6,10,16,19-Tetra­oxatrispiro­[4.2.2.4.2.2]nona­deca­ne

Wang, J.-K.; Wang, H.-B.; Wu, C.-R.; Wang, J.-T.

doi:10.1107/S1600536808001785

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o498

doi:10.1107/S1600536808001785

Open

access

6,10,16,19-Tetraoxatrispiro[4.2.2.4.2.2]nonadecane

Ji-Kui Wang,^a Hai-Bo Wang,^a Cong-Ren Wu ^a and Jin-Tang Wang ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: wjt@njut.edu.cn

(Received 2 January 2008; accepted 17 January 2008; online 23 January 2008)

The asymmetric unit of the title compound, C₁₅H₂₄O₄, contains one half-molecule; a twofold rotation axis passes through the central C atom. The non-planar six- and five-membered rings adopt chair and envelope conformations, respectively. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules.

Related literature

For general background, see: Jermy & Pandurangan (2005 ). For related literature, see: Sun et al. (2001 ). For ring conformation puckering parameters, see: Cremer & Pople (1975 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₂₄O₄
M_r = 268.34
Monoclinic, C 2/c
a = 25.605 (5) Å
b = 5.5820 (11) Å
c = 10.337 (2) Å
β = 90.22 (3)°
V = 1477.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.965, T_max = 0.982
1547 measured reflections
1457 independent reflections
864 reflections with I > 2σ(I)
R_int = 0.050
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.173
S = 0.93
1457 reflections
87 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6B⋯O2ⁱ	0.97	2.58	3.413 (4)	143
Symmetry code: (i) x, y+1, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001785/hk2414sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808001785/hk2414Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is an important intermediate in the synthesis of pesticides (Jermy & Pandurangan, 2005). The crystal structure determination of (I) has been carried out in order to elucidate the molecular conformation.

The asymmetric unit of the title compound, (I), contains one-half molecule (Fig. 1), in which the bond lengths are within normal ranges (Allen et al., 1987).

Ring B (O1/O2/C5—C8) is not planar, having total puckering amplitude, Q_T, of 0.943 (3) Å. It adopts chair conformation [ϕ = -32.96 (2)° and θ = 58.52 (3)°] (Cremer & Pople, 1975). Ring A has envelope conformation with atom C1 displaced by -0.222 (3) Å from the plane of the other ring atoms.

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules, in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Jermy & Pandurangan (2005). For related literature, see: Sun et al. (2001). For ring conformation puckering parameters, see: Cremer & Pople (1975). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared from a mixture of 2,2-bis-(hydroxymethyl) propane-1,3-diol (0.68 g, 5 mmol), cyclopentanone (10 mmol), freshly activated catalyst TiO2/SO4(2-)(0.6 g, 0.32 mmol) and cyclohexane (80 ml), heated with stirring at refluxing temperature for 2 h, using a Dean-Stark apparatus in a nitrogen atmosphere (Sun et al., 2001). The progress of the reaction was monitored by thin-layer chromatography. After cooling to room temperature, the catalyst was filtered off, the crude product was isolated by distillation and the solid was recrystallized from ethanol. Crystals of (I) were obtained by dissolving the title compound (1.0 g) in toluene (15 ml) and evaporating the solvent slowly at room temperature for about 7 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: X-CAD4 (Harms & Wocadlo, 1995); 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: PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title molecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (A) 1 - x, y, 1/2 - z.]
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

6,10,16,19-Tetraoxatrispiro[4.2.2.4.2.2]nonadecane top

Crystal data top

C₁₅H₂₄O₄	F(000) = 584
M_r = 268.34	D_x = 1.206 Mg m⁻³
Monoclinic, C2/c	Melting point: 401 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 25.605 (5) Å	Cell parameters from 25 reflections
b = 5.5820 (11) Å	θ = 10–13°
c = 10.337 (2) Å	µ = 0.09 mm⁻¹
β = 90.22 (3)°	T = 294 K
V = 1477.4 (5) Å³	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	864 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 26.0°, θ_min = 1.6°
ω/2θ scans	h = −31→31
Absorption correction: ψ scan (North et al., 1968)	k = 0→6
T_min = 0.965, T_max = 0.982	l = 0→12
1547 measured reflections	3 standard reflections every 120 min
1457 independent reflections	intensity decay: none

