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

Zeng, W.-L.

doi:10.1107/S1600536811026201

organic compounds

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Volume 67| Part 8| August 2011| Page o1937

doi:10.1107/S1600536811026201

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2,2-Dimethyl-5-(2,3,4-trimethoxybenzylidene)-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 27 June 2011; accepted 1 July 2011; online 6 July 2011)

The title compound, C₁₆H₁₈O₇, was prepared by the reaction of 2,2-dimethyl-1,3-dioxane-4,6-dione and 2,3,4-trimethoxybenzaldehyde. The 1,3-dioxane ring is in a slightly distorted boat conformation. The crystal structure is stabilized by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For related structures, see: Zeng (2011a ,b ).

Experimental

Crystal data

C₁₆H₁₈O₇
M_r = 322.30
Monoclinic, P 2₁ /c
a = 12.722 (3) Å
b = 9.2669 (19) Å
c = 13.537 (3) Å
β = 98.83 (3)°
V = 1577.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.22 × 0.18 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer
14870 measured reflections
3613 independent reflections
3073 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.131
S = 1.03
3613 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O4ⁱ	0.96	2.46	3.392 (2)	163
C16—H16B⋯O5ⁱⁱ	0.96	2.58	3.397 (2)	143
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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: 10.1107/S1600536811026201/lh5270sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026201/lh5270Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026201/lh5270Isup3.cml

checkCIF report

Comment top

In previous papers the crystal structures of 2,2-Dimethyl-5-[(5-methylfuran-2-yl)methylidene]-1,3- dioxane-4,6-dione and (5-(3,4-Dimethylbenzylidene)-2,2- dimethyl-1,3-dioxane-4,6-dione are reported (Zeng. 2011a,b). As part of the search for new Meldrum's acids, the molecular structure of title compound (I) has been synthesized and its crystal structure is reported herein. The crystal structure of the title compound is shown in Fig. 1. The 1,3-dioxane ring exhibits a slightly distorted boat conformation. The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1).

Related literature top

For related structures, see: Zeng (2011a,b).

Experimental top

A 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 the 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 2,3,4-trimethoxybenzaldehyde (11.76g,0.06 mol) was added. The solution was then filtered and concentrated. Single crystals were obtained by evaporation of an petroleum ether-ethylacetate (3:1 v/v) solution of (I) 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 (I), drawn with 30% probability ellipsoids and spheres of arbritrary size for the H atoms.

2,2-Dimethyl-5-(2,3,4-trimethoxybenzylidene)-1,3-dioxane-4,6-dione top

Crystal data top

C₁₆H₁₈O₇	F(000) = 680
M_r = 322.30	D_x = 1.358 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3073 reflections
a = 12.722 (3) Å	θ = 3.0–27.5°
b = 9.2669 (19) Å	µ = 0.11 mm⁻¹
c = 13.537 (3) Å	T = 293 K
β = 98.83 (3)°	Block, yellow
V = 1577.0 (5) Å³	0.22 × 0.18 × 0.16 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	3073 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 27.5°, θ_min = 3.0°
ϕ and ω scans	h = −16→16
14870 measured reflections	k = −12→10
3613 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0828P)² + 0.1973P] where P = (F_o² + 2F_c²)/3
3613 reflections	(Δ/σ)_max < 0.001
208 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₆H₁₈O₇	V = 1577.0 (5) Å³
M_r = 322.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.722 (3) Å	µ = 0.11 mm⁻¹
b = 9.2669 (19) Å	T = 293 K
c = 13.537 (3) Å	0.22 × 0.18 × 0.16 mm
β = 98.83 (3)°

