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The title mol­ecule, C27H24O9, was formed via a transannular electrophilic addition of a putative cyclo­triveratrylene tri­ketone and is made up of an anthrone and an isobenzofuran­one ring that are connected via one C atom to form a spiro compound. The anthracene and isobenzofuran­one ring systems of the spiro compound are both essentially planar and perpendicular to each other, with an angle of 89.90 (2)° between them. The rigid mol­ecule crystallizes with large voids of 598.7 Å3, or 21.5% of the unit-cell volume, that are partially filled with unmodelled disordered solvent mol­ecules. The voids stretch as infinite channels along the [101] direction. The packing of the structure is partially stabilized by a range of weak C—H...O hydrogen bonds and also by C—H...π inter­actions. No significant π–π inter­actions are present in the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051136/sj2373sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051136/sj2373Isup2.hkl
Contains datablock I

CCDC reference: 667411

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.056
  • wR factor = 0.179
  • Data-to-parameter ratio = 20.8

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT601_ALERT_2_A Structure Contains Solvent Accessible VOIDS of . 596.00 A   3
Author Response: The structure exhibits large regions filled with heavily disordered solvent molecules. No obvious solvent model was discernible from the difference density Fourier maps (and data collection at 100 K did not improve of the data quality) and thus a correction for the diffuse solvent was applied using the Squeeze algorithm implemented in Platon by A. L/ Spek. The void volume was calculated by Platon as 598.7 cubic Angstroms, the number of electrons it corrected for as 52.0.

Alert level C PLAT128_ALERT_4_C Non-standard setting of Space group P2/c .... P2/n PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.95 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.34 Ratio PLAT482_ALERT_4_C Small D-H..A Angle Rep for C12 .. CG1 .. 99.00 Deg.
1 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL006_ALERT_1_A _publ_requested_journal is missing e.g. 'Acta Crystallographica Section C'
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing

Comment top

We are interested in apex-modified cyclotriveratrylene (CTV) derivatives and recently reported the isolation and conformational crown/saddle dynamics of CTV mono-oxime (Lutz, French et al., 2007). In the course of studying the Beckmann rearrangement of the CTV oxime, we isolated and reported the structure of a helical pentacycle formed via a tandem Beckmann and subsequent electrophilic addition sequence (Lutz, Zeller et al., 2007).

Cookson et al. (1968) reported the isolation of a CTV derivative from oxidation of CTV with sodium dichromate in acetic acid that they thought was the CTV triketone. The triketone, however, has in fact never been isolated, but the compound isolated by Cookson was shortly thereafter identified using UV– and NMR-spectroscopic methods (Baldwin & Kelly, 1968) to have a spiro structure, produced via acid-catalyzed electrophilic addition and rearrangement of the putative triketone under the acidic conditions Fig. 1. Both this spiro compound, the crystal structure of which will be descibed here, and the tandem Beckman/electrophilic addition products (Lutz, Zeller & Becker, 2007) are formed via trans-annular electrophilic addition to somehow related cationic intermediates. Interestingly, the spiro derivative is a structural analogue to the cyclized lactone form of the exceedingly useful fluorescent spirolactone fluorescein. The title compound contains a diaryl ketone rather than the diaryl ether of fluorescein.

The title compound crystallizes with large regions filled with heavily disordered solvent molecules. The voids make up 598.7 Å3 or 21.5% of the unit cell volume and stretch as infinite channels along the direction [101] with y = 0.5 (Fig. 4). 1H NMR spectra of dissolved crystals indicated the presence of both methylene chloride and ethyl acetate, the solvents the crystals were grown from. However, with the data collected at room temperature, no obvious solvent model was discernible from difference maps, and data collection at 100 K did not improve the data quality: even at a slow cooling rates the crystal quality suffered upon cooling resulting in significantely larger R values, and the disorder of the diffuse solvent molecules persists even at 100 K. Thus a correction for the diffuse solvent was applied using the Squeeze algorithm implemented in PLATON (Spek, 2003, 2007). The number of electrons within the voids was estimated by PLATON to be 52, indicating that the voids are only partially filled with solvent.

The anthrone and isobenzofuranone ring systems, Fig. 2, are both essentially planar with r.m.s. deviations from the mean square planes of only 0.12 and 0.01 Å, respectively, and they are basically perpendicular to each other with an angle of 89.90 (2)° between them. Also the methoxy groups are in plane with the ring systems they are bonded to. The largest deviation is observed for C17 which is located 0.321 (3) Å outside of the plane of the anthrone ring sytem.

