The racemic form of the title secondary monoalcohol, C16H14O, forms crystals in which the molecules are linked into chains by hydrogen bonding. The chain architecture is unusual; adjacent molecules are related pseudosymmetrically, by either a pseudo-diad or a pseudo-glide plane, while alternate molecules are related exactly by a crystallographic glide plane.
Supporting information
CCDC reference: 214386
The title compound was first synthesized by Wawzonek and Hallum (1953). Our sample was provided by Professor Marie-Joséphe Brienne, Collége de France, Paris.
The absolute structure has not been determined experimentally. Our coordinates and drawings arbitrarily show S and R configurations at C102 and C202, respectively. All H atoms appeared in difference syntheses in stereochemically acceptable positions. In the final calculations, hydroxyl H atoms were freely refined. The other H atoms were placed in positions calculated using the HFIX option in SHELXL97 (Sheldrick, 1997) and then refined riding on their parent C atoms, with C—H distances of 1.00, 0.99 and 0.95 Å, respectively, for methine, methylene and aromatic C atoms and Uiso(H) values of 1.2Ueq(C). At a late stage in the analysis (R1 = 0.068 for observed data, wR2 = 0.180 for all data) two peaks of 0.8 e Å−3 with coordinates derived from those of O1 and O2 by inversion through the origin were found in the difference map. Accordingly, O1 and O2 have been disordered over two sites with occupancies α and 1-α [α = 0.856 (8)] after refinement. This disordered model led to significantly lower agreement indices and a featureless difference synthesis. There is no indication that disorder affects any of the C atoms.
Data collection: COLLECT (Nonius, 1997–2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
Crystal data top
C16H14O | F(000) = 944 |
Mr = 222.27 | Dx = 1.271 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 2967 reflections |
a = 14.3719 (3) Å | θ = 2.9–27.5° |
b = 22.8650 (6) Å | µ = 0.08 mm−1 |
c = 7.0703 (1) Å | T = 100 K |
V = 2323.40 (8) Å3 | Needle, colourless |
Z = 8 | 0.40 × 0.17 × 0.12 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | Rint = 0.057 |
CCD; rotation images; thick slices scans | θmax = 27.5°, θmin = 3° |
17231 measured reflections | h = 0→18 |
2863 independent reflections | k = 0→29 |
2385 reflections with I > 2σ(I) | l = 0→9 |
Refinement top
Refinement on F2 | 1 restraint |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.055 | w = 1/[σ2(Fo2) + 1.24P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.141 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.34 e Å−3 |
2863 reflections | Δρmin = −0.24 e Å−3 |
324 parameters | |
Crystal data top
C16H14O | V = 2323.40 (8) Å3 |
Mr = 222.27 | Z = 8 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 14.3719 (3) Å | µ = 0.08 mm−1 |
b = 22.8650 (6) Å | T = 100 K |
