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

Li, Z.; Tang, Q.; Wu, K.; Yu, S.; Sun, X.

doi:10.1107/S1600536810024712

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1864

doi:10.1107/S1600536810024712

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

Zhengyi Li,^a Qiuzheng Tang,^a Kang Wu,^a Shuling Yu ^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 6 June 2010; accepted 24 June 2010; online 30 June 2010)

In the title compound, C₁₉H₁₆Cl₄O₄, 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, and the dihedral angle between the two benzene rings is 76.6 (1)°. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules into chains along the c axis.

Related literature

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

Experimental

Crystal data

C₁₉H₁₆Cl₄O₄
M_r = 450.12
Monoclinic, P 2/c
a = 14.365 (2) Å
b = 5.7397 (9) Å
c = 11.7464 (19) Å
β = 93.275 (3)°
V = 966.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 295 K
0.21 × 0.21 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.878, T_max = 0.905
5044 measured reflections
1686 independent reflections
1444 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.160
S = 1.02
1686 reflections
123 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O2ⁱ	0.93	2.58	3.425 (3)	152
Symmetry code: (i) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: SMART (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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810024712/ez2218sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810024712/ez2218Isup2.hkl

checkCIF report

Comment top

Owing to their 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(2,4-dichlorophenyl)-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 (C9). The two non-planar six-membered heterocycles [(O1, O2 and C7–C10) and (O1A, O2A and C7A–C10A)] both adopt chair conformations, and the dihedral angle between the two benzene rings (C1–C6 and C1A–C6A) is 76.6 (1)°. In the crystal structure, intermolecular C—H···O hydrogen bonds link the molecules to form one-dimensional chain along the c axis (Fig. 2).

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 2,4-dichlorobenzaldehyde (5 mmol, 0.88 g) and pentaerythritol (3 mmol, 0.41 g) in toluene (25 ml), phosphotungstic acid (1 mol%, 16.5 mg) was added as catalyst. The mixture was refluxed for 6 h to complete the reaction. After reaction, the mixture was allowed to cool to room temperature, and dichloromethane (25 ml) was added to dissolve the product. The insoluble residues were filtered off and the filtrate was dried over anhydrous Na₂SO₄. The solvent was evaporated under vacuum and the product recrystallized from ethanol to afford a white solid (71% yield, m.p. 469–470 K). Single crystals suitable for X-ray diffraction were also obtained by evaporation of an ethanol solution.

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [Symmetry code: -x + 1, y, -z + 1/2].
	Fig. 2. One-dimensional stack running along the c axis. Hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₁₉H₁₆Cl₄O₄	F(000) = 460
M_r = 450.12	D_x = 1.546 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.365 (2) Å	Cell parameters from 2876 reflections
b = 5.7397 (9) Å	θ = 2.8–29.5°
c = 11.7464 (19) Å	µ = 0.64 mm⁻¹
β = 93.275 (3)°	T = 295 K
V = 966.9 (3) Å³	Block, colorless
Z = 2	0.21 × 0.21 × 0.16 mm

Data collection top

Bruker APEXII CCD diffractometer	1686 independent reflections
Radiation source: fine-focus sealed tube	1444 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→17
T_min = 0.878, T_max = 0.905	k = −6→6
5044 measured reflections	l = −13→8

