Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012056/bk1498sup1.cif | |
Structure factor file (SHELXL table format) https://doi.org/10.1107/S0108270199012056/bk1498Isup2.sft | |
Structure factor file (SHELXL table format) https://doi.org/10.1107/S0108270199012056/bk1498IIsup3.sft |
CCDC references: 140966; 140967
A Pyrex irradiation vessel equipped with argon inlet and Teflon-coated magnetic stirbar was charged with benzene (56 ml), 9-phenylanthracene (151 mg, 0.59 mmol), and 1,3-cyclohexadiene (5.9 ml, 1.0 M) (Kaupp & Teufel, 1980). The solution was deaerated by purging with argon for 30 min prior to irradiation. Irradiation of the solution was performed with stirring under argon, using a Hanovia 450 W medium pressure mercury lamp housed in a water-cooled quartz immersion well. A cylindrical uranium glass filter was used to cut off light with wavelengths shorter than about 330 nm. The temperature of the solution during irradiation was maintained at 292 + 2 K. Progress of the reaction was monitored by means of thin-layer chromatography and NMR spectroscopic analysis. When complete (3 h), the irradiation was stopped and the solvent was evaporated under reduced pressure. The crude product was chromatographed over Woelm (activity I) alumina. Products eluted fractionally with dichloromethane and petroleum ether. Fractions determined to contain adduct (I) were combined and recrystallized from dichloromethane-ethanol to afford colorless prisms, m.p. 459 K, proton NMR (chloroform-d): 7.56 (m), 7.47 (m), 7.31 (m), 7.11 (m), 6.92 (m), 6.25 (d, 7.7 Hz), 5.78 (m), 5.68 (m), 4.18 (d, 1.9 Hz), 3.07 (bd, 10.0 Hz), 2.42 (m), 1.88 (m), 1.67 (m), 1.23 (m), 0.84 p.p.m. (m). Adduct (I) (100 mg) was dissolved in 50 ml e thyl acetate in a 100 ml round-bottom flask containing a magnetic stirbar, and 25 mg 10% Pd/C powder was added. The stirred suspension was deaerated by repeated evacuation and charging with hydrogen gas. Hydrogenation was effected by allowing the mixture to stir for 24 h at room temperature under a slight positive pressure of hydrogen (although the initial uptake of hydrogen was rapid, suggesting that the reaction probably was complete in about 30 min). The product was collected by filtration through celite, and the solvent was removed at reduced pressure. The crude product was passed through a short column of Woelm alumina (ICN, activity I) eluting with dichloromethane-petroleum ether. Fractions containing product (II) were combined and recrystallized from ethyl acetate to afford 87 mg (86%) of colorless needles, proton NMR (chloroform-d): 7.55 (m), 7.42 (m), 7.32 (m), 7.05–7.19 (m), 6.91 (m), 6.20 (d, 8.1 Hz), 4.06 (d, 8.1), 2.46 (m), 2.04 (m), 1.64 (m), 1.27- 1.53 (m), 0.78 (m), 0.22 (m).
H atoms were were located but not refined; for (I) the temperature factors of hydrogen were refined in the early stages of refinement, but were fixed in the later stages.
For both compounds, data collection: CAD-4-PC (Enraf-Nonius, 1993); cell refinement: SET4 and CELDIM in CAD-4-PC; data reduction: DATRD2 in NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SOLVER in NRCVAX; program(s) used to refine structure: LSTSQ in NRCVAX; molecular graphics: NRCVAX; software used to prepare material for publication: TABLES in NRCVAX (January 94 version).
C26H22 | F(000) = 356.10 |
Mr = 334.46 | ? #Insert any comments here. |
Triclinic, P1 | Dx = 1.248 Mg m−3 |
a = 9.3991 (7) Å | Mo Kα radiation, λ = 0.70930 Å |
b = 9.7733 (4) Å | Cell parameters from 25 reflections |
c = 10.5899 (7) Å | θ = 7.9–18.3° |
α = 90.376 (4)° | µ = 0.07 mm−1 |
β = 71.465 (5)° | T = 293 K |
γ = 104.463 (5)° | Prism, colorless |
V = 890.29 (10) Å3 | 0.48 × 0.47 × 0.47 mm |
Z = 2 |
Nonius CAD-4 diffractometer | Rint = 0.009 |
Radiation source: xray tube | θmax = 24.9°, θmin = 0.0° |
Graphite monochromator | h = −11→10 |
ω scan b/P/b | k = 0→11 |
3306 measured reflections | l = −12→12 |
3120 independent reflections | 5 standard reflections every 120 min |
2527 reflections with Inet > 2.0σ(Inet) | intensity decay: 1.5% |
Refinement on F | H-atom parameters not refined |
Least-squares matrix: block diagonal per atom | 1/[σ2(F) + 0.0003F2] |
R[F2 > 2σ(F2)] = 0.042 | (Δ/σ)max < 0.001 |
wR(F2) = 0.050 | Δρmax = 0.16 e Å−3 |