c = 7.0703 (1) Å | 0.40 × 0.17 × 0.12 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2385 reflections with I > 2σ(I) |
17231 measured reflections | Rint = 0.057 |
2863 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 1 restraint |
wR(F2) = 0.141 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.34 e Å−3 |
2863 reflections | Δρmin = −0.24 e Å−3 |
324 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C101 | 0.6182 (2) | 0.14290 (12) | 0.1204 (5) | 0.0250 (7) | |
H101 | 0.6572 | 0.156 | 0.0113 | 0.03* | |
C102 | 0.6522 (2) | 0.16967 (13) | 0.3125 (6) | 0.0325 (8) | |
H102 | 0.7145 | 0.1527 | 0.3432 | 0.039* | |
C103 | 0.5841 (2) | 0.15254 (14) | 0.4695 (5) | 0.0317 (7) | |
H13A | 0.5504 | 0.1877 | 0.5143 | 0.038* | |
H13B | 0.6188 | 0.1358 | 0.5778 | 0.038* | |
C104 | 0.5136 (2) | 0.10697 (12) | 0.3938 (4) | 0.0254 (7) | |
H104 | 0.4717 | 0.0921 | 0.496 | 0.03* | |
C105 | 0.4597 (2) | 0.13735 (12) | 0.2384 (5) | 0.0234 (6) | |
C106 | 0.5165 (2) | 0.15814 (11) | 0.0936 (5) | 0.0232 (7) | |
C107 | 0.6258 (2) | 0.07728 (12) | 0.1547 (5) | 0.0224 (6) | |
C108 | 0.57027 (18) | 0.05830 (12) | 0.3051 (4) | 0.0206 (6) | |
C109 | 0.3645 (2) | 0.14696 (13) | 0.2329 (5) | 0.0283 (7) | |
H109 | 0.3256 | 0.132 | 0.3302 | 0.034* | |
C110 | 0.3265 (2) | 0.17840 (13) | 0.0850 (6) | 0.0327 (8) | |
H110 | 0.2613 | 0.1851 | 0.0812 | 0.039* | |
C111 | 0.3826 (2) | 0.20023 (13) | −0.0580 (5) | 0.0335 (8) | |
H111 | 0.3559 | 0.2219 | −0.1589 | 0.04* | |
C112 | 0.4784 (2) | 0.19034 (12) | −0.0534 (5) | 0.0307 (7) | |
H112 | 0.5172 | 0.2056 | −0.1503 | 0.037* | |
C113 | 0.6846 (2) | 0.03828 (13) | 0.0640 (5) | 0.0282 (7) | |
H113 | 0.7226 | 0.0509 | −0.038 | 0.034* | |
C114 | 0.6872 (2) | −0.02004 (13) | 0.1246 (5) | 0.0298 (7) | |
H114 | 0.7277 | −0.0471 | 0.0641 | 0.036* | |
C115 | 0.6310 (2) | −0.03854 (13) | 0.2728 (5) | 0.0286 (7) | |
H115 | 0.633 | −0.0782 | 0.3123 | 0.034* | |
C116 | 0.5721 (2) | 0.00041 (12) | 0.3633 (5) | 0.0260 (7) | |
H116 | 0.5335 | −0.0124 | 0.4641 | 0.031* | |
O1 | 0.65976 (19) | 0.23177 (10) | 0.3135 (5) | 0.0256 (8) | 0.856 (8) |
H1 | 0.715 (4) | 0.2364 (19) | 0.266 (9) | 0.077 (18)* | |
O1' | 0.6631 (17) | 0.2341 (10) | 0.185 (5) | 0.056 (7)* | 0.144 (8) |
C201 | 0.6178 (2) | 0.36156 (12) | 0.5562 (5) | 0.0260 (7) | |
H201 | 0.6508 | 0.3532 | 0.4347 | 0.031* | |
C202 | 0.6625 (2) | 0.32924 (13) | 0.7232 (5) | 0.0299 (8) | |
H202 | 0.7272 | 0.3443 | 0.7404 | 0.036* | |
C203 | 0.6065 (2) | 0.34264 (14) | 0.9035 (5) | 0.0327 (8) | |
H23A | 0.6485 | 0.3591 | 1.0009 | 0.039* | |
H23B | 0.5796 | 0.306 | 0.9539 | 0.039* | |
C204 | 0.5267 (2) | 0.38716 (12) | 0.8610 (5) | 0.0267 (7) | |
H204 | 0.4905 | 0.3975 | 0.977 | 0.032* | |
C205 | 0.4665 (2) | 0.35950 (12) | 0.7108 (5) | 0.0252 (7) | |
C206 | 0.5165 (2) | 0.34405 (12) | 0.5475 (5) | 0.0248 (7) | |
C207 | 0.62434 (19) | 0.42600 (12) | 0.6105 (5) | 0.0250 (7) | |
