organic compounds
Bicyclo[2.2.1]hept-7-yl p-bromobenzoate
aDepartment of Chemistry, Weber State University, Ogden, Utah 84408-2503, and bDepartment of Chemistry, University of Utah, Salt Lake City, Utah, 84112, USA
*Correspondence e-mail: blloyd@weber.edu
The title compound, C14H15BrO2, contains a sterically unencumbered norbornyl group. The dihedral angle between the plane of the carboxylate group and the mean plane of the adjacent benzene ring is 5.3 (2)°. The dihedral angle between the plane of the carboxylate group and the norbornyl methano C—O bond is 4.5 (1)°, the methano C atom deviating by 0.141 (2) Å from this plane. In the crystal, molecules pack as pairs of enantiomers, with a distance of 3.747 (1) Å between the centroids of nearest parallel benzene rings.
Related literature
For calculated and experimental norbornane and related structures, see: Allinger et al. (1989); Pfund et al. (1980). For related polycyclic p-bromobenzoate structures, see: Lloyd & Arif (2012); Lloyd et al. (1995, 2000). For a high resolution low temperature powder synchrotron X-ray diffraction structure of norbornane, see: Fitch & Jobic (1993). For some norbornyl bond lengths and angles, see: Watson et al. (1992). For possible C—O bond-length correlation to reactivity in a 7-norbornenyl benzoate, see: Jones et al. (1992).
Experimental
Crystal data
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Data collection: COLLECT (Nonius, 1998); cell 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 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812041268/fj2598sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812041268/fj2598Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812041268/fj2598Isup3.mol
Supporting information file. DOI: 10.1107/S1600536812041268/fj2598Isup4.cml
7-Norbornyl p-bromobenzoate (title compound 1) was made from commercial bicyclo[2.2.1]heptan-7-ol (7-norborneol, Alfa Products). Under a dry nitrogen atmosphere, 1.06 g freshly distilled (about 300 K, 7 Pa) p-bromobenzoyl chloride, 15 ml reagent grade dichloromethane, 0.802 g dry, freshly distilled (from CaH2 under N2) pyridine, and 0.540 g of sublimed (373 K, 7 Pa) 7-norborneol were combined and the mixture was refluxed for 15 min, then stirred for 2 d at 296 K. The reaction mixture was poured into 10 ml of 5% HCl solution, and layers were separated. The dichloromethane layer was washed twice more with 5% HCl solution, the dichloromethane was evaporated, and the residue was dissolved in about 3 ml of ether. The mixture was chromatographed on Florisil (petroleum ether, then ether). Recovered 1.22 g of 1, 85.3% yield, mp 350–351 K after two recrystallizations from petroleum ether/ether: 1H NMR (CDCl3, 90 MHz) δ 1.10–1.57 (4 H, m), 1.57–2.09 (4 H, m), 2.31 (2 H, m), 4.99 (1 H, s), 7.57 (2 H, d), 7.88 (2 H, d). Crystals were regrown slowly by dissolving 1.0 g of 1 in 5 ml of anhydrous ether in a 30 ml beaker. The beaker was placed inside a desiccator along with a 20 ml beaker containing 15 ml of petroleum ether (bp 303–333 K), and the desiccator was placed inside a freezer at 253 K. A one-hole rubber stopper was placed in the desiccator neck with glass wool inserted into the hole, allowing for slow evaporation. Crystals began forming after 3 d and they were filtered out after 5 d. One of these crystals was selected for X-ray analysis.
A colorless prism shaped crystal 0.30 × 0.25 × 0.18 mm in size was mounted on a glass fiber with traces of viscous oil and then transferred to a Nonius KappaCCD diffractometer equipped with Mo Kα radiation (λ = 0.71073 Å). Ten frames of data were collected at 150 (1) K with an oscillation range of 1 °/frame and an exposure time of 20 sec/frame (Nonius, 1998). Indexing and based on all observed reflection from those ten frames, indicated a monoclinic P lattice. A total of 5495 reflections (Θmax = 27.48°) were indexed, integrated and corrected for and absorption effects using DENZO– SMN and SCALEPAC (Otwinowski & Minor, 1997). Post of the gave a = 11.7401 (2) Å, b = 6.3767 (1) Å, c = 17.7462 (3) Å, β =109.584 (1)°, and V = 1251.68 (4) Å3. Axial photographs and were consistent with the compound having crystallized in the monoclinic P21/c.
