3,9-Di-tert-butyl-2,4,8,10-tetra­oxaspiro­[5.5]undeca­ne

Li, Z.; Chen, L.; Tang, Q.; Sun, X.

doi:10.1107/S1600536810049524

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3368

https://doi.org/10.1107/S1600536810049524

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3,9-Di-tert-butyl-2,4,8,10-tetraoxaspiro[5.5]undecane

Zhengyi Li,^a Liang Chen,^a Qiuzheng Tang ^a and Xiaoqiang Sun ^a ^*

^aKey Laboratory of Fine Chemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, People's Republic of China
^*Correspondence e-mail: chemsxq@yahoo.com.cn

(Received 23 November 2010; accepted 26 November 2010; online 30 November 2010)

The title compound, C₁₅H₂₈O₄, was prepared by the condensation of pivalaldehyde with pentaerythritol. In the crystal, the two halves of the molecule are related by a crystallographic twofold rotation axis passing through the central spiro-C atom. The two non-planar six-membered heterocycles both adopt chair conformations with the two tert-butyl groups both located in the equatorial positions.

Related literature

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

Experimental

Crystal data

C₁₅H₂₈O₄
M_r = 272.37
Monoclinic, C 2/c
a = 26.726 (4) Å
b = 5.7894 (8) Å
c = 11.2635 (15) Å
β = 113.846 (4)°
V = 1594.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 295 K
0.35 × 0.32 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.972, T_max = 0.988
4400 measured reflections
1513 independent reflections
1347 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.145
S = 1.03
1513 reflections
90 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810049524/si2313sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810049524/si2313Isup2.hkl

checkCIF report

Comment top

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-di(tert-butyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (Fig. 1).

In the title compound, a 2-fold rotation axis passes through the central spiro-C atom (C1). The two non-planar sixmembered heterocycle [(O1/O2/C1–C4) and (O1A/O2A/C1/C2A–C4A)] both adopt chair conformations. The two tert-butyl groups locate at the equatorial position of C3 and C3A in the two six-member O-heterocycles, respectively, which give the title molecule with minimum conformational energy.

Related literature top

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

Experimental top

To a solution of pivaldehyde (7.3 mmol,0.63 g) and pentaerythritol (4 mmol, 0.54 g) in toluene (30 ml), phosphotungstic acid (30 mg) was added as catalyst. The mixtures were refluxed for 6 h to complete the reaction. After reaction, the solvent was evaporated under vacuum and the resulting solid was washed with 5% sodium bicarbonate (20 ml) and 50% ethanol (20 ml). The pure product recrystallized from ethanol to afford a white solid (65% yield, m.p. 451–452 K). Single crystals suitable for X-ray diffraction were also obtained by evaporation of an ethanol solution.

Structure description top

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

Computing details top

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [symmetry code: -x, y, -z + 1/2].

3,9-Di-tert-butyl-2,4,8,10-tetraoxaspiro[5.5]undecane top

Crystal data top

C₁₅H₂₈O₄	F(000) = 600
M_r = 272.37	D_x = 1.135 Mg m⁻³
Monoclinic, C2/c	Melting point = 451–452 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 26.726 (4) Å	Cell parameters from 3133 reflections
b = 5.7894 (8) Å	θ = 3.1–25.8°
c = 11.2635 (15) Å	µ = 0.08 mm⁻¹
β = 113.846 (4)°	T = 295 K
V = 1594.0 (4) Å³	Block, colorless
Z = 4	0.35 × 0.32 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	1513 independent reflections
Radiation source: fine-focus sealed tube	1347 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
φ and ω scans	θ_max = 25.8°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −26→32
T_min = 0.972, T_max = 0.988	k = −6→7
4400 measured 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.1P)² + 0.4P] where P = (F_o² + 2F_c²)/3
1513 reflections	(Δ/σ)_max < 0.001
90 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₅H₂₈O₄	V = 1594.0 (4) Å³
M_r = 272.37	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 26.726 (4) Å	µ = 0.08 mm⁻¹
b = 5.7894 (8) Å	T = 295 K
c = 11.2635 (15) Å	0.35 × 0.32 × 0.15 mm
β = 113.846 (4)°

