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Candibirin A [systematic name: 9,9'-(1,4-dioxane-2,5-diyldi­methyl­ene­dioxy)­di(7H-furo­[3,2-g]­chromen-7-one)], a new furano­coumarin dimer, was isolated from Heracleum candicans WALL. 1H NMR and MS spectra had indicated that the title compound was a dimer of heraclenin or heraclenol, but the linkage structure and its chirality were undetermined. The dioxane linkage, having the R,R configuration, has now been elucidated from di­methyl sulfoxide-solvated crystals, C32H28O10·2C2H6OS. Candibirin A is thus a dimerization product from heraclenin formed by reaction at the epoxy group. Di­methyl­form­amide-solvated crystals, C32H28O10·C3H7NO, adopt a different conformation, with a folded structure that differs from the extended structure in the dimethyl sulfoxide solvate. However, the puckering of the dioxane linker unit is very similar in the two conformers. This result shows that the rotation of the ether bonds, in the linker between the furano­coumarin and dioxane moieties, causes the conformational flexibility of (I).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104024291/gd1348sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104024291/gd1348Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104024291/gd1348IIsup3.hkl
Contains datablock II

CCDC references: 257029; 257030

Comment top

Candibirin A, (I), is a new furanocoumarin dimer isolated from Heracleum candicans WALL., which is a herbal medicine used as an antipyretic. 1H NMR and MS spectra indicated that (I) is a dimer of the previously reported furanocoumarins heraclenin, having an epoxy group (Bal-Tembeet et al., 1996), and heraclenol, having two hydroxy groups (Benkiki et al., 2002). However, the linkage structure and its chirality is unknown, since the dimerization pathway is unknown. We have therefore prepared dimethylsulfoxide (DMSO)-solvated crystals of (I) with no chemical modification (DMSO form), and the absolute configuration was determined using the anomalous dispersion effects from the DMSO S atoms. A different solvate was obtained from the dimethylformamide (DMF) solution (DMF form), where a second conformer of (I) was found.

The structure of (I) in the DMSO form is shown in Fig. 1. The two furanocoumarin moieties are linked by the dioxane ring. There are two DMSO molecules in the asymmetric unit, and one of them is disordered over two sets of sites. The R configurations of atoms C14 and C34 are evidenced by Flack (1983) parameter calculations from 3379 Friedel pairs. This configuration agrees with those previously deduced for heraclenin (Bal-Tembeet et al., 1996) and heraclenol (Benkiki et al., 2002). The presence of the dioxane ring and its configurations indicate that (I) is a dimerization product formed by reactions between the epoxy groups of heraclenin molecules.

In the DMSO form, the two furanocoumarin rings are separated from one another, and the molecule of (I) is extended. Conversely, a folded molecule is observed in the DMF form (Fig. 2). The DMF molecule is held between the two furanocoumarin rings, with an angle of approximately 25.3° (Fig. 2 inset). The plane of the DMF molecule is approximately perpendicular to those of the furanocoumarin rings. The molecular conformations of the DMSO and DMF forms seem to be very different from one another. However, when the heat of formation was calculated using the semi-empirical AM1 method implemented in MOPAC 2000 (Dewar et al., 1985) (−851.7 and −870.8 kJ mol−1 for the DMSO and DMF forms, respectively), it was found that the energy gap between these structures is only −19.1 kJ mol−1, despite the different disposition of the bulky furanocoumarin rings. To compare the conformations, molecular fitting was carried out (Fig. 3). The puckerings of the dioxane moieties are very similar to one another, and the conformational differences are mainly due to the differences betweeen the respective values of the C1—O12—C21–O32 and C22—C21—O32—C33 torsion angles (Table 1).