The structure was solved by a combination of direct and heavy atom methods using SIR97 (Altomare et al., 1999). All of the non-hydrogen atoms were refined with anisotropic displacement coefficients. Hydrogen atoms were located and refined isotropically using SHELXL97 (Sheldrick, 2008). The weighting scheme employed was w = 1/[σ2(Fo2) + (0.0254P)2 + 0.4883P] where P = (Fo2 + 2Fc2) /3. The converged to R1 = 0.0224, wR2 = 0.0527, and S = 1.025 for 2469 reflections with I > 2σ(I), and R1 = 0.0294, wR2 = 0.0552, and S = 1.025 for 2882 unique reflections and 215 parameters, where R1 = Σ (|| Fo | – |Fc ||) / Σ |Fo|, wR2 = [Σ(w(Fo2 – Fc2)2) / Σ(Fo2)2]1/2, and S = Goodness-of-fit on F2 = [Σ (w(Fo2 – Fc2)2 / (n-p)] 1/2, n is the number of reflections and p is the number of parameters refined.
The maximum Δ/σ in the final cycle of the least-squares was 0.001, and the residual peaks on the final difference-Fourier map ranged from -0.35 to 0.382 e/Å3. Scattering factors were taken from the International Tables for Crystallography, Volume C, Chapters 4 pp 206–222 and 6 pp 476–516.
Data collection: COLLECT (Nonius, 1998); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); 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 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).Fig. 1. ORTEP-3 drawing of the title compound showing 50% displacement ellipsoids. | |
Fig. 2. Cell packing diagram for the title compound. | |
Fig. 3. Compounds 1, 2, and 3. |
C14H15BrO2 | F(000) = 600 |
Mr = 295.17 | Dx = 1.566 Mg m−3 |
Monoclinic, P21/c | Melting point: 351 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 11.7401 (2) Å | Cell parameters from 3135 reflections |
b = 6.3767 (1) Å | θ = 1.0–27.5° |
c = 17.7462 (3) Å | µ = 3.27 mm−1 |
β = 109.584 (1)° | T = 150 K |
V = 1251.68 (4) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.25 × 0.18 mm |
Nonius KappaCCD Diffractometer | 2882 independent reflections |
Radiation source: fine-focus sealed tube | 2469 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
Phi and ω scans | θmax = 27.5°, θmin = 2.4° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −15→15 |
Tmin = 0.440, Tmax = 0.591 | k = −8→8 |
5495 measured reflections | l = −22→23 |
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)] = 0.022 | All H-atom parameters refined |
wR(F2) = 0.055 | w = 1/[σ2(Fo2) + (0.0254P)2 + 0.4883P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
2882 reflections | Δρmax = 0.38 e Å−3 |
215 parameters | Δρmin = −0.35 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0091 (7) |
C14H15BrO2 | V = 1251.68 (4) Å3 |
Mr = 295.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.7401 (2) Å | µ = 3.27 mm−1 |
