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

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

doi:10.1107/S1600536809026877

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1875

doi:10.1107/S1600536809026877

Open

access

3-(2-Furylmethylene)-1,5-dioxaspiro[5.5]undecane-2,4-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 24 June 2009; accepted 9 July 2009; online 15 July 2009)

In the title molecule, C₁₄H₁₄O₅, the 1,3-dioxane ring is in an envelope conformation with the ring C atom common to the cyclohexane ring forming the flap. The other five atoms of the 1,3-dioxane ring are essentially planar [maximum deviation from the least-squares plane = 0.041 (3) Å] and form a dihedral angle of 13.75 (2)° with the furan ring. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds form extended chains along [101].

Related literature

For the applications and conformational features of spiro compounds, see: Yaozhong et al. (1998 ); Lian et al. (2008 ); Wei et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₄O₅
M_r = 262.25
Triclinic, $[P \overline 1]$
a = 7.0634 (14) Å
b = 9.5103 (19) Å
c = 10.183 (2) Å
α = 64.91 (3)°
β = 82.38 (3)°
γ = 84.76 (3)°
V = 613.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.18 × 0.15 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
6043 measured reflections
2779 independent reflections
1456 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.285
S = 1.11
2779 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O3ⁱ	0.97	2.59	3.470 (4)	151
C14—H14A⋯O3ⁱⁱ	0.93	2.50	3.230 (2)	135
Symmetry codes: (i) -x, -y+1, -z+2; (ii) -x-1, -y+1, -z+1.

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/S1600536809026877/lh2856sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026877/lh2856Isup2.hkl

checkCIF report

Comment top

Spiro compounds are widely used in medicine, catalysis and optical material (Lian et al., 2008; Yaozhong et al., 1998; Wei et al., 2008) owing to their interesting conformational features. We report here the synthesis and structure of the title compound, (I) (Fig. 1), as part of our ongoing studies on new spiro compounds with potentially higher bioactivity.

The 1,3-dioxane ring is in an envelope conformation with atom C1 forming the flap and the mean plane of the other five atoms (O1/O2/C1/C7—C9) form a dihedral angle of 13.75 (2)° with the furan ring O5/C11-C14). The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1, Fig. 2).

Related literature top

For the applications and conformational features of spiro compounds, see: Yaozhong 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 conc. 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 4 h. The mixture was cooled and filtered, and then an ethanol solution of furan-2-carbaldehyde (5.76 g,0.06 mol) was added. The solution was then filtered and concentrated. Single crystals were obtained by evaporation of an acetone-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.
	Fig. 2. Part of the crystal structure of (I) with hydrogen bonds drawn as dashed lines.

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

Crystal data top

C₁₄H₁₄O₅	Z = 2
M_r = 262.25	F(000) = 276
Triclinic, P1	D_x = 1.420 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0634 (14) Å	Cell parameters from 6043 reflections
b = 9.5103 (19) Å	θ = 3.5–27.5°
c = 10.183 (2) Å	µ = 0.11 mm⁻¹
α = 64.91 (3)°	T = 293 K
β = 82.38 (3)°	Block, colorless
γ = 84.76 (3)°	0.18 × 0.15 × 0.12 mm
V = 613.6 (2) Å³

Data collection top

Bruker SMART CCD diffractometer	1456 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 27.5°, θ_min = 3.5°
ω scans	h = −9→9
6043 measured reflections	k = −12→12
2779 independent reflections	l = −13→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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.285	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.1559P)² + 0.0401P] where P = (F_o² + 2F_c²)/3
2779 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₄H₁₄O₅	γ = 84.76 (3)°
M_r = 262.25	V = 613.6 (2) Å³
Triclinic, P1	Z = 2
a = 7.0634 (14) Å	Mo Kα radiation
b = 9.5103 (19) Å	µ = 0.11 mm⁻¹
c = 10.183 (2) Å	T = 293 K
α = 64.91 (3)°	0.18 × 0.15 × 0.12 mm
β = 82.38 (3)°