Data collection top

Bruker APEXII CCD diffractometer	1513 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1347 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.988	R_int = 0.019
4400 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
1513 reflections	Δρ_min = −0.25 e Å⁻³
90 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
C1	0.0000	0.5543 (3)	0.2500	0.0352 (4)
C2	0.03372 (5)	0.4010 (2)	0.36479 (11)	0.0457 (4)
H2A	0.0094	0.3201	0.3953	0.055*
H2B	0.0531	0.2865	0.3366	0.055*
C3	0.10728 (4)	0.66075 (19)	0.42765 (10)	0.0374 (3)
H3	0.1261	0.5544	0.3918	0.045*
C4	0.03957 (4)	0.7056 (2)	0.21734 (10)	0.0387 (3)
H4A	0.0598	0.6105	0.1811	0.046*
H4B	0.0191	0.8192	0.1527	0.046*
C5	0.14972 (5)	0.7871 (2)	0.54331 (11)	0.0433 (3)
C6	0.12174 (6)	0.9403 (3)	0.60883 (13)	0.0582 (4)
H6A	0.0987	1.0505	0.5473	0.087*
H6B	0.1490	1.0204	0.6805	0.087*
H6C	0.1000	0.8462	0.6398	0.087*
C7	0.18565 (6)	0.6080 (3)	0.64011 (15)	0.0683 (5)
H7A	0.1634	0.5132	0.6692	0.102*
H7B	0.2128	0.6855	0.7131	0.102*
H7C	0.2034	0.5130	0.5988	0.102*
C8	0.18477 (6)	0.9364 (3)	0.49431 (15)	0.0643 (4)
H8A	0.1981	0.8436	0.4427	0.096*
H8B	0.2152	0.9985	0.5670	0.096*
H8C	0.1630	1.0607	0.4426	0.096*
O1	0.07228 (3)	0.53230 (14)	0.46900 (7)	0.0424 (3)
O2	0.07695 (3)	0.82062 (13)	0.33090 (7)	0.0382 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0386 (8)	0.0345 (8)	0.0284 (8)	0.000	0.0094 (6)	0.000
C2	0.0484 (7)	0.0370 (6)	0.0406 (7)	−0.0019 (5)	0.0065 (6)	0.0047 (5)
C3	0.0360 (6)	0.0408 (6)	0.0326 (6)	0.0058 (4)	0.0111 (5)	0.0006 (4)
C4	0.0391 (6)	0.0486 (7)	0.0266 (5)	−0.0005 (5)	0.0114 (5)	−0.0003 (4)
C5	0.0410 (6)	0.0457 (7)	0.0337 (6)	0.0034 (5)	0.0052 (5)	−0.0004 (5)
C6	0.0714 (9)	0.0581 (8)	0.0399 (7)	0.0047 (7)	0.0173 (6)	−0.0101 (6)
C7	0.0557 (8)	0.0646 (9)	0.0557 (8)	0.0097 (7)	−0.0074 (7)	0.0053 (7)
C8	0.0473 (7)	0.0774 (11)	0.0579 (9)	−0.0140 (7)	0.0107 (6)	−0.0029 (7)
O1	0.0457 (5)	0.0433 (5)	0.0310 (5)	−0.0019 (3)	0.0081 (4)	0.0060 (3)
O2	0.0382 (5)	0.0424 (5)	0.0296 (5)	−0.0031 (3)	0.0090 (4)	0.0028 (3)

Geometric parameters (Å, º) top

C1—C2ⁱ	1.5261 (14)	C4—H4B	0.9700
C1—C2	1.5261 (14)	C5—C6	1.5288 (18)
C1—C4ⁱ	1.5281 (14)	C5—C7	1.5293 (17)
C1—C4	1.5282 (14)	C5—C8	1.5322 (19)
C2—O1	1.4281 (14)	C6—H6A	0.9600
C2—H2A	0.9700	C6—H6B	0.9600
C2—H2B	0.9700	C6—H6C	0.9600
C3—O2	1.4096 (12)	C7—H7A	0.9600
C3—O1	1.4132 (13)	C7—H7B	0.9600
C3—C5	1.5244 (15)	C7—H7C	0.9600
C3—H3	0.9800	C8—H8A	0.9600
C4—O2	1.4299 (13)	C8—H8B	0.9600
C4—H4A	0.9700	C8—H8C	0.9600