b = 6.3767 (1) Å | T = 150 K |
c = 17.7462 (3) Å | 0.30 × 0.25 × 0.18 mm |
β = 109.584 (1)° |
Nonius KappaCCD Diffractometer | 2882 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2469 reflections with I > 2σ(I) |
Tmin = 0.440, Tmax = 0.591 | Rint = 0.015 |
5495 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.055 | All H-atom parameters refined |
S = 1.03 | Δρmax = 0.38 e Å−3 |
2882 reflections | Δρmin = −0.35 e Å−3 |
215 parameters |
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL-97 input file. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.29724 (11) | −0.03809 (19) | 0.03440 (7) | 0.0345 (3) | |
O2 | 0.17768 (10) | 0.23527 (18) | 0.03757 (6) | 0.0275 (2) | |
Br1 | 0.470495 (15) | 0.70360 (3) | −0.187891 (10) | 0.03601 (8) | |
C1 | 0.20441 (14) | 0.1660 (3) | 0.18033 (9) | 0.0284 (3) | |
C2 | 0.12314 (16) | 0.0547 (3) | 0.22003 (10) | 0.0357 (4) | |
C3 | −0.00686 (16) | 0.0964 (3) | 0.16107 (11) | 0.0341 (4) | |
C4 | 0.01573 (14) | 0.2271 (3) | 0.09468 (9) | 0.0268 (3) | |
C5 | 0.05962 (15) | 0.4456 (3) | 0.12780 (10) | 0.0313 (4) | |
C6 | 0.18971 (16) | 0.4036 (3) | 0.18646 (10) | 0.0336 (4) | |
C7 | 0.13181 (14) | 0.1242 (3) | 0.09249 (9) | 0.0253 (3) | |
C8 | 0.26378 (13) | 0.1393 (3) | 0.01604 (8) | 0.0244 (3) | |
C9 | 0.31177 (13) | 0.2786 (2) | −0.03379 (8) | 0.0224 (3) | |
C10 | 0.39565 (15) | 0.1984 (3) | −0.06648 (9) | 0.0274 (3) | |
C11 | 0.44332 (15) | 0.3225 (3) | −0.11205 (10) | 0.0303 (4) | |
C12 | 0.40660 (13) | 0.5289 (3) | −0.12504 (8) | 0.0257 (3) | |
C13 | 0.32412 (15) | 0.6139 (3) | −0.09307 (10) | 0.0291 (3) | |
C14 | 0.27768 (14) | 0.4878 (3) | −0.04697 (9) | 0.0270 (3) | |
H1 | 0.2846 (17) | 0.116 (3) | 0.1972 (10) | 0.029 (4)* | |
H2A | 0.1403 (19) | −0.093 (4) | 0.2256 (12) | 0.049 (6)* | |
H2B | 0.1354 (16) | 0.109 (3) | 0.2741 (11) | 0.036 (5)* | |
H3A | −0.0457 (17) | −0.037 (3) | 0.1400 (12) | 0.039 (5)* | |
H3B | −0.0543 (18) | 0.179 (3) | 0.1874 (12) | 0.038 (5)* | |
H4 | −0.0512 (17) | 0.230 (3) | 0.0436 (11) | 0.031 (5)* | |
H5A | 0.0057 (17) | 0.507 (3) | 0.1529 (11) | 0.034 (5)* | |
H5B | 0.0597 (17) | 0.540 (3) | 0.0856 (11) | 0.035 (5)* | |
H6A | 0.2006 (18) | 0.443 (3) | 0.2418 (12) | 0.046 (6)* | |
H6B | 0.2501 (18) | 0.476 (3) | 0.1699 (12) | 0.043 (5)* | |
H7 | 0.1235 (16) | −0.023 (3) | 0.0794 (10) | 0.029 (5)* | |
H10 | 0.4167 (17) | 0.061 (3) | −0.0576 (11) | 0.038 (5)* | |
H11 | 0.5023 (19) | 0.270 (3) | −0.1319 (13) | 0.042 (5)* | |
H13 | 0.3001 (19) | 0.760 (3) | −0.1028 (12) | 0.040 (5)* | |
H14 | 0.2213 (17) | 0.543 (3) | −0.0241 (11) | 0.035 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0420 (7) | 0.0262 (6) | 0.0433 (7) | 0.0084 (5) | 0.0250 (5) | 0.0038 (5) |