S = 2.03 | Δρmin = −0.20 e Å−3 |
2526 reflections | Extinction correction: Larson (1970) |
236 parameters | Extinction coefficient: 0.79 (11) |
C26H22 | γ = 104.463 (5)° |
Mr = 334.46 | V = 890.29 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.3991 (7) Å | Mo Kα radiation |
b = 9.7733 (4) Å | µ = 0.07 mm−1 |
c = 10.5899 (7) Å | T = 293 K |
α = 90.376 (4)° | 0.48 × 0.47 × 0.47 mm |
β = 71.465 (5)° |
Nonius CAD-4 diffractometer | Rint = 0.009 |
3306 measured reflections | 5 standard reflections every 120 min |
3120 independent reflections | intensity decay: 1.5% |
2527 reflections with Inet > 2.0σ(Inet) |
R[F2 > 2σ(F2)] = 0.042 | 236 parameters |
wR(F2) = 0.050 | H-atom parameters not refined |
S = 2.03 | Δρmax = 0.16 e Å−3 |
2526 reflections | Δρmin = −0.20 e Å−3 |
Experimental. ? #Insert any special details here. |
Refinement. ? #Insert any special details here. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.66296 (18) | 0.78052 (16) | 0.96484 (16) | 0.0400 (10) | |
C2 | 0.82338 (19) | 0.81725 (18) | 0.93994 (18) | 0.0486 (10) | |
C3 | 0.88355 (19) | 0.82162 (18) | 1.04308 (2) | 0.0505 (11) | |
C4 | 0.78480 (18) | 0.79082 (17) | 1.17357 (18) | 0.0449 (11) | |
C4a | 0.62561 (17) | 0.75557 (16) | 1.19930 (16) | 0.0361 (9) | |
C5 | 0.34789 (19) | 0.88392 (17) | 1.45918 (16) | 0.0432 (10) | |
C6 | 0.2395 (2) | 0.95896 (19) | 1.46574 (17) | 0.0510 (11) | |
C7 | 0.1725 (2) | 0.95238 (19) | 1.36688 (18) | 0.0502 (11) | |
C8 | 0.21343 (18) | 0.87095 (17) | 1.25958 (16) | 0.0406 (10) | |
C8a | 0.32545 (16) | 0.79899 (15) | 1.24967 (14) | 0.0332 (8) | |
C9 | 0.38382 (16) | 0.70242 (15) | 1.14113 (15) | 0.0321 (8) | |
C9a | 0.56354 (17) | 0.74977 (15) | 1.09536 (15) | 0.0340 (9) | |
C10 | 0.50456 (17) | 0.71465 (16) | 1.33420 (15) | 0.0373 (9) | |
C10a | 0.39132 (17) | 0.80403 (16) | 1.35164 (15) | 0.0359 (9) | |
C11 | 0.33687 (17) | 0.55181 (15) | 1.21896 (15) | 0.0337 (9) | |
C12 | 0.16317 (18) | 0.48710 (17) | 1.27215 (16) | 0.0419 (10) | |
C13 | 0.09612 (19) | 0.39442 (18) | 1.37731 (18) | 0.0481 (10) | |
C14 | 0.1827 (2) | 0.36218 (19) | 1.46361 (19) | 0.0546 (11) | |
C15 | 0.30132 (19) | 0.49778 (18) | 1.46931 (16) | 0.0440 (10) | |
C16 | 0.41399 (17) | 0.55831 (16) | 1.33088 (15) | 0.0358 (9) | |
C17 | 0.32674 (16) | 0.70455 (16) | 1.02133 (15) | 0.0336 (8) | |
C18 | 0.26641 (19) | 0.58167 (16) | 0.96789 (16) | 0.0406 (9) | |
C19 | 0.2199 (2) | 0.58919 (18) | 0.85687 (17) | 0.0484 (11) | |
C20 | 0.2345 (2) | 0.7178 (2) | 0.79633 (17) | 0.0499 (11) | |
C21 | 0.2982 (2) | 0.84099 (18) | 0.84534 (17) | 0.0467 (10) | |
C22 | 0.34306 (18) | 0.83335 (17) | 0.95686 (16) | 0.0399 (9) | |
H1 | 0.6218 | 0.7800 | 0.8904 | 0.037* | |
H2 | 0.8917 | 0.8367 | 0.8487 | 0.063* | |
H3 | 0.9984 | 0.8466 | 1.0253 | 0.068* | |
H4 | 0.8233 | 0.7924 | 1.2494 | 0.051* | |
H5 | 0.3940 | 0.8840 | 1.5311 | 0.049* | |
H6 | 0.2125 | 1.0157 | 1.5392 | 0.061* | |
H7 | 0.0932 | 1.0069 | 1.3701 | 0.062* | |
H8 | 0.1647 | 0.8689 | 1.1876 | 0.043* | |
H10 | 0.5515 | 0.7242 | 1.4091 | 0.036* | |
H11 | 0.3805 | 0.4886 | 1.1532 | 0.036* | |
H12 | 0.1030 | 0.5117 | 1.2195 | 0.047* | |
H13 | −0.0148 | 0.3554 | 1.4039 | 0.062* | |
H14A | 0.1119 | 0.3308 | 1.5534 | 0.073* | |
H14B | 0.2435 | 0.2901 | 1.4249 | 0.073* | |
H15A | 0.2453 | 0.5713 | 1.5066 | 0.047* | |
H15B | 0.3603 | 0.4813 | 1.5308 | 0.047* | |
H16 | 0.4882 | 0.5015 | 1.3074 | 0.039* | |
H18 | 0.2581 | 0.4894 | 1.0062 | 0.033* | |
H19 | 0.1764 | 0.4992 | 0.8231 | 0.057* | |
H20 | 0.2016 | 0.7244 | 0.7183 | 0.058* | |
H21 | 0.3111 | 0.9348 | 0.8039 | 0.053* | |
H22 | 0.3868 | 0.9196 | 0.9911 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0409 (9) | 0.0337 (9) | 0.0423 (10) | 0.0094 (7) | −0.0097 (8) | −0.0033 (7) |
C2 | 0.0381 (9) | 0.0410 (10) | 0.0539 (11) | 0.0059 (7) | −0.0007 (8) | 0.0018 (8) |
C3 | 0.0298 (9) | 0.0449 (10) | 0.0703 (13) | 0.0043 (7) | −0.0116 (9) | −0.0012 (9) |
C4 | 0.0342 (9) | 0.0421 (10) | 0.0590 (11) | 0.0055 (7) | −0.0194 (8) | −0.0030 (8) |
C4a | 0.0334 (8) | 0.0310 (8) | 0.0437 (9) | 0.0052 (6) | −0.0147 (7) | −0.0018 (7) |
C5 | 0.0464 (10) | 0.0395 (9) | 0.0378 (9) | 0.0005 (8) | −0.0140 (8) | −0.0066 (7) |
C6 | 0.0543 (11) | 0.0455 (10) | 0.0459 (10) | 0.0123 (9) | −0.0072 (9) | −0.0157 (8) |
