Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803011255/bt6282sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803011255/bt6282Isup2.hkl |
CCDC reference: 214860
A mixture of magnesium (0.2866 g, 11.78 mmol), freshly distilled tetrahydrofuran (20 ml), and 1,2-dibromoethane (0.30 ml, 3.48 mmol), maintained under argon, was gently heated until bubbles appeared on the Mg surface. para-Bromo-tert-butylbenzene (1.774 g, 8.33 mmol) was injected, the mixture was refluxed for 30 min, and a solution of 9-fluorenone (1.00 g, 5.56 mmol) in tetrahydrofuran (15 ml) was added. This mixture was refluxed for 5 h, cooled, diluted with water then 6 N H2SO4 and extracted with ether. The extracts were dried and concentrated to a yellow oil, which was purified by column chromatography (2:1 hexanes–ethyl acetate). Concentration of the major fraction left an oil which, after several days, provided a yellow solid, 1.426 g (84.9% yield), yellow crystals (from hexanes), m.p. 392–395 K (literature m.p. 391–393 K; Weber, Dörpinghaus & Csöregh, 1990). The melt failed to crystallize on cooling, even in an ice bath, but its NMR was identical to that of the crystalline product, showing that no decomposition had occurred on melting. NMR (CDCl3): 1H, δ 1.27 (s, 9 H), 2.423 (s, 1 H), 7.22–7.38 (m, 9 H), 7.64–7.67 (m, 3 H); 13C, δ 31.30, 34.39, 83.56, 120.04, 124.81, 125.03, 125.12, 128.35, 128.99, 139.55, 140.06, 149.99, 150.41.
The rotational orientations of the methyl H atoms in molecule 1 (Fig. 1) were refined by the circular Fourier method available in SHELXL97 (Sheldrick, 1997); the hydroxyl H atom position for both molecules was determined in a similar manner. The tertiary butyl group of molecule 2 is somewhat rotationally disordered and thus its H atoms were placed in geometrically favorable positions but were not refined. All H atoms are riding with C—H distances ranging from 0.82 to 0.96 Å.
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SIR92 (Burla et al., 1989); program(s) used to refine structure: LS in TEXSAN (Molecular Structure Corporation, 1997) and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: TEXSAN, SHELXL97 and PLATON.
C23H22O | F(000) = 672 |
Mr = 314.41 | Dx = 1.181 Mg m−3 |
Triclinic, P1 | Melting point = 392–395 K |
a = 10.2843 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 12.1135 (2) Å | Cell parameters from 5098 reflections |
c = 14.5033 (2) Å | θ = 2.3–27.8° |
α = 82.915 (1)° | µ = 0.07 mm−1 |
β = 80.656 (1)° | T = 170 K |
γ = 87.563 (1)° | Prism, pale yellow |
V = 1768.75 (5) Å3 | 0.36 × 0.33 × 0.20 mm |
Z = 4 |
Bruker CCD area-detector diffractometer | 4292 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.036 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ϕ and ω scans | h = −12→12 |
20884 measured reflections | k = −14→14 |
6224 independent reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0651P)2 + 0.1886P] where P = (Fo2 + 2Fc2)/3 |
6224 reflections | (Δ/σ)max < 0.001 |
438 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C23H22O | γ = 87.563 (1)° |
Mr = 314.41 | V = 1768.75 (5) Å3 |
Triclinic, P1 | Z = 4 |
a = 10.2843 (2) Å | Mo Kα radiation |
b = 12.1135 (2) Å | µ = 0.07 mm−1 |
c = 14.5033 (2) Å | T = 170 K |
α = 82.915 (1)° | 0.36 × 0.33 × 0.20 mm |
β = 80.656 (1)° |
Bruker CCD area-detector diffractometer | 4292 reflections with I > 2σ(I) |
20884 measured reflections | Rint = 0.036 |
6224 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.44 e Å−3 |