The packing of the structure is partially stabilized by a range of weak C—H···O hydrogen bonds formed by methyl H atoms C15B and C17b and by the aromatic hydrogen atoms H20 and H23 to both keto and methoxy oxygen atoms. There are also three C—H···Cπ-arom interactions with H···centroid distances that could be interpreted as stabilizing, but two of these are intramolecular interactions forced by the spiro-geometry of the molecule (C2—H2···Cg1 and C12—H12···Cg1), and only the interaction C28—H28B···Cg2 may be seen as truely positively contributing to the packing interactions (Cg1 and Cg2 define the ring centroids of O9 C14 C19 C24 C25 and C8 C9 C10 C11 C12 C13, respectively) Fig. 3 & 4. See the hydrogen bonding table for metric parameters of the C—H···O and C—H···π interactions. No significant ππ interactions are present in the structure of the title compound.

Related literature top

Cookson et al. (1968) described the first synthesis of the title molecule. Baldwin & Kelly (1968) subsequently reported its correct identification as a spiro compound by UV and NMR methods. Lutz, French et al. (2007) and Lutz, Zeller & Becker (2007) give background information on other compounds derived from cyclotriveratrylene. PLATON (Spek, 2003, 2007) was used to correct the data set for diffuse solvent effects. For related literature, see Herbstein (2000).

Experimental top

A 500-ml round bottom flask was charged with cyclotriveratrylene (13.52 g, 30 mmol), sodium dichromate dihydrate (16.1 g, 54.0 mmol), glacial acetic acid (91 ml), and deionized water (107 ml). The orange reaction mixture was brought to reflux in a hot oil bath (408–413 K, 135–140 °C). Within one hour the reaction mixture turned from orange brown to dark green. The reaction was monitored by TLC (20/80, ethyl acetate/methylene chloride) and proton NMR. After 48 h at reflux, the reaction mixture was cooled to ambient temperature.

Cautiously and with stirring, 80 grams solid sodium bicarbonate were added until gas evolution ceased and pH 9 was achieved. The alkaline solution was then extracted with methylene chloride (2 × 200 ml), and the combined methylene chloride layers were washed successively with deionized water (100 ml) and brine (200 ml), then dried over sodium sulfate. Chromatography on silica gel, eluting with an eluent gradient (15/85, 20/80, 30/70 - ethyl acetate/ methylene chloride), afforded the spiro lactone which was crystallized from ethyl acetate/ methylene chloride to afford the title compound (1.37 g, 9.3%) as off-white plates (mp 546–548 K, 273–275 °C, lit (Cookson et al., 1968): 560–562 K (287–289 °C).

Refinement top

The structure exhibits large regions filled with heavily disordered solvent molecules. No obvious solvent model was discernible from the difference density Fourier maps and data collection at 100 K did not improve of the data quality (the crystal quality suffers upon cooling and the disorder of the solvent persists). Thus a correction for the diffuse solvent was applied using the Squeeze algorithm implemented in PLATON (Spek, 2007). The void volume was calculated by PLATON as 598.7 Å3, the number of electrons it corrected for as 52.0.

Hydrogen atoms were added in calculated positions with C—H distances of 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively, and were refined with Uiso(H) = xUeq(C) (x = 1.2 for C—H and 1.5 for CH3). Methyl hydrogen atoms were allowed to rotate to best fit the experimental electron density.

The s.u. values of the cell parameters are taken from the software recognizing that the values are unreasonably small (Herbstein, 2000).

Structure description top

We are interested in apex-modified cyclotriveratrylene (CTV) derivatives and recently reported the isolation and conformational crown/saddle dynamics of CTV mono-oxime (Lutz, French et al., 2007). In the course of studying the Beckmann rearrangement of the CTV oxime, we isolated and reported the structure of a helical pentacycle formed via a tandem Beckmann and subsequent electrophilic addition sequence (Lutz, Zeller et al., 2007).