C2ⁱ—C1—C2	108.90 (12)	C3—C5—C7	108.66 (10)
C2ⁱ—C1—C4ⁱ	107.94 (6)	C6—C5—C7	109.75 (11)
C2—C1—C4ⁱ	111.00 (7)	C3—C5—C8	108.36 (10)
C2ⁱ—C1—C4	111.00 (7)	C6—C5—C8	109.63 (11)
C2—C1—C4	107.94 (6)	C7—C5—C8	109.89 (11)
C4ⁱ—C1—C4	110.06 (13)	C5—C6—H6A	109.5
O1—C2—C1	111.69 (9)	C5—C6—H6B	109.5
O1—C2—H2A	109.3	H6A—C6—H6B	109.5
C1—C2—H2A	109.3	C5—C6—H6C	109.5
O1—C2—H2B	109.3	H6A—C6—H6C	109.5
C1—C2—H2B	109.3	H6B—C6—H6C	109.5
H2A—C2—H2B	107.9	C5—C7—H7A	109.5
O2—C3—O1	110.49 (8)	C5—C7—H7B	109.5
O2—C3—C5	110.02 (9)	H7A—C7—H7B	109.5
O1—C3—C5	109.50 (8)	C5—C7—H7C	109.5
O2—C3—H3	108.9	H7A—C7—H7C	109.5
O1—C3—H3	108.9	H7B—C7—H7C	109.5
C5—C3—H3	108.9	C5—C8—H8A	109.5
O2—C4—C1	110.67 (7)	C5—C8—H8B	109.5
O2—C4—H4A	109.5	H8A—C8—H8B	109.5
C1—C4—H4A	109.5	C5—C8—H8C	109.5
O2—C4—H4B	109.5	H8A—C8—H8C	109.5
C1—C4—H4B	109.5	H8B—C8—H8C	109.5
H4A—C4—H4B	108.1	C3—O1—C2	111.29 (8)
C3—C5—C6	110.53 (10)	C3—O2—C4	111.17 (8)

C2ⁱ—C1—C2—O1	171.24 (12)	O1—C3—C5—C7	64.11 (12)
C4ⁱ—C1—C2—O1	−70.06 (12)	O2—C3—C5—C8	−54.91 (12)
C4—C1—C2—O1	50.64 (12)	O1—C3—C5—C8	−176.52 (10)
C2ⁱ—C1—C4—O2	−170.67 (8)	O2—C3—O1—C2	61.88 (11)
C2—C1—C4—O2	−51.39 (12)	C5—C3—O1—C2	−176.78 (9)
C4ⁱ—C1—C4—O2	69.89 (7)	C1—C2—O1—C3	−56.61 (11)
O2—C3—C5—C6	65.24 (12)	O1—C3—O2—C4	−63.27 (10)
O1—C3—C5—C6	−56.37 (13)	C5—C3—O2—C4	175.71 (8)
O2—C3—C5—C7	−174.28 (10)	C1—C4—O2—C3	58.78 (11)

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₂₈O₄
M_r	272.37
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	26.726 (4), 5.7894 (8), 11.2635 (15)
β (°)	113.846 (4)
V (Å³)	1594.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.32 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.972, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	4400, 1513, 1347
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.612

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.145, 1.03
No. of reflections	1513
No. of parameters	90
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.25

Computer programs: APEX2 (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We gratefully acknowledge financial support from the Natural Science Foundation of China (No. 20872051).

References

Bruker (2000). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cismaş, C., Terec, A., Mager, S. & Grosu, I. (2005). Curr. Org. Chem. 9, 1287–1314. Google Scholar
Mihiş, A., Condamine, E., Bogdan, E., Terec, A., Kurtán, T. & Grosu, I. (2008). Molecules, 13, 2848–2858. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, X., Yu, S.-L., Li, Z.-Y. & Yang, Y. (2010). J. Mol. Struct. 973, 152–156. Web of Science CSD CrossRef CAS Google Scholar