The racemate of pinoresinol

Stomberg, R.; Langer, V.; Li, S.; Lundquist, K.

doi:10.1107/S1600536801011084

The racemate of pinoresinol

R. Stomberg, V. Langer, S. Li and K. Lundquist

The molecules in the crystals of (±)-pinoresinol, C₂₀H₂₂O₆, were found to be statistically disordered. A model of the disorder was deduced. The crystal structure of (±)-pinoresinol is compared with published crystal structures of (+)-pinoresinol and the related compound (-)-syringaresinol. Bond lengths and angles in the crystal structure of (+)-pinoresinol are reasonable, while the crystal structure of (-)-syringaresinol exhibits anomalies resembling those observed for (±)-pinoresinol before the disorder was resolved. The conformation of the dioxabicyclooctane ring system in (±)-pinoresinol differs from that of (+)-pinoresinol, but is similar to that of (-)-syringaresinol.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011084/cf6084sup1.cif Contains datablocks I, n
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011084/cf6084Isup2.hkl Contains datablock I

CCDC reference: 170892

checkCIF report

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

Comment top

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).

Experimental top

Crystals of racemic pinoresinol (Freudenberg, 1968), suitable for X-ray diffraction analysis, were obtained on crystallization from ethyl acetate/hexane.

Computing details top

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.

Figures top

	Fig. 1. The numbering scheme for the title compound. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. The overlapping molecules showing that the functional groups are positioned in the same directions. The molecule with higher occupancy is shown with filled bonds, while that with lower occupancy is shown with broken lines.
	Fig. 3. The hydrogen-bond network in the title compound.

(I) top

Crystal data top

C₂₀H₂₂O₆	F(000) = 760
M_r = 358.38	D_x = 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

Data collection top

Siemens SMART CCD diffractometer	2986 independent reflections
Radiation source: fine-focus sealed tube	2052 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
w scans	θ_max = 25.1°, θ_min = 2.0°
Absorption correction: multi-scan (Blessing; 1995)	h = −9→9
T_min = 0.942, T_max = 0.991	k = −21→22
11738 measured reflections	l = −14→14

Refinement top

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(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2986 reflections	Δρ_max = 0.18 e Å⁻³
345 parameters	Δρ_min = −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)

Crystal data top

C₂₀H₂₂O₆	V = 1781.4 (2) Å³
M_r = 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)°

Data collection top

Siemens SMART CCD diffractometer	2986 independent reflections
Absorption correction: multi-scan (Blessing; 1995)	2052 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.991	R_int = 0.030
11738 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	286 restraints
wR(F²) = 0.146	Riding
S = 1.00	Δρ_max = 0.18 e Å⁻³
2986 reflections	Δρ_min = −0.18 e Å⁻³
345 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O2^iv	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
M_r	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)
T_min, T_max	0.942, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	11738, 2986, 2052
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and SADABS (Sheldrick, 1996), SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top

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···O2^iv	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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