Cookson et al. (1968) reported the isolation of a CTV derivative from oxidation of CTV with sodium dichromate in acetic acid that they thought was the CTV triketone. The triketone, however, has in fact never been isolated, but the compound isolated by Cookson was shortly thereafter identified using UV– and NMR-spectroscopic methods (Baldwin & Kelly, 1968) to have a spiro structure, produced via acid-catalyzed electrophilic addition and rearrangement of the putative triketone under the acidic conditions Fig. 1. Both this spiro compound, the crystal structure of which will be descibed here, and the tandem Beckman/electrophilic addition products (Lutz, Zeller & Becker, 2007) are formed via trans-annular electrophilic addition to somehow related cationic intermediates. Interestingly, the spiro derivative is a structural analogue to the cyclized lactone form of the exceedingly useful fluorescent spirolactone fluorescein. The title compound contains a diaryl ketone rather than the diaryl ether of fluorescein.

The title compound crystallizes with large regions filled with heavily disordered solvent molecules. The voids make up 598.7 Å3 or 21.5% of the unit cell volume and stretch as infinite channels along the direction [101] with y = 0.5 (Fig. 4). 1H NMR spectra of dissolved crystals indicated the presence of both methylene chloride and ethyl acetate, the solvents the crystals were grown from. However, with the data collected at room temperature, no obvious solvent model was discernible from difference maps, and data collection at 100 K did not improve the data quality: even at a slow cooling rates the crystal quality suffered upon cooling resulting in significantely larger R values, and the disorder of the diffuse solvent molecules persists even at 100 K. Thus a correction for the diffuse solvent was applied using the Squeeze algorithm implemented in PLATON (Spek, 2003, 2007). The number of electrons within the voids was estimated by PLATON to be 52, indicating that the voids are only partially filled with solvent.

The anthrone and isobenzofuranone ring systems, Fig. 2, are both essentially planar with r.m.s. deviations from the mean square planes of only 0.12 and 0.01 Å, respectively, and they are basically perpendicular to each other with an angle of 89.90 (2)° between them. Also the methoxy groups are in plane with the ring systems they are bonded to. The largest deviation is observed for C17 which is located 0.321 (3) Å outside of the plane of the anthrone ring sytem.

The packing of the structure is partially stabilized by a range of weak C—H···O hydrogen bonds formed by methyl H atoms C15B and C17b and by the aromatic hydrogen atoms H20 and H23 to both keto and methoxy oxygen atoms. There are also three C—H···Cπ-arom interactions with H···centroid distances that could be interpreted as stabilizing, but two of these are intramolecular interactions forced by the spiro-geometry of the molecule (C2—H2···Cg1 and C12—H12···Cg1), and only the interaction C28—H28B···Cg2 may be seen as truely positively contributing to the packing interactions (Cg1 and Cg2 define the ring centroids of O9 C14 C19 C24 C25 and C8 C9 C10 C11 C12 C13, respectively) Fig. 3 & 4. See the hydrogen bonding table for metric parameters of the C—H···O and C—H···π interactions. No significant ππ interactions are present in the structure of the title compound.