C7 | 0.0476 (10) | 0.0487 (10) | 0.0530 (11) | 0.0203 (8) | −0.0089 (9) | −0.0094 (8) |
C8 | 0.0374 (9) | 0.0414 (9) | 0.0446 (10) | 0.0123 (7) | −0.0138 (8) | −0.0055 (7) |
C8a | 0.0320 (8) | 0.0295 (8) | 0.0360 (9) | 0.0041 (6) | −0.0110 (7) | −0.0043 (6) |
C9 | 0.0311 (8) | 0.0315 (8) | 0.0348 (8) | 0.0074 (6) | −0.0132 (7) | −0.0050 (6) |
C9a | 0.0334 (8) | 0.0268 (8) | 0.0418 (9) | 0.0072 (6) | −0.0131 (7) | −0.0050 (6) |
C10 | 0.0356 (8) | 0.0388 (9) | 0.0392 (9) | 0.0045 (7) | −0.0184 (7) | −0.0026 (7) |
C10a | 0.0336 (8) | 0.0326 (8) | 0.0376 (9) | 0.0014 (6) | −0.0119 (7) | −0.0027 (7) |
C11 | 0.0331 (8) | 0.0307 (8) | 0.0369 (8) | 0.0067 (6) | −0.0123 (7) | −0.0046 (6) |
C12 | 0.0363 (9) | 0.0447 (10) | 0.0444 (10) | 0.0036 (7) | −0.0185 (8) | −0.0045 (8) |
C13 | 0.0376 (9) | 0.0487 (10) | 0.0503 (11) | −0.0022 (8) | −0.0142 (8) | −0.0005 (8) |
C14 | 0.0482 (11) | 0.0509 (11) | 0.0572 (12) | 0.0012 (9) | −0.0155 (9) | 0.0115 (9) |
C15 | 0.0405 (9) | 0.0499 (10) | 0.0414 (9) | 0.0062 (8) | −0.0171 (8) | 0.0052 (8) |
C16 | 0.0315 (8) | 0.0363 (9) | 0.0402 (9) | 0.0085 (7) | −0.0131 (7) | −0.0011 (7) |
C17 | 0.0305 (8) | 0.0357 (8) | 0.0349 (8) | 0.0083 (6) | −0.0113 (7) | −0.0055 (7) |
C18 | 0.0480 (10) | 0.0349 (9) | 0.0411 (9) | 0.0093 (7) | −0.0187 (8) | −0.0049 (7) |
C19 | 0.0584 (11) | 0.0463 (10) | 0.0443 (10) | 0.0090 (8) | −0.0256 (9) | −0.0132 (8) |
C20 | 0.0558 (11) | 0.0594 (12) | 0.0384 (10) | 0.0125 (9) | −0.0227 (8) | −0.0037 (8) |
C21 | 0.0515 (10) | 0.0442 (10) | 0.0444 (10) | 0.0107 (8) | −0.0169 (8) | 0.0044 (8) |
C22 | 0.0407 (9) | 0.0374 (9) | 0.0414 (9) | 0.0068 (7) | −0.0159 (8) | −0.0038 (7) |
C1—C2 | 1.396 (2) | C10—H10 | 1.017 |
C1—C9a | 1.385 (2) | C11—C12 | 1.512 (2) |
C1—H1 | 0.982 | C11—C16 | 1.567 (2) |
C2—C3 | 1.376 (3) | C11—H11 | 0.987 |
C2—H2 | 0.964 | C12—C13 | 1.319 (2) |
C3—C4 | 1.384 (3) | C12—H12 | 0.979 |
C3—H3 | 1.000 | C13—C14 | 1.484 (3) |
C4—C4a | 1.384 (2) | C13—H13 | 0.963 |
C4—H4 | 0.979 | C14—C15 | 1.519 (2) |
C4a—C9a | 1.395 (2) | C14—H14A | 0.970 |
C4a—C10 | 1.497 (2) | C14—H14B | 1.019 |
C5—C6 | 1.381 (3) | C15—C16 | 1.527 (2) |
C5—C10a | 1.388 (2) | C15—H15A | 1.002 |
C5—H5 | 0.989 | C15—H15B | 1.017 |
C6—C7 | 1.377 (3) | C16—H16 | 0.968 |
C6—H6 | 0.957 | C17—C18 | 1.393 (2) |
C7—C8 | 1.391 (2) | C17—C22 | 1.386 (2) |
C7—H7 | 1.011 | C18—C19 | 1.387 (2) |
C8—C8a | 1.383 (2) | C18—H18 | 0.966 |
C8—H8 | 1.004 | C19—C20 | 1.371 (3) |
C8a—C9 | 1.535 (2) | C19—H19 | 0.988 |
C8a—C10a | 1.400 (2) | C20—C21 | 1.380 (2) |
C9—C9a | 1.547 (2) | C20—H20 | 0.977 |
C9—C11 | 1.581 (2) | C21—C22 | 1.383 (2) |
C9—C17 | 1.528 (2) | C21—H21 | 0.982 |
C10—C10a | 1.506 (2) | C22—H22 | 0.963 |
C10—C16 | 1.559 (2) | ||
C2—C1—C9a | 119.33 (15) | C9—C11—C12 | 113.35 (12) |
C2—C1—H1 | 120.0 | C9—C11—C16 | 110.59 (11) |
C9a—C1—H1 | 120.7 | C9—C11—H11 | 106.3 |
C1—C2—C3 | 120.91 (16) | C12—C11—C16 | 112.22 (12) |
C1—C2—H2 | 118.8 | C12—C11—H11 | 106.5 |
C3—C2—H2 | 120.3 | C16—C11—H11 | 107.4 |
C2—C3—C4 | 120.02 (15) | C11—C12—C13 | 122.69 (14) |
C2—C3—H3 | 121.0 | C11—C12—H12 | 116.1 |
C4—C3—H3 | 119.0 | C13—C12—H12 | 121.1 |
C3—C4—C4a | 119.48 (16) | C12—C13—C14 | 122.02 (15) |
C3—C4—H4 | 122.4 | C12—C13—H13 | 118.2 |
C4a—C4—H4 | 118.2 | C14—C13—H13 | 119.4 |
C4—C4a—C9a | 120.90 (15) | C13—C14—C15 | 107.96 (14) |
C4—C4a—C10 | 125.64 (14) | C13—C14—H14A | 109.9 |
C9a—C4a—C10 | 113.40 (13) | C13—C14—H14B | 111.9 |
C6—C5—C10a | 119.97 (15) | C15—C14—H14A | 108.6 |
C6—C5—H5 | 121.2 | C15—C14—H14B | 106.7 |
C10a—C5—H5 | 118.8 | H14A—C14—H14B | 111.6 |
C5—C6—C7 | 120.01 (15) | C14—C15—C16 | 112.15 (14) |
C5—C6—H6 | 119.2 | C14—C15—H15A | 108.8 |
C7—C6—H6 | 120.8 | C14—C15—H15B | 110.5 |
C6—C7—C8 | 120.53 (15) | C16—C15—H15A | 106.7 |
C6—C7—H7 | 121.0 | C16—C15—H15B | 110.6 |
C8—C7—H7 | 118.5 | H15A—C15—H15B | 107.9 |
C7—C8—C8a | 119.99 (15) | C10—C16—C11 | 108.69 (12) |
C7—C8—H8 | 119.4 | C10—C16—C15 | 111.02 (13) |
C8a—C8—H8 | 120.6 | C10—C16—H16 | 108.1 |
C8—C8a—C9 | 127.67 (13) | C11—C16—C15 | 114.67 (12) |
C8—C8a—C10a | 119.22 (14) | C11—C16—H16 | 108.2 |
C9—C8a—C10a | 112.99 (13) | C15—C16—H16 | 105.9 |
C8a—C9—C9a | 106.65 (11) | C9—C17—C18 | 122.85 (13) |
C8a—C9—C11 | 104.22 (11) | C9—C17—C22 | 119.49 (13) |
