 | Acta Crystallographica Section E Acta Crystallographica Section E CRYSTALLOGRAPHIC COMMUNICATIONS |
journal menu
organic compounds
| CRYSTALLOGRAPHIC COMMUNICATIONS |
accessendo,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.]](../../../../../../logos/arrows/e_arr.gif "Lloyd, B. A. & Arif, A. M. (2012a). Acta Cryst. E68, o2209.")
,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).
![[Scheme 1]](hb7005scheme1.gif)
Experimental
Crystal data
|
Refinement
|
|
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 (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536812051902/hb7005sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536812051902/hb7005Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812051902/hb7005Isup3.mol
Supporting information file. DOI: 10.1107/S1600536812051902/hb7005Isup4.cml
Compound 1-OPBB was synthesized via the steps shown in Fig. 4 and described below. Products were verified by 90 MHz 1H NMR spectroscopy in CDCl3 solvent. The most recent methods for synthesizing precursor compound 6 are found in Chow (1996). See also Melder & Prinzbach (1991) for substrate syntheses.
Into 70 ml of CH2Cl2 were dissolved 2.0 g of 6 and 0.1 g of 10% Pd/C was added. The mixture was stirred under H2 (~9 × 10 4 Pa) at 298 K for 12 h. The mixture was vacuum filtered to remove catalyst, and CH2Cl2 was removed under vacuum yielding 2.0 g of white powder 7: mp 400.5 - 401.5 K. 1H NMR: δ 1.58 (4H, m), 2.52 (2H, m), 3.50 (2H, m), 3.68 (3H, s), 3.75 (3H, s), 4.22 (1H, m).
Into 100 ml of absolute ethanol were dissolved 6.7 g of 7. Over a 2 h period, 19.6 g of Na (washed twice in absolute ethanol) were added as small (~0.3 g) pieces under a dry, N2 atmosphere while refluxing and mechanically stirring. After 6 h the mixture was cooled to 298 K and 200 g of crushed ice were slowly and cautiously added while stirring. The mixture was extracted with 3 × 100 ml of ether, and combined ether extracts were washed with water, saturated brine, and dried over MgSO4. Solvent removal under vacuum yielded 3.2 g (85%) of pale yellow oil 8. 1H NMR: δ 1.22 (4H, bs), 1.28 (1H, m), 1.46 (1H, d, J \sim 9 Hz), 2.09 (2H, bs), 2.41 (2H, m), 2.72 (2H, m), 3.13 (3H, s), 3.18 (3H, s), 6.03 (2H, m).
Into 50 ml of tetrahydrofuran were dissolved 3.0 g of 8. The solution was cooled to 273 K and poured into 35 ml of 20% aqueous HClO4 in an ice bath. The mixture warmed to 298 K overnight, was then poured into 100 ml of water, and extracted with 3 × 50 ml of ether. Combined ether extracts were washed with water, saturated NaHCO3, saturated brine, and dried over MgSO4. Ether was evaporated under vacuum yielding 2.2 g of colorless oil 9 that crystallized upon standing: mp 330.0–331.5 K. 1H NMR: δ 1.18 (4H, bs), 1.29 (2H, m), 2.23 (2H, m), 2.32 (2H, m), 2.93 (2H, m), 6.34 (2H, m).
Into 100 ml of absolute ether were placed 0.126 g of LiAlH4 under a dry N2 atmosphere. After stirring for 1 h at 298 K, the mixture was cooled to 195 K and a 2.1 g solution of 9 in 20 ml of absolute ether was slowly added over 30 min. The mixture was stirred for 1 h at 195 K, and allowed to warm up overnight. Excess LiAlH4 was then neutralized by slowly adding 0.9 ml of saturated aqueous NH4Cl and stirring 30 min. About 1 g of MgSO4 was added and the mixture stirred 30 min more. Vacuum filtration removed solids. Ether was evaporated under vacuum, yielding 1.5 g (70%) of white 1-OH crystals which were further purified by preparative (1.5 m × 0.0063 m stainless steel column, 20% DEGS on 60/80 Chromosorb W AW, injector 483 K, column 438 K, detector 483 K, He carrier 75 ml/min, 1-OH 5.85 min): mp 406.5–407.5 K. 1H NMR: δ 1.28 (4H, bs), 1.40 (1H, d, J~9 Hz), 1.66 (1H, d, J~9 Hz), 1.92 (1H, bs), 2.13 (2H, m), 2.44 (2H, m), 2.54 (2H, m), 3.72 (1H, bs), 5.98 (2H, m). 13C NMR (CDCl3, 20 MHz): δ 25.9, 39.4, 46.0, 47.46, 47.50, 90.7, 129.8.
