Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010300684X/sq1013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010300684X/sq1013Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010300684X/sq1013IIsup3.hkl |
CCDC references: 214169; 214170
A sample of (+)-nootkatone, [α]D = +166°, was purchased from Aromor Inc., Israel. A suitable single-crystal was chosen without recrystallization. To a solution of tetrahydronootkatone (0.5 g, 2.25 mmol), also obtained from Aromor, in glacial acetic acid (11 ml) was added 1 equivalent of a 1 M solution of Br2 in acetic acid. The solution was stirred at room temperature for 1 h under a positive N2 pressure. The reaction mixture was then poured over water and extracted with CHCl3. The organic layers were combined, dried over Na2SO4, filtered, and concentrated to give a thick oil. The dibromo derivative [(II), m.p. 406–408 K, [α]D = +0.28°] was crystallized from hexanes (0.531 g, 32.6% yield).
H atoms were treated as riding in idealized positions, with C—H distances in the range 0.95–1.00 Å, depending on the atom type. A torsional parameter was refined for each methyl group. Displacement parameters for H atoms were assigned as Uiso = 1.2Ueq of the attached atom (1.5 for methyl groups). Friedel pairs were averaged for (I). For the dibromo derivative, (II), the absolute configuration was determined by refinement of the Flack (1983) parameter, using 4216 Friedel pairs. All residual peaks greater than 0.69 e Å−3 were within 1.1 Å of bromine positions.
For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEP-3 (Farrugia, 1997) for (I); ORTEP-3 (Farrugia, 1997) and CrystMol (Duchamp, 1999) for (II). For both compounds, software used to prepare material for publication: SHELXL97.
C15H22O | F(000) = 240 |
Mr = 218.33 | Dx = 1.119 Mg m−3 |
Monoclinic, P21 | Melting point: 309-311K K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 5.903 (2) Å | Cell parameters from 1493 reflections |
b = 9.495 (4) Å | θ = 2.5–27.5° |
c = 11.630 (6) Å | µ = 0.07 mm−1 |
β = 96.09 (2)° | T = 150 K |
V = 648.2 (5) Å3 | Needle fragment, colorless |
Z = 2 | 0.32 × 0.25 × 0.20 mm |
Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer | 1202 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Graphite monochromator | θmax = 27.5°, θmin = 2.7° |
ω scans with κ offsets | h = −7→7 |
7526 measured reflections | k = −12→12 |
1577 independent 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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0459P)2 + 0.044P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
1577 reflections | Δρmax = 0.16 e Å−3 |
149 parameters | Δρmin = −0.15 e Å−3 |
1 restraint | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.041 (9) |
C15H22O | V = 648.2 (5) Å3 |
Mr = 218.33 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.903 (2) Å | µ = 0.07 mm−1 |
b = 9.495 (4) Å | T = 150 K |
c = 11.630 (6) Å | 0.32 × 0.25 × 0.20 mm |
β = 96.09 (2)° |
Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer | 1202 reflections with I > 2σ(I) |
7526 measured reflections | Rint = 0.023 |
1577 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 1 restraint |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.16 e Å−3 |
1577 reflections | Δρmin = −0.15 e Å−3 |
149 parameters |
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 > σ(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 | 0.9245 (3) | 0.4298 (2) | 0.40302 (15) | 0.0544 (5) | |
C1 | 0.8374 (4) | 0.3090 (3) | 0.56883 (19) | 0.0324 (5) | |
H1 | 0.9146 | 0.2268 | 0.5475 | 0.039* | |
C2 | 0.8218 (4) | 0.4282 (3) | 0.4894 (2) | 0.0379 (6) | |
C3 | 0.6720 (4) | 0.5467 (3) | 0.5196 (2) | 0.0393 (6) | |
H3A | 0.5118 | 0.5248 | 0.4912 | 0.047* | |
H3B | 0.7157 | 0.6337 | 0.4806 | 0.047* | |
C4 | 0.6917 (4) | 0.5713 (2) | 0.65075 (19) | 0.0317 (6) | |
H4 | 0.8555 | 0.5923 | 0.6758 | 0.038* | |
C5 | 0.6313 (3) | 0.4369 (3) | 0.71613 (18) | 0.0274 (5) | |
C6 | 0.7166 (4) | 0.4560 (2) | 0.84551 (18) | 0.0287 (5) | |
H6A | 0.8755 | 0.4908 | 0.8514 | 0.034* | |
H6B | 0.6231 | 0.5299 | 0.8777 | 0.034* | |
C7 | 0.7101 (4) | 0.3238 (2) | 0.92099 (19) | 0.0280 (5) | |
H7 | 0.5486 | 0.2903 | 0.9148 | 0.034* | |
C8 | 0.8507 (4) | 0.2093 (3) | 0.8705 (2) | 0.0343 (6) | |