C8a—C9—C17 | 114.74 (12) | C18—C17—C22 | 117.56 (14) |
C9a—C9—C11 | 105.42 (11) | C17—C18—C19 | 120.70 (15) |
C9a—C9—C17 | 110.37 (12) | C17—C18—H18 | 120.7 |
C11—C9—C17 | 114.68 (12) | C19—C18—H18 | 118.6 |
C1—C9a—C4a | 119.36 (14) | C18—C19—C20 | 120.64 (15) |
C1—C9a—C9 | 126.40 (13) | C18—C19—H19 | 117.9 |
C4a—C9a—C9 | 114.20 (13) | C20—C19—H19 | 121.5 |
C4a—C10—C10a | 108.34 (12) | C19—C20—C21 | 119.61 (15) |
C4a—C10—C16 | 106.18 (12) | C19—C20—H20 | 121.3 |
C4a—C10—H10 | 112.4 | C21—C20—H20 | 119.0 |
C10a—C10—C16 | 107.14 (12) | C20—C21—C22 | 119.68 (15) |
C10a—C10—H10 | 111.5 (8) | C20—C21—H21 | 121.7 |
C16—C10—H10 | 111.1 | C22—C21—H21 | 118.6 |
C5—C10a—C8a | 120.22 (14) | C17—C22—C21 | 121.78 (14) |
C5—C10a—C10 | 125.27 (14) | C17—C22—H22 | 118.8 |
C8a—C10a—C10 | 114.48 (13) | C21—C22—H22 | 119.4 |
C9a—C1—C2—C3 | 0.77 (18) | C8a—C9—C11—C16 | −59.1 (2) |
C2—C1—C9a—C4a | −0.25 (18) | C9a—C9—C11—C12 | −180.0 (3) |
C2—C1—C9a—C9 | −177.8 (4) | C9a—C9—C11—C16 | 53.00 (19) |
C1—C2—C3—C4 | −0.69 (18) | C17—C9—C11—C12 | −58.4 (2) |
C2—C3—C4—C4a | 0.08 (18) | C17—C9—C11—C16 | 174.6 (3) |
C3—C4—C4a—C9a | 0.44 (18) | C8a—C9—C17—C18 | −133.1 (3) |
C3—C4—C4a—C10 | 177.6 (4) | C8a—C9—C17—C22 | 50.8 (2) |
C4—C4a—C9a—C1 | −0.35 (18) | C9a—C9—C17—C18 | 106.4 (3) |
C4—C4a—C9a—C9 | 177.5 (4) | C9a—C9—C17—C22 | −69.7 (2) |
C10—C4a—C9a—C1 | −177.9 (4) | C11—C9—C17—C18 | −12.48 (16) |
C10—C4a—C9a—C9 | −0.06 (15) | C11—C9—C17—C22 | 171.4 (3) |
C4—C4a—C10—C10a | 129.1 (3) | C4a—C10—C10a—C5 | −127.5 (3) |
C4—C4a—C10—C16 | −116.1 (3) | C4a—C10—C10a—C8a | 54.2 (2) |
C9a—C4a—C10—C10a | −53.5 (2) | C16—C10—C10a—C5 | 118.3 (3) |
C9a—C4a—C10—C16 | 61.3 (2) | C16—C10—C10a—C8a | −60.0 (2) |
C10a—C5—C6—C7 | 1.21 (18) | C4a—C10—C16—C11 | −60.7 (2) |
C6—C5—C10a—C8a | −0.10 (18) | C4a—C10—C16—C15 | 172.3 (3) |
C6—C5—C10a—C10 | −178.3 (4) | C10a—C10—C16—C11 | 55.0 (2) |
C5—C6—C7—C8 | −0.26 (18) | C10a—C10—C16—C15 | −72.0 (2) |
C6—C7—C8—C8a | −1.83 (18) | C9—C11—C12—C13 | −153.8 (4) |
C7—C8—C8a—C9 | 178.8 (4) | C16—C11—C12—C13 | −27.59 (19) |
C7—C8—C8a—C10a | 2.91 (18) | C9—C11—C16—C10 | 3.35 (14) |
C8—C8a—C9—C9a | 131.9 (3) | C9—C11—C16—C15 | 128.2 (3) |
C8—C8a—C9—C11 | −116.9 (3) | C12—C11—C16—C10 | −124.3 (3) |
C8—C8a—C9—C17 | 9.36 (16) | C12—C11—C16—C15 | 0.59 (16) |
C10a—C8a—C9—C9a | −52.0 (2) | C11—C12—C13—C14 | 9.18 (17) |
C10a—C8a—C9—C11 | 59.2 (2) | C12—C13—C14—C15 | 34.6 (2) |
C10a—C8a—C9—C17 | −174.5 (3) | C13—C14—C15—C16 | −58.5 (2) |
C8—C8a—C10a—C5 | −1.96 (18) | C14—C15—C16—C10 | 165.0 (4) |
C8—C8a—C10a—C10 | 176.4 (3) | C14—C15—C16—C11 | 41.3 (2) |
C9—C8a—C10a—C5 | −178.4 (3) | C9—C17—C18—C19 | −178.3 (4) |
C9—C8a—C10a—C10 | −0.03 (15) | C22—C17—C18—C19 | −2.11 (18) |
C8a—C9—C9a—C1 | −129.7 (3) | C9—C17—C22—C21 | 177.8 (4) |
C8a—C9—C9a—C4a | 52.7 (2) | C18—C17—C22—C21 | 1.47 (18) |
C11—C9—C9a—C1 | 119.9 (3) | C17—C18—C19—C20 | 0.96 (18) |
C11—C9—C9a—C4a | −57.7 (2) | C18—C19—C20—C21 | 0.92 (18) |
C17—C9—C9a—C1 | −4.44 (16) | C19—C20—C21—C22 | −1.56 (18) |
C17—C9—C9a—C4a | 177.9 (3) | C20—C21—C22—C17 | 0.35 (18) |
C8a—C9—C11—C12 | 67.9 (2) |
C26H24 | F(000) = 360.10 |
Mr = 336.47 | ? #Insert any comments here. |
Triclinic, P1 | Dx = 1.243 Mg m−3 |
a = 9.2213 (6) Å | Mo Kα radiation, λ = 0.70930 Å |
b = 9.8777 (10) Å | Cell parameters from 25 reflections |
c = 10.7390 (8) Å | θ = 8.4–17.6° |
α = 90.738 (8)° | µ = 0.07 mm−1 |
β = 107.829 (6)° | T = 293 K |
γ = 104.052 (7)° | Needle, colorless |
V = 899.28 (13) Å3 | 0.30 × 0.30 × 0.30 mm |
Z = 2 |
Nonius CAD-4 diffractometer | Rint = 0.014 |
Radiation source: xray tube | θmax = 25.0°, θmin = 2.0° |
Graphite monochromator | h = −10→10 |
ω scan b/P/b | k = 0→11 |
3334 measured reflections | l = −12→12 |
3147 independent reflections | 3 standard reflections every 120 min |
2444 reflections with Inet > 2.0σ(Inet) | intensity decay: 1.5% |
Refinement on F | H-atom parameters not refined |
Least-squares matrix: full | 1/[σ2(F) + 0.0002F2] |
R[F2 > 2σ(F2)] = 0.041 | (Δ/σ)max < 0.001 |
wR(F2) = 0.044 | Δρmax = 0.15 e Å−3 |
S = 1.94 | Δρmin = −0.17 e Å−3 |
2442 reflections | Extinction correction: Larson (1970) |
236 parameters | Extinction coefficient: 0.57 (7) |
C26H24 | γ = 104.052 (7)° |
Mr = 336.47 | V = 899.28 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2213 (6) Å | Mo Kα radiation |