Data collection top

Bruker SMART CCD diffractometer	3073 reflections with I > 2σ(I)
14870 measured reflections	R_int = 0.033
3613 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.03	Δρ_max = 0.33 e Å⁻³
3613 reflections	Δρ_min = −0.25 e Å⁻³
208 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	0.52394 (8)	0.12332 (10)	0.25642 (7)	0.0477 (2)
O3	0.30226 (7)	0.11922 (11)	0.24083 (6)	0.0475 (2)
O7	0.01954 (7)	0.41504 (10)	−0.11404 (7)	0.0455 (2)
O5	−0.04628 (7)	0.11016 (11)	0.07142 (6)	0.0470 (2)
O6	−0.09078 (7)	0.23104 (10)	−0.06837 (6)	0.0423 (2)
O4	0.17489 (8)	0.46436 (11)	−0.02499 (9)	0.0549 (3)
O1	0.61501 (7)	0.18353 (12)	0.09474 (8)	0.0535 (3)
C14	0.10299 (10)	0.38024 (13)	−0.04308 (9)	0.0390 (3)
C9	0.35150 (10)	0.14559 (12)	0.15946 (9)	0.0373 (3)
C13	0.09149 (9)	0.24390 (13)	0.01095 (8)	0.0361 (3)
C12	−0.01832 (9)	0.18810 (13)	0.00905 (8)	0.0361 (3)
C8	0.46155 (10)	0.14555 (13)	0.16543 (9)	0.0387 (3)
C4	0.28552 (10)	0.18482 (13)	0.07028 (9)	0.0390 (3)
C7	0.50721 (10)	0.18263 (13)	0.08077 (10)	0.0413 (3)
C6	0.44249 (11)	0.21837 (16)	−0.00816 (10)	0.0467 (3)
H6A	0.4726	0.2408	−0.0647	0.056*
C5	0.33352 (11)	0.22040 (15)	−0.01229 (10)	0.0455 (3)
H5A	0.2910	0.2462	−0.0718	0.055*
C10	0.17081 (10)	0.17055 (14)	0.06602 (9)	0.0395 (3)
H10A	0.1493	0.1002	0.1076	0.047*
C11	−0.05435 (10)	0.30305 (14)	−0.15114 (9)	0.0414 (3)
C15	−0.15002 (13)	0.37887 (18)	−0.20694 (12)	0.0561 (4)
H15A	−0.1781	0.4445	−0.1628	0.084*
H15B	−0.2033	0.3090	−0.2316	0.084*
H15C	−0.1296	0.4315	−0.2621	0.084*
C3	0.32531 (14)	−0.01527 (18)	0.29164 (13)	0.0626 (4)
H3A	0.2861	−0.0216	0.3467	0.094*
H3B	0.4001	−0.0210	0.3162	0.094*
H3C	0.3052	−0.0934	0.2461	0.094*
C2	0.58511 (12)	−0.00798 (17)	0.26325 (14)	0.0616 (4)
H2A	0.6262	−0.0156	0.3287	0.092*
H2B	0.6320	−0.0068	0.2141	0.092*
H2C	0.5379	−0.0891	0.2515	0.092*
C16	−0.00279 (14)	0.19646 (17)	−0.21299 (10)	0.0563 (4)
H16A	0.0574	0.1530	−0.1724	0.084*
H16B	0.0203	0.2456	−0.2683	0.084*
H16C	−0.0532	0.1230	−0.2377	0.084*
C1	0.66751 (13)	0.2140 (2)	0.01138 (14)	0.0695 (5)
H1A	0.7431	0.2112	0.0321	0.104*
H1B	0.6471	0.3082	−0.0143	0.104*
H1C	0.6476	0.1432	−0.0399	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0458 (5)	0.0472 (5)	0.0461 (5)	−0.0004 (4)	−0.0054 (4)	0.0007 (4)
O3	0.0486 (5)	0.0564 (6)	0.0394 (5)	0.0052 (4)	0.0130 (4)	0.0080 (4)
O7	0.0446 (5)	0.0398 (5)	0.0518 (5)	0.0001 (4)	0.0062 (4)	0.0080 (4)
O5	0.0473 (5)	0.0564 (5)	0.0399 (5)	−0.0060 (4)	0.0141 (4)	0.0081 (4)
O6	0.0350 (4)	0.0527 (5)	0.0392 (4)	−0.0028 (4)	0.0058 (3)	0.0051 (4)
O4	0.0456 (5)	0.0437 (5)	0.0765 (7)	−0.0090 (4)	0.0134 (5)	−0.0020 (5)
O1	0.0344 (5)	0.0634 (6)	0.0636 (6)	−0.0038 (4)	0.0109 (4)	−0.0018 (5)
C14	0.0361 (6)	0.0377 (6)	0.0455 (6)	0.0008 (5)	0.0134 (5)	−0.0020 (5)
C9	0.0402 (6)	0.0364 (6)	0.0360 (6)	−0.0007 (5)	0.0082 (5)	−0.0009 (4)
C13	0.0350 (6)	0.0407 (6)	0.0336 (5)	−0.0019 (4)	0.0082 (4)	−0.0017 (4)
C12	0.0356 (6)	0.0412 (6)	0.0329 (5)	−0.0005 (4)	0.0096 (4)	−0.0022 (4)
C8	0.0385 (6)	0.0352 (6)	0.0408 (6)	−0.0010 (5)	0.0012 (5)	−0.0018 (4)
C4	0.0358 (6)	0.0426 (6)	0.0389 (6)	0.0011 (5)	0.0072 (5)	0.0003 (5)
C7	0.0359 (6)	0.0390 (6)	0.0499 (7)	−0.0017 (5)	0.0097 (5)	−0.0046 (5)
C6	0.0438 (7)	0.0554 (7)	0.0435 (7)	0.0023 (6)	0.0149 (5)	0.0022 (6)
C5	0.0421 (7)	0.0567 (8)	0.0381 (6)	0.0051 (6)	0.0072 (5)	0.0042 (5)
C10	0.0390 (6)	0.0454 (6)	0.0349 (5)	−0.0004 (5)	0.0079 (5)	0.0008 (5)
C11	0.0442 (7)	0.0437 (6)	0.0364 (6)	−0.0003 (5)	0.0063 (5)	0.0044 (5)
C15	0.0520 (8)	0.0605 (9)	0.0524 (8)	0.0052 (6)	−0.0034 (6)	0.0089 (6)
C3	0.0726 (10)	0.0571 (9)	0.0623 (9)	−0.0038 (7)	0.0240 (8)	0.0149 (7)
C2	0.0482 (8)	0.0536 (8)	0.0775 (10)	0.0039 (6)	−0.0074 (7)	0.0128 (7)
C16	0.0732 (10)	0.0582 (8)	0.0390 (6)	0.0102 (7)	0.0131 (6)	0.0002 (6)
C1	0.0452 (8)	0.0925 (13)	0.0762 (11)	−0.0078 (8)	0.0267 (8)	−0.0085 (9)

