Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107046975/bm3037sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107046975/bm3037Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270107046975/bm3037sup3.pdf |
CCDC reference: 672545
For related literature, see: Brock & Duncan (1994); Etter (1990); Etter, MacDonald & Bernstein (1990); Jeffrey & Saenger (1991); McGregor et al. (2006); Schweizer et al. (1981); Steiner (2002); Taylor & Macrae (2001).
The title compound was synthesized by the reduction of 1-(4-methoxyphenyl)-2,2-dimethyl-1-propanone with sodium borohydride. [Please give brief details of quantities, solvents, reaction temperatures etc.] Prismatic colourless crystals were obtained by recrystallization from toluene solution upon cooling to 280 K.
The hydroxy group in molecule B (see Fig. 1 [Disorder not shown in Fig. 1]) is disordered. It was resolved by finding alternative positions from the difference Fourier map, and was subsequently refined over two positions with an occupancy of 0.787 (3) for the major conformer. Due to the absence of significant anomalous scattering effects, the measured Friedel pairs have been merged. H atoms were positioned geometrically and constrained to ride on their parent atoms, with O—H = 0.84 Å and Uiso(H) = 1.5Ueq(O), and with C—H = 0.95–1.00 Å and Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for methyl groups.
Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Version 1.08; Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).
C12H18O2 | Dx = 1.186 Mg m−3 |
Mr = 194.26 | Melting point: 313 K |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 26338 reflections |
a = 20.8868 (6) Å | θ = 2.3–28.8° |
b = 6.00175 (18) Å | µ = 0.08 mm−1 |
c = 17.3531 (5) Å | T = 173 K |
V = 2175.34 (11) Å3 | Prism, colourless |
Z = 8 | 0.53 × 0.37 × 0.15 mm |
F(000) = 848 |
Oxford Diffraction KM-4 CCD area-detector diffractometer | 2812 independent reflections |
Radiation source: fine-focus sealed tube | 2553 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω scans | θmax = 28.6°, θmin = 3.1° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2005) | h = −28→28 |
Tmin = 0.956, Tmax = 0.988 | k = −8→8 |
33345 measured reflections | l = −22→23 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0487P)2 + 0.0706P] where P = (Fo2 + 2Fc2)/3 |
2812 reflections | (Δ/σ)max < 0.001 |
278 parameters | Δρmax = 0.20 e Å−3 |
9 restraints | Δρmin = −0.18 e Å−3 |
C12H18O2 | V = 2175.34 (11) Å3 |
Mr = 194.26 | Z = 8 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 20.8868 (6) Å | µ = 0.08 mm−1 |
b = 6.00175 (18) Å | T = 173 K |
c = 17.3531 (5) Å | 0.53 × 0.37 × 0.15 mm |
Oxford Diffraction KM-4 CCD area-detector diffractometer | 2812 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2005) | 2553 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 0.988 | Rint = 0.018 |
33345 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 9 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.20 e Å−3 |
2812 reflections | Δρmin = −0.18 e Å−3 |
278 parameters |
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 I > 2σ(I) is used only for calculating R-factors and is not relevant to the choice of reflections for refinement. The final INS file consists the following commands used for the disorder modeling:.. FVAR 4.03033 0.78705.. simu 0.005 C27 C27a sadi 0.002 c27 o21 c27a o21a sadi 0.002 c27 c28 c27a c28 PART 1 C27 1 0.614196 0.413565 0.633698 21.00000 0.01313 0.01946 = 0.01946 0.00264 0.00188 0.00045 AFIX 13 H27 2 0.621509 0.248906 0.634071 21.00000 - 1.20000 AFIX 0 O21 3 0.547261 0.455657 0.646182 21.00000 0.01567 0.03103 = 0.02815 - 0.00474 0.00417 - 0.00506 AFIX 147 H21 2 0.525779 0.346510 0.630383 21.00000 - 1.50000 AFIX 0 PART 2 C27A 1 0.603435 0.476695 0.635582 - 21.00000 0.02628 AFIX 13 H27A 2 0.562423 0.560832 0.641686 - 21.00000 - 1.20000 AFIX 0 O21A 3 0.596219 0.239822 0.643366 - 21.00000 0.02814 0.02390 = 0.03453 0.00946 - 0.01395 - 0.00935 AFIX 147 H21A 2 0.564575 0.197233 0.617374 - 21.00000 - 1.50000 AFIX 0 PART 0 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.47506 (5) | 0.07793 (18) | 0.59169 (6) | 0.0220 (2) | |
H1 | 0.4660 | 0.0015 | 0.6308 | 0.033* | |
O2 | 0.55631 (5) | 0.20131 (17) | 0.23957 (6) | 0.0230 (2) | |
C1 | 0.47430 (6) | 0.0542 (2) | 0.45348 (8) | 0.0160 (3) | |
C2 | 0.50802 (7) | 0.2521 (2) | 0.44385 (8) | 0.0183 (3) | |
H2 | 0.5118 | 0.3519 | 0.4861 | 0.022* | |
C3 | 0.53637 (7) | 0.3074 (2) | 0.37374 (9) | 0.0193 (3) | |
H3 | 0.5595 | 0.4428 | 0.3684 | 0.023* | |
C4 | 0.53053 (6) | 0.1624 (2) | 0.31160 (8) | 0.0184 (3) | |
C5 | 0.49822 (7) | −0.0387 (2) | 0.32022 (9) | 0.0197 (3) | |
H5 | 0.4948 | −0.1389 | 0.2780 | 0.024* | |
C6 | 0.47100 (7) | −0.0922 (2) | 0.39090 (9) | 0.0180 (3) | |
H6 | 0.4497 | −0.2310 | 0.3968 | 0.022* | |
C7 | 0.43822 (6) | −0.0002 (2) | 0.52676 (8) | 0.0164 (3) | |
H7 | 0.4347 | −0.1660 | 0.5307 | 0.020* | |
C8 | 0.36917 (6) | 0.0987 (2) | 0.52742 (8) | 0.0180 (3) | |
C9 | 0.37051 (7) | 0.3533 (2) | 0.51973 (10) | 0.0241 (3) | |
H9A | 0.3854 | 0.3939 | 0.4680 | 0.036* | |
H9B | 0.3997 | 0.4158 | 0.5583 | 0.036* | |
H9C | 0.3273 | 0.4128 | 0.5279 | 0.036* | |
C10 | 0.33679 (8) | 0.0363 (3) | 0.60384 (10) | 0.0290 (4) | |
H10A | 0.2928 | 0.0934 | 0.6042 | 0.043* | |
H10B | 0.3608 | 0.1020 | 0.6468 | 0.043* | |
H10C | 0.3361 | −0.1261 | 0.6094 | 0.043* | |
C11 | 0.33044 (8) | −0.0012 (3) | 0.46121 (10) | 0.0253 (3) | |
H11A | 0.3317 | −0.1641 | 0.4645 | 0.038* | |
H11B | 0.3488 | 0.0467 | 0.4120 | 0.038* | |
H11C | 0.2860 | 0.0498 | 0.4647 | 0.038* | |
C12 | 0.58955 (8) | 0.4076 (3) | 0.22978 (10) | 0.0290 (4) | |
H12A | 0.5599 | 0.5317 | 0.2381 | 0.043* | |
H12B | 0.6069 | 0.4157 | 0.1774 | 0.043* | |
H12C | 0.6246 | 0.4167 | 0.2671 | 0.043* | |
C27 | 0.61420 (8) | 0.4136 (4) | 0.63370 (11) | 0.0173 (4) | 0.787 (3) |
H27 | 0.6215 | 0.2489 | 0.6341 | 0.021* | 0.787 (3) |
O21 | 0.54726 (6) | 0.4557 (2) | 0.64618 (8) | 0.0250 (4) | 0.787 (3) |
H21 | 0.5258 | 0.3465 | 0.6304 | 0.037* | 0.787 (3) |
C27A | 0.6034 (4) | 0.4767 (9) | 0.6356 (5) | 0.026 (2)* | 0.213 (3) |
H27A | 0.5624 | 0.5608 | 0.6417 | 0.032* | 0.213 (3) |
O21A | 0.5962 (3) | 0.2398 (8) | 0.6434 (4) | 0.0289 (16) | 0.213 (3) |
H21A | 0.5646 | 0.1972 | 0.6174 | 0.043* | 0.213 (3) |
O22 | 0.70957 (5) | 0.73408 (19) | 0.34740 (6) | 0.0237 (2) | |
C21 | 0.63463 (7) | 0.5057 (3) | 0.55560 (9) | 0.0220 (3) | |
C22 | 0.61170 (7) | 0.7037 (3) | 0.52447 (9) | 0.0238 (3) | |
H22 | 0.5796 | 0.7841 | 0.5514 | 0.029* | |
C23 | 0.63470 (7) | 0.7873 (3) | 0.45468 (9) | 0.0210 (3) | |
H23 | 0.6184 | 0.9226 | 0.4342 | 0.025* | |
C24 | 0.68204 (7) | 0.6688 (2) | 0.41559 (8) | 0.0189 (3) | |
C25 | 0.70449 (7) | 0.4678 (2) | 0.44528 (9) | 0.0223 (3) | |
H25 | 0.7362 | 0.3857 | 0.4182 | 0.027* | |
C26 | 0.68054 (7) | 0.3879 (2) | 0.51415 (9) | 0.0225 (3) | |
H26 | 0.6957 | 0.2497 | 0.5336 | 0.027* | |
C28 | 0.65265 (7) | 0.5205 (2) | 0.70188 (9) | 0.0204 (3) | |
C29 | 0.64782 (9) | 0.7742 (3) | 0.70457 (10) | 0.0289 (3) | |
H29A | 0.6709 | 0.8301 | 0.7498 | 0.043* | |
H29B | 0.6027 | 0.8181 | 0.7080 | 0.043* | |
H29C | 0.6667 | 0.8373 | 0.6577 | 0.043* | |
C30 | 0.62705 (8) | 0.4271 (3) | 0.77822 (9) | 0.0292 (3) | |
H30A | 0.6535 | 0.4819 | 0.8209 | 0.044* | |
H30B | 0.6287 | 0.2639 | 0.7769 | 0.044* | |
H30C | 0.5827 | 0.4758 | 0.7856 | 0.044* | |
C31 | 0.72248 (7) | 0.4491 (3) | 0.69301 (9) | 0.0241 (3) | |
H31A | 0.7402 | 0.5138 | 0.6457 | 0.036* | |
H31B | 0.7249 | 0.2862 | 0.6901 | 0.036* | |
H31C | 0.7472 | 0.5015 | 0.7375 | 0.036* | |
C32 | 0.68837 (9) | 0.9378 (3) | 0.31457 (9) | 0.0295 (4) | |
H32A | 0.6427 | 0.9270 | 0.3024 | 0.044* | |
H32B | 0.7125 | 0.9677 | 0.2673 | 0.044* | |
H32C | 0.6953 | 1.0593 | 0.3514 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0226 (5) | 0.0292 (6) | 0.0143 (5) | −0.0067 (4) | −0.0037 (4) | 0.0015 (4) |
O2 | 0.0266 (5) | 0.0246 (5) | 0.0179 (5) | 0.0000 (4) | 0.0049 (4) | 0.0013 (4) |
C1 | 0.0125 (6) | 0.0194 (6) | 0.0160 (6) | 0.0012 (5) | −0.0009 (5) | 0.0008 (5) |
C2 | 0.0178 (6) | 0.0189 (6) | 0.0181 (7) | −0.0015 (5) | −0.0018 (5) | −0.0042 (5) |
C3 | 0.0169 (6) | 0.0193 (6) | 0.0218 (7) | −0.0028 (5) | −0.0009 (5) | 0.0004 (5) |
C4 | 0.0161 (6) | 0.0229 (7) | 0.0161 (7) | 0.0038 (5) | 0.0008 (5) | 0.0019 (5) |
C5 | 0.0199 (7) | 0.0209 (7) | 0.0183 (7) | 0.0033 (6) | −0.0007 (5) | −0.0043 (5) |
C6 | 0.0170 (6) | 0.0173 (6) | 0.0198 (7) | 0.0000 (5) | −0.0015 (5) | −0.0009 (5) |
C7 | 0.0163 (6) | 0.0171 (6) | 0.0157 (6) | −0.0027 (5) | −0.0015 (5) | −0.0005 (5) |
C8 | 0.0165 (6) | 0.0199 (6) | 0.0175 (6) | 0.0002 (5) | 0.0010 (5) | 0.0013 (5) |
C9 | 0.0263 (7) | 0.0196 (6) | 0.0265 (7) | 0.0031 (5) | 0.0050 (6) | −0.0003 (6) |
C10 | 0.0224 (7) | 0.0371 (9) | 0.0274 (8) | 0.0024 (6) | 0.0081 (6) | 0.0095 (7) |
C11 | 0.0175 (6) | 0.0288 (8) | 0.0296 (8) | 0.0004 (6) | −0.0047 (6) | 0.0001 (7) |
C12 | 0.0356 (9) | 0.0259 (8) | 0.0254 (8) | 0.0002 (6) | 0.0107 (7) | 0.0049 (6) |
C27 | 0.0131 (9) | 0.0195 (11) | 0.0195 (9) | 0.0005 (8) | 0.0019 (7) | 0.0026 (8) |
O21 | 0.0157 (7) | 0.0310 (8) | 0.0282 (8) | −0.0051 (5) | 0.0042 (6) | −0.0047 (6) |
O21A | 0.028 (3) | 0.024 (3) | 0.035 (3) | −0.009 (2) | −0.014 (2) | 0.009 (2) |
O22 | 0.0246 (5) | 0.0291 (5) | 0.0174 (5) | 0.0048 (4) | 0.0025 (4) | 0.0008 (4) |
C21 | 0.0165 (6) | 0.0308 (7) | 0.0187 (7) | −0.0082 (6) | −0.0034 (5) | 0.0031 (6) |
C22 | 0.0169 (6) | 0.0342 (8) | 0.0203 (7) | 0.0029 (6) | −0.0005 (6) | −0.0024 (6) |
C23 | 0.0192 (7) | 0.0246 (7) | 0.0192 (7) | 0.0031 (6) | −0.0035 (5) | −0.0014 (6) |
C24 | 0.0173 (6) | 0.0236 (7) | 0.0159 (6) | −0.0018 (5) | −0.0027 (5) | −0.0026 (5) |
C25 | 0.0224 (7) | 0.0225 (7) | 0.0219 (7) | 0.0025 (5) | −0.0031 (6) | −0.0051 (6) |
C26 | 0.0248 (7) | 0.0201 (6) | 0.0226 (7) | −0.0026 (6) | −0.0057 (6) | −0.0003 (6) |
C28 | 0.0196 (7) | 0.0241 (7) | 0.0175 (6) | −0.0022 (6) | 0.0016 (6) | 0.0018 (6) |
C29 | 0.0374 (9) | 0.0252 (8) | 0.0241 (8) | 0.0039 (6) | 0.0042 (7) | −0.0006 (6) |
C30 | 0.0287 (8) | 0.0375 (9) | 0.0212 (7) | −0.0057 (7) | 0.0032 (6) | 0.0058 (7) |
C31 | 0.0228 (7) | 0.0290 (8) | 0.0205 (7) | 0.0018 (6) | −0.0022 (6) | −0.0021 (6) |
C32 | 0.0373 (9) | 0.0316 (8) | 0.0198 (7) | 0.0037 (7) | 0.0030 (7) | 0.0046 (6) |
O1—C7 | 1.4428 (17) | C27—H27 | 1.0000 |
O1—H1 | 0.8400 | O21—H21 | 0.8400 |
C1—C7 | 1.5138 (19) | O21A—C27A | 1.436 (3) |
O2—C4 | 1.3809 (17) | C27A—C21 | 1.543 (11) |
O2—C12 | 1.4294 (19) | C27A—C28 | 1.565 (3) |
C1—C2 | 1.3908 (19) | C27A—H27A | 1.0000 |
C1—C6 | 1.398 (2) | O21A—H21A | 0.8400 |
C2—C3 | 1.393 (2) | O22—C24 | 1.3727 (18) |
C2—H2 | 0.9500 | O22—C32 | 1.4198 (19) |
C3—C4 | 1.391 (2) | C21—C22 | 1.390 (2) |
C3—H3 | 0.9500 | C21—C26 | 1.392 (2) |
C4—C5 | 1.391 (2) | C22—C23 | 1.396 (2) |
C5—C6 | 1.389 (2) | C22—H22 | 0.9500 |
C5—H5 | 0.9500 | C23—C24 | 1.394 (2) |
C6—H6 | 0.9500 | C23—H23 | 0.9500 |
C7—C8 | 1.5598 (18) | C24—C25 | 1.393 (2) |
C7—H7 | 1.0000 | C25—C26 | 1.381 (2) |
C8—C11 | 1.528 (2) | C25—H25 | 0.9500 |
C8—C9 | 1.534 (2) | C26—H26 | 0.9500 |
C8—C10 | 1.535 (2) | C28—C29 | 1.527 (2) |
C9—H9A | 0.9800 | C28—C31 | 1.528 (2) |
C9—H9B | 0.9800 | C28—C30 | 1.535 (2) |
C9—H9C | 0.9800 | C29—H29A | 0.9800 |
C10—H10A | 0.9800 | C29—H29B | 0.9800 |
C10—H10B | 0.9800 | C29—H29C | 0.9800 |
C10—H10C | 0.9800 | C30—H30A | 0.9800 |