b = 9.8777 (10) Å | µ = 0.07 mm−1 |
c = 10.7390 (8) Å | T = 293 K |
α = 90.738 (8)° | 0.30 × 0.30 × 0.30 mm |
β = 107.829 (6)° |
Nonius CAD-4 diffractometer | Rint = 0.014 |
3334 measured reflections | 3 standard reflections every 120 min |
3147 independent reflections | intensity decay: 1.5% |
2444 reflections with Inet > 2.0σ(Inet) |
R[F2 > 2σ(F2)] = 0.041 | 236 parameters |
wR(F2) = 0.044 | H-atom parameters not refined |
S = 1.94 | Δρmax = 0.15 e Å−3 |
2442 reflections | Δρmin = −0.17 e Å−3 |
Experimental. ? #Insert any special details here. |
Refinement. ? #Insert any special details here. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.66684 (19) | 0.78197 (17) | 0.02077 (16) | 0.0381 (11) | |
C2 | 0.8285 (2) | 0.81943 (19) | 0.04288 (18) | 0.0458 (11) | |
C3 | 0.8879 (2) | 0.82325 (19) | −0.06063 (19) | 0.0488 (11) | |
C4 | 0.7860 (2) | 0.79172 (19) | −0.18781 (18) | 0.0429 (11) | |
C4a | 0.62543 (18) | 0.75632 (16) | −0.21079 (16) | 0.0350 (9) | |
C5 | 0.34505 (2) | 0.88662 (18) | −0.45824 (17) | 0.0432 (11) | |
C6 | 0.2390 (2) | 0.96387 (19) | −0.45991 (19) | 0.0523 (12) | |
C7 | 0.1731 (2) | 0.95932 (19) | −0.3605 (2) | 0.0513 (12) | |
C8 | 0.2139 (2) | 0.87746 (18) | −0.25780 (18) | 0.0422 (11) | |
C8a | 0.32483 (18) | 0.80348 (16) | −0.25194 (16) | 0.0342 (9) | |
C9 | 0.38185 (18) | 0.70552 (16) | −0.14901 (15) | 0.0317 (9) | |
C9a | 0.56357 (18) | 0.75029 (16) | −0.10652 (16) | 0.0325 (10) | |
C10 | 0.50039 (19) | 0.71614 (17) | −0.34281 (16) | 0.0371 (10) | |
C10a | 0.38867 (18) | 0.80692 (16) | −0.35502 (16) | 0.0363 (10) | |
C11 | 0.32988 (19) | 0.55663 (16) | −0.22954 (15) | 0.0338 (9) | |
C12 | 0.15118 (19) | 0.50022 (18) | −0.28968 (17) | 0.0419 (10) | |
C13 | 0.1079 (2) | 0.35693 (19) | −0.36541 (18) | 0.0502 (11) | |
C14 | 0.1970 (2) | 0.35330 (19) | −0.46305 (19) | 0.0531 (12) | |
C15 | 0.2932 (2) | 0.49818 (19) | −0.47310 (17) | 0.0431 (10) | |
C16 | 0.41032 (19) | 0.56257 (17) | −0.33911 (16) | 0.0361 (9) | |
C17 | 0.32604 (18) | 0.70707 (16) | −0.02911 (15) | 0.0331 (9) | |
C18 | 0.2687 (2) | 0.58597 (18) | 0.02368 (17) | 0.0421 (10) | |
C19 | 0.2249 (2) | 0.59227 (19) | 0.13564 (18) | 0.0508 (12) | |
C20 | 0.2406 (2) | 0.7187 (2) | 0.19886 (18) | 0.0523 (12) | |
C21 | 0.3013 (2) | 0.84058 (19) | 0.15060 (18) | 0.0484 (11) | |
C22 | 0.3436 (2) | 0.83423 (17) | 0.03818 (17) | 0.0400 (10) | |
H1 | 0.624 | 0.781 | 0.096 | 0.038* | |
H2 | 0.902 | 0.842 | 0.134 | 0.060* | |
H3 | 1.000 | 0.846 | −0.044 | 0.053* | |
H4 | 0.829 | 0.795 | −0.262 | 0.048* | |
H5 | 0.390 | 0.887 | −0.532 | 0.049* | |
H6 | 0.209 | 1.023 | −0.532 | 0.066* | |
H7 | 0.094 | 1.012 | −0.363 | 0.067* | |
H8 | 0.167 | 0.877 | −0.188 | 0.042* | |
H10 | 0.547 | 0.724 | −0.417 | 0.036* | |
H11 | 0.371 | 0.488 | −0.165 | 0.036* | |
H12A | 0.110 | 0.570 | −0.349 | 0.049* | |
H12B | 0.096 | 0.495 | −0.221 | 0.040* | |
H13A | −0.009 | 0.329 | −0.411 | 0.070* | |
H13B | 0.131 | 0.287 | −0.301 | 0.087* | |
H14A | 0.123 | 0.311 | −0.551 | 0.083* | |
H14B | 0.271 | 0.293 | −0.432 | 0.073* | |
H15A | 0.223 | 0.560 | −0.509 | 0.050* | |
H15B | 0.353 | 0.492 | −0.535 | 0.043* | |
H16 | 0.490 | 0.505 | −0.312 | 0.041* | |
H18 | 0.261 | 0.496 | −0.016 | 0.044* | |
H19 | 0.185 | 0.506 | 0.171 | 0.056* | |
H20 | 0.205 | 0.726 | 0.277 | 0.066* | |
H21 | 0.316 | 0.931 | 0.194 | 0.053* | |
H22 | 0.386 | 0.922 | 0.006 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0395 (10) | 0.0355 (10) | 0.0382 (10) | 0.0074 (8) | 0.0128 (8) | 0.0033 (8) |
C2 | 0.0367 (10) | 0.0481 (11) | 0.0445 (11) | 0.0057 (8) | 0.0055 (9) | 0.0005 (9) |
C3 | 0.0292 (9) | 0.0527 (12) | 0.0593 (13) | 0.0027 (8) | 0.0133 (9) | −0.0014 (10) |
C4 | 0.0337 (10) | 0.0475 (11) | 0.0476 (11) | 0.0042 (8) | 0.0182 (9) | −0.0002 (9) |
C4a | 0.0322 (9) | 0.0327 (9) | 0.0399 (10) | 0.0052 (7) | 0.0139 (8) | 0.0000 (7) |
C5 | 0.0456 (11) | 0.0369 (10) | 0.0389 (10) | −0.0019 (8) | 0.0115 (9) | 0.0052 (8) |
C6 | 0.0566 (12) | 0.0405 (11) | 0.0494 (12) | 0.0076 (9) | 0.0054 (10) | 0.0117 (9) |
C7 | 0.0480 (11) | 0.0435 (11) | 0.0575 (13) | 0.0165 (9) | 0.0063 (10) | 0.0048 (10) |
C8 | 0.0392 (10) | 0.0395 (10) | 0.0485 (11) | 0.0104 (8) | 0.0147 (9) | 0.0032 (8) |
C8a | 0.0312 (9) | 0.0310 (9) | 0.0385 (10) | 0.0031 (7) | 0.0123 (8) | 0.0010 (7) |