O2 | 0.0331 (6) | 0.0299 (6) | 0.0262 (5) | 0.0085 (5) | 0.0190 (5) | 0.0049 (5) |
Br1 | 0.03629 (11) | 0.04188 (13) | 0.03518 (11) | −0.00802 (7) | 0.01902 (8) | 0.00085 (8) |
C1 | 0.0223 (7) | 0.0396 (10) | 0.0243 (7) | 0.0034 (7) | 0.0093 (6) | 0.0054 (7) |
C2 | 0.0356 (9) | 0.0473 (11) | 0.0288 (8) | 0.0035 (8) | 0.0169 (7) | 0.0101 (8) |
C3 | 0.0299 (8) | 0.0427 (11) | 0.0349 (9) | −0.0027 (8) | 0.0177 (7) | 0.0010 (8) |
C4 | 0.0227 (7) | 0.0357 (9) | 0.0231 (7) | 0.0029 (6) | 0.0090 (6) | 0.0000 (6) |
C5 | 0.0347 (9) | 0.0312 (9) | 0.0333 (8) | 0.0059 (7) | 0.0184 (7) | −0.0013 (7) |
C6 | 0.0326 (9) | 0.0396 (10) | 0.0301 (8) | −0.0049 (7) | 0.0125 (7) | −0.0081 (8) |
C7 | 0.0294 (8) | 0.0267 (8) | 0.0245 (7) | 0.0020 (6) | 0.0151 (6) | 0.0015 (6) |
C8 | 0.0244 (7) | 0.0296 (8) | 0.0203 (7) | 0.0036 (6) | 0.0090 (6) | −0.0045 (6) |
C9 | 0.0214 (7) | 0.0273 (8) | 0.0179 (6) | 0.0016 (6) | 0.0056 (5) | −0.0030 (6) |
C10 | 0.0304 (8) | 0.0273 (8) | 0.0285 (8) | 0.0068 (7) | 0.0153 (6) | 0.0003 (7) |
C11 | 0.0269 (8) | 0.0389 (10) | 0.0295 (8) | 0.0053 (7) | 0.0154 (6) | −0.0017 (7) |
C12 | 0.0221 (7) | 0.0343 (9) | 0.0207 (7) | −0.0046 (6) | 0.0074 (6) | −0.0025 (6) |
C13 | 0.0300 (8) | 0.0263 (8) | 0.0326 (8) | 0.0009 (7) | 0.0125 (7) | −0.0010 (7) |
C14 | 0.0266 (7) | 0.0293 (8) | 0.0284 (8) | 0.0046 (6) | 0.0134 (6) | −0.0027 (7) |
O1—C8 | 1.206 (2) | C5—C6 | 1.556 (2) |
O2—C8 | 1.3421 (17) | C5—H5A | 0.971 (19) |
O2—C7 | 1.4469 (18) | C5—H5B | 0.96 (2) |
Br1—C12 | 1.8997 (15) | C6—H6A | 0.98 (2) |
C1—C7 | 1.529 (2) | C6—H6B | 0.97 (2) |
C1—C6 | 1.533 (3) | C7—H7 | 0.966 (19) |
C1—C2 | 1.537 (2) | C8—C9 | 1.491 (2) |
C1—H1 | 0.944 (18) | C9—C14 | 1.390 (2) |
C2—C3 | 1.557 (2) | C9—C10 | 1.397 (2) |
C2—H2A | 0.96 (2) | C10—C11 | 1.377 (2) |
C2—H2B | 0.984 (19) | C10—H10 | 0.91 (2) |
C3—C4 | 1.537 (2) | C11—C12 | 1.380 (2) |
C3—H3A | 0.98 (2) | C11—H11 | 0.94 (2) |
C3—H3B | 0.99 (2) | C12—C13 | 1.386 (2) |
C4—C7 | 1.525 (2) | C13—C14 | 1.383 (2) |
C4—C5 | 1.533 (2) | C13—H13 | 0.97 (2) |
C4—H4 | 0.981 (19) | C14—H14 | 0.953 (19) |
C8—O2—C7 | 117.02 (12) | C1—C6—H6A | 110.0 (13) |
C7—C1—C6 | 101.97 (13) | C5—C6—H6A | 113.4 (12) |
C7—C1—C2 | 99.62 (13) | C1—C6—H6B | 109.8 (12) |
C6—C1—C2 | 108.80 (14) | C5—C6—H6B | 111.6 (12) |
C7—C1—H1 | 114.8 (11) | H6A—C6—H6B | 108.6 (17) |
C6—C1—H1 | 116.0 (12) | O2—C7—C4 | 110.13 (13) |
C2—C1—H1 | 113.8 (11) | O2—C7—C1 | 113.28 (13) |
C1—C2—C3 | 103.42 (13) | C4—C7—C1 | 95.54 (12) |
C1—C2—H2A | 111.1 (13) | O2—C7—H7 | 110.2 (10) |
C3—C2—H2A | 111.2 (13) | C4—C7—H7 | 114.0 (11) |
C1—C2—H2B | 112.1 (12) | C1—C7—H7 | 113.0 (10) |
C3—C2—H2B | 112.7 (11) | O1—C8—O2 | 124.01 (14) |
H2A—C2—H2B | 106.5 (17) | O1—C8—C9 | 124.44 (13) |
