3-(4-Fluoro­benzyl­idene)-1,5-dioxa­spiro­[5.5]undecane-2,4-dione

Zeng, W.-L.

doi:10.1107/S1600536810054395

organic compounds

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Volume 67| Part 2| February 2011| Page o276

doi:10.1107/S1600536810054395

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3-(4-Fluorobenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-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 21 December 2010; accepted 27 December 2010; online 8 January 2011)

In the title molecule, C₁₆H₁₅FO₄, the fused 1,3-dioxane and cyclohexane rings exhibit a bath and a chair conformation, respectively. In the crystal, weak intermolecular C—H⋯O hydrogen bonds link the molecules into centrosymmetric dimers.

Related literature

For related structures, see: Zeng & Jian (2009 ); Zeng et al. (2009 ). For applications of spiro compounds, see: Jiang et al. (1998 ); Lian et al. (2008 ); Wei et al. (2008 ).

Experimental

Crystal data

C₁₆H₁₅FO₄
M_r = 290.28
Triclinic, $[P \overline 1]$
a = 5.6690 (11) Å
b = 10.130 (2) Å
c = 12.160 (2) Å
α = 100.68 (3)°
β = 90.73 (3)°
γ = 91.20 (3)°
V = 686.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.25 × 0.18 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
6753 measured reflections
3124 independent reflections
2481 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.127
S = 1.11
3124 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O2ⁱ	0.93	2.47	3.3405 (17)	156
Symmetry code: (i) -x+1, -y, -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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810054395/cv5023sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810054395/cv5023Isup2.hkl

checkCIF report

Comment top

Spiro compounds are widely used in medicine, catalysis and optical material (Lian et al., 2008; Jiang et al., 1998; Wei et al., 2008). As a part of our search for new spiro compounds with potentially high bioactivity (Zeng et al., 2009a,b), the title compound, (I), has been synthesized. Herewith we present its crystal structure.

In (I) (Fig. 1), the 1,3-dioxane ring is in a bath conformation with atom C4 atom common to the cyclohexane forming the flap. The cyclohexane ring exists in a distorted chair comformation. In the crystal structure, weak intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers.

Related literature top

For related structures, see: Zeng & Jian (2009); Zeng, Zhang & Jian (2009). For applications of spiro compounds, see: Jiang et al. (1998); Lian et al. (2008); Wei et al. (2008).

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, cyclohexanone (5.88 g, 0.06 mol) was added dropwise into solution for 1 h. The reaction was allowed to proceed for 3 h. The mixture was cooled and filtered, and then an ethanol solution of 4-fluorobenzaldehyde (7.44g,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 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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), drawn with 30% probability displacement ellipsoids.

3-(4-Fluorobenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione top

Crystal data top

C₁₆H₁₅FO₄	Z = 2
M_r = 290.28	F(000) = 304
Triclinic, P1	D_x = 1.405 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6690 (11) Å	Cell parameters from 2481 reflections
b = 10.130 (2) Å	θ = 3.4–27.5°
c = 12.160 (2) Å	µ = 0.11 mm⁻¹
α = 100.68 (3)°	T = 293 K
β = 90.73 (3)°	Block, colourless
γ = 91.20 (3)°	0.25 × 0.18 × 0.12 mm
V = 686.0 (2) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2481 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 27.5°, θ_min = 3.4°
phi and ω scans	h = −6→7
6753 measured reflections	k = −13→13
3124 independent reflections	l = −15→15