6224 reflections | Δρmin = −0.25 e Å−3 |
438 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.28797 (12) | −0.04523 (9) | 0.92572 (8) | 0.0331 (3) | |
C1 | 0.06054 (19) | 0.05220 (15) | 0.81484 (13) | 0.0354 (4) | |
C2 | −0.0671 (2) | 0.08518 (16) | 0.80304 (14) | 0.0414 (5) | |
C3 | −0.13864 (19) | 0.15862 (16) | 0.85911 (14) | 0.0406 (5) | |
C4 | −0.08574 (18) | 0.19832 (15) | 0.93043 (13) | 0.0357 (5) | |
C4A | 0.04015 (17) | 0.16182 (13) | 0.94523 (12) | 0.0299 (4) | |
C4B | 0.11604 (17) | 0.18015 (13) | 1.01953 (12) | 0.0290 (4) | |
C5 | 0.08287 (19) | 0.23499 (15) | 1.09947 (13) | 0.0366 (5) | |
C6 | 0.1710 (2) | 0.23047 (16) | 1.16231 (14) | 0.0404 (5) | |
C7 | 0.29009 (19) | 0.17193 (16) | 1.14736 (14) | 0.0399 (5) | |
C8 | 0.32502 (19) | 0.11853 (15) | 1.06689 (13) | 0.0354 (4) | |
C8A | 0.23762 (17) | 0.12393 (13) | 1.00357 (12) | 0.0288 (4) | |
C9 | 0.25194 (17) | 0.07046 (13) | 0.91236 (12) | 0.0288 (4) | |
C9A | 0.11371 (17) | 0.09179 (14) | 0.88579 (12) | 0.0300 (4) | |
C10 | 0.35697 (17) | 0.12665 (14) | 0.83613 (12) | 0.0279 (4) | |
C11 | 0.45848 (17) | 0.06810 (14) | 0.78887 (13) | 0.0324 (4) | |
C12 | 0.55235 (18) | 0.12193 (15) | 0.71964 (13) | 0.0342 (4) | |
C13 | 0.54835 (17) | 0.23588 (14) | 0.69511 (12) | 0.0286 (4) | |
C14 | 0.44411 (19) | 0.29426 (15) | 0.74315 (13) | 0.0380 (5) | |
C15 | 0.35117 (19) | 0.24137 (15) | 0.81179 (14) | 0.0387 (5) | |
C16 | 0.65144 (18) | 0.29805 (15) | 0.62091 (12) | 0.0329 (4) | |
C17 | 0.5849 (2) | 0.37132 (17) | 0.54769 (14) | 0.0459 (5) | |
C18 | 0.7293 (2) | 0.37222 (17) | 0.66990 (15) | 0.0491 (6) | |
C19 | 0.7496 (2) | 0.21884 (17) | 0.56987 (14) | 0.0500 (6) | |
H1 | 0.2426 | −0.0753 | 0.9732 | 0.050* | |
H1A | 0.1092 | 0.0046 | 0.7760 | 0.042* | |
H2 | −0.1053 | 0.0576 | 0.7569 | 0.050* | |
H3 | −0.2231 | 0.1815 | 0.8488 | 0.049* | |
H4 | −0.1334 | 0.2482 | 0.9675 | 0.043* | |
H5 | 0.0030 | 0.2739 | 1.1103 | 0.044* | |
H6 | 0.1502 | 0.2673 | 1.2156 | 0.048* | |
H7 | 0.3470 | 0.1683 | 1.1914 | 0.048* | |
H8 | 0.4053 | 0.0802 | 1.0561 | 0.042* | |
H11 | 0.4647 | −0.0087 | 0.8033 | 0.039* | |
H12 | 0.6198 | 0.0799 | 0.6890 | 0.041* | |
H14 | 0.4372 | 0.3710 | 0.7284 | 0.046* | |
H15 | 0.2833 | 0.2831 | 0.8424 | 0.046* | |
H17A | 0.5351 | 0.3257 | 0.5171 | 0.069* | |
H17B | 0.6508 | 0.4095 | 0.5018 | 0.069* | |
H17C | 0.5269 | 0.4247 | 0.5782 | 0.069* | |
H18A | 0.7938 | 0.4120 | 0.6239 | 0.074* | |
H18B | 0.7727 | 0.3268 | 0.7153 | 0.074* | |
H18C | 0.6700 | 0.4242 | 0.7011 | 0.074* | |
H19A | 0.7035 | 0.1730 | 0.5370 | 0.075* | |
H19B | 0.7930 | 0.1726 | 0.6149 | 0.075* | |
H19C | 0.8139 | 0.2612 | 0.5257 | 0.075* | |
O1' | 0.22095 (12) | 0.81038 (10) | 0.80260 (9) | 0.0348 (3) | |
C1' | 0.40119 (18) | 0.69327 (17) | 0.95036 (13) | 0.0382 (5) | |
C2' | 0.4017 (2) | 0.63328 (19) | 1.03864 (14) | 0.0481 (6) | |
C3' | 0.3287 (2) | 0.5385 (2) | 1.06536 (15) | 0.0542 (6) | |
C4' | 0.2542 (2) | 0.50033 (17) | 1.00573 (15) | 0.0477 (5) | |
C4A' | 0.25258 (17) | 0.55975 (15) | 0.91731 (13) | 0.0334 (4) | |
C4B' | 0.18234 (17) | 0.54095 (14) | 0.84080 (13) | 0.0332 (4) | |
C5' | 0.09488 (19) | 0.45932 (16) | 0.83357 (16) | 0.0456 (5) | |
C6' | 0.0416 (2) | 0.46175 (19) | 0.75214 (19) | 0.0563 (6) | |
C7' | 0.0720 (2) | 0.5457 (2) | 0.67930 (17) | 0.0559 (6) | |
C8' | 0.15744 (19) | 0.62937 (17) | 0.68613 (14) | 0.0426 (5) | |
C8A' | 0.21194 (17) | 0.62576 (14) | 0.76687 (12) | 0.0303 (4) | |
C9' | 0.30074 (17) | 0.71102 (14) | 0.79346 (12) | 0.0289 (4) | |
C9A' | 0.32564 (17) | 0.65627 (14) | 0.89023 (12) | 0.0304 (4) | |
C10' | 0.42488 (17) | 0.73504 (13) | 0.72157 (12) | 0.0276 (4) | |
C11' | 0.43504 (18) | 0.83302 (15) | 0.66085 (13) | 0.0373 (5) | |
C12' | 0.54749 (19) | 0.85501 (16) | 0.59434 (14) | 0.0412 (5) | |
C13' | 0.65353 (18) | 0.78098 (15) | 0.58501 (12) | 0.0327 (4) | |
C14' | 0.64180 (18) | 0.68266 (15) | 0.64652 (13) | 0.0362 (5) | |
C15' | 0.53011 (18) | 0.66017 (15) | 0.71275 (13) | 0.0347 (5) | |
C16' | 0.77835 (19) | 0.80600 (17) | 0.51269 (13) | 0.0404 (5) | |
C17' | 0.8841 (2) | 0.8442 (3) | 0.56314 (19) | 0.0826 (9) | |
C18' | 0.7546 (3) | 0.9003 (3) | 0.43683 (18) | 0.0934 (11) | |
C19' | 0.8273 (3) | 0.7044 (2) | 0.4655 (2) | 0.0958 (11) | |
H1' | 0.2526 | 0.8499 | 0.8349 | 0.052* | |
H1A' | 0.4507 | 0.7570 | 0.9322 | 0.046* | |
H2' | 0.4518 | 0.6574 | 1.0799 | 0.058* | |
H3' | 0.3298 | 0.4997 | 1.1247 | 0.065* | |
H4' | 0.2058 | 0.4360 | 1.0241 | 0.057* | |
H5' | 0.0726 | 0.4036 | 0.8832 | 0.055* | |
H6' | −0.0154 | 0.4063 | 0.7462 | 0.068* | |
H7' | 0.0349 | 0.5464 | 0.6249 | 0.067* | |
H8' | 0.1771 | 0.6863 | 0.6372 | 0.051* | |
H11' | 0.3657 | 0.8849 | 0.6646 | 0.045* | |
H12' | 0.5514 | 0.9218 | 0.5548 | 0.049* | |
H14' | 0.7110 | 0.6306 | 0.6430 | 0.043* | |
H15' | 0.5259 | 0.5933 | 0.7521 | 0.042* | |
H17A' | 0.8527 | 0.9090 | 0.5927 | 0.124* | |
H17B' | 0.9622 | 0.8618 | 0.5185 | 0.124* | |
H17C' | 0.9042 | 0.7858 | 0.6101 | 0.124* | |
H18A' | 0.7234 | 0.9656 | 0.4658 | 0.140* | |
H18B' | 0.6899 | 0.8785 | 0.4022 | 0.140* | |
H18C' | 0.8355 | 0.9161 | 0.3948 | 0.140* | |
H19A' | 0.8431 | 0.6444 | 0.5124 | 0.144* | |
H19B' | 0.9077 | 0.7211 | 0.4231 | 0.144* | |
H19C' | 0.7621 | 0.6831 | 0.4310 | 0.144* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0394 (8) | 0.0260 (6) | 0.0313 (7) | −0.0032 (6) | −0.0001 (6) | 0.0010 (5) |
C1 | 0.0401 (11) | 0.0364 (10) | 0.0291 (10) | −0.0039 (9) | −0.0064 (9) | 0.0004 (8) |
C2 | 0.0442 (12) | 0.0451 (12) | 0.0351 (11) | −0.0098 (10) | −0.0129 (10) | 0.0071 (9) |
C3 | 0.0301 (10) | 0.0451 (12) | 0.0420 (12) | −0.0058 (9) | −0.0066 (9) | 0.0154 (9) |
C4 | 0.0285 (10) | 0.0332 (10) | 0.0403 (12) | −0.0034 (8) | 0.0020 (9) | 0.0066 (8) |
C4A | 0.0277 (10) | 0.0263 (9) | 0.0320 (10) | −0.0072 (8) | 0.0025 (8) | 0.0038 (8) |
C4B | 0.0280 (10) | 0.0253 (9) | 0.0306 (10) | −0.0078 (8) | 0.0041 (8) | −0.0004 (7) |
C5 | 0.0330 (11) | 0.0320 (10) | 0.0408 (12) | −0.0050 (8) | 0.0077 (9) | −0.0056 (8) |
C6 | 0.0442 (12) | 0.0432 (11) | 0.0323 (11) | −0.0122 (10) | 0.0053 (10) | −0.0103 (9) |
C7 | 0.0382 (11) | 0.0472 (12) | 0.0340 (11) | −0.0097 (9) | −0.0031 (9) | −0.0040 (9) |
C8 | 0.0327 (10) | 0.0379 (11) | 0.0345 (11) | −0.0039 (8) | −0.0024 (9) | −0.0028 (8) |
C8A | 0.0295 (10) | 0.0259 (9) | 0.0289 (10) | −0.0062 (8) | 0.0010 (8) | −0.0003 (7) |
C9 | 0.0323 (10) | 0.0240 (9) | 0.0292 (10) | −0.0007 (8) | −0.0032 (8) | −0.0022 (7) |
C9A | 0.0301 (10) | 0.0284 (9) | 0.0291 (10) | −0.0074 (8) | −0.0010 (8) | 0.0042 (8) |
C10 | 0.0283 (10) | 0.0291 (9) | 0.0265 (10) | −0.0015 (8) | −0.0046 (8) | −0.0033 (7) |
C11 | 0.0325 (10) | 0.0257 (9) | 0.0367 (11) | 0.0009 (8) | −0.0019 (9) | 0.0004 (8) |
C12 | 0.0296 (10) | 0.0344 (10) | 0.0359 (11) | 0.0040 (8) | 0.0013 (8) | −0.0032 (8) |
C13 | 0.0277 (10) | 0.0339 (10) | 0.0241 (9) | −0.0020 (8) | −0.0056 (8) | −0.0006 (7) |
C14 | 0.0418 (12) | 0.0272 (10) | 0.0407 (12) | −0.0021 (9) | 0.0020 (9) | 0.0012 (8) |