C9 | 0.0302 (8) | 0.0312 (9) | 0.0349 (9) | 0.0058 (7) | 0.0139 (7) | 0.0017 (7) |
C9a | 0.0317 (9) | 0.0283 (9) | 0.0379 (10) | 0.0061 (7) | 0.0129 (8) | 0.0021 (7) |
C10 | 0.0354 (9) | 0.0429 (10) | 0.0348 (10) | 0.0051 (8) | 0.0178 (8) | 0.0003 (8) |
C10a | 0.0347 (9) | 0.0332 (9) | 0.0364 (10) | 0.0009 (7) | 0.0109 (8) | 0.0006 (8) |
C11 | 0.0347 (9) | 0.0320 (9) | 0.0341 (9) | 0.0057 (7) | 0.0126 (7) | 0.0003 (7) |
C12 | 0.0365 (10) | 0.0452 (10) | 0.0420 (10) | 0.0006 (8) | 0.0180 (8) | −0.0050 (8) |
C13 | 0.0517 (11) | 0.0441 (11) | 0.0464 (11) | −0.0038 (9) | 0.0168 (9) | −0.0044 (9) |
C14 | 0.0507 (12) | 0.0485 (12) | 0.0541 (12) | 0.0028 (9) | 0.0170 (10) | −0.0131 (9) |
C15 | 0.0425 (10) | 0.0496 (11) | 0.0372 (10) | 0.0067 (8) | 0.0170 (8) | −0.0049 (8) |
C16 | 0.0343 (9) | 0.0381 (10) | 0.0362 (9) | 0.0078 (7) | 0.0129 (8) | −0.0012 (8) |
C17 | 0.0298 (8) | 0.0347 (9) | 0.0345 (9) | 0.0063 (7) | 0.0116 (7) | 0.0013 (7) |
C18 | 0.0515 (11) | 0.0360 (10) | 0.0413 (10) | 0.0086 (8) | 0.0208 (9) | 0.0004 (8) |
C19 | 0.0644 (13) | 0.0467 (11) | 0.0439 (11) | 0.0058 (10) | 0.0277 (10) | 0.0075 (9) |
C20 | 0.0580 (12) | 0.0614 (13) | 0.0409 (11) | 0.0094 (10) | 0.0256 (10) | −0.0015 (10) |
C21 | 0.0511 (11) | 0.0463 (11) | 0.0475 (11) | 0.0063 (9) | 0.0207 (9) | −0.0109 (9) |
C22 | 0.0394 (10) | 0.0362 (10) | 0.0449 (10) | 0.0041 (8) | 0.0187 (8) | −0.0008 (8) |
C1—C2 | 1.389 (2) | C11—C12 | 1.528 (2) |
C1—C9a | 1.386 (2) | C11—C16 | 1.566 (2) |
C1—H1 | 1.00 | C11—H11 | 1.03 |
C2—C3 | 1.378 (3) | C12—C13 | 1.524 (2) |
C2—H2 | 0.99 | C12—H12A | 1.01 |
C3—C4 | 1.381 (3) | C12—H12B | 1.01 |
C3—H3 | 0.96 | C13—C14 | 1.522 (3) |
C4—C4a | 1.378 (2) | C13—H13A | 1.01 |
C4—H4 | 0.98 | C13—H13B | 0.99 |
C4a—C9a | 1.400 (2) | C14—C15 | 1.514 (3) |
C4a—C10 | 1.503 (2) | C14—H14A | 1.00 |
C5—C6 | 1.374 (3) | C14—H14B | 1.00 |
C5—C10a | 1.384 (2) | C15—C16 | 1.527 (2) |
C5—H5 | 1.00 | C15—H15A | 0.99 |
C6—C7 | 1.377 (3) | C15—H15B | 1.00 |
C6—H6 | 0.99 | C16—H16 | 1.01 |
C7—C8 | 1.389 (3) | C17—C18 | 1.388 (2) |
C7—H7 | 0.98 | C17—C22 | 1.390 (2) |
C8—C8a | 1.382 (2) | C18—C19 | 1.386 (2) |
C8—H8 | 0.97 | C18—H18 | 0.96 |
C8a—C9 | 1.534 (2) | C19—C20 | 1.368 (3) |
C8a—C10a | 1.401 (2) | C19—H19 | 0.98 |
C9—C9a | 1.542 (2) | C20—C21 | 1.378 (3) |
C9—C11 | 1.585 (2) | C20—H20 | 1.00 |
C9—C17 | 1.527 (2) | C21—C22 | 1.383 (2) |
C10—C10a | 1.500 (2) | C21—H21 | 0.96 |
C10—C16 | 1.550 (2) | C22—H22 | 0.98 |
C10—H10 | 1.01 | ||
C2—C1—C9a | 119.94 (15) | C12—C11—C16 | 110.19 (13) |
C2—C1—H1 | 120.7 | C12—C11—H11 | 108.4 |
C9a—C1—H1 | 119.3 | C16—C11—H11 | 107.4 |
C1—C2—C3 | 120.65 (16) | C11—C12—C13 | 111.27 (14) |
C1—C2—H2 | 119.5 | C11—C12—H12A | 108.1 |
C3—C2—H2 | 119.8 | C11—C12—H12B | 112.0 |
C2—C3—C4 | 119.87 (15) | C13—C12—H12A | 110.9 |
C2—C3—H3 | 119.8 | C13—C12—H12B | 109.9 |
C4—C3—H3 | 120.3 | H12A—C12—H12B | 104.5 |
C3—C4—C4a | 119.89 (16) | C12—C13—C14 | 113.13 (14) |
C3—C4—H4 | 119.7 | C12—C13—H13A | 108.3 |
C4a—C4—H4 | 120.4 | C12—C13—H13B | 108.2 |
C4—C4a—C9a | 120.84 (15) | C14—C13—H13A | 111.2 |
C4—C4a—C10 | 126.02 (15) | C14—C13—H13B | 109.1 |
C9a—C4a—C10 | 113.10 (13) | H13A—C13—H13B | 106.7 |
C6—C5—C10a | 120.10 (16) | C13—C14—C15 | 111.48 (14) |
C6—C5—H5 | 120.3 | C13—C14—H14A | 110.6 |
C10a—C5—H5 | 119.6 | C13—C14—H14B | 108.4 |
C5—C6—C7 | 120.05 (16) | C15—C14—H14A | 110.3 |
C5—C6—H6 | 120.9 | C15—C14—H14B | 108.1 |
C7—C6—H6 | 119.1 | H14A—C14—H14B | 107.9 |
C6—C7—C8 | 120.26 (17) | C14—C15—C16 | 110.77 (15) |
C6—C7—H7 | 120.4 | C14—C15—H15A | 110.7 |
C8—C7—H7 | 119.3 | C14—C15—H15B | 109.6 |
C7—C8—C8a | 120.41 (16) | C16—C15—H15A | 109.9 |
C7—C8—H8 | 118.8 | C16—C15—H15B | 108.6 |
C8a—C8—H8 | 120.7 | H15A—C15—H15B | 107.1 |
C8—C8a—C9 | 127.93 (14) | C10—C16—C11 | 109.19 (12) |
C8—C8a—C10a | 118.66 (15) | C10—C16—C15 | 112.30 (14) |
C9—C8a—C10a | 113.24 (13) | C10—C16—H16 | 108.4 |
C8a—C9—C9a | 106.04 (12) | C11—C16—C15 | 112.45 (13) |
C8a—C9—C11 | 104.34 (12) | C11—C16—H16 | 106.4 |
C8a—C9—C17 | 115.20 (12) | C15—C16—H16 | 107.9 |
C9a—C9—C11 | 106.01 (12) | C9—C17—C18 | 122.99 (14) |
C9a—C9—C17 | 110.25 (13) | C9—C17—C22 | 119.69 (14) |
C11—C9—C17 | 114.25 (12) | C18—C17—C22 | 117.12 (14) |