Into 5 ml of freshly distilled dry pyridine (from CaH2) were dissolved 0.086 g of pure 1-OH, and 0.14 g of freshly recrystallized (from hexanes) 4-bromobenzoyl chloride with stirring under a dry N2 atmosphere. The mixture was warmed briefly until reagents dissolved, and stirred overnight at 298 K. The mixture was poured into 100 ml of cold water, and extracted with 2 × 50 ml of ether. Combined ether extracts were washed with water, twice with 10% HCl, twice with NaHCO3, and with saturated brine. The ether solution was dried over MgSO4, filtered, and ether was evaporated under vacuum, yielding crude 1-OPBB. Recrystallization from a 1:4 CHCl3 / hexane mixture yielded 0.15 g (86%) of white 1-OPBB crystals. These were dissolved in ~5 ml of CH2Cl2 and passed down a 0.05 m × 0.005 m silica gel column, eluting with distilled CH2Cl2, and solvent was evaporated. The residual white crystals were sublimed (353 K, 1.3 Pa) yielding pure white 1-OPBB crystals: mp 409.5–410.5 K. 1H NMR: δ 1.30 (4H, bs), 1.43 (1H, d, J~9 Hz), 1.68 (1H, d, J~9 Hz), 2.18 (2H, m), 2.65 (2H, m), 2.83 (2H, m), 4.76 (1H, bs), 6.21 (2H, m), 7.76 (2H, d, J~9 Hz), 8.05 (2H, d, J~9 Hz).
About 0.1 g of sublimed 1-OPBB was dissolved in 15 ml of absolute ethanol by warming on a steam bath for 5 min. This solution was placed in a crystallizing dish and covered with plastic wrap. Three small holes were made in the plastic wrap with a hot wire and ethanol slowly evaporated at 298 K. About ten crystals were eventually removed from the evaporating dish, and one of these was selected for the X-ray structure analysis.
A colorless plate shaped crystal 0.23 × 0.20 × 0.13 mm in size was mounted on a quartz fiber with epoxy resin, and 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 6702 reflections (Θmax = 27.49°) were indexed, integrated and corrected for and absorption effects using DENZO– SMN and SCALEPAC (Otwinowski & Minor, 1997). Post of the gave a = 13.2569 (2) Å, b = 10.5045 (2) Å, c = 12.2039 (2) Å, β = 116.0122 (9)°, and V = 1527.32 (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) + (0.0223P)2 + 0.8628P] where P = (Fo2 + 2Fc2) /3. The converged to R1 = 0.0276, wR2 = 0.0577, and S = 1.029 for 2700 reflections with I > 2σ(I), and R1 = 0.0452, wR2 = 0.0632 and S = 1.029 for 3500 unique reflections and 276 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 -0.457 to 0.397 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 (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).
![[Figure 1]](./hb7005fig1thm.gif) | Fig. 1. ORTEP-3 drawing of the title compound showing 50% displacement ellipsoids. |
![[Figure 2]](./hb7005fig2thm.gif) | Fig. 2. Cell packing diagram for the title compound. |
![[Figure 3]](./hb7005fig3thm.gif) | Fig. 3. Compound 1- to 5-OPBB structures. |
![[Figure 4]](./hb7005fig4thm.gif) | Fig. 4. Synthesis scheme for 1-OPBB. |
| C19H19BrO2 | F(000) = 736 |
| Mr = 359.25 | Dx = 1.562 Mg m−3 |
