anti-1′,6′,7′,8′,9′,14′,15′,16′-Octa­chloro­dispiro­[1,3-dioxolane-2,17′-penta­cyclo­[12.2.1.16,9.02,13.05,10]octa­decane-18′,2′′-1,3-dioxolane]-7′,15′-diene

Tenbusch, M.E.; Brooker, M.D.; Timmerman, J.C.; Jones, D.S.; Etzkorn, M.

doi:10.1107/S1600536810024669

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o1882

https://doi.org/10.1107/S1600536810024669

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anti-1′,6′,7′,8′,9′,14′,15′,16′-Octachlorodispiro[1,3-dioxolane-2,17′-pentacyclo[12.2.1.1^6,9.0^2,13.0^5,10]octadecane-18′,2′′-1,3-dioxolane]-7′,15′-diene

Megan E. Tenbusch,^a Matthew D. Brooker,^a Jacob C. Timmerman,^a Daniel S. Jones ^a ^* and Markus Etzkorn ^a ^*

^aDepartment of Chemistry, The University of North Carolina at Charlotte, 9201 University City Blvd, Charlotte, NC 28223, USA
^*Correspondence e-mail: djones@uncc.edu, metzkorn@uncc.edu

(Received 15 June 2010; accepted 23 June 2010; online 3 July 2010)

The title compound, C₂₂H₂₀Cl₈O₄, was prepared as part of the synthesis of precursors for the preparation of fluorinated molecular tweezers. The molecule sits on an inversion center, thus requiring that the cyclooctane ring adopt a chair conformation.

Related literature

For related structures, see: Garcia et al. (1991b ,c ). For related chemistry on analogous polycyclic scaffolds, see: Garcia et al. (1991a ); Chou et al. (2005 )

Experimental

Crystal data

C₂₂H₂₀Cl₈O₄
M_r = 631.98
Monoclinic, P 2₁ /c
a = 9.5332 (7) Å
b = 7.9121 (6) Å
c = 17.014 (2) Å
β = 101.099 (8)°
V = 1259.3 (2) Å³
Z = 2
Cu Kα radiation
μ = 8.44 mm⁻¹
T = 295 K
0.25 × 0.20 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.190, T_max = 0.561
4703 measured reflections
2275 independent reflections
1702 reflections with I > 2σ(I)
R_int = 0.047
3 standard reflections every 62 reflections intensity decay: 13%

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.118
S = 1.05
2275 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: DIRDIF08 (Beurskens et al., 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810024669/jh2171sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810024669/jh2171Isup2.hkl

checkCIF report

Comment top

The twofold Diels-Alder reaction of cyclooctadiene 1 with two equivalents of cyclopentadiene or cyclopentadienone derivatives (2a-c) furnishes the corresponding polycyclic bisadducts endo,endo,syn-3 and endo,endo,anti- 4 in a 1:4 ratio (Garcia et al., 1991a,b,c). For the synthesis of compounds with new luminescent properties (Chou et al., 2005) or the construction of molecular tweezers syn derivative 3 is an ideal starting material with the required orientation of both double bonds on one side of the molecule. Nevertheless, the separation of syn isomer 3c from anti ketal 4c prior to subsequent functionalization was often unsatisfactory in our hands. Thus, we converted cyclooctadiene 1 with the spiroketal 2 d to the spiropolycyclic bisadducts 3 d and 4 d in 85–90% yield, typically with an isomer distribution that did not differ significantly from the non-spirocyclic ketal case (1+2c). Furthermore, compound 3 d was easily separated from anti-isomer 4 d by repeated recrystallization from hot diethyl ether, i.e., the ether solution becomes more enriched in syn-isomer 3 d, and initially the clean anti-isomer 4 d precipitates upon cooling. We were able to grow single crystals of 4 d from chloroform and determined the crystal structure of compound 4 d, thus confirming the correct spectroscopic assignment of both isomers.

Two closely related structures have been found. The first (Garcia et al., 1991b) has an open ketal structure on each of the bridgehead carbon atoms, while the second (Garcia et al., 1991c) has no substituents on the bridgehead carbon atoms. Each of these two structures sits on an inversion center and thus assumes a conformation nearly identical to that of the title compound.