Experimental top

Acetone extractions were obtained from dried roots of H. candicans WALL., and (I) was purified by column chromatography as described previously (Xiao et al., 1997). HR-EIMS m/z: 572.1681 [M]+ (calculated for C32H28O10: 572.1683); 1H NMR (CDCl3): δH 7.76 (2H,d, J = 9.6 Hz, C5/25—H), 7.69 (2H, d, J = 2.1 Hz, C11/31—H), 7.37 (2H, s, C7/27—H), 6.82 (2H, d, J = 2.1 Hz, C10/30—H), 6.36 (2H, d, J = 9.6 Hz, C4/24—H), 4.49 (2H, dd, J = 11.0 and 7.3 Hz, C13/33—Ha), 4.43 (2H, dd, J = 11.0 and 3.9 Hz, C13/33—Hb), 3.99 (2H, dd, J = 7.3 and 3.9 Hz, C14/34—H), 1.14 (12H, s, C16/36—H3 and C17/37—H3). Compound (I) (10 mg) was dissolved in either DMSO or DMF (0.1–0.2 ml), after which water (approximately 0.02 ml) was added to each solution. Crystals with different crystal forms grew from the two solutions over a period of about a week.

Refinement top

A full-sphere data set was collected for the DMSO form to aid in the determination of the absolute configuration of the structure. A full-sphere data set was also collected for the DMF form, but Friedel pairs were merged in the refinement because of the absence of significant anomalous scattering effects. The absolute configuration of the DMF form was assumed from that of the DMSO form. H atoms were placed at calculated positions [C—H = 0.95–1.00 Å, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(parent atom) for all other atoms] and were included in the structure-factor calculation as riding.

Computing details top

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2001).

