Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011084/cf6084sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011084/cf6084Isup2.hkl |
CCDC reference: 170892
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (Please check) = 0.000 Å
- H-atom completeness 92%
- Disorder in main residue
- R factor = 0.046
- wR factor = 0.146
- Data-to-parameter ratio = 8.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
PLAT_301 Alert A Main Residue Disorder ........................ 92.00 Perc.
Author response: That is the issue of the contribution. |
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.14 From the CIF: _reflns_number_total 2986 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 3196 Completeness (_total/calc) 93.43% Alert C: < 95% complete PLAT_030 Alert C Refined Extinction parameter within range .... 3.14 Sigma PLAT_302 Alert C Anion/Solvent Disorder ....................... 8.00 Perc. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C20 H22 O6 Atom count from the _atom_site data: C20 H20.218 O6 CELLZ_01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C20 H22 O6 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 80.00 80.00 0.00 H 88.00 80.87 7.13 O 24.00 24.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional?
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
Crystals of racemic pinoresinol (Freudenberg, 1968), suitable for X-ray diffraction analysis, were obtained on crystallization from ethyl acetate/hexane.
H atoms were constrained to ideal geometry using an appropriate riding model, with O—H = 0.82 Å and C—H = 0.93–0.98 Å
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 1996); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C20H22O6 | F(000) = 760 |
Mr = 358.38 | Dx = 1.336 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0692 (6) Å | Cell parameters from 5063 reflections |
b = 18.5615 (13) Å | θ = 2.0–25.1° |
c = 12.1622 (9) Å | µ = 0.10 mm−1 |
β = 102.061 (1)° | T = 296 K |
V = 1781.4 (2) Å3 | Needle, colorless |
Z = 4 | 0.61 × 0.14 × 0.09 mm |
Siemens SMART CCD diffractometer | 2986 independent reflections |
Radiation source: fine-focus sealed tube | 2052 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
w scans | θmax = 25.1°, θmin = 2.0° |
Absorption correction: multi-scan (Blessing; 1995) | h = −9→9 |
Tmin = 0.942, Tmax = 0.991 | k = −21→22 |
11738 measured reflections | l = −14→14 |
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)] = 0.046 | Riding |
wR(F2) = 0.146 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2986 reflections | Δρmax = 0.18 e Å−3 |
345 parameters | Δρmin = −0.18 e Å−3 |
286 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0044 (14) |
C20H22O6 | V = 1781.4 (2) Å3 |
Mr = 358.38 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.0692 (6) Å | µ = 0.10 mm−1 |
b = 18.5615 (13) Å | T = 296 K |
c = 12.1622 (9) Å | 0.61 × 0.14 × 0.09 mm |
β = 102.061 (1)° |
Siemens SMART CCD diffractometer | 2986 independent reflections |