C208 | 0.57468 (19) | 0.43973 (13) | 0.7747 (5) | 0.0242 (7) | |
C209 | 0.3721 (2) | 0.34676 (13) | 0.7225 (6) | 0.0299 (7) | |
H209 | 0.3374 | 0.3579 | 0.8311 | 0.036* | |
C210 | 0.3292 (2) | 0.31781 (13) | 0.5750 (6) | 0.0314 (8) | |
H210 | 0.2645 | 0.3095 | 0.5822 | 0.038* | |
C211 | 0.3792 (2) | 0.30053 (12) | 0.4157 (5) | 0.0323 (8) | |
H211 | 0.349 | 0.2797 | 0.3169 | 0.039* | |
C212 | 0.4734 (2) | 0.31383 (12) | 0.4018 (5) | 0.0312 (8) | |
H212 | 0.5079 | 0.3023 | 0.2935 | 0.037* | |
C213 | 0.6769 (2) | 0.46819 (14) | 0.5184 (6) | 0.0333 (8) | |
H213 | 0.7107 | 0.4588 | 0.4071 | 0.04* | |
C214 | 0.6789 (2) | 0.52472 (13) | 0.5927 (6) | 0.0362 (9) | |
H214 | 0.7156 | 0.5539 | 0.5324 | 0.043* | |
C215 | 0.6286 (2) | 0.53890 (13) | 0.7524 (6) | 0.0345 (9) | |
H215 | 0.6299 | 0.5778 | 0.7996 | 0.041* | |
C216 | 0.5758 (2) | 0.49640 (13) | 0.8452 (5) | 0.0302 (7) | |
H216 | 0.5411 | 0.5061 | 0.9552 | 0.036* | |
O2 | 0.66724 (18) | 0.26707 (10) | 0.6876 (4) | 0.0243 (8) | 0.856 (8) |
H2 | 0.651 (4) | 0.259 (2) | 0.572 (10) | 0.10 (2)* | |
O2' | 0.6604 (16) | 0.2697 (11) | 0.820 (5) | 0.078 (8)* | 0.144 (8) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C101 | 0.0205 (14) | 0.0201 (14) | 0.0343 (18) | −0.0032 (11) | 0.0081 (13) | 0.0014 (13) |
C102 | 0.0210 (14) | 0.0214 (15) | 0.055 (2) | 0.0000 (12) | −0.0082 (15) | −0.0050 (15) |
C103 | 0.0372 (17) | 0.0274 (15) | 0.0305 (18) | 0.0012 (14) | −0.0086 (15) | −0.0047 (13) |
C104 | 0.0277 (15) | 0.0266 (14) | 0.0218 (16) | −0.0013 (12) | 0.0001 (13) | −0.0037 (12) |
C105 | 0.0246 (14) | 0.0166 (13) | 0.0291 (17) | −0.0007 (11) | 0.0034 (13) | −0.0043 (12) |
C106 | 0.0231 (14) | 0.0154 (12) | 0.0311 (18) | −0.0019 (11) | −0.0018 (13) | −0.0021 (12) |
C107 | 0.0186 (13) | 0.0192 (13) | 0.0294 (17) | −0.0040 (11) | −0.0014 (12) | −0.0007 (12) |
C108 | 0.0162 (13) | 0.0237 (13) | 0.0220 (15) | −0.0015 (11) | −0.0017 (11) | −0.0007 (12) |
C109 | 0.0257 (15) | 0.0239 (15) | 0.0353 (18) | 0.0003 (12) | 0.0029 (14) | −0.0075 (14) |
C110 | 0.0267 (15) | 0.0240 (14) | 0.048 (2) | 0.0053 (13) | −0.0090 (16) | −0.0112 (15) |
C111 | 0.0430 (19) | 0.0186 (14) | 0.039 (2) | 0.0062 (13) | −0.0144 (16) | −0.0032 (14) |
C112 | 0.0394 (18) | 0.0214 (14) | 0.0314 (19) | 0.0009 (13) | 0.0022 (15) | −0.0002 (13) |
C113 | 0.0244 (14) | 0.0268 (15) | 0.0333 (19) | −0.0009 (12) | 0.0055 (14) | −0.0016 (13) |
C114 | 0.0275 (15) | 0.0211 (14) | 0.041 (2) | 0.0021 (12) | −0.0018 (15) | −0.0065 (13) |
C115 | 0.0265 (15) | 0.0185 (13) | 0.041 (2) | −0.0018 (12) | −0.0100 (14) | 0.0022 (13) |
C116 | 0.0252 (14) | 0.0235 (14) | 0.0293 (17) | −0.0053 (12) | −0.0055 (13) | 0.0046 (13) |
O1 | 0.0241 (14) | 0.0178 (12) | 0.035 (2) | −0.0044 (10) | 0.0041 (11) | −0.0050 (11) |
C201 | 0.0223 (15) | 0.0213 (14) | 0.0346 (18) | 0.0020 (11) | 0.0018 (13) | −0.0042 (13) |
