(+) Pinoresinol–dioxane (1/1)

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organic papers

o1972

Rolf Stomberget al. C₂₀H₂₂O₆C₄H₈O₂ DOI: 10.1107/S1600536803026114 Acta Cryst.(2003). E59, o1972±o1974 Acta Crystallographica Section E

Structure Reports

Online ISSN 1600-5368

(+)-Pinoresinol±dioxane (1/1)

Rolf Stomberg,a_Wilson

Ibrahim,b_{Vratislav Langer}c_{* and}

Knut Lundquistd

a_{Department of Chemistry, Division of Inorganic}

Chemistry, GoÈteborg University, SE-412 96 GoÈteborg, Sweden,b_{Department of Organic} Chemistry, Chalmers University of Technology, SE-412 96 GoÈteborg, Sweden,c_{Department of} Environmental Inorganic Chemistry, Chalmers University of Technology, SE-412 96 GoÈteborg, Sweden, andd_{Department of Forest Products} and Chemical Engineering, Chalmers University of Technology, SE-41296 GoÈteborg, Sweden

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 153 K

Mean(C±C) = 0.003 AÊ Rfactor = 0.041 wRfactor = 0.121

Data-to-parameter ratio = 11.2

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

The crystal structure of a dioxane solvate of (+)-pinoresinol, C20H22O6C4H8O2, has been determined. The solvate is

stabilized by hydrogen bonding between the pinoresinol and dioxane molecules. The ®ve-membered rings in the central dioxabicyclooctane ring system of the pinoresinol molecules adopt envelope conformations, with the benzylic C atoms as ¯aps.

Comment

(+)-Pinoresinol, (Ia), was originally isolated from softwood species (Erdtman, 1955) but was later found to be a widely distributed constituent of plant extractives. Its absolute con®guration was determined by Freudenberg & Sidhu (1961). We have reported crystal structures of (Ia) (Lundquist & Stomberg, 1988) and the racemic form of pinoresinol (Stomberget al., 2001). A procedure for the isolation of (+)-pinoresinol from resinous exudates of softwood species has been described by Erdtman (1955). Gripenberg & Petrell (1960) found that crude (+)-pinoresinol obtained according to Erdtman (1955) could be conveniently puri®ed via the dioxane solvate. We report here the crystal structure of a dioxane solvate of (+)-pinoresinol, (I). The solvate crystallizes from solutions of (+)-pinoresinol in dioxane.

A perspective drawing of the molecules in (I) and the atomic numbering are shown in Fig. 1. There are OÐH O and CÐH O hydrogen bonds in the crystal structure of (I) (Table 1); the network of hydrogen bonds is shown in Fig. 2. On the ®rst-level graph-set (Bernsteinet al., 1995; Grellet al., 1999), the hydrogen bonds denoted as [a] and [c] (see Table 1) are intramolecular bonds of typeS(5). Hydrogen bonds [b], [d], [f] and [g] form interactions of type D(2) between the pinoresinol and dioxane molecules, and hydrogen bond [e] forms aC(8) chain. On the second-level graph-set, a number of hydrogen-bond patterns were recognized, the most impor-tant of which areC2

2(20) chains formed by hydrogen bonds [b]

and [d] in theacplane, andC2

2(18) chains formed by hydrogen

bonds [f] and [g] in theadirection. Two rings are also apparent

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in Fig. 2,viz. oneR2

2(17) ring, formed by bonds of type [e], and

oneR3

3(10) ring, formed by bonds of types [e], [d] and [f]. The

assignment of graph-set descriptors was performed using

PLUTO, as described by Motherwellet al.(1999).

