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

Wang, X.-Y.; Shi, J.-H.; Zhang, M.; Ng, S.W.

doi:10.1107/S1600536810002400

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o426

https://doi.org/10.1107/S1600536810002400

Open

access

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

Xiao-Yong Wang,^a Jiang-Hua Shi,^a Min Zhang ^a and Seik Weng Ng ^b ^*

^aDepartment of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou Hunan 425100, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 19 January 2010; accepted 19 January 2010; online 23 January 2010)

The complete molecule of the title compound, C₁₉H₁₈Cl₂O₄, is generated by a crystallographic twofold axis that passes through the spiro C atom. The 1,3-dioxane ring adopts a chair conformation and the phenyl substituent occupies an equatorial site.

Related literature

For the crystal structure of 3,9-diphenyl-2,4,8,10-tetraoxaspiro[5.5]undecane, see: Wang et al. (2006 ).

Experimental

Crystal data

C₁₉H₁₈Cl₂O₄
M_r = 381.23
Monoclinic, C 2/c
a = 10.7116 (5) Å
b = 9.4693 (5) Å
c = 17.7080 (9) Å
β = 106.745 (1)°
V = 1719.98 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 173 K
0.46 × 0.42 × 0.22 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.838, T_max = 0.917
6932 measured reflections
1883 independent reflections
1707 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.092
S = 1.00
1883 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810002400/bt5174sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810002400/bt5174Isup2.hkl

checkCIF report

Related literature top

For the crystal structure of 3,9-diphenyl-2,4,8,10-tetraoxaspiro[5.5]undecane, see: Wang et al. (2006).

Experimental top

Pentaerythritol (2 g, 0.014 mol), 2-chlorobenzaldehyde(4.6 g, 0.033 mol), toluene (12 ml) and a catalytic amount (0.2 g) of p-toluenesulfonic acid were heated for 4 hours. The mixture was cooled and then filtered. The organic phase was washed with water and 5% sodium bicarbonate (20 ml). The solvent was evaporated and the product recrystallized from ethyl acetate to afford colourless crystals (yield 70%); m.p. 418.5–419 K.

Structure description top

For the crystal structure of 3,9-diphenyl-2,4,8,10-tetraoxaspiro[5.5]undecane, see: Wang et al. (2006).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot of C₁₉H₁₈Cl₂O₄ at the 70% probability level; hydrogen atoms are shown as spheres of arbitrary radius.

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

Crystal data top

C₁₉H₁₈Cl₂O₄	F(000) = 792
M_r = 381.23	D_x = 1.472 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5105 reflections
a = 10.7116 (5) Å	θ = 2.4–27.1°
b = 9.4693 (5) Å	µ = 0.40 mm⁻¹
c = 17.7080 (9) Å	T = 173 K
β = 106.745 (1)°	Block, yellow
V = 1719.98 (15) Å³	0.46 × 0.42 × 0.22 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1883 independent reflections
Radiation source: fine-focus sealed tube	1707 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ω scans	θ_max = 27.1°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.838, T_max = 0.917	k = −12→11
6932 measured reflections	l = −22→22

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0542P)² + 1.3419P] where P = (F_o² + 2F_c²)/3
1883 reflections	(Δ/σ)_max = 0.001
114 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₉H₁₈Cl₂O₄	V = 1719.98 (15) Å³
M_r = 381.23	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 10.7116 (5) Å	µ = 0.40 mm⁻¹
b = 9.4693 (5) Å	T = 173 K
c = 17.7080 (9) Å	0.46 × 0.42 × 0.22 mm
β = 106.745 (1)°

