3,9-Dimethyl-3,9-bis­(4-nitro­phen­yl)-2,4,8,10-tetra­oxaspiro­[5.5]undeca­ne

Xiaoqiang Sun; Bin Yu; Xiuqin Zhang; Xuqiang Chao; Qiang Chen

doi:10.1107/S1600536811015017

. 2011 May 7;67(Pt 6):o1319. doi: 10.1107/S1600536811015017

3,9-Dimethyl-3,9-bis(4-nitrophenyl)-2,4,8,10-tetraoxaspiro[5.5]undecane

Xiaoqiang Sun ^a, Bin Yu ^b, Xiuqin Zhang ^b,^*, Xuqiang Chao ^b, Qiang Chen ^b

PMCID: PMC3120352 PMID: 21754717

Abstract

In the title compound, C₂₁H₂₂N₂O₈, both of the nonplanar six-membered heterocycles adopt chair conformations. The dihedral angle between the terminal benzene rings is 58.22 (11)°. Weak intermolecular C—H⋯O interactions are observed 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

C₂₁H₂₂N₂O₈
M _r = 430.41
Triclinic,
a = 7.4215 (12) Å
b = 11.8790 (18) Å
c = 13.522 (3) Å
α = 115.280 (4)°
β = 94.426 (4)°
γ = 103.444 (3)°
V = 1027.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 K
0.21 × 0.21 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.976, T _max = 0.986
5588 measured reflections
3563 independent reflections
2980 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.187
S = 1.07
3563 reflections
282 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015017/is2689sup1.cif

e-67-o1319-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015017/is2689Isup2.hkl

e-67-o1319-Isup2.hkl^{(174.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811015017/is2689Isup3.cml

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

Enhanced figure: interactive version of Fig. 1

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O2ⁱ	0.97	2.56	3.515 (3)	168
C10—H10B⋯O1ⁱ	0.97	2.59	3.533 (3)	164
C17—H17⋯O4ⁱⁱ	0.93	2.45	3.337 (3)	160
C20—H20⋯O7ⁱⁱⁱ	0.93	2.37	3.242 (3)	155

Open in a new tab

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

Acknowledgments

The authors are grateful to Changzhou University and the Natural Science Foundation of China (grant No. 20872051) for financial support.

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-dimethyl-3,9-di(4-nitrophenyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (Fig. 1).

In the title compound, the two non-planar six-membered heterocycle adopt chair conformations. The dihedral angle between the nitrobenzene rings is 58.22 (11)°. In the crystal structure, weak intermolecular C—H···O interactions contribute to the crystal packing (Table 1).

Experimental

To a solution of p-nitroacetophen (2.06 g, 12.5 mmol) and pentaerythritol (0.68 g, 5 mmol) in toluene(30 ml), p-toluenesulfonic acid (0.05 g, 0.3 mmol) as catalyst was added, respectively. Then, the mixtures were refluxed for 6 h to complete the reaction. After reaction, the mixtures were allowed to cool to the room temperature, chloroform (30 ml) was added to dissolve the product, the remain residue was purified by recrystallization using ethanol to provide the title compound as a white solid (85% yield, m.p. 516–517 K). Single crystals suitable for X-ray diffraction were obtained by evaporation of an ethanol and chloroform mixed solution.