Geometric parameters (Å, º) top

O2—C8	1.3745 (15)	C6—C5	1.3789 (19)
O2—C2	1.4396 (18)	C6—H6A	0.9300
O3—C9	1.3702 (14)	C5—H5A	0.9300
O3—C3	1.4319 (18)	C10—H10A	0.9300
O7—C14	1.3567 (16)	C11—C15	1.5044 (19)
O7—C11	1.4379 (16)	C11—C16	1.5085 (19)
O5—C12	1.2056 (14)	C15—H15A	0.9600
O6—C12	1.3453 (15)	C15—H15B	0.9600
O6—C11	1.4406 (14)	C15—H15C	0.9600
O4—C14	1.1981 (15)	C3—H3A	0.9600
O1—C7	1.3553 (15)	C3—H3B	0.9600
O1—C1	1.4251 (19)	C3—H3C	0.9600
C14—C13	1.4783 (17)	C2—H2A	0.9600
C9—C8	1.3898 (17)	C2—H2B	0.9600
C9—C4	1.4082 (17)	C2—H2C	0.9600
C13—C10	1.3436 (17)	C16—H16A	0.9600
C13—C12	1.4861 (16)	C16—H16B	0.9600
C8—C7	1.4048 (18)	C16—H16C	0.9600
C4—C5	1.3931 (17)	C1—H1A	0.9600
C4—C10	1.4576 (17)	C1—H1B	0.9600
C7—C6	1.3901 (19)	C1—H1C	0.9600