Figures top
[Figure 1] Fig. 1. A view of Candibirin A in the DMSO form. Displacement ellipsoids are drawn at the 50% probability level. There are two DMSO molecules in the asymmetric unit, and one DMSO molecule is disordered over two sites. The inset shows the electron density, drawn using TURBO-FRODO (Roussel et al., 2002), around the disordered DMSO molecules at the 1.0 and 2.5σ level.
[Figure 2] Fig. 2. A view of Candibirin A in the DMF form. Displacement ellipsoids are drawn at the 50% probability level. The inset shows the disposition of the DMF molecule and furanocoumarin moieties.
[Figure 3] Fig. 3. A superimposition of the structures of the DMSO and DMF forms. Figure drawn using RasMol (Bernstein, 2000) and POV-RAY (POV-Team, 1991).
(I) 9,9'-(1,4-dioxane-2,5-diyldimethylenedioxy)di(7H-furo[3,2-g]chromen-7-one) dimethyl sulfoxide disolvate top
Crystal data top
C32H28O10·2C2H6OSDx = 1.392 Mg m3
Mr = 728.80Melting point = 364–370 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5833 reflections
a = 10.903 (2) Åθ = 2.3–28.2°
b = 13.068 (2) ŵ = 0.22 mm1
c = 24.400 (4) ÅT = 200 K
V = 3476.5 (11) Å3Needle, colourless
Z = 40.50 × 0.20 × 0.04 mm
F(000) = 1536
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
7659 independent reflections
Radiation source: MacScience, M18XCE rotating anode7041 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 8.366 pixels mm-1θmax = 27.1°, θmin = 2.1°
ω scanh = 1313
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 1616
Tmin = 0.913, Tmax = 1.0l = 3131
30564 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.099 w = 1/[σ2(Fo2) + (0.0729P)2 + 0.5601P]
where P = (Fo2 + 2Fc2)/3
S = 0.90(Δ/σ)max = 0.003
7659 reflectionsΔρmax = 0.40 e Å3
498 parametersΔρmin = 0.19 e Å3
18 restraintsAbsolute structure: Flack (1983), 3379 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.04 (6)
Crystal data top
C32H28O10·2C2H6OSV = 3476.5 (11) Å3
Mr = 728.80Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 10.903 (2) ŵ = 0.22 mm1
b = 13.068 (2) ÅT = 200 K
c = 24.400 (4) Å0.50 × 0.20 × 0.04 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
7659 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
7041 reflections with I > 2σ(I)
Tmin = 0.913, Tmax = 1.0Rint = 0.026
30564 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.099Δρmax = 0.40 e Å3
S = 0.90Δρmin = 0.19 e Å3
7659 reflectionsAbsolute structure: Flack (1983), 3379 Friedel pairs
498 parametersAbsolute structure parameter: 0.04 (6)
18 restraints
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*/UeqOcc. (<1)
S1A0.15725 (5)0.81176 (4)0.466258 (17)0.04392 (12)
O1A0.1606 (2)0.74413 (11)0.51541 (5)0.0664 (5)
C1A0.2781 (3)0.9002 (2)0.47354 (12)0.0763 (8)
H11A0.26910.93690.50830.114*
H12A0.27590.94910.44310.114*
H13A0.35670.86370.47320.114*
C2A0.0334 (3)0.8963 (2)0.47584 (11)0.0701 (7)
H21A0.04340.85730.47710.105*
H22A0.03040.94510.44540.105*
H23A0.04420.93350.51040.105*
S1B0.71444 (19)0.41444 (9)0.36750 (4)0.0511 (5)0.551 (3)
O1B0.7189 (5)0.4712 (3)0.42049 (14)0.0912 (15)0.551 (3)
C1B0.6009 (6)0.3191 (6)0.3757 (4)0.077 (3)0.551 (3)
H11B0.61780.27960.40900.115*0.551 (3)
H12B0.60170.27340.34390.115*0.551 (3)
H13B0.52010.35160.37880.115*0.551 (3)
C2B0.8404 (4)0.3288 (4)0.36807 (17)0.0552 (10)0.551 (3)
H21B0.91670.36750.37250.083*0.551 (3)
H22B0.84280.29090.33340.083*0.551 (3)
H23B0.83130.28060.39860.083*0.551 (3)
S1C0.6283 (2)0.41609 (10)0.36918 (5)0.0526 (6)0.449 (3)
O1C0.5890 (5)0.4601 (4)0.42268 (18)0.0869 (16)0.449 (3)
C1C0.6093 (8)0.2823 (4)0.3740 (5)0.0458 (17)0.449 (3)
H11C0.64350.25810.40880.069*0.449 (3)