We have compared the conformation of the pinoresinol molecule in the crystal structure of pinoresinol±dioxane (1/1) with those of the pinoresinol molecules in the crystal struc-tures of (Ia) (Lundquist & Stomberg, 1988) and the racemic form of pinoresinol (Stomberget al., 2001). To describe the conformation of the ®ve-membered rings in the central

di-oxabicyclooctane ring system we have used the program

PLATON(Spek, 2002). In (I), the ®ve-membered rings in this

ring system adopt envelope conformations, with the benzylic C atoms as ¯aps (Fig. 1). The conformation of the pinoresinol molecules in the solvate is similar to that of the pinoresinol molecules in the racemate (Stomberget al., 2001). The mol-ecules in the crystal structure of (Ia) also adopt envelope conformations, but in this case, the O atoms constitute the ¯aps. Furthermore, the ¯aps point in the same direction in the solvate (Fig. 1) and the racemate, while they point in different directions in (Ia).

Experimental

(+)-Pinoresinol, (Ia), was obtained from a resinous exudate of spruce according to the procedure described by Gripenberg & Petrell (1960). Solutions of (Ia) in a small amount of dioxane gave crystals of the solvate (I) on standing at room temperature.

Crystal data

C20H22O6C4H8O2

Mr= 446.48

Monoclinic,P21

a= 9.8318 (16) AÊ

b= 6.066 (3) AÊ

c= 18.493 (2) AÊ

= 92.891 (13)

V= 1101.5 (6) AÊ3

Z= 2

Dx= 1.346 Mg mÿ3

MoKradiation Cell parameters from 25

re¯ections

= 23.4±24.9

= 0.10 mmÿ1

T= 153 (1) K Block, colourless 0.550.350.35 mm

Data collection

Rigaku AFC-6 diffractometer

!scans

3660 measured re¯ections 3479 independent re¯ections 2765 re¯ections withI> 2(I)

Rint= 0.013

max= 30.0

h= 0!13

k= 0!8

l=ÿ25!25 3 standard re¯ections

every 150 re¯ections intensity decay: none

Re®nement

Re®nement onF2

R[F2_{> 2}₍_F2_{)] = 0.041}

wR(F2_{) = 0.121}

S= 1.04 3479 re¯ections 311 parameters

H-atom parameters constrained

w= 1/[2₍_F

o2) + (0.0679P)2

+ 0.1302P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.33 e AÊÿ3

min=ÿ0.22 e AÊÿ3

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

[a] O2ÐH2A O1 0.82 2.24 2.671 (3) 113 [b] O2ÐH2A O8i _0.82 _1.98 _{2.718 (2)} ₁₄₉ [c] O6ÐH6A O5 0.82 2.22 2.663 (3) 114 [d] O6ÐH6A O7 0.82 2.00 2.710 (2) 145 [e] C19ÐH19 O6ii _0.98 _2.37 _{3.221 (3)} ₁₄₅ [f] C23ÐH23A O3ii _0.97 _2.55 _{3.465 (3)} ₁₅₈ [g] C23ÐH23B O4iii _0.97 _2.56 _{3.480 (3)} ₁₅₈

Symmetry codes: (i)xÿ1;y;1z; (ii) 2ÿx;1

2y;ÿz; (iii) 3ÿx;12y;ÿz.

H atoms were re®ned isotropically and were constrained to an ideal geometry using an appropriate riding model. For OH groups, the OÐH distances (0.82 AÊ) and CÐOÐH angles (109.5_{) were}

®xed, while the torsion angles were allowed to re®ne, with the starting position based on the circular Fourier synthesis. For methyl groups, the CÐH distances (0.96 AÊ) and CÐCÐH angles (109.5_{) were kept}

Acta Cryst.(2003). E59, o1972±o1974 Rolf Stomberget al. C₂₀H₂₂O₆C₄H₈O₂

o1973

organic papers

Figure 1

A perspective drawing of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level.

Figure 2

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organic papers

o1974

Rolf Stomberget al. C₂₀H₂₂O₆C₄H₈O₂ Acta Cryst.(2003). E59, o1972±o1974

®xed, while the torsion angles were allowed to re®ne with the starting position based on a threefold averaged circular Fourier synthesis. For aromatic H atoms, the CÐH distance was ®xed at 0.93 AÊ and for tertiary H atoms at 0.98 AÊ. For secondary H atoms, the CÐH distance was ®xed to 0.97 AÊ, withUiso(H) = 1.2Ueq(C).