Absorption correction: multi-scan (Blessing; 1995) | 2052 reflections with I > 2σ(I) |
Tmin = 0.942, Tmax = 0.991 | Rint = 0.030 |
11738 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 286 restraints |
wR(F2) = 0.146 | Riding |
S = 1.00 | Δρmax = 0.18 e Å−3 |
2986 reflections | Δρmin = −0.18 e Å−3 |
345 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. Data were collected using a Siemens SMART CCD diffractometer at room temperature. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 30 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames·Final cell parameters were obtained by refinement on the position of 6826 reflections with I>10σ(I) after integration of all the frames data using SAINT (Siemens, 1995). The data were empirically corrected for absorption and other effects using SADABS (Sheldrick, 1996) based on the method of Blessing (1995). The structure was solved by direct methods and refined by full-matrix least squares on all F2 data using SHELXTL (Bruker, 1997). All non-H atoms were refined anisotropically. Hydrogen atoms were constrained to the ideal geometry using an appropriate riding model. For hydroxyl groups, the O–H distances (0.82 Å) and C–O–H angles (109.5°) were kept fixed, the torsion angle was chosen to maximize the electron density. For methyl groups, the C–H distances (0.93 Å) and C–C–H angles (109.5°) were kept fixed, while the torsion angles were allowed to refine with the starting position based on the threefold averaged circular Fourier synthesis. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.3935 (7) | 0.27324 (15) | 0.6702 (3) | 0.0412 (11) | 0.919 (3) |
C2 | 0.4258 (8) | 0.20148 (17) | 0.6502 (4) | 0.0411 (12) | 0.919 (3) |
H2 | 0.3757 | 0.1805 | 0.5820 | 0.049* | 0.919 (3) |
C3 | 0.5320 (6) | 0.16086 (16) | 0.7312 (3) | 0.0408 (10) | 0.919 (3) |
C4 | 0.6113 (6) | 0.19216 (19) | 0.8322 (3) | 0.0421 (11) | 0.919 (3) |
C5 | 0.5819 (9) | 0.26330 (19) | 0.8516 (3) | 0.0580 (16) | 0.919 (3) |
H5 | 0.6363 | 0.2849 | 0.9184 | 0.070* | 0.919 (3) |
C6 | 0.4712 (10) | 0.30330 (18) | 0.7719 (3) | 0.0605 (17) | 0.919 (3) |
H6 | 0.4490 | 0.3510 | 0.7871 | 0.073* | 0.919 (3) |
C7 | 0.4865 (6) | 0.05261 (16) | 0.6240 (3) | 0.0996 (16) | 0.919 (3) |
H7A | 0.3662 | 0.0540 | 0.6192 | 0.149* | 0.919 (3) |
H7B | 0.5239 | 0.0034 | 0.6272 | 0.149* | 0.919 (3) |
H7C | 0.5129 | 0.0755 | 0.5590 | 0.149* | 0.919 (3) |
C8 | 0.2821 (3) | 0.31988 (11) | 0.58261 (19) | 0.0414 (6) | 0.919 (3) |
H8 | 0.1870 | 0.3377 | 0.6137 | 0.050* | 0.919 (3) |
C9 | 0.3704 (3) | 0.38419 (10) | 0.54156 (16) | 0.0394 (6) | 0.919 (3) |
H9 | 0.4877 | 0.3721 | 0.5389 | 0.047* | 0.919 (3) |
C10 | 0.3634 (7) | 0.45430 (17) | 0.6034 (3) | 0.0554 (19) | 0.919 (3) |
H10A | 0.3031 | 0.4477 | 0.6638 | 0.066* | 0.919 (3) |
H10B | 0.4770 | 0.4711 | 0.6354 | 0.066* | 0.919 (3) |
C11 | 0.1005 (5) | 0.50964 (15) | 0.3348 (2) | 0.0443 (9) | 0.919 (3) |
C12 | 0.1147 (10) | 0.5844 (2) | 0.3359 (4) | 0.0434 (18) | 0.919 (3) |
