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accessBicyclo[2.2.1]hept-2-en-7-yl 4-bromobenzoate
aDepartment of Chemistry, Weber State University, Ogden, Utah 84403, USA, and bDepartment of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA
*Correspondence e-mail: blloyd@weber.edu
The structure of the title compound, C14H13BrO2, which contains a norbornenyl group and a 4-bromobenzoate ester at the single C-atom bridge, has been redetermined [see McDonald & Trotter (1965![[Macdonald, A. C. & Trotter, J. (1965). Acta Cryst. 19, 456-463.]](../../../../../../logos/arrows/e_arr.gif "Macdonald, A. C. & Trotter, J. (1965). Acta Cryst. 19, 456-463.")
). Acta Cryst. 19, 456–463] to modern standards to establish high-precision geometrical data to compare with norbornyl and other tetracyclic 4-bromobenzoates. Possible structural evidence is sought to help explain solvolytic reactivities.
Related literature
For the previous of the title compound, see: McDonald & Trotter (1965). For a discussion, see: Coots (1983); Lloyd et al. (1995). For an analogous p-nitrobenzoate structure, see: Jones et al. (1992). For related tetracyclic 4-bromobenzoate structures, see: Lloyd et al. (2000) and references therein. For a theoretical discussion, solvolysis rates and molecular orbital calculations, see: Chow (1998). For further synthetic details, see: Coots (1983); Lloyd et al. (1993).
![[Scheme 1]](hb6776scheme1.gif)
Experimental
Crystal data
|
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, 1999), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812027882/hb6776sup1.cif
Supporting information file. DOI: https://doi.org/10.1107/S1600536812027882/hb6776Isup2.mol
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027882/hb6776Isup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812027882/hb6776Isup4.cml
Anti-7-norbornenyl 4-bromobenzoate (title compound 1) was prepared (Coots, 1983) from anti-7-norbornenol, which was made from 7-norbornenone reduction (Lloyd et al., 1993, and references therein). In 25 ml of freshly distilled (from KOH under N2) dry pyridine was dissolved 0.700 g of sublimed (373 K, 1600 Pa) anti-7-norbornenol and 1.80 g of sublimed (373 K, 7 Pa) 4-bromobenzoyl chloride was added with stirring. The mixture was heated to 373 K for 5 min and set in a refrigerator overnight. The mixture was poured into 100 ml of cold water, and extracted three times with 100 ml of ether. Combined ether extracts were washed with cold 10% H2SO4 solution, saturated NaHCO3 solution, water, and finally saturated brine solution. The ether mixture was filtered, and ether was removed on a rotary evaporator (333 K maximum, 1600 Pa). Crude 1 residue was recrystallized from hexane yielding 1.21 g (65.0% yield) of 1. (343 K, 1 Pa) further purified 1: mp 345–346 K. 1H NMR (CDCl3, 90 MHz): δ 1.10–1.14 (2 H, AB q, J= 4 Hz), 1.85 (2 H, m), 2.89 (2 H, m), 4.58 (1 H, bs), 6.08 (2 H, m), 7.56 (2 H, d, J = 9 Hz), 7.87 (2 H, d, J = 9 Hz), infrared (CCl4): 3066, 2980, 2878, 1723, 1597, 1485, 1396, 1308, 1275, 1118, 1088, 1011, 854, 760 cm-1. Anal. Calcd for C14H13BrO2: C 57.36, H 4.47. Found: C 57.11, H 4.49.
A 63.5 mg sample of 1 was dissolved by warming in 1.2 ml of freshly distilled absolute ethanol in a 10 ml beaker. The beaker was covered with aluminium foil, secured by a rubber band, and a pinhole was made in the foil for slow evaporation. About half of the ethanol had evaporated after 40 h at 296 K. A few small seed crystals were then added, which did not visibly dissolve. Crystal clumps began to grow. After 5 d total, about 0.2 ml of ethanol remained, and crystals were filtered out. One of these crystals was selected for X-ray analysis.
