Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051136/sj2373sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051136/sj2373Isup2.hkl |
CCDC reference: 667411
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (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
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).
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).
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).
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 π–π 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).
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).
C27H24O9 | F(000) = 1032 |
Mr = 492.46 | Dx = 1.173 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 7450 reflections |
a = 13.1371 (7) Å | θ = 2.8–30.5° |
b = 13.3281 (7) Å | µ = 0.09 mm−1 |
c = 16.6587 (9) Å | T = 298 K |
β = 107.043 (1)° | Block, colourless |
V = 2788.7 (3) Å3 | 0.48 × 0.42 × 0.27 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 6913 independent reflections |
Radiation source: fine-focus sealed tube | 5390 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 28.3°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | h = −17→17 |
Tmin = 0.950, Tmax = 0.976 | k = −17→17 |
28518 measured reflections | l = −22→22 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.179 | H-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 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C27H24O9 | V = 2788.7 (3) Å3 |
Mr = 492.46 | Z = 4 |
Monoclinic, P2/n | Mo Kα radiation |
a = 13.1371 (7) Å | µ = 0.09 mm−1 |
b = 13.3281 (7) Å | T = 298 K |
c = 16.6587 (9) Å | 0.48 × 0.42 × 0.27 mm |
β = 107.043 (1)° |
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 = 0.976 | Rint = 0.033 |
28518 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.179 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.27 e Å−3 |
6913 reflections | Δρmin = −0.19 e Å−3 |
333 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.34942 (10) | 0.82325 (10) | 0.93258 (8) | 0.0422 (3) | |
C2 | 0.35260 (12) | 0.72354 (12) | 0.95840 (10) | 0.0528 (3) | |
H2 | 0.3407 | 0.7083 | 1.0094 | 0.063* | |
C3 | 0.37327 (14) | 0.64693 (12) | 0.90925 (11) | 0.0599 (4) | |
C4 | 0.38934 (14) | 0.67010 (13) | 0.83124 (11) | 0.0603 (4) | |
C5 | 0.38604 (13) | 0.76802 (12) | 0.80559 (10) | 0.0541 (4) | |
H5 | 0.3964 | 0.7831 | 0.7540 | 0.065* | |
C6 | 0.36720 (11) | 0.84590 (11) | 0.85632 (9) | 0.0449 (3) | |