Data collection top

Bruker SMART APEX diffractometer	1883 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1707 reflections with I > 2σ(I)
T_min = 0.838, T_max = 0.917	R_int = 0.015
6932 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.00	Δρ_max = 0.30 e Å⁻³
1883 reflections	Δρ_min = −0.25 e Å⁻³
114 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	−0.05287 (3)	0.53900 (4)	0.14620 (2)	0.04156 (14)
O1	0.30941 (9)	0.51739 (10)	0.13408 (5)	0.0283 (2)
O2	0.31431 (8)	0.34130 (10)	0.22630 (5)	0.0298 (2)
C1	−0.00068 (12)	0.40843 (14)	0.09327 (7)	0.0261 (3)
C2	−0.09394 (12)	0.34711 (16)	0.03040 (8)	0.0329 (3)
H2	−0.1815	0.3799	0.0160	0.040*
C3	−0.05826 (13)	0.23835 (18)	−0.01081 (8)	0.0381 (3)
H3	−0.1214	0.1960	−0.0539	0.046*
C4	0.07000 (15)	0.19038 (18)	0.01047 (9)	0.0398 (3)
H4	0.0941	0.1134	−0.0168	0.048*
C5	0.16221 (13)	0.25578 (16)	0.07170 (8)	0.0342 (3)
H5	0.2501	0.2242	0.0852	0.041*
C6	0.12931 (12)	0.36636 (14)	0.11379 (7)	0.0259 (3)
C7	0.23515 (12)	0.44177 (14)	0.17524 (8)	0.0265 (3)
H7	0.1960	0.5084	0.2059	0.032*
C8	0.40974 (12)	0.59806 (14)	0.18815 (8)	0.0303 (3)
H8A	0.3692	0.6690	0.2148	0.036*
H8B	0.4614	0.6491	0.1586	0.036*
C9	0.5000	0.50311 (19)	0.2500	0.0240 (3)
C10	0.41483 (12)	0.41154 (15)	0.28641 (7)	0.0291 (3)
H10A	0.4699	0.3402	0.3216	0.035*
H10B	0.3743	0.4715	0.3187	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0294 (2)	0.0446 (2)	0.0492 (2)	0.01101 (14)	0.00891 (16)	−0.00178 (15)
O1	0.0231 (4)	0.0307 (5)	0.0247 (4)	−0.0053 (4)	−0.0034 (4)	0.0058 (4)
O2	0.0220 (4)	0.0323 (5)	0.0290 (5)	−0.0030 (4)	−0.0024 (4)	0.0091 (4)
C1	0.0204 (6)	0.0298 (6)	0.0271 (6)	0.0012 (5)	0.0051 (5)	0.0078 (5)
C2	0.0182 (6)	0.0495 (8)	0.0282 (6)	−0.0041 (5)	0.0022 (5)	0.0102 (6)
C3	0.0283 (7)	0.0560 (9)	0.0275 (6)	−0.0157 (6)	0.0042 (5)	−0.0035 (6)
C4	0.0353 (7)	0.0459 (9)	0.0389 (8)	−0.0068 (6)	0.0120 (6)	−0.0098 (6)
C5	0.0223 (6)	0.0391 (7)	0.0390 (7)	0.0011 (5)	0.0055 (5)	−0.0028 (6)
C6	0.0194 (6)	0.0293 (6)	0.0262 (6)	−0.0012 (5)	0.0024 (5)	0.0052 (5)
C7	0.0191 (6)	0.0295 (6)	0.0278 (6)	0.0013 (5)	0.0016 (5)	0.0039 (5)
C8	0.0258 (6)	0.0259 (6)	0.0304 (6)	−0.0036 (5)	−0.0057 (5)	0.0046 (5)
C9	0.0208 (8)	0.0257 (8)	0.0214 (8)	0.000	−0.0004 (6)	0.000
C10	0.0224 (6)	0.0376 (7)	0.0232 (6)	−0.0006 (5)	0.0000 (5)	0.0051 (5)

Geometric parameters (Å, º) top

Cl1—C1	1.7384 (14)	C5—C6	1.388 (2)
O1—C7	1.4181 (15)	C5—H5	0.9500
O1—C8	1.4361 (15)	C6—C7	1.5062 (17)
O2—C7	1.4141 (15)	C7—H7	1.0000
O2—C10	1.4402 (15)	C8—C9	1.5272 (16)
C1—C2	1.3906 (18)	C8—H8A	0.9900
C1—C6	1.3921 (17)	C8—H8B	0.9900
C2—C3	1.378 (2)	C9—C8ⁱ	1.5272 (16)
C2—H2	0.9500	C9—C10	1.5293 (16)
C3—C4	1.392 (2)	C9—C10ⁱ	1.5293 (16)
C3—H3	0.9500	C10—H10A	0.9900
C4—C5	1.385 (2)	C10—H10B	0.9900
C4—H4	0.9500