C11—H11A | 0.9800 | C30—H30B | 0.9800 |
C11—H11B | 0.9800 | C30—H30C | 0.9800 |
C11—H11C | 0.9800 | C31—H31A | 0.9800 |
C12—H12A | 0.9800 | C31—H31B | 0.9800 |
C12—H12B | 0.9800 | C31—H31C | 0.9800 |
C12—H12C | 0.9800 | C32—H32A | 0.9800 |
O21—C27 | 1.437 (2) | C32—H32B | 0.9800 |
C21—C27 | 1.525 (2) | C32—H32C | 0.9800 |
C27—C28 | 1.567 (2) | ||
O1—C7—C1 | 108.69 (10) | O22—C24—C23 | 124.82 (14) |
O1—C7—C8 | 111.33 (11) | O22—C24—C25 | 115.15 (13) |
O1—C7—H7 | 108.0 | O22—C32—H32A | 109.5 |
O2—C4—C3 | 124.17 (13) | O22—C32—H32B | 109.5 |
O2—C4—C5 | 115.68 (12) | O22—C32—H32C | 109.5 |
O2—C12—H12A | 109.5 | C21—C22—C23 | 121.72 (14) |
O2—C12—H12B | 109.5 | C21—C22—H22 | 119.1 |
O2—C12—H12C | 109.5 | C21—C26—H26 | 119.3 |
C1—C2—C3 | 121.56 (13) | C21—C27—C28 | 112.27 (14) |
C1—C2—H2 | 119.2 | C21—C27A—C28 | 111.4 (6) |
C1—C6—H6 | 119.3 | C21—C27—H27 | 108.7 |
C1—C7—H7 | 108.0 | C21—C27A—H27A | 113.6 |
C1—C7—C8 | 112.60 (11) | C22—C21—C26 | 118.07 (14) |
C2—C1—C6 | 117.91 (13) | C22—C21—C27 | 123.98 (16) |
C2—C1—C7 | 122.49 (13) | C22—C21—C27A | 107.5 (3) |
C2—C3—H3 | 120.3 | C22—C23—H23 | 120.6 |
C3—C2—H2 | 119.2 | C23—C22—H22 | 119.1 |
C4—O2—C12 | 116.32 (12) | C24—O22—C32 | 117.46 (12) |
C4—C3—C2 | 119.39 (13) | C24—C23—C22 | 118.87 (14) |
C4—C3—H3 | 120.3 | C24—C23—H23 | 120.6 |
C4—C5—H5 | 120.2 | C24—C25—H25 | 120.0 |
C5—C4—C3 | 120.13 (13) | C25—C24—C23 | 120.03 (14) |
C5—C6—C1 | 121.34 (13) | C25—C26—C21 | 121.37 (14) |
C5—C6—H6 | 119.3 | C25—C26—H26 | 119.3 |
C6—C1—C7 | 119.49 (12) | C26—C21—C27 | 117.92 (15) |
C6—C5—C4 | 119.60 (13) | C26—C21—C27A | 134.3 (3) |
C6—C5—H5 | 120.2 | C26—C25—C24 | 119.91 (14) |
C7—O1—H1 | 109.5 | C26—C25—H25 | 120.0 |
C8—C7—H7 | 108.0 | C27—O21—H21 | 109.5 |
C8—C9—H9A | 109.5 | C27A—O21A—H21A | 109.5 |
C8—C9—H9B | 109.5 | C28—C27—H27 | 108.7 |
C8—C9—H9C | 109.5 | C28—C27A—H27A | 113.6 |
C8—C10—H10A | 109.5 | C28—C29—H29A | 109.5 |
C8—C10—H10B | 109.5 | C28—C29—H29B | 109.5 |
C8—C10—H10C | 109.5 | C28—C29—H29C | 109.5 |
C8—C11—H11A | 109.5 | C28—C30—H30A | 109.5 |
C8—C11—H11B | 109.5 | C28—C30—H30B | 109.5 |
C8—C11—H11C | 109.5 | C28—C30—H30C | 109.5 |
C9—C8—C7 | 111.19 (11) | C28—C31—H31A | 109.5 |
C9—C8—C10 | 109.03 (12) | C28—C31—H31B | 109.5 |
C10—C8—C7 | 108.72 (12) | C28—C31—H31C | 109.5 |
C11—C8—C7 | 109.56 (12) | C29—C28—C27 | 113.42 (15) |
C11—C8—C9 | 109.58 (12) | C29—C28—C27A | 98.4 (2) |
C11—C8—C10 | 108.71 (12) | C29—C28—C30 | 108.35 (13) |
H9A—C9—H9B | 109.5 | C29—C28—C31 | 110.22 (13) |
H9A—C9—H9C | 109.5 | C30—C28—C27 | 108.88 (13) |
H9B—C9—H9C | 109.5 | C30—C28—C27A | 110.1 (4) |
H10A—C10—H10B | 109.5 | C31—C28—C27 | 107.37 (13) |
H10A—C10—H10C | 109.5 | C31—C28—C27A | 120.4 (4) |
H10B—C10—H10C | 109.5 | C31—C28—C30 | 108.49 (13) |
H11A—C11—H11B | 109.5 | H29A—C29—H29B | 109.5 |
H11A—C11—H11C | 109.5 | H29A—C29—H29C | 109.5 |