C202 | 0.0249 (15) | 0.0213 (14) | 0.043 (2) | 0.0003 (12) | −0.0066 (15) | −0.0032 (14) |
C203 | 0.0402 (18) | 0.0240 (14) | 0.0338 (19) | −0.0067 (14) | −0.0135 (16) | 0.0038 (13) |
C204 | 0.0288 (15) | 0.0244 (14) | 0.0268 (18) | −0.0031 (12) | −0.0018 (14) | −0.0028 (12) |
C205 | 0.0260 (15) | 0.0156 (13) | 0.0341 (19) | 0.0002 (11) | −0.0037 (14) | 0.0028 (12) |
C206 | 0.0242 (15) | 0.0164 (12) | 0.0337 (19) | 0.0050 (11) | −0.0015 (13) | −0.0002 (13) |
C207 | 0.0171 (13) | 0.0220 (13) | 0.0359 (19) | 0.0039 (11) | −0.0002 (13) | −0.0024 (13) |
C208 | 0.0171 (13) | 0.0215 (14) | 0.0341 (19) | 0.0020 (11) | −0.0026 (12) | −0.0006 (12) |
C209 | 0.0254 (15) | 0.0249 (15) | 0.0393 (19) | −0.0008 (12) | 0.0043 (15) | 0.0041 (14) |
C210 | 0.0222 (15) | 0.0251 (14) | 0.047 (2) | −0.0055 (12) | −0.0067 (15) | 0.0081 (15) |
C211 | 0.0383 (18) | 0.0186 (13) | 0.040 (2) | −0.0036 (13) | −0.0130 (15) | 0.0001 (14) |
C212 | 0.0343 (17) | 0.0196 (13) | 0.040 (2) | 0.0034 (13) | −0.0040 (15) | −0.0038 (13) |
C213 | 0.0220 (15) | 0.0312 (16) | 0.047 (2) | 0.0000 (13) | 0.0044 (15) | 0.0033 (15) |
C214 | 0.0271 (16) | 0.0227 (14) | 0.059 (3) | −0.0017 (13) | −0.0008 (17) | 0.0064 (16) |
C215 | 0.0266 (16) | 0.0162 (13) | 0.061 (3) | 0.0034 (12) | −0.0109 (16) | −0.0032 (15) |
C216 | 0.0245 (15) | 0.0236 (14) | 0.042 (2) | 0.0057 (12) | −0.0048 (15) | −0.0065 (14) |
O2 | 0.0284 (14) | 0.0182 (12) | 0.0263 (18) | 0.0050 (10) | −0.0063 (11) | −0.0051 (10) |
Geometric parameters (Å, º) top
C101—C106 | 1.514 (4) | C201—C206 | 1.511 (4) |
C101—C107 | 1.524 (4) | C201—C207 | 1.526 (4) |
C101—C102 | 1.568 (5) | C201—C202 | 1.533 (5) |
C101—H101 | 1 | C201—H201 | 1 |
C102—O1 | 1.424 (4) | C202—O2 | 1.445 (4) |
C102—C103 | 1.531 (5) | C202—C203 | 1.538 (5) |
C102—H102 | 1 | C202—H202 | 1 |
C103—C104 | 1.548 (4) | C203—C204 | 1.564 (4) |
C103—H13A | 0.99 | C203—H23A | 0.99 |
C103—H13B | 0.99 | C203—H23B | 0.99 |
C104—C105 | 1.513 (4) | C204—C205 | 1.508 (4) |
C104—C108 | 1.515 (4) | C204—C208 | 1.514 (4) |
C104—H104 | 1 | C204—H204 | 1 |
C105—C109 | 1.387 (4) | C205—C209 | 1.390 (4) |
C105—C106 | 1.392 (4) | C205—C206 | 1.405 (5) |
C106—C112 | 1.386 (5) | C206—C212 | 1.386 (5) |
C107—C113 | 1.386 (4) | C207—C213 | 1.387 (4) |
C107—C108 | 1.398 (4) | C207—C208 | 1.398 (4) |
C108—C116 | 1.386 (4) | C208—C216 | 1.389 (4) |
C109—C110 | 1.381 (5) | C209—C210 | 1.381 (5) |
C109—H109 | 0.95 | C209—H209 | 0.95 |
C110—C111 | 1.386 (5) | C210—C211 | 1.393 (5) |
C110—H110 | 0.95 | C210—H210 | 0.95 |
C111—C112 | 1.396 (5) | C211—C212 | 1.392 (5) |
C111—H111 | 0.95 | C211—H211 | 0.95 |
C112—H112 | 0.95 | C212—H212 | 0.95 |
C113—C114 | 1.401 (4) | C213—C214 | 1.395 (4) |
C113—H113 | 0.95 | C213—H213 | 0.95 |
C114—C115 | 1.389 (5) | C214—C215 | 1.380 (6) |
C114—H114 | 0.95 | C214—H214 | 0.95 |
C115—C116 | 1.385 (4) | C215—C216 | 1.397 (5) |
C115—H115 | 0.95 | C215—H215 | 0.95 |