H8A | 0.8446 | 0.1222 | 0.9169 | 0.041* | |
H8B | 1.0117 | 0.2398 | 0.8744 | 0.041* | |
C9 | 0.7605 (4) | 0.1786 (3) | 0.7443 (2) | 0.0352 (6) | |
H9A | 0.8611 | 0.1087 | 0.7122 | 0.042* | |
H9B | 0.6065 | 0.1367 | 0.7419 | 0.042* | |
C10 | 0.7490 (3) | 0.3088 (2) | 0.67038 (18) | 0.0283 (5) | |
C11 | 0.7807 (4) | 0.3577 (2) | 1.04696 (19) | 0.0328 (6) | |
C12 | 0.6291 (4) | 0.4579 (3) | 1.1030 (2) | 0.0431 (7) | |
H12A | 0.6755 | 0.4612 | 1.1864 | 0.065* | |
H12B | 0.4709 | 0.4257 | 1.0892 | 0.065* | |
H12C | 0.6421 | 0.5522 | 1.0700 | 0.065* | |
C13 | 0.9638 (4) | 0.3046 (3) | 1.1070 (2) | 0.0452 (7) | |
H13A | 0.9998 | 0.3298 | 1.1859 | 0.054* | |
H13B | 1.0593 | 0.2412 | 1.0712 | 0.054* | |
C14 | 0.3711 (4) | 0.4100 (3) | 0.7018 (2) | 0.0397 (6) | |
H14A | 0.3148 | 0.4110 | 0.6194 | 0.060* | |
H14B | 0.2944 | 0.4839 | 0.7420 | 0.060* | |
H14C | 0.3394 | 0.3181 | 0.7349 | 0.060* | |
C15 | 0.5564 (5) | 0.7019 (3) | 0.6779 (2) | 0.0473 (7) | |
H15A | 0.6193 | 0.7846 | 0.6422 | 0.071* | |
H15B | 0.5665 | 0.7152 | 0.7619 | 0.071* | |
H15C | 0.3965 | 0.6897 | 0.6471 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0656 (12) | 0.0614 (13) | 0.0393 (10) | −0.0189 (11) | 0.0202 (9) | −0.0027 (10) |
C1 | 0.0315 (11) | 0.0327 (12) | 0.0330 (12) | −0.0024 (10) | 0.0037 (10) | −0.0046 (11) |
C2 | 0.0368 (12) | 0.0485 (16) | 0.0287 (11) | −0.0164 (12) | 0.0044 (10) | −0.0046 (12) |
C3 | 0.0409 (13) | 0.0428 (15) | 0.0327 (13) | −0.0061 (12) | −0.0042 (11) | 0.0093 (11) |
C4 | 0.0324 (11) | 0.0326 (14) | 0.0290 (12) | −0.0024 (10) | −0.0018 (10) | 0.0046 (10) |
C5 | 0.0242 (10) | 0.0287 (11) | 0.0289 (11) | −0.0007 (9) | 0.0020 (9) | 0.0016 (10) |
C6 | 0.0312 (11) | 0.0260 (12) | 0.0287 (11) | 0.0003 (9) | 0.0025 (9) | 0.0006 (10) |
C7 | 0.0284 (11) | 0.0259 (12) | 0.0298 (11) | −0.0007 (9) | 0.0031 (9) | 0.0002 (10) |
C8 | 0.0432 (13) | 0.0256 (12) | 0.0347 (13) | 0.0026 (10) | 0.0064 (11) | 0.0022 (10) |
C9 | 0.0459 (14) | 0.0257 (13) | 0.0349 (13) | 0.0003 (11) | 0.0086 (11) | −0.0030 (10) |
C10 | 0.0233 (10) | 0.0300 (12) | 0.0312 (12) | −0.0035 (9) | 0.0004 (9) | −0.0002 (10) |
C11 | 0.0402 (14) | 0.0270 (12) | 0.0319 (12) | −0.0009 (10) | 0.0076 (11) | 0.0019 (10) |
C12 | 0.0556 (16) | 0.0426 (16) | 0.0324 (13) | 0.0069 (13) | 0.0110 (11) | −0.0009 (12) |
C13 | 0.0531 (15) | 0.0436 (15) | 0.0371 (13) | 0.0117 (13) | −0.0038 (12) | 0.0007 (13) |
C14 | 0.0264 (11) | 0.0484 (17) | 0.0443 (14) | −0.0025 (11) | 0.0031 (10) | −0.0025 (12) |
C15 | 0.0597 (17) | 0.0369 (14) | 0.0429 (15) | 0.0118 (13) | −0.0052 (13) | 0.0048 (13) |
O1—C2 | 1.228 (3) | C8—C9 | 1.534 (3) |
C1—C10 | 1.341 (3) | C8—H8A | 0.9900 |
C1—C2 | 1.457 (4) | C8—H8B | 0.9900 |
C1—H1 | 0.9500 | C9—C10 | 1.504 (3) |
C2—C3 | 1.496 (4) | C9—H9A | 0.9900 |
C3—C4 | 1.536 (3) | C9—H9B | 0.9900 |
C3—H3A | 0.9900 | C11—C13 | 1.323 (3) |
C3—H3B | 0.9900 | C11—C12 | 1.501 (3) |
C4—C15 | 1.526 (4) | C12—H12A | 0.9800 |
C4—C5 | 1.546 (3) | C12—H12B | 0.9800 |
C4—H4 | 1.0000 | C12—H12C | 0.9800 |
C5—C10 | 1.524 (3) | C13—H13A | 0.9500 |
C5—C6 | 1.546 (3) | C13—H13B | 0.9500 |
C5—C14 | 1.549 (3) | C14—H14A | 0.9800 |
C6—C7 | 1.535 (3) | C14—H14B | 0.9800 |
C6—H6A | 0.9900 | C14—H14C | 0.9800 |
C6—H6B | 0.9900 | C15—H15A | 0.9800 |
C7—C11 | 1.515 (3) | C15—H15B | 0.9800 |
C7—C8 | 1.523 (3) | C15—H15C | 0.9800 |
C7—H7 | 1.0000 | ||
C10—C1—C2 | 123.7 (2) | C9—C8—H8A | 109.5 |
C10—C1—H1 | 118.2 | C7—C8—H8B | 109.5 |
C2—C1—H1 | 118.2 | C9—C8—H8B | 109.5 |
O1—C2—C1 | 121.7 (2) | H8A—C8—H8B | 108.1 |
O1—C2—C3 | 122.5 (2) | C10—C9—C8 | 112.37 (19) |
C1—C2—C3 | 115.8 (2) | C10—C9—H9A | 109.1 |
C2—C3—C4 | 111.27 (18) | C8—C9—H9A | 109.1 |
C2—C3—H3A | 109.4 | C10—C9—H9B | 109.1 |
C4—C3—H3A | 109.4 | C8—C9—H9B | 109.1 |
C2—C3—H3B | 109.4 | H9A—C9—H9B | 107.9 |
C4—C3—H3B | 109.4 | C1—C10—C9 | 120.4 (2) |
H3A—C3—H3B | 108.0 | C1—C10—C5 | 122.8 (2) |
C15—C4—C3 | 110.07 (19) | C9—C10—C5 | 116.82 (19) |
C15—C4—C5 | 114.6 (2) | C13—C11—C12 | 120.2 (2) |
C3—C4—C5 | 111.48 (19) | C13—C11—C7 | 123.7 (2) |
C15—C4—H4 | 106.8 | C12—C11—C7 | 116.05 (19) |
C3—C4—H4 | 106.8 | C11—C12—H12A | 109.5 |
C5—C4—H4 | 106.8 | C11—C12—H12B | 109.5 |
C10—C5—C6 | 108.66 (17) | H12A—C12—H12B | 109.5 |
C10—C5—C4 | 110.44 (16) | C11—C12—H12C | 109.5 |
C6—C5—C4 | 108.28 (18) | H12A—C12—H12C | 109.5 |