A colorless prism shaped crystal 0.35 × 0.33 × 0.30 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 reflections from those ten frames, indicated a monoclinic P lattice. A total of 5345 reflections (Θmax = 27.46°) were indexed, integrated and corrected for and absorption effects using DENZO– SMN and SCALEPAC (Otwinowski & Minor, 1997). Post of the gave a = 14.0633 (2) Å, b = 10.04880 (10) Å, c = 8.66680 (10) Å, β =100.0718 (7)°, and V = 1205.91 (3) 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) + (0.0214P)2 + 0.7334P] where P = (Fo2 + 2Fc2) /3. The converged to R1 = 0.0211, wR2 = 0.0494, and S = 1.052 for 2509 reflections with I > 2σ(I), and R1 = 0.0245, wR2 = 0.0508, and S = 1.052 for 2754 unique reflections and 207 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 0.002, and the residual peaks on the final difference-Fourier map ranged from -0.311 to 0.365 e/Å3. The structure was analyzed with WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Considerably improved precision is obtained for the present, low temperature structure of the title compound 1 over earlier structures. An ORTEP-3 drawing of 1 is shown in Fig. 1, and a cell packing diagram is shown in Fig. 2.
No nonhydrogen atom intermolecular contacts exist shorter than van der Waals radii sums. The closest contacts are shown in Table 1. Structure 1 least squares planes are defined as C1—C7—C4 (plane 1), C2—C3—C4—C5 (plane 2), C1—C6—C5—C4 (plane 3) and H2—C2—C3—H3 (plane 4). Structure 1 interplanar angles are compared to those of norbornyl structure 2 in Table 2.
The 2:4 angle shows that C2 and C3 are pyramidalized similarly as in other norbornenyl containing 4-bromobenzoate structures. The larger 1:2 and smaller 1:3 angle in 1 versus 2 may be a consequence of substituting an etheno bridge for an ethano bridge. The C1—C2, C2=C3, and C3—C4 bonds are shorter in 1 versus 2 as expected, but C1—C7 and C4—C7 are longer in 1 than in 2. These longer bonds possibly compensate for what might otherwise be even closer C2···C7 and C3···C7 intramolecular contacts in 1 (Table 3). A wider 1:2 angle in 1 versus 2 should also help relieve these contacts. Norbornenyl group bond lengths are all longer by 0.010 to 0.032 Å for structure 1 versus the 293 K p-nitrobenzoate ester (Jones et al.,1992). The C7—O2 bond length, 1.445 (2) Å, is shorter than in the p-nitrobenzoate, 1.458 (3) Å, but is virtually the same as that of 2, 1.447 (2) Å, and gives no indication of the huge solvolytic reactivity difference between 1 and 2 derivatives.
For the previous of the title compound, see: McDonald & Trotter (1965). For a discussion, see: Coots (1983); Lloyd et al. (1995). For an analogous p-nitrobenzoate structure, see: Jones et al. (1992). For related tetracyclic 4-bromobenzoate structures, see: Lloyd et al. (2000) and references therein. For a theoretical discussion, solvolysis rates and calculations, see: Chow (1998). For further synthetic details, see: Coots (1983); Lloyd et al. (1993).
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, 1999), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./hb6776fig1thm.gif) | Fig. 1. The molecular structure of the title compound, showing 50% displacement ellipsoids. |