C7 | 0.36996 (11) | 0.95007 (11) | 0.82749 (8) | 0.0455 (3) | |
C8 | 0.35822 (10) | 1.03066 (10) | 0.88464 (8) | 0.0412 (3) | |
C9 | 0.36988 (11) | 1.12998 (11) | 0.86106 (9) | 0.0466 (3) | |
H9 | 0.3815 | 1.1431 | 0.8096 | 0.056* | |
C10 | 0.36419 (11) | 1.20803 (11) | 0.91344 (9) | 0.0485 (3) | |
C11 | 0.34511 (11) | 1.18716 (11) | 0.99085 (9) | 0.0477 (3) | |
C12 | 0.33219 (11) | 1.08972 (11) | 1.01351 (8) | 0.0463 (3) | |
H12 | 0.3184 | 1.0768 | 1.0642 | 0.056* | |
C13 | 0.33963 (9) | 1.00990 (10) | 0.96077 (8) | 0.0398 (3) | |
C14 | 0.32111 (10) | 0.90436 (10) | 0.98646 (7) | 0.0388 (3) | |
C15 | 0.3615 (2) | 0.52032 (15) | 1.00657 (16) | 0.0937 (8) | |
H15A | 0.4143 | 0.5524 | 1.0516 | 0.140* | |
H15B | 0.3680 | 0.4488 | 1.0131 | 0.140* | |
H15C | 0.2918 | 0.5407 | 1.0077 | 0.140* | |
C16 | 0.4172 (3) | 0.6076 (2) | 0.70589 (15) | 0.1035 (8) | |
H16A | 0.3542 | 0.6409 | 0.6724 | 0.155* | |
H16B | 0.4254 | 0.5449 | 0.6801 | 0.155* | |
H16C | 0.4781 | 0.6492 | 0.7100 | 0.155* | |
C17 | 0.40321 (18) | 1.33035 (15) | 0.82300 (13) | 0.0754 (5) | |
H17A | 0.4693 | 1.2982 | 0.8251 | 0.113* | |
H17B | 0.4108 | 1.4017 | 0.8192 | 0.113* | |
H17C | 0.3485 | 1.3069 | 0.7747 | 0.113* | |
C18 | 0.3161 (2) | 1.25420 (16) | 1.11426 (12) | 0.0790 (6) | |
H18A | 0.2482 | 1.2218 | 1.1040 | 0.119* | |
H18B | 0.3145 | 1.3177 | 1.1410 | 0.119* | |
H18C | 0.3704 | 1.2127 | 1.1501 | 0.119* | |
C19 | 0.20836 (10) | 0.89023 (10) | 0.99188 (7) | 0.0378 (3) | |
C20 | 0.11237 (10) | 0.89863 (10) | 0.92945 (8) | 0.0421 (3) | |
H20 | 0.1096 | 0.9158 | 0.8747 | 0.050* | |
C21 | 0.02056 (10) | 0.88043 (12) | 0.95190 (8) | 0.0482 (3) | |
C22 | 0.02465 (11) | 0.85366 (14) | 1.03585 (9) | 0.0543 (4) | |
C23 | 0.12101 (11) | 0.84651 (13) | 1.09667 (9) | 0.0519 (4) | |
H23 | 0.1251 | 0.8296 | 1.1517 | 0.062* | |
C24 | 0.21265 (10) | 0.86565 (11) | 1.07280 (8) | 0.0425 (3) | |
C25 | 0.32414 (11) | 0.86351 (12) | 1.12375 (8) | 0.0464 (3) | |
O9 | 0.38586 (7) | 0.88831 (8) | 1.07356 (6) | 0.0457 (2) | |
C27 | −0.08961 (15) | 0.9150 (2) | 0.81444 (11) | 0.0907 (8) | |
H27A | −0.0549 | 0.9783 | 0.8142 | 0.136* | |
H27B | −0.1637 | 0.9210 | 0.7839 | 0.136* | |
H27C | −0.0572 | 0.8650 | 0.7883 | 0.136* | |
C28 | −0.07232 (16) | 0.8096 (3) | 1.13055 (13) | 0.1115 (11) | |
H28A | −0.0353 | 0.7471 | 1.1458 | 0.167* | |
H28B | −0.1445 | 0.8023 | 1.1318 | 0.167* | |
H28C | −0.0376 | 0.8607 | 1.1696 | 0.167* | |
O1 | 0.37672 (14) | 0.54860 (10) | 0.92837 (10) | 0.0835 (4) | |
O2 | 0.40807 (15) | 0.58972 (11) | 0.78676 (10) | 0.0886 (5) | |
O3 | 0.38453 (11) | 0.96868 (9) | 0.75960 (7) | 0.0650 (3) | |
O4 | 0.37502 (11) | 1.30698 (9) | 0.89689 (8) | 0.0662 (3) | |
O5 | 0.33848 (11) | 1.26936 (9) | 1.03752 (7) | 0.0656 (3) | |
O6 | −0.07941 (8) | 0.88615 (12) | 0.89859 (7) | 0.0694 (4) | |
O7 | −0.07162 (8) | 0.83723 (14) | 1.04795 (7) | 0.0807 (5) | |
O8 | 0.36383 (9) | 0.84470 (11) | 1.19671 (6) | 0.0683 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0388 (6) | 0.0497 (7) | 0.0418 (6) | 0.0019 (5) | 0.0176 (5) | −0.0031 (5) |
C2 | 0.0618 (9) | 0.0523 (8) | 0.0515 (8) | 0.0030 (6) | 0.0279 (7) | 0.0017 (6) |
C3 | 0.0726 (10) | 0.0490 (8) | 0.0658 (10) | 0.0076 (7) | 0.0324 (8) | 0.0004 (7) |
C4 | 0.0730 (10) | 0.0542 (9) | 0.0618 (9) | 0.0076 (7) | 0.0322 (8) | −0.0077 (7) |
C5 | 0.0631 (9) | 0.0573 (8) | 0.0501 (8) | 0.0044 (7) | 0.0294 (7) | −0.0046 (6) |
C6 | 0.0442 (7) | 0.0522 (7) | 0.0437 (7) | 0.0016 (5) | 0.0211 (5) | −0.0027 (6) |
C7 | 0.0479 (7) | 0.0534 (8) | 0.0412 (6) | −0.0012 (6) | 0.0225 (6) | −0.0031 (5) |
C8 | 0.0372 (6) | 0.0504 (7) | 0.0395 (6) | −0.0017 (5) | 0.0166 (5) | −0.0022 (5) |
C9 | 0.0474 (7) | 0.0543 (8) | 0.0427 (7) | −0.0017 (6) | 0.0203 (6) | 0.0023 (6) |
C10 | 0.0486 (7) | 0.0477 (7) | 0.0529 (8) | −0.0026 (6) | 0.0206 (6) | 0.0003 (6) |
C11 | 0.0486 (7) | 0.0503 (7) | 0.0470 (7) | −0.0038 (6) | 0.0184 (6) | −0.0071 (6) |
C12 | 0.0494 (7) | 0.0540 (8) | 0.0390 (6) | −0.0036 (6) | 0.0186 (5) | −0.0043 (5) |
C13 | 0.0347 (6) | 0.0490 (7) | 0.0377 (6) | −0.0030 (5) | 0.0136 (5) | −0.0017 (5) |
C14 | 0.0364 (6) | 0.0487 (7) | 0.0333 (6) | 0.0009 (5) | 0.0131 (5) | −0.0005 (5) |
C15 | 0.155 (2) | 0.0540 (11) | 0.0931 (15) | 0.0093 (12) | 0.0686 (16) | 0.0100 (10) |
C16 | 0.154 (2) | 0.0929 (16) | 0.0772 (14) | 0.0276 (16) | 0.0558 (16) | −0.0206 (12) |
C17 | 0.1085 (16) | 0.0566 (10) | 0.0755 (12) | −0.0067 (9) | 0.0496 (12) | 0.0078 (8) |
C18 | 0.1155 (16) | 0.0720 (11) | 0.0632 (11) | −0.0147 (11) | 0.0475 (11) | −0.0201 (9) |
C19 | 0.0378 (6) | 0.0449 (6) | 0.0344 (6) | −0.0002 (5) | 0.0163 (5) | −0.0009 (5) |
C20 | 0.0420 (6) | 0.0539 (7) | 0.0325 (6) | 0.0007 (5) | 0.0144 (5) | 0.0016 (5) |
C21 | 0.0371 (6) | 0.0706 (9) | 0.0367 (6) | −0.0013 (6) | 0.0104 (5) | 0.0034 (6) |
C22 | 0.0404 (7) | 0.0850 (11) | 0.0418 (7) | −0.0022 (7) | 0.0189 (6) | 0.0072 (7) |