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.06P)² + 4.5P] where P = (F_o² + 2F_c²)/3
1457 reflections	(Δ/σ)_max < 0.001
87 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₅H₂₄O₄	V = 1477.4 (5) Å³
M_r = 268.34	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 25.605 (5) Å	µ = 0.09 mm⁻¹
b = 5.5820 (11) Å	T = 294 K
c = 10.337 (2) Å	0.30 × 0.20 × 0.10 mm
β = 90.22 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	864 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.050
T_min = 0.965, T_max = 0.982	3 standard reflections every 120 min
1547 measured reflections	intensity decay: none
1457 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 0.93	Δρ_max = 0.26 e Å⁻³
1457 reflections	Δρ_min = −0.22 e Å⁻³
87 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
O1	0.43380 (7)	0.3857 (4)	0.41870 (16)	0.0381 (5)
O2	0.42692 (7)	0.0861 (3)	0.26166 (16)	0.0324 (5)
C1	0.30826 (17)	0.3438 (9)	0.3294 (5)	0.0889 (15)
H1A	0.2819	0.3125	0.2638	0.107*
H1B	0.2974	0.4816	0.3797	0.107*
C2	0.31481 (15)	0.1237 (9)	0.4179 (4)	0.0803 (13)
H2A	0.2973	0.1514	0.4996	0.096*
H2B	0.2993	−0.0159	0.3773	0.096*
C3	0.36848 (12)	0.0842 (7)	0.4393 (3)	0.0503 (9)
H3A	0.3768	−0.0835	0.4262	0.060*
H3B	0.3777	0.1271	0.5274	0.060*
C4	0.35773 (13)	0.3897 (7)	0.2697 (3)	0.0567 (10)
H4A	0.3662	0.5588	0.2750	0.068*
H4B	0.3567	0.3436	0.1792	0.068*
C5	0.39900 (11)	0.2397 (5)	0.3435 (3)	0.0336 (7)
C6	0.46853 (11)	0.5234 (5)	0.3396 (2)	0.0342 (7)
H6A	0.4922	0.6138	0.3945	0.041*
H6B	0.4484	0.6366	0.2884	0.041*
C7	0.5000	0.3637 (7)	0.2500	0.0278 (8)
C8	0.46173 (10)	0.2072 (5)	0.1738 (2)	0.0337 (7)
H8A	0.4417	0.3060	0.1145	0.040*
H8B	0.4809	0.0901	0.1235	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0461 (12)	0.0405 (12)	0.0275 (9)	0.0017 (10)	−0.0016 (8)	−0.0038 (9)
O2	0.0368 (10)	0.0236 (10)	0.0368 (10)	−0.0008 (9)	0.0005 (8)	−0.0038 (8)
C1	0.076 (3)	0.098 (4)	0.093 (3)	0.005 (3)	−0.001 (2)	0.016 (3)
C2	0.069 (3)	0.089 (3)	0.083 (3)	−0.005 (3)	0.006 (2)	0.009 (3)
C3	0.052 (2)	0.053 (2)	0.0460 (17)	−0.0121 (17)	0.0100 (15)	−0.0008 (16)
C4	0.057 (2)	0.052 (2)	0.061 (2)	0.0252 (18)	−0.0165 (17)	−0.0025 (17)
C5	0.0338 (14)	0.0256 (15)	0.0413 (15)	0.0057 (12)	−0.0035 (12)	−0.0032 (12)
C6	0.0469 (16)	0.0252 (15)	0.0306 (13)	−0.0021 (13)	−0.0012 (12)	−0.0044 (11)
C7	0.040 (2)	0.023 (2)	0.0204 (16)	0.000	−0.0036 (15)	0.000
C8	0.0393 (15)	0.0322 (16)	0.0296 (13)	−0.0017 (13)	−0.0019 (12)	−0.0004 (12)