Related literature top

For related structures see: Garcia et al. (1991b,c). For related chemistry see: Garcia et al. (1991a); Chou et al. (2005)

Experimental top

A mixture of cyclooctadiene 1 (3 g, 29 mmol) and spiroketal 2 d (15 g, 57 mmol) was refluxed in toluene (5 ml) for three hours. The beige paste was filtered, washed with methylene chloride (70 ml), dried and washed again with methanol (ca 15 ml) to remove small amounts of the mono-Diels-Alder adduct. The remaining colorless solid (14.5 g, 83%) contained a 1:4 mixture of 3 d and 4 d, respectively. After one recrystallization from hot diethyl ether the pure anti-isomer 4 d was obtained as a colorless precipitate.

Mp.> 295 °C (decomposition); IR (KBr): ν~ = 2952, 2905 (CH₂),1596 (C═C), 1467 (CH₂deformation), 1355, 1284, 1267, 1245, 1222, 1181, 1132, 1105,1091, 1037 (C—Cl), 1009, 946, 891, 851, 809, 770, 730 cm^-1; ¹H NMR (CDCl₃; 500 MHz): δ = 4.20–4.10 (m, 8H; H-4, -5, -4", -5"), 2.78–2.62 (m, 4H; H-2', -5', 10', -13'), 2.20–2.00 (m, 4H; H-3', -4', -11', -12'), 0.95–0.75 (m, 4H; H-3', -4', -11', -12'); ¹³C NMR (CDCL₃,75.6 MHz): δ=128.5 (C-7', -8', -15', -16'), 120.5 (C-17', -18'), 77.6 (C-1', -6', 9', -14'), 67.7* (C-4, -4"), 66.5* (C-5, -5"), 51.8(C-2', -5', -10', 13'), 21.9 (C-3', -4', -11', -12'); EA: calc. C (41.81) H (3.19); found C: 41.83, H: 3.16 (calc.).

Structure description top

For related structures see: Garcia et al. (1991b,c). For related chemistry see: Garcia et al. (1991a); Chou et al. (2005)

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: DIRDIF08 (Beurskens et al., 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of the title compound with 50% probability displacement ellipsoids. [Symmetry code: (i) -x + 2, -y + 2, -z + 2]
	Fig. 2. Synthesis scheme.

anti-1',6',7',8',9',14',15',16'-Octachlorodispiro[1,3-dioxolane- 2,17'-pentacyclo[12.2.1.1^6,9.0^2,13.0^5,10]octadecane-18',2''-1,3- dioxolane]-7',15'-diene top

Crystal data top

C₂₂H₂₀Cl₈O₄	F(000) = 640
M_r = 631.98	D_x = 1.677 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 9.5332 (7) Å	θ = 5.3–18.2°
b = 7.9121 (6) Å	µ = 8.44 mm⁻¹
c = 17.014 (2) Å	T = 295 K
β = 101.099 (8)°	Prism, colorless
V = 1259.3 (2) Å³	0.25 × 0.20 × 0.08 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.047
Graphite monochromator	θ_max = 67.4°, θ_min = 4.7°
non–profiled ω/2θ scans	h = −11→11
Absorption correction: multi-scan (Blessing, 1995)	k = −9→9
T_min = 0.190, T_max = 0.561	l = −20→0
4703 measured reflections	3 standard reflections every 62 reflections
2275 independent reflections	intensity decay: 13%
1702 reflections with I > 2σ(I)

Refinement top

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)] = 0.041	H-atom parameters constrained
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0607P)² + 0.5139P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2275 reflections	Δρ_max = 0.36 e Å⁻³
155 parameters	Δρ_min = −0.47 e Å⁻³
0 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0010 (3)