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.133P)²] where P = (F_o² + 2F_c²)/3
1686 reflections	(Δ/σ)_max = 0.001
123 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₉H₁₆Cl₄O₄	V = 966.9 (3) Å³
M_r = 450.12	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 14.365 (2) Å	µ = 0.64 mm⁻¹
b = 5.7397 (9) Å	T = 295 K
c = 11.7464 (19) Å	0.21 × 0.21 × 0.16 mm
β = 93.275 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1686 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1444 reflections with I > 2σ(I)
T_min = 0.878, T_max = 0.905	R_int = 0.022
5044 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.02	Δρ_max = 0.35 e Å⁻³
1686 reflections	Δρ_min = −0.40 e Å⁻³
123 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
Cl1	0.11833 (4)	1.10777 (11)	0.35541 (6)	0.0638 (3)
Cl2	0.09727 (5)	0.41534 (13)	0.65874 (6)	0.0751 (3)
O1	0.39049 (10)	1.0814 (2)	0.40196 (12)	0.0428 (4)
O2	0.37013 (9)	0.7923 (2)	0.26477 (12)	0.0414 (4)
C1	0.12123 (14)	0.7578 (4)	0.50648 (19)	0.0483 (6)
H1	0.0599	0.7995	0.5178	0.058*
C2	0.17289 (14)	0.8801 (3)	0.43034 (18)	0.0415 (5)
C3	0.26501 (12)	0.8219 (3)	0.41278 (16)	0.0361 (5)
C4	0.30282 (15)	0.6348 (4)	0.47363 (19)	0.0455 (5)
H4	0.3642	0.5922	0.4629	0.055*
C5	0.25309 (15)	0.5092 (4)	0.5495 (2)	0.0498 (6)
H5	0.2801	0.3841	0.5894	0.060*
C6	0.16219 (16)	0.5739 (4)	0.56487 (19)	0.0469 (6)
C7	0.32422 (14)	0.9531 (3)	0.33360 (17)	0.0388 (5)
H7	0.2855	1.0590	0.2857	0.047*
C8	0.44930 (15)	1.2158 (4)	0.3327 (2)	0.0492 (6)
H8A	0.4948	1.2992	0.3814	0.059*
H8B	0.4118	1.3298	0.2898	0.059*
C9	0.5000	1.0610 (4)	0.2500	0.0365 (6)
C10	0.42682 (15)	0.9102 (4)	0.18627 (17)	0.0427 (5)
H10A	0.3877	1.0073	0.1357	0.051*
H10B	0.4575	0.7965	0.1402	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0494 (4)	0.0675 (5)	0.0753 (6)	0.0257 (3)	0.0111 (3)	0.0162 (3)
Cl2	0.0745 (6)	0.0858 (6)	0.0674 (6)	−0.0222 (3)	0.0251 (4)	0.0137 (3)
O1	0.0476 (9)	0.0412 (8)	0.0411 (9)	−0.0055 (6)	0.0148 (7)	−0.0084 (5)
O2	0.0405 (8)	0.0478 (8)	0.0371 (8)	−0.0064 (6)	0.0124 (6)	−0.0095 (6)
C1	0.0344 (10)	0.0593 (13)	0.0524 (14)	0.0033 (9)	0.0125 (9)	−0.0040 (10)
C2	0.0357 (10)	0.0456 (12)	0.0435 (12)	0.0069 (8)	0.0048 (8)	−0.0030 (8)
C3	0.0316 (10)	0.0439 (10)	0.0331 (10)	0.0029 (8)	0.0033 (8)	−0.0044 (8)
C4	0.0355 (11)	0.0532 (13)	0.0480 (13)	0.0095 (8)	0.0043 (9)	0.0047 (9)
C5	0.0486 (12)	0.0515 (12)	0.0491 (13)	0.0040 (10)	0.0016 (10)	0.0098 (10)
C6	0.0476 (13)	0.0525 (12)	0.0414 (12)	−0.0086 (9)	0.0108 (9)	−0.0005 (9)
C7	0.0348 (10)	0.0474 (11)	0.0347 (11)	0.0071 (8)	0.0052 (8)	0.0018 (8)
C8	0.0559 (14)	0.0384 (11)	0.0554 (14)	−0.0039 (9)	0.0225 (11)	−0.0064 (9)
C9	0.0404 (15)	0.0340 (13)	0.0362 (15)	0.000	0.0114 (11)	0.000
C10	0.0417 (11)	0.0554 (12)	0.0315 (11)	−0.0013 (8)	0.0082 (9)	−0.0012 (8)

Geometric parameters (Å, º) top

Cl1—C2	1.737 (2)	C4—H4	0.9300
Cl2—C6	1.741 (2)	C5—C6	1.379 (3)
O1—C7	1.417 (3)	C5—H5	0.9300
O1—C8	1.431 (2)	C7—H7	0.9800
O2—C7	1.414 (2)	C8—C9	1.531 (2)
O2—C10	1.434 (2)	C8—H8A	0.9700
C1—C6	1.373 (3)	C8—H8B	0.9700
C1—C2	1.386 (3)	C9—C10ⁱ	1.525 (2)
C1—H1	0.9300	C9—C10	1.525 (2)
C2—C3	1.391 (3)	C9—C8ⁱ	1.531 (2)
C3—C4	1.384 (3)	C10—H10A	0.9700
C3—C7	1.499 (3)	C10—H10B	0.9700
C4—C5	1.378 (3)