C116—H116 | 0.95 | C216—H216 | 0.95 |
O1—H1 | 0.87 (5) | O2—H2 | 0.87 (7) |
O1'—H1 | 0.95 (5) | | |
| | | |
C106—C101—C107 | 108.4 (2) | C206—C201—C207 | 109.0 (2) |
C106—C101—C102 | 108.6 (2) | C206—C201—C202 | 107.9 (3) |
C107—C101—C102 | 103.0 (3) | C207—C201—C202 | 104.2 (3) |
C106—C101—H101 | 112.1 | C206—C201—H201 | 111.8 |
C107—C101—H101 | 112.1 | C207—C201—H201 | 111.8 |
C102—C101—H101 | 112.1 | C202—C201—H201 | 111.8 |
O1—C102—C103 | 107.5 (3) | O2—C202—C201 | 111.1 (3) |
O1—C102—C101 | 114.7 (3) | O2—C202—C203 | 111.4 (3) |
C103—C102—C101 | 109.2 (2) | C201—C202—C203 | 108.9 (2) |
O1—C102—H102 | 108.4 | O2—C202—H202 | 108.5 |
C103—C102—H102 | 108.4 | C201—C202—H202 | 108.5 |
C101—C102—H102 | 108.4 | C203—C202—H202 | 108.5 |
C102—C103—C104 | 109.8 (3) | C202—C203—C204 | 110.7 (3) |
C102—C103—H13A | 109.7 | C202—C203—H23A | 109.5 |
C104—C103—H13A | 109.7 | C204—C203—H23A | 109.5 |
C102—C103—H13B | 109.7 | C202—C203—H23B | 109.5 |
C104—C103—H13B | 109.7 | C204—C203—H23B | 109.5 |
H13A—C103—H13B | 108.2 | H23A—C203—H23B | 108.1 |
C105—C104—C108 | 108.2 (2) | C205—C204—C208 | 108.1 (3) |
C105—C104—C103 | 106.1 (2) | C205—C204—C203 | 106.5 (2) |
C108—C104—C103 | 106.6 (2) | C208—C204—C203 | 105.0 (2) |
C105—C104—H104 | 111.9 | C205—C204—H204 | 112.3 |
C108—C104—H104 | 111.9 | C208—C204—H204 | 112.3 |
C103—C104—H104 | 111.9 | C203—C204—H204 | 112.3 |
C109—C105—C106 | 120.2 (3) | C209—C205—C206 | 119.7 (3) |
C109—C105—C104 | 126.8 (3) | C209—C205—C204 | 127.2 (3) |
C106—C105—C104 | 113.0 (3) | C206—C205—C204 | 113.0 (3) |
C112—C106—C105 | 120.1 (3) | C212—C206—C205 | 120.5 (3) |
C112—C106—C101 | 126.7 (3) | C212—C206—C201 | 126.3 (3) |
C105—C106—C101 | 113.3 (3) | C205—C206—C201 | 113.1 (3) |
C113—C107—C108 | 120.0 (3) | C213—C207—C208 | 120.8 (3) |
C113—C107—C101 | 127.1 (3) | C213—C207—C201 | 125.9 (3) |
C108—C107—C101 | 112.7 (3) | C208—C207—C201 | 113.2 (3) |
C116—C108—C107 | 120.7 (3) | C216—C208—C207 | 120.1 (3) |
C116—C108—C104 | 126.1 (3) | C216—C208—C204 | 127.0 (3) |
C107—C108—C104 | 113.2 (2) | C207—C208—C204 | 112.9 (3) |
C110—C109—C105 | 119.6 (3) | C210—C209—C205 | 119.4 (3) |
C110—C109—H109 | 120.2 | C210—C209—H209 | 120.3 |
C105—C109—H109 | 120.2 | C205—C209—H209 | 120.3 |
C109—C110—C111 | 120.6 (3) | C209—C210—C211 | 121.1 (3) |
C109—C110—H110 | 119.7 | C209—C210—H210 | 119.5 |
C111—C110—H110 | 119.7 | C211—C210—H210 | 119.5 |
C110—C111—C112 | 119.9 (3) | C212—C211—C210 | 119.8 (3) |
C110—C111—H111 | 120 | C212—C211—H211 | 120.1 |
C112—C111—H111 | 120 | C210—C211—H211 | 120.1 |
C106—C112—C111 | 119.5 (3) | C206—C212—C211 | 119.4 (3) |
C106—C112—H112 | 120.2 | C206—C212—H212 | 120.3 |
C111—C112—H112 | 120.2 | C211—C212—H212 | 120.3 |
C107—C113—C114 | 119.2 (3) | C207—C213—C214 | 118.6 (3) |
C107—C113—H113 | 120.4 | C207—C213—H213 | 120.7 |
C114—C113—H113 | 120.4 | C214—C213—H213 | 120.7 |
