endo,endo-Tetra­cyclo­[6.2.1.13,6.02,7]dodeca-9-en-anti-11-yl 4-bromo­benzoate

Lloyd, B.A.; Arif, A.M.; Coots, R.J.

doi:10.1107/S1600536812051902

Volume 69
Part 2
Pages o202-o203
February 2013

Received 28 November 2012
Accepted 26 December 2012
Online 9 January 2013

Key indicators
Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.003 Å
R = 0.028
wR = 0.063
Data-to-parameter ratio = 12.7
Details

endo,endo-Tetracyclo[6.2.1.1^3,6.0^2,7]dodeca-9-en-anti-11-yl 4-bromobenzoate

Barry A. Lloyd,^a ^* Atta M. Arif ^b and Robert J. Coots ^c

^aChemistry Department, Weber State University, Ogden, Utah 84408-2503, USA,^bChemistry Department, University of Utah, Salt Lake City, Utah 84112, USA, and ^cColonial Chemical, Inc., 225 Colonial Drive, South Pittsburg, Tennessee 37380, USA
Correspondence e-mail: blloyd@weber.edu

The title compound 1-OPBB, C₁₉H₁₉BrO₂, contains a dechlorinated and hydrogenated isodrin backbone with an anti-4-bromobenzoate substituent at one of the methano bridges. The dihedral angle between the CO₂ ester plane and the benzene ring plane is 8.5 (2)°. In the crystal, the ester groups stack over benzene rings: the molecules pack as conformational enantiomers, with nearest parallel benzene ring planes separated by a perpendicular distance of 3.339 (1) Å. The nearest benzene-ring centroids are 5.266 (1) Å apart. Possible structural correlation with enhanced solvolytic reactivity is investigated.

Related literature

For related norbornyl and norbornenyl 4-bromobenzoate structures, see: Lloyd & Arif (2012a,b). For a structure containing the same tetracyclic framework, see: Lloyd et al. (1995). For the isomeric endo,exo-structure, see: Lloyd et al. (1994). For solvolysis rate information, see: Coots (1983); Chow & Jiang (2000). For molecular orbital results, see: Furusaki & Matsumoto (1978); Chow (1998, 1999). For synthetic procedures, see: Chow (1996); Melder & Prinzbach (1991); Coots (1983).

Experimental

Crystal data

C₁₉H₁₉BrO₂
M_r = 359.25
Monoclinic, P 2₁ /c
a = 13.2569 (2) Å
b = 10.5045 (2) Å
c = 12.2039 (2) Å
= 116.0122 (9)°
V = 1527.32 (4) Å³
Z = 4
Mo K radiation
= 2.70 mm^-1
T = 150 K
0.23 × 0.20 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) T_min = 0.576, T_max = 0.721
6702 measured reflections
3500 independent reflections
2700 reflections with I > 2(I)
R_int = 0.021

Refinement

R[F² > 2(F²)] = 0.028
wR(F²) = 0.063
S = 1.03
3500 reflections
276 parameters
All H-atom parameters refined
_max = 0.40 e Å^-3
_min = -0.46 e Å^-3

Table 1
Possible structure/reactivity relationships (°, Å)

	1-OPBB	2-OPBB	3-OPBB	4-OPBB	5-OPBB
Solvolysis rate^a	210	480	28	1.0	10^-11
1:2 interplanar angle^b	121.9 (2)	119.8 (6)	122.9 (3)	124.5 (1)	121.2 (1)
3:4 interplanar angle	132.0 (1)	132.4 (4)	128.1 (2)
C11-O2 bond length^b	1.450 (2)	1.460 (7)	1.437 (3)	1.445 (2)	1.447 (2)
Notes: (a) Rates determined in 80% dioxane-d₈/20% D₂O at 383 K, from NMR peak integrations; (b) C1/C7/C4 is plane 1 and C1/C2/C3/C4 is plane 2 for 4-OPBB and 5-OPBB; bond length is C7-O2 for 4-OPBB and 5-OPBB.

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 2012), ORTEP-3 (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB7005 ).

Acknowledgements

We thank the Weber State Chemistry Department, the University of Utah Chemistry Department X-ray crystallographic facility, Drs Greg D. Lyon and Gary J. Stroebel for developing syntheses, and the late Professor Evan L. Allred, who began this work.

References

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