010) and 2,2-dimethyl-5-[(5-methylfuran-2-yl)methylidene]-1,3-dioxane-4,6-dione (Zeng, 2011) have been reported. As part of this ongoing search for new Meldrum's acid compounds, the title compound has been synthesized and its structure is reported here.

In the title compound (Fig. 1), bond lengths and angles fall in the usual ranges. The 1,3-dioxane ring exhibits an envelope conformation with the dimethyl-substituted carbon C4 atom forming the flap. In the crystal structure, the molecules interact through a weak intermolecular C—H···O hydrogen bond (Table 1) to form chains parallel to the b axis.

Related literature top

For related structures, see: Zeng (2010, 2011).

Experimental top

The mixture of malonic acid (6.24 g, 0.06 mol) and acetic anhydride (9 ml) in concentrated 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 the solution and the reaction was allowed to proceed for 2 h. The mixture was then cooled and filtered, and an ethanol solution of 3,4-dimethylbenzaldehyde (8.04 g, 0.06 mol) was added. The solution was then filtered and concentrated. Single crystals were obtained by slow evaporation of a petroleum ether/ethylacetate (4:1 v/v) solution at room temperature over a period of several days.

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 the title compound, with displacement ellipsoids drawn at the 30% probability level.

5-(3,4-Dimethylbenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione top

Crystal data top

C₁₅H₁₆O₄	F(000) = 552
M_r = 260.28	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1211 reflections
a = 16.8249 (15) Å	θ = 2.6–21.6°
b = 7.1390 (6) Å	µ = 0.09 mm⁻¹
c = 11.7101 (11) Å	T = 298 K
β = 108.612 (1)°	Block, yellow
V = 1333.0 (2) Å³	0.45 × 0.32 × 0.30 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2341 independent reflections
Radiation source: fine-focus sealed tube	1330 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −19→20
T_min = 0.959, T_max = 0.972	k = −8→8
6611 measured reflections	l = −13→11