C4—C3—C2 | 103.05 (13) | O2—C8—C9 | 111.55 (13) |
C4—C3—H3A | 110.9 (11) | C14—C9—C10 | 119.00 (14) |
C2—C3—H3A | 109.6 (12) | C14—C9—C8 | 121.81 (13) |
C4—C3—H3B | 110.0 (11) | C10—C9—C8 | 119.17 (14) |
C2—C3—H3B | 110.7 (11) | C11—C10—C9 | 121.02 (15) |
H3A—C3—H3B | 112.2 (16) | C11—C10—H10 | 121.0 (12) |
C7—C4—C5 | 102.27 (13) | C9—C10—H10 | 117.9 (12) |
C7—C4—C3 | 99.88 (13) | C10—C11—C12 | 118.71 (14) |
C5—C4—C3 | 108.73 (13) | C10—C11—H11 | 120.7 (13) |
C7—C4—H4 | 115.4 (11) | C12—C11—H11 | 120.5 (13) |
C5—C4—H4 | 113.6 (11) | C11—C12—C13 | 121.77 (15) |
C3—C4—H4 | 115.4 (11) | C11—C12—Br1 | 119.64 (11) |
C4—C5—C6 | 103.21 (13) | C13—C12—Br1 | 118.59 (13) |
C4—C5—H5A | 110.9 (11) | C14—C13—C12 | 118.87 (16) |
C6—C5—H5A | 114.0 (11) | C14—C13—H13 | 120.9 (12) |
C4—C5—H5B | 111.2 (11) | C12—C13—H13 | 120.2 (12) |
C6—C5—H5B | 111.8 (11) | C13—C14—C9 | 120.61 (14) |
H5A—C5—H5B | 105.9 (16) | C13—C14—H14 | 120.3 (12) |
C1—C6—C5 | 103.36 (13) | C9—C14—H14 | 119.1 (12) |
C7—C1—C2—C3 | −35.57 (17) | C6—C1—C7—C4 | −54.16 (14) |
C6—C1—C2—C3 | 70.69 (17) | C2—C1—C7—C4 | 57.56 (15) |
C1—C2—C3—C4 | −0.06 (19) | C7—O2—C8—O1 | 6.3 (2) |
C2—C3—C4—C7 | 35.81 (17) | C7—O2—C8—C9 | −174.22 (12) |
C2—C3—C4—C5 | −70.86 (17) | O1—C8—C9—C14 | −174.03 (15) |
C7—C4—C5—C6 | −33.78 (15) | O2—C8—C9—C14 | 6.5 (2) |
C3—C4—C5—C6 | 71.24 (15) | O1—C8—C9—C10 | 4.3 (2) |
C7—C1—C6—C5 | 34.25 (15) | O2—C8—C9—C10 | −175.22 (13) |
C2—C1—C6—C5 | −70.38 (16) | C14—C9—C10—C11 | −0.8 (2) |
C4—C5—C6—C1 | −0.36 (16) | C8—C9—C10—C11 | −179.21 (15) |
C8—O2—C7—C4 | −166.14 (13) | C9—C10—C11—C12 | 0.0 (2) |
C8—O2—C7—C1 | 88.22 (16) | C10—C11—C12—C13 | 0.5 (2) |
C5—C4—C7—O2 | −63.24 (15) | C10—C11—C12—Br1 | −179.84 (12) |
C3—C4—C7—O2 | −175.05 (13) | C11—C12—C13—C14 | 0.0 (2) |
C5—C4—C7—C1 | 54.04 (14) | Br1—C12—C13—C14 | −179.71 (12) |
C3—C4—C7—C1 | −57.76 (15) | C12—C13—C14—C9 | −0.9 (2) |
C6—C1—C7—O2 | 60.55 (15) | C10—C9—C14—C13 | 1.3 (2) |
C2—C1—C7—O2 | 172.27 (13) | C8—C9—C14—C13 | 179.63 (14) |
Experimental details
Crystal data | |
Chemical formula | C14H15BrO2 |
Mr | 295.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 11.7401 (2), 6.3767 (1), 17.7462 (3) |
β (°) | 109.584 (1) |
V (Å3) | 1251.68 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.27 |
Crystal size (mm) | 0.30 × 0.25 × 0.18 |
Data collection | |
Diffractometer | Nonius KappaCCD Diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.440, 0.591 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5495, 2882, 2469 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.055, 1.03 |
No. of reflections | 2882 |
No. of parameters | 215 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.38, −0.35 |