C23 | 0.0443 (7) | 0.0804 (10) | 0.0347 (6) | 0.0013 (7) | 0.0176 (5) | 0.0077 (6) |
C24 | 0.0389 (6) | 0.0567 (7) | 0.0335 (6) | 0.0024 (5) | 0.0128 (5) | 0.0012 (5) |
C25 | 0.0430 (7) | 0.0618 (8) | 0.0359 (6) | 0.0016 (6) | 0.0138 (5) | −0.0004 (6) |
O9 | 0.0370 (5) | 0.0627 (6) | 0.0371 (5) | 0.0021 (4) | 0.0104 (4) | 0.0018 (4) |
C27 | 0.0496 (9) | 0.177 (2) | 0.0399 (8) | 0.0076 (12) | 0.0042 (7) | 0.0125 (11) |
C28 | 0.0528 (10) | 0.232 (3) | 0.0572 (11) | −0.0124 (14) | 0.0275 (8) | 0.0384 (16) |
O1 | 0.1349 (13) | 0.0486 (7) | 0.0837 (9) | 0.0129 (7) | 0.0581 (9) | 0.0029 (6) |
O2 | 0.1426 (14) | 0.0599 (8) | 0.0828 (9) | 0.0164 (8) | 0.0632 (9) | −0.0102 (7) |
O3 | 0.0956 (9) | 0.0632 (7) | 0.0502 (6) | −0.0026 (6) | 0.0431 (6) | −0.0024 (5) |
O4 | 0.0938 (9) | 0.0494 (6) | 0.0679 (7) | −0.0064 (6) | 0.0430 (7) | −0.0004 (5) |
O5 | 0.0939 (9) | 0.0524 (6) | 0.0597 (7) | −0.0077 (6) | 0.0368 (6) | −0.0113 (5) |
O6 | 0.0382 (5) | 0.1238 (11) | 0.0437 (6) | −0.0032 (6) | 0.0083 (4) | 0.0122 (6) |
O7 | 0.0392 (6) | 0.1572 (14) | 0.0492 (6) | −0.0051 (7) | 0.0185 (5) | 0.0239 (7) |
O8 | 0.0516 (6) | 0.1142 (10) | 0.0359 (5) | 0.0038 (6) | 0.0080 (4) | 0.0105 (6) |
C1—C6 | 1.3905 (18) | C16—H16A | 0.9600 |
C1—C2 | 1.394 (2) | C16—H16B | 0.9600 |
C1—C14 | 1.5193 (18) | C16—H16C | 0.9600 |
C2—C3 | 1.385 (2) | C17—O4 | 1.420 (2) |
C2—H2 | 0.9300 | C17—H17A | 0.9600 |
C3—O1 | 1.346 (2) | C17—H17B | 0.9600 |
C3—C4 | 1.411 (2) | C17—H17C | 0.9600 |
C4—O2 | 1.365 (2) | C18—O5 | 1.408 (2) |
C4—C5 | 1.370 (2) | C18—H18A | 0.9600 |
C5—C6 | 1.4055 (19) | C18—H18B | 0.9600 |
C5—H5 | 0.9300 | C18—H18C | 0.9600 |
C6—C7 | 1.473 (2) | C19—C24 | 1.3723 (17) |
C7—O3 | 1.2265 (16) | C19—C20 | 1.3840 (18) |
C7—C8 | 1.4731 (18) | C20—C21 | 1.3848 (18) |
C8—C13 | 1.3878 (17) | C20—H20 | 0.9300 |
C8—C9 | 1.402 (2) | C21—O6 | 1.3549 (17) |
C9—C10 | 1.374 (2) | C21—C22 | 1.4291 (19) |
C9—H9 | 0.9300 | C22—O7 | 1.3554 (17) |
C10—O4 | 1.3633 (19) | C22—C23 | 1.373 (2) |
C10—C11 | 1.412 (2) | C23—C24 | 1.3976 (18) |
C11—O5 | 1.3608 (17) | C23—H23 | 0.9300 |
C11—C12 | 1.377 (2) | C24—C25 | 1.4620 (19) |
C12—C13 | 1.4012 (19) | C25—O8 | 1.2002 (17) |
C12—H12 | 0.9300 | C25—O9 | 1.3649 (16) |
C13—C14 | 1.5107 (19) | C27—O6 | 1.421 (2) |
C14—O9 | 1.4667 (15) | C27—H27A | 0.9600 |
C14—C19 | 1.5218 (16) | C27—H27B | 0.9600 |
C15—O1 | 1.426 (3) | C27—H27C | 0.9600 |
C15—H15A | 0.9600 | C28—O7 | 1.427 (2) |
C15—H15B | 0.9600 | C28—H28A | 0.9600 |
