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

Zeng, W.-L.

doi:10.1107/S1600536810033155

organic compounds

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Volume 66| Part 9| September 2010| Page o2366

https://doi.org/10.1107/S1600536810033155

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5-(4-Fluorobenzylidene)-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 8 August 2010; accepted 17 August 2010; online 21 August 2010)

The title compound, C₁₃H₁₁FO₄, was prepared by the reaction of 2,2-dimethyl-1,3-dioxane-4,6-dione and 4-fluorobenzaldehyde in ethanol. The 1,3-dioxane ring adopts an envelope conformation. The crystal structure is stabilized by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For background information on the use of Meldrum's acid (2,2-dimethyl-1,3-dioxane-4,6-dione) in organic synthesis, see: Kuhn et al. (2003 ); Casadesus et al. (2006 ). For a related structure, see: Zeng & Jian (2009 ).

Experimental

Crystal data

C₁₃H₁₁FO₄
M_r = 250.22
Monoclinic, P 2₁ /c
a = 10.607 (2) Å
b = 10.413 (2) Å
c = 11.366 (2) Å
β = 106.09 (3)°
V = 1206.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.17 × 0.15 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
11341 measured reflections
2748 independent reflections
1773 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.182
S = 1.16
2748 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O1ⁱ	0.93	2.47	3.373 (3)	164
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

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: https://doi.org/10.1107/S1600536810033155/lh5116sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810033155/lh5116Isup2.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). We have recently reported the crystal structure of 5-(2-fluorobenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (Zeng & Jian, 2009). As part of our search for new Meldrum's acid derivatives the title compound,(I)(Fig. 1), has been synthesized and its crystal structure is reported herein. The crystal structure analysis confirms the title compound with atom C7 connected to a benzene ring via the C7-C8 single bond [1.451 (2)Å] and a 1,3-dioxane ring via the C7═C5 double bond [1.349 (2)Å]. The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1).

Related literature top

For background information on the use of Meldrum's acid (2,2-dimethyl-1,3-dioxane-4,6-dione) in organic synthesis, see: Kuhn et al. (2003); Casadesus et al. (2006). For a related structure, see: Zeng & Jian (2009).

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 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 4-fluorobenzaldehyde (7.67g,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.

Structure description top

For background information on the use of Meldrum's acid (2,2-dimethyl-1,3-dioxane-4,6-dione) in organic synthesis, see: Kuhn et al. (2003); Casadesus et al. (2006). For a related structure, see: Zeng & Jian (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.

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

Crystal data top

C₁₃H₁₁FO₄	F(000) = 520
M_r = 250.22	D_x = 1.378 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2748 reflections
a = 10.607 (2) Å	θ = 3.0–27.5°
b = 10.413 (2) Å	µ = 0.11 mm⁻¹
c = 11.366 (2) Å	T = 293 K
β = 106.09 (3)°	Block, colorless
V = 1206.2 (4) Å³	0.17 × 0.15 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1773 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 27.5°, θ_min = 3.0°
φ and ω scans	h = −13→13
11341 measured reflections	k = −13→13
2748 independent reflections	l = −14→13

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) = 0.182	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2748 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₃H₁₁FO₄	V = 1206.2 (4) Å³
M_r = 250.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.607 (2) Å	µ = 0.11 mm⁻¹
b = 10.413 (2) Å	T = 293 K
c = 11.366 (2) Å	0.17 × 0.15 × 0.10 mm
β = 106.09 (3)°