C10—C5—C14 | 108.32 (19) | H12B—C12—H12C | 109.5 |
C6—C5—C14 | 109.93 (17) | C11—C13—H13A | 120.0 |
C4—C5—C14 | 111.17 (19) | C11—C13—H13B | 120.0 |
C7—C6—C5 | 115.81 (18) | H13A—C13—H13B | 120.0 |
C7—C6—H6A | 108.3 | C5—C14—H14A | 109.5 |
C5—C6—H6A | 108.3 | C5—C14—H14B | 109.5 |
C7—C6—H6B | 108.3 | H14A—C14—H14B | 109.5 |
C5—C6—H6B | 108.3 | C5—C14—H14C | 109.5 |
H6A—C6—H6B | 107.4 | H14A—C14—H14C | 109.5 |
C11—C7—C8 | 114.82 (17) | H14B—C14—H14C | 109.5 |
C11—C7—C6 | 110.97 (18) | C4—C15—H15A | 109.5 |
C8—C7—C6 | 108.41 (18) | C4—C15—H15B | 109.5 |
C11—C7—H7 | 107.4 | H15A—C15—H15B | 109.5 |
C8—C7—H7 | 107.4 | C4—C15—H15C | 109.5 |
C6—C7—H7 | 107.4 | H15A—C15—H15C | 109.5 |
C7—C8—C9 | 110.89 (18) | H15B—C15—H15C | 109.5 |
C7—C8—H8A | 109.5 | ||
C10—C1—C2—O1 | 172.4 (2) | C11—C7—C8—C9 | 177.82 (19) |
C10—C1—C2—C3 | −8.1 (3) | C6—C7—C8—C9 | −57.5 (2) |
O1—C2—C3—C4 | −142.6 (2) | C7—C8—C9—C10 | 55.0 (3) |
C1—C2—C3—C4 | 37.9 (3) | C2—C1—C10—C9 | 176.45 (19) |
C2—C3—C4—C15 | 174.2 (2) | C2—C1—C10—C5 | −2.9 (3) |
C2—C3—C4—C5 | −57.5 (3) | C8—C9—C10—C1 | 130.8 (2) |
C15—C4—C5—C10 | 171.74 (19) | C8—C9—C10—C5 | −49.8 (3) |
C3—C4—C5—C10 | 45.9 (2) | C6—C5—C10—C1 | −135.4 (2) |
C15—C4—C5—C6 | −69.4 (2) | C4—C5—C10—C1 | −16.7 (3) |
C3—C4—C5—C6 | 164.77 (18) | C14—C5—C10—C1 | 105.2 (2) |
C15—C4—C5—C14 | 51.5 (3) | C6—C5—C10—C9 | 45.3 (2) |
C3—C4—C5—C14 | −74.4 (2) | C4—C5—C10—C9 | 163.92 (18) |
C10—C5—C6—C7 | −49.6 (2) | C14—C5—C10—C9 | −74.1 (2) |
C4—C5—C6—C7 | −169.61 (18) | C8—C7—C11—C13 | 6.8 (3) |
C14—C5—C6—C7 | 68.8 (3) | C6—C7—C11—C13 | −116.5 (3) |
C5—C6—C7—C11 | −175.80 (18) | C8—C7—C11—C12 | −173.2 (2) |
C5—C6—C7—C8 | 57.2 (2) | C6—C7—C11—C12 | 63.4 (2) |
C15H24Br2O | F(000) = 768 |
Mr = 380.16 | Dx = 1.612 Mg m−3 |
Monoclinic, P21 | Melting point: 406-408K K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 13.500 (3) Å | Cell parameters from 4844 reflections |
b = 6.1403 (10) Å | θ = 2.5–30.5° |
c = 18.909 (5) Å | µ = 5.16 mm−1 |
β = 92.145 (7)° | T = 100 K |
V = 1566.3 (6) Å3 | Needle, colorless |
Z = 4 | 0.30 × 0.05 × 0.02 mm |
Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer | 9388 independent reflections |
Radiation source: fine-focus sealed tube | 7482 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
ω scans with κ offsets | θmax = 30.5°, θmin = 3.0° |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) | h = −19→19 |
Tmin = 0.385, Tmax = 0.902 | k = −8→8 |
19375 measured reflections | l = −27→26 |
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)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + 4.911P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
9388 reflections | Δρmax = 1.09 e Å−3 |
333 parameters | Δρmin = −0.66 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 4216 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.019 (11) |
C15H24Br2O | V = 1566.3 (6) Å3 |
Mr = 380.16 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 13.500 (3) Å | µ = 5.16 mm−1 |
b = 6.1403 (10) Å | T = 100 K |
c = 18.909 (5) Å | 0.30 × 0.05 × 0.02 mm |
β = 92.145 (7)° |
Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer | 9388 independent reflections |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) | 7482 reflections with I > 2σ(I) |
Tmin = 0.385, Tmax = 0.902 | Rint = 0.063 |
19375 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.095 | Δρmax = 1.09 e Å−3 |
S = 1.10 | Δρmin = −0.66 e Å−3 |
9388 reflections | Absolute structure: Flack (1983), 4216 Friedel pairs |
333 parameters | Absolute structure parameter: 0.019 (11) |
1 restraint |
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 > σ(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 | ||
Br1A | 0.31947 (3) | 0.63431 (9) | 0.38734 (3) | 0.02530 (12) | |
Br2A | 0.71950 (3) | 0.65096 (9) | 0.46932 (3) | 0.02331 (11) | |
O1A | 0.5042 (3) | 0.7030 (5) | 0.47129 (19) | 0.0210 (8) | |
C1A | 0.4379 (3) | 0.4506 (7) | 0.3845 (3) | 0.0161 (10) | |
H1A | 0.4218 | 0.3072 | 0.4064 | 0.019* | |
C2A | 0.5197 (3) | 0.5570 (7) | 0.4304 (3) | 0.0155 (9) | |
C3A | 0.6222 (3) | 0.4556 (7) | 0.4236 (2) | 0.0145 (9) | |
H3A | 0.6229 | 0.3180 | 0.4519 | 0.017* | |
C4A | 0.6501 (3) | 0.3935 (9) | 0.3483 (2) | 0.0153 (8) | |
H4A | 0.6590 | 0.5318 | 0.3213 | 0.018* | |
C5A | 0.5647 (3) | 0.2638 (7) | 0.3104 (3) | 0.0135 (9) | |
C6A | 0.5925 (4) | 0.2194 (8) | 0.2334 (3) | 0.0196 (10) | |
H6A1 | 0.6124 | 0.3587 | 0.2117 | 0.024* | |
H6A2 | 0.6508 | 0.1216 | 0.2339 | 0.024* | |
C7A | 0.5095 (3) | 0.1164 (8) | 0.1864 (2) | 0.0190 (10) | |
H7A | 0.4912 | −0.0249 | 0.2087 | 0.023* | |
C8A | 0.4182 (4) | 0.2649 (8) | 0.1875 (3) | 0.0233 (11) | |
H8A1 | 0.4337 | 0.4055 | 0.1648 | 0.028* | |
H8A2 | 0.3630 | 0.1963 | 0.1597 | 0.028* | |
C9A | 0.3859 (3) | 0.3066 (8) | 0.2625 (3) | 0.0186 (10) | |
H9A1 | 0.3650 | 0.1674 | 0.2837 | 0.022* | |
H9A2 | 0.3281 | 0.4060 | 0.2609 | 0.022* | |
C10A | 0.4695 (3) | 0.4077 (9) | 0.3095 (2) | 0.0148 (8) | |
H10A | 0.4868 | 0.5513 | 0.2882 | 0.018* | |
C11A | 0.5450 (4) | 0.0648 (9) | 0.1117 (3) | 0.0241 (11) | |
H11A | 0.5755 | 0.2002 | 0.0928 | 0.029* | |
C12A | 0.6244 (4) | −0.1118 (13) | 0.1140 (3) | 0.0372 (14) | |
H12A | 0.5987 | −0.2422 | 0.1369 | 0.056* | |
H12B | 0.6830 | −0.0591 | 0.1409 | 0.056* | |
H12C | 0.6425 | −0.1477 | 0.0657 | 0.056* | |
C13A | 0.4611 (4) | −0.0035 (11) | 0.0597 (3) | 0.0337 (14) | |
H13A | 0.4881 | −0.0319 | 0.0132 | 0.050* | |
H13B | 0.4119 | 0.1136 | 0.0556 | 0.050* | |
H13C | 0.4295 | −0.1359 | 0.0770 | 0.050* | |
C14A | 0.5487 (4) | 0.0440 (7) | 0.3484 (3) | 0.0180 (10) | |
H14A | 0.4898 | −0.0281 | 0.3275 | 0.027* | |
H14B | 0.5393 | 0.0702 | 0.3988 | 0.027* | |
H14C | 0.6068 | −0.0493 | 0.3428 | 0.027* | |
C15A | 0.7499 (4) | 0.2750 (9) | 0.3515 (3) | 0.0220 (10) | |
H15A | 0.7428 | 0.1355 | 0.3760 | 0.033* | |
H15B | 0.7993 | 0.3648 | 0.3772 | 0.033* | |
H15C | 0.7715 | 0.2487 | 0.3033 | 0.033* | |
Br1B | −0.18748 (3) | 0.40480 (9) | 0.09903 (3) | 0.02568 (11) | |
Br2B | 0.21533 (3) | 0.40203 (11) | 0.04876 (3) | 0.02671 (12) | |
O1B | 0.0012 (3) | 0.3464 (5) | 0.02916 (19) | 0.0216 (8) | |
C1B | −0.0709 (3) | 0.5932 (7) | 0.1113 (3) | 0.0159 (10) | |
H1B | −0.0871 | 0.7364 | 0.0886 | 0.019* | |
C2B | 0.0140 (4) | 0.4910 (7) | 0.0715 (3) | 0.0161 (9) | |
C3B | 0.1152 (3) | 0.5943 (7) | 0.0865 (2) | 0.0145 (9) | |
H3B | 0.1167 | 0.7319 | 0.0583 | 0.017* | |
C4B | 0.1396 (3) | 0.6571 (9) | 0.1641 (2) | 0.0149 (8) | |
H4B | 0.1477 | 0.5193 | 0.1919 | 0.018* | |
C5B | 0.0514 (3) | 0.7868 (7) | 0.1950 (3) | 0.0149 (9) | |
C6B | 0.0746 (3) | 0.8319 (7) | 0.2737 (3) | 0.0160 (9) | |
H6B1 | 0.1320 | 0.9318 | 0.2780 | 0.019* | |
H6B2 | 0.0938 | 0.6935 | 0.2973 | 0.019* | |
C7B | −0.0126 (3) | 0.9326 (8) | 0.3124 (2) | 0.0183 (10) | |
H7B | −0.0332 | 1.0662 | 0.2854 | 0.022* | |
C8B | −0.0995 (4) | 0.7742 (8) | 0.3068 (3) | 0.0216 (10) | |
H8B1 | −0.0807 | 0.6354 | 0.3304 | 0.026* | |
H8B2 | −0.1566 | 0.8359 | 0.3314 | 0.026* | |
C9B | −0.1293 (4) | 0.7307 (8) | 0.2297 (3) | 0.0204 (10) | |
H9B1 | −0.1515 | 0.8684 | 0.2069 | 0.024* | |
H9B2 | −0.1857 | 0.6274 | 0.2273 | 0.024* | |
C10B | −0.0433 (3) | 0.6359 (9) | 0.1893 (2) | 0.0148 (8) | |
H10B | −0.0252 | 0.4930 | 0.2115 | 0.018* | |
C11B | 0.0138 (4) | 1.0057 (8) | 0.3891 (3) | 0.0213 (11) | |
H11B | −0.0490 | 1.0596 | 0.4093 | 0.026* | |
C12B | 0.0518 (4) | 0.8221 (8) | 0.4373 (3) | 0.0236 (11) | |
H12D | 0.1155 | 0.7695 | 0.4208 | 0.035* | |
H12E | 0.0038 | 0.7023 | 0.4362 | 0.035* | |
H12F | 0.0606 | 0.8766 | 0.4858 | 0.035* | |
C13B | 0.0860 (4) | 1.1991 (9) | 0.3898 (3) | 0.0314 (13) | |
H13D | 0.0954 | 1.2537 | 0.4383 | 0.047* | |
H13E | 0.0587 | 1.3153 | 0.3594 | 0.047* | |
H13F | 0.1499 | 1.1517 | 0.3723 | 0.047* | |
C14B | 0.0340 (4) | 1.0032 (7) | 0.1551 (3) | 0.0185 (10) | |
H14D | −0.0298 | 1.0649 | 0.1678 | 0.028* | |
H14E | 0.0337 | 0.9765 | 0.1040 | 0.028* | |
H14F | 0.0873 | 1.1056 | 0.1683 | 0.028* | |
C15B | 0.2377 (4) | 0.7796 (9) | 0.1696 (3) | 0.0207 (10) | |
H15D | 0.2895 | 0.6921 | 0.1483 | 0.031* | |
H15E | 0.2558 | 0.8065 | 0.2195 | 0.031* | |
H15F | 0.2310 | 0.9188 | 0.1446 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1A | 0.0172 (2) | 0.0302 (3) | 0.0285 (3) | 0.0093 (2) | 0.00145 (18) | −0.0048 (3) |
Br2A | 0.0201 (2) | 0.0270 (2) | 0.0225 (2) | −0.0045 (2) | −0.00245 (18) | −0.0052 (2) |
O1A | 0.0268 (18) | 0.0178 (17) | 0.0185 (18) | 0.0024 (14) | 0.0034 (15) | −0.0039 (14) |
C1A | 0.012 (2) | 0.016 (2) | 0.020 (2) | 0.0058 (17) | 0.0015 (17) | 0.0010 (18) |
C2A | 0.014 (2) | 0.016 (2) | 0.017 (2) | −0.0019 (18) | 0.0002 (18) | 0.0055 (19) |
C3A | 0.014 (2) | 0.013 (2) | 0.016 (2) | −0.0021 (16) | −0.0011 (17) | 0.0004 (17) |
C4A | 0.0152 (19) | 0.015 (2) | 0.015 (2) | −0.002 (2) | −0.0006 (15) | 0.002 (2) |
C5A | 0.014 (2) | 0.013 (2) | 0.014 (2) | 0.0001 (17) | −0.0005 (17) | −0.0006 (18) |
C6A | 0.018 (2) | 0.024 (2) | 0.017 (3) | 0.0019 (19) | 0.0055 (18) | −0.001 (2) |
C7A | 0.021 (2) | 0.018 (2) | 0.017 (2) | 0.002 (2) | −0.0017 (17) | −0.002 (2) |
C8A | 0.024 (3) | 0.022 (3) | 0.023 (3) | 0.000 (2) | −0.005 (2) | 0.001 (2) |
C9A | 0.014 (2) | 0.024 (2) | 0.017 (3) | 0.0033 (19) | −0.0012 (18) | −0.004 (2) |
C10A | 0.0175 (19) | 0.0141 (19) | 0.013 (2) | 0.004 (2) | −0.0015 (15) | −0.002 (2) |
C11A | 0.028 (3) | 0.029 (3) | 0.016 (3) | −0.001 (2) | 0.002 (2) | 0.000 (2) |
C12A | 0.032 (3) | 0.054 (4) | 0.026 (3) | 0.009 (3) | 0.001 (2) | −0.011 (3) |
C13A | 0.035 (3) | 0.047 (3) | 0.019 (3) | 0.000 (3) | 0.001 (2) | −0.003 (3) |
C14A | 0.020 (2) | 0.014 (2) | 0.021 (3) | 0.0016 (18) | 0.001 (2) | −0.0021 (19) |
C15A | 0.019 (2) | 0.022 (2) | 0.025 (3) | 0.0008 (19) | 0.0008 (19) | −0.007 (2) |
Br1B | 0.0182 (2) | 0.0256 (2) | 0.0330 (3) | −0.0054 (2) | −0.00305 (19) | −0.0070 (3) |
Br2B | 0.0232 (2) | 0.0346 (3) | 0.0224 (3) | 0.0103 (3) | 0.00155 (18) | −0.0071 (3) |
O1B | 0.0277 (18) | 0.0182 (18) | 0.0187 (19) | 0.0012 (14) | −0.0019 (15) | −0.0008 (14) |
C1B | 0.016 (2) | 0.012 (2) | 0.020 (2) | −0.0019 (16) | −0.0022 (17) | −0.0010 (17) |
C2B | 0.021 (2) | 0.015 (2) | 0.012 (2) | 0.0007 (19) | −0.0023 (18) | 0.0026 (19) |
C3B | 0.016 (2) | 0.016 (2) | 0.011 (2) | 0.0092 (17) | 0.0034 (16) | −0.0021 (17) |
C4B | 0.0157 (19) | 0.016 (2) | 0.012 (2) | 0.004 (2) | −0.0034 (15) | −0.003 (2) |
C5B | 0.014 (2) | 0.015 (2) | 0.016 (2) | 0.0008 (17) | −0.0009 (18) | 0.0015 (19) |
C6B | 0.015 (2) | 0.014 (2) | 0.018 (2) | −0.0014 (17) | 0.0008 (18) | −0.0011 (18) |
C7B | 0.024 (2) | 0.019 (2) | 0.012 (2) | 0.000 (2) | 0.0018 (17) | −0.0029 (19) |
C8B | 0.019 (2) | 0.024 (3) | 0.022 (3) | −0.001 (2) | 0.003 (2) | −0.003 (2) |
C9B | 0.015 (2) | 0.022 (2) | 0.025 (3) | 0.0034 (19) | 0.0018 (19) | −0.002 (2) |
C10B | 0.0153 (19) | 0.0134 (19) | 0.015 (2) | 0.000 (2) | 0.0000 (15) | 0.000 (2) |
C11B | 0.020 (2) | 0.023 (2) | 0.021 (3) | 0.003 (2) | 0.001 (2) | −0.006 (2) |
C12B | 0.030 (3) | 0.026 (3) | 0.015 (3) | 0.004 (2) | 0.003 (2) | 0.002 (2) |
C13B | 0.042 (3) | 0.027 (3) | 0.025 (3) | −0.004 (2) | −0.006 (2) | 0.000 (2) |
C14B | 0.023 (2) | 0.012 (2) | 0.020 (3) | −0.0002 (18) | 0.002 (2) | −0.0004 (19) |
C15B | 0.018 (2) | 0.027 (3) | 0.017 (3) | 0.001 (2) | 0.0010 (19) | 0.001 (2) |
Br1A—C1A | 1.959 (4) | Br1B—C1B | 1.960 (4) |
Br2A—C3A | 1.956 (4) | Br2B—C3B | 1.950 (4) |
O1A—C2A | 1.207 (6) | O1B—C2B | 1.203 (6) |
C1A—C10A | 1.520 (6) | C1B—C10B | 1.529 (6) |
C1A—C2A | 1.526 (6) | C1B—C2B | 1.530 (7) |
C1A—H1A | 1.0000 | C1B—H1B | 1.0000 |
C2A—C3A | 1.527 (6) | C2B—C3B | 1.523 (6) |
C3A—C4A | 1.535 (6) | C3B—C4B | 1.542 (6) |
C3A—H3A | 1.0000 | C3B—H3B | 1.0000 |
C4A—C15A | 1.530 (6) | C4B—C15B | 1.523 (6) |
C4A—C5A | 1.554 (6) | C4B—C5B | 1.564 (6) |
C4A—H4A | 1.0000 | C4B—H4B | 1.0000 |
C5A—C6A | 1.543 (7) | C5B—C6B | 1.535 (7) |
C5A—C14A | 1.547 (6) | C5B—C14B | 1.541 (6) |
C5A—C10A | 1.560 (6) | C5B—C10B | 1.579 (6) |
C6A—C7A | 1.540 (7) | C6B—C7B | 1.538 (6) |
C6A—H6A1 | 0.9900 | C6B—H6B1 | 0.9900 |
C6A—H6A2 | 0.9900 | C6B—H6B2 | 0.9900 |
C7A—C8A | 1.533 (7) | C7B—C8B | 1.525 (7) |
C7A—C11A | 1.541 (7) | C7B—C11B | 1.547 (7) |
C7A—H7A | 1.0000 | C7B—H7B | 1.0000 |
C8A—C9A | 1.521 (7) | C8B—C9B | 1.522 (7) |
C8A—H8A1 | 0.9900 | C8B—H8B1 | 0.9900 |
C8A—H8A2 | 0.9900 | C8B—H8B2 | 0.9900 |
C9A—C10A | 1.540 (6) | C9B—C10B | 1.529 (6) |
C9A—H9A1 | 0.9900 | C9B—H9B1 | 0.9900 |
C9A—H9A2 | 0.9900 | C9B—H9B2 | 0.9900 |
C10A—H10A | 1.0000 | C10B—H10B | 1.0000 |
C11A—C12A | 1.524 (8) | C11B—C12B | 1.527 (7) |
C11A—C13A | 1.531 (8) | C11B—C13B | 1.536 (7) |
C11A—H11A | 1.0000 | C11B—H11B | 1.0000 |
C12A—H12A | 0.9800 | C12B—H12D | 0.9800 |
C12A—H12B | 0.9800 | C12B—H12E | 0.9800 |
C12A—H12C | 0.9800 | C12B—H12F | 0.9800 |
C13A—H13A | 0.9800 | C13B—H13D | 0.9800 |
C13A—H13B | 0.9800 | C13B—H13E | 0.9800 |
C13A—H13C | 0.9800 | C13B—H13F | 0.9800 |
C14A—H14A | 0.9800 | C14B—H14D | 0.9800 |
C14A—H14B | 0.9800 | C14B—H14E | 0.9800 |
C14A—H14C | 0.9800 | C14B—H14F | 0.9800 |
C15A—H15A | 0.9800 | C15B—H15D | 0.9800 |
C15A—H15B | 0.9800 | C15B—H15E | 0.9800 |
C15A—H15C | 0.9800 | C15B—H15F | 0.9800 |
C10A—C1A—C2A | 112.5 (4) | C10B—C1B—C2B | 112.7 (4) |
C10A—C1A—Br1A | 112.5 (3) | C10B—C1B—Br1B | 112.4 (3) |
C2A—C1A—Br1A | 108.2 (3) | C2B—C1B—Br1B | 108.2 (3) |
C10A—C1A—H1A | 107.8 | C10B—C1B—H1B | 107.8 |
C2A—C1A—H1A | 107.8 | C2B—C1B—H1B | 107.8 |
Br1A—C1A—H1A | 107.8 | Br1B—C1B—H1B | 107.8 |
O1A—C2A—C1A | 122.9 (4) | O1B—C2B—C3B | 122.4 (4) |
O1A—C2A—C3A | 122.5 (4) | O1B—C2B—C1B | 122.6 (4) |
C1A—C2A—C3A | 114.6 (4) | C3B—C2B—C1B | 114.9 (4) |
C2A—C3A—C4A | 115.7 (4) | C2B—C3B—C4B | 116.1 (4) |
C2A—C3A—Br2A | 107.9 (3) | C2B—C3B—Br2B | 108.0 (3) |
C4A—C3A—Br2A | 112.2 (3) | C4B—C3B—Br2B | 111.9 (3) |
C2A—C3A—H3A | 106.8 | C2B—C3B—H3B | 106.8 |
C4A—C3A—H3A | 106.8 | C4B—C3B—H3B | 106.8 |
Br2A—C3A—H3A | 106.8 | Br2B—C3B—H3B | 106.8 |
C15A—C4A—C3A | 109.1 (4) | C15B—C4B—C3B | 110.0 (4) |
C15A—C4A—C5A | 114.3 (4) | C15B—C4B—C5B | 113.3 (4) |
C3A—C4A—C5A | 110.6 (3) | C3B—C4B—C5B | 110.1 (3) |
C15A—C4A—H4A | 107.5 | C15B—C4B—H4B | 107.7 |
C3A—C4A—H4A | 107.5 | C3B—C4B—H4B | 107.7 |
C5A—C4A—H4A | 107.5 | C5B—C4B—H4B | 107.7 |
C6A—C5A—C14A | 109.1 (4) | C6B—C5B—C14B | 109.9 (4) |
C6A—C5A—C4A | 108.9 (4) | C6B—C5B—C4B | 108.9 (4) |
C14A—C5A—C4A | 110.4 (4) | C14B—C5B—C4B | 111.1 (4) |
C6A—C5A—C10A | 108.6 (4) | C6B—C5B—C10B | 107.9 (4) |
C14A—C5A—C10A | 111.7 (4) | C14B—C5B—C10B | 111.4 (4) |
C4A—C5A—C10A | 108.2 (4) | C4B—C5B—C10B | 107.5 (4) |
C7A—C6A—C5A | 114.8 (4) | C5B—C6B—C7B | 113.7 (4) |
C7A—C6A—H6A1 | 108.6 | C5B—C6B—H6B1 | 108.8 |
C5A—C6A—H6A1 | 108.6 | C7B—C6B—H6B1 | 108.8 |
C7A—C6A—H6A2 | 108.6 | C5B—C6B—H6B2 | 108.8 |
C5A—C6A—H6A2 | 108.6 | C7B—C6B—H6B2 | 108.8 |
H6A1—C6A—H6A2 | 107.5 | H6B1—C6B—H6B2 | 107.7 |
C8A—C7A—C6A | 108.4 (4) | C8B—C7B—C6B | 108.2 (4) |
C8A—C7A—C11A | 114.3 (4) | C8B—C7B—C11B | 113.5 (4) |
C6A—C7A—C11A | 111.6 (4) | C6B—C7B—C11B | 114.1 (4) |
C8A—C7A—H7A | 107.4 | C8B—C7B—H7B | 106.9 |
C6A—C7A—H7A | 107.4 | C6B—C7B—H7B | 106.9 |
C11A—C7A—H7A | 107.4 | C11B—C7B—H7B | 106.9 |
C9A—C8A—C7A | 111.8 (4) | C9B—C8B—C7B | 110.7 (4) |
C9A—C8A—H8A1 | 109.3 | C9B—C8B—H8B1 | 109.5 |
C7A—C8A—H8A1 | 109.3 | C7B—C8B—H8B1 | 109.5 |
C9A—C8A—H8A2 | 109.3 | C9B—C8B—H8B2 | 109.5 |
C7A—C8A—H8A2 | 109.3 | C7B—C8B—H8B2 | 109.5 |
H8A1—C8A—H8A2 | 107.9 | H8B1—C8B—H8B2 | 108.1 |
C8A—C9A—C10A | 112.1 (4) | C8B—C9B—C10B | 111.5 (4) |
C8A—C9A—H9A1 | 109.2 | C8B—C9B—H9B1 | 109.3 |
C10A—C9A—H9A1 | 109.2 | C10B—C9B—H9B1 | 109.3 |
C8A—C9A—H9A2 | 109.2 | C8B—C9B—H9B2 | 109.3 |
C10A—C9A—H9A2 | 109.2 | C10B—C9B—H9B2 | 109.3 |
H9A1—C9A—H9A2 | 107.9 | H9B1—C9B—H9B2 | 108.0 |
C1A—C10A—C9A | 112.5 (4) | C1B—C10B—C9B | 112.6 (4) |
C1A—C10A—C5A | 110.3 (3) | C1B—C10B—C5B | 109.5 (4) |
C9A—C10A—C5A | 111.4 (4) | C9B—C10B—C5B | 111.8 (4) |
C1A—C10A—H10A | 107.5 | C1B—C10B—H10B | 107.6 |
C9A—C10A—H10A | 107.5 | C9B—C10B—H10B | 107.6 |
C5A—C10A—H10A | 107.5 | C5B—C10B—H10B | 107.6 |
C12A—C11A—C13A | 109.0 (5) | C12B—C11B—C13B | 111.5 (4) |
C12A—C11A—C7A | 111.3 (4) | C12B—C11B—C7B | 114.0 (4) |
C13A—C11A—C7A | 113.4 (4) | C13B—C11B—C7B | 110.9 (4) |
C12A—C11A—H11A | 107.6 | C12B—C11B—H11B | 106.7 |
C13A—C11A—H11A | 107.6 | C13B—C11B—H11B | 106.7 |
C7A—C11A—H11A | 107.6 | C7B—C11B—H11B | 106.7 |
C11A—C12A—H12A | 109.5 | C11B—C12B—H12D | 109.5 |
C11A—C12A—H12B | 109.5 | C11B—C12B—H12E | 109.5 |
H12A—C12A—H12B | 109.5 | H12D—C12B—H12E | 109.5 |
C11A—C12A—H12C | 109.5 | C11B—C12B—H12F | 109.5 |
H12A—C12A—H12C | 109.5 | H12D—C12B—H12F | 109.5 |
H12B—C12A—H12C | 109.5 | H12E—C12B—H12F | 109.5 |
C11A—C13A—H13A | 109.5 | C11B—C13B—H13D | 109.5 |
C11A—C13A—H13B | 109.5 | C11B—C13B—H13E | 109.5 |
H13A—C13A—H13B | 109.5 | H13D—C13B—H13E | 109.5 |
C11A—C13A—H13C | 109.5 | C11B—C13B—H13F | 109.5 |
H13A—C13A—H13C | 109.5 | H13D—C13B—H13F | 109.5 |
H13B—C13A—H13C | 109.5 | H13E—C13B—H13F | 109.5 |
C5A—C14A—H14A | 109.5 | C5B—C14B—H14D | 109.5 |
C5A—C14A—H14B | 109.5 | C5B—C14B—H14E | 109.5 |
H14A—C14A—H14B | 109.5 | H14D—C14B—H14E | 109.5 |
C5A—C14A—H14C | 109.5 | C5B—C14B—H14F | 109.5 |
H14A—C14A—H14C | 109.5 | H14D—C14B—H14F | 109.5 |