C7—O1—C8	110.41 (9)	O1—C7—C6	106.55 (10)
C7—O2—C10	110.16 (10)	O2—C7—H7	110.2
C2—C1—C6	121.55 (13)	O1—C7—H7	110.2
C2—C1—Cl1	117.40 (10)	C6—C7—H7	110.2
C6—C1—Cl1	121.04 (10)	O1—C8—C9	111.25 (10)
C3—C2—C1	119.41 (12)	O1—C8—H8A	109.4
C3—C2—H2	120.3	C9—C8—H8A	109.4
C1—C2—H2	120.3	O1—C8—H8B	109.4
C2—C3—C4	120.21 (13)	C9—C8—H8B	109.4
C2—C3—H3	119.9	H8A—C8—H8B	108.0
C4—C3—H3	119.9	C8ⁱ—C9—C8	107.86 (14)
C5—C4—C3	119.45 (14)	C8ⁱ—C9—C10	111.27 (7)
C5—C4—H4	120.3	C8—C9—C10	107.75 (7)
C3—C4—H4	120.3	C8ⁱ—C9—C10ⁱ	107.75 (7)
C6—C5—C4	121.57 (12)	C8—C9—C10ⁱ	111.27 (7)
C6—C5—H5	119.2	C10—C9—C10ⁱ	110.92 (16)
C4—C5—H5	119.2	O2—C10—C9	111.10 (9)
C5—C6—C1	117.72 (12)	O2—C10—H10A	109.4
C5—C6—C7	119.39 (11)	C9—C10—H10A	109.4
C1—C6—C7	122.75 (12)	O2—C10—H10B	109.4
O2—C7—O1	110.28 (9)	C9—C10—H10B	109.4
O2—C7—C6	109.32 (10)	H10A—C10—H10B	108.0

C6—C1—C2—C3	2.55 (19)	C8—O1—C7—C6	177.43 (10)
Cl1—C1—C2—C3	−176.83 (11)	C5—C6—C7—O2	−50.34 (15)
C1—C2—C3—C4	0.1 (2)	C1—C6—C7—O2	133.95 (12)
C2—C3—C4—C5	−2.1 (2)	C5—C6—C7—O1	68.83 (15)
C3—C4—C5—C6	1.5 (2)	C1—C6—C7—O1	−106.88 (13)
C4—C5—C6—C1	1.0 (2)	C7—O1—C8—C9	58.27 (13)
C4—C5—C6—C7	−174.90 (13)	O1—C8—C9—C8ⁱ	−171.63 (13)
C2—C1—C6—C5	−3.07 (19)	O1—C8—C9—C10	−51.41 (14)
Cl1—C1—C6—C5	176.29 (10)	O1—C8—C9—C10ⁱ	70.39 (14)
C2—C1—C6—C7	172.71 (12)	C7—O2—C10—C9	−58.74 (14)
Cl1—C1—C6—C7	−7.93 (17)	C8ⁱ—C9—C10—O2	169.66 (10)
C10—O2—C7—O1	64.19 (13)	C8—C9—C10—O2	51.61 (14)
C10—O2—C7—C6	−178.97 (10)	C10ⁱ—C9—C10—O2	−70.41 (9)
C8—O1—C7—O2	−64.03 (13)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈Cl₂O₄
M_r	381.23
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	10.7116 (5), 9.4693 (5), 17.7080 (9)
β (°)	106.745 (1)
V (Å³)	1719.98 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.46 × 0.42 × 0.22

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.838, 0.917
No. of measured, independent and observed [I > 2σ(I)] reflections	6932, 1883, 1707
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.092, 1.00
No. of reflections	1883
No. of parameters	114
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.25

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank the Key Subject Construction Project of Hunan Province (No. 2006–180), the Key Scientific Research Project of Hunan Provincial Education Department (No. 08 A023, 05 C736), The NSF of Hunan Province (09 J J3028) and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2003). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, J.-K., Yan, D.-Y., Liu, L.-J., Liu, S. & Wang, J.-T. (2006). Acta Cryst. E62, o3062–o3063. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar