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

Abstract

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,

• a = 10.7116 (5) Å

• b = 9.4693 (5) Å

• c = 17.7080 (9) Å

• β = 106.745 (1)°

• V = 1719.98 (15) ų

• 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[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Experimental

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.

Refinement

H-atoms were placed in calculated positions (C—H 0.95–0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C).

Figures

Fig. 1.

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

Crystal data

C19H18Cl2O4	F(000) = 792
Mr = 381.23	Dx = 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

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

Refinement

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(Fo2) + (0.0542P)2 + 1.3419P] where P = (Fo2 + 2Fc2)/3
1883 reflections	(Δ/σ)max = 0.001
114 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, y, −z+1/2.