Cookson et al. (1968) described the first synthesis of the title molecule. Baldwin & Kelly (1968) subsequently reported its correct identification as a spiro compound by UV and NMR methods. Lutz, French et al. (2007) and Lutz, Zeller & Becker (2007) give background information on other compounds derived from cyclotriveratrylene. PLATON (Spek, 2003, 2007) was used to correct the data set for diffuse solvent effects. For related literature, see Herbstein (2000).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. Synthesis of the title compound.
[Figure 2] Fig. 2. Thermal elliposoid representation of the title compound with the atomic numbering scheme. Thermal displacement parameters are at the 50% probabilty level.
[Figure 3] Fig. 3. Packing diagram of the title compound with 50% probability thermal ellipsoids. Blue dashed lines indicate close C—H···O and C—H···Cπ-arom interactions. View along the b axis.
[Figure 4] Fig. 4. Extended packing diagram (50% probability thermal ellipsoids) showing the large solvent filled channels stretching along the a-c diagonal. View is along [101].
2,3,5',6,6',7-Hexamethoxy-3'H,10H-spiro[anthracene-9,1'-isobenzofuran]- 3',10-dione top
Crystal data top
C27H24O9F(000) = 1032
Mr = 492.46Dx = 1.173 Mg m3
Monoclinic, P2/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yacCell parameters from 7450 reflections
a = 13.1371 (7) Åθ = 2.8–30.5°
b = 13.3281 (7) ŵ = 0.09 mm1
c = 16.6587 (9) ÅT = 298 K
β = 107.043 (1)°Block, colourless
V = 2788.7 (3) Å30.48 × 0.42 × 0.27 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer
6913 independent reflections
Radiation source: fine-focus sealed tube5390 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ω scansθmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
h = 1717
Tmin = 0.950, Tmax = 0.976k = 1717
28518 measured reflectionsl = 2222
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.179H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.1077P)2 + 0.2344P]
where P = (Fo2 + 2Fc2)/3
6913 reflections(Δ/σ)max < 0.001
333 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C27H24O9V = 2788.7 (3) Å3
Mr = 492.46Z = 4
Monoclinic, P2/nMo Kα radiation
a = 13.1371 (7) ŵ = 0.09 mm1
b = 13.3281 (7) ÅT = 298 K
c = 16.6587 (9) Å0.48 × 0.42 × 0.27 mm
β = 107.043 (1)°
Data collection top
Bruker SMART APEX CCD
diffractometer
6913 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
5390 reflections with I > 2σ(I)
Tmin = 0.950, Tmax = 0.976Rint = 0.033
28518 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.179H-atom parameters constrained
S = 1.08Δρmax = 0.27 e Å3
6913 reflectionsΔρmin = 0.19 e Å3
333 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.34942 (10)0.82325 (10)0.93258 (8)0.0422 (3)
C20.35260 (12)0.72354 (12)0.95840 (10)0.0528 (3)
H20.34070.70831.00940.063*
C30.37327 (14)0.64693 (12)0.90925 (11)0.0599 (4)
C40.38934 (14)0.67010 (13)0.83124 (11)0.0603 (4)
C50.38604 (13)0.76802 (12)0.80559 (10)0.0541 (4)
H50.39640.78310.75400.065*
C60.36720 (11)0.84590 (11)0.85632 (9)0.0449 (3)
C70.36996 (11)0.95007 (11)0.82749 (8)0.0455 (3)
C80.35822 (10)1.03066 (10)0.88464 (8)0.0412 (3)
C90.36988 (11)1.12998 (11)0.86106 (9)0.0466 (3)
H90.38151.14310.80960.056*
C100.36419 (11)1.20803 (11)0.91344 (9)0.0485 (3)
C110.34511 (11)1.18716 (11)0.99085 (9)0.0477 (3)