H12 | 0.1733 | 0.6074 | 0.4003 | 0.052* | 0.919 (3) |
C13 | 0.0429 (8) | 0.62500 (16) | 0.2424 (4) | 0.0411 (13) | 0.919 (3) |
C14 | −0.0378 (6) | 0.59100 (16) | 0.1437 (3) | 0.0566 (12) | 0.919 (3) |
C15 | −0.0460 (5) | 0.51741 (16) | 0.1401 (3) | 0.0774 (13) | 0.919 (3) |
H15 | −0.0959 | 0.4944 | 0.0735 | 0.093* | 0.919 (3) |
C16 | 0.0199 (6) | 0.47673 (16) | 0.2356 (3) | 0.0725 (15) | 0.919 (3) |
H16 | 0.0096 | 0.4268 | 0.2328 | 0.087* | 0.919 (3) |
C17 | 0.1226 (4) | 0.73650 (12) | 0.3366 (2) | 0.0499 (7) | 0.919 (3) |
H17A | 0.0698 | 0.7254 | 0.3983 | 0.075* | 0.919 (3) |
H17B | 0.1152 | 0.7874 | 0.3222 | 0.075* | 0.919 (3) |
H17C | 0.2395 | 0.7223 | 0.3550 | 0.075* | 0.919 (3) |
C18 | 0.1658 (3) | 0.46449 (10) | 0.43848 (17) | 0.0419 (6) | 0.919 (3) |
H18 | 0.0681 | 0.4496 | 0.4692 | 0.050* | 0.919 (3) |
C19 | 0.2658 (3) | 0.39747 (10) | 0.42296 (16) | 0.0389 (6) | 0.919 (3) |
H19 | 0.3398 | 0.4065 | 0.3700 | 0.047* | 0.919 (3) |
C20 | 0.1644 (4) | 0.32813 (11) | 0.3925 (2) | 0.0438 (7) | 0.919 (3) |
H20A | 0.1869 | 0.3080 | 0.3235 | 0.053* | 0.919 (3) |
H20B | 0.0440 | 0.3379 | 0.3816 | 0.053* | 0.919 (3) |
O1 | 0.5695 (4) | 0.08928 (14) | 0.7220 (3) | 0.0629 (9) | 0.919 (3) |
O2 | 0.7171 (5) | 0.15339 (12) | 0.91308 (19) | 0.0530 (7) | 0.919 (3) |
H2A | 0.7154 | 0.1109 | 0.8942 | 0.080* | 0.919 (3) |
O3 | 0.2157 (6) | 0.27864 (11) | 0.4834 (3) | 0.0505 (11) | 0.919 (3) |
O4 | 0.2760 (3) | 0.50572 (9) | 0.52292 (16) | 0.0509 (6) | 0.919 (3) |
O5 | 0.0384 (4) | 0.69863 (11) | 0.2390 (2) | 0.0512 (6) | 0.919 (3) |
O6 | −0.1097 (5) | 0.62933 (12) | 0.04972 (19) | 0.0813 (9) | 0.919 (3) |
H6A | −0.0917 | 0.6724 | 0.0614 | 0.122* | 0.919 (3) |
C1D | 0.141 (4) | 0.5077 (15) | 0.321 (2) | 0.031 (10)* | 0.081 (3) |
C2D | 0.109 (8) | 0.5801 (17) | 0.340 (3) | 0.019 (13)* | 0.081 (3) |
C3D | 0.030 (9) | 0.6237 (17) | 0.251 (4) | 0.047 (17)* | 0.081 (3) |
C4D | −0.077 (5) | 0.5904 (16) | 0.160 (3) | 0.043 (12)* | 0.081 (3) |
C5D | −0.093 (4) | 0.5166 (16) | 0.165 (3) | 0.050 (11)* | 0.081 (3) |
C6D | 0.055 (8) | 0.480 (2) | 0.220 (4) | 0.093 (17)* | 0.081 (3) |
C7D | 0.103 (12) | 0.748 (3) | 0.302 (5) | 0.17 (3)* | 0.081 (3) |
C8D | 0.244 (3) | 0.4589 (10) | 0.4102 (15) | 0.037 (7)* | 0.081 (3) |
C9D | 0.1434 (18) | 0.4032 (8) | 0.4626 (11) | 0.017 (5)* | 0.081 (3) |
C10D | 0.111 (4) | 0.3315 (13) | 0.405 (2) | 0.056 (13)* | 0.081 (3) |
C11D | 0.412 (8) | 0.2720 (16) | 0.653 (3) | 0.039 (14)* | 0.081 (3) |
C12D | 0.395 (9) | 0.1975 (17) | 0.649 (4) | 0.038 (13)* | 0.081 (3) |
C13D | 0.493 (5) | 0.1570 (15) | 0.734 (3) | 0.023 (10)* | 0.081 (3) |
C14D | 0.574 (6) | 0.1887 (19) | 0.834 (3) | 0.028 (11)* | 0.081 (3) |
C15D | 0.544 (10) | 0.260 (2) | 0.850 (3) | 0.047 (13)* | 0.081 (3) |
C16D | 0.485 (11) | 0.303 (2) | 0.755 (3) | 0.053 (14)* | 0.081 (3) |
C17D | 0.399 (7) | 0.050 (3) | 0.637 (6) | 0.14 (2)* | 0.081 (3) |
C18D | 0.341 (3) | 0.3182 (10) | 0.5516 (18) | 0.039 (8)* | 0.081 (3) |
C19D | 0.2595 (19) | 0.3878 (7) | 0.5781 (11) | 0.012 (4)* | 0.081 (3) |