Data collection top

Bruker SMART CCD diffractometer	1773 reflections with I > 2σ(I)
11341 measured reflections	R_int = 0.042
2748 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 1.16	Δρ_max = 0.16 e Å⁻³
2748 reflections	Δρ_min = −0.24 e Å⁻³
163 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	0.19531 (11)	0.04581 (14)	0.03108 (11)	0.0683 (4)
O4	0.48662 (11)	0.09217 (13)	−0.12156 (11)	0.0669 (4)
O1	0.29516 (11)	0.01292 (14)	−0.12672 (11)	0.0685 (4)
C7	0.46120 (16)	0.27281 (18)	0.07462 (14)	0.0588 (4)
H7A	0.4452	0.3029	0.1462	0.071*
O3	0.27783 (14)	0.17669 (16)	0.18433 (12)	0.0848 (5)
C5	0.38086 (15)	0.17577 (16)	0.02221 (13)	0.0541 (4)
C4	0.39340 (15)	0.09646 (17)	−0.08040 (15)	0.0566 (4)
C8	0.56723 (16)	0.34028 (17)	0.04331 (14)	0.0577 (4)
C6	0.28220 (17)	0.13664 (19)	0.08633 (16)	0.0625 (5)
C3	0.17201 (16)	0.0255 (2)	−0.09776 (16)	0.0661 (5)
C13	0.65632 (18)	0.4046 (2)	0.13807 (17)	0.0693 (5)
H13A	0.6460	0.4008	0.2166	0.083*
C9	0.5822 (2)	0.3527 (2)	−0.07392 (17)	0.0706 (5)
H9A	0.5226	0.3128	−0.1394	0.085*
F1	0.86826 (14)	0.55357 (17)	−0.01890 (16)	0.1227 (6)
C10	0.6833 (2)	0.4228 (2)	−0.0945 (2)	0.0837 (6)
H10A	0.6928	0.4306	−0.1731	0.100*
C2	0.0951 (2)	0.1370 (2)	−0.16850 (19)	0.0837 (6)
H2A	0.1444	0.2149	−0.1462	0.126*
H2B	0.0128	0.1447	−0.1494	0.126*
H2C	0.0794	0.1222	−0.2547	0.126*
C12	0.75946 (19)	0.4739 (2)	0.1185 (2)	0.0806 (6)
H12A	0.8200	0.5144	0.1828	0.097*
C11	0.7695 (2)	0.4809 (2)	0.0023 (2)	0.0814 (6)
C1	0.1052 (2)	−0.1014 (2)	−0.1254 (2)	0.0918 (7)
H1A	0.1597	−0.1669	−0.0775	0.138*
H1B	0.0900	−0.1205	−0.2109	0.138*
H1C	0.0229	−0.0986	−0.1058	0.138*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0660 (7)	0.0800 (9)	0.0650 (8)	−0.0019 (6)	0.0283 (6)	0.0010 (6)
O4	0.0655 (7)	0.0787 (9)	0.0648 (8)	0.0073 (6)	0.0321 (6)	−0.0021 (6)
O1	0.0620 (7)	0.0813 (9)	0.0663 (8)	−0.0011 (6)	0.0244 (6)	−0.0140 (6)
C7	0.0654 (9)	0.0671 (11)	0.0449 (8)	0.0118 (8)	0.0173 (7)	0.0042 (7)
O3	0.0943 (10)	0.1107 (13)	0.0621 (8)	−0.0072 (8)	0.0427 (7)	−0.0087 (7)
C5	0.0562 (8)	0.0627 (10)	0.0464 (8)	0.0083 (7)	0.0192 (6)	0.0048 (7)
C4	0.0580 (9)	0.0631 (10)	0.0500 (8)	0.0089 (7)	0.0169 (7)	0.0027 (7)
C8	0.0615 (9)	0.0602 (10)	0.0516 (9)	0.0086 (7)	0.0162 (7)	0.0035 (7)
C6	0.0659 (10)	0.0709 (12)	0.0552 (10)	0.0076 (8)	0.0244 (8)	0.0058 (8)
C3	0.0568 (9)	0.0811 (13)	0.0635 (10)	0.0024 (8)	0.0219 (8)	−0.0051 (9)
C13	0.0696 (11)	0.0759 (13)	0.0609 (10)	0.0036 (9)	0.0157 (8)	−0.0028 (9)
C9	0.0817 (12)	0.0749 (13)	0.0558 (10)	−0.0003 (10)	0.0199 (9)	0.0067 (8)
F1	0.0936 (9)	0.1271 (13)	0.1624 (16)	−0.0198 (9)	0.0608 (10)	0.0147 (10)
C10	0.0994 (15)	0.0889 (16)	0.0738 (13)	0.0043 (12)	0.0424 (12)	0.0138 (11)
C2	0.0683 (11)	0.0995 (16)	0.0783 (13)	0.0120 (11)	0.0121 (10)	0.0050 (12)
C12	0.0655 (11)	0.0870 (15)	0.0845 (14)	−0.0003 (10)	0.0130 (10)	−0.0014 (11)
C11	0.0621 (10)	0.0815 (14)	0.1091 (16)	0.0033 (10)	0.0377 (11)	0.0108 (13)
C1	0.0819 (13)	0.0876 (16)	0.1103 (18)	−0.0143 (11)	0.0337 (12)	−0.0196 (13)