C120.33219 (11)1.08972 (11)1.01351 (8)0.0463 (3)
H120.31841.07681.06420.056*
C130.33963 (9)1.00990 (10)0.96077 (8)0.0398 (3)
C140.32111 (10)0.90436 (10)0.98646 (7)0.0388 (3)
C150.3615 (2)0.52032 (15)1.00657 (16)0.0937 (8)
H15A0.41430.55241.05160.140*
H15B0.36800.44881.01310.140*
H15C0.29180.54071.00770.140*
C160.4172 (3)0.6076 (2)0.70589 (15)0.1035 (8)
H16A0.35420.64090.67240.155*
H16B0.42540.54490.68010.155*
H16C0.47810.64920.71000.155*
C170.40321 (18)1.33035 (15)0.82300 (13)0.0754 (5)
H17A0.46931.29820.82510.113*
H17B0.41081.40170.81920.113*
H17C0.34851.30690.77470.113*
C180.3161 (2)1.25420 (16)1.11426 (12)0.0790 (6)
H18A0.24821.22181.10400.119*
H18B0.31451.31771.14100.119*
H18C0.37041.21271.15010.119*
C190.20836 (10)0.89023 (10)0.99188 (7)0.0378 (3)
C200.11237 (10)0.89863 (10)0.92945 (8)0.0421 (3)
H200.10960.91580.87470.050*
C210.02056 (10)0.88043 (12)0.95190 (8)0.0482 (3)
C220.02465 (11)0.85366 (14)1.03585 (9)0.0543 (4)
C230.12101 (11)0.84651 (13)1.09667 (9)0.0519 (4)
H230.12510.82961.15170.062*
C240.21265 (10)0.86565 (11)1.07280 (8)0.0425 (3)
C250.32414 (11)0.86351 (12)1.12375 (8)0.0464 (3)
O90.38586 (7)0.88831 (8)1.07356 (6)0.0457 (2)
C270.08961 (15)0.9150 (2)0.81444 (11)0.0907 (8)
H27A0.05490.97830.81420.136*
H27B0.16370.92100.78390.136*
H27C0.05720.86500.78830.136*
C280.07232 (16)0.8096 (3)1.13055 (13)0.1115 (11)
H28A0.03530.74711.14580.167*
H28B0.14450.80231.13180.167*
H28C0.03760.86071.16960.167*
O10.37672 (14)0.54860 (10)0.92837 (10)0.0835 (4)
O20.40807 (15)0.58972 (11)0.78676 (10)0.0886 (5)
O30.38453 (11)0.96868 (9)0.75960 (7)0.0650 (3)
O40.37502 (11)1.30698 (9)0.89689 (8)0.0662 (3)
O50.33848 (11)1.26936 (9)1.03752 (7)0.0656 (3)
O60.07941 (8)0.88615 (12)0.89859 (7)0.0694 (4)
O70.07162 (8)0.83723 (14)1.04795 (7)0.0807 (5)
O80.36383 (9)0.84470 (11)1.19671 (6)0.0683 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0388 (6)0.0497 (7)0.0418 (6)0.0019 (5)0.0176 (5)0.0031 (5)
C20.0618 (9)0.0523 (8)0.0515 (8)0.0030 (6)0.0279 (7)0.0017 (6)
C30.0726 (10)0.0490 (8)0.0658 (10)0.0076 (7)0.0324 (8)0.0004 (7)
C40.0730 (10)0.0542 (9)0.0618 (9)0.0076 (7)0.0322 (8)0.0077 (7)
C50.0631 (9)0.0573 (8)0.0501 (8)0.0044 (7)0.0294 (7)0.0046 (6)
C60.0442 (7)0.0522 (7)0.0437 (7)0.0016 (5)0.0211 (5)0.0027 (6)
C70.0479 (7)0.0534 (8)0.0412 (6)0.0012 (6)0.0225 (6)0.0031 (5)
C80.0372 (6)0.0504 (7)0.0395 (6)0.0017 (5)0.0166 (5)0.0022 (5)
C90.0474 (7)0.0543 (8)0.0427 (7)0.0017 (6)0.0203 (6)0.0023 (6)
C100.0486 (7)0.0477 (7)0.0529 (8)0.0026 (6)0.0206 (6)0.0003 (6)
C110.0486 (7)0.0503 (7)0.0470 (7)0.0038 (6)0.0184 (6)0.0071 (6)
C120.0494 (7)0.0540 (8)0.0390 (6)0.0036 (6)0.0186 (5)0.0043 (5)
C130.0347 (6)0.0490 (7)0.0377 (6)0.0030 (5)0.0136 (5)0.0017 (5)
C140.0364 (6)0.0487 (7)0.0333 (6)0.0009 (5)0.0131 (5)0.0005 (5)
C150.155 (2)0.0540 (11)0.0931 (15)0.0093 (12)0.0686 (16)0.0100 (10)
C160.154 (2)0.0929 (16)0.0772 (14)0.0276 (16)0.0558 (16)0.0206 (12)
C170.1085 (16)0.0566 (10)0.0755 (12)0.0067 (9)0.0496 (12)0.0078 (8)
C180.1155 (16)0.0720 (11)0.0632 (11)0.0147 (11)0.0475 (11)0.0201 (9)
C190.0378 (6)0.0449 (6)0.0344 (6)0.0002 (5)0.0163 (5)0.0009 (5)
C200.0420 (6)0.0539 (7)0.0325 (6)0.0007 (5)0.0144 (5)0.0016 (5)
C210.0371 (6)0.0706 (9)0.0367 (6)0.0013 (6)0.0104 (5)0.0034 (6)
C220.0404 (7)0.0850 (11)0.0418 (7)0.0022 (7)0.0189 (6)0.0072 (7)