C8—O2—C2	114.60 (11)	O7—C11—C15	105.86 (11)
C9—O3—C3	117.14 (11)	O6—C11—C15	105.95 (11)
C14—O7—C11	118.31 (10)	O7—C11—C16	110.48 (11)
C12—O6—C11	118.63 (9)	O6—C11—C16	110.34 (11)
C7—O1—C1	118.55 (12)	C15—C11—C16	114.48 (12)
O4—C14—O7	118.68 (12)	C11—C15—H15A	109.5
O4—C14—C13	125.83 (12)	C11—C15—H15B	109.5
O7—C14—C13	115.29 (10)	H15A—C15—H15B	109.5
O3—C9—C8	122.28 (11)	C11—C15—H15C	109.5
O3—C9—C4	116.70 (11)	H15A—C15—H15C	109.5
C8—C9—C4	120.82 (11)	H15B—C15—H15C	109.5
C10—C13—C14	125.73 (11)	O3—C3—H3A	109.5
C10—C13—C12	117.23 (11)	O3—C3—H3B	109.5
C14—C13—C12	116.94 (10)	H3A—C3—H3B	109.5
O5—C12—O6	118.84 (11)	O3—C3—H3C	109.5
O5—C12—C13	125.03 (11)	H3A—C3—H3C	109.5
O6—C12—C13	116.13 (10)	H3B—C3—H3C	109.5
O2—C8—C9	119.34 (11)	O2—C2—H2A	109.5
O2—C8—C7	120.90 (11)	O2—C2—H2B	109.5
C9—C8—C7	119.44 (11)	H2A—C2—H2B	109.5
C5—C4—C9	118.16 (11)	O2—C2—H2C	109.5
C5—C4—C10	123.32 (12)	H2A—C2—H2C	109.5
C9—C4—C10	118.16 (11)	H2B—C2—H2C	109.5
O1—C7—C6	124.85 (12)	C11—C16—H16A	109.5
O1—C7—C8	115.09 (12)	C11—C16—H16B	109.5
C6—C7—C8	120.04 (11)	H16A—C16—H16B	109.5
C5—C6—C7	119.77 (12)	C11—C16—H16C	109.5
C5—C6—H6A	120.1	H16A—C16—H16C	109.5
C7—C6—H6A	120.1	H16B—C16—H16C	109.5
C6—C5—C4	121.74 (12)	O1—C1—H1A	109.5
C6—C5—H5A	119.1	O1—C1—H1B	109.5
C4—C5—H5A	119.1	H1A—C1—H1B	109.5
C13—C10—C4	129.65 (11)	O1—C1—H1C	109.5
C13—C10—H10A	115.2	H1A—C1—H1C	109.5
C4—C10—H10A	115.2	H1B—C1—H1C	109.5
O7—C11—O6	109.50 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O4ⁱ	0.96	2.46	3.392 (2)	163
C16—H16B···O5ⁱⁱ	0.96	2.58	3.397 (2)	143

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈O₇
M_r	322.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.722 (3), 9.2669 (19), 13.537 (3)
β (°)	98.83 (3)
V (Å³)	1577.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.22 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14870, 3613, 3073
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.131, 1.03
No. of reflections	3613
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.25

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
C3—H3A···O4ⁱ	0.96	2.46	3.392 (2)	163
C16—H16B···O5ⁱⁱ	0.96	2.58	3.397 (2)	143

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

References

Bruker (1997). SMART and SAINT. 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. (2011a). Acta Cryst. E67, o1351. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zeng, W.-L. (2011b). Acta Cryst. E67, o478. Web of Science CSD CrossRef IUCr Journals Google Scholar

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doi:10.1107/S1600536811026201

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