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

Zeng, W.-L.; Jian, F.-F.

doi:10.1107/S1600536809038811

organic compounds

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Volume 65| Part 10| October 2009| Page o2587

doi:10.1107/S1600536809038811

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

Wu-Lan Zeng ^a and Fang-Fang Jian ^b ^*

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

(Received 18 September 2009; accepted 25 September 2009; online 30 September 2009)

The title compound, C₁₃H₁₁FO₄, was prepared by the reaction of 2,2-dimethyl-1,3-dioxane-4,6-dione and 2-fluorobenzaldehyde in ethanol. In the crystal structure, molecules are linked into chains by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For background to the use of Meldrum's acid as a reagent in organic synthesis, see: Kuhn et al. (2003 ); Casadesus et al. (2006 ).

Experimental

Crystal data

C₁₃H₁₁FO₄
M_r = 250.22
Triclinic, $[P \overline 1]$
a = 5.9907 (12) Å
b = 7.6135 (15) Å
c = 13.712 (3) Å
α = 104.66 (3)°
β = 97.00 (3)°
γ = 98.50 (3)°
V = 590.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.18 × 0.15 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
5846 measured reflections
2680 independent reflections
2232 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.122
S = 1.09
2680 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1ⁱ	0.93	2.42	3.343 (4)	174
Symmetry code: (i) x-1, 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/S1600536809038811/lh2910sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809038811/lh2910Isup2.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 report here the synthesis and structure of the title compound,(I) (Fig. 1). The crystal structure analysis confirms the structure of the title compound with atom C7 connected to the 1,3-dioxane ring via a C4-C7 single bond [1.464 (2)Å] and the phenyl ring via a C7═C9 double bond [1.334 (2)Å]. The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1).

Related literature top

For background to the use of Meldrum's acid as a reagent in organic synthesis, see: Kuhn et al. (2003); Casadesus et al. (2006).

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 2-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 (2:1 v/v) solution of (I) at room temperature over a period of one week.

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

Crystal data top

C₁₃H₁₁FO₄	Z = 2
M_r = 250.22	F(000) = 260
Triclinic, P1	D_x = 1.408 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.9907 (12) Å	Cell parameters from 2680 reflections
b = 7.6135 (15) Å	θ = 3.1–27.5°
c = 13.712 (3) Å	µ = 0.12 mm⁻¹
α = 104.66 (3)°	T = 293 K
β = 97.00 (3)°	Block, colorless
γ = 98.50 (3)°	0.18 × 0.15 × 0.10 mm
V = 590.0 (2) Å³

Data collection top

Bruker SMART CCD diffractometer	2232 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.015
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ϕ and ω scans	h = −7→7
5846 measured reflections	k = −9→9
2680 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0689P)² + 0.0762P] where P = (F_o² + 2F_c²)/3
2680 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₁₁FO₄	γ = 98.50 (3)°
M_r = 250.22	V = 590.0 (2) Å³
Triclinic, P1	Z = 2
a = 5.9907 (12) Å	Mo Kα radiation
b = 7.6135 (15) Å	µ = 0.12 mm⁻¹
c = 13.712 (3) Å	T = 293 K
α = 104.66 (3)°	0.18 × 0.15 × 0.10 mm
β = 97.00 (3)°