Data collection: TEXRAY (Molecular Structure Corporation, 1985); cell re®nement: TEXRAY; data reduction: TEXRAY; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to re®ne structure:SHELXTL; molecular graphics: DIAMOND(Brandenburg, 2000); software used to prepare material for publication:SHELXTL.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995).Angew. Chem. Int. Ed. Engl.34, 1555±1573.

Brandenburg, K. (2000). DIAMOND. Version 2.1d. Crystal Impact GbR, Bonn, Germany.

Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Erdtman, H. (1955). Lignans, inModern Methods of Plant Analysis, edited by K. Paech & M. V. Tracey, Vol. III, pp. 428±449. Berlin±GoÈttingen± Heidelberg: Springer±Verlag.

Freudenberg, K. & Sidhu, G. S. (1961).Chem. Ber.94, 851±862. Grell, J., Bernstein, J. & Tinhofer, G. (1999).Acta Cryst.B55, 1030±1043. Gripenberg, J. & Petrell, I. (1960).Acta Chem. Scand.14, 226.

Lundquist, K. & Stomberg, R. (1988).Holzforschung,42, 375±384. Molecular Structure Corporation (1985). TEXSAN. TEXRAY Structure

Analysis Package.MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.

Motherwell, W. D. S., Shields, G. P. & Allen, F. H. (1999).Acta Cryst.B55, 1044±1056.

Spek, A. L.(2002).PLATON.Utrecht University, The Netherlands. Stomberg, R., Langer, V., Li, S. & Lundquist K. (2001).Acta Cryst.E57, o692±

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supporting information

sup-1 Acta Cryst. (2003). E59, o1972–o1974

supporting information

Acta Cryst. (2003). E59, o1972–o1974 [https://doi.org/10.1107/S1600536803026114]

(+)-Pinoresinol

–

dioxane (1/1)

Rolf Stomberg, Wilson Ibrahim, Vratislav Langer and Knut Lundquist

(+)-pinoresinol–dioxane (1/1)

Crystal data

C20H22O6·C4H8O2

Mr = 446.48

Monoclinic, P21

Hall symbol: P 2yb

a = 9.8318 (16) Å

b = 6.066 (3) Å

c = 18.493 (2) Å

β = 92.891 (13)°

V = 1101.5 (6) Å3

Z = 2

F(000) = 476

Dx = 1.346 Mg m−3

Mo Kα radiation, λ = 0.71069 Å Cell parameters from 25 reflections

θ = 23.4–24.9°

µ = 0.10 mm−1

T = 153 K Plate, colourless 0.55 × 0.35 × 0.35 mm

Data collection

Rigaku AFC6 diffractometer

Radiation source: normal-focus rotating anode Graphite monochromator

ω scans

3660 measured reflections 3479 independent reflections 2765 reflections with I > 2σI

Rint = 0.013

θmax = 30.0°, θmin = 2.1°

h = 0→13

k = 0→8

l = −25→25

3 standard reflections every 150 reflections intensity decay: none

Refinement

Refinement on F2

Least-squares matrix: full

R[F2_{> 2}_σ₍_F2_{)] = 0.041}

wR(F2_{) = 0.121}

S = 1.04 3479 reflections 311 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2₍_F

o2) + (0.0679P)2 + 0.1302P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.33 e Å−3

Δρmin = −0.22 e Å−3

Special details

Experimental. Data were collected at low temperature using a Rigaku AFC6R diffractometer equiped with a low temperature device. The data were collected using ω-scan. Scans of (1.22 + 0.30tanθ) were made at a speed of 8.0ο/min. The weak reflections (I<10.0σI) were rescanned (maximum 3 rescans) and the counts were accumulated to assure good

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supporting information

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.