![[Figure 2]](./hb6776fig2thm.gif) | Fig. 2. Packing diagram for the title compound. |
![[Figure 3]](./hb6776fig3thm.gif) | Fig. 3. Compounds 1 and 2. |
| C14H13BrO2 | F(000) = 592 |
| Mr = 293.15 | Dx = 1.615 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2911 reflections |
| a = 14.0633 (2) Å | θ = 1.0–27.5° |
| b = 10.0488 (1) Å | µ = 3.40 mm−1 |
| c = 8.6668 (1) Å | T = 150 K |
| β = 100.0718 (7)° | Prism, colourless |
| V = 1205.91 (3) Å3 | 0.35 × 0.33 × 0.30 mm |
| Z = 4 |
| Nonius KappaCCD diffractometer | 2754 independent reflections |
| Radiation source: fine-focus sealed tube | 2509 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.011 |
| Phi and ω scan | θmax = 27.5°, θmin = 2.9° |
| Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −18→18 |
| Tmin = 0.383, Tmax = 0.429 | k = −13→12 |
| 5345 measured reflections | l = −11→11 |
| 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)] = 0.021 | All H-atom parameters refined |
| wR(F2) = 0.051 | w = 1/[σ2(Fo2) + (0.0214P)2 + 0.7334P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.002 |
| 2754 reflections | Δρmax = 0.37 e Å−3 |
| 207 parameters | Δρmin = −0.31 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0136 (7) |
| C14H13BrO2 | V = 1205.91 (3) Å3 |
| Mr = 293.15 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 14.0633 (2) Å | µ = 3.40 mm−1 |
| b = 10.0488 (1) Å | T = 150 K |
| c = 8.6668 (1) Å | 0.35 × 0.33 × 0.30 mm |
| β = 100.0718 (7)° |
| Nonius KappaCCD diffractometer | 2754 independent reflections |
| Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2509 reflections with I > 2σ(I) |
| Tmin = 0.383, Tmax = 0.429 | Rint = 0.011 |
| 5345 measured reflections |
| R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
| wR(F2) = 0.051 | All H-atom parameters refined |
| S = 1.05 | Δρmax = 0.37 e Å−3 |
| 2754 reflections | Δρmin = −0.31 e Å−3 |
| 207 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 | ||
| Br1 | 0.231948 (11) | 0.573233 (17) | 0.252195 (18) | 0.02573 (7) | |
| O1 | 0.65735 (9) | 0.74458 (13) | 0.02284 (16) | 0.0335 (3) | |
| O2 | 0.70549 (8) | 0.56513 (11) | 0.17202 (13) | 0.0208 (2) | |
| C1 | 0.86438 (11) | 0.67318 (16) | 0.27173 (19) | 0.0211 (3) | |
| C2 | 0.96258 (12) | 0.64248 (18) | 0.2314 (2) | 0.0251 (3) | |
| C3 | 0.96191 (11) | 0.51593 (18) | 0.18542 (18) | 0.0240 (3) | |
| C4 | 0.86326 (11) | 0.45889 (16) | 0.19263 (18) | 0.0201 (3) | |
| C5 | 0.85573 (12) | 0.44703 (16) | 0.36921 (18) | 0.0221 (3) | |
| C6 | 0.85694 (12) | 0.59406 (17) | 0.42354 (19) | 0.0232 (3) | |
| C7 | 0.80342 (11) | 0.58488 (15) | 0.14674 (18) | 0.0189 (3) | |
| C8 | 0.63967 (11) | 0.65365 (15) | 0.10386 (18) | 0.0203 (3) | |
| C9 | 0.54164 (11) | 0.62660 (15) | 0.13984 (17) | 0.0180 (3) | |
| C10 | 0.52464 (12) | 0.53263 (16) | 0.25011 (18) | 0.0214 (3) | |
| C11 | 0.43223 (12) | 0.51475 (16) | 0.28209 (18) | 0.0218 (3) | |
| C12 | 0.35770 (11) | 0.59175 (15) | 0.20240 (17) | 0.0193 (3) | |
| C13 | 0.37227 (11) | 0.68339 (16) | 0.08950 (19) | 0.0219 (3) | |
| C14 | 0.46492 (11) | 0.69994 (16) | 0.05865 (18) | 0.0213 (3) | |
| H1 | 0.8462 (13) | 0.7672 (19) | 0.273 (2) | 0.024 (5)* | |
| H2 | 1.0163 (16) | 0.701 (2) | 0.248 (2) | 0.036 (5)* | |