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.201	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0016P)²] where P = (F_o² + 2F_c²)/3
2341 reflections	(Δ/σ)_max < 0.001
176 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₅H₁₆O₄	V = 1333.0 (2) Å³
M_r = 260.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.8249 (15) Å	µ = 0.09 mm⁻¹
b = 7.1390 (6) Å	T = 298 K
c = 11.7101 (11) Å	0.45 × 0.32 × 0.30 mm
β = 108.612 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2341 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1330 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.972	R_int = 0.040
6611 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.201	H-atom parameters constrained
S = 1.09	Δρ_max = 0.15 e Å⁻³
2341 reflections	Δρ_min = −0.15 e Å⁻³
176 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
O1	0.30755 (12)	0.6940 (3)	0.53926 (17)	0.0576 (6)
O2	0.39334 (12)	0.4548 (3)	0.50624 (17)	0.0579 (6)
O3	0.21388 (14)	0.6469 (3)	0.62839 (19)	0.0710 (7)
O4	0.39031 (14)	0.1691 (3)	0.5720 (2)	0.0791 (8)
C1	0.27252 (18)	0.5845 (4)	0.6047 (3)	0.0523 (8)
C2	0.30722 (17)	0.3945 (4)	0.6311 (3)	0.0518 (8)
C3	0.36633 (19)	0.3278 (4)	0.5704 (3)	0.0554 (8)
C4	0.38899 (17)	0.6503 (4)	0.5324 (3)	0.0508 (8)
C5	0.45580 (18)	0.6974 (5)	0.6484 (3)	0.0626 (9)
H5A	0.4516	0.8273	0.6669	0.094*
H5B	0.5100	0.6735	0.6406	0.094*
H5C	0.4486	0.6216	0.7121	0.094*
C6	0.3971 (2)	0.7532 (5)	0.4258 (3)	0.0675 (9)
H6A	0.3536	0.7135	0.3546	0.101*
H6B	0.4509	0.7270	0.4172	0.101*
H6C	0.3921	0.8854	0.4370	0.101*
C7	0.28095 (18)	0.2646 (4)	0.6950 (3)	0.0603 (9)
H7	0.3045	0.1474	0.6928	0.072*
C8	0.22436 (18)	0.2659 (4)	0.7661 (3)	0.0564 (8)
C9	0.18336 (19)	0.0988 (4)	0.7737 (3)	0.0618 (9)
H9	0.1947	−0.0067	0.7349	0.074*
C10	0.12658 (19)	0.0834 (5)	0.8362 (3)	0.0616 (9)
C11	0.11383 (19)	0.2368 (5)	0.9012 (3)	0.0629 (9)
C12	0.1564 (2)	0.3997 (5)	0.8989 (3)	0.0676 (9)
H12	0.1492	0.5014	0.9443	0.081*
C13	0.20958 (19)	0.4168 (5)	0.8313 (3)	0.0657 (9)
H13	0.2359	0.5308	0.8292	0.079*
C14	0.0815 (2)	−0.1001 (5)	0.8349 (3)	0.0894 (12)
H14A	0.1023	−0.1921	0.7918	0.134*
H14B	0.0225	−0.0828	0.7960	0.134*
H14C	0.0913	−0.1419	0.9162	0.134*
C15	0.0553 (2)	0.2249 (6)	0.9743 (3)	0.0873 (12)
H15A	0.0004	0.1895	0.9231	0.131*
H15B	0.0523	0.3446	1.0101	0.131*
H15C	0.0756	0.1329	1.0367	0.131*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0568 (12)	0.0537 (13)	0.0679 (13)	0.0146 (10)	0.0280 (10)	0.0096 (10)
O2	0.0655 (13)	0.0499 (13)	0.0608 (13)	0.0058 (10)	0.0238 (10)	−0.0083 (11)
O3	0.0672 (14)	0.0724 (17)	0.0842 (16)	0.0231 (12)	0.0395 (13)	0.0142 (12)
O4	0.0819 (17)	0.0485 (15)	0.113 (2)	0.0095 (12)	0.0404 (14)	−0.0078 (13)
C1	0.0512 (18)	0.054 (2)	0.0523 (17)	0.0059 (15)	0.0178 (14)	0.0017 (15)
C2	0.0458 (16)	0.0447 (18)	0.0641 (19)	0.0000 (13)	0.0164 (14)	−0.0030 (15)
C3	0.0544 (18)	0.045 (2)	0.066 (2)	0.0024 (15)	0.0183 (15)	−0.0080 (16)
C4	0.0535 (18)	0.0467 (19)	0.0570 (18)	0.0075 (14)	0.0241 (14)	−0.0031 (14)
C5	0.063 (2)	0.065 (2)	0.059 (2)	−0.0037 (16)	0.0175 (16)	−0.0079 (16)
C6	0.071 (2)	0.074 (2)	0.066 (2)	0.0139 (17)	0.0331 (16)	0.0138 (18)
C7	0.0519 (18)	0.0481 (19)	0.076 (2)	0.0015 (15)	0.0136 (16)	0.0016 (16)
C8	0.0520 (18)	0.048 (2)	0.065 (2)	−0.0037 (15)	0.0132 (15)	0.0094 (16)
C9	0.063 (2)	0.053 (2)	0.063 (2)	−0.0030 (15)	0.0103 (16)	0.0072 (15)
C10	0.0559 (19)	0.057 (2)	0.063 (2)	−0.0132 (15)	0.0063 (16)	0.0142 (17)
C11	0.059 (2)	0.061 (2)	0.063 (2)	0.0000 (17)	0.0122 (16)	0.0134 (18)
C12	0.074 (2)	0.060 (2)	0.070 (2)	−0.0043 (17)	0.0241 (18)	0.0107 (17)
C13	0.066 (2)	0.054 (2)	0.077 (2)	−0.0098 (16)	0.0234 (18)	0.0074 (17)
C14	0.093 (3)	0.078 (3)	0.087 (3)	−0.032 (2)	0.015 (2)	0.007 (2)
C15	0.083 (3)	0.099 (3)	0.086 (3)	−0.010 (2)	0.035 (2)	0.014 (2)

Geometric parameters (Å, º) top

O1—C1	1.354 (3)	C7—H7	0.9300
O1—C4	1.432 (3)	C8—C13	1.388 (4)
O2—C3	1.346 (4)	C8—C9	1.395 (4)
O2—C4	1.436 (3)	C9—C10	1.381 (4)
O3—C1	1.193 (3)	C9—H9	0.9300
O4—C3	1.201 (3)	C10—C11	1.389 (4)
C1—C2	1.470 (4)	C10—C14	1.511 (4)
C2—C7	1.351 (4)	C11—C12	1.371 (4)
C2—C3	1.474 (4)	C11—C15	1.500 (4)
C4—C6	1.492 (4)	C12—C13	1.377 (4)
C4—C5	1.499 (4)	C12—H12	0.9300
C5—H5A	0.9600	C13—H13	0.9300
C5—H5B	0.9600	C14—H14A	0.9600
C5—H5C	0.9600	C14—H14B	0.9600
C6—H6A	0.9600	C14—H14C	0.9600
C6—H6B	0.9600	C15—H15A	0.9600
C6—H6C	0.9600	C15—H15B	0.9600
C7—C8	1.452 (4)	C15—H15C	0.9600