C230.0443 (7)0.0804 (10)0.0347 (6)0.0013 (7)0.0176 (5)0.0077 (6)
C240.0389 (6)0.0567 (7)0.0335 (6)0.0024 (5)0.0128 (5)0.0012 (5)
C250.0430 (7)0.0618 (8)0.0359 (6)0.0016 (6)0.0138 (5)0.0004 (6)
O90.0370 (5)0.0627 (6)0.0371 (5)0.0021 (4)0.0104 (4)0.0018 (4)
C270.0496 (9)0.177 (2)0.0399 (8)0.0076 (12)0.0042 (7)0.0125 (11)
C280.0528 (10)0.232 (3)0.0572 (11)0.0124 (14)0.0275 (8)0.0384 (16)
O10.1349 (13)0.0486 (7)0.0837 (9)0.0129 (7)0.0581 (9)0.0029 (6)
O20.1426 (14)0.0599 (8)0.0828 (9)0.0164 (8)0.0632 (9)0.0102 (7)
O30.0956 (9)0.0632 (7)0.0502 (6)0.0026 (6)0.0431 (6)0.0024 (5)
O40.0938 (9)0.0494 (6)0.0679 (7)0.0064 (6)0.0430 (7)0.0004 (5)
O50.0939 (9)0.0524 (6)0.0597 (7)0.0077 (6)0.0368 (6)0.0113 (5)
O60.0382 (5)0.1238 (11)0.0437 (6)0.0032 (6)0.0083 (4)0.0122 (6)
O70.0392 (6)0.1572 (14)0.0492 (6)0.0051 (7)0.0185 (5)0.0239 (7)
O80.0516 (6)0.1142 (10)0.0359 (5)0.0038 (6)0.0080 (4)0.0105 (6)
Geometric parameters (Å, º) top
C1—C61.3905 (18)C16—H16A0.9600
C1—C21.394 (2)C16—H16B0.9600
C1—C141.5193 (18)C16—H16C0.9600
C2—C31.385 (2)C17—O41.420 (2)
C2—H20.9300C17—H17A0.9600
C3—O11.346 (2)C17—H17B0.9600
C3—C41.411 (2)C17—H17C0.9600
C4—O21.365 (2)C18—O51.408 (2)
C4—C51.370 (2)C18—H18A0.9600
C5—C61.4055 (19)C18—H18B0.9600
C5—H50.9300C18—H18C0.9600
C6—C71.473 (2)C19—C241.3723 (17)
C7—O31.2265 (16)C19—C201.3840 (18)
C7—C81.4731 (18)C20—C211.3848 (18)
C8—C131.3878 (17)C20—H200.9300
C8—C91.402 (2)C21—O61.3549 (17)
C9—C101.374 (2)C21—C221.4291 (19)
C9—H90.9300C22—O71.3554 (17)
C10—O41.3633 (19)C22—C231.373 (2)
C10—C111.412 (2)C23—C241.3976 (18)
C11—O51.3608 (17)C23—H230.9300
C11—C121.377 (2)C24—C251.4620 (19)
C12—C131.4012 (19)C25—O81.2002 (17)
C12—H120.9300C25—O91.3649 (16)
C13—C141.5107 (19)C27—O61.421 (2)
C14—O91.4667 (15)C27—H27A0.9600
C14—C191.5218 (16)C27—H27B0.9600
C15—O11.426 (3)C27—H27C0.9600
C15—H15A0.9600C28—O71.427 (2)
C15—H15B0.9600C28—H28A0.9600
C15—H15C0.9600C28—H28B0.9600
C16—O21.407 (3)C28—H28C0.9600
C6—C1—C2119.41 (12)H16A—C16—H16C109.5
C6—C1—C14121.41 (12)H16B—C16—H16C109.5
C2—C1—C14119.11 (12)O4—C17—H17A109.5
C3—C2—C1120.93 (14)O4—C17—H17B109.5
C3—C2—H2119.5H17A—C17—H17B109.5
C1—C2—H2119.5O4—C17—H17C109.5
O1—C3—C2125.22 (15)H17A—C17—H17C109.5
O1—C3—C4115.30 (14)H17B—C17—H17C109.5
C2—C3—C4119.45 (15)O5—C18—H18A109.5
O2—C4—C5124.92 (15)O5—C18—H18B109.5
O2—C4—C3115.32 (16)H18A—C18—H18B109.5
C5—C4—C3119.76 (14)O5—C18—H18C109.5
C4—C5—C6120.73 (14)H18A—C18—H18C109.5
C4—C5—H5119.6H18B—C18—H18C109.5
C6—C5—H5119.6C24—C19—C20121.57 (11)
C1—C6—C5119.70 (14)C24—C19—C14109.11 (11)
C1—C6—C7121.95 (12)C20—C19—C14129.32 (11)
C5—C6—C7118.33 (12)C19—C20—C21117.18 (11)
O3—C7—C6121.11 (13)C19—C20—H20121.4
O3—C7—C8121.51 (13)C21—C20—H20121.4
C6—C7—C8117.35 (11)O6—C21—C20124.53 (12)
C13—C8—C9120.48 (12)O6—C21—C22113.99 (12)
C13—C8—C7121.67 (12)C20—C21—C22121.48 (12)
C9—C8—C7117.82 (12)O7—C22—C23125.28 (13)
C10—C9—C8120.42 (12)O7—C22—C21114.63 (12)
C10—C9—H9119.8C23—C22—C21120.09 (12)
C8—C9—H9119.8C22—C23—C24117.53 (12)
O4—C10—C9125.15 (13)C22—C23—H23121.2
O4—C10—C11115.61 (13)C24—C23—H23121.2
C9—C10—C11119.23 (13)C19—C24—C23122.15 (12)
O5—C11—C12124.68 (13)C19—C24—C25108.70 (11)
O5—C11—C10114.93 (13)C23—C24—C25129.15 (12)
C12—C11—C10120.36 (13)O8—C25—O9120.74 (13)
C11—C12—C13120.49 (13)O8—C25—C24130.98 (13)
C11—C12—H12119.8O9—C25—C24108.28 (11)
C13—C12—H12119.8C25—O9—C14111.40 (10)