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

x y z Uiso*/Ueq

C1 0.86723 (18) 0.7651 (4) 0.39457 (10) 0.0237 (4)

C2 0.78063 (19) 0.6263 (4) 0.43133 (10) 0.0248 (4)

H2 0.7484 0.4974 0.4093 0.042 (8)*

C3 0.74239 (18) 0.6788 (4) 0.50015 (10) 0.0228 (4)

C4 0.79078 (19) 0.8737 (4) 0.53375 (10) 0.0245 (4)

C5 0.8747 (2) 1.0127 (4) 0.49705 (11) 0.0273 (4)

H5 0.9060 1.1427 0.5188 0.043 (8)*

C6 0.91258 (19) 0.9590 (4) 0.42766 (11) 0.0262 (4)

H6 0.9688 1.0539 0.4033 0.042 (8)*

C7 0.5873 (2) 0.3774 (4) 0.50649 (13) 0.0316 (5)

H7A 0.5392 0.4286 0.4632 0.036 (7)*

H7B 0.5237 0.3164 0.5387 0.052 (9)*

H7C 0.6516 0.2661 0.4942 0.044 (8)*

C8 0.91926 (19) 0.6906 (4) 0.32359 (10) 0.0255 (4)

H8 0.9848 0.5711 0.3331 0.038 (7)*

C9 0.9850 (2) 0.8631 (4) 0.27647 (10) 0.0263 (4)

H9 0.9351 1.0029 0.2765 0.029 (7)*

C10 1.1386 (2) 0.8986 (5) 0.29093 (11) 0.0335 (5)

H10A 1.1580 1.0537 0.2991 0.040*

H10B 1.1708 0.8164 0.3334 0.040*

C11 1.15336 (18) 0.6312 (4) 0.11523 (10) 0.0254 (4)

C12 1.23149 (19) 0.7870 (4) 0.08078 (10) 0.0261 (4)

H12 1.2661 0.9084 0.1063 0.046 (8)*

C13 1.25762 (19) 0.7606 (4) 0.00794 (10) 0.0250 (4)

C14 1.20537 (19) 0.5794 (4) −0.03067 (10) 0.0276 (4)

C15 1.1261 (2) 0.4272 (4) 0.00362 (11) 0.0311 (5)

H15 1.0891 0.3081 −0.0222 0.039 (8)*

C16 1.1013 (2) 0.4517 (4) 0.07677 (11) 0.0293 (4)

H16 1.0495 0.3471 0.0998 0.034 (7)*

C17 1.4086 (2) 1.0689 (4) 0.00630 (13) 0.0339 (5)

H17A 1.3457 1.1710 0.0260 0.045 (8)*

H17B 1.4651 1.1451 −0.0264 0.051 (9)*

H17C 1.4646 1.0053 0.0449 0.048 (8)*

C18 1.11777 (19) 0.6620 (4) 0.19303 (10) 0.0262 (4)

H18 1.1279 0.5212 0.2187 0.039 (7)*

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H19 0.9491 0.8590 0.1635 0.033 (7)*

C20 0.8610 (2) 0.5794 (6) 0.20753 (11) 0.0430 (7)

H20A 0.7896 0.6026 0.1702 0.052*

H20B 0.8975 0.4321 0.2022 0.052*

C21 1.4511 (3) 0.5275 (5) −0.23373 (13) 0.0390 (6)

H21A 1.3798 0.4182 −0.2299 0.047*

H21B 1.5376 0.4575 −0.2206 0.047*

C22 1.4521 (3) 0.6092 (6) −0.30944 (13) 0.0560 (9)

H22A 1.4701 0.4875 −0.3416 0.067*

H22B 1.3633 0.6694 −0.3237 0.067*

C23 1.5316 (2) 0.9530 (5) −0.26788 (13) 0.0366 (5)

H23A 1.4453 1.0235 −0.2811 0.044*

H23B 1.6033 1.0617 −0.2715 0.044*

C24 1.5301 (3) 0.8708 (6) −0.19247 (13) 0.0517 (8)