H14B—C14A—H14C | 109.5 | H14E—C14B—H14F | 109.5 |
C4A—C15A—H15A | 109.5 | C4B—C15B—H15D | 109.5 |
C4A—C15A—H15B | 109.5 | C4B—C15B—H15E | 109.5 |
H15A—C15A—H15B | 109.5 | H15D—C15B—H15E | 109.5 |
C4A—C15A—H15C | 109.5 | C4B—C15B—H15F | 109.5 |
H15A—C15A—H15C | 109.5 | H15D—C15B—H15F | 109.5 |
H15B—C15A—H15C | 109.5 | H15E—C15B—H15F | 109.5 |
C10A—C1A—C2A—O1A | 138.4 (5) | C10B—C1B—C2B—O1B | 138.6 (5) |
Br1A—C1A—C2A—O1A | 13.5 (6) | Br1B—C1B—C2B—O1B | 13.7 (6) |
C10A—C1A—C2A—C3A | −44.8 (5) | C10B—C1B—C2B—C3B | −44.4 (5) |
Br1A—C1A—C2A—C3A | −169.8 (3) | Br1B—C1B—C2B—C3B | −169.4 (3) |
O1A—C2A—C3A—C4A | −142.1 (5) | O1B—C2B—C3B—C4B | −142.6 (4) |
C1A—C2A—C3A—C4A | 41.1 (6) | C1B—C2B—C3B—C4B | 40.5 (5) |
O1A—C2A—C3A—Br2A | −15.4 (6) | O1B—C2B—C3B—Br2B | −16.0 (5) |
C1A—C2A—C3A—Br2A | 167.8 (3) | C1B—C2B—C3B—Br2B | 167.1 (3) |
C2A—C3A—C4A—C15A | −174.6 (4) | C2B—C3B—C4B—C15B | −174.0 (4) |
Br2A—C3A—C4A—C15A | 60.9 (5) | Br2B—C3B—C4B—C15B | 61.4 (5) |
C2A—C3A—C4A—C5A | −48.1 (5) | C2B—C3B—C4B—C5B | −48.4 (5) |
Br2A—C3A—C4A—C5A | −172.6 (3) | Br2B—C3B—C4B—C5B | −173.0 (3) |
C15A—C4A—C5A—C6A | −60.5 (5) | C15B—C4B—C5B—C6B | −60.5 (5) |
C3A—C4A—C5A—C6A | 175.9 (4) | C3B—C4B—C5B—C6B | 175.8 (4) |
C15A—C4A—C5A—C14A | 59.2 (5) | C15B—C4B—C5B—C14B | 60.7 (5) |
C3A—C4A—C5A—C14A | −64.4 (5) | C3B—C4B—C5B—C14B | −63.0 (5) |
C15A—C4A—C5A—C10A | −178.3 (4) | C15B—C4B—C5B—C10B | −177.2 (4) |
C3A—C4A—C5A—C10A | 58.1 (5) | C3B—C4B—C5B—C10B | 59.1 (5) |
C14A—C5A—C6A—C7A | 66.7 (5) | C14B—C5B—C6B—C7B | 65.6 (5) |
C4A—C5A—C6A—C7A | −172.8 (4) | C4B—C5B—C6B—C7B | −172.5 (4) |
C10A—C5A—C6A—C7A | −55.3 (5) | C10B—C5B—C6B—C7B | −56.0 (5) |
C5A—C6A—C7A—C8A | 56.6 (5) | C5B—C6B—C7B—C8B | 60.0 (5) |
C5A—C6A—C7A—C11A | −176.6 (4) | C5B—C6B—C7B—C11B | −172.6 (4) |
C6A—C7A—C8A—C9A | −55.7 (5) | C6B—C7B—C8B—C9B | −59.1 (5) |
C11A—C7A—C8A—C9A | 179.1 (4) | C11B—C7B—C8B—C9B | 173.2 (4) |
C7A—C8A—C9A—C10A | 57.4 (5) | C7B—C8B—C9B—C10B | 58.9 (6) |
C2A—C1A—C10A—C9A | −178.3 (4) | C2B—C1B—C10B—C9B | −178.0 (4) |
Br1A—C1A—C10A—C9A | −55.8 (5) | Br1B—C1B—C10B—C9B | −55.4 (5) |
C2A—C1A—C10A—C5A | 56.7 (5) | C2B—C1B—C10B—C5B | 57.0 (5) |
Br1A—C1A—C10A—C5A | 179.2 (3) | Br1B—C1B—C10B—C5B | 179.6 (3) |
C8A—C9A—C10A—C1A | 179.9 (4) | C8B—C9B—C10B—C1B | −179.3 (4) |
C8A—C9A—C10A—C5A | −55.7 (5) | C8B—C9B—C10B—C5B | −55.5 (5) |
C6A—C5A—C10A—C1A | 178.6 (4) | C6B—C5B—C10B—C1B | 178.2 (4) |
C14A—C5A—C10A—C1A | 58.2 (5) | C14B—C5B—C10B—C1B | 57.5 (5) |
C4A—C5A—C10A—C1A | −63.5 (5) | C4B—C5B—C10B—C1B | −64.5 (5) |
C6A—C5A—C10A—C9A | 52.9 (5) | C6B—C5B—C10B—C9B | 52.6 (5) |
C14A—C5A—C10A—C9A | −67.5 (5) | C14B—C5B—C10B—C9B | −68.1 (5) |
C4A—C5A—C10A—C9A | 170.8 (4) | C4B—C5B—C10B—C9B | 169.9 (4) |
C8A—C7A—C11A—C12A | −170.6 (5) | C8B—C7B—C11B—C12B | 65.2 (6) |
C6A—C7A—C11A—C12A | 65.9 (6) | C6B—C7B—C11B—C12B | −59.3 (6) |
C8A—C7A—C11A—C13A | −47.2 (6) | C8B—C7B—C11B—C13B | −168.0 (4) |
C6A—C7A—C11A—C13A | −170.8 (5) | C6B—C7B—C11B—C13B | 67.4 (5) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C15H22O | C15H24Br2O |
Mr | 218.33 | 380.16 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 |
Temperature (K) | 150 | 100 |
a, b, c (Å) | 5.903 (2), 9.495 (4), 11.630 (6) | 13.500 (3), 6.1403 (10), 18.909 (5) |
β (°) | 96.09 (2) | 92.145 (7) |
V (Å3) | 648.2 (5) | 1566.3 (6) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 5.16 |
Crystal size (mm) | 0.32 × 0.25 × 0.20 | 0.30 × 0.05 × 0.02 |
Data collection | ||
Diffractometer | Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer | Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer |
Absorption correction | – | Multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | – | 0.385, 0.902 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7526, 1577, 1202 | 19375, 9388, 7482 |
Rint | 0.023 | 0.063 |
(sin θ/λ)max (Å−1) | 0.650 | 0.714 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.098, 1.06 | 0.053, 0.095, 1.10 |
No. of reflections | 1577 | 9388 |
No. of parameters | 149 | 333 |
No. of restraints | 1 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.15 | 1.09, −0.66 |
Absolute structure | ? | Flack (1983), 4216 Friedel pairs |
Absolute structure parameter | ? | 0.019 (11) |
Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and CrystMol (Duchamp, 1999), SHELXL97.