H11B—C11—H11C | 109.5 | H29B—C29—H29C | 109.5 |
H12A—C12—H12C | 109.5 | H30A—C30—H30B | 109.5 |
H12A—C12—H12B | 109.5 | H30A—C30—H30C | 109.5 |
H12B—C12—H12C | 109.5 | H30B—C30—H30C | 109.5 |
O21—C27—C21 | 110.04 (16) | H31A—C31—H31B | 109.5 |
O21—C27—C28 | 108.23 (14) | H31A—C31—H31C | 109.5 |
O21—C27—H27 | 108.7 | H31B—C31—H31C | 109.5 |
O21A—C27A—C21 | 103.9 (6) | H32A—C32—H32B | 109.5 |
O21A—C27A—C28 | 99.6 (3) | H32A—C32—H32C | 109.5 |
O21A—C27A—H27A | 113.6 | H32B—C32—H32C | 109.5 |
C2—C1—C7—O1 | −38.41 (17) | O21A—C27A—C21—C26 | −37.6 (5) |
C6—C1—C7—O1 | 145.45 (12) | O21A—C27A—C28—C29 | −167.7 (6) |
O1—C7—C8—C10 | −57.25 (15) | O21A—C27A—C28—C30 | −54.6 (7) |
O1—C7—C8—C11 | −175.93 (11) | O21A—C27A—C28—C31 | 72.8 (7) |
O1—C7—C8—C9 | 62.79 (15) | C28—C27—C21—C22 | −83.13 (19) |
C2—C1—C7—C8 | 85.42 (15) | C28—C27A—C21—C22 | −106.9 (4) |
C6—C1—C7—C8 | −90.72 (15) | C28—C27—C21—C26 | 94.74 (19) |
C6—C1—C2—C3 | 1.7 (2) | C28—C27A—C21—C26 | 68.7 (4) |
C7—C1—C2—C3 | −174.49 (13) | C26—C21—C22—C23 | −1.6 (2) |
C1—C2—C3—C4 | 0.5 (2) | C27—C21—C22—C23 | 176.25 (13) |
C12—O2—C4—C3 | −1.5 (2) | C27A—C21—C22—C23 | 174.8 (2) |
C12—O2—C4—C5 | 179.87 (13) | C21—C22—C23—C24 | −0.2 (2) |
C2—C3—C4—O2 | 179.56 (13) | C32—O22—C24—C23 | 0.3 (2) |
C2—C3—C4—C5 | −1.8 (2) | C32—O22—C24—C25 | 179.95 (13) |
O2—C4—C5—C6 | 179.71 (12) | C22—C23—C24—O22 | −178.77 (13) |
C3—C4—C5—C6 | 1.0 (2) | C22—C23—C24—C25 | 1.6 (2) |
C4—C5—C6—C1 | 1.3 (2) | O22—C24—C25—C26 | 179.24 (12) |
C2—C1—C6—C5 | −2.6 (2) | C23—C24—C25—C26 | −1.1 (2) |
C7—C1—C6—C5 | 173.74 (12) | C24—C25—C26—C21 | −0.8 (2) |
C1—C7—C8—C9 | −59.57 (15) | C22—C21—C26—C25 | 2.1 (2) |
C1—C7—C8—C10 | −179.61 (12) | C27—C21—C26—C25 | −175.86 (13) |
C1—C7—C8—C11 | 61.71 (15) | C27A—C21—C26—C25 | −173.1 (2) |
O21—C27—C21—C22 | 37.5 (2) | C21—C27—C28—C29 | 56.7 (2) |
O21—C27—C21—C26 | −144.65 (15) | C21—C27—C28—C30 | 177.37 (15) |
O21—C27—C28—C29 | −64.98 (19) | C21—C27—C28—C31 | −65.36 (19) |
O21—C27—C28—C30 | 55.7 (2) | C21—C27A—C28—C29 | 83.1 (4) |
O21—C27—C28—C31 | 173.00 (15) | C21—C27A—C28—C31 | −36.4 (4) |
O21A—C27A—C21—C22 | 146.7 (3) | C21—C27A—C28—C30 | −163.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O21—H21···O1 | 0.84 | 2.04 | 2.883 (2) | 179 |
O1—H1···O2i | 0.84 | 2.29 | 3.134 (2) | 178 |
C31—H31C···O22ii | 0.98 | 2.53 | 3.481 (2) | 163 |
Symmetry codes: (i) −x+1, −y, z+1/2; (ii) −x+3/2, y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H18O2 |
Mr | 194.26 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 173 |
a, b, c (Å) | 20.8868 (6), 6.00175 (18), 17.3531 (5) |
V (Å3) | 2175.34 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.53 × 0.37 × 0.15 |
Data collection | |
Diffractometer | Oxford Diffraction KM-4 CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2005) |
