rac-3,9-Bis(3-chloro­phen­yl)-2,4,8,10-tetra­oxaspiro­[5.5]undeca­ne

Zhengyi Li; Beibei Zhou; Liang Chen; Ling Ge; Xiaoqiang Sun

doi:10.1107/S1600536811037172

. 2011 Sep 17;67(Pt 10):o2672. doi: 10.1107/S1600536811037172

rac-3,9-Bis(3-chlorophenyl)-2,4,8,10-tetraoxaspiro[5.5]undecane

Zhengyi Li ^a, Beibei Zhou ^a, Liang Chen ^a, Ling Ge ^a, Xiaoqiang Sun ^a,^*

PMCID: PMC3201504 PMID: 22058783

Abstract

In the title compound, C₁₉H₁₈Cl₂O₄, the two non-planar six-membered heterocycles passing through the spiro-C atom both adopt chair conformations, and the dihedral angle between the two benzene rings is 7.2 (1)°. In the crystal, the enantiomers with R and S configurations are generated by the symmetry elements of the centrosymmetric space group, forming a racemic crystal. Intermolecular C—H⋯π and weak C—H⋯O interactions link the molecules in the crystal structure.

Related literature

For general background to spiranes, see: Cismaş et al. (2005 ▶); Mihiş et al. (2008 ▶); Sun et al. (2010 ▶).

Experimental

Crystal data

C₁₉H₁₈Cl₂O₄
M _r = 381.23
Monoclinic,
a = 13.0924 (13) Å
b = 5.8473 (6) Å
c = 23.061 (2) Å
β = 92.865 (2)°
V = 1763.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.892, T _max = 0.926
9216 measured reflections
3083 independent reflections
2669 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.091
S = 1.01
3083 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811037172/kp2345sup1.cif

e-67-o2672-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037172/kp2345Isup2.hkl

e-67-o2672-Isup2.hkl^{(151.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037172/kp2345Isup3.cml

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

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

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯Cg1ⁱ	0.97	2.70	3.632 (2)	162
C9—H9A⋯O3ⁱⁱ	0.97	2.64	3.402 (2)	135
C11—H11B⋯O3ⁱⁱⁱ	0.97	2.61	3.530 (2)	158

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

Acknowledgments

We gratefully acknowledge financial support from the Natural Science Foundation of China (Nos. 20872051 and 21002009) and the Priority Academic Program Development of Jiangsu Higher Education Institutions.

supplementary crystallographic information

Comment

Owing to the characteristic axial and helical chirality, the stereochemistry of spiranes with six-membered rings has been extensively studied (Cismaş et al., 2005). In the past three decades, most of these investigations were carried out with spiranes containing 1,3-dioxane units (Mihiş et al., 2008; Sun et al., 2010). We herein present the structure of 3,9-bis(3-chlorophenyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (Fig. 1).

In the title compound, the two nonplanar six-membered heterocycles [(O1, O2 and C7–C10) and (O3, O4 and C10–C13)] passing through the spiro-C atom (C10) both adopt chair conformations, and the dihedral angle between the two benzene rings (C1–C6 and C14–C19) is 7.2 (1)°. In the crystal packing structure (Fig. 2), the enantiomers with R and S configurations are generated by the symmetry elements of the centrosymmetric groups forming a racemate. Intermolecular weak C–H···O interactions link molecules with the same configuration (R or S) into the two chains chains along the b axis. The chains are further connected by C–H···π interactions [C12–H12B···Cg1ⁱ = 2.70 Å; (i) -x + 2, -y, -z + 1; Cg1 is the centroid of benzene ring (C1–C6); Table 1] creating a racemic network.

Experimental

To a solution of 3-chlorobenzaldehyde (7.32 mmol, 1.03 g) and pentaerythritol (4 mmol, 0.54 g) in toluene (30 mL), phosphotungstic acid (30 mg) as catalyst was added, respectively. The mixtures were refluxed for 4 h to complete the reaction. After reaction, the mixture was evaporated under vacuum and the residuces were washed with 5% sodium bicarboinate (20 mL) and 50% ethanol (20 mL), respectively. The pure product recrystallised from ethanol to afford colourless crystals (yield 65%, m.p. 397–398 K). Single crystals suitable for X-ray diffraction were also obtained by evaporation of an enthanol solution.