C8—C13—C12119.01 (12)O6—C27—H27A109.5
C8—C13—C14122.05 (11)O6—C27—H27B109.5
C12—C13—C14118.86 (11)H27A—C27—H27B109.5
O9—C14—C13108.73 (10)O6—C27—H27C109.5
O9—C14—C1108.02 (10)H27A—C27—H27C109.5
C13—C14—C1114.04 (10)H27B—C27—H27C109.5
O9—C14—C19102.45 (9)O7—C28—H28A109.5
C13—C14—C19111.87 (10)O7—C28—H28B109.5
C1—C14—C19110.98 (10)H28A—C28—H28B109.5
O1—C15—H15A109.5O7—C28—H28C109.5
O1—C15—H15B109.5H28A—C28—H28C109.5
H15A—C15—H15B109.5H28B—C28—H28C109.5
O1—C15—H15C109.5C3—O1—C15118.01 (14)
H15A—C15—H15C109.5C4—O2—C16117.77 (16)
H15B—C15—H15C109.5C10—O4—C17117.17 (13)
O2—C16—H16A109.5C11—O5—C18117.95 (13)
O2—C16—H16B109.5C21—O6—C27117.04 (12)
H16A—C16—H16B109.5C22—O7—C28117.07 (13)
O2—C16—H16C109.5
C6—C1—C2—C30.0 (2)C6—C1—C14—C1313.64 (17)
C14—C1—C2—C3177.03 (14)C2—C1—C14—C13169.44 (12)
C1—C2—C3—O1179.18 (17)C6—C1—C14—C19113.80 (13)
C1—C2—C3—C41.2 (3)C2—C1—C14—C1963.12 (16)
O1—C3—C4—O21.1 (3)O9—C14—C19—C241.95 (14)
C2—C3—C4—O2179.32 (17)C13—C14—C19—C24118.25 (12)
O1—C3—C4—C5179.22 (17)C1—C14—C19—C24113.14 (12)
C2—C3—C4—C51.0 (3)O9—C14—C19—C20178.28 (13)
O2—C4—C5—C6179.35 (17)C13—C14—C19—C2061.98 (17)
C3—C4—C5—C60.2 (3)C1—C14—C19—C2066.64 (18)
C2—C1—C6—C51.2 (2)C24—C19—C20—C210.5 (2)
C14—C1—C6—C5175.67 (13)C14—C19—C20—C21179.28 (14)
C2—C1—C6—C7177.02 (13)C19—C20—C21—O6179.53 (15)
C14—C1—C6—C76.1 (2)C19—C20—C21—C220.3 (2)
C4—C5—C6—C11.4 (2)O6—C21—C22—O70.8 (2)
C4—C5—C6—C7176.93 (15)C20—C21—C22—O7179.36 (16)
C1—C6—C7—O3179.16 (14)O6—C21—C22—C23179.11 (16)
C5—C6—C7—O32.6 (2)C20—C21—C22—C230.7 (3)
C1—C6—C7—C82.9 (2)O7—C22—C23—C24179.71 (17)
C5—C6—C7—C8175.40 (13)C21—C22—C23—C240.4 (3)
O3—C7—C8—C13178.71 (13)C20—C19—C24—C230.8 (2)
C6—C7—C8—C133.34 (19)C14—C19—C24—C23178.98 (13)
O3—C7—C8—C93.3 (2)C20—C19—C24—C25179.50 (13)
C6—C7—C8—C9174.62 (12)C14—C19—C24—C250.70 (15)
C13—C8—C9—C100.7 (2)C22—C23—C24—C190.4 (2)
C7—C8—C9—C10177.28 (13)C22—C23—C24—C25179.97 (16)
C8—C9—C10—O4179.59 (14)C19—C24—C25—O8179.15 (17)
C8—C9—C10—C110.8 (2)C23—C24—C25—O80.5 (3)
O4—C10—C11—O51.0 (2)C19—C24—C25—O90.96 (16)
C9—C10—C11—O5178.61 (13)C23—C24—C25—O9179.39 (15)
O4—C10—C11—C12179.55 (13)O8—C25—O9—C14177.79 (14)
C9—C10—C11—C120.1 (2)C24—C25—O9—C142.30 (16)
O5—C11—C12—C13179.46 (13)C13—C14—O9—C25121.13 (12)
C10—C11—C12—C131.1 (2)C1—C14—O9—C25114.62 (12)
C9—C8—C13—C120.30 (19)C19—C14—O9—C252.59 (14)
C7—C8—C13—C12178.21 (12)C2—C3—O1—C152.2 (3)
C9—C8—C13—C14176.85 (12)C4—C3—O1—C15179.8 (2)
C7—C8—C13—C145.25 (19)C5—C4—O2—C164.8 (3)
C11—C12—C13—C81.2 (2)C3—C4—O2—C16175.6 (2)
C11—C12—C13—C14177.86 (12)C9—C10—O4—C175.6 (2)
C8—C13—C14—O9133.87 (12)C11—C10—O4—C17174.81 (16)
C12—C13—C14—O949.58 (15)C12—C11—O5—C180.4 (2)
C8—C13—C14—C113.27 (17)C10—C11—O5—C18177.99 (16)
C12—C13—C14—C1170.18 (11)C20—C21—O6—C271.4 (3)
C8—C13—C14—C19113.70 (13)C22—C21—O6—C27178.44 (19)
C12—C13—C14—C1962.85 (15)C23—C22—O7—C280.5 (3)
C6—C1—C14—O9134.63 (12)C21—C22—O7—C28179.6 (2)
C2—C1—C14—O948.45 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C23—H23···O8i0.932.503.3892 (17)161
C20—H20···O3ii0.932.373.2965 (16)175
C17—H17B···O2iii0.962.563.513 (2)171
C15—H15B···O5iv0.962.483.411 (2)165
C2—H2···Cg10.932.562.8621 (17)100
C12—H12···Cg10.932.622.9142 (16)99
C28—H28B···Cg2v0.962.883.671 (2)141
Symmetry codes: (i) x+1/2, y, z+5/2; (ii) x+1/2, y, z+3/2; (iii) x, y+1, z; (iv) x, y1, z; (v) x, y+2, z+2.