C15 | 0.0388 (11) | 0.0296 (10) | 0.0421 (12) | 0.0025 (9) | 0.0086 (9) | −0.0028 (8) |
C16 | 0.0305 (10) | 0.0375 (10) | 0.0287 (10) | −0.0027 (8) | −0.0031 (8) | 0.0027 (8) |
C17 | 0.0429 (12) | 0.0561 (13) | 0.0345 (12) | −0.0020 (10) | −0.0047 (10) | 0.0091 (10) |
C18 | 0.0484 (13) | 0.0540 (13) | 0.0439 (13) | −0.0193 (11) | −0.0098 (10) | 0.0078 (10) |
C19 | 0.0428 (13) | 0.0551 (13) | 0.0423 (13) | 0.0033 (11) | 0.0112 (10) | 0.0078 (10) |
O1' | 0.0318 (7) | 0.0333 (7) | 0.0388 (8) | 0.0003 (6) | −0.0017 (6) | −0.0082 (6) |
C1' | 0.0291 (10) | 0.0502 (12) | 0.0356 (11) | −0.0011 (9) | −0.0019 (9) | −0.0110 (9) |
C2' | 0.0397 (12) | 0.0735 (16) | 0.0328 (12) | 0.0065 (11) | −0.0091 (10) | −0.0108 (11) |
C3' | 0.0554 (14) | 0.0696 (15) | 0.0329 (12) | 0.0089 (12) | −0.0068 (11) | 0.0092 (11) |
C4' | 0.0464 (13) | 0.0462 (12) | 0.0446 (13) | −0.0016 (10) | −0.0007 (11) | 0.0096 (10) |
C4A' | 0.0287 (10) | 0.0360 (10) | 0.0331 (11) | 0.0006 (8) | 0.0000 (8) | −0.0018 (8) |
C4B' | 0.0272 (10) | 0.0280 (9) | 0.0432 (11) | −0.0007 (8) | −0.0003 (9) | −0.0058 (8) |
C5' | 0.0366 (12) | 0.0318 (11) | 0.0669 (15) | −0.0055 (9) | −0.0033 (11) | −0.0049 (10) |
C6' | 0.0439 (13) | 0.0486 (13) | 0.0832 (19) | −0.0111 (11) | −0.0153 (13) | −0.0235 (13) |
C7' | 0.0460 (13) | 0.0701 (16) | 0.0598 (15) | −0.0036 (12) | −0.0194 (12) | −0.0247 (13) |
C8' | 0.0394 (12) | 0.0517 (12) | 0.0386 (12) | −0.0056 (10) | −0.0075 (10) | −0.0095 (9) |
C8A' | 0.0243 (9) | 0.0339 (10) | 0.0324 (10) | −0.0005 (8) | −0.0004 (8) | −0.0083 (8) |
C9' | 0.0267 (9) | 0.0292 (9) | 0.0301 (10) | −0.0014 (8) | −0.0016 (8) | −0.0042 (7) |
C9A' | 0.0245 (9) | 0.0365 (10) | 0.0287 (10) | −0.0001 (8) | 0.0010 (8) | −0.0057 (8) |
C10' | 0.0286 (10) | 0.0278 (9) | 0.0265 (10) | −0.0028 (8) | −0.0042 (8) | −0.0036 (7) |
C11' | 0.0312 (10) | 0.0370 (11) | 0.0394 (11) | 0.0051 (9) | 0.0011 (9) | 0.0018 (9) |
C12' | 0.0409 (12) | 0.0361 (11) | 0.0401 (12) | 0.0002 (9) | 0.0035 (9) | 0.0078 (9) |
C13' | 0.0316 (10) | 0.0400 (11) | 0.0264 (10) | −0.0047 (9) | −0.0019 (8) | −0.0054 (8) |
C14' | 0.0323 (11) | 0.0376 (11) | 0.0357 (11) | 0.0061 (9) | −0.0005 (9) | −0.0016 (8) |
C15' | 0.0393 (11) | 0.0294 (10) | 0.0314 (11) | 0.0005 (8) | 0.0015 (9) | 0.0022 (8) |
C16' | 0.0351 (11) | 0.0512 (12) | 0.0314 (11) | −0.0024 (9) | 0.0017 (9) | 0.0003 (9) |
C17' | 0.0470 (15) | 0.135 (3) | 0.0625 (17) | −0.0305 (16) | 0.0098 (13) | −0.0145 (17) |
C18' | 0.0620 (17) | 0.132 (3) | 0.0591 (17) | 0.0152 (17) | 0.0232 (14) | 0.0445 (17) |
C19' | 0.091 (2) | 0.087 (2) | 0.091 (2) | −0.0107 (17) | 0.0563 (18) | −0.0278 (17) |
O1—C9 | 1.4321 (19) | O1'—C9' | 1.435 (2) |
C1—C9A | 1.384 (3) | C1'—C9A' | 1.382 (3) |
C1—C2 | 1.387 (3) | C1'—C2' | 1.393 (3) |
C2—C3 | 1.386 (3) | C2'—C3' | 1.379 (3) |
C3—C4 | 1.387 (3) | C3'—C4' | 1.376 (3) |
C4—C4A | 1.391 (2) | C4'—C4A' | 1.393 (3) |
C4A—C9A | 1.396 (2) | C4A'—C9A' | 1.397 (2) |
C4A—C4B | 1.472 (3) | C4A'—C4B' | 1.463 (3) |
C4B—C5 | 1.394 (2) | C4B'—C5' | 1.389 (3) |
C4B—C8A | 1.398 (2) | C4B'—C8A' | 1.395 (2) |
C5—C6 | 1.381 (3) | C8'—C8A' | 1.373 (3) |
C6—C7 | 1.389 (3) | C5'—C6' | 1.377 (3) |
C7—C8 | 1.393 (3) | C6'—C7' | 1.379 (3) |
C8A—C8 | 1.380 (2) | C7'—C8' | 1.392 (3) |
C8A—C9 | 1.527 (2) | C8A'—C9' | 1.530 (2) |
C9—C10 | 1.530 (2) | C9A'—C9' | 1.532 (2) |
C9—C9A | 1.536 (2) | C9'—C10' | 1.525 (2) |
C10—C11 | 1.374 (2) | C10'—C15' | 1.382 (2) |
C10—C15 | 1.392 (2) | C10'—C11' | 1.385 (2) |