| Monoclinic, P21/c | Melting point = 409.5–410.5 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 13.2569 (2) Å | Cell parameters from 3686 reflections |
| b = 10.5045 (2) Å | θ = 1.0–27.5° |
| c = 12.2039 (2) Å | µ = 2.70 mm−1 |
| β = 116.0122 (9)° | T = 150 K |
| V = 1527.32 (4) Å3 | Plate, colourless |
| Z = 4 | 0.23 × 0.20 × 0.13 mm |
| Nonius KappaCCD diffractometer | 3500 independent reflections |
| Radiation source: fine-focus sealed tube | 2700 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.021 |
| Phi and ω scan | θmax = 27.5°, θmin = 2.6° |
| Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −17→17 |
| Tmin = 0.576, Tmax = 0.721 | k = −13→13 |
| 6702 measured reflections | l = −15→15 |
| 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)] = 0.028 | All H-atom parameters refined |
| wR(F2) = 0.063 | w = 1/[σ2(Fo2) + (0.0223P)2 + 0.8628P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max = 0.001 |
| 3500 reflections | Δρmax = 0.40 e Å−3 |
| 276 parameters | Δρmin = −0.46 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: 0.0021 (3) |
| C19H19BrO2 | V = 1527.32 (4) Å3 |
| Mr = 359.25 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 13.2569 (2) Å | µ = 2.70 mm−1 |
| b = 10.5045 (2) Å | T = 150 K |
| c = 12.2039 (2) Å | 0.23 × 0.20 × 0.13 mm |
| β = 116.0122 (9)° |
| Nonius KappaCCD diffractometer | 3500 independent reflections |
| Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2700 reflections with I > 2σ(I) |
| Tmin = 0.576, Tmax = 0.721 | Rint = 0.021 |
| 6702 measured reflections |
| R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
| wR(F2) = 0.063 | All H-atom parameters refined |
| S = 1.03 | Δρmax = 0.40 e Å−3 |
| 3500 reflections | Δρmin = −0.46 e Å−3 |
| 276 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 >σ2(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 | 0.398775 (17) | 0.50046 (2) | 0.33147 (2) | 0.03521 (8) | |
| O1 | 0.39056 (11) | −0.15520 (13) | 0.34637 (12) | 0.0279 (3) | |
| O2 | 0.29976 (11) | −0.10151 (12) | 0.45837 (12) | 0.0242 (3) | |
| C1 | 0.22157 (16) | −0.24807 (18) | 0.55731 (16) | 0.0229 (4) | |
| C2 | 0.11279 (15) | −0.16903 (17) | 0.48370 (16) | 0.0206 (4) | |
| C3 | −0.00178 (16) | −0.18682 (18) | 0.48681 (17) | 0.0247 (4) | |
| C4 | −0.04236 (18) | −0.3253 (2) | 0.47273 (18) | 0.0271 (4) | |
| C5 | −0.06898 (17) | −0.3574 (2) | 0.33847 (18) | 0.0263 (4) | |
| C6 | −0.04154 (16) | −0.23344 (18) | 0.29110 (17) | 0.0242 (4) | |
| C7 | 0.08449 (15) | −0.20150 (17) | 0.34772 (16) | 0.0202 (4) | |
| C8 | 0.17988 (15) | −0.29568 (18) | 0.36060 (17) | 0.0215 (4) | |
| C9 | 0.17465 (16) | −0.41722 (18) | 0.42422 (18) | 0.0245 (4) | |
| C10 | 0.19923 (16) | −0.38922 (18) | 0.53953 (18) | 0.0256 (4) | |
| C11 | 0.27888 (16) | −0.23479 (17) | 0.47187 (17) | 0.0224 (4) | |
| C12 | −0.07986 (17) | −0.1352 (2) | 0.35926 (19) | 0.0283 (4) | |
| C13 | 0.35672 (14) | −0.07544 (18) | 0.39376 (16) | 0.0220 (4) | |