C115—C114—C113 | 120.3 (3) | C215—C214—C213 | 121.0 (3) |
C115—C114—H114 | 119.8 | C215—C214—H214 | 119.5 |
C113—C114—H114 | 119.8 | C213—C214—H214 | 119.5 |
C116—C115—C114 | 120.5 (3) | C214—C215—C216 | 120.4 (3) |
C116—C115—H115 | 119.7 | C214—C215—H215 | 119.8 |
C114—C115—H115 | 119.7 | C216—C215—H215 | 119.8 |
C115—C116—C108 | 119.2 (3) | C208—C216—C215 | 119.1 (3) |
C115—C116—H116 | 120.4 | C208—C216—H216 | 120.4 |
C108—C116—H116 | 120.4 | C215—C216—H216 | 120.4 |
C102—O1—H1 | 101 (3) | C202—O2—H2 | 111 (4) |
| | | |
C106—C101—C102—O1 | −70.4 (3) | C206—C201—C202—O2 | 68.0 (3) |
C107—C101—C102—O1 | 174.8 (3) | C207—C201—C202—O2 | −176.2 (2) |
C106—C101—C102—C103 | 50.2 (3) | C206—C201—C202—C203 | −55.0 (3) |
C107—C101—C102—C103 | −64.6 (3) | C207—C201—C202—C203 | 60.7 (3) |
O1—C102—C103—C104 | 133.8 (3) | O2—C202—C203—C204 | −126.0 (3) |
C101—C102—C103—C104 | 8.8 (3) | C201—C202—C203—C204 | −3.2 (3) |
C102—C103—C104—C105 | −63.0 (3) | C202—C203—C204—C205 | 58.6 (3) |
C102—C103—C104—C108 | 52.1 (3) | C202—C203—C204—C208 | −55.9 (3) |
C108—C104—C105—C109 | 126.1 (3) | C208—C204—C205—C209 | −126.3 (3) |
C103—C104—C105—C109 | −119.8 (3) | C203—C204—C205—C209 | 121.3 (3) |
C108—C104—C105—C106 | −55.9 (3) | C208—C204—C205—C206 | 56.3 (3) |
C103—C104—C105—C106 | 58.2 (3) | C203—C204—C205—C206 | −56.1 (3) |
C109—C105—C106—C112 | 2.3 (4) | C209—C205—C206—C212 | −3.0 (4) |
C104—C105—C106—C112 | −175.8 (3) | C204—C205—C206—C212 | 174.7 (3) |
C109—C105—C106—C101 | −179.0 (3) | C209—C205—C206—C201 | 179.3 (3) |
C104—C105—C106—C101 | 2.9 (3) | C204—C205—C206—C201 | −3.0 (3) |
C107—C101—C106—C112 | −129.3 (3) | C207—C201—C206—C212 | 131.3 (3) |
C102—C101—C106—C112 | 119.5 (3) | C202—C201—C206—C212 | −116.1 (3) |
C107—C101—C106—C105 | 52.1 (3) | C207—C201—C206—C205 | −51.1 (3) |
C102—C101—C106—C105 | −59.1 (3) | C202—C201—C206—C205 | 61.5 (3) |
C106—C101—C107—C113 | 130.2 (3) | C206—C201—C207—C213 | −130.6 (3) |
C102—C101—C107—C113 | −114.8 (3) | C202—C201—C207—C213 | 114.4 (3) |
C106—C101—C107—C108 | −54.7 (3) | C206—C201—C207—C208 | 52.7 (4) |
C102—C101—C107—C108 | 60.2 (3) | C202—C201—C207—C208 | −62.3 (3) |
C113—C107—C108—C116 | −1.0 (4) | C213—C207—C208—C216 | 1.4 (4) |
C101—C107—C108—C116 | −176.5 (3) | C201—C207—C208—C216 | 178.3 (3) |
C113—C107—C108—C104 | 177.3 (3) | C213—C207—C208—C204 | −176.4 (3) |
C101—C107—C108—C104 | 1.9 (4) | C201—C207—C208—C204 | 0.5 (4) |
C105—C104—C108—C116 | −128.7 (3) | C205—C204—C208—C216 | 127.7 (3) |
C103—C104—C108—C116 | 117.6 (3) | C203—C204—C208—C216 | −119.0 (3) |
C105—C104—C108—C107 | 53.0 (3) | C205—C204—C208—C207 | −54.7 (3) |
C103—C104—C108—C107 | −60.7 (3) | C203—C204—C208—C207 | 58.7 (3) |
C106—C105—C109—C110 | −1.4 (4) | C206—C205—C209—C210 | 1.5 (4) |
C104—C105—C109—C110 | 176.4 (3) | C204—C205—C209—C210 | −175.8 (3) |
C105—C109—C110—C111 | 0.2 (5) | C205—C209—C210—C211 | 0.8 (5) |