C11—C12 | 1.394 (2) | C11'—C12' | 1.393 (3) |
C12—C13 | 1.383 (2) | C12'—C13' | 1.382 (3) |
C13—C14 | 1.396 (2) | C13'—C14' | 1.394 (3) |
C14—C15 | 1.379 (3) | C13'—C16' | 1.535 (3) |
C13—C16 | 1.532 (2) | C14'—C15' | 1.386 (3) |
C16—C17 | 1.529 (2) | C16'—C19' | 1.510 (3) |
C16—C18 | 1.535 (3) | C16'—C17' | 1.522 (3) |
C16—C19 | 1.529 (3) | C16'—C18' | 1.526 (3) |
O1—H1 | 0.8200 | O1'—H1' | 0.8200 |
C1—H1A | 0.9300 | C1'—H1A' | 0.9300 |
C2—H2 | 0.9300 | C2'—H2' | 0.9300 |
C3—H3 | 0.9300 | C3'—H3' | 0.9300 |
C4—H4 | 0.9300 | C4'—H4' | 0.9300 |
C5—H5 | 0.9300 | C5'—H5' | 0.9300 |
C6—H6 | 0.9300 | C6'—H6' | 0.9300 |
C7—H7 | 0.9300 | C7'—H7' | 0.9300 |
C8—H8 | 0.9300 | C8'—H8' | 0.9300 |
C11—H11 | 0.9300 | C11'—H11' | 0.9300 |
C12—H12 | 0.9300 | C12'—H12' | 0.9300 |
C14—H14 | 0.9300 | C14'—H14' | 0.9300 |
C15—H15 | 0.9300 | C15'—H15' | 0.9300 |
C17—H17A | 0.9600 | C17'—H17A' | 0.9600 |
C17—H17B | 0.9600 | C17'—H17B' | 0.9600 |
C17—H17C | 0.9600 | C17'—H17C' | 0.9600 |
C18—H18A | 0.9600 | C18'—H18A' | 0.9600 |
C18—H18B | 0.9600 | C18'—H18B' | 0.9600 |
C18—H18C | 0.9600 | C18'—H18C' | 0.9600 |
C19—H19A | 0.9600 | C19'—H19A' | 0.9600 |
C19—H19B | 0.9600 | C19'—H19B' | 0.9600 |
C19—H19C | 0.9600 | C19'—H19C' | 0.9600 |
C9A—C1—C2 | 118.43 (18) | C9A—C1—H1A | 120.8 |
C3—C2—C1 | 120.92 (19) | C2—C1—H1A | 120.8 |
C2—C3—C4 | 120.78 (18) | C3—C2—H2 | 119.5 |
C3—C4—C4A | 118.55 (18) | C1—C2—H2 | 119.5 |
C4—C4A—C9A | 120.24 (17) | C2—C3—H3 | 119.6 |
C4—C4A—C4B | 130.94 (17) | C4—C3—H3 | 119.6 |
C6—C5—C4B | 118.70 (18) | C3—C4—H4 | 120.7 |
C9A—C4A—C4B | 108.77 (15) | C4A—C4—H4 | 120.7 |
C5—C4B—C8A | 119.86 (17) | C6—C5—H5 | 120.6 |
C5—C4B—C4A | 131.38 (16) | C4B—C5—H5 | 120.6 |
C8A—C4B—C4A | 108.63 (15) | C5—C6—H6 | 119.4 |
C5—C6—C7 | 121.16 (18) | C7—C6—H6 | 119.4 |
C6—C7—C8 | 120.51 (19) | C6—C7—H7 | 119.7 |
C8—C8A—C4B | 121.37 (16) | C8—C7—H7 | 119.7 |
C8—C8A—C9 | 128.07 (16) | C8A—C8—H8 | 120.8 |
C4B—C8A—C9 | 110.52 (15) | C7—C8—H8 | 120.8 |
C8A—C8—C7 | 118.36 (18) | C10—C11—H11 | 119.5 |
O1—C9—C8A | 112.17 (14) | C12—C11—H11 | 119.5 |
O1—C9—C10 | 107.16 (13) | C13—C12—H12 | 118.9 |
C8A—C9—C10 | 111.97 (14) | C11—C12—H12 | 118.9 |
O1—C9—C9A | 113.30 (14) | C15—C14—H14 | 119.1 |
C8A—C9—C9A | 101.28 (14) | C13—C14—H14 | 119.1 |
C10—C9—C9A | 111.02 (13) | C14—C15—H15 | 119.4 |
C1—C9A—C4A | 120.94 (17) | C10—C15—H15 | 119.4 |
C1—C9A—C9 | 128.91 (16) | C16—C17—H17A | 109.5 |
C4A—C9A—C9 | 110.14 (15) | C16—C17—H17B | 109.5 |
C11—C10—C15 | 117.47 (16) | H17A—C17—H17B | 109.5 |
C11—C10—C9 | 122.58 (15) | C16—C17—H17C | 109.5 |
C15—C10—C9 | 119.95 (15) | H17A—C17—H17C | 109.5 |
C10—C11—C12 | 121.08 (16) | H17B—C17—H17C | 109.5 |
C13—C12—C11 | 122.11 (17) | C16—C18—H18A | 109.5 |
C12—C13—C14 | 116.22 (16) | C16—C18—H18B | 109.5 |
C12—C13—C16 | 123.50 (16) | H18A—C18—H18B | 109.5 |
C14—C13—C16 | 120.27 (15) | C16—C18—H18C | 109.5 |
C15—C14—C13 | 121.85 (17) | H18A—C18—H18C | 109.5 |
C14—C15—C10 | 121.26 (17) | H18B—C18—H18C | 109.5 |
C17—C16—C19 | 108.40 (15) | C16—C19—H19A | 109.5 |
C17—C16—C13 | 110.59 (15) | C16—C19—H19B | 109.5 |
C19—C16—C13 | 112.29 (15) | H19A—C19—H19B | 109.5 |
C17—C16—C18 | 108.85 (16) | C16—C19—H19C | 109.5 |
C19—C16—C18 | 107.87 (16) | H19A—C19—H19C | 109.5 |
C13—C16—C18 | 108.76 (15) | H19B—C19—H19C | 109.5 |
C9A'—C1'—C2' | 118.76 (19) | C9'—O1'—H1' | 109.5 |
C3'—C2'—C1' | 120.6 (2) | C9A'—C1'—H1A' | 120.6 |
C4'—C3'—C2' | 121.14 (19) | C2'—C1'—H1A' | 120.6 |
C3'—C4'—C4A' | 118.8 (2) | C4'—C3'—H3' | 119.4 |