H24A 1.6188 0.8103 −0.1782 0.062*

H24B 1.5124 0.9927 −0.1603 0.062*

O1 0.65778 (15) 0.5576 (3) 0.54108 (7) 0.0295 (3)

O2 0.75570 (17) 0.9280 (3) 0.60194 (8) 0.0353 (4)

H2A 0.6918 0.8507 0.6134 0.051 (9)*

O3 0.80826 (15) 0.6066 (4) 0.27825 (8) 0.0402 (5)

O4 1.20418 (14) 0.8221 (4) 0.22813 (7) 0.0348 (4)

O5 1.33514 (16) 0.8991 (3) −0.03163 (8) 0.0326 (4)

O6 1.23224 (18) 0.5481 (4) −0.10141 (8) 0.0416 (5)

H6A 1.2894 0.6379 −0.1133 0.060 (10)*

O7 1.42862 (19) 0.7052 (4) −0.18529 (9) 0.0434 (5)

O8 1.5538 (2) 0.7757 (4) −0.31618 (9) 0.0467 (5)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C1 0.0198 (7) 0.0274 (10) 0.0239 (8) −0.0003 (8) 0.0016 (6) −0.0013 (8)

C2 0.0229 (8) 0.0262 (10) 0.0253 (8) −0.0019 (8) 0.0010 (7) −0.0011 (8)

C3 0.0199 (8) 0.0233 (9) 0.0253 (8) −0.0033 (8) 0.0019 (6) 0.0011 (8)

C4 0.0225 (8) 0.0279 (10) 0.0230 (8) −0.0008 (8) 0.0005 (7) −0.0014 (8)

C5 0.0260 (9) 0.0268 (10) 0.0291 (9) −0.0053 (9) 0.0022 (7) −0.0030 (9)

C6 0.0218 (8) 0.0301 (11) 0.0269 (9) −0.0045 (8) 0.0034 (7) 0.0024 (8)

C7 0.0295 (10) 0.0225 (10) 0.0435 (12) −0.0056 (9) 0.0079 (9) −0.0025 (9)

C8 0.0216 (8) 0.0303 (10) 0.0247 (8) −0.0028 (8) 0.0025 (6) −0.0043 (8)

C9 0.0258 (9) 0.0314 (11) 0.0217 (8) −0.0006 (8) 0.0024 (7) 0.0001 (8)

C10 0.0300 (10) 0.0448 (14) 0.0260 (9) −0.0095 (10) 0.0048 (7) −0.0041 (10)

C11 0.0194 (8) 0.0326 (11) 0.0244 (8) 0.0010 (8) 0.0022 (6) 0.0006 (8)

C12 0.0231 (8) 0.0283 (10) 0.0270 (8) −0.0015 (8) 0.0017 (7) −0.0029 (9)

C13 0.0205 (8) 0.0285 (10) 0.0262 (8) −0.0014 (8) 0.0024 (6) 0.0012 (8)

C14 0.0232 (8) 0.0359 (12) 0.0241 (8) −0.0034 (9) 0.0035 (7) −0.0021 (9)

C15 0.0275 (9) 0.0345 (12) 0.0315 (10) −0.0094 (10) 0.0029 (8) −0.0066 (10)

C16 0.0256 (9) 0.0322 (11) 0.0305 (10) −0.0063 (9) 0.0058 (7) 0.0001 (9)

C17 0.0349 (10) 0.0250 (11) 0.0424 (11) −0.0069 (9) 0.0085 (9) −0.0043 (10)

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C19 0.0216 (8) 0.0416 (13) 0.0215 (8) 0.0014 (9) −0.0006 (6) −0.0002 (9)

C20 0.0276 (10) 0.072 (2) 0.0301 (10) −0.0145 (13) 0.0072 (8) −0.0175 (13)

C21 0.0431 (12) 0.0302 (12) 0.0450 (13) −0.0026 (11) 0.0132 (10) −0.0003 (11)