Crystal data top

C₂₂H₂₀Cl₈O₄	V = 1259.3 (2) Å³
M_r = 631.98	Z = 2
Monoclinic, P2₁/c	Cu Kα radiation
a = 9.5332 (7) Å	µ = 8.44 mm⁻¹
b = 7.9121 (6) Å	T = 295 K
c = 17.014 (2) Å	0.25 × 0.20 × 0.08 mm
β = 101.099 (8)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1702 reflections with I > 2σ(I)
Absorption correction: multi-scan (Blessing, 1995)	R_int = 0.047
T_min = 0.190, T_max = 0.561	3 standard reflections every 62 reflections
4703 measured reflections	intensity decay: 13%
2275 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.05	Δρ_max = 0.36 e Å⁻³
2275 reflections	Δρ_min = −0.47 e Å⁻³
155 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.56200 (8)	0.74022 (12)	1.00965 (5)	0.0547 (3)
Cl4	0.77203 (10)	0.88651 (12)	0.73738 (5)	0.0557 (3)
Cl2	0.79698 (10)	0.44785 (12)	0.98707 (7)	0.0657 (3)
Cl3	0.93205 (10)	0.54119 (14)	0.82005 (6)	0.0648 (3)
O1	0.5602 (2)	0.9949 (3)	0.85728 (14)	0.0479 (5)
O2	0.5274 (2)	0.7211 (3)	0.81904 (14)	0.0494 (6)
C5	0.7945 (3)	0.9248 (4)	0.97774 (18)	0.0380 (6)
H5	0.7385	1.0223	0.9895	0.046*
C10	0.9019 (3)	0.8836 (4)	1.05363 (19)	0.0410 (7)
H10A	0.9704	0.8028	1.0405	0.049*
H10B	0.8517	0.8296	1.0914	0.049*
C11	0.9836 (3)	1.0369 (4)	1.09459 (19)	0.0434 (7)
H11A	0.9466	1.1379	1.0655	0.052*
H11B	0.9643	1.0463	1.1483	0.052*
C7	0.7734 (3)	0.8387 (4)	0.83817 (19)	0.0424 (7)
C1	0.4108 (3)	0.9714 (5)	0.8255 (2)	0.0544 (9)
H1A	0.3719	1.0666	0.7925	0.065*
H1B	0.3574	0.9574	0.8682	0.065*
C8	0.8224 (3)	0.6619 (4)	0.8649 (2)	0.0439 (7)
C6	0.8545 (3)	0.9680 (4)	0.89984 (17)	0.0381 (6)
H6	0.8212	1.0815	0.8822	0.046*
C3	0.6241 (3)	0.8363 (4)	0.86189 (19)	0.0404 (7)
C4	0.6875 (3)	0.7784 (4)	0.94892 (18)	0.0392 (7)
C9	0.7714 (3)	0.6257 (4)	0.9301 (2)	0.0432 (7)
C2	0.4067 (4)	0.8167 (6)	0.7776 (3)	0.0729 (12)
H2A	0.318	0.7555	0.7762	0.088*
H2B	0.4167	0.8422	0.7232	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0427 (4)	0.0648 (5)	0.0619 (5)	−0.0091 (4)	0.0232 (4)	−0.0018 (4)
Cl4	0.0560 (5)	0.0698 (6)	0.0420 (4)	−0.0103 (4)	0.0113 (3)	−0.0032 (4)
Cl2	0.0621 (6)	0.0497 (5)	0.0861 (7)	0.0058 (4)	0.0161 (5)	0.0163 (4)
Cl3	0.0525 (5)	0.0752 (6)	0.0686 (6)	0.0162 (4)	0.0161 (4)	−0.0218 (5)
O1	0.0365 (11)	0.0445 (12)	0.0602 (14)	0.0041 (9)	0.0033 (10)	−0.0058 (10)
O2	0.0357 (11)	0.0508 (13)	0.0591 (14)	−0.0048 (9)	0.0021 (10)	−0.0114 (11)
C5	0.0330 (14)	0.0402 (15)	0.0423 (16)	−0.0014 (12)	0.0113 (12)	−0.0037 (12)
C10	0.0362 (15)	0.0455 (16)	0.0430 (16)	−0.0041 (13)	0.0119 (13)	0.0019 (13)
C11	0.0381 (16)	0.0537 (18)	0.0406 (17)	−0.0047 (13)	0.0127 (13)	−0.0034 (14)
C7	0.0374 (15)	0.0500 (18)	0.0412 (16)	−0.0025 (14)	0.0108 (13)	−0.0043 (13)
C1	0.0339 (16)	0.062 (2)	0.065 (2)	0.0057 (15)	0.0040 (15)	0.0036 (17)
C8	0.0331 (14)	0.0465 (17)	0.0527 (18)	0.0015 (13)	0.0097 (13)	−0.0124 (14)
C6	0.0356 (15)	0.0406 (15)	0.0388 (16)	−0.0018 (12)	0.0086 (12)	−0.0017 (12)
C3	0.0331 (15)	0.0401 (15)	0.0474 (17)	−0.0008 (12)	0.0061 (13)	−0.0062 (13)
C4	0.0329 (14)	0.0427 (16)	0.0442 (16)	−0.0007 (12)	0.0126 (12)	−0.0020 (13)
C9	0.0361 (15)	0.0390 (15)	0.0538 (19)	0.0000 (13)	0.0071 (14)	−0.0007 (14)
C2	0.046 (2)	0.077 (3)	0.085 (3)	0.008 (2)	−0.014 (2)	−0.015 (2)