C4'—C4A'—C9A' | 120.23 (18) | C2'—C3'—H3' | 119.4 |
C4'—C4A'—C4B' | 131.09 (18) | C3'—C2'—H2' | 119.7 |
C9A'—C4A'—C4B' | 108.67 (15) | C1'—C2'—H2' | 119.7 |
C5'—C4B'—C8A' | 119.71 (18) | C3'—C4'—H4' | 120.6 |
C5'—C4B'—C4A' | 131.34 (18) | C4A'—C4'—H4' | 120.6 |
C8A'—C4B'—C4A' | 108.92 (15) | C8A'—C8'—H8' | 120.8 |
C6'—C5'—C4B' | 119.3 (2) | C7'—C8'—H8' | 120.8 |
C5'—C6'—C7' | 120.5 (2) | C6'—C5'—H5' | 120.4 |
C6'—C7'—C8' | 120.9 (2) | C4B'—C5'—H5' | 120.4 |
C8A'—C8'—C7' | 118.4 (2) | C5'—C6'—H6' | 119.7 |
C8'—C8A'—C4B' | 121.17 (17) | C7'—C6'—H6' | 119.7 |
C8'—C8A'—C9' | 128.11 (17) | C6'—C7'—H7' | 119.5 |
C4B'—C8A'—C9' | 110.60 (15) | C8'—C7'—H7' | 119.5 |
C1'—C9A'—C4A' | 120.47 (17) | C10'—C11'—H11' | 119.5 |
C1'—C9A'—C9' | 128.83 (17) | C12'—C11'—H11' | 119.5 |
C4A'—C9A'—C9' | 110.61 (15) | C11'—C12'—H12' | 118.9 |
O1'—C9'—C10' | 110.43 (13) | C13'—C12'—H12' | 118.9 |
O1'—C9'—C8A' | 105.80 (13) | C15'—C14'—H14' | 119.0 |
C10'—C9'—C8A' | 113.69 (14) | C13'—C14'—H14' | 119.0 |
O1'—C9'—C9A' | 110.50 (14) | C10'—C15'—H15' | 119.3 |
C10'—C9'—C9A' | 114.77 (14) | C14'—C15'—H15' | 119.3 |
C8A'—C9'—C9A' | 100.98 (14) | C16'—C17'—H17A' | 109.5 |
C15'—C10'—C11' | 117.27 (16) | C16'—C17'—H17B' | 109.5 |
C15'—C10'—C9' | 122.02 (15) | H17A'—C17'—H17B' | 109.5 |
C11'—C10'—C9' | 120.69 (15) | C16'—C17'—H17C' | 109.5 |
C10'—C11'—C12' | 121.03 (17) | H17A'—C17'—H17C' | 109.5 |
C13'—C12'—C11' | 122.25 (17) | H17B'—C17'—H17C' | 109.5 |
C12'—C13'—C14' | 116.07 (17) | C16'—C18'—H18A' | 109.5 |
C12'—C13'—C16' | 122.24 (16) | C16'—C18'—H18B' | 109.5 |
C14'—C13'—C16' | 121.68 (16) | H18A'—C18'—H18B' | 109.5 |
C15'—C14'—C13' | 121.98 (17) | C16'—C18'—H18C' | 109.5 |
C10'—C15'—C14' | 121.40 (16) | H18A'—C18'—H18C' | 109.5 |
C19'—C16'—C17' | 109.8 (2) | H18B'—C18'—H18C' | 109.5 |
C19'—C16'—C18' | 108.5 (2) | C16'—C19'—H19A' | 109.5 |
C17'—C16'—C18' | 107.0 (2) | C16'—C19'—H19B' | 109.5 |
C19'—C16'—C13' | 111.12 (18) | H19A'—C19'—H19B' | 109.5 |
C17'—C16'—C13' | 108.54 (16) | C16'—C19'—H19C' | 109.5 |
C18'—C16'—C13' | 111.77 (17) | H19A'—C19'—H19C' | 109.5 |
C9—O1—H1 | 109.5 | H19B'—C19'—H19C' | 109.5 |
C9A—C1—C2—C3 | 1.9 (3) | C9A'—C1'—C2'—C3' | 0.3 (3) |
C1—C2—C3—C4 | −2.0 (3) | C1'—C2'—C3'—C4' | 0.4 (3) |
C2—C3—C4—C4A | −0.7 (3) | C2'—C3'—C4'—C4A' | −0.5 (3) |
C3—C4—C4A—C9A | 3.6 (2) | C3'—C4'—C4A'—C9A' | 0.0 (3) |
C3—C4—C4A—C4B | −173.41 (17) | C3'—C4'—C4A'—C4B' | −178.88 (19) |
C4—C4A—C4B—C5 | 3.4 (3) | C4'—C4A'—C4B'—C5' | 1.0 (3) |
C9A—C4A—C4B—C5 | −173.92 (17) | C9A'—C4A'—C4B'—C5' | −178.01 (19) |
C4—C4A—C4B—C8A | 179.06 (17) | C4'—C4A'—C4B'—C8A' | 178.92 (19) |
C9A—C4A—C4B—C8A | 1.79 (19) | C9A'—C4A'—C4B'—C8A' | −0.1 (2) |
C8A—C4B—C5—C6 | −1.2 (2) | C8A'—C4B'—C5'—C6' | 1.8 (3) |
C4A—C4B—C5—C6 | 174.09 (17) | C4A'—C4B'—C5'—C6' | 179.59 (19) |
C4B—C5—C6—C7 | −0.5 (3) | C4B'—C5'—C6'—C7' | −1.6 (3) |
C5—C6—C7—C8 | 1.7 (3) | C5'—C6'—C7'—C8' | 0.3 (3) |
C5—C4B—C8A—C8 | 1.9 (2) | C6'—C7'—C8'—C8A' | 0.7 (3) |
C4A—C4B—C8A—C8 | −174.38 (15) | C7'—C8'—C8A'—C4B' | −0.4 (3) |
C5—C4B—C8A—C9 | 179.94 (15) | C7'—C8'—C8A'—C9' | −175.81 (17) |
C4A—C4B—C8A—C9 | 3.65 (19) | C5'—C4B'—C8A'—C8' | −0.9 (3) |
C4B—C8A—C8—C7 | −0.8 (3) | C4A'—C4B'—C8A'—C8' | −179.10 (16) |
C9—C8A—C8—C7 | −178.44 (16) | C5'—C4B'—C8A'—C9' | 175.28 (16) |
C6—C7—C8—C8A | −1.0 (3) | C4A'—C4B'—C8A'—C9' | −2.93 (19) |
C8—C8A—C9—O1 | 49.7 (2) | C2'—C1'—C9A'—C4A' | −0.8 (3) |
C4B—C8A—C9—O1 | −128.14 (15) | C2'—C1'—C9A'—C9' | 175.27 (17) |