C20D | 0.367 (6) | 0.4561 (16) | 0.600 (3) | 0.041 (17)* | 0.081 (3) |
O1D | 0.081 (4) | 0.6905 (17) | 0.223 (3) | 0.058 (11)* | 0.081 (3) |
O2D | −0.168 (4) | 0.6297 (19) | 0.074 (3) | 0.081 (13)* | 0.081 (3) |
O3D | 0.327 (3) | 0.5021 (12) | 0.5028 (18) | 0.050 (9)* | 0.081 (3) |
O4D | 0.199 (7) | 0.2792 (14) | 0.485 (4) | 0.075 (16)* | 0.081 (3) |
O5D | 0.519 (4) | 0.0849 (15) | 0.725 (3) | 0.036 (7)* | 0.081 (3) |
O6D | 0.689 (8) | 0.153 (3) | 0.915 (4) | 0.14 (2)* | 0.081 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.053 (2) | 0.0301 (15) | 0.0371 (15) | −0.0028 (10) | 0.0019 (18) | 0.0056 (10) |
C2 | 0.048 (3) | 0.0336 (16) | 0.0378 (16) | −0.0026 (12) | 0.0007 (14) | 0.0014 (9) |
C3 | 0.048 (3) | 0.0332 (15) | 0.0399 (16) | 0.0002 (13) | 0.0065 (15) | 0.0016 (9) |
C4 | 0.050 (3) | 0.0361 (16) | 0.0358 (15) | −0.0039 (14) | 0.0002 (15) | 0.0094 (9) |
C5 | 0.087 (5) | 0.0350 (16) | 0.0412 (16) | −0.0058 (16) | −0.0106 (15) | 0.0013 (10) |
C6 | 0.100 (4) | 0.0297 (15) | 0.0430 (17) | 0.0036 (13) | −0.006 (2) | −0.0006 (11) |
C7 | 0.168 (4) | 0.0446 (17) | 0.0618 (19) | 0.033 (2) | −0.032 (2) | −0.0215 (13) |
C8 | 0.0461 (14) | 0.0314 (12) | 0.0434 (13) | −0.0016 (9) | 0.0020 (12) | 0.0012 (9) |
C9 | 0.0440 (12) | 0.0307 (11) | 0.0400 (11) | 0.0002 (9) | 0.0007 (10) | 0.0053 (8) |
C10 | 0.075 (3) | 0.0301 (17) | 0.048 (2) | −0.0018 (11) | −0.0158 (12) | 0.0077 (10) |
C11 | 0.054 (2) | 0.0330 (15) | 0.0418 (14) | 0.0100 (12) | −0.0006 (15) | 0.0026 (10) |
C12 | 0.050 (3) | 0.0347 (19) | 0.040 (2) | 0.0022 (12) | −0.0043 (11) | 0.0035 (10) |
C13 | 0.047 (2) | 0.0314 (16) | 0.0419 (17) | 0.0039 (10) | 0.0023 (15) | 0.0028 (9) |
C14 | 0.082 (3) | 0.0419 (17) | 0.0368 (15) | 0.0123 (14) | −0.009 (2) | 0.0032 (10) |
C15 | 0.129 (3) | 0.0402 (16) | 0.0451 (18) | 0.0120 (17) | −0.023 (2) | −0.0083 (12) |
C16 | 0.123 (3) | 0.0277 (14) | 0.0495 (16) | 0.0096 (16) | −0.022 (2) | −0.0023 (11) |
C17 | 0.0592 (16) | 0.0338 (13) | 0.0483 (14) | −0.0085 (11) | −0.0079 (12) | 0.0033 (10) |
C18 | 0.0538 (14) | 0.0280 (12) | 0.0394 (12) | 0.0026 (10) | −0.0009 (11) | −0.0013 (9) |
C19 | 0.0471 (13) | 0.0305 (11) | 0.0372 (11) | 0.0011 (9) | 0.0042 (10) | 0.0017 (8) |
C20 | 0.0547 (18) | 0.0282 (13) | 0.0415 (13) | 0.0025 (11) | −0.0058 (13) | 0.0027 (9) |
O1 | 0.088 (3) | 0.0385 (12) | 0.0510 (12) | 0.0185 (14) | −0.0121 (17) | −0.0048 (8) |
O2 | 0.0699 (14) | 0.0381 (10) | 0.0398 (10) | 0.0018 (8) | −0.0143 (9) | 0.0072 (6) |
O3 | 0.0702 (18) | 0.0238 (10) | 0.0455 (12) | −0.0052 (7) | −0.0155 (10) | 0.0035 (6) |
O4 | 0.0765 (15) | 0.0252 (9) | 0.0406 (10) | 0.0039 (9) | −0.0117 (11) | −0.0007 (7) |
O5 | 0.0667 (17) | 0.0306 (11) | 0.0474 (12) | 0.0030 (10) | −0.0085 (12) | 0.0053 (8) |
O6 | 0.135 (3) | 0.0447 (12) | 0.0426 (12) | 0.0160 (14) | −0.0301 (16) | 0.0025 (9) |
C1—C6 | 1.381 (4) | C17—H17C | 0.960 |
C1—C2 | 1.388 (4) | C18—O4 | 1.432 (2) |
C1—C8 | 1.514 (3) | C18—C19 | 1.516 (3) |