Tmin, Tmax | 0.956, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33345, 2812, 2553 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.674 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.073, 1.09 |
No. of reflections | 2812 |
No. of parameters | 278 |
No. of restraints | 9 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.18 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), SHELXS97 (Sheldrick, 1990), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Version 1.08; Farrugia, 1997), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).
O1—C7 | 1.4428 (17) | O21—C27 | 1.437 (2) |
C1—C7 | 1.5138 (19) | C21—C27 | 1.525 (2) |
O2—C4 | 1.3809 (17) | O22—C24 | 1.3727 (18) |
O2—C12 | 1.4294 (19) | O22—C32 | 1.4198 (19) |
O21—C27—C21—C22 | 37.5 (2) | O21A—C27A—C21—C22 | 146.7 (3) |
O21—C27—C21—C26 | −144.65 (15) | O21A—C27A—C21—C26 | −37.6 (5) |
O21—C27—C28—C29 | −64.98 (19) | O21A—C27A—C28—C29 | −167.7 (6) |
O21—C27—C28—C30 | 55.7 (2) | O21A—C27A—C28—C30 | −54.6 (7) |
O21—C27—C28—C31 | 173.00 (15) | O21A—C27A—C28—C31 | 72.8 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O21—H21···O1 | 0.84 | 2.04 | 2.883 (2) | 179 |
O1—H1···O2i | 0.84 | 2.29 | 3.134 (2) | 178 |
C31—H31C···O22ii | 0.98 | 2.53 | 3.481 (2) | 163 |
Symmetry codes: (i) −x+1, −y, z+1/2; (ii) −x+3/2, y, z+1/2. |
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Three different basic motifs have been described for the hydrogen-bonded networks found in crystals of mono-alcohols (Brock & Duncan, 1994). Two of the most important factors on which the formation of hydrogen-bonded systems depend are the number and size of the groups connected to the carbinol C atom. Primary mono-alcohols tend to form extended chain structures which contain ···Ohydroxy—H···O hydroxy—H··· bond sequences (Taylor & Macrae, 2001). Secondary mono-alcohols tend to form chains or rings, and steric effects determine which motif is formed. Hence, secondary mono-alcohols with bulky groups connected to the carbinol C atom usually exhibit a finite motif, i.e. ring structures, instead of chains (McGregor et al., 2006). As reported by Taylor & Macrae (2001), tertiary mono-alcohols either form finite motifs via O—H···O hydrogen bonds or do not exhibit any O—H···O hydrogen bonding. Furthermore, there is a third possibility, namely the formation of dimers: Brock & Duncan (1994) postulate that dimers form when an extended hydrogen-bonded structure is precluded. Closed dimers are said to be less likely to form than those with a dangling H atom and a free acceptor (Jeffrey & Saenger, 1991; Schweizer et al., 1981). The title compound, (I), is a further interesting example, from the point of view of systematization of hydrogen-bonded networks displayed in mono-alcohols, of a secondary mono-alcohol with two bulky substituents at the carbinol C atom.