C1—O1—C4	120.2 (2)	C8—C7—H7	112.6
C3—O2—C4	119.1 (2)	C13—C8—C9	116.8 (3)
O3—C1—O1	117.2 (3)	C13—C8—C7	125.9 (3)
O3—C1—C2	126.7 (3)	C9—C8—C7	117.3 (3)
O1—C1—C2	115.8 (3)	C10—C9—C8	122.7 (3)
C7—C2—C1	124.8 (3)	C10—C9—H9	118.6
C7—C2—C3	115.8 (3)	C8—C9—H9	118.6
C1—C2—C3	118.7 (3)	C9—C10—C11	118.8 (3)
O4—C3—O2	118.2 (3)	C9—C10—C14	119.5 (3)
O4—C3—C2	124.9 (3)	C11—C10—C14	121.6 (3)
O2—C3—C2	116.9 (3)	C12—C11—C10	119.0 (3)
O1—C4—O2	109.8 (2)	C12—C11—C15	120.1 (3)
O1—C4—C6	106.6 (2)	C10—C11—C15	120.9 (3)
O2—C4—C6	106.0 (2)	C11—C12—C13	121.7 (3)
O1—C4—C5	110.7 (2)	C11—C12—H12	119.1
O2—C4—C5	109.7 (2)	C13—C12—H12	119.1
C6—C4—C5	113.9 (3)	C12—C13—C8	120.7 (3)
C4—C5—H5A	109.5	C12—C13—H13	119.6
C4—C5—H5B	109.5	C8—C13—H13	119.6
H5A—C5—H5B	109.5	C10—C14—H14A	109.5
C4—C5—H5C	109.5	C10—C14—H14B	109.5
H5A—C5—H5C	109.5	H14A—C14—H14B	109.5
H5B—C5—H5C	109.5	C10—C14—H14C	109.5
C4—C6—H6A	109.5	H14A—C14—H14C	109.5
C4—C6—H6B	109.5	H14B—C14—H14C	109.5
H6A—C6—H6B	109.5	C11—C15—H15A	109.5
C4—C6—H6C	109.5	C11—C15—H15B	109.5
H6A—C6—H6C	109.5	H15A—C15—H15B	109.5
H6B—C6—H6C	109.5	C11—C15—H15C	109.5
C2—C7—C8	134.7 (3)	H15A—C15—H15C	109.5
C2—C7—H7	112.6	H15B—C15—H15C	109.5

C4—O1—C1—O3	164.6 (2)	C1—C2—C7—C8	−8.5 (6)
C4—O1—C1—C2	−19.9 (4)	C3—C2—C7—C8	−179.5 (3)
O3—C1—C2—C7	−5.1 (5)	C2—C7—C8—C13	−31.0 (6)
O1—C1—C2—C7	179.9 (3)	C2—C7—C8—C9	151.5 (3)
O3—C1—C2—C3	165.6 (3)	C13—C8—C9—C10	3.9 (4)
O1—C1—C2—C3	−9.4 (4)	C7—C8—C9—C10	−178.4 (3)
C4—O2—C3—O4	−160.0 (3)	C8—C9—C10—C11	−4.5 (4)
C4—O2—C3—C2	21.6 (4)	C8—C9—C10—C14	177.0 (3)
C7—C2—C3—O4	1.7 (4)	C9—C10—C11—C12	1.6 (4)
C1—C2—C3—O4	−169.8 (3)	C14—C10—C11—C12	−180.0 (3)
C7—C2—C3—O2	180.0 (3)	C9—C10—C11—C15	−177.7 (3)
C1—C2—C3—O2	8.5 (4)	C14—C10—C11—C15	0.8 (5)
C1—O1—C4—O2	47.5 (3)	C10—C11—C12—C13	1.8 (5)
C1—O1—C4—C6	161.9 (2)	C15—C11—C12—C13	−178.9 (3)
C1—O1—C4—C5	−73.7 (3)	C11—C12—C13—C8	−2.5 (5)
C3—O2—C4—O1	−48.1 (3)	C9—C8—C13—C12	−0.4 (5)
C3—O2—C4—C6	−162.8 (2)	C7—C8—C13—C12	−177.8 (3)
C3—O2—C4—C5	73.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6C···O4ⁱ	0.96	2.58	3.447 (4)	151

Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₆O₄
M_r	260.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	16.8249 (15), 7.1390 (6), 11.7101 (11)
β (°)	108.612 (1)
V (Å³)	1333.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.45 × 0.32 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.959, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	6611, 2341, 1330
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.201, 1.09
No. of reflections	2341
No. of parameters	176
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.15

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
C6—H6C···O4ⁱ	0.96	2.58	3.447 (4)	151

Symmetry code: (i) x, y+1, z.

References

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zeng, W.-L. (2010). Acta Cryst. E66, o2319. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zeng, W.-L. (2011). Acta Cryst. E67, o478. Web of Science CSD CrossRef IUCr Journals Google Scholar

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doi:10.1107/S1600536811016497

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