C22 0.086 (2) 0.0508 (18) 0.0323 (12) −0.0345 (18) 0.0166 (13) −0.0117 (13)

C23 0.0334 (11) 0.0323 (12) 0.0451 (12) −0.0046 (10) 0.0103 (9) −0.0004 (11)

C24 0.0679 (18) 0.0539 (19) 0.0340 (12) −0.0288 (16) 0.0099 (12) −0.0092 (13)

O1 0.0336 (7) 0.0288 (8) 0.0265 (7) −0.0088 (7) 0.0062 (5) 0.0006 (7)

O2 0.0397 (8) 0.0402 (10) 0.0267 (7) −0.0131 (8) 0.0092 (6) −0.0074 (7)

O3 0.0266 (7) 0.0652 (13) 0.0294 (7) −0.0172 (9) 0.0071 (6) −0.0143 (9)

O4 0.0235 (6) 0.0541 (11) 0.0270 (7) −0.0086 (8) 0.0037 (5) −0.0078 (8)

O5 0.0337 (7) 0.0341 (9) 0.0304 (7) −0.0121 (8) 0.0053 (6) −0.0010 (7)

O6 0.0446 (9) 0.0542 (12) 0.0272 (7) −0.0235 (10) 0.0113 (7) −0.0108 (8)

O7 0.0540 (10) 0.0442 (11) 0.0339 (8) −0.0168 (9) 0.0202 (7) −0.0077 (9)

O8 0.0623 (11) 0.0427 (11) 0.0375 (8) −0.0181 (11) 0.0263 (8) −0.0075 (9)

Geometric parameters (Å, º)

C1—C6 1.390 (3) C14—C15 1.383 (3)

C1—C2 1.398 (3) C15—C16 1.395 (3)

C1—C8 1.502 (3) C15—H15 0.9300

C2—C3 1.382 (3) C16—H16 0.9300

C2—H2 0.9300 C17—O5 1.423 (3)

C3—O1 1.367 (2) C17—H17A 0.9600

C3—C4 1.407 (3) C17—H17B 0.9600

C4—O2 1.364 (2) C17—H17C 0.9600

C4—C5 1.382 (3) C18—O4 1.425 (3)

C5—C6 1.393 (3) C18—C19 1.535 (3)

C5—H5 0.9300 C18—H18 0.9800

C6—H6 0.9300 C19—C20 1.528 (4)

C7—O1 1.428 (3) C19—H19 0.9800

C7—H7A 0.9600 C20—O3 1.441 (2)

C7—H7B 0.9600 C20—H20A 0.9700

C7—H7C 0.9600 C20—H20B 0.9700

C8—O3 1.436 (2) C21—O7 1.426 (3)

C8—C9 1.526 (3) C21—C22 1.486 (4)

C8—H8 0.9800 C21—H21A 0.9700

C9—C10 1.535 (3) C21—H21B 0.9700

C9—C19 1.542 (3) C22—O8 1.431 (3)

C9—H9 0.9800 C22—H22A 0.9700

C10—O4 1.434 (2) C22—H22B 0.9700

C10—H10A 0.9700 C23—O8 1.422 (3)

C10—H10B 0.9700 C23—C24 1.482 (4)

C11—C16 1.384 (3) C23—H23A 0.9700

C11—C12 1.392 (3) C23—H23B 0.9700

C11—C18 1.509 (3) C24—O7 1.427 (3)

C12—C13 1.393 (3) C24—H24A 0.9700

C12—H12 0.9300 C24—H24B 0.9700

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C13—C14 1.395 (3) O6—H6A 0.8200

C14—O6 1.361 (2)