| H3 | 1.0125 (16) | 0.463 (2) | 0.159 (2) | 0.034 (5)* | |
| H4 | 0.8436 (14) | 0.380 (2) | 0.131 (2) | 0.028 (5)* | |
| H5A | 0.9080 (15) | 0.3962 (19) | 0.426 (2) | 0.026 (5)* | |
| H5B | 0.7950 (15) | 0.4041 (19) | 0.381 (2) | 0.027 (5)* | |
| H6A | 0.9089 (14) | 0.615 (2) | 0.506 (2) | 0.026 (5)* | |
| H6B | 0.7984 (15) | 0.617 (2) | 0.459 (2) | 0.027 (5)* | |
| H7 | 0.8006 (13) | 0.6132 (18) | 0.037 (2) | 0.017 (4)* | |
| H14 | 0.4765 (15) | 0.761 (2) | −0.018 (2) | 0.033 (5)* | |
| H13 | 0.3204 (15) | 0.731 (2) | 0.033 (2) | 0.029 (5)* | |
| H11 | 0.4224 (15) | 0.452 (2) | 0.359 (2) | 0.030 (5)* | |
| H10 | 0.5770 (16) | 0.482 (2) | 0.304 (2) | 0.036 (5)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.01967 (10) | 0.03112 (11) | 0.02766 (10) | −0.00351 (6) | 0.00762 (6) | −0.00290 (6) |
| O1 | 0.0210 (6) | 0.0299 (7) | 0.0502 (8) | 0.0011 (5) | 0.0083 (5) | 0.0176 (6) |
| O2 | 0.0139 (5) | 0.0219 (6) | 0.0261 (5) | 0.0013 (4) | 0.0024 (4) | 0.0042 (4) |
| C1 | 0.0182 (7) | 0.0185 (7) | 0.0269 (8) | −0.0005 (6) | 0.0048 (6) | −0.0018 (6) |
| C2 | 0.0170 (7) | 0.0291 (9) | 0.0296 (8) | −0.0016 (7) | 0.0048 (6) | 0.0040 (7) |
| C3 | 0.0184 (8) | 0.0313 (9) | 0.0236 (8) | 0.0053 (7) | 0.0070 (6) | 0.0031 (7) |
| C4 | 0.0200 (7) | 0.0193 (8) | 0.0212 (7) | 0.0033 (6) | 0.0037 (6) | −0.0018 (6) |
| C5 | 0.0200 (8) | 0.0245 (8) | 0.0224 (7) | 0.0032 (6) | 0.0054 (6) | 0.0052 (6) |
| C6 | 0.0214 (8) | 0.0290 (9) | 0.0195 (7) | 0.0020 (6) | 0.0040 (6) | −0.0033 (6) |
| C7 | 0.0158 (7) | 0.0215 (8) | 0.0198 (7) | 0.0012 (6) | 0.0042 (5) | 0.0012 (6) |
| C8 | 0.0174 (7) | 0.0190 (8) | 0.0235 (7) | 0.0005 (6) | 0.0005 (6) | −0.0010 (6) |
| C9 | 0.0172 (7) | 0.0161 (7) | 0.0199 (7) | −0.0012 (6) | 0.0007 (5) | −0.0024 (6) |
| C10 | 0.0220 (8) | 0.0197 (7) | 0.0216 (7) | 0.0023 (6) | 0.0009 (6) | 0.0018 (6) |
| C11 | 0.0246 (8) | 0.0201 (8) | 0.0206 (7) | −0.0005 (6) | 0.0034 (6) | 0.0015 (6) |
| C12 | 0.0173 (7) | 0.0205 (8) | 0.0202 (7) | −0.0034 (6) | 0.0034 (6) | −0.0044 (6) |
| C13 | 0.0177 (7) | 0.0211 (8) | 0.0253 (8) | 0.0014 (6) | −0.0012 (6) | 0.0015 (6) |
| C14 | 0.0197 (7) | 0.0186 (7) | 0.0245 (7) | −0.0015 (6) | 0.0011 (6) | 0.0042 (6) |
| Br1—C12 | 1.9014 (15) | C5—H5A | 0.96 (2) |
| O1—C8 | 1.2045 (19) | C5—H5B | 0.98 (2) |
| O2—C8 | 1.3438 (18) | C6—H6A | 0.95 (2) |
| O2—C7 | 1.4454 (18) | C6—H6B | 0.96 (2) |
| C1—C2 | 1.514 (2) | C7—H7 | 0.985 (18) |
| C1—C7 | 1.540 (2) | C8—C9 | 1.491 (2) |
| C1—C6 | 1.556 (2) | C9—C14 | 1.392 (2) |
| C1—H1 | 0.979 (19) | C9—C10 | 1.394 (2) |
| C2—C3 | 1.332 (3) | C10—C11 | 1.387 (2) |
| C2—H2 | 0.95 (2) | C10—H10 | 0.95 (2) |
| C3—C4 | 1.512 (2) | C11—C12 | 1.386 (2) |
| C3—H3 | 0.95 (2) | C11—H11 | 0.95 (2) |
| C4—C7 | 1.534 (2) | C12—C13 | 1.385 (2) |
| C4—C5 | 1.557 (2) | C13—C14 | 1.385 (2) |
| C4—H4 | 0.97 (2) | C13—H13 | 0.94 (2) |
| C5—C6 | 1.550 (2) | C14—H14 | 0.94 (2) |
| C8—O2—C7 | 116.34 (12) | C1—C6—H6B | 109.7 (12) |
| C2—C1—C7 | 97.94 (12) | H6A—C6—H6B | 107.3 (16) |
| C2—C1—C6 | 106.86 (13) | O2—C7—C4 | 109.97 (12) |
| C7—C1—C6 | 100.89 (12) | O2—C7—C1 | 113.61 (12) |
| C2—C1—H1 | 116.7 (11) | C4—C7—C1 | 94.61 (12) |
| C7—C1—H1 | 116.6 (11) | O2—C7—H7 | 107.9 (10) |