O1—C2 | 1.228 (3) | C11—C13 | 1.323 (3) |
C1—C10 | 1.341 (3) | C11—C12 | 1.501 (3) |
C1—C2 | 1.457 (4) | ||
C10—C1—C2—C3 | −8.1 (3) | C7—C8—C9—C10 | 55.0 (3) |
C1—C2—C3—C4 | 37.9 (3) | C2—C1—C10—C5 | −2.9 (3) |
C2—C3—C4—C5 | −57.5 (3) | C8—C9—C10—C5 | −49.8 (3) |
C3—C4—C5—C10 | 45.9 (2) | C4—C5—C10—C1 | −16.7 (3) |
C10—C5—C6—C7 | −49.6 (2) | C6—C5—C10—C9 | 45.3 (2) |
C5—C6—C7—C8 | 57.2 (2) | C6—C7—C11—C12 | 63.4 (2) |
C6—C7—C8—C9 | −57.5 (2) |
Br1A—C1A | 1.959 (4) | Br1B—C1B | 1.960 (4) |
Br2A—C3A | 1.956 (4) | Br2B—C3B | 1.950 (4) |
O1A—C2A | 1.207 (6) | O1B—C2B | 1.203 (6) |
C10A—C1A—C2A—C3A | −44.8 (5) | C10B—C1B—C2B—C3B | −44.4 (5) |
C1A—C2A—C3A—C4A | 41.1 (6) | C1B—C2B—C3B—C4B | 40.5 (5) |
C2A—C3A—C4A—C5A | −48.1 (5) | C2B—C3B—C4B—C5B | −48.4 (5) |
C3A—C4A—C5A—C10A | 58.1 (5) | C3B—C4B—C5B—C10B | 59.1 (5) |
C10A—C5A—C6A—C7A | −55.3 (5) | C10B—C5B—C6B—C7B | −56.0 (5) |
C5A—C6A—C7A—C8A | 56.6 (5) | C5B—C6B—C7B—C8B | 60.0 (5) |
C6A—C7A—C8A—C9A | −55.7 (5) | C6B—C7B—C8B—C9B | −59.1 (5) |
C7A—C8A—C9A—C10A | 57.4 (5) | C7B—C8B—C9B—C10B | 58.9 (6) |
C2A—C1A—C10A—C5A | 56.7 (5) | C2B—C1B—C10B—C5B | 57.0 (5) |
C8A—C9A—C10A—C5A | −55.7 (5) | C8B—C9B—C10B—C5B | −55.5 (5) |
C4A—C5A—C10A—C1A | −63.5 (5) | C4B—C5B—C10B—C1B | −64.5 (5) |
C6A—C5A—C10A—C9A | 52.9 (5) | C6B—C5B—C10B—C9B | 52.6 (5) |
C6A—C7A—C11A—C12A | 65.9 (6) | C6B—C7B—C11B—C12B | −59.3 (6) |
Nootkatone, (I), the major flavorant of grapefruit, is a valencene-class sesquiterpene ketone, which was first isolated from Alaskan yellow cedar (Erdtman & Hirose, 1962), and is a minor component of some vetiver oils. Part of the interest in this class of compounds is their termiticidic and insect repellent activity, particularly towards the Formosan subterranean termite (Zhu, Henderson, Chen, Fei & Laine, 2001; Zhu, Henderson, Chen, Fei, Maistrello & Laine, 2001). Nootkatone appears to be non-toxic to humans, as it is currently added to juices to impart a grapefruit essence. We have been studying nootkatone because of its potent and seemingly receptor-specific activity, and its potential commercial importance as a termiticide. Since absolute structure is usually an important factor controlling biological activity, we have determined the crystal structure of this low-melting (m.p. 309–311 K) natural product and sought to definitively establish its absolute structure. We are not aware of any previous absolute structure determinations by X-ray methods of valencene-class sesquiterpenoids or those of the eremophilene class, differing from the valencenes by the configuration at C4 and C5. To this end, we attempted to synthesize a bromo derivative of nootkatone, but were unsuccessful in growing suitable crystals of any such compounds. We thus turned to bromination of tetrahydronootkatone, which has the same absolute configuration, because a published synthesis of 3-α-bromo-tetrahydronootkatone (m.p. 353–351 K) was available (MacLeod, 1965). In our hands, the MacLeod synthesis did not yield the expected product, but instead yielded compound (II) (m.p. 406–408 K; Sauer et al., 2003), a dibromo derivative. Fortunately, it crystallized well and was sufficient for absolute configuration determination. We report here the low-temperature structures of both nootkatone, (I), and the dibromo derivative (II).
The structure of (I) is shown in Fig. 1, which illustrates its valencene-type skeleton, with methyl groups C14 and C15 α-oriented, and the substituent at C7 β-oriented. The C5–C10 ring is in a slightly flattened chair conformation, with endocyclic torsion angles in the range 45.3 (2)–57.5 (2)°, the flattening being a result of the C1═C10 double bond. The presence of the C1═C10 unsaturation in the other ring and the ketone conjugated to it causes it to have a conformation in which all atoms but C4 are nearly coplanar. Atom C4 lies 0.624 (2) Å out of the best plane of the other five, which exhibit a maximum deviation of 0.074 (2) Å for C2. The packing for (I) is unremarkable; in particular, molecules do not form carbonyl–carbonyl intermolcular interactions of the type described by Allen et al. (1998). The absolute configuration of (I) is inferred to be that shown in Fig. 1, corresponding to the configuration directly determined for (II). The skeleton of nootkatone is shared with tetrahydronootkatone, vetivone and valencene, all of which have the same configuration. All have strong repellent properties against the Formosan subterranean termite except for valencene, which lacks the C2-ketone group and is relatively inactive. Thus, we conclude that the binding site must recognize the stereochemistry of the skeleton, but require the ketone.
The absolute structure of (II) is shown in Fig. 2, which illustrates one of the two independent molecules. There are no significant differences between corresponding bond distances in the two molecules, nor between their endocyclic torsion angles. Both rings in the molecule have chair conformations; that carrying the ketone being slightly flattened, with endocyclic torsion angles in the range 40.5 (5)–64.5 (5)°, while the other ring is much less flattened compared to that of (I), having torsion angles in the range 52.6 (5)–60.0 (5)°. The main difference between molecules A and B is in the rotation of the isopropyl group with respect to the main skeleton. The difference in rotation is 125.2 (8)°, such that C13 is anti to C6 in the molecule A and anti to C8 in the molecule B.
The most remarkable feature of the structure of (II) is its packing. Both molecules form zigzag chains of carbonyl–carbonyl intermolecular interactions in the [010] direction, propagated by 21 axes. The geometry of the interactions is the perpendicular motif, reported by Allen et al. (1998) to occur in about 1.3% of the carbonyl-containing structures in the Cambridge Structural Database (Allen & Kennard, 1993). The C═O···C angles here are nearly linear, with C2A═O1A···C2Ai = 176.4 (4)° and C2B═O1B···C2Bii = 175.8 (4)° [symmetry codes: (i) 1 − x, 1/2 + y, 1 − z; (ii) −x, 1/2 + y, −z]. The C···O distances are much shorter than expected [2.886 (6) Å for the the A chain and 2.898 (6) Å for the B chain], representing some of the shortest such interactions known. Allen et al. (1998) reported that only 26% of such interactions are shorter than the sum of C and O van der Waals radii (3.22 Å), with a median of 3.35 Å. The shortness of these contacts may be related to the fact that the ketone substituent is flanked by two C—Br bonds, both of which are equatorial on the six-membered ring. Thus, each carbonyl–carbonyl interaction is accompanied by two intermolecular Br···Br interactions. These distances are 4.067 (1) and 4.218 (1) Å for the A chain, and 4.147 (1) and 4.172 (1) Å for the B chain, slightly longer than 3.70 Å, which is twice the van der Waals radius of Br (Bondi, 1964).