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) = 0.127	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.075P)² + 0.0414P] where P = (F_o² + 2F_c²)/3
3124 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₆H₁₅FO₄	γ = 91.20 (3)°
M_r = 290.28	V = 686.0 (2) Å³
Triclinic, P1	Z = 2
a = 5.6690 (11) Å	Mo Kα radiation
b = 10.130 (2) Å	µ = 0.11 mm⁻¹
c = 12.160 (2) Å	T = 293 K
α = 100.68 (3)°	0.25 × 0.18 × 0.12 mm
β = 90.73 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2481 reflections with I > 2σ(I)
6753 measured reflections	R_int = 0.029
3124 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.11	Δρ_max = 0.22 e Å⁻³
3124 reflections	Δρ_min = −0.22 e Å⁻³
190 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	0.41354 (13)	0.17850 (9)	0.73171 (7)	0.0412 (2)
O3	0.23315 (15)	0.01227 (9)	0.59454 (6)	0.0443 (2)
O2	0.54128 (17)	0.12738 (11)	0.89002 (8)	0.0566 (3)
O1	0.19126 (18)	−0.19449 (10)	0.62363 (8)	0.0542 (3)
C8	0.21663 (19)	−0.07730 (12)	0.66337 (10)	0.0397 (3)
F1	−0.52419 (17)	−0.46737 (10)	0.87835 (8)	0.0718 (3)
C7	0.41388 (19)	0.09907 (13)	0.80943 (9)	0.0390 (3)
C11	−0.0075 (2)	−0.18139 (12)	0.86756 (9)	0.0386 (3)
C9	0.25581 (19)	−0.02211 (12)	0.78410 (9)	0.0369 (3)
C4	0.23557 (19)	0.15348 (12)	0.64363 (9)	0.0373 (3)
C15	−0.3686 (2)	−0.29703 (14)	0.79341 (12)	0.0483 (3)
H15A	−0.4931	−0.3097	0.7417	0.058*
C10	0.1751 (2)	−0.07673 (12)	0.86916 (10)	0.0395 (3)
H10A	0.2448	−0.0435	0.9387	0.047*
C14	−0.3539 (2)	−0.37296 (13)	0.87486 (11)	0.0477 (3)
C5	−0.00563 (19)	0.19627 (13)	0.68678 (10)	0.0398 (3)
H5A	−0.0431	0.1530	0.7494	0.048*
H5B	−0.1233	0.1671	0.6282	0.048*
C16	−0.1937 (2)	−0.20081 (13)	0.78976 (11)	0.0446 (3)
H16A	−0.2004	−0.1483	0.7347	0.053*
C3	0.3168 (2)	0.22760 (16)	0.55360 (11)	0.0510 (3)
H3A	0.2194	0.1992	0.4869	0.061*
H3B	0.4783	0.2043	0.5348	0.061*
C13	−0.1757 (3)	−0.35709 (15)	0.95384 (11)	0.0526 (3)
H13A	−0.1711	−0.4106	1.0082	0.063*
C12	−0.0029 (2)	−0.25937 (14)	0.95053 (10)	0.0473 (3)
H12A	0.1176	−0.2457	1.0043	0.057*
C6	−0.0155 (2)	0.34786 (14)	0.72405 (12)	0.0522 (3)
H6A	−0.1749	0.3723	0.7460	0.063*
H6B	0.0879	0.3758	0.7887	0.063*
C2	0.3031 (3)	0.37944 (17)	0.59021 (14)	0.0625 (4)
H2A	0.4182	0.4098	0.6497	0.075*
H2B	0.3421	0.4226	0.5277	0.075*
C1	0.0590 (3)	0.42054 (17)	0.63108 (15)	0.0642 (4)
H1A	−0.0536	0.3997	0.5692	0.077*
H1B	0.0590	0.5168	0.6584	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0287 (4)	0.0539 (5)	0.0422 (4)	−0.0084 (3)	−0.0059 (3)	0.0136 (4)
O3	0.0462 (5)	0.0525 (5)	0.0318 (4)	0.0047 (4)	0.0000 (3)	0.0016 (4)
O2	0.0543 (5)	0.0664 (6)	0.0495 (5)	−0.0195 (5)	−0.0240 (4)	0.0156 (5)
O1	0.0602 (6)	0.0480 (5)	0.0484 (5)	−0.0020 (4)	0.0003 (4)	−0.0067 (4)
C8	0.0311 (5)	0.0475 (7)	0.0380 (6)	0.0005 (5)	0.0000 (4)	0.0010 (5)
F1	0.0644 (6)	0.0712 (6)	0.0810 (6)	−0.0309 (5)	−0.0030 (5)	0.0207 (5)
C7	0.0310 (5)	0.0482 (6)	0.0372 (6)	−0.0030 (5)	−0.0034 (4)	0.0074 (5)
C11	0.0361 (5)	0.0410 (6)	0.0376 (6)	0.0002 (4)	0.0015 (4)	0.0046 (5)
C9	0.0314 (5)	0.0411 (6)	0.0366 (5)	−0.0003 (4)	−0.0036 (4)	0.0034 (5)
C4	0.0291 (5)	0.0487 (6)	0.0333 (5)	−0.0018 (4)	−0.0031 (4)	0.0065 (5)
C15	0.0362 (6)	0.0545 (7)	0.0530 (7)	−0.0033 (5)	−0.0068 (5)	0.0078 (6)
C10	0.0369 (6)	0.0432 (6)	0.0372 (6)	−0.0014 (5)	−0.0047 (5)	0.0052 (5)
C14	0.0420 (6)	0.0451 (7)	0.0539 (7)	−0.0085 (5)	0.0047 (5)	0.0049 (6)
C5	0.0282 (5)	0.0493 (7)	0.0414 (6)	−0.0010 (5)	−0.0013 (4)	0.0077 (5)
C16	0.0383 (6)	0.0495 (7)	0.0481 (7)	0.0010 (5)	−0.0037 (5)	0.0152 (6)
C3	0.0416 (6)	0.0738 (9)	0.0413 (6)	−0.0025 (6)	0.0023 (5)	0.0203 (6)
C13	0.0590 (8)	0.0550 (8)	0.0468 (7)	−0.0084 (6)	−0.0006 (6)	0.0184 (6)
C12	0.0471 (7)	0.0560 (7)	0.0389 (6)	−0.0066 (6)	−0.0049 (5)	0.0098 (5)
C6	0.0469 (7)	0.0505 (7)	0.0573 (8)	0.0049 (6)	−0.0003 (6)	0.0047 (6)
C2	0.0610 (8)	0.0695 (10)	0.0644 (9)	−0.0146 (7)	−0.0041 (7)	0.0339 (8)
C1	0.0693 (9)	0.0531 (8)	0.0738 (10)	0.0022 (7)	−0.0094 (8)	0.0216 (7)