Data collection top

Bruker SMART CCD diffractometer	1456 reflections with I > 2σ(I)
6043 measured reflections	R_int = 0.031
2779 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	0 restraints
wR(F²) = 0.285	H-atom parameters constrained
S = 1.11	Δρ_max = 0.48 e Å⁻³
2779 reflections	Δρ_min = −0.35 e Å⁻³
172 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	0.2535 (3)	0.2890 (3)	0.7823 (3)	0.0604 (7)
O1	0.0683 (3)	0.4802 (3)	0.8363 (3)	0.0619 (7)
O4	0.1675 (3)	0.1935 (4)	0.6368 (3)	0.0709 (8)
O5	−0.4171 (3)	0.3169 (3)	0.4940 (3)	0.0651 (7)
O3	−0.2004 (4)	0.5790 (3)	0.7400 (3)	0.0726 (8)
C9	−0.0519 (5)	0.3713 (4)	0.6897 (4)	0.0539 (8)
C2	0.3594 (5)	0.3844 (4)	0.9383 (4)	0.0611 (9)
H2A	0.3191	0.4343	1.0035	0.073*
H2B	0.4318	0.4577	0.8525	0.073*
C7	−0.0735 (5)	0.4822 (4)	0.7561 (4)	0.0550 (8)
C8	0.1248 (4)	0.2756 (4)	0.7003 (4)	0.0524 (8)
C10	−0.2000 (5)	0.3676 (4)	0.6195 (4)	0.0556 (9)
H10A	−0.3012	0.4351	0.6257	0.067*
C1	0.1860 (5)	0.3406 (4)	0.8941 (4)	0.0553 (8)
C13	−0.2757 (5)	0.1442 (5)	0.4174 (4)	0.0637 (9)
H13A	−0.2541	0.0765	0.3723	0.076*
C6	0.0755 (5)	0.2159 (4)	1.0210 (4)	0.0591 (9)
H6A	−0.0295	0.1863	0.9867	0.071*
H6B	0.0224	0.2560	1.0918	0.071*
C11	−0.2361 (4)	0.2852 (4)	0.5395 (4)	0.0542 (8)
C14	−0.4363 (6)	0.2284 (5)	0.4246 (5)	0.0697 (10)
H14A	−0.5473	0.2254	0.3860	0.084*
C5	0.2062 (6)	0.0738 (5)	1.0931 (5)	0.0708 (11)
H5A	0.1356	−0.0024	1.1779	0.085*
H5B	0.2478	0.0272	1.0254	0.085*
C4	0.3771 (6)	0.1165 (5)	1.1386 (5)	0.0770 (12)
H4A	0.3361	0.1520	1.2146	0.092*
H4B	0.4608	0.0251	1.1787	0.092*
C3	0.4854 (5)	0.2409 (5)	1.0140 (5)	0.0751 (12)
H3A	0.5407	0.2005	0.9440	0.090*
H3B	0.5893	0.2702	1.0496	0.090*
C12	−0.1479 (5)	0.1787 (5)	0.4913 (4)	0.0654 (10)
H12A	−0.0241	0.1369	0.5055	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0605 (14)	0.0740 (17)	0.0588 (14)	0.0104 (11)	−0.0124 (11)	−0.0400 (13)
O1	0.0783 (16)	0.0523 (15)	0.0644 (15)	0.0134 (11)	−0.0225 (12)	−0.0321 (12)
O4	0.0637 (14)	0.089 (2)	0.0877 (19)	0.0176 (13)	−0.0172 (13)	−0.0652 (17)
O5	0.0641 (14)	0.0686 (17)	0.0778 (17)	0.0096 (11)	−0.0223 (12)	−0.0433 (14)
O3	0.0799 (17)	0.0654 (17)	0.0807 (18)	0.0260 (13)	−0.0212 (14)	−0.0403 (15)
C9	0.0649 (19)	0.0522 (19)	0.0511 (18)	0.0083 (14)	−0.0129 (14)	−0.0280 (16)
C2	0.065 (2)	0.060 (2)	0.067 (2)	−0.0029 (16)	−0.0113 (16)	−0.0333 (18)
C7	0.0639 (19)	0.0490 (19)	0.0562 (19)	0.0063 (14)	−0.0102 (15)	−0.0264 (16)
C8	0.0567 (18)	0.056 (2)	0.0497 (17)	0.0035 (14)	−0.0042 (13)	−0.0288 (16)
C10	0.0621 (19)	0.055 (2)	0.0515 (18)	0.0086 (14)	−0.0084 (14)	−0.0254 (16)
C1	0.070 (2)	0.052 (2)	0.0520 (18)	0.0160 (15)	−0.0160 (15)	−0.0307 (16)
C13	0.079 (2)	0.060 (2)	0.067 (2)	0.0098 (17)	−0.0219 (17)	−0.0397 (19)
C6	0.0599 (19)	0.059 (2)	0.066 (2)	−0.0009 (15)	−0.0098 (16)	−0.0322 (18)
C11	0.0547 (18)	0.0522 (19)	0.061 (2)	0.0055 (13)	−0.0150 (14)	−0.0279 (17)
C14	0.074 (2)	0.072 (3)	0.084 (3)	0.0043 (18)	−0.0272 (19)	−0.049 (2)
C5	0.089 (3)	0.053 (2)	0.066 (2)	0.0002 (18)	−0.0142 (19)	−0.0202 (19)
C4	0.093 (3)	0.066 (3)	0.077 (3)	0.018 (2)	−0.036 (2)	−0.031 (2)
C3	0.063 (2)	0.079 (3)	0.101 (3)	0.0110 (19)	−0.028 (2)	−0.052 (3)
C12	0.067 (2)	0.065 (2)	0.077 (2)	0.0113 (17)	−0.0228 (18)	−0.041 (2)