| C14 | 0.37096 (14) | 0.06479 (18) | 0.38565 (16) | 0.0205 (4) | |
| C15 | 0.41471 (16) | 0.1085 (2) | 0.30735 (18) | 0.0270 (4) | |
| C16 | 0.42547 (16) | 0.2376 (2) | 0.29232 (18) | 0.0282 (4) | |
| C17 | 0.39139 (15) | 0.32290 (19) | 0.35609 (17) | 0.0251 (4) | |
| C18 | 0.35028 (16) | 0.28140 (19) | 0.43685 (18) | 0.0256 (4) | |
| C19 | 0.33979 (16) | 0.15274 (19) | 0.45069 (17) | 0.0235 (4) | |
| H1 | 0.2663 (16) | −0.2218 (18) | 0.6399 (18) | 0.023 (5)* | |
| H2 | 0.1343 (15) | −0.0796 (19) | 0.4998 (16) | 0.017 (5)* | |
| H3 | −0.0063 (16) | −0.143 (2) | 0.5549 (18) | 0.026 (5)* | |
| H4A | −0.1142 (19) | −0.326 (2) | 0.4858 (19) | 0.038 (6)* | |
| H4B | 0.0117 (17) | −0.381 (2) | 0.5314 (18) | 0.025 (5)* | |
| H5A | −0.1481 (19) | −0.375 (2) | 0.2916 (19) | 0.032 (6)* | |
| H5B | −0.0256 (18) | −0.431 (2) | 0.3317 (19) | 0.033 (6)* | |
| H6 | −0.0785 (18) | −0.225 (2) | 0.203 (2) | 0.034 (6)* | |
| H7 | 0.0949 (16) | −0.1252 (19) | 0.3064 (17) | 0.021 (5)* | |
| H8 | 0.1927 (17) | −0.3042 (19) | 0.2898 (19) | 0.030 (5)* | |
| H9 | 0.1568 (18) | −0.498 (2) | 0.3870 (19) | 0.032 (6)* | |
| H10 | 0.1999 (19) | −0.444 (2) | 0.601 (2) | 0.039 (6)* | |
| H11 | 0.3488 (18) | −0.279 (2) | 0.4991 (18) | 0.030 (6)* | |
| H12A | −0.1611 (19) | −0.143 (2) | 0.3404 (19) | 0.035 (6)* | |
| H12B | −0.0617 (18) | −0.050 (2) | 0.3443 (18) | 0.030 (5)* | |
| H15 | 0.4371 (18) | 0.046 (2) | 0.2652 (19) | 0.031 (6)* | |
| H16 | 0.4559 (18) | 0.268 (2) | 0.2405 (19) | 0.031 (6)* | |
| H18 | 0.3300 (17) | 0.338 (2) | 0.4785 (19) | 0.029 (6)* | |
| H19 | 0.3133 (16) | 0.1248 (19) | 0.5017 (18) | 0.022 (5)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.03566 (13) | 0.02801 (12) | 0.04882 (14) | 0.00147 (9) | 0.02486 (10) | 0.01104 (10) |
| O1 | 0.0274 (7) | 0.0271 (8) | 0.0316 (8) | −0.0003 (6) | 0.0152 (6) | −0.0057 (6) |
| O2 | 0.0253 (7) | 0.0204 (7) | 0.0312 (7) | −0.0038 (5) | 0.0163 (6) | −0.0024 (5) |
| C1 | 0.0270 (10) | 0.0230 (10) | 0.0163 (9) | −0.0028 (8) | 0.0072 (8) | −0.0019 (7) |
| C2 | 0.0246 (9) | 0.0169 (9) | 0.0204 (9) | −0.0021 (7) | 0.0101 (7) | −0.0015 (7) |
| C3 | 0.0284 (10) | 0.0245 (10) | 0.0245 (10) | −0.0017 (9) | 0.0147 (8) | −0.0039 (8) |
| C4 | 0.0296 (10) | 0.0272 (11) | 0.0270 (10) | −0.0055 (9) | 0.0146 (8) | 0.0000 (8) |
| C5 | 0.0240 (10) | 0.0263 (11) | 0.0257 (10) | −0.0058 (9) | 0.0081 (8) | −0.0034 (8) |
| C6 | 0.0244 (10) | 0.0255 (10) | 0.0192 (9) | −0.0008 (8) | 0.0064 (8) | 0.0031 (7) |
| C7 | 0.0243 (9) | 0.0181 (9) | 0.0188 (9) | −0.0002 (7) | 0.0101 (7) | 0.0029 (7) |
| C8 | 0.0261 (10) | 0.0205 (9) | 0.0202 (9) | −0.0001 (8) | 0.0123 (8) | −0.0012 (7) |
| C9 | 0.0261 (10) | 0.0176 (9) | 0.0290 (10) | −0.0005 (8) | 0.0114 (8) | −0.0024 (8) |
| C10 | 0.0272 (10) | 0.0209 (10) | 0.0263 (10) | 0.0004 (8) | 0.0096 (8) | 0.0058 (8) |
| C11 | 0.0240 (10) | 0.0169 (9) | 0.0263 (10) | −0.0008 (8) | 0.0111 (8) | −0.0006 (7) |