Geometric parameters (Å, º) top

O1—C5	1.434 (3)	C3—H3B	0.9700
O1—C6	1.434 (3)	C4—C5	1.547 (4)
O2—C5	1.402 (3)	C4—H4A	0.9700
O2—C8	1.443 (3)	C4—H4B	0.9700
C1—C4	1.434 (5)	C6—C7	1.519 (3)
C1—C2	1.540 (6)	C6—H6A	0.9700
C1—H1A	0.9700	C6—H6B	0.9700
C1—H1B	0.9700	C7—C6ⁱ	1.519 (3)
C2—C3	1.408 (5)	C7—C8	1.529 (3)
C2—H2A	0.9700	C7—C8ⁱ	1.529 (3)
C2—H2B	0.9700	C8—H8A	0.9700
C3—C5	1.533 (4)	C8—H8B	0.9700
C3—H3A	0.9700

C5—O1—C6	112.37 (19)	H4A—C4—H4B	108.6
C5—O2—C8	114.2 (2)	O2—C5—O1	110.9 (2)
C4—C1—C2	107.7 (4)	O2—C5—C3	107.8 (2)
C4—C1—H1A	110.2	O1—C5—C3	106.8 (2)
C2—C1—H1A	110.2	O2—C5—C4	112.5 (2)
C4—C1—H1B	110.2	O1—C5—C4	112.4 (2)
C2—C1—H1B	110.2	C3—C5—C4	106.0 (3)
H1A—C1—H1B	108.5	O1—C6—C7	111.4 (2)
C3—C2—C1	108.8 (4)	O1—C6—H6A	109.4
C3—C2—H2A	109.9	C7—C6—H6A	109.4
C1—C2—H2A	109.9	O1—C6—H6B	109.4
C3—C2—H2B	109.9	C7—C6—H6B	109.4
C1—C2—H2B	109.9	H6A—C6—H6B	108.0
H2A—C2—H2B	108.3	C6—C7—C6ⁱ	108.1 (3)
C2—C3—C5	108.0 (3)	C6—C7—C8	107.99 (15)
C2—C3—H3A	110.1	C6ⁱ—C7—C8	111.22 (14)
C5—C3—H3A	110.1	C6—C7—C8ⁱ	111.22 (14)
C2—C3—H3B	110.1	C6ⁱ—C7—C8ⁱ	107.99 (15)
C5—C3—H3B	110.1	C8—C7—C8ⁱ	110.3 (3)
H3A—C3—H3B	108.4	O2—C8—C7	109.86 (18)
C1—C4—C5	107.1 (3)	O2—C8—H8A	109.7
C1—C4—H4A	110.3	C7—C8—H8A	109.7
C5—C4—H4A	110.3	O2—C8—H8B	109.7
C1—C4—H4B	110.3	C7—C8—H8B	109.7
C5—C4—H4B	110.3	H8A—C8—H8B	108.2

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···O2ⁱⁱ	0.97	2.58	3.413 (4)	143

Symmetry code: (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₂₄O₄
M_r	268.34
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	25.605 (5), 5.5820 (11), 10.337 (2)
β (°)	90.22 (3)
V (Å³)	1477.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.965, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	1547, 1457, 864
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.173, 0.93
No. of reflections	1457
No. of parameters	87
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.22

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), X-CAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···O2ⁱ	0.97	2.58	3.413 (4)	143.00

Symmetry code: (i) x, y+1, z.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Version 5. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Jermy, B. R. & Pandurangan, A. (2005). Appl. Catal. A, 295, 185–192. CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, X., Wang, X.-F., Jin, T.-S. & Li, T.-S. (2001). J. Hebei Univ. (Nat. Sci. Ed.), 21, 49–52. CAS Google Scholar