Geometric parameters (Å, º) top

Cl1—C4	1.751 (3)	C11—H11A	0.97
Cl4—C7	1.754 (3)	C11—H11B	0.97
Cl2—C9	1.700 (3)	C7—C8	1.516 (4)
Cl3—C8	1.701 (3)	C7—C3	1.553 (4)
O1—C3	1.391 (4)	C7—C6	1.560 (4)
O1—C1	1.435 (4)	C1—C2	1.467 (6)
O2—C3	1.397 (4)	C1—H1A	0.97
O2—C2	1.443 (4)	C1—H1B	0.97
C5—C10	1.521 (4)	C8—C9	1.326 (5)
C5—C4	1.559 (4)	C6—C11ⁱ	1.528 (4)
C5—C6	1.579 (4)	C6—H6	0.98
C5—H5	0.98	C3—C4	1.557 (4)
C10—C11	1.535 (4)	C4—C9	1.517 (4)
C10—H10A	0.97	C2—H2A	0.97
C10—H10B	0.97	C2—H2B	0.97
C11—C6ⁱ	1.528 (4)

C3—O1—C1	107.2 (2)	H1A—C1—H1B	109
C3—O2—C2	107.3 (3)	C9—C8—C7	108.0 (3)
C10—C5—C4	113.6 (3)	C9—C8—Cl3	127.6 (3)
C10—C5—C6	117.7 (2)	C7—C8—Cl3	124.3 (2)
C4—C5—C6	102.6 (2)	C11ⁱ—C6—C7	112.9 (2)
C10—C5—H5	107.5	C11ⁱ—C6—C5	117.9 (2)
C4—C5—H5	107.5	C7—C6—C5	102.1 (2)
C6—C5—H5	107.5	C11ⁱ—C6—H6	107.8
C5—C10—C11	114.6 (3)	C7—C6—H6	107.8
C5—C10—H10A	108.6	C5—C6—H6	107.8
C11—C10—H10A	108.6	O1—C3—O2	108.7 (2)
C5—C10—H10B	108.6	O1—C3—C7	112.8 (3)
C11—C10—H10B	108.6	O2—C3—C7	114.7 (3)
H10A—C10—H10B	107.6	O1—C3—C4	113.9 (2)
C6ⁱ—C11—C10	115.3 (3)	O2—C3—C4	113.6 (3)
C6ⁱ—C11—H11A	108.5	C7—C3—C4	92.5 (2)
C10—C11—H11A	108.5	C9—C4—C3	99.0 (2)
C6ⁱ—C11—H11B	108.5	C9—C4—C5	108.6 (2)
C10—C11—H11B	108.5	C3—C4—C5	101.0 (2)
H11A—C11—H11B	107.5	C9—C4—Cl1	115.8 (2)
C8—C7—C3	99.0 (2)	C3—C4—Cl1	115.3 (2)
C8—C7—C6	108.6 (3)	C5—C4—Cl1	115.0 (2)
C3—C7—C6	101.2 (2)	C8—C9—C4	107.3 (3)
C8—C7—Cl4	115.9 (2)	C8—C9—Cl2	128.4 (3)
C3—C7—Cl4	115.0 (2)	C4—C9—Cl2	124.2 (2)
C6—C7—Cl4	115.2 (2)	O2—C2—C1	103.4 (3)
O1—C1—C2	103.6 (3)	O2—C2—H2A	111.1
O1—C1—H1A	111	C1—C2—H2A	111.1
C2—C1—H1A	111	O2—C2—H2B	111.1
O1—C1—H1B	111	C1—C2—H2B	111.1
C2—C1—H1B	111	H2A—C2—H2B	109

Symmetry code: (i) −x+2, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₀Cl₈O₄
M_r	631.98
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	9.5332 (7), 7.9121 (6), 17.014 (2)
β (°)	101.099 (8)
V (Å³)	1259.3 (2)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	8.44
Crystal size (mm)	0.25 × 0.20 × 0.08

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.190, 0.561
No. of measured, independent and observed [I > 2σ(I)] reflections	4703, 2275, 1702
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.118, 1.05
No. of reflections	2275
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.47

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), DIRDIF08 (Beurskens et al., 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

This work was supported in part by funds provided by The University of North Carolina at Charlotte.

References

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