C109—C110—C111—C112 | 0.2 (5) | C209—C210—C211—C212 | −1.7 (5) |
C105—C106—C112—C111 | −1.9 (4) | C205—C206—C212—C211 | 2.1 (4) |
C101—C106—C112—C111 | 179.6 (3) | C201—C206—C212—C211 | 179.5 (3) |
C110—C111—C112—C106 | 0.7 (5) | C210—C211—C212—C206 | 0.2 (4) |
C108—C107—C113—C114 | 0.2 (5) | C208—C207—C213—C214 | −0.2 (5) |
C101—C107—C113—C114 | 175.0 (3) | C201—C207—C213—C214 | −176.6 (3) |
C107—C113—C114—C115 | 0.5 (5) | C207—C213—C214—C215 | −1.2 (5) |
C113—C114—C115—C116 | −0.4 (5) | C213—C214—C215—C216 | 1.3 (5) |
C114—C115—C116—C108 | −0.4 (5) | C207—C208—C216—C215 | −1.3 (4) |
C107—C108—C116—C115 | 1.1 (4) | C204—C208—C216—C215 | 176.2 (3) |
C104—C108—C116—C115 | −177.0 (3) | C214—C215—C216—C208 | 0.0 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.87 (5) | 1.91 (5) | 2.761 (4) | 165 (4) |
O2—H2···O1 | 0.87 (7) | 1.94 (7) | 2.768 (4) | 159 (5) |
Symmetry code: (i) −x+3/2, y, z−1/2. |
Experimental details
Crystal data |
Chemical formula | C16H14O |
Mr | 222.27 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 100 |
a, b, c (Å) | 14.3719 (3), 22.8650 (6), 7.0703 (1) |
V (Å3) | 2323.40 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.40 × 0.17 × 0.12 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17231, 2863, 2385 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.141, 1.03 |
No. of reflections | 2863 |
No. of parameters | 324 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.24 |
Selected geometric parameters (Å, º) topC101—C102 | 1.568 (5) | C201—C202 | 1.533 (5) |
C102—O1 | 1.424 (4) | C202—O2 | 1.445 (4) |
C102—C103 | 1.531 (5) | C202—C203 | 1.538 (5) |
C103—C104 | 1.548 (4) | C203—C204 | 1.564 (4) |
| | | |
O1—C102—C103 | 107.5 (3) | O2—C202—C201 | 111.1 (3) |
O1—C102—C101 | 114.7 (3) | O2—C202—C203 | 111.4 (3) |
C103—C102—C101 | 109.2 (2) | C201—C202—C203 | 108.9 (2) |
| | | |
O1—C102—C103—C104 | 133.8 (3) | O2—C202—C203—C204 | −126.0 (3) |
C101—C102—C103—C104 | 8.8 (3) | C201—C202—C203—C204 | −3.2 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.87 (5) | 1.91 (5) | 2.761 (4) | 165 (4) |
O2—H2···O1 | 0.87 (7) | 1.94 (7) | 2.768 (4) | 159 (5) |
Symmetry code: (i) −x+3/2, y, z−1/2. |
Our interest in the modes of hydrogen bonding adopted by polycyclic monoalcohols (Morris et al., 2001, 2002) has led us to determine the crystal structure of the racemic form of the secondary alcohol (I) (Fig. 1 and Table 1). Monoalcohols in general show a preference for trigonal and tetragonal space groups, and their crystal structures frequently contain more than one crystallographically independent molecule (i.e. Z' > 1) (Brock & Duncan, 1994). These preferences are thought to arise from steric constraints in forming hydrogen bonds. Consistently with this view, we have recently shown (Fraile et al., 2003) that tertiary monoalcohols display these preferences in a particularly pronounced fashion.