Data collection top

Bruker SMART CCD diffractometer	2232 reflections with I > 2σ(I)
5846 measured reflections	R_int = 0.015
2680 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.09	Δρ_max = 0.29 e Å⁻³
2680 reflections	Δρ_min = −0.21 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
O4	0.24998 (15)	0.52398 (12)	0.08949 (6)	0.0433 (2)
F	−0.21328 (14)	0.74829 (12)	0.22191 (7)	0.0610 (3)
O3	0.42130 (16)	0.39182 (13)	0.21066 (7)	0.0487 (2)
O2	0.19470 (18)	0.81052 (13)	0.13437 (7)	0.0532 (3)
C10	0.22839 (19)	0.67636 (17)	0.16038 (9)	0.0387 (3)
O1	0.5140 (2)	0.54637 (16)	0.37345 (8)	0.0694 (4)
C4	0.0848 (2)	0.93620 (17)	0.35028 (9)	0.0418 (3)
C11	0.2576 (2)	0.35465 (17)	0.11792 (9)	0.0413 (3)
C7	0.2194 (2)	0.78997 (18)	0.34775 (9)	0.0436 (3)
H7A	0.2780	0.7790	0.4115	0.052*
C9	0.2713 (2)	0.66953 (16)	0.26804 (9)	0.0390 (3)
C6	−0.2546 (2)	1.0510 (2)	0.29876 (11)	0.0521 (3)
H6A	−0.3967	1.0306	0.2578	0.063*
C5	−0.1258 (2)	0.91420 (18)	0.29004 (9)	0.0430 (3)
C8	0.4099 (2)	0.53311 (18)	0.29079 (10)	0.0455 (3)
C3	0.1648 (3)	1.1072 (2)	0.42261 (11)	0.0547 (4)
H3A	0.3034	1.1261	0.4660	0.066*
C13	0.3522 (3)	0.2316 (2)	0.03544 (11)	0.0592 (4)
H13A	0.5007	0.2923	0.0301	0.089*
H13B	0.2516	0.2058	−0.0286	0.089*
H13C	0.3649	0.1179	0.0520	0.089*
C2	0.0417 (3)	1.2483 (2)	0.43080 (12)	0.0613 (4)
H2A	0.1004	1.3627	0.4775	0.074*
C1	−0.1683 (3)	1.2195 (2)	0.36964 (12)	0.0582 (4)
H1A	−0.2522	1.3141	0.3762	0.070*
C12	0.0242 (3)	0.2714 (2)	0.13214 (12)	0.0566 (4)
H12A	−0.0266	0.3564	0.1856	0.085*
H12B	0.0317	0.1583	0.1503	0.085*
H12C	−0.0815	0.2462	0.0696	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0517 (5)	0.0425 (5)	0.0385 (4)	0.0132 (4)	0.0100 (4)	0.0124 (4)
F	0.0480 (5)	0.0557 (5)	0.0669 (5)	0.0051 (4)	−0.0003 (4)	0.0021 (4)
O3	0.0514 (5)	0.0451 (5)	0.0475 (5)	0.0221 (4)	−0.0027 (4)	0.0065 (4)
O2	0.0690 (6)	0.0492 (5)	0.0510 (5)	0.0235 (5)	0.0113 (4)	0.0233 (4)
C10	0.0364 (5)	0.0409 (6)	0.0410 (6)	0.0114 (5)	0.0064 (5)	0.0129 (5)
O1	0.0878 (8)	0.0677 (7)	0.0492 (6)	0.0420 (6)	−0.0159 (5)	0.0068 (5)
C4	0.0452 (6)	0.0436 (7)	0.0389 (6)	0.0171 (5)	0.0077 (5)	0.0103 (5)
C11	0.0442 (6)	0.0387 (6)	0.0402 (6)	0.0099 (5)	0.0034 (5)	0.0098 (5)
C7	0.0463 (6)	0.0461 (7)	0.0387 (6)	0.0170 (5)	0.0013 (5)	0.0100 (5)
C9	0.0390 (6)	0.0393 (6)	0.0394 (6)	0.0128 (5)	0.0017 (5)	0.0114 (5)
C6	0.0409 (6)	0.0620 (9)	0.0593 (8)	0.0191 (6)	0.0085 (6)	0.0218 (7)
C5	0.0411 (6)	0.0440 (7)	0.0440 (6)	0.0089 (5)	0.0080 (5)	0.0110 (5)
C8	0.0485 (7)	0.0431 (7)	0.0441 (6)	0.0183 (5)	−0.0014 (5)	0.0092 (5)
C3	0.0550 (8)	0.0542 (8)	0.0479 (7)	0.0200 (6)	−0.0012 (6)	0.0007 (6)
C13	0.0701 (9)	0.0534 (8)	0.0528 (8)	0.0230 (7)	0.0137 (7)	0.0042 (6)
C2	0.0728 (10)	0.0465 (8)	0.0605 (8)	0.0221 (7)	0.0086 (7)	0.0022 (6)
C1	0.0653 (9)	0.0537 (8)	0.0661 (9)	0.0319 (7)	0.0188 (7)	0.0200 (7)
C12	0.0525 (8)	0.0538 (8)	0.0599 (8)	−0.0008 (6)	0.0093 (6)	0.0155 (6)