C7—O1—C8	110.95 (15)	O1—C7—C3	107.23 (15)
C7—O2—C10	111.11 (15)	O2—C7—H7	110.1
C6—C1—C2	118.81 (19)	O1—C7—H7	110.1
C6—C1—H1	120.6	C3—C7—H7	110.1
C2—C1—H1	120.6	O1—C8—C9	111.43 (16)
C1—C2—C3	121.53 (19)	O1—C8—H8A	109.3
C1—C2—Cl1	117.74 (15)	C9—C8—H8A	109.3
C3—C2—Cl1	120.73 (16)	O1—C8—H8B	109.3
C4—C3—C2	117.28 (19)	C9—C8—H8B	109.3
C4—C3—C7	119.37 (17)	H8A—C8—H8B	108.0
C2—C3—C7	123.34 (17)	C10ⁱ—C9—C10	110.8 (2)
C5—C4—C3	122.52 (19)	C10ⁱ—C9—C8ⁱ	107.54 (12)
C5—C4—H4	118.7	C10—C9—C8ⁱ	110.94 (12)
C3—C4—H4	118.7	C10ⁱ—C9—C8	110.94 (12)
C4—C5—C6	118.3 (2)	C10—C9—C8	107.54 (12)
C4—C5—H5	120.9	C8ⁱ—C9—C8	109.1 (2)
C6—C5—H5	120.9	O2—C10—C9	110.67 (14)
C1—C6—C5	121.6 (2)	O2—C10—H10A	109.5
C1—C6—Cl2	119.24 (17)	C9—C10—H10A	109.5
C5—C6—Cl2	119.17 (18)	O2—C10—H10B	109.5
O2—C7—O1	110.06 (16)	C9—C10—H10B	109.5
O2—C7—C3	109.08 (16)	H10A—C10—H10B	108.1

C6—C1—C2—C3	−0.6 (3)	C8—O1—C7—O2	62.5 (2)
C6—C1—C2—Cl1	178.60 (17)	C8—O1—C7—C3	−179.01 (15)
C1—C2—C3—C4	0.7 (3)	C4—C3—C7—O2	47.8 (2)
Cl1—C2—C3—C4	−178.44 (16)	C2—C3—C7—O2	−133.17 (19)
C1—C2—C3—C7	−178.38 (19)	C4—C3—C7—O1	−71.4 (2)
Cl1—C2—C3—C7	2.5 (3)	C2—C3—C7—O1	107.7 (2)
C2—C3—C4—C5	−0.4 (3)	C7—O1—C8—C9	−57.8 (2)
C7—C3—C4—C5	178.70 (19)	O1—C8—C9—C10ⁱ	−69.6 (2)
C3—C4—C5—C6	0.0 (4)	O1—C8—C9—C10	51.7 (2)
C2—C1—C6—C5	0.1 (3)	O1—C8—C9—C8ⁱ	172.1 (2)
C2—C1—C6—Cl2	−178.77 (16)	C7—O2—C10—C9	59.2 (2)
C4—C5—C6—C1	0.2 (3)	C10ⁱ—C9—C10—O2	69.36 (13)
C4—C5—C6—Cl2	179.05 (17)	C8ⁱ—C9—C10—O2	−171.24 (15)
C10—O2—C7—O1	−63.4 (2)	C8—C9—C10—O2	−52.1 (2)
C10—O2—C7—C3	179.21 (15)

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
C5—H5···O2ⁱⁱ	0.93	2.58	3.425 (3)	152
C7—H7···Cl1	0.98	2.60	3.113 (2)	113

Symmetry code: (ii) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₆Cl₄O₄
M_r	450.12
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	295
a, b, c (Å)	14.365 (2), 5.7397 (9), 11.7464 (19)
β (°)	93.275 (3)
V (Å³)	966.9 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.21 × 0.21 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.878, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	5044, 1686, 1444
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.160, 1.02
No. of reflections	1686
No. of parameters	123
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.40

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2ⁱ	0.93	2.58	3.425 (3)	152

Symmetry code: (i) x, −y+1, z+1/2.

Acknowledgements

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

References

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