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

Abstract

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,

• a = 25.605 (5) Å

• b = 5.5820 (11) Å

• c = 10.337 (2) Å

• β = 90.22 (3)°

• V = 1477.4 (5) ų

• 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[F ² > 2σ(F ²)] = 0.067

• wR(F ²) = 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

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 ▶).

Supplementary Material

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
C6—H6B⋯O2i	0.97	2.58	3.413 (4)	143

Symmetry code: (i) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically, with C—H = 0.97 Å for methylene H, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Figures

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.

Crystal data

C15H24O4	F000 = 584
Mr = 268.34	Dx = 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 = 10–13º
c = 10.337 (2) Å	µ = 0.09 mm−1
β = 90.22 (3)º	T = 294 (2) K
V = 1477.4 (5) Å3	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.050
Radiation source: fine-focus sealed tube	θmax = 26.0º
Monochromator: graphite	θmin = 1.6º
T = 294(2) K	h = −31→31
ω/2θ scans	k = 0→6
Absorption correction: ψ scan(North et al., 1968)	l = 0→12
Tmin = 0.965, Tmax = 0.982	3 standard reflections
1547 measured reflections	every 120 min
1457 independent reflections	intensity decay: none
864 reflections with I > 2σ(I)

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.067	H-atom parameters constrained
wR(F2) = 0.173	w = 1/[σ2(Fo2) + (0.06P)2 + 4.5P] where P = (Fo2 + 2Fc2)/3
S = 0.93	(Δ/σ)max < 0.001
1457 reflections	Δρmax = 0.26 e Å−3
87 parameters	Δρmin = −0.21 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

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

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