C2—C3 | 1.385 (3) | C18—H18 | 0.980 |
C2—H2 | 0.930 | C19—C20 | 1.528 (3) |
C3—O1 | 1.372 (3) | C19—H19 | 0.980 |
C3—C4 | 1.389 (3) | C20—O3 | 1.430 (3) |
C4—C5 | 1.371 (4) | C20—H20A | 0.970 |
C4—O2 | 1.365 (3) | C20—H20B | 0.970 |
C5—C6 | 1.388 (5) | O2—H2A | 0.820 |
C5—H5 | 0.930 | O6—H6A | 0.820 |
C6—H6 | 0.930 | C1D—C6D | 1.383 (19) |
C7—O1 | 1.414 (3) | C1D—C2D | 1.395 (19) |
C7—H7A | 0.960 | C1D—C8D | 1.521 (17) |
C7—H7B | 0.960 | C2D—C3D | 1.390 (18) |
C7—H7C | 0.960 | C3D—C4D | 1.400 (18) |
C8—O3 | 1.435 (3) | C3D—O1D | 1.37 (2) |
C8—C9 | 1.527 (3) | C4D—C5D | 1.378 (18) |
C8—H8 | 0.980 | C4D—O2D | 1.361 (18) |
C9—C19 | 1.531 (3) | C5D—C6D | 1.41 (2) |
C9—C10 | 1.510 (5) | C7D—O1D | 1.42 (2) |
C9—H9 | 0.980 | C8D—O3D | 1.431 (17) |
C10—O4 | 1.441 (3) | C8D—C9D | 1.533 (16) |
C10—H10A | 0.970 | C9D—C10D | 1.500 (18) |
C10—H10B | 0.970 | C9D—C19D | 1.544 (14) |
C11—C16 | 1.387 (3) | C10D—O4D | 1.443 (19) |
C11—C12 | 1.392 (4) | C11D—C16D | 1.383 (19) |
C11—C18 | 1.514 (3) | C11D—C12D | 1.391 (19) |
C12—C13 | 1.386 (4) | C11D—C18D | 1.517 (17) |
C12—H12 | 0.930 | C12D—C13D | 1.388 (18) |
C13—O5 | 1.367 (3) | C13D—O5D | 1.364 (18) |
C13—C14 | 1.392 (4) | C13D—C14D | 1.387 (18) |
C14—C15 | 1.368 (3) | C14D—C15D | 1.374 (19) |
C14—O6 | 1.368 (3) | C14D—O6D | 1.372 (18) |
C15—C16 | 1.394 (4) | C15D—C16D | 1.399 (19) |
C15—H15 | 0.930 | C17D—O5D | 1.43 (2) |
C16—H16 | 0.930 | C18D—O4D | 1.455 (19) |
C17—O5 | 1.424 (3) | C18D—C19D | 1.514 (16) |
C17—H17A | 0.960 | C19D—C20D | 1.527 (18) |
C17—H17B | 0.960 | C20D—O3D | 1.435 (19) |
C6—C1—C2 | 118.5 (3) | C19—C18—H18 | 107.8 |
C6—C1—C8 | 119.4 (3) | C20—C19—C9 | 104.75 (16) |
C2—C1—C8 | 122.1 (3) | C20—C19—C18 | 116.7 (2) |
C3—C2—C1 | 120.6 (3) | C9—C19—C18 | 102.59 (16) |
C3—C2—H2 | 119.7 | C20—C19—H19 | 110.8 |
C1—C2—H2 | 119.7 | C9—C19—H19 | 110.8 |
O1—C3—C2 | 125.7 (3) | C18—C19—H19 | 110.8 |
O1—C3—C4 | 114.1 (3) | C19—C20—O3 | 107.45 (17) |
C2—C3—C4 | 120.2 (3) | C19—C20—H20A | 110.2 |
C5—C4—O2 | 119.3 (3) | O3—C20—H20A | 110.2 |
C5—C4—C3 | 119.4 (3) | C19—C20—H20B | 110.2 |
O2—C4—C3 | 121.3 (3) | O3—C20—H20B | 110.2 |
C4—C5—C6 | 120.3 (3) | H20A—C20—H20B | 108.5 |
C4—C5—H5 | 119.9 | C3—O1—C7 | 117.4 (2) |
C6—C5—H5 | 119.9 | C8—O3—C20 | 107.70 (17) |
C1—C6—C5 | 120.9 (3) | C18—O4—C10 | 105.99 (17) |
C1—C6—H6 | 119.5 | C13—O5—C17 | 117.6 (2) |
C5—C6—H6 | 119.5 | C6D—C1D—C2D | 115 (2) |
O3—C8—C1 | 110.4 (2) | C6D—C1D—C8D | 121 (2) |
O3—C8—C9 | 105.1 (3) | C2D—C1D—C8D | 123 (2) |
C1—C8—C9 | 115.3 (3) | C3D—C2D—C1D | 120 (3) |
O3—C8—H8 | 108.6 | C4D—C3D—C2D | 118 (2) |
C1—C8—H8 | 108.6 | C4D—C3D—O1D | 112 (3) |
C9—C8—H8 | 108.6 | C2D—C3D—O1D | 127 (3) |
C19—C9—C10 | 105.05 (18) | C5D—C4D—O2D | 122 (2) |
C19—C9—C8 | 103.32 (16) | C5D—C4D—C3D | 117 (2) |
C10—C9—C8 | 116.2 (3) | O2D—C4D—C3D | 121 (2) |
C19—C9—H9 | 110.6 | C4D—C5D—C6D | 115 (3) |
C10—C9—H9 | 110.6 | C1D—C6D—C5D | 117 (3) |
C8—C9—H9 | 110.6 | O3D—C8D—C1D | 108.9 (17) |
O4—C10—C9 | 107.2 (2) | O3D—C8D—C9D | 104.7 (14) |