Computer programs: COLLECT (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 2012), ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009), Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).
Acknowledgements
We thank the Weber State Chemistry Department for supporting this work, the University of Utah Chemistry Department X-ray crystallographic facility, and the late Professor Evan L. Allred who began this work.
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Many norbornyl structures have been previously determined, but precise bond lengths and angles are derivative dependent (Watson et al., 1992). The Cambridge Crystallographic Database contains only five 7-norbornyl benzoate structures, but these are complicated by additional substituents and their associated steric interactions (for example, see Pfund et al., 1980). An ORTEP-3 drawing (Farrugia, 2012) of title compound structure 1 is shown in Fig. 1, and a cell packing diagram is shown in Fig. 2. Structure 1 norbornyl group bond lengths and bond angles agree with reported values, but their precision is about ten times better than geometry averaged values (Watson et al., 1992). Structure 1 was determined so that bond length, bond angle, least-squares plane, and nonbonding contact comparisons could be made with other related p-bromobenzoate structures (Lloyd & Arif, 2012, Lloyd et al., 2000 and Lloyd et al., 1995).
No nonhydrogen atom intermolecular contacts exist shorter than van der Waals radii sums, the smallest being O1i···C13ii at 3.257 (2) Å [symmetry code: (ii) x, -1 + y, z]. Least squares planes are defined as C1—C7—C4 (plane 1), C1—C2—C3—C4 (plane 2), and C1—C6—C5—C4 (plane 3). Interplanar 1:2, 1:3, and 1:4 angles are: 121.2 (1)°, 125.5 (1)°, and 113.3 (1)°, respectively. Angle 1:2 is 1.4° larger than the corresponding 296 K structure 2 (Fig. 3) angle (Lloyd et al., 1995), but smaller than corresponding angles of our other seven norbornenyl structures. Structure 1 angle 1: 3 is larger than analogous angles in all eight norbornenyl structures, and angle 2:3 is smaller for all except structure 3. Smaller 1:2 and larger 1:3 angles in structure 1 are likely a consequence of a longer C2—C3 norbornyl single bond (versus a shorter norbornenyl C2=C3 double bond) which bends C7 toward plane 2. The slightly larger structure 1 2:3 angle versus 3 might result from intramolecular H3B···H5A and H2B···H6A contacts, 2.35 (3) and 2.40 (3) Å, respectively (Lloyd & Arif, 2012). Reactant structural features (such as C7—O2 bond length) that might portend the large norbornenyl: norbornyl solvolytic reactivity ratio are not obvious, and the late transition state idea (Jones et al., 1992) is supported.