| C12 | 0.0248 (11) | 0.0252 (11) | 0.0342 (11) | 0.0011 (8) | 0.0124 (9) | 0.0016 (9) |
| C13 | 0.0153 (9) | 0.0279 (10) | 0.0187 (9) | −0.0018 (8) | 0.0036 (7) | −0.0011 (8) |
| C14 | 0.0138 (9) | 0.0263 (10) | 0.0183 (9) | −0.0006 (7) | 0.0043 (7) | 0.0006 (7) |
| C15 | 0.0227 (10) | 0.0325 (12) | 0.0291 (10) | 0.0005 (8) | 0.0145 (8) | −0.0027 (9) |
| C16 | 0.0248 (10) | 0.0340 (12) | 0.0308 (11) | −0.0016 (9) | 0.0167 (9) | 0.0047 (9) |
| C17 | 0.0190 (9) | 0.0261 (10) | 0.0277 (10) | 0.0004 (8) | 0.0080 (8) | 0.0061 (8) |
| C18 | 0.0248 (10) | 0.0270 (11) | 0.0274 (10) | 0.0015 (8) | 0.0136 (8) | −0.0002 (8) |
| C19 | 0.0230 (10) | 0.0275 (11) | 0.0226 (9) | −0.0017 (8) | 0.0124 (8) | 0.0030 (8) |
| Br1—C17 | 1.8986 (19) | C7—C8 | 1.558 (3) |
| O1—C13 | 1.211 (2) | C7—H7 | 0.989 (19) |
| O2—C13 | 1.338 (2) | C8—C9 | 1.512 (3) |
| O2—C11 | 1.450 (2) | C8—C11 | 1.553 (3) |
| C1—C10 | 1.509 (3) | C8—H8 | 0.96 (2) |
| C1—C11 | 1.542 (2) | C9—C10 | 1.331 (3) |
| C1—C2 | 1.562 (3) | C9—H9 | 0.95 (2) |
| C1—H1 | 0.96 (2) | C10—H10 | 0.94 (2) |
| C2—C3 | 1.547 (3) | C11—H11 | 0.96 (2) |
| C2—C7 | 1.570 (2) | C12—H12A | 1.00 (2) |
| C2—H2 | 0.977 (19) | C12—H12B | 0.96 (2) |
| C3—C4 | 1.534 (3) | C13—C14 | 1.494 (3) |
| C3—C12 | 1.541 (3) | C14—C19 | 1.393 (3) |
| C3—H3 | 0.98 (2) | C14—C15 | 1.395 (3) |
| C4—C5 | 1.554 (3) | C15—C16 | 1.384 (3) |
| C4—H4A | 1.03 (2) | C15—H15 | 0.96 (2) |
| C4—H4B | 0.96 (2) | C16—C17 | 1.386 (3) |
| C5—C6 | 1.532 (3) | C16—H16 | 0.94 (2) |
| C5—H5A | 0.97 (2) | C17—C18 | 1.389 (3) |
| C5—H5B | 0.98 (2) | C18—C19 | 1.377 (3) |
| C6—C7 | 1.539 (3) | C18—H18 | 0.90 (2) |
| C6—C12 | 1.545 (3) | C19—H19 | 0.89 (2) |
| C6—H6 | 0.97 (2) | ||
| C13—O2—C11 | 116.73 (14) | C9—C8—C7 | 111.72 (15) |
| C10—C1—C11 | 96.63 (15) | C11—C8—C7 | 99.44 (14) |
| C10—C1—C2 | 111.48 (15) | C9—C8—H8 | 116.9 (12) |
| C11—C1—C2 | 99.63 (14) | C11—C8—H8 | 114.3 (12) |
| C10—C1—H1 | 115.2 (12) | C7—C8—H8 | 115.3 (12) |
| C11—C1—H1 | 115.1 (12) | C10—C9—C8 | 108.14 (17) |
| C2—C1—H1 | 116.1 (12) | C10—C9—H9 | 126.9 (13) |
| C3—C2—C1 | 126.18 (16) | C8—C9—H9 | 125.0 (13) |
| C3—C2—C7 | 102.57 (14) | C9—C10—C1 | 108.11 (17) |
| C1—C2—C7 | 102.99 (14) | C9—C10—H10 | 128.1 (14) |
| C3—C2—H2 | 108.3 (11) | C1—C10—H10 | 123.8 (14) |
| C1—C2—H2 | 106.3 (11) | O2—C11—C1 | 109.83 (14) |
| C7—C2—H2 | 109.6 (11) | O2—C11—C8 | 115.36 (15) |
| C4—C3—C12 | 100.00 (16) | C1—C11—C8 | 94.35 (14) |
| C4—C3—C2 | 114.30 (16) | O2—C11—H11 | 107.6 (13) |
| C12—C3—C2 | 99.46 (15) | C1—C11—H11 | 114.3 (12) |
| C4—C3—H3 | 113.4 (12) | C8—C11—H11 | 115.1 (13) |
| C12—C3—H3 | 115.3 (12) | C3—C12—C6 | 94.28 (15) |
| C2—C3—H3 | 113.0 (12) | C3—C12—H12A | 112.4 (12) |
| C3—C4—C5 | 103.31 (15) | C6—C12—H12A | 113.3 (12) |
| C3—C4—H4A | 107.0 (12) | C3—C12—H12B | 113.9 (13) |
| C5—C4—H4A | 111.3 (12) | C6—C12—H12B | 110.4 (13) |
| C3—C4—H4B | 112.8 (12) | H12A—C12—H12B | 111.5 (18) |
| C5—C4—H4B | 113.7 (12) | O1—C13—O2 | 124.28 (17) |