C1—C9a—C4a | 118.81 (14) | C17—C18—C19 | 121.13 (15) |
C1—C9a—C9 | 126.94 (14) | C17—C18—H18 | 120.2 |
C4a—C9a—C9 | 114.25 (14) | C19—C18—H18 | 118.6 |
C4a—C10—C10a | 107.87 (13) | C18—C19—C20 | 120.66 (16) |
C4a—C10—C16 | 105.55 (13) | C18—C19—H19 | 119.7 |
C4a—C10—H10 | 112.2 | C20—C19—H19 | 119.6 |
C10a—C10—C16 | 108.35 (13) | C19—C20—C21 | 119.38 (16) |
C10a—C10—H10 | 111.9 | C19—C20—H20 | 121.9 |
C16—C10—H10 | 110.7 | C21—C20—H20 | 118.6 |
C5—C10a—C8a | 120.44 (15) | C20—C21—C22 | 119.92 (16) |
C5—C10a—C10 | 125.31 (15) | C20—C21—H21 | 121.5 |
C8a—C10a—C10 | 114.24 (14) | C22—C21—H21 | 118.6 |
C9—C11—C12 | 113.48 (13) | C17—C22—C21 | 121.72 (15) |
C9—C11—C16 | 110.01 (12) | C17—C22—H22 | 119.7 |
C9—C11—H11 | 107.2 | C21—C22—H22 | 118.6 |
C9a—C1—C2—C3 | −1.09 (14) | C2—C1—C9a—C4a | 0.27 (14) |
C2—C1—C9a—C9 | 179.3 (3) | C1—C2—C3—C4 | 1.01 (14) |
C2—C3—C4—C4a | −0.12 (14) | C3—C4—C4a—C9a | −0.71 (14) |
C3—C4—C4a—C10 | −178.4 (3) | C4—C4a—C9a—C1 | 0.63 (14) |
C4—C4a—C9a—C9 | −178.6 (3) | C10—C4a—C9a—C1 | 178.6 (3) |
C10—C4a—C9a—C9 | −0.57 (12) | C4—C4a—C10—C10a | −127.6 (3) |
C4—C4a—C10—C16 | 116.7 (3) | C9a—C4a—C10—C10a | 54.54 (17) |
C9a—C4a—C10—C16 | −61.13 (18) | C10a—C5—C6—C7 | −1.65 (15) |
C6—C5—C10a—C8a | 0.41 (15) | C6—C5—C10a—C10 | 178.8 (3) |
C5—C6—C7—C8 | 0.38 (15) | C6—C7—C8—C8a | 2.16 (15) |
C7—C8—C8a—C9 | −178.4 (3) | C7—C8—C8a—C10a | −3.35 (15) |
C8—C8a—C9—C9a | −131.7 (3) | C8—C8a—C9—C11 | 116.6 (3) |
C8—C8a—C9—C17 | −9.45 (14) | C10a—C8a—C9—C9a | 53.07 (17) |
C10a—C8a—C9—C11 | −58.63 (17) | C10a—C8a—C9—C17 | 175.3 (3) |
C8—C8a—C10a—C5 | 2.08 (15) | C8—C8a—C10a—C10 | −176.5 (3) |
C9—C8a—C10a—C5 | 177.8 (3) | C9—C8a—C10a—C10 | −0.71 (12) |
C8a—C9—C9a—C1 | 128.2 (3) | C8a—C9—C9a—C4a | −52.70 (17) |
C11—C9—C9a—C1 | −121.3 (3) | C11—C9—C9a—C4a | 57.82 (17) |
C17—C9—C9a—C1 | 2.87 (13) | C17—C9—C9a—C4a | −178.0 (3) |
C8a—C9—C11—C12 | −63.59 (18) | C8a—C9—C11—C16 | 60.37 (17) |
C9a—C9—C11—C12 | −175.3 (3) | C9a—C9—C11—C16 | −51.34 (16) |
C17—C9—C11—C12 | 63.09 (18) | C17—C9—C11—C16 | −173.0 (3) |
C8a—C9—C17—C18 | 135.5 (3) | C8a—C9—C17—C22 | −49.71 (17) |
C9a—C9—C17—C18 | −104.6 (2) | C9a—C9—C17—C22 | 70.22 (19) |
C11—C9—C17—C18 | 14.70 (14) | C11—C9—C17—C22 | −170.5 (3) |
C4a—C10—C10a—C5 | 127.3 (3) | C4a—C10—C10a—C8a | −54.23 (17) |
C16—C10—C10a—C5 | −118.9 (3) | C16—C10—C10a—C8a | 59.58 (18) |
C4a—C10—C16—C11 | 62.58 (18) | C4a—C10—C16—C15 | −172.0 (3) |
C10a—C10—C16—C11 | −52.76 (16) | C10a—C10—C16—C15 | 72.7 (2) |
C9—C11—C12—C13 | −179.8 (3) | C16—C11—C12—C13 | 56.34 (18) |
C9—C11—C16—C10 | −6.05 (12) | C9—C11—C16—C15 | −131.4 (3) |
C12—C11—C16—C10 | 119.8 (2) | C12—C11—C16—C15 | −5.54 (13) |
C11—C12—C13—C14 | −50.58 (18) | C12—C13—C14—C15 | −6.89 (13) |
C13—C14—C15—C16 | 58.09 (19) | C14—C15—C16—C10 | −174.8 (3) |
C14—C15—C16—C11 | −51.16 (17) | C9—C17—C18—C19 | 177.5 (3) |
C22—C17—C18—C19 | 2.59 (15) | C9—C17—C22—C21 | −177.1 (3) |
C18—C17—C22—C21 | −2.00 (15) | C17—C18—C19—C20 | −1.49 (15) |
C18—C19—C20—C21 | −0.33 (15) | C19—C20—C21—C22 | 0.94 (15) |
C20—C21—C22—C17 | 0.26 (15) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C26H22 | C26H24 |
Mr | 334.46 | 336.47 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 9.3991 (7), 9.7733 (4), 10.5899 (7) | 9.2213 (6), 9.8777 (10), 10.7390 (8) |
α, β, γ (°) | 90.376 (4), 71.465 (5), 104.463 (5) | 90.738 (8), 107.829 (6), 104.052 (7) |
V (Å3) | 890.29 (10) | 899.28 (13) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.07 |
Crystal size (mm) | 0.48 × 0.47 × 0.47 | 0.30 × 0.30 × 0.30 |
Data collection | ||
Diffractometer | Nonius CAD-4 diffractometer | Nonius CAD-4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [Inet > 2.0σ(Inet)] reflections | 3306, 3120, 2527 | 3334, 3147, 2444 |
Rint | 0.009 | 0.014 |
(sin θ/λ)max (Å−1) | 0.594 | 0.596 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.050, 2.03 | 0.041, 0.044, 1.94 |
No. of reflections | 2526 | 2442 |
No. of parameters | 236 | 236 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters not refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.16, −0.20 | 0.15, −0.17 |
Computer programs: CAD-4-PC (Enraf-Nonius, 1993), SET4 and CELDIM in CAD-4-PC, DATRD2 in NRCVAX (Gabe et al., 1989), SOLVER in NRCVAX, LSTSQ in NRCVAX, TABLES in NRCVAX (January 94 version).
