3-[(5-Methyl­furan-2-yl)methyl­ene]-1,5-dioxaspiro­[5.5]undecane-2,4-dione

Wu-Lan Zeng; Hua-Xiang Zhang; Fang-Fang Jian

doi:10.1107/S160053680902947X

. 2009 Jul 29;65(Pt 8):o2035. doi: 10.1107/S160053680902947X

3-[(5-Methylfuran-2-yl)methylene]-1,5-dioxaspiro[5.5]undecane-2,4-dione

Wu-Lan Zeng ^a, Hua-Xiang Zhang ^a, Fang-Fang Jian ^a,^*

PMCID: PMC2977103 PMID: 21583701

Abstract

There are two crystallographically independent molecules in the asymmetric unit of the title compound, C₁₅H₁₆O₅. In each, the 1,3-dioxane ring is in an envelope conformation with the C atom common to the cyclohexane ring forming the flap. The dihedral angles between the five essentially planar [maximum deviations from the least-squares planes of 0.049 (3) and 0.042 (3) Å] atoms of the 1,3-dioxane ring and the furan ring in the two molecules are 7.15 (1) and 6.80 (1)°. The crystal structure is stabilized by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For background to the applications of spiro compounds, see: Yaozhong et al. (1998 ▶); Lian et al. (2008 ▶); Wei et al. (2008 ▶). For the crystal structure of 3-(furan-2-ylmethylene)-1,5-dioxaspiro[5.5]undecane-2,4-dione, see: Zeng & Jian (2009 ▶).

Experimental

Crystal data

C₁₅H₁₆O₅
M _r = 276.28
Monoclinic,
a = 19.314 (4) Å
b = 6.8289 (14) Å
c = 20.468 (4) Å
β = 97.04 (3)°
V = 2679.2 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.22 × 0.18 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.978, T _max = 0.985
21978 measured reflections
6028 independent reflections
3716 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.198
S = 1.02
6028 reflections
363 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to refine structure: SHELXS97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680902947X/lh2861sup1.cif

e-65-o2035-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902947X/lh2861Isup2.hkl

e-65-o2035-Isup2.hkl^{(295.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4A—H4AA⋯O4Bⁱ	0.93	2.59	3.408 (3)	147
C1B—H1BA⋯O4Aⁱⁱ	0.93	2.50	3.376 (3)	157
C12B—H12B⋯O4Bⁱ	0.97	2.53	3.420 (3)	152
C13A—H13A⋯O4Aⁱⁱ	0.97	2.54	3.405 (3)	149

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Symmetry codes: (i) Inline graphic ; (ii) .

supplementary crystallographic information

Comment

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), as part of our ongoing studies on new spiro compounds with potentially higher bioactivity and have recently determined the crystal structure of 3-(furan-2-ylmethylene)-1,5-dioxaspiro[5.5]undecane-2,4-dione, (Zeng & Jian, 2009).

The asymmetric unit of (I) is shown in Fig. 1. In both independent molecules, the 1,3-dioxane ring is in an envelope conformation with atoms C9A and C9B forming the flap in each. The mean planes of the other five essentially planar atoms (O5A/O6A/C6A—C8A and O5B/O6B/C6B—C8B) form dihedral angles of 7.15 (1)° and 6.80 (1)° with the furan ring (O2A/C1A-C4A and O2B/C1B-C4B). The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1).

Experimental

A 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 5-methylfuran-2-carbaldehyde (6.60 g,0.06 mol) was added. The solution was then filtered and concentrated. Single crystals were obtained by evaporation of an acetone-petroleum aether (2:1 v/v) solution of (I) at room temperature over a period of one week.