| H4A—C4—H4B | 108.5 (16) | O1—C13—C14 | 124.53 (17) |
| C6—C5—C4 | 103.38 (16) | O2—C13—C14 | 111.18 (16) |
| C6—C5—H5A | 108.5 (13) | C19—C14—C15 | 119.22 (18) |
| C4—C5—H5A | 110.6 (12) | C19—C14—C13 | 122.57 (17) |
| C6—C5—H5B | 112.8 (13) | C15—C14—C13 | 118.19 (17) |
| C4—C5—H5B | 112.8 (12) | C16—C15—C14 | 120.73 (19) |
| H5A—C5—H5B | 108.7 (18) | C16—C15—H15 | 121.7 (13) |
| C5—C6—C7 | 113.99 (16) | C14—C15—H15 | 117.6 (13) |
| C5—C6—C12 | 100.17 (16) | C15—C16—C17 | 118.77 (19) |
| C7—C6—C12 | 99.27 (15) | C15—C16—H16 | 121.4 (13) |
| C5—C6—H6 | 114.0 (13) | C17—C16—H16 | 119.9 (13) |
| C7—C6—H6 | 113.5 (12) | C16—C17—C18 | 121.42 (19) |
| C12—C6—H6 | 114.2 (13) | C16—C17—Br1 | 119.62 (15) |
| C6—C7—C8 | 125.45 (16) | C18—C17—Br1 | 118.95 (15) |
| C6—C7—C2 | 103.35 (14) | C19—C18—C17 | 119.16 (19) |
| C8—C7—C2 | 102.95 (14) | C19—C18—H18 | 120.7 (13) |
| C6—C7—H7 | 108.4 (11) | C17—C18—H18 | 120.1 (13) |
| C8—C7—H7 | 106.1 (11) | C18—C19—C14 | 120.66 (18) |
| C2—C7—H7 | 110.0 (11) | C18—C19—H19 | 120.2 (13) |
| C9—C8—C11 | 96.33 (14) | C14—C19—H19 | 119.1 (13) |
| C10—C1—C2—C3 | 51.8 (2) | C13—O2—C11—C1 | 175.24 (15) |
| C11—C1—C2—C3 | 152.94 (17) | C13—O2—C11—C8 | −79.7 (2) |
| C10—C1—C2—C7 | −64.62 (18) | C10—C1—C11—O2 | 173.37 (14) |
| C11—C1—C2—C7 | 36.49 (16) | C2—C1—C11—O2 | 60.18 (17) |
| C1—C2—C3—C4 | −48.0 (2) | C10—C1—C11—C8 | 54.41 (15) |
| C7—C2—C3—C4 | 68.68 (19) | C2—C1—C11—C8 | −58.77 (15) |
| C1—C2—C3—C12 | −153.53 (17) | C9—C8—C11—O2 | −168.60 (15) |
| C7—C2—C3—C12 | −36.89 (17) | C7—C8—C11—O2 | −55.28 (18) |
| C12—C3—C4—C5 | 36.59 (19) | C9—C8—C11—C1 | −54.24 (15) |
| C2—C3—C4—C5 | −68.6 (2) | C7—C8—C11—C1 | 59.08 (15) |
| C3—C4—C5—C6 | −0.5 (2) | C4—C3—C12—C6 | −57.68 (17) |
| C4—C5—C6—C7 | 69.3 (2) | C2—C3—C12—C6 | 59.25 (16) |
| C4—C5—C6—C12 | −35.73 (19) | C5—C6—C12—C3 | 57.45 (17) |
| C5—C6—C7—C8 | 48.1 (2) | C7—C6—C12—C3 | −59.15 (16) |
| C12—C6—C7—C8 | 153.65 (17) | C11—O2—C13—O1 | 0.4 (2) |
| C5—C6—C7—C2 | −68.78 (19) | C11—O2—C13—C14 | 179.24 (14) |
| C12—C6—C7—C2 | 36.79 (17) | O1—C13—C14—C19 | −173.99 (17) |
| C3—C2—C7—C6 | −0.02 (17) | O2—C13—C14—C19 | 7.2 (2) |
| C1—C2—C7—C6 | 132.22 (15) | O1—C13—C14—C15 | 7.6 (3) |
| C3—C2—C7—C8 | −131.80 (15) | O2—C13—C14—C15 | −171.21 (16) |
| C1—C2—C7—C8 | 0.43 (17) | C19—C14—C15—C16 | −1.1 (3) |
| C6—C7—C8—C9 | −53.2 (2) | C13—C14—C15—C16 | 177.33 (17) |
| C2—C7—C8—C9 | 63.86 (18) | C14—C15—C16—C17 | −0.3 (3) |
| C6—C7—C8—C11 | −153.94 (16) | C15—C16—C17—C18 | 2.0 (3) |
| C2—C7—C8—C11 | −36.89 (16) | C15—C16—C17—Br1 | −177.12 (15) |
| C11—C8—C9—C10 | 35.27 (19) | C16—C17—C18—C19 | −2.2 (3) |
| C7—C8—C9—C10 | −67.5 (2) | Br1—C17—C18—C19 | 176.96 (14) |
| C8—C9—C10—C1 | 0.1 (2) | C17—C18—C19—C14 | 0.6 (3) |
| C11—C1—C10—C9 | −35.77 (19) | C15—C14—C19—C18 | 1.0 (3) |
| C2—C1—C10—C9 | 67.3 (2) | C13—C14—C19—C18 | −177.42 (17) |
Experimental details
| Crystal data | |
| Chemical formula | C19H19BrO2 |