C4a—C10 | 1.497 (2) | C11—C12 | 1.512 (2) |
C8a—C9 | 1.535 (2) | C11—C16 | 1.567 (2) |
C9—C9a | 1.547 (2) | C12—C13 | 1.319 (2) |
C9—C11 | 1.581 (2) | C13—C14 | 1.484 (3) |
C9—C17 | 1.528 (2) | C14—C15 | 1.519 (2) |
C10—C10a | 1.506 (2) | C15—C16 | 1.527 (2) |
C10—C16 | 1.559 (2) |
C4a—C10 | 1.503 (2) | C11—C12 | 1.528 (2) |
C8a—C9 | 1.534 (2) | C11—C16 | 1.566 (2) |
C9—C9a | 1.542 (2) | C12—C13 | 1.524 (2) |
C9—C11 | 1.585 (2) | C13—C14 | 1.522 (3) |
C9—C17 | 1.527 (2) | C14—C15 | 1.514 (3) |
C10—C10a | 1.500 (2) | C15—C16 | 1.527 (2) |
C10—C16 | 1.550 (2) | ||
C4—C4a—C9a | 120.84 (15) | C4a—C10—C16 | 105.55 (13) |
C4—C4a—C10 | 126.02 (15) | C10a—C10—C16 | 108.35 (13) |
C9a—C4a—C10 | 113.10 (13) | C5—C10a—C8a | 120.44 (15) |
C8—C8a—C9 | 127.93 (14) | C5—C10a—C10 | 125.31 (15) |
C8—C8a—C10a | 118.66 (15) | C8a—C10a—C10 | 114.24 (14) |
C9—C8a—C10a | 113.24 (13) | C9—C11—C12 | 113.48 (13) |
C8a—C9—C9a | 106.04 (12) | C9—C11—C16 | 110.01 (12) |
C8a—C9—C11 | 104.34 (12) | C12—C11—C16 | 110.19 (13) |
C8a—C9—C17 | 115.20 (12) | C11—C12—C13 | 111.27 (14) |
C9a—C9—C11 | 106.01 (12) | C12—C13—C14 | 113.13 (14) |
C9a—C9—C17 | 110.25 (13) | C13—C14—C15 | 111.48 (14) |
C11—C9—C17 | 114.25 (12) | C14—C15—C16 | 110.77 (15) |
C1—C9a—C4a | 118.81 (14) | C10—C16—C11 | 109.19 (12) |
C1—C9a—C9 | 126.94 (14) | C10—C16—C15 | 112.30 (14) |
C4a—C9a—C9 | 114.25 (14) | C11—C16—C15 | 112.45 (13) |
C4a—C10—C10a | 107.87 (13) |
The double bond of (I) is proximal to the phenyl substituent. This regiochemistry is consistent with a stepwise mechanism for formation of (I) which involves the more stable biradical intermediate (Kaupp & Teufel, 1980; Wang et al., 1982). The cyclohexenyl ring in (II) adopts a boat conformation. Two H atoms (determined by NMR decoupling experiments to be attached to C12 and C15) are found to be highly shielded in the NMR spectrum of (II). The endo H atoms H12A and H15A are assigned to these resonances at 0.22 and 0.78 p.p.m., respectively. A single hydrogen (H15A) of (I) appears at a similarly high field (0.84 p.p.m.). The large shieldings of H15A and H12A are ascribed to their positions within the anisotropic shielding regions of two (for H15A) or three (for H12A) neighboring benzene rings.
Bond distances about carbon atoms C9 and C10 are similar in (I) and (II), and indicate the presence of significant steric effects involving the phenyl group attached to C9. Thus, the bond distances involving the bicyclic framework about C9 are observed to be 0.022–0.050 Å longer than the corresponding distances about C10. For example, the interannular C9—C11 bond is 1.581 (2) Å in (I) and 1.585 (2) Å in (II), whereas the related C10—C16 bond distances are 1.559 (2) Å in (I) and 1.550 (2) Å in (II). The phenyl substituents are rotated slightly from the plane defined by the bridgehead carbons (C9, C10, C11 and C16). The dihedral angle between this plane and the plane of the phenyl groups is 12.08 (7) in (I) and 13.39 (8) in (II). This orientation precludes significant hyperconjugation between the phenyl substituent and the C9—C11 σ bond, and discounts σ-π through-bond coupling (Osawa et al., 1983) as contributing to elongation of the bonds in these molecules (Baldridge et al., 1997). One carbon (C12) of the double bond of (I) exhibits a close contact [3.022 (2) Å] with a carbon (C8a) of the subjacent phenyl ring. However, the resulting π-π interactions (Dougherty et al., 1986), if any, do not contribute to lengthening of the C9—C11 bond, which is 0.004 Å longer in (II) (in which this bond is saturated) than in (I).
The cell constant of (I) and (II) are similar. Except for atoms near the double bond of (I), the structures of (I) and (II) are nearly superimposable. The resemblance of the polycyclic frameworks of (I) and (II) apparently allows for similar packing (Figs. 3 and 4).