Geometric parameters (Å, º) top

O4—C7	1.3500 (15)	C14—C13	1.371 (2)
O4—C4	1.4458 (13)	C5—C6	1.5208 (19)
O3—C8	1.3463 (16)	C5—H5A	0.9700
O3—C4	1.4440 (15)	C5—H5B	0.9700
O2—C7	1.1972 (14)	C16—H16A	0.9300
O1—C8	1.2008 (15)	C3—C2	1.524 (2)
C8—C9	1.4830 (16)	C3—H3A	0.9700
F1—C14	1.3511 (15)	C3—H3B	0.9700
C7—C9	1.4872 (16)	C13—C12	1.3845 (19)
C11—C12	1.3922 (17)	C13—H13A	0.9300
C11—C16	1.3948 (17)	C12—H12A	0.9300
C11—C10	1.4635 (17)	C6—C1	1.519 (2)
C9—C10	1.3411 (17)	C6—H6A	0.9700
C4—C3	1.5092 (18)	C6—H6B	0.9700
C4—C5	1.5138 (16)	C2—C1	1.517 (2)
C15—C14	1.365 (2)	C2—H2A	0.9700
C15—C16	1.3827 (18)	C2—H2B	0.9700
C15—H15A	0.9300	C1—H1A	0.9700
C10—H10A	0.9300	C1—H1B	0.9700