C15—H15C | 0.9600 | C28—H28B | 0.9600 |
C16—O2 | 1.407 (3) | C28—H28C | 0.9600 |
C6—C1—C2 | 119.41 (12) | H16A—C16—H16C | 109.5 |
C6—C1—C14 | 121.41 (12) | H16B—C16—H16C | 109.5 |
C2—C1—C14 | 119.11 (12) | O4—C17—H17A | 109.5 |
C3—C2—C1 | 120.93 (14) | O4—C17—H17B | 109.5 |
C3—C2—H2 | 119.5 | H17A—C17—H17B | 109.5 |
C1—C2—H2 | 119.5 | O4—C17—H17C | 109.5 |
O1—C3—C2 | 125.22 (15) | H17A—C17—H17C | 109.5 |
O1—C3—C4 | 115.30 (14) | H17B—C17—H17C | 109.5 |
C2—C3—C4 | 119.45 (15) | O5—C18—H18A | 109.5 |
O2—C4—C5 | 124.92 (15) | O5—C18—H18B | 109.5 |
O2—C4—C3 | 115.32 (16) | H18A—C18—H18B | 109.5 |
C5—C4—C3 | 119.76 (14) | O5—C18—H18C | 109.5 |
C4—C5—C6 | 120.73 (14) | H18A—C18—H18C | 109.5 |
C4—C5—H5 | 119.6 | H18B—C18—H18C | 109.5 |
C6—C5—H5 | 119.6 | C24—C19—C20 | 121.57 (11) |
C1—C6—C5 | 119.70 (14) | C24—C19—C14 | 109.11 (11) |
C1—C6—C7 | 121.95 (12) | C20—C19—C14 | 129.32 (11) |
C5—C6—C7 | 118.33 (12) | C19—C20—C21 | 117.18 (11) |
O3—C7—C6 | 121.11 (13) | C19—C20—H20 | 121.4 |
O3—C7—C8 | 121.51 (13) | C21—C20—H20 | 121.4 |
C6—C7—C8 | 117.35 (11) | O6—C21—C20 | 124.53 (12) |
C13—C8—C9 | 120.48 (12) | O6—C21—C22 | 113.99 (12) |
C13—C8—C7 | 121.67 (12) | C20—C21—C22 | 121.48 (12) |
C9—C8—C7 | 117.82 (12) | O7—C22—C23 | 125.28 (13) |
C10—C9—C8 | 120.42 (12) | O7—C22—C21 | 114.63 (12) |
C10—C9—H9 | 119.8 | C23—C22—C21 | 120.09 (12) |
C8—C9—H9 | 119.8 | C22—C23—C24 | 117.53 (12) |
O4—C10—C9 | 125.15 (13) | C22—C23—H23 | 121.2 |
O4—C10—C11 | 115.61 (13) | C24—C23—H23 | 121.2 |
C9—C10—C11 | 119.23 (13) | C19—C24—C23 | 122.15 (12) |
O5—C11—C12 | 124.68 (13) | C19—C24—C25 | 108.70 (11) |
O5—C11—C10 | 114.93 (13) | C23—C24—C25 | 129.15 (12) |
C12—C11—C10 | 120.36 (13) | O8—C25—O9 | 120.74 (13) |
C11—C12—C13 | 120.49 (13) | O8—C25—C24 | 130.98 (13) |
C11—C12—H12 | 119.8 | O9—C25—C24 | 108.28 (11) |
C13—C12—H12 | 119.8 | C25—O9—C14 | 111.40 (10) |
C8—C13—C12 | 119.01 (12) | O6—C27—H27A | 109.5 |
C8—C13—C14 | 122.05 (11) | O6—C27—H27B | 109.5 |
C12—C13—C14 | 118.86 (11) | H27A—C27—H27B | 109.5 |
O9—C14—C13 | 108.73 (10) | O6—C27—H27C | 109.5 |
O9—C14—C1 | 108.02 (10) | H27A—C27—H27C | 109.5 |
C13—C14—C1 | 114.04 (10) | H27B—C27—H27C | 109.5 |
O9—C14—C19 | 102.45 (9) | O7—C28—H28A | 109.5 |
C13—C14—C19 | 111.87 (10) | O7—C28—H28B | 109.5 |
C1—C14—C19 | 110.98 (10) | H28A—C28—H28B | 109.5 |
O1—C15—H15A | 109.5 | O7—C28—H28C | 109.5 |
O1—C15—H15B | 109.5 | H28A—C28—H28C | 109.5 |
H15A—C15—H15B | 109.5 | H28B—C28—H28C | 109.5 |