The polycyclic and sterically hindered secondary alcohol (I) crystallizes in the non-centrosymmetric but non-chiral space group Pca21 (No. 29) with Z' equal to 2. Chains of molecules running parallel to the short c axis are linked by conventional hydrogen bonds (Table 2 and Fig. 2). In itself, this is not an unusual arrangement in homomolecular monoalcohol crystal structures (Brock & Duncan, 1994). However, the translationally repeated unit of the chain, consisting of four molecules related by an exact c-glide normal to a and by additional pseudosymmetry, is unusual and merits discussion.
The asymmetric unit we have chosen contains two enantiomeric molecules, and the coordinates of the atoms of molecule 2 are approximately related to those of the corresponding atoms of molecule 1 by the pseudosymmetric operation (x, 1/2 − y, 1/2 + z-δ); δ is 0.01–0.09 for individual C atoms, rising to 0.13 for the two O atoms, and its mean value is 0.038. If δ were 0 this operation would correspond exactly to that of a c-glide plane normal to the b axis, and the space group would become Iba2 (No. 45). The pseudosymmetry causes the hkl reflections to be systematically weak when h+k+l = 2n+1, this pseudo-absence being especially pronounced for the hk0 zone.
In each chain, the unit repeated by translation comprises four molecules linked by ···H—O1i···H—O2i···H—O1···H—O2··· hydrogen bonds; the symmetry operation (i), (3/2 − x, y, z − 1/2), defines a c-glide normal to a, and the molecule containing O1 is related to that containing O2 and O2i by pseudo-operations approximating respectively to a c-glide normal to b (see above) and to a diad axis parallel to c (3/2 − x, 1/2 − y, z-δ). Thus the chain sequence is ···RSSR··· where R and S indicate the configuration at Cn02 (n = 1 or 2) in successive molecules. The hydrogen bonds in each chain therefore connect pairs of molecules which may be of the same, or of opposite, chiralities.
The tendency for monoalcohols to crystallize with two or more molecules in the asymmetric unit is well established, and this feature of the structure of (I) is therefore not surprising. However, in their survey of hydrogen-bonding motifs adopted by monoalcohols, Brock & Duncan (1994) found only five out of 55 structures in which four molecules make up the translational repeat unit. Of these, only one, namely ethanol, resembles (I) in generating the chain by application of a glide operation to two independent molecules. However, the two independent ethanol molecules are not pseudosymmetrically related (Jonsson, 1976).
The two crystallographically independent molecules of (II) are structurally nearly identical. A least-squares fit of the positions of corresponding C or O atoms gives an r.m.s. Δ of 0.057 Å, with the O atoms showing the largest individual discrepancy [0.174 (5) Å]. Furthermore, for bond lengths and angles, the r.m.s. Δ values are respectively 0.011 Å and 1.1° (PLATON; Spek, 2003). Table 1 lists only the distances and angles in the CH(OH)—CH bridging units where the differences between the two molecules are greatest. Though complicated by minor disorder of the O atoms (see below), these differences are probably a consequence of the differing orientations of the OH bonds [Cn01—Cn02—On—H = −85 (4) and 8(4)° for n = 1 and 2, respectively]. This result illustrates the factors that cause sterically hindered alcohols to crystallize with Z' greater than 1; a pseudosymmetric relationship between molecules 1 and 2 permits differing hydrogen-bond orientations, which would be precluded if 1 and 2 were related exactly by space-group symmetry. Each molecule contains two C8 units (defined by an aromatic ring plus the two C atoms directly attached to it), which are coplanar to within 0.05 Å and which define dihedral angles of 53.4 (1) and 52.8 (1)°. The mean Car—Car and Car—Csp3 bond lengths are 1.391 and 1.516 Å, and their respective ranges are 1.380 (6)–1.405 (5) and 1.508 (4)–1.526 (4) Å. The atomic Uij values are moderately well reproduced by a TLS analysis [Schomacher & Trueblood, 1968; R2 = (ΣΔU2/ΣU2)1/2 = 0.16 and 0.14 for individual molecules]. The worst discrepancy in the Hirshfeld (1976) rigid-bond test is the value of ΔU for C202—C203 [0.008(24) Å2].