| C6—C1—H1 | 115.3 (11) | C4—C7—H7 | 114.6 (11) |
| C3—C2—C1 | 107.73 (14) | C1—C7—H7 | 115.8 (11) |
| C3—C2—H2 | 127.0 (13) | O1—C8—O2 | 124.19 (14) |
| C1—C2—H2 | 124.9 (13) | O1—C8—C9 | 123.57 (14) |
| C2—C3—C4 | 107.94 (14) | O2—C8—C9 | 112.24 (13) |
| C2—C3—H3 | 129.8 (13) | C14—C9—C10 | 119.66 (14) |
| C4—C3—H3 | 122.1 (13) | C14—C9—C8 | 117.47 (14) |
| C3—C4—C7 | 98.17 (12) | C10—C9—C8 | 122.87 (14) |
| C3—C4—C5 | 106.87 (13) | C11—C10—C9 | 120.26 (14) |
| C7—C4—C5 | 100.92 (12) | C11—C10—H10 | 120.3 (13) |
| C3—C4—H4 | 117.4 (12) | C9—C10—H10 | 119.4 (13) |
| C7—C4—H4 | 116.1 (12) | C12—C11—C10 | 118.78 (15) |
| C5—C4—H4 | 114.8 (12) | C12—C11—H11 | 122.2 (13) |
| C6—C5—C4 | 103.10 (12) | C10—C11—H11 | 119.0 (13) |
| C6—C5—H5A | 112.8 (12) | C13—C12—C11 | 122.07 (15) |
| C4—C5—H5A | 111.4 (12) | C13—C12—Br1 | 118.94 (12) |
| C6—C5—H5B | 110.7 (12) | C11—C12—Br1 | 118.99 (12) |
| C4—C5—H5B | 110.2 (11) | C12—C13—C14 | 118.46 (14) |
| H5A—C5—H5B | 108.6 (16) | C12—C13—H13 | 120.9 (12) |
| C5—C6—C1 | 103.23 (12) | C14—C13—H13 | 120.6 (12) |
| C5—C6—H6A | 114.0 (12) | C13—C14—C9 | 120.74 (15) |
| C1—C6—H6A | 111.2 (12) | C13—C14—H14 | 120.0 (13) |
| C5—C6—H6B | 111.4 (12) | C9—C14—H14 | 119.2 (13) |
| C7—C1—C2—C3 | −34.61 (16) | C2—C1—C7—C4 | 52.53 (13) |
| C6—C1—C2—C3 | 69.37 (17) | C6—C1—C7—C4 | −56.44 (13) |
| C1—C2—C3—C4 | 0.40 (18) | C7—O2—C8—O1 | 1.3 (2) |
| C2—C3—C4—C7 | 34.14 (16) | C7—O2—C8—C9 | −178.68 (12) |
| C2—C3—C4—C5 | −69.96 (16) | O1—C8—C9—C14 | 8.7 (2) |
| C3—C4—C5—C6 | 66.21 (15) | O2—C8—C9—C14 | −171.27 (13) |
| C7—C4—C5—C6 | −35.90 (15) | O1—C8—C9—C10 | −171.07 (16) |
| C4—C5—C6—C1 | 0.34 (15) | O2—C8—C9—C10 | 8.9 (2) |
| C2—C1—C6—C5 | −66.69 (16) | C14—C9—C10—C11 | −1.8 (2) |
| C7—C1—C6—C5 | 35.16 (15) | C8—C9—C10—C11 | 178.00 (14) |
| C8—O2—C7—C4 | −164.96 (12) | C9—C10—C11—C12 | 0.1 (2) |
| C8—O2—C7—C1 | 90.43 (15) | C10—C11—C12—C13 | 1.6 (2) |
| C3—C4—C7—O2 | −169.53 (12) | C10—C11—C12—Br1 | −177.29 (12) |
| C5—C4—C7—O2 | −60.49 (15) | C11—C12—C13—C14 | −1.5 (2) |
| C3—C4—C7—C1 | −52.35 (13) | Br1—C12—C13—C14 | 177.42 (12) |
| C5—C4—C7—C1 | 56.70 (13) | C12—C13—C14—C9 | −0.3 (2) |
| C2—C1—C7—O2 | 166.68 (12) | C10—C9—C14—C13 | 1.9 (2) |
| C6—C1—C7—O2 | 57.71 (15) | C8—C9—C14—C13 | −177.88 (14) |
Experimental details
| Crystal data | |
| Chemical formula | C14H13BrO2 |
| Mr | 293.15 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 150 |
| a, b, c (Å) | 14.0633 (2), 10.0488 (1), 8.6668 (1) |
| β (°) | 100.0718 (7) |
| V (Å3) | 1205.91 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 3.40 |
| Crystal size (mm) | 0.35 × 0.33 × 0.30 |
| Data collection | |
| Diffractometer | Nonius KappaCCD |
| Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
| Tmin, Tmax | 0.383, 0.429 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5345, 2754, 2509 |
| Rint | 0.011 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.051, 1.05 |
| No. of reflections | 2754 |
| No. of parameters | 207 |
| H-atom treatment | All H-atom parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.37, −0.31 |
Computer programs: COLLECT (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), publCIF (Westrip, 2010).