C8—C8A—C9—C10 | −70.8 (2) | C4'—C4A'—C9A'—C1' | 0.6 (3) |
C4B—C8A—C9—C10 | 111.33 (16) | C4B'—C4A'—C9A'—C1' | 179.74 (16) |
C8—C8A—C9—C9A | 170.85 (17) | C4'—C4A'—C9A'—C9' | −176.07 (16) |
C4B—C8A—C9—C9A | −7.02 (17) | C4B'—C4A'—C9A'—C9' | 3.0 (2) |
C2—C1—C9A—C4A | 1.0 (3) | C8'—C8A'—C9'—O1' | 65.1 (2) |
C2—C1—C9A—C9 | −178.63 (16) | C4B'—C8A'—C9'—O1' | −110.77 (16) |
C4—C4A—C9A—C1 | −3.8 (2) | C8'—C8A'—C9'—C10' | −56.3 (2) |
C4B—C4A—C9A—C1 | 173.80 (15) | C4B'—C8A'—C9'—C10' | 127.87 (16) |
C4—C4A—C9A—C9 | 175.92 (15) | C8'—C8A'—C9'—C9A' | −179.74 (18) |
C4B—C4A—C9A—C9 | −6.46 (18) | C4B'—C8A'—C9'—C9A' | 4.43 (18) |
O1—C9—C9A—C1 | −51.9 (2) | C1'—C9A'—C9'—O1' | −69.2 (2) |
C8A—C9—C9A—C1 | −172.18 (17) | C4A'—C9A'—C9'—O1' | 107.16 (16) |
C10—C9—C9A—C1 | 68.8 (2) | C1'—C9A'—C9'—C10' | 56.5 (2) |
O1—C9—C9A—C4A | 128.44 (15) | C4A'—C9A'—C9'—C10' | −127.18 (16) |
C8A—C9—C9A—C4A | 8.12 (17) | C1'—C9A'—C9'—C8A' | 179.18 (17) |
C10—C9—C9A—C4A | −110.91 (15) | C4A'—C9A'—C9'—C8A' | −4.48 (18) |
O1—C9—C10—C11 | 3.9 (2) | C8A'—C9'—C10'—C15' | −74.2 (2) |
C8A—C9—C10—C11 | 127.33 (18) | C9A'—C9'—C10'—C15' | 41.4 (2) |
C9A—C9—C10—C11 | −120.28 (18) | O1'—C9'—C10'—C11' | −14.2 (2) |
O1—C9—C10—C15 | −176.62 (16) | C8A'—C9'—C10'—C11' | 104.51 (19) |
C8A—C9—C10—C15 | −53.2 (2) | C9A'—C9'—C10'—C11' | −139.92 (17) |
C9A—C9—C10—C15 | 59.2 (2) | O1'—C9'—C10'—C15' | 167.05 (15) |
C15—C10—C11—C12 | 0.4 (3) | C15'—C10'—C11'—C12' | −0.5 (3) |
C9—C10—C11—C12 | 179.85 (16) | C9'—C10'—C11'—C12' | −179.30 (17) |
C10—C11—C12—C13 | 0.0 (3) | C10'—C11'—C12'—C13' | 0.3 (3) |
C11—C12—C13—C14 | −0.5 (3) | C11'—C12'—C13'—C14' | −0.2 (3) |
C11—C12—C13—C16 | 178.64 (17) | C11'—C12'—C13'—C16' | −179.05 (18) |
C12—C13—C14—C15 | 0.6 (3) | C12'—C13'—C14'—C15' | 0.4 (3) |
C16—C13—C14—C15 | −178.56 (17) | C16'—C13'—C14'—C15' | 179.18 (17) |
C13—C14—C15—C10 | −0.2 (3) | C11'—C10'—C15'—C14' | 0.6 (3) |
C11—C10—C15—C14 | −0.3 (3) | C9'—C10'—C15'—C14' | 179.40 (17) |
C9—C10—C15—C14 | −179.76 (17) | C13'—C14'—C15'—C10' | −0.6 (3) |
C12—C13—C16—C17 | 127.56 (19) | C12'—C13'—C16'—C19' | −138.4 (2) |
C14—C13—C16—C17 | −53.3 (2) | C14'—C13'—C16'—C19' | 42.8 (3) |
C12—C13—C16—C19 | 6.3 (2) | C12'—C13'—C16'—C17' | 100.7 (2) |
C14—C13—C16—C19 | −174.56 (17) | C14'—C13'—C16'—C17' | −78.1 (2) |
C12—C13—C16—C18 | −113.0 (2) | C12'—C13'—C16'—C18' | −17.1 (3) |
C14—C13—C16—C18 | 66.1 (2) | C14'—C13'—C16'—C18' | 164.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1′i—H1′i···O1 | 0.82 | 2.02 | 2.8276 (17) | 167 |
O1—H1···C4ii | 0.82 | 2.40 | 3.175 (2) | 159 |
Symmetry codes: (i) x, y−1, z; (ii) −x, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C23H22O |
Mr | 314.41 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 170 |
a, b, c (Å) | 10.2843 (2), 12.1135 (2), 14.5033 (2) |
α, β, γ (°) | 82.915 (1), 80.656 (1), 87.563 (1) |
V (Å3) | 1768.75 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.36 × 0.33 × 0.20 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20884, 6224, 4292 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.128, 1.07 |
No. of reflections | 6224 |
No. of parameters | 438 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.25 |
Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SIR92 (Burla et al., 1989), LS in TEXSAN (Molecular Structure Corporation, 1997) and SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2000), TEXSAN, SHELXL97 and PLATON.
D—H···A | D—H | H···A | D···A | D—H···A |
O1'i—H1'i···O1 | 0.82 | 2.02 | 2.8276 (17) | 167 |