O4—C10—H10A | 110.3 | C1D—C8D—C9D | 116.1 (19) |
C9—C10—H10A | 110.3 | C10D—C9D—C19D | 105.8 (13) |
O4—C10—H10B | 110.3 | C10D—C9D—C8D | 117.3 (18) |
C9—C10—H10B | 110.3 | C19D—C9D—C8D | 103.3 (11) |
H10A—C10—H10B | 108.5 | O4D—C10D—C9D | 105.8 (18) |
C16—C11—C12 | 118.0 (3) | C16D—C11D—C12D | 118 (2) |
C16—C11—C18 | 119.9 (2) | C16D—C11D—C18D | 121 (2) |
C12—C11—C18 | 122.1 (2) | C12D—C11D—C18D | 121 (2) |
C13—C12—C11 | 121.0 (3) | C13D—C12D—C11D | 118 (2) |
C13—C12—H12 | 119.5 | O5D—C13D—C12D | 123 (2) |
C11—C12—H12 | 119.5 | O5D—C13D—C14D | 116 (2) |
O5—C13—C12 | 124.9 (3) | C12D—C13D—C14D | 121 (2) |
O5—C13—C14 | 115.0 (2) | C15D—C14D—O6D | 119 (3) |
C12—C13—C14 | 120.1 (3) | C15D—C14D—C13D | 118 (2) |
C15—C14—O6 | 118.9 (3) | O6D—C14D—C13D | 123 (3) |
C15—C14—C13 | 119.4 (2) | C14D—C15D—C16D | 119 (3) |
O6—C14—C13 | 121.7 (2) | C11D—C16D—C15D | 120 (2) |
C14—C15—C16 | 120.5 (3) | O4D—C18D—C11D | 107 (2) |
C14—C15—H15 | 119.8 | O4D—C18D—C19D | 102 (2) |
C16—C15—H15 | 119.8 | C11D—C18D—C19D | 115 (2) |
C11—C16—C15 | 120.9 (3) | C20D—C19D—C9D | 102.5 (12) |
C11—C16—H16 | 119.5 | C20D—C19D—C18D | 119 (2) |
C15—C16—H16 | 119.5 | C9D—C19D—C18D | 99.9 (11) |
O4—C18—C11 | 110.94 (19) | O3D—C20D—C19D | 109.5 (16) |
O4—C18—C19 | 105.12 (17) | C7D—O1D—C3D | 121 (3) |
C11—C18—C19 | 116.9 (2) | C8D—O3D—C20D | 107.4 (17) |
O4—C18—H18 | 107.8 | C18D—O4D—C10D | 105 (2) |
C11—C18—H18 | 107.8 | C13D—O5D—C17D | 114 (3) |
C6—C1—C2—C3 | 0.7 (9) | C6D—C1D—C2D—C3D | −15 (8) |
C8—C1—C2—C3 | 178.3 (5) | C8D—C1D—C2D—C3D | 173 (5) |
C1—C2—C3—O1 | 178.2 (5) | C1D—C2D—C3D—C4D | 26 (10) |
C1—C2—C3—C4 | −1.8 (9) | C1D—C2D—C3D—O1D | −131 (7) |
O1—C3—C4—C5 | −179.2 (5) | C2D—C3D—C4D—C5D | −1 (9) |
C2—C3—C4—C5 | 0.8 (8) | O1D—C3D—C4D—C5D | 159 (5) |
O1—C3—C4—O2 | 0.3 (7) | C2D—C3D—C4D—O2D | 175 (6) |
C2—C3—C4—O2 | −179.7 (5) | O1D—C3D—C4D—O2D | −24 (9) |
O2—C4—C5—C6 | −178.2 (6) | O2D—C4D—C5D—C6D | 150 (5) |
C3—C4—C5—C6 | 1.3 (9) | C3D—C4D—C5D—C6D | −34 (7) |
C2—C1—C6—C5 | 1.3 (10) | C2D—C1D—C6D—C5D | −21 (8) |
C8—C1—C6—C5 | −176.3 (6) | C8D—C1D—C6D—C5D | 152 (4) |
C4—C5—C6—C1 | −2.4 (11) | C4D—C5D—C6D—C1D | 46 (7) |
C6—C1—C8—O3 | 179.4 (6) | C6D—C1D—C8D—O3D | 176 (4) |
C2—C1—C8—O3 | 1.8 (7) | C2D—C1D—C8D—O3D | −12 (5) |
C6—C1—C8—C9 | 60.5 (6) | C6D—C1D—C8D—C9D | −66 (5) |
C2—C1—C8—C9 | −117.1 (5) | C2D—C1D—C8D—C9D | 106 (4) |
O3—C8—C9—C19 | 31.4 (3) | O3D—C8D—C9D—C10D | −151.4 (19) |
C1—C8—C9—C19 | 153.3 (3) | C1D—C8D—C9D—C10D | 89 (2) |
O3—C8—C9—C10 | 145.9 (3) | O3D—C8D—C9D—C19D | −35.5 (19) |
C1—C8—C9—C10 | −92.3 (3) | C1D—C8D—C9D—C19D | −155.5 (17) |
C19—C9—C10—O4 | −5.4 (4) | C19D—C9D—C10D—O4D | 2 (4) |
C8—C9—C10—O4 | −118.9 (3) | C8D—C9D—C10D—O4D | 116 (4) |
C16—C11—C12—C13 | 3.2 (9) | C16D—C11D—C12D—C13D | −19 (11) |
C18—C11—C12—C13 | −175.1 (5) | C18D—C11D—C12D—C13D | 166 (6) |
C11—C12—C13—O5 | 174.3 (7) | C11D—C12D—C13D—O5D | −163 (6) |
C11—C12—C13—C14 | −3.2 (10) | C11D—C12D—C13D—C14D | 15 (10) |
O5—C13—C14—C15 | −177.4 (5) | O5D—C13D—C14D—C15D | −176 (5) |