| Contact | Distance (Å) | Contact | Distance (Å) |
| Br1i···C5vi | 3.707 (2) | Br1i···H7iv | 3.10 (2) |
| Br1i···C6vi | 3.676 (2) | O1i···H6Bv | 2.56 (2) |
| H11i···O1ii | 2.66 (2) | H14i···C11v | 2.84 (2) |
| * [symmetry codes: (ii) 1-x, -1/2+y, 1/2 -z; (iv) 1-x, 1-y, -z; (v) x, 3/2-y, -1/2+z; (vi) 1-x, 1-y, 1-z] |
| Structure | 1 : 2 | 1 : 3 | 2 : 3 | 2 : 4 |
| 1 | 124.5 (1) | 122.7 (1) | 112.8 (1) | 6 (1) |
| 2 | 121.2 (1) | 125.5 (1) | 113.3 (1) |
| Contact | Structure 1 Distance (Å) | Structure 2 Distance (Å) |
| C2···C7 | 2.304 (2) | 2.342 (2) |
| C3···C7 | 2.302 (2) | 2.343 (3) |
| C5···C7 | 2.384 (2) | 2.381 (3) |
| C6···C7 | 2.387 (2) | 2.379 (3) |
| C2···C6 | 2.466 (2) | 2.496 (3) |
| C3···C5 | 2.465 (2) | 2.495 (3) |
| H3B···H5A | 2.35 (3) | |
| H2B···H6A | 2.40 (3) |
Acknowledgements
We thank the Weber State Chemistry Department, the University of Utah Chemistry Department X-ray crystallographic facility, Professor Evan L. Allred who began this work, and Dr Robert J. Coots for synthesizing the 4-bromobenzoate ester from anti-7-norbornenol.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Considerably improved precision is obtained for the present, low temperature structure of the title compound 1 over earlier structures. An ORTEP-3 drawing of 1 is shown in Fig. 1, and a cell packing diagram is shown in Fig. 2.
No nonhydrogen atom intermolecular contacts exist shorter than van der Waals radii sums. The closest contacts are shown in Table 1. Structure 1 least squares planes are defined as C1—C7—C4 (plane 1), C2—C3—C4—C5 (plane 2), C1—C6—C5—C4 (plane 3) and H2—C2—C3—H3 (plane 4). Structure 1 interplanar angles are compared to those of norbornyl structure 2 in Table 2.
The 2:4 angle shows that C2 and C3 are pyramidalized similarly as in other norbornenyl containing 4-bromobenzoate structures. The larger 1:2 and smaller 1:3 angle in 1 versus 2 may be a consequence of substituting an etheno bridge for an ethano bridge. The C1—C2, C2=C3, and C3—C4 bonds are shorter in 1 versus 2 as expected, but C1—C7 and C4—C7 are longer in 1 than in 2. These longer bonds possibly compensate for what might otherwise be even closer C2···C7 and C3···C7 intramolecular contacts in 1 (Table 3). A wider 1:2 angle in 1 versus 2 should also help relieve these contacts. Norbornenyl group bond lengths are all longer by 0.010 to 0.032 Å for structure 1 versus the 293 K p-nitrobenzoate ester (Jones et al.,1992). The C7—O2 bond length, 1.445 (2) Å, is shorter than in the p-nitrobenzoate, 1.458 (3) Å, but is virtually the same as that of 2, 1.447 (2) Å, and gives no indication of the huge solvolytic reactivity difference between 1 and 2 derivatives.