| Mr | 359.25 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 150 |
| a, b, c (Å) | 13.2569 (2), 10.5045 (2), 12.2039 (2) |
| β (°) | 116.0122 (9) |
| V (Å3) | 1527.32 (4) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 2.70 |
| Crystal size (mm) | 0.23 × 0.20 × 0.13 |
| Data collection | |
| Diffractometer | Nonius KappaCCD diffractometer |
| Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
| Tmin, Tmax | 0.576, 0.721 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6702, 3500, 2700 |
| Rint | 0.021 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.063, 1.03 |
| No. of reflections | 3500 |
| No. of parameters | 276 |
| H-atom treatment | All H-atom parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.40, −0.46 |
Computer programs: COLLECT (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 2012), ORTEP-3 (Farrugia, 2012) and PLATON (Spek, 2009), Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).
| 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. |
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. Web of Science CrossRef CAS IUCr Journals Google Scholar
Chow, T. J. (1996). J. Chin. Chem. Soc. (Tapei), 43, 101–107. CAS Google Scholar
Chow, T. J. (1998). J. Phys. Org. Chem. 11, 871–878. CrossRef CAS Google Scholar
Chow, T. J. (1999). Advances in Strained and Interesting Organic Molecules, Suppl. 1, Carbocyclic and Cage Compounds and their Building Blocks, pp. 87–107. Google Scholar
Chow, T. J. & Jiang, T.-S. (2000). Synth. Commun. 30, 4473–4478. Web of Science CrossRef CAS Google Scholar
Coots, R. J. (1983). PhD dissertation, University of Utah, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Furusaki, A. & Matsumoto, T. (1978). Bull. Chem. Soc. Jpn, 51, 16–20. CrossRef CAS Web of Science Google Scholar
Lloyd, B. A. & Arif, A. M. (2012a). Acta Cryst. E68, o2209. CSD CrossRef IUCr Journals Google Scholar
Lloyd, B. A. & Arif, A. M. (2012b). Acta Cryst. E68, o3086–o3087. CSD CrossRef IUCr Journals Google Scholar
Lloyd, B. A., Arif, A. M., Coots, R. J. & Allred, E. L. (1994). Acta Cryst. C50, 777–781. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Lloyd, B. A., Arif, A. M., Coots, R. J. & Allred, E. L. (1995). Acta Cryst. C51, 2059–2062. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
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. Web of Science CrossRef CAS IUCr Journals Google Scholar
Melder, J.-P. & Prinzbach, H. (1991). Chem. Ber. 124, 1271–1289. CrossRef CAS Web of Science Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
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. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
| CRYSTALLOGRAPHIC COMMUNICATIONS |
An ORTEP-3 drawing (Farrugia, 2012) and a cell packing diagram of the title compound, 1-OPBB, are shown in Figs. 1 and 2, respectively. A Cambridge Structural Database search found only one other structure (2-OPBB) containing this tetracyclic monoene structure (Lloyd et al., 1995).