O1—C15—H15C | 109.5 | C3—O1—C15 | 118.01 (14) |
H15A—C15—H15C | 109.5 | C4—O2—C16 | 117.77 (16) |
H15B—C15—H15C | 109.5 | C10—O4—C17 | 117.17 (13) |
O2—C16—H16A | 109.5 | C11—O5—C18 | 117.95 (13) |
O2—C16—H16B | 109.5 | C21—O6—C27 | 117.04 (12) |
H16A—C16—H16B | 109.5 | C22—O7—C28 | 117.07 (13) |
O2—C16—H16C | 109.5 | ||
C6—C1—C2—C3 | 0.0 (2) | C6—C1—C14—C13 | −13.64 (17) |
C14—C1—C2—C3 | 177.03 (14) | C2—C1—C14—C13 | 169.44 (12) |
C1—C2—C3—O1 | −179.18 (17) | C6—C1—C14—C19 | 113.80 (13) |
C1—C2—C3—C4 | −1.2 (3) | C2—C1—C14—C19 | −63.12 (16) |
O1—C3—C4—O2 | −1.1 (3) | O9—C14—C19—C24 | −1.95 (14) |
C2—C3—C4—O2 | −179.32 (17) | C13—C14—C19—C24 | −118.25 (12) |
O1—C3—C4—C5 | 179.22 (17) | C1—C14—C19—C24 | 113.14 (12) |
C2—C3—C4—C5 | 1.0 (3) | O9—C14—C19—C20 | 178.28 (13) |
O2—C4—C5—C6 | −179.35 (17) | C13—C14—C19—C20 | 61.98 (17) |
C3—C4—C5—C6 | 0.2 (3) | C1—C14—C19—C20 | −66.64 (18) |
C2—C1—C6—C5 | 1.2 (2) | C24—C19—C20—C21 | −0.5 (2) |
C14—C1—C6—C5 | −175.67 (13) | C14—C19—C20—C21 | 179.28 (14) |
C2—C1—C6—C7 | −177.02 (13) | C19—C20—C21—O6 | 179.53 (15) |
C14—C1—C6—C7 | 6.1 (2) | C19—C20—C21—C22 | −0.3 (2) |
C4—C5—C6—C1 | −1.4 (2) | O6—C21—C22—O7 | 0.8 (2) |
C4—C5—C6—C7 | 176.93 (15) | C20—C21—C22—O7 | −179.36 (16) |
C1—C6—C7—O3 | −179.16 (14) | O6—C21—C22—C23 | −179.11 (16) |
C5—C6—C7—O3 | 2.6 (2) | C20—C21—C22—C23 | 0.7 (3) |
C1—C6—C7—C8 | 2.9 (2) | O7—C22—C23—C24 | 179.71 (17) |
C5—C6—C7—C8 | −175.40 (13) | C21—C22—C23—C24 | −0.4 (3) |
O3—C7—C8—C13 | 178.71 (13) | C20—C19—C24—C23 | 0.8 (2) |
C6—C7—C8—C13 | −3.34 (19) | C14—C19—C24—C23 | −178.98 (13) |
O3—C7—C8—C9 | −3.3 (2) | C20—C19—C24—C25 | −179.50 (13) |
C6—C7—C8—C9 | 174.62 (12) | C14—C19—C24—C25 | 0.70 (15) |
C13—C8—C9—C10 | 0.7 (2) | C22—C23—C24—C19 | −0.4 (2) |
C7—C8—C9—C10 | −177.28 (13) | C22—C23—C24—C25 | −179.97 (16) |
C8—C9—C10—O4 | 179.59 (14) | C19—C24—C25—O8 | −179.15 (17) |
C8—C9—C10—C11 | −0.8 (2) | C23—C24—C25—O8 | 0.5 (3) |
O4—C10—C11—O5 | 1.0 (2) | C19—C24—C25—O9 | 0.96 (16) |
C9—C10—C11—O5 | −178.61 (13) | C23—C24—C25—O9 | −179.39 (15) |
O4—C10—C11—C12 | 179.55 (13) | O8—C25—O9—C14 | 177.79 (14) |
C9—C10—C11—C12 | −0.1 (2) | C24—C25—O9—C14 | −2.30 (16) |
O5—C11—C12—C13 | 179.46 (13) | C13—C14—O9—C25 | 121.13 (12) |
C10—C11—C12—C13 | 1.1 (2) | C1—C14—O9—C25 | −114.62 (12) |
C9—C8—C13—C12 | 0.30 (19) | C19—C14—O9—C25 | 2.59 (14) |
C7—C8—C13—C12 | 178.21 (12) | C2—C3—O1—C15 | −2.2 (3) |