Experimental details

Crystal data
Chemical formulaC27H24O9
Mr492.46
Crystal system, space groupMonoclinic, P2/n
Temperature (K)298
a, b, c (Å)13.1371 (7), 13.3281 (7), 16.6587 (9)
β (°) 107.043 (1)
V3)2788.7 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.48 × 0.42 × 0.27
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2007)
Tmin, Tmax0.950, 0.976
No. of measured, independent and
observed [I > 2σ(I)] reflections
28518, 6913, 5390
Rint0.033
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.179, 1.08
No. of reflections6913
No. of parameters333
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.19

Computer programs: SMART (Bruker, 2002), SAINT-Plus (Bruker, 2003), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C23—H23···O8i0.932.503.3892 (17)161.3
C20—H20···O3ii0.932.373.2965 (16)175.0
C17—H17B···O2iii0.962.563.513 (2)170.9
C15—H15B···O5iv0.962.483.411 (2)164.6
C2—H2···Cg10.932.562.8621 (17)100
C12—H12···Cg10.932.622.9142 (16)99
C28—H28B···Cg2v0.962.883.671 (2)141
Symmetry codes: (i) x+1/2, y, z+5/2; (ii) x+1/2, y, z+3/2; (iii) x, y+1, z; (iv) x, y1, z; (v) x, y+2, z+2.
 

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