Geometric parameters (Å, º) top

O4—C10	1.3460 (15)	C9—C8	1.4904 (17)
O4—C11	1.4434 (15)	C6—C5	1.3753 (19)
F—C5	1.3529 (16)	C6—C1	1.381 (2)
O3—C8	1.3457 (16)	C6—H6A	0.9300
O3—C11	1.4460 (15)	C3—C2	1.380 (2)
O2—C10	1.1996 (15)	C3—H3A	0.9300
C10—C9	1.4826 (16)	C13—H13A	0.9600
O1—C8	1.1979 (16)	C13—H13B	0.9600
C4—C5	1.3843 (18)	C13—H13C	0.9600
C4—C3	1.3978 (19)	C2—C1	1.379 (2)
C4—C7	1.4639 (17)	C2—H2A	0.9300
C11—C13	1.5018 (18)	C1—H1A	0.9300
C11—C12	1.5041 (19)	C12—H12A	0.9600
C7—C9	1.3385 (17)	C12—H12B	0.9600
C7—H7A	0.9300	C12—H12C	0.9600

C10—O4—C11	119.32 (9)	C6—C5—C4	123.07 (13)
C8—O3—C11	118.75 (9)	O1—C8—O3	119.85 (12)
O2—C10—O4	119.30 (11)	O1—C8—C9	124.13 (12)
O2—C10—C9	124.62 (11)	O3—C8—C9	115.98 (11)
O4—C10—C9	115.80 (10)	C2—C3—C4	121.18 (14)
C5—C4—C3	116.79 (12)	C2—C3—H3A	119.4
C5—C4—C7	124.51 (12)	C4—C3—H3A	119.4
C3—C4—C7	118.56 (12)	C11—C13—H13A	109.5
O4—C11—O3	109.41 (10)	C11—C13—H13B	109.5
O4—C11—C13	106.34 (11)	H13A—C13—H13B	109.5
O3—C11—C13	106.18 (11)	C11—C13—H13C	109.5
O4—C11—C12	110.47 (11)	H13A—C13—H13C	109.5
O3—C11—C12	110.71 (11)	H13B—C13—H13C	109.5
C13—C11—C12	113.52 (12)	C1—C2—C3	119.93 (14)
C9—C7—C4	130.10 (11)	C1—C2—H2A	120.0
C9—C7—H7A	114.9	C3—C2—H2A	120.0
C4—C7—H7A	114.9	C2—C1—C6	120.39 (13)
C7—C9—C10	125.14 (11)	C2—C1—H1A	119.8
C7—C9—C8	117.26 (11)	C6—C1—H1A	119.8
C10—C9—C8	117.09 (10)	C11—C12—H12A	109.5
C5—C6—C1	118.59 (13)	C11—C12—H12B	109.5
C5—C6—H6A	120.7	H12A—C12—H12B	109.5
C1—C6—H6A	120.7	C11—C12—H12C	109.5
F—C5—C6	118.32 (12)	H12A—C12—H12C	109.5
F—C5—C4	118.57 (12)	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱ	0.93	2.42	3.343 (4)	174
C7—H7A···O1	0.93	2.42	2.798 (2)	104

Symmetry code: (i) x−1, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁FO₄
M_r	250.22
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.9907 (12), 7.6135 (15), 13.712 (3)
α, β, γ (°)	104.66 (3), 97.00 (3), 98.50 (3)
V (Å³)	590.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.18 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5846, 2680, 2232
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.122, 1.09
No. of reflections	2680
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.21

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
C1—H1A···O1ⁱ	0.93	2.42	3.343 (4)	174

Symmetry code: (i) x−1, y+1, z.

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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2587

doi:10.1107/S1600536809038811

Open

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