C7—O4—C4	118.46 (9)	H5A—C5—H5B	108.0
C8—O3—C4	118.15 (9)	C15—C16—C11	120.91 (12)
O1—C8—O3	119.04 (11)	C15—C16—H16A	119.5
O1—C8—C9	124.97 (12)	C11—C16—H16A	119.5
O3—C8—C9	115.69 (10)	C4—C3—C2	112.08 (12)
O2—C7—O4	119.51 (11)	C4—C3—H3A	109.2
O2—C7—C9	125.10 (12)	C2—C3—H3A	109.2
O4—C7—C9	115.36 (9)	C4—C3—H3B	109.2
C12—C11—C16	118.66 (11)	C2—C3—H3B	109.2
C12—C11—C10	118.86 (11)	H3A—C3—H3B	107.9
C16—C11—C10	122.37 (11)	C14—C13—C12	118.29 (13)
C10—C9—C8	125.84 (11)	C14—C13—H13A	120.9
C10—C9—C7	118.84 (10)	C12—C13—H13A	120.9
C8—C9—C7	115.16 (11)	C13—C12—C11	120.75 (12)
O3—C4—O4	108.60 (10)	C13—C12—H12A	119.6
O3—C4—C3	106.43 (10)	C11—C12—H12A	119.6
O4—C4—C3	106.66 (10)	C1—C6—C5	111.29 (12)
O3—C4—C5	110.87 (10)	C1—C6—H6A	109.4
O4—C4—C5	111.68 (9)	C5—C6—H6A	109.4
C3—C4—C5	112.35 (11)	C1—C6—H6B	109.4
C14—C15—C16	118.30 (12)	C5—C6—H6B	109.4
C14—C15—H15A	120.8	H6A—C6—H6B	108.0
C16—C15—H15A	120.8	C1—C2—C3	111.48 (13)
C9—C10—C11	128.90 (11)	C1—C2—H2A	109.3
C9—C10—H10A	115.6	C3—C2—H2A	109.3
C11—C10—H10A	115.6	C1—C2—H2B	109.3
F1—C14—C15	118.41 (12)	C3—C2—H2B	109.3
F1—C14—C13	118.51 (13)	H2A—C2—H2B	108.0
C15—C14—C13	123.08 (12)	C2—C1—C6	110.99 (13)
C4—C5—C6	111.58 (11)	C2—C1—H1A	109.4
C4—C5—H5A	109.3	C6—C1—H1A	109.4
C6—C5—H5A	109.3	C2—C1—H1B	109.4
C4—C5—H5B	109.3	C6—C1—H1B	109.4
C6—C5—H5B	109.3	H1A—C1—H1B	108.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O2ⁱ	0.93	2.47	3.3405 (17)	156
C10—H10A···O2	0.93	2.54	2.874 (2)	101

Symmetry code: (i) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅FO₄
M_r	290.28
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.6690 (11), 10.130 (2), 12.160 (2)
α, β, γ (°)	100.68 (3), 90.73 (3), 91.20 (3)
V (Å³)	686.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.18 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6753, 3124, 2481
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.127, 1.11
No. of reflections	3124
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O2ⁱ	0.93	2.47	3.3405 (17)	156

Symmetry code: (i) −x+1, −y, −z+2.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jiang, Y. Z., Xue, S., Li, Z., Deng, J. G., Mi, A. Q. & Albert, S. C. C. (1998). Tetrahedron, 9, 3185–3189. CrossRef CAS Google Scholar
Lian, Y., Guo, J. J., Liu, X. M. & Wei, R. B. (2008). Chem. Res. Chin. Univ. 24, 441–444. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wei, R. B., Liu, B., Liu, Y., Guo, J. J. & Zhang, D. W. (2008). Chin. J. Org. Chem. 28, 1501–1514. CAS Google Scholar
Zeng, W.-L. & Jian, F. (2009). Acta Cryst. E65, o1875. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zeng, W.-L., Zhang, H.-X. & Jian, F.-F. (2009). Acta Cryst. E65, o2035. Web of Science CSD CrossRef IUCr Journals Google Scholar

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