Geometric parameters (Å, º) top

O2—C6	1.348 (2)	C13—C12	1.379 (3)
O2—C3	1.432 (2)	C13—H13A	0.9300
O4—C4	1.2063 (19)	C9—C10	1.370 (3)
O1—C4	1.347 (2)	C9—H9A	0.9300
O1—C3	1.4388 (19)	F1—C11	1.367 (2)
C7—C5	1.349 (2)	C10—C11	1.362 (3)
C7—C8	1.451 (2)	C10—H10A	0.9300
C7—H7A	0.9300	C2—H2A	0.9600
O3—C6	1.202 (2)	C2—H2B	0.9600
C5—C4	1.465 (2)	C2—H2C	0.9600
C5—C6	1.488 (2)	C12—C11	1.356 (3)
C8—C9	1.391 (2)	C12—H12A	0.9300
C8—C13	1.392 (3)	C1—H1A	0.9600
C3—C1	1.491 (3)	C1—H1B	0.9600
C3—C2	1.516 (3)	C1—H1C	0.9600

C6—O2—C3	118.82 (14)	C8—C13—H13A	119.1
C4—O1—C3	120.31 (14)	C10—C9—C8	121.03 (19)
C5—C7—C8	133.77 (16)	C10—C9—H9A	119.5
C5—C7—H7A	113.1	C8—C9—H9A	119.5
C8—C7—H7A	113.1	C11—C10—C9	118.7 (2)
C7—C5—C4	126.02 (15)	C11—C10—H10A	120.6
C7—C5—C6	115.63 (15)	C9—C10—H10A	120.6
C4—C5—C6	117.82 (15)	C3—C2—H2A	109.5
O4—C4—O1	116.92 (15)	C3—C2—H2B	109.5
O4—C4—C5	126.49 (16)	H2A—C2—H2B	109.5
O1—C4—C5	116.36 (14)	C3—C2—H2C	109.5
C9—C8—C13	117.60 (18)	H2A—C2—H2C	109.5
C9—C8—C7	125.56 (16)	H2B—C2—H2C	109.5
C13—C8—C7	116.70 (15)	C11—C12—C13	117.8 (2)
O3—C6—O2	118.56 (17)	C11—C12—H12A	121.1
O3—C6—C5	124.86 (18)	C13—C12—H12A	121.1
O2—C6—C5	116.53 (15)	C12—C11—C10	123.1 (2)
O2—C3—O1	109.70 (13)	C12—C11—F1	118.2 (2)
O2—C3—C1	106.49 (17)	C10—C11—F1	118.6 (2)
O1—C3—C1	106.23 (16)	C3—C1—H1A	109.5
O2—C3—C2	110.14 (16)	C3—C1—H1B	109.5
O1—C3—C2	109.73 (16)	H1A—C1—H1B	109.5
C1—C3—C2	114.39 (16)	C3—C1—H1C	109.5
C12—C13—C8	121.71 (19)	H1A—C1—H1C	109.5
C12—C13—H13A	119.1	H1B—C1—H1C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1ⁱ	0.93	2.47	3.373 (3)	164

Symmetry code: (i) −x+1, y+1/2, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁FO₄
M_r	250.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.607 (2), 10.413 (2), 11.366 (2)
β (°)	106.09 (3)
V (Å³)	1206.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.17 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11341, 2748, 1773
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.182, 1.16
No. of reflections	2748
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.24

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
C10—H10A···O1ⁱ	0.93	2.47	3.373 (3)	164

Symmetry code: (i) −x+1, y+1/2, −z−1/2.

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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2366

https://doi.org/10.1107/S1600536810033155

Open

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