C9—C8—C13—C14 | 176.85 (12) | C4—C3—O1—C15 | 179.8 (2) |
C7—C8—C13—C14 | −5.25 (19) | C5—C4—O2—C16 | −4.8 (3) |
C11—C12—C13—C8 | −1.2 (2) | C3—C4—O2—C16 | 175.6 (2) |
C11—C12—C13—C14 | −177.86 (12) | C9—C10—O4—C17 | −5.6 (2) |
C8—C13—C14—O9 | 133.87 (12) | C11—C10—O4—C17 | 174.81 (16) |
C12—C13—C14—O9 | −49.58 (15) | C12—C11—O5—C18 | −0.4 (2) |
C8—C13—C14—C1 | 13.27 (17) | C10—C11—O5—C18 | 177.99 (16) |
C12—C13—C14—C1 | −170.18 (11) | C20—C21—O6—C27 | −1.4 (3) |
C8—C13—C14—C19 | −113.70 (13) | C22—C21—O6—C27 | 178.44 (19) |
C12—C13—C14—C19 | 62.85 (15) | C23—C22—O7—C28 | −0.5 (3) |
C6—C1—C14—O9 | −134.63 (12) | C21—C22—O7—C28 | 179.6 (2) |
C2—C1—C14—O9 | 48.45 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···O8i | 0.93 | 2.50 | 3.3892 (17) | 161 |
C20—H20···O3ii | 0.93 | 2.37 | 3.2965 (16) | 175 |
C17—H17B···O2iii | 0.96 | 2.56 | 3.513 (2) | 171 |
C15—H15B···O5iv | 0.96 | 2.48 | 3.411 (2) | 165 |
C2—H2···Cg1 | 0.93 | 2.56 | 2.8621 (17) | 100 |
C12—H12···Cg1 | 0.93 | 2.62 | 2.9142 (16) | 99 |
C28—H28B···Cg2v | 0.96 | 2.88 | 3.671 (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, y−1, z; (v) −x, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C27H24O9 |
Mr | 492.46 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 298 |
a, b, c (Å) | 13.1371 (7), 13.3281 (7), 16.6587 (9) |
β (°) | 107.043 (1) |
V (Å3) | 2788.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.48 × 0.42 × 0.27 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.950, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28518, 6913, 5390 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.179, 1.08 |
No. of reflections | 6913 |
No. of parameters | 333 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.19 |
Computer programs: SMART (Bruker, 2002), SAINT-Plus (Bruker, 2003), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···O8i | 0.93 | 2.50 | 3.3892 (17) | 161.3 |
C20—H20···O3ii | 0.93 | 2.37 | 3.2965 (16) | 175.0 |
C17—H17B···O2iii | 0.96 | 2.56 | 3.513 (2) | 170.9 |
C15—H15B···O5iv | 0.96 | 2.48 | 3.411 (2) | 164.6 |
C2—H2···Cg1 | 0.93 | 2.56 | 2.8621 (17) | 100 |
C12—H12···Cg1 | 0.93 | 2.62 | 2.9142 (16) | 99 |
C28—H28B···Cg2v | 0.96 | 2.88 | 3.671 (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, y−1, z; (v) −x, −y+2, −z+2. |
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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 π–π interactions are present in the structure of the title compound.