Geometric parameters (Å, º) top

O2—C8	1.361 (4)	C13—C14	1.340 (5)
O2—C1	1.433 (4)	C13—C12	1.390 (5)
O1—C7	1.368 (4)	C13—H13A	0.9300
O1—C1	1.438 (4)	C6—C5	1.525 (5)
O4—C8	1.206 (4)	C6—H6A	0.9700
O5—C14	1.333 (5)	C6—H6B	0.9700
O5—C11	1.382 (4)	C11—C12	1.371 (5)
O3—C7	1.199 (4)	C14—H14A	0.9300
C9—C10	1.354 (5)	C5—C4	1.495 (6)
C9—C8	1.463 (5)	C5—H5A	0.9700
C9—C7	1.463 (5)	C5—H5B	0.9700
C2—C1	1.507 (5)	C4—C3	1.493 (6)
C2—C3	1.522 (6)	C4—H4A	0.9700
C2—H2A	0.9700	C4—H4B	0.9700
C2—H2B	0.9700	C3—H3A	0.9700
C10—C11	1.405 (5)	C3—H3B	0.9700
C10—H10A	0.9300	C12—H12A	0.9300
C1—C6	1.512 (5)

C8—O2—C1	118.6 (2)	C5—C6—H6A	109.6
C7—O1—C1	117.9 (3)	C1—C6—H6B	109.6
C14—O5—C11	107.2 (3)	C5—C6—H6B	109.6
C10—C9—C8	124.7 (3)	H6A—C6—H6B	108.1
C10—C9—C7	116.0 (3)	C12—C11—O5	107.1 (3)
C8—C9—C7	119.3 (3)	C12—C11—C10	140.0 (3)
C1—C2—C3	110.5 (3)	O5—C11—C10	112.9 (3)
C1—C2—H2A	109.5	O5—C14—C13	111.5 (3)
C3—C2—H2A	109.5	O5—C14—H14A	124.2
C1—C2—H2B	109.5	C13—C14—H14A	124.2
C3—C2—H2B	109.5	C4—C5—C6	111.3 (3)
H2A—C2—H2B	108.1	C4—C5—H5A	109.4
O3—C7—O1	117.7 (3)	C6—C5—H5A	109.4
O3—C7—C9	125.2 (3)	C4—C5—H5B	109.4
O1—C7—C9	117.0 (3)	C6—C5—H5B	109.4
O4—C8—O2	118.5 (3)	H5A—C5—H5B	108.0
O4—C8—C9	125.1 (3)	C3—C4—C5	111.9 (3)
O2—C8—C9	116.3 (3)	C3—C4—H4A	109.2
C9—C10—C11	134.7 (3)	C5—C4—H4A	109.2
C9—C10—H10A	112.7	C3—C4—H4B	109.2
C11—C10—H10A	112.7	C5—C4—H4B	109.2
O2—C1—O1	110.2 (3)	H4A—C4—H4B	107.9
O2—C1—C2	106.7 (3)	C4—C3—C2	112.3 (3)
O1—C1—C2	106.3 (3)	C4—C3—H3A	109.1
O2—C1—C6	111.0 (3)	C2—C3—H3A	109.1
O1—C1—C6	110.2 (3)	C4—C3—H3B	109.1
C2—C1—C6	112.3 (3)	C2—C3—H3B	109.1
C14—C13—C12	106.0 (4)	H3A—C3—H3B	107.9
C14—C13—H13A	127.0	C11—C12—C13	108.1 (3)
C12—C13—H13A	127.0	C11—C12—H12A	125.9
C1—C6—C5	110.3 (3)	C13—C12—H12A	125.9
C1—C6—H6A	109.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O3ⁱ	0.97	2.59	3.470 (4)	151
C14—H14A···O3ⁱⁱ	0.93	2.50	3.230 (2)	135
C10—H10A···O3	0.93	2.34	2.764 (3)	107
C12—H12A···O4	0.93	2.27	2.879 (2)	122

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄O₅
M_r	262.25
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.0634 (14), 9.5103 (19), 10.183 (2)
α, β, γ (°)	64.91 (3), 82.38 (3), 84.76 (3)
V (Å³)	613.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.18 × 0.15 × 0.12

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6043, 2779, 1456
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.285, 1.11
No. of reflections	2779
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.35

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
C2—H2A···O3ⁱ	0.97	2.59	3.470 (4)	151
C14—H14A···O3ⁱⁱ	0.93	2.50	3.230 (2)	135

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

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. 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., Guo, J. J., Liu, Y. & Zhang, D. W. (2008). Chin. J. Org. Chem. 28, 1501–1514. CAS Google Scholar
Yaozhong, J., Song, X., Zhi, J., Deng, J., Aiqiao, M. & Chan, A. S. C. (1998). Tetrahedron Assymetry, 9, 3185–3189. CrossRef Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1875

doi:10.1107/S1600536809026877

Open

access