C6—C1—C2 119.04 (18) C11—C16—H16 119.9

C6—C1—C8 121.58 (18) C15—C16—H16 119.9

C2—C1—C8 119.12 (19) O5—C17—H17A 109.5

C3—C2—C1 120.7 (2) O5—C17—H17B 109.5

C3—C2—H2 119.7 H17A—C17—H17B 109.5

C1—C2—H2 119.7 O5—C17—H17C 109.5

O1—C3—C2 126.0 (2) H17A—C17—H17C 109.5

O1—C3—C4 114.12 (17) H17B—C17—H17C 109.5

C2—C3—C4 119.89 (19) O4—C18—C11 110.93 (17)

O2—C4—C5 119.4 (2) O4—C18—C19 104.25 (18)

O2—C4—C3 121.02 (19) C11—C18—C19 113.65 (16)

C5—C4—C3 119.53 (18) O4—C18—H18 109.3

C4—C5—C6 120.3 (2) C11—C18—H18 109.3

C4—C5—H5 119.9 C19—C18—H18 109.3

C6—C5—H5 119.9 C20—C19—C18 116.3 (2)

C1—C6—C5 120.60 (19) C20—C19—C9 104.80 (16)

C1—C6—H6 119.7 C18—C19—C9 102.70 (15)

C5—C6—H6 119.7 C20—C19—H19 110.8

O1—C7—H7A 109.5 C18—C19—H19 110.8

O1—C7—H7B 109.5 C9—C19—H19 110.8

H7A—C7—H7B 109.5 O3—C20—C19 106.4 (2)

O1—C7—H7C 109.5 O3—C20—H20A 110.4

H7A—C7—H7C 109.5 C19—C20—H20A 110.4

H7B—C7—H7C 109.5 O3—C20—H20B 110.4

O3—C8—C1 109.55 (15) C19—C20—H20B 110.4

O3—C8—C9 103.96 (16) H20A—C20—H20B 108.6

C1—C8—C9 117.75 (19) O7—C21—C22 110.4 (2)

O3—C8—H8 108.4 O7—C21—H21A 109.6

C1—C8—H8 108.4 C22—C21—H21A 109.6

C9—C8—H8 108.4 O7—C21—H21B 109.6

C8—C9—C10 115.99 (18) C22—C21—H21B 109.6

C8—C9—C19 101.40 (18) H21A—C21—H21B 108.1

C10—C9—C19 104.24 (16) O8—C22—C21 110.8 (2)

C8—C9—H9 111.5 O8—C22—H22A 109.5

C10—C9—H9 111.5 C21—C22—H22A 109.5

C19—C9—H9 111.5 O8—C22—H22B 109.5

O4—C10—C9 106.99 (16) C21—C22—H22B 109.5

O4—C10—H10A 110.3 H22A—C22—H22B 108.1

C9—C10—H10A 110.3 O8—C23—C24 110.2 (3)

O4—C10—H10B 110.3 O8—C23—H23A 109.6

C9—C10—H10B 110.3 C24—C23—H23A 109.6

H10A—C10—H10B 108.6 O8—C23—H23B 109.6

C16—C11—C12 119.81 (18) C24—C23—H23B 109.6

C16—C11—C18 119.32 (19) H23A—C23—H23B 108.1

(9)

supporting information

C11—C12—C13 119.8 (2) O7—C24—H24A 109.4

C11—C12—H12 120.1 C23—C24—H24A 109.4

C13—C12—H12 120.1 O7—C24—H24B 109.4

O5—C13—C12 125.5 (2) C23—C24—H24B 109.4

O5—C13—C14 114.22 (17) H24A—C24—H24B 108.0

C12—C13—C14 120.29 (19) C3—O1—C7 117.29 (16)

O6—C14—C15 119.3 (2) C4—O2—H2A 109.5

O6—C14—C13 121.2 (2) C8—O3—C20 105.85 (15)

C15—C14—C13 119.55 (18) C18—O4—C10 107.89 (16)

C14—C15—C16 120.3 (2) C13—O5—C17 117.57 (17)

C14—C15—H15 119.9 C14—O6—H6A 109.5

C16—C15—H15 119.9 C24—O7—C21 110.02 (19)

