Structure of an unusual cage dimer diol
vinay kumar1999
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The title compound arises from an unexpected rearrangement and oxidation. The molecules contain a center of symmetry and are held together by hydrogen bonds. The relatively strainfree molecules are closely packed with a density of 1.441 g cm Ϫ3. The compound crystallizes in space group P-1 with cell dimensions a ϭ 8.999(3), b ϭ 9.142(2), c ϭ 8.625(3) Å , Ͱ ϭ 95.47(3), ͱ ϭ 105.06(3), and Ͳ ϭ 83.08(2)Њ There are two independent molecules per cell with each sitting on a center of symmetry.
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Journal of Chemical Crystallography, Vol. 29, No. 12, 1999
Structure of an unusual cage dimer diol
Satish G. Bodige,(1) William H. Watson,(1)* Alan P. Marchand,(2) and V. Satish Kumar(2)
Received February 7, 2000
The title compound arises from an unexpected rearrangement and oxidation. The molecules
contain a center of symmetry and are held together by hydrogen bonds. The relatively strainfree molecules are closely packed with a density of 1.441 g cm⫺3. The compound crystallizes
in space group P-1 with cell dimensions a ⫽ 8.999(3), b ⫽ 9.142(2), c ⫽ 8.625(3) Å, 움 ⫽
95.47(3), 웁 ⫽ 105.06(3), and 웂 ⫽ 83.08(2)⬚ There are two independent molecules per cell
with each sitting on a center of symmetry.
KEY WORDS: Cage molecule; decacycloicosane; molecular rearrangement.
limited applications.5 In the present study, 2b was
converted into the corresponding cage diiodide, 3,
via photolysis of a benzene solution of 2b in the
presence PhI(Oac)2 . At some point during the photolysis rearrangement with concomitant oxidation
ensued, thereby affording a new product, 4, decacylo[9.9.0.01,5 .02,8 .04,7 .06,10 .011,17 .012,15 .013,20 .014,18]-icosane-10,20-diol. The structure of 4 was established
by an X-ray crystallographic study.
Introduction
Thiele’s ester 1b is prepared by the Scheme 1
shown below.1 The ester undergoes intramolecular
[2 ⫹ 2] photcyclization2 to provide 2b which is a useful
synthetic entry into the pentacyclo[5.4.02,5 .03,10 .05,8]
decane ring system. Recently, 2b has been employed
as a starting material in the synthesis of other, complex polycarbocyclic ring systems.2,3 The present
study is an extension of past work4 designed to exploit
Thiele’s ester as a reagent for the preparation of new
energetic hydrocarbons for use as fuels in volume-
Experimental
Synthesis
To a cooled (⫺78⬚C) solution of MeLi (26.0 mL,
36 mmol, 1.5 M solution in ether) in THF (10 mL)
was added compound 3 (3.00 g, 7.81 mmol) in THF
(40 mL) slowly with stirring during 0.5 h. After the
addition of 3 was completed, the reaction mixture
was stirred at ⫺78⬚C for 2 h. The external cold bath
was removed, and the reaction mixture was allowed
to warm gradually to ambient temperature while stirring. The mixture was cooled to 0⬚C and quenched
via careful dropwise addition of saturated aqueous
NH4Cl (10 mL) to the stirred mixture. The organic
layer was separated and then washed sequentially
with cold water (2 mL) and brine (2 mL). The aqueous layer was extracted with diethyl ether (2 ⫻ 20
(1)
Department of Chemistry, Texas Christian University, Box
298860, Fort Worth, Texas 76129.
(2)
Department of Chemistry, University of North Texas, Box
305070, Denton, TX 76203 USA.
* To whom correspondence should be addressed.
1261
1074-1542/99/1200-1261$16.00/0 1999 Plenum Publishing Corporation
1262
Bodige, Watson, Marchand, and Kumar
Table 1. Crystal Data and Structure Refinement
Compound
CCDC deposit no.
Color/shape
Formula weight
Temperature, K
Crystal system
Space group
Unit cell dimensions
(7460 reflections in full range)
Volume, Å3
Z
Density (calculated), (g cm⫺3)
Absorption coefficient, cm⫺1
Trans. factors
2max(⬚)
Reflections collected
(hkl) range
Independent/observed reflections
Rint
Final R indices [I ⱖ 2 (I)]
No. variables
R, wR
(⌬/ )max
max ; min(e/Å3)
C20H22O2
CCDC-1003/5737
colorless/prism
294.39
298
Triclinic
P-1
a ⫽ 8.999(3) Å
b ⫽ 9.142(2) Å
c ⫽ 8.625(3) Å
움 ⫽ 95.47(3)⬚
웁 ⫽ 105.06(3)⬚
웂 ⫽ 83.08(2)⬚
678.7(4)
2
1.441
7.14(CuK움)
.738–1.00
156.8
2990
0, 11; ⫺11, 11; ⫺10, 10
2990
0.034
2003
200
0.055; 0.055
0.00
0.26; ⫺0.30
separated from solution. One of these crystals was
isolated and air-dried. X-ray analysis established
the structure as that of compound 4. Exact mass:
Calcd. for C20H20O2 : [M ⫹ H] ⫽ 295.169085; Found:
m/z ⫽ 295.168278.
X-ray analysis
X-ray data were collected on a Rigaku AFC-6S
diffractometer using the 웆-2 mode at fixed scan rate
with multiple scans for weak reflections. The scan
width and rate were determined by scanning several
strong reflections prior to data collection. The data
were corrected for Lorentz-polarization effects and
a -scan empirical absorption correction was applied.
The structure was solved using SIR926 and refined
using TEXAN.7 Structural data were checked using
PLATON.8 Table 1 contains crystal data, collection
parameters and refinement criteria. Table 2 reports
atomic positional parameters while Table 6 gives selected bond distances and valence angles. Figure 1 is
a thermal ellipsoid plot of the diol.
Discussion
mL). The combined organic extracts were washed
sequentially with water (10 mL) and brine (10 mL),
and then dried (MgSO4), filtered, and concentrated
in vacuo to a net volume of 2 mL. After sitting in a
refrigerator for 1 h, a flaky colorless solid was recovered by filtration, washed with diethyl ether (2 mL)
and dried in vacuo. A C20H20 hydrocarbon (200 mg,
20%) was obtained: mp 78–79⬚C (at this point the
sample became purple and resolidified providing a
refractory solid); IR(KBr, cm⫺1) 2985(s), 2949(s),
1454(m), 1402(m), 1253(m), 772(m); 1H NMR(C6D6)
웃 1.24 (AB, JAB ⫽ 11.0 Hz, 2H), 1.37 (AB, JAB ⫽ 11.0
Hz, 2H), 1.64 (AB, JAB ⫽ 11.0 Hz, 2H), 2.00 (AB,
JAB ⫽ 11.0 Hz, 2H), 2.45 (s, 2H), 2.82 (M, 6H), 2.93
(m, 4H); 13C NMR (C6D6) 웃 37.2(t), 38.8(t), 40.2(d),
41.1(d), 44.8(d), 46.6(d), 49.0(s), 49.3(d), 51.6(d),
53.3(s). Exact mass: Calcd for C20H20 : [M ⫹ H]
m/z ⫽ 261.164326; Found: m/z ⫽ 261.164970; Calcd:
for C20H20 : C, 92.25%; H, 7.75%; Found: C, 92.90%;
H, 7.56%.
The compound C20H20 was dissolved in CdCl3 in
an NMR tube and was allowed to stand at ambient
temperature for several days. During this time, it
was noted that a small quantity of colorless crystals
The two independent molecules of the diol are
held together by hydrogen bonds between O(1)⭈⭈⭈
O(2) (2 ⫺ x, 1 ⫺ y, 1 ⫺ z) ⫽ 2.935(2) Å (O(1)UH(1)
⭈⭈⭈O(2) ⫽ 163⬚) and O(2) ⭈⭈⭈ O(1) (x,1 ⫹ y, z) ⫽
Fig. 1. Thermal ellipsoid drawing of the title compound. Ellipsoids
are drawn at the 30% probability level. H atoms are represented
by spheres of arbitrary size.
Structure of unusual cage dimer diol
1263
Table 2. Selected Bond Distances (Å) and Valence Angles (⬚)
Molecule 1
O(1)UC(1)
C(1)UC(1⬘)
C(1)UC(2)
C(1)UC(7⬘)
C(1)UC(10⬘)
C(2)UC(3)
C(2)UC(6)
C(3)UC(4)
C(4)UC(5)
C(4)UC(10)
C(5)UC(6)
C(5)UC(8)
C(6)UC(7)
C(7)UC(8)
C(8)UC(9)
C(9)UC(10)
C(1⬘)C(2)C(2)
C(1⬘)C(1)C(7⬘)
C(1⬘)C(1)C(10⬘)
C(2)C(1)C(7⬘)
C(7⬘)C(1)C(10⬘)
O(1)C(2)C(1)
O(1)C(2)C(3)
O(1)C(2)C(6)
C(1)C(2)C(3)
C(1)C(2)C(6)
C(2)C(3)C(4)
C(3)C(4)C(5)
C(3)C(4)C(10)
C(5)C(4)C(10)
C(4)C(5)C(6)
C(4)C(5)C(8)
C(6)C(5)C(8)
C(2)C(6)C(5)
C(2)C(6)C(7)
C(5)C(6)C(7)
C(1⬘)C(7)C(6)
C(1⬘)C(7)C(8)
C(6)C(7)C(8)
C(5)C(8)C(7)
C(5)C(8)C(9)
C(7)C(8)C(9)
C(8)C(9)C(10)
Molecule 2
1.450(3)
1.544(5)
1.561(4)
1.543(4)
1.564(4)
1.524(4)
1.558(4)
1.518(4)
1.535(4)
1.552(4)
1.558(4)
1.550(4)
1.567(4)
1.563(4)
1.522(5)
1.539(4)
100.8(3)
104.7(3)
113.3(3)
125.6(2)
100.6(2)
116.2(2)
109.8(2)
114.0(2)
109.6(2)
102.8(2)
101.8(2)
103.6(3)
114.2(3)
101.4(2)
100.6(2)
104.2(3)
91.7(2)
107.6(2)
109.4(2)
86.7(2)
99.2(2)
104.7(2)
90.9(2)
87.1(2)
105.3(2)
105.2(2)
95.6(2)
O(2)UC(12)
C(11)UC(11⬘)
C(11)UC(12)
C(11)UC(17⬘)
C(11)UC(20⬘)
C(12)UC(13)
C(12)UC(16)
C(13)UC(14)
C(14)UC(15)
C(14)UC(20)
C(15)UC(16)
C(15)UC(18)
C(16)UC(17)
C(17)UC(18)
C(18)UC(19)
C(19)UC(20)
C(11⬘)C(11)C(12)
C(11⬘)C(11)C(17⬘)
C(11⬘)C(11)C(20⬘)
C(12)C(11)C(17⬘)
C(17⬘)C(1)C(20⬘)
O(2)C(12)C(11)
O(2)C(12)C(13)
O(2)C(12)C(16)
C(11)C(12)C(13)
C(11)C(12)C(16)
C(12)C(13)C(14)
C(13)C(14)C(15)
C(13)C(14)C(20)
C(15)C(14)C(20)
C(14)C(15)C(16)
C(14)C(15)C(18)
C(16)C(15)C(18)
C(12)C(16)C(15)
C(12)C(16)C(17)
C(15)C(16)C(17)
C(11)C(17)C(16)
C(11)C(17)C(18)
C(16)C(17)C(18)
C(15)C(18)C(17)
C(15)C(18)C(19)
C(17)C(18)C(19)
C(18)C(19)C(20)
1.456(3)
1.549(5)
1.546(4)
1.554(4)
1.567(4)
1.536(4)
1.563(4)
1.523(4)
1.551(4)
1.545(4)
1.557(4)
1.547(4)
1.562(4)
1.557(4)
1.524(4)
1.535(4)
101.6(3)
103.6(3)
113.7(3)
125.4(2)
100.2(2)
116.3(2)
112.8(2)
110.6(2)
109.9(2)
102.4(2)
101.8(2)
103.0(3)
114.9(3)
101.2(2)
100.9(2)
103.8(3)
91.7(2)
107.5(2)
109.5(2)
86.5(2)
100.1(2)
104.7(2)
91.1(2)
87.0(2)
105.5(3)
105.5(2)
95.5(2)
2.830(2) Å, (O(2)UH(12) ⭈⭈⭈ O(1) ⫽ 169⬚). The cage
molecules are densely packed (d ⫽ 1.441 g/cm3) with
no voids for solvent molecules. Molecular Mechanics9
indicates the strain in the molecule is minimal and
primarily associated with bending (앑48 kcal/mol)
and torsional distortions (앑30 kcal/mol). The molecule is about 18 kcal/mol more stable than the isomer
with the two four-membered rings on the same side
relative to the C(2)UC(1)UC(1⬘)UC(2⬘) plane. The
bond lengths fall within the normal limits with the
largest being 1.567(3) Å. The four-membered rings
are folded with alternate torsion angles of ⫾14.3(1)⬚.
All five-membered rings are in half-chair or distorted
half-chair conformations10 while all six-membered
rings11 are chair or distorted chair conformations except for C(1⬘)C(7)C8)C(5)C(4)C(10) which is best
described as a slightly twisted boat.
The formation of the diol 4 is entirely unexpected. Experiments that are designed to clarify the
origin of 4 in this reaction and to establish a mechanism for its formation are underway.
Acknowledgments
We thank the Robert A. Welch Foundation
(Grants P-0074 (W.H.W.) and B-0963 (A.P.M.) and
the Office of Naval Research (Grant N00014-98-10478, A.P.M.) for their financial support of this study.
We thank Professor Jennifer S. Brodbelt (Department of Chemistry, University of Texas at Austin)
for obtaining the high-resolution chemical ionization
mass spectra data.
References
1. (a) Thiele, J. Chem. Ber. 1900, 33, 666; (b) Thiele, J. Chem.
Ber. 1901, 34, 68.
2. Dunn, G.L.; Donohue, J.K. Tetrahedron Lett. 1968, 3485.
3. Marchand, A.P.; Zhao, D.; Ngooi, T.-K.; Vidyasagar, V. Tetrahedron 1993, 49, 2613 and references cited therein.
4. Marchand, A.P.; Namboothiri, I.N.N.; Lewis, S.B.; Watson,
W.H.; Krawiec, M. Tetrahedron 1998, 54, 12691.
5. (a) Marchand, A.P.; Deshpande, M.N.; Reddy, G.M.; Watson,
W.H.; Nagl, A. In Reprints, Papers Presented at the 198th
national Meeting of the American Chemical Society, Miami
Beach, FL, September 10–15, 1989; Symposium on Chemical
Aspects of Hypersonic Propulsion; Division of Fuel Chemistry, American Chemical Society: Washington, DC 1989, 34,
946. (b) Segal, C.; Friedauer, M.J.; Udaykumar, H. S. Shyy,
W.; Marchand, A.P. Journal of Propulsion and Power 1997,
13, 246.
6. Altomare, A.; Cascarano, M.; Giacovazzo, D.; Guagliardi, A.
J. Appl. Crystallogr. 1993, 26, 343.
7. TEXSAN-TEXRAY Structure Analysis Package; Vers. 1.7-1;
Molecular Structure Corporation, March 1995.
8. Spek, A.L. Acta Crystallogr. 1990, A46, 194.
9. PCModel for Windows, Version 7.00; Serena Software, June
12, 1998.
10. Cremer, D.; Pople, J.A. J. Am. Chem. Soc. 1978, 97, 1354.
11. (a) Boeyens, J.C.A. J. Cryst. Mol. Struct. 1978, 8, 317; (b)
Evans, G.C.; Boeyens, J.C.A. Acta Crystallogr. 1989, B45, 581.
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