Since no separation of enantiomers had been undertaken after synthesis, the crystal examined was obtained from a racemic mixture. There are two independent molecules in the asymmetric unit of (I), labelled A and B. The only chiral centres of the molecules of (I) are at the carbinol C atoms, i.e. atoms C7 and C27. In the hydroxy group region of molecule B, disorder was identified and modelled as a superposition of two fragments, one defined by atoms C27, H27, O21 and H21, and the other by atoms C27A, H27A, O21A and H21A. Depending on which of the components is considered, the resulting conformation of molecule B is either S or R. This is reflected in the different values of the appropriate torsion angles (Table 1). In the following discussion, only the geometric parameters of the major component, i.e. that with an occupancy factor of 0.787 (3), will be presented.
The geometric parameters of molecules A and B are very similar and the most significant differences between the two unique molecules of (I) are found in the hydroxy and methoxy group regions (Table 1). For example, in molecule A the C1—C7 bond of 1.5138 (19) Å is about 0.011 (3) Å longer than C21—C27 in molecule B. These differences might be caused by the disorder. However, the fact that the O atom of the hydroxy group of molecule A forms two strong O—H···O hydrogen bonds may also be significant. The different strength of the intermolecular interactions in which atoms O2 and O22 participate (Table 2) may also be a reason for the small differences between the two unique molecules in the methoxy group region. Moreover, the anisotropic displacement coefficients of the C atoms which constitute the phenyl ring of molecule B are larger than those of the corresponding atoms of molecule A.
The title compound exhibits a dimeric structure with graph-set notation D (Etter, 1990) formed by Ohydroxy—H···Ohydroxy hydrogen bonding (Table 2) which links an A molecule and a B molecule (Fig. 1). This motif occurs irrespective of which disorder component is considered. Within each dimer, the major component of molecule B has the opposite configuration to that of molecule A. Although two bulky groups attached to the carbinol C atom hinder the association of more than two molecules via Ohydroxy—H···O hydroxy bonds, the O atoms from the methoxy groups enable the dimeric structure to form other more complex supramolecular networks. The geometric parameters of the hydrogen bonds which are present in the crystal structure of (I) are shown in Table 2.
The dimers are assembled into extended chains with dangling B molecules. This results from the fact that the dimers are not closed. Each molecule A is linked with two other symmetry-related A molecules by a strong Ohydroxy—H···Omethoxy bond (Table 2). These interactions link the dimers into a chain along the c axis (Fig. 2). This chain can be designated by the first-level graph-set notation N1 = C(8)[D] (Etter et al., 1990). Another way of describing this chain is with the p21 rod group characterized by a 21 screw axis along the c axis (International Tables for Crystallography, 2002). [AUTHOR: axis "Z" replaced by "c" - correct?]
The chains further self-organize through weak C—H···O interactions to generate a layer. This is indicated by the geometry of the bond, as well as the fact that the H atom is directed towards the O22 lone electron pair (Steiner, 2002). Within a layer, every B molecule is linked with two other B molecules which belong to an adjacent chain to form an extended C(9) chain motif. The H31C···O22ii distance is 2.53 Å [symmetry code: (ii) -x + 3/2, y, z + 1/2] and the C31—H31C···O22ii angle is 163°. The supramolecular structure which results from these interactions is a layer with pb21a symmetry (Fig. 2) (International Tables for Crystallography, 2002). These supramolecular layers are parallel to (010), hence the non-periodic direction is that parallel to b. The basis vectors of the layer group, aL and bL, are consistent with the original a and c basis vectors, respectively. Within a layer, each chain is related to the adjacent chain by an a-glide plane.
In summary, the bulky tert-butyl group and the phenyl ring on the carbinol C atom of (I) induce steric hindrance which effectively precludes the formation of a chain-like structure with ···Ohydroxy—H···Ohydroxy sequences. Instead, molecules form dimers with a dangling H atom, and their open structure enables the dimers to arrange themselves into a hydrogen-bonded chain structure via interactions of methoxy O atoms with dangling H atoms.