3,5-Dinitrobenzoate esters 1-, 2- and 3-ODNB (Fig. 3) solvolyze faster (Table 1) in 80% dioxane-d8/20% D2O at 383 K than 4-ODNB (Coots, 1983). The 1-ODNB rate increase was explained by long range σ-orbital through-space and through-bond mixing with the homoconjugated π-system, that stabilizes the intermediate carbocation (Chow & Jiang, 2000, Chow, 1999, Chow, 1998, Furusaki & Matsumoto, 1978). The 1-OPBB X-ray crystal structure provides experimental verification for some of the calculated results.
No nonhydrogen atom intermolecular contacts exist in 1-OPBB shorter than van der Waals radii sums, the closest being C13i···C14ii at 3.430 (3) Å [symmetry code: (ii) 1 - x, -y, 1 - z]. The closest tetracyclic hydrogen intermolecular contact is H3i···H12Biii 2.34 (3) Å [symmetry code (iii) -x, -y, 1 - z]. Least squares planes are defined as C1—C11—C8 (plane 1), C1—C10—C9—C8 (plane 2), C1—C2—C7—C8 (plane 3), C2—C3—C6—C7 (plane 4), C3—C4—C5—C6 (plane 5), C3—C12—C6 (plane 6), H9—C9—C10—H10 (plane 7), C14—C15—C16—C17—C18—C19 (plane 8) and O1—C13—O2 (plane 9). Interplanar angles are: 1:2 121.9 (2)°, 1:3 119.9 (1)°, 2:3 118.2 (1)°, 3:4 132.0 (1)°, 4:5 119.1 (1)°, 4:6 119.6 (1)°, 5:6 121.4 (1)°, and 8:9 8.5 (2)o. The largest carbon atom deviation from planarity is 0.003 (1) Å in plane 5. The greatest difference between symmetry-related bond lengths is 0.011 (4) Å (for C1—C11 versus C8—C11, and between symmetry-related bond angles is 0.78 (20)° (between C2—C7—C6 and C3—C2—C7). Bonds C1—C2, C2—C7, C4—C5 and C7—C8 are somewhat longer than usual, similar to analogous bonds in 2- (Lloyd et al., 1995), isomeric 3- (Lloyd, et al., 1994), 4-, and 5-OPBB (Lloyd & Arif, 2012a,b). Less alkenic C pyramidalization is apparent in 1-OPBB (2:7 angle 2 (1)°) than in 3-OPBB (comparable 2:4 angle (6 (1)°).
The 1:2 interplanar angle (Table 1) is a logical structure/solvolysis reactivity indicator for these compounds. A smaller angle should portend faster solvolysis as the homoconjugated π-bond provides anchimeric assistance. Solvolytic reactivities are inverse to 1:2 angles for 1-, 2-, 3-, and 4-OPBB, but differences are small relative to the calculated ~30° substrate to transition state 1:2 angle bending (Chow, 1999 and Chow, 1998), and other structural features are certainly involved. The 1-OPBB 3:4 angle is near that of endo,endo 2-OPBB, and larger than in 3-OPBB, consistent with more interbridge C4—C5···C9═C10 steric repulsion in endo,endo than in endo,exo structures. The 1-OPBB 4:6 angle is 1.9 (5)° larger, and the 5:6 angle is 5.2 (8)° smaller than in 2-OPBB, which probably reflects the close C12···C13 contact (2.70 (1) Å) in the latter. A longer C11—O2 (structures 1-, 2-, 3-OPBB) or C7—O2 (structures 4- and 5-OPBB) bond should also imply faster solvolysis, but they do not fit the expected pattern for 3- and 5-OPBB.
Short intramolecular van der Waals contacts demonstrate C4—C5···C9═C10 and C9═C10···C11 steric interactions: C4···C10 3.014 (4), C5···C9 2.993 (3), H5B···C9 2.39 (3), H4B···C10 2.45 (3), C9···C11 2.284 (3) and C10···C11 2.279 (3) Å. Theoretical values for 1-Cl (Chow, 1999 and Chow, 1998) agree closely: C4···C10 (and C5···C9) 2.94 (semiempirical AM1) or 3.00 Å (ab initio HF/3–21 G), C9···C11 (and C10···C11) 2.33 (AM1) or 2.30 Å (HF/3–21 G), and interplanar 1:2 angle 122° (HF/3–21 G).