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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 [sigma](C-C) = 0.003 Å
R = 0.028
wR = 0.063
Data-to-parameter ratio = 12.7
Details
Open access

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

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[Lloyd, B. A. & Arif, A. M. (2012a). Acta Cryst. E68, o2209.],b[Lloyd, B. A. & Arif, A. M. (2012b). Acta Cryst. E68, o3086-o3087.]). For a structure containing the same tetracyclic framework, see: Lloyd et al. (1995[Lloyd, B. A., Arif, A. M., Coots, R. J. & Allred, E. L. (1995). Acta Cryst. C51, 2059-2062.]). For the isomeric endo,exo-structure, see: Lloyd et al. (1994[Lloyd, B. A., Arif, A. M., Coots, R. J. & Allred, E. L. (1994). Acta Cryst. C50, 777-781.]). For solvolysis rate information, see: Coots (1983[Coots, R. J. (1983). PhD dissertation, University of Utah, USA.]); Chow & Jiang (2000[Chow, T. J. & Jiang, T.-S. (2000). Synth. Commun. 30, 4473-4478.]). For molecular orbital results, see: Furusaki & Matsumoto (1978[Furusaki, A. & Matsumoto, T. (1978). Bull. Chem. Soc. Jpn, 51, 16-20.]); Chow (1998[Chow, T. J. (1998). J. Phys. Org. Chem. 11, 871-878.], 1999[Chow, T. J. (1999). Advances in Strained and Interesting Organic Molecules, Suppl. 1, Carbocyclic and Cage Compounds and their Building Blocks, pp. 87-107.]). For synthetic procedures, see: Chow (1996[Chow, T. J. (1996). J. Chin. Chem. Soc. (Tapei), 43, 101-107.]); Melder & Prinzbach (1991[Melder, J.-P. & Prinzbach, H. (1991). Chem. Ber. 124, 1271-1289.]); Coots (1983[Coots, R. J. (1983). PhD dissertation, University of Utah, USA.]).

[Scheme 1]

Experimental

Crystal data
  • C19H19BrO2

  • Mr = 359.25

  • Monoclinic, P 21 /c

  • a = 13.2569 (2) Å

  • b = 10.5045 (2) Å

  • c = 12.2039 (2) Å

  • [beta] = 116.0122 (9)°

  • V = 1527.32 (4) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 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[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) Tmin = 0.576, Tmax = 0.721

  • 6702 measured reflections

  • 3500 independent reflections

  • 2700 reflections with I > 2[sigma](I)

  • Rint = 0.021

Refinement
  • R[F2 > 2[sigma](F2)] = 0.028

  • wR(F2) = 0.063

  • S = 1.03

  • 3500 reflections

  • 276 parameters

  • All H-atom parameters refined

  • [Delta][rho]max = 0.40 e Å-3

  • [Delta][rho]min = -0.46 e Å-3

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

  1-OPBB 2-OPBB 3-OPBB 4-OPBB 5-OPBB
Solvolysis ratea 210 480 28 1.0 10-11
1:2 interplanar angleb 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 lengthb 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[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999[Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]), ORTEP-3 (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).


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

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119.  [ISI] [CrossRef] [ChemPort] [details]
Chow, T. J. (1996). J. Chin. Chem. Soc. (Tapei), 43, 101-107.  [ChemPort]
Chow, T. J. (1998). J. Phys. Org. Chem. 11, 871-878.  [CrossRef] [ChemPort]
Chow, T. J. (1999). Advances in Strained and Interesting Organic Molecules, Suppl. 1, Carbocyclic and Cage Compounds and their Building Blocks, pp. 87-107.
Chow, T. J. & Jiang, T.-S. (2000). Synth. Commun. 30, 4473-4478.  [ISI] [CrossRef] [ChemPort]
Coots, R. J. (1983). PhD dissertation, University of Utah, USA.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [ISI] [CrossRef] [ChemPort] [details]
Furusaki, A. & Matsumoto, T. (1978). Bull. Chem. Soc. Jpn, 51, 16-20.  [CrossRef] [ChemPort] [ISI]
Lloyd, B. A. & Arif, A. M. (2012a). Acta Cryst. E68, o2209.  [CSD] [CrossRef] [details]
Lloyd, B. A. & Arif, A. M. (2012b). Acta Cryst. E68, o3086-o3087.  [CSD] [CrossRef] [details]
Lloyd, B. A., Arif, A. M., Coots, R. J. & Allred, E. L. (1994). Acta Cryst. C50, 777-781.  [CrossRef] [details]
Lloyd, B. A., Arif, A. M., Coots, R. J. & Allred, E. L. (1995). Acta Cryst. C51, 2059-2062.  [CSD] [CrossRef] [details]
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.  [ISI] [CrossRef] [ChemPort] [details]
Melder, J.-P. & Prinzbach, H. (1991). Chem. Ber. 124, 1271-1289.  [CrossRef] [ChemPort]
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [ISI] [CrossRef] [details]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [ISI] [CrossRef] [ChemPort] [details]


Acta Cryst (2013). E69, o202-o203   [ doi:10.1107/S1600536812051902 ]

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