O1—H1···C4ii | 0.82 | 2.40 | 3.175 (2) | 159 |
Symmetry codes: (i) x, y−1, z; (ii) −x, −y, −z+2. |
We previously reported the crystal structure of sp-9-(ortho-tert-butylphenyl)-9-fluorenol (Robinson et al., 1998; see also Meyers et al., 1999) as well as that of 9-(ortho-isopropylphenyl)-9-fluorenol (Hou et al., 1999). We wanted to compare the crystal structure of the title compound, (I), with that of its ortho-tert-butyl isomer. The structure of (I), with the atom numbering, is shown in Fig. 1.
As illustrated, compound (I) crystallizes in two slightly different conformations within the asymmetric unit, molecules numbered 1 and 2. Fig. 2 shows that molecule 1 is hydrogen bonded to molecule 2 via conventional O—H···O interaction, the O atom of molecule 2 being the donor, and the O atom of molecule 1 being the acceptor. In addition, there appears to be a strong interaction between the hydroxyl H atom of molecule 1 and the π-electrons nearest to C4 of the fluorene ring of a centrosymmetrically related molecule 1, an interaction which may be interpreted as an O—H···π(arene) bond (Ferguson et al., 1994). The end result is a cluster of four hydrogen-bonded molecules situated about an inversion center, denoted by a plus sign at the center of Fig. 2. Detailed hydrogen-bonding geometry is given in Table 1. Since the inversion center is located at the cell origin each cell corner will be surrounded by an identical group of four molecules, thereby defining the molecular packing of the structure, shown in Fig. 3. It is interesting to note that the related 9-(ortho-tert-butylphenyl)-9-fluorenol (Robinson et al., 1998) likewise crystallizes in two different molecular conformations and also shows the same type of intermolecular O—H···O—H hydrogen bonding between the two different molecular conformers. We have recently re-examined the X-ray data of the ortho-tert-butyl isomer and feel confident now to suggest that this compound also exhibits O—H···π(arene) bonding but, in this case, it is between the two different molecular conformers. It is interesting to find the hydrogen-bonding similarities exhibited by these two structures, since the 9-(ortho-tert-butylphenyl)-9-fluorenol has considerable steric and rotational constraints while, in contrast, (I) has no such encumberances. We therefore must refute the statement that we previously reported for 9-(ortho-tert-butylphenyl)-9-fluorenol (Robinson et al., 1998), viz. `It is reasonable to believe that stabilization of the molecular packing is attained via the intermolecular H bonding which, because of the large steric effects, is best enabled between structures (1a) and (1 b).'
While compound (I) melted quite sharply, the melt failed to crystallize on cooling or even in an ice bath, over several days, although its NMR was identical to that of crystalline (I). The same phenomenon was exhibited by isomeric 9-(ortho-tert-butylphenyl)-9-fluorenol, although its melt did crystallize after standing for several days. It is possible that this phenomenon is associated with the rather complex O—H···O—H and O—H···π(fluorene) hydrogen bonding and resulting molecular packing patterns, which are similar in both compounds. It might be energetically unfavorable for these molecules in the melt to readily reorganize into the complex hydrogen-bonded pattern required for their crystallization, a pattern much more easily attained from a slowly evaporating solution.