C12—C13—C14—C15 | 0.3 (9) | C12D—C13D—C14D—C15D | 5 (9) |
O5—C13—C14—O6 | 2.4 (9) | O5D—C13D—C14D—O6D | 7 (9) |
C12—C13—C14—O6 | −179.8 (6) | C12D—C13D—C14D—O6D | −172 (7) |
O6—C14—C15—C16 | −177.4 (5) | O6D—C14D—C15D—C16D | 155 (8) |
C13—C14—C15—C16 | 2.5 (8) | C13D—C14D—C15D—C16D | −22 (10) |
C12—C11—C16—C15 | −0.5 (8) | C12D—C11D—C16D—C15D | 2 (12) |
C18—C11—C16—C15 | 178.0 (4) | C18D—C11D—C16D—C15D | 177 (7) |
C14—C15—C16—C11 | −2.4 (8) | C14D—C15D—C16D—C11D | 19 (12) |
C16—C11—C18—O4 | 167.2 (4) | C16D—C11D—C18D—O4D | −148 (7) |
C12—C11—C18—O4 | −14.5 (6) | C12D—C11D—C18D—O4D | 27 (7) |
C16—C11—C18—C19 | 46.7 (5) | C16D—C11D—C18D—C19D | −35 (7) |
C12—C11—C18—C19 | −135.0 (5) | C12D—C11D—C18D—C19D | 140 (6) |
C10—C9—C19—C20 | −139.1 (3) | C10D—C9D—C19D—C20D | 148 (3) |
C8—C9—C19—C20 | −16.8 (2) | C8D—C9D—C19D—C20D | 24 (2) |
C10—C9—C19—C18 | −16.8 (3) | C10D—C9D—C19D—C18D | 25 (2) |
C8—C9—C19—C18 | 105.5 (2) | C8D—C9D—C19D—C18D | −99.3 (16) |
O4—C18—C19—C20 | 147.5 (2) | O4D—C18D—C19D—C20D | −153 (3) |
C11—C18—C19—C20 | −89.0 (3) | C11D—C18D—C19D—C20D | 92 (3) |
O4—C18—C19—C9 | 33.7 (2) | O4D—C18D—C19D—C9D | −42 (3) |
C11—C18—C19—C9 | 157.2 (2) | C11D—C18D—C19D—C9D | −158 (3) |
C9—C19—C20—O3 | −3.3 (4) | C9D—C19D—C20D—O3D | −5 (4) |
C18—C19—C20—O3 | −115.9 (3) | C18D—C19D—C20D—O3D | 104 (3) |
C2—C3—O1—C7 | −3.3 (7) | C4D—C3D—O1D—C7D | 144 (6) |
C4—C3—O1—C7 | 176.7 (4) | C2D—C3D—O1D—C7D | −58 (10) |
C1—C8—O3—C20 | −159.9 (4) | C1D—C8D—O3D—C20D | 158 (3) |
C9—C8—O3—C20 | −34.9 (4) | C9D—C8D—O3D—C20D | 33 (3) |
C19—C20—O3—C8 | 23.9 (5) | C19D—C20D—O3D—C8D | −18 (4) |
C11—C18—O4—C10 | −165.5 (4) | C11D—C18D—O4D—C10D | 167 (4) |
C19—C18—O4—C10 | −38.3 (4) | C19D—C18D—O4D—C10D | 46 (5) |
C9—C10—O4—C18 | 27.1 (4) | C9D—C10D—O4D—C18D | −29 (5) |
C12—C13—O5—C17 | 4.0 (8) | C12D—C13D—O5D—C17D | −18 (8) |
C14—C13—O5—C17 | −178.4 (5) | C14D—C13D—O5D—C17D | 163 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O4i | 0.82 | 2.19 | 2.847 (3) | 137 |
O6—H6A···O3ii | 0.82 | 2.23 | 2.903 (3) | 140 |
C2—H2···O6iii | 0.93 | 2.58 | 3.409 (5) | 149 |
C12—H12···O2iv | 0.93 | 2.41 | 3.328 (5) | 168 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C20H22O6 |
Mr | 358.38 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 8.0692 (6), 18.5615 (13), 12.1622 (9) |
β (°) | 102.061 (1) |
V (Å3) | 1781.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.61 × 0.14 × 0.09 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (Blessing; 1995) |
Tmin, Tmax | 0.942, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11738, 2986, 2052 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.598 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.146, 1.00 |
No. of reflections | 2986 |
No. of parameters | 345 |
No. of restraints | 286 |
H-atom treatment | Riding |
Δρmax, Δρmin (e Å−3) | 0.18, −0.18 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and SADABS (Sheldrick, 1996), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O4i | 0.82 | 2.19 | 2.847 (3) | 136.9 |