C11—C16—C15 120.3 (2) C23—O8—C22 110.41 (18)

C6—C1—C2—C3 −1.2 (3) C12—C11—C16—C15 −0.4 (3)

C8—C1—C2—C3 173.12 (18) C18—C11—C16—C15 176.1 (2)

C1—C2—C3—O1 179.45 (19) C14—C15—C16—C11 1.4 (3)

C1—C2—C3—C4 0.0 (3) C16—C11—C18—O4 166.43 (19)

O1—C3—C4—O2 1.2 (3) C12—C11—C18—O4 −17.1 (3)

C2—C3—C4—O2 −179.30 (19) C16—C11—C18—C19 −76.5 (3)

O1—C3—C4—C5 −178.51 (19) C12—C11—C18—C19 100.0 (2)

C2—C3—C4—C5 1.0 (3) O4—C18—C19—C20 −148.36 (17)

O2—C4—C5—C6 179.4 (2) C11—C18—C19—C20 90.7 (2)

C3—C4—C5—C6 −0.8 (3) O4—C18—C19—C9 −34.6 (2)

C2—C1—C6—C5 1.3 (3) C11—C18—C19—C9 −155.47 (19)

C8—C1—C6—C5 −172.8 (2) C8—C9—C19—C20 20.3 (2)

C4—C5—C6—C1 −0.3 (3) C10—C9—C19—C20 141.1 (2)

C6—C1—C8—O3 −138.4 (2) C8—C9—C19—C18 −101.68 (19)

C2—C1—C8—O3 47.5 (3) C10—C9—C19—C18 19.1 (2)

C6—C1—C8—C9 −19.9 (3) C18—C19—C20—O3 116.6 (2)

C2—C1—C8—C9 165.94 (18) C9—C19—C20—O3 4.0 (3)

O3—C8—C9—C10 −150.31 (19) O7—C21—C22—O8 57.5 (3)

C1—C8—C9—C10 88.3 (2) O8—C23—C24—O7 −57.5 (3)

O3—C8—C9—C19 −38.1 (2) C2—C3—O1—C7 −9.3 (3)

C1—C8—C9—C19 −159.49 (16) C4—C3—O1—C7 170.11 (17)

C8—C9—C10—O4 112.8 (2) C1—C8—O3—C20 169.2 (2)

C19—C9—C10—O4 2.3 (3) C9—C8—O3—C20 42.5 (3)

C16—C11—C12—C13 −0.5 (3) C19—C20—O3—C8 −28.8 (3)

C18—C11—C12—C13 −176.90 (18) C11—C18—O4—C10 160.50 (19)

C11—C12—C13—O5 −178.5 (2) C19—C18—O4—C10 37.8 (2)

C11—C12—C13—C14 0.3 (3) C9—C10—O4—C18 −25.2 (3)

O5—C13—C14—O6 0.4 (3) C12—C13—O5—C17 8.0 (3)

C12—C13—C14—O6 −178.5 (2) C14—C13—O5—C17 −170.81 (18)

O5—C13—C14—C15 179.7 (2) C23—C24—O7—C21 57.4 (3)

C12—C13—C14—C15 0.7 (3) C22—C21—O7—C24 −57.0 (3)

O6—C14—C15—C16 177.7 (2) C24—C23—O8—C22 56.9 (3)

(10)

supporting information

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

[a]O2—H2A···O1 0.82 2.24 2.671 (3) 113

[b]O2—H2A···O8i _0.82 _1.98 _{2.718 (2)} ₁₄₉

[c]O6—H6A···O5 0.82 2.22 2.663 (3) 114

[d]O6—H6A···O7 0.82 2.00 2.710 (2) 145

[e]C19—H19···O6ii _0.98 _2.37 _{3.221 (3)} ₁₄₅

[f]C23—H23A···O3ii _0.97 _2.55 _{3.465 (3)} ₁₅₈

[g]C23—H23B···O4iii _0.97 _2.56 _{3.480 (3)} ₁₅₈