O6—H6A···O3ii | 0.82 | 2.23 | 2.903 (3) | 140.1 |
C2—H2···O6iii | 0.93 | 2.58 | 3.409 (5) | 149.3 |
C12—H12···O2iv | 0.93 | 2.41 | 3.328 (5) | 167.6 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+3/2. |
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The crystal structure of (+)-pinoresinol [(1) in Scheme] has been described in a previous paper (Lundquist & Stomberg, 1988). We present here a structure determination of the racemic form of pinoresinol. (±)-Pinoresinol crystallizes in the monoclinic centrosymmetric space group P21/c (No. 14), while (+)-pinoresinol crystallizes in the orthorhombic non-centrosymmetric space group P212121 (No. 19). The structure was solved using a standard direct methods technique (Bruker, 1997). However, refinement converged with rather high R factors (R1 = 0.0547 for observed reflections and wR2 = 0.1609 for all reflections) and some unexpected bond lengths of chemically equivalent C–C single bonds were obtained. For example, the distances (for numbering see Fig. 1) C8–C9, C9–C10 and C18–C19 were 1.509 (4), 1.507 (4) and 1.502 (4) Å, respectively. In general, they were too short and no explanation could be given in terms of thermal motion of these atoms, situated in the centre of the molecule. Discrepancies of the same kind, but even more pronounced, were observed by Bryan & Fallon (1976) for the closely related compound (-)-syringaresinol [the mirror image of (2) in Scheme 1]. They explain these anomalies by transmission of a σ-inductive effect from the aryl groups. We think that disorder is a more probable explanation. In our case, there were several residual peaks in the difference Fourier synthesis with a maximum of 0.60 and a minimum of -0.22 e Å-3. The two highest maxima, 0.60 and 0.59 e Å-3, were ca 1.54 Å apart, typical for a C–C single-bond distance. The line connecting them was parallel to the C9–C19 bond. This led us to the assumption that the molecules in the crystals are disordered (overlapping) and we found the transformation to be [0.5 - x, 0.7854 - y, 1 - z]. The two overlapping molecules were refined with restraints to the same geometry and their occupancies converged to 0.91877 (3) and 0.08123 (3), respectively. The R factors dropped and the difference Fourier synthesis became more flat with maximum and minimum electron density of 0.176 and -0.182 e Å-3. The abovementioned distances adopted more reasonable values, namely 1.527 (3) (C8–C9), 1.510 (5) (C9–C10) and 1.516 (3) Å (C18–C19).
The conformations of the molecules in the crystals of (+)-pinoresinol and (±)-pinoresinol are different. The most striking is the difference in the angle between the aromatic ring planes [116.2 (1)° for (+)-pinoresinol and 19.9 (2)° for (±)-pinoresinol] and the geometry of the dioxabicyclooctane ring system. The conformation of this ring system is similar in (±)-pinoresinol (this work) and (-)-syringaresinol (Bryan & Fallon, 1976).