H12C0.65210.24900.34350.069*0.449 (3)
H13C0.52180.26550.37240.069*0.449 (3)
C2C0.7900 (6)0.4183 (7)0.3690 (3)0.090 (3)0.449 (3)
H21C0.81850.48940.36950.136*0.449 (3)
H22C0.82040.38430.33580.136*0.449 (3)
H23C0.82090.38250.40140.136*0.449 (3)
C10.28323 (16)0.27607 (12)0.25822 (6)0.0277 (3)
C20.38609 (15)0.26870 (12)0.22505 (6)0.0287 (3)
O20.49653 (11)0.28602 (9)0.25005 (5)0.0322 (2)
C30.60495 (16)0.28647 (14)0.22135 (7)0.0373 (4)
O30.69646 (12)0.30371 (13)0.24724 (6)0.0496 (3)
C40.59840 (18)0.26553 (18)0.16344 (8)0.0464 (5)
H40.67180.26520.14250.056*
C50.4927 (2)0.24669 (18)0.13870 (7)0.0473 (5)
H50.49200.23240.10050.057*
C60.37874 (17)0.24752 (14)0.16863 (7)0.0352 (4)
C70.26555 (18)0.23256 (16)0.14385 (7)0.0391 (4)
H70.25990.21790.10580.047*
C80.16150 (17)0.23944 (13)0.17579 (6)0.0342 (3)
C90.17246 (16)0.26063 (12)0.23197 (6)0.0300 (3)
O90.05933 (11)0.26830 (10)0.25545 (5)0.0353 (3)
C100.03164 (18)0.23526 (15)0.16574 (8)0.0403 (4)
H100.00720.22220.13160.048*
C110.02381 (17)0.25333 (15)0.21355 (8)0.0410 (4)
H110.11030.25560.21820.049*
O120.29792 (10)0.30942 (9)0.31078 (4)0.0320 (2)
C130.23055 (16)0.25640 (13)0.35269 (6)0.0303 (3)
H1310.26340.18640.35770.036*
H1320.14280.25130.34260.036*
C140.24521 (14)0.31749 (12)0.40457 (6)0.0267 (3)
H140.33090.34460.40620.032*
O140.16269 (11)0.40120 (8)0.40189 (4)0.0299 (2)
C150.22031 (15)0.25426 (12)0.45664 (6)0.0283 (3)
C160.10797 (17)0.18687 (15)0.45113 (7)0.0373 (4)
H1610.08800.15690.48680.056*
H1620.12460.13210.42470.056*
H1630.03860.22800.43820.056*
C170.33305 (18)0.19297 (15)0.47204 (7)0.0404 (4)
H1710.40050.23980.48080.061*
H1720.35680.14920.44120.061*
H1730.31480.15030.50410.061*
C210.28214 (16)0.45849 (13)0.64109 (6)0.0313 (3)
C220.38356 (16)0.47089 (12)0.67462 (6)0.0302 (3)
O220.49513 (11)0.47459 (9)0.64862 (5)0.0347 (3)
C230.60127 (16)0.49270 (14)0.67658 (8)0.0359 (4)
O230.69212 (13)0.50192 (12)0.64861 (6)0.0485 (3)
C240.59438 (19)0.49833 (15)0.73522 (8)0.0428 (4)
H240.66770.50610.75590.051*
C250.48830 (19)0.49288 (15)0.76109 (7)0.0413 (4)
H250.48680.49750.79990.050*
C260.37580 (17)0.48017 (13)0.73208 (7)0.0345 (4)
C270.26182 (18)0.47888 (13)0.75740 (7)0.0380 (4)
H270.25530.48360.79610.046*
C280.15850 (18)0.47058 (12)0.72541 (7)0.0361 (4)
C290.16994 (17)0.46045 (12)0.66848 (7)0.0336 (3)
O290.05678 (12)0.45435 (11)0.64468 (5)0.0425 (3)
C300.0273 (2)0.47100 (15)0.73589 (8)0.0443 (4)
H300.01210.47680.77050.053*
C310.02691 (18)0.46159 (16)0.68680 (9)0.0456 (5)
H310.11330.46010.68170.055*
O320.30184 (11)0.43987 (11)0.58701 (5)0.0398 (3)
C330.21704 (16)0.48007 (14)0.54730 (6)0.0330 (3)
H3310.23040.55440.54210.040*
H3320.13150.46910.55960.040*
O340.19016 (11)0.32413 (9)0.50049 (4)0.0319 (2)
C340.24087 (14)0.42313 (12)0.49440 (6)0.0277 (3)
H340.33140.41700.48870.033*
C350.18294 (15)0.47675 (12)0.44404 (6)0.0282 (3)
C360.05642 (16)0.51938 (14)0.45609 (7)0.0355 (4)
H3610.01770.54130.42180.053*
H3620.06370.57810.48090.053*
H3630.00610.46630.47340.053*
C370.26861 (17)0.55843 (14)0.42164 (7)0.0369 (4)
H3710.34610.52670.41040.055*
H3720.28460.60960.45010.055*
H3730.23030.59170.39000.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0686 (3)0.0378 (2)0.02539 (19)0.0028 (2)0.0078 (2)0.00343 (17)
O1A0.1260 (15)0.0388 (7)0.0344 (7)0.0006 (9)0.0159 (9)0.0014 (6)
C1A0.088 (2)0.0812 (18)0.0595 (16)0.0246 (15)0.0151 (14)0.0018 (14)
C2A0.0829 (18)0.0684 (15)0.0589 (15)0.0225 (14)0.0168 (13)0.0131 (12)
S1B0.0635 (12)0.0597 (7)0.0303 (5)0.0111 (7)0.0022 (6)0.0011 (4)
O1B0.151 (4)0.074 (2)0.0493 (19)0.023 (3)0.000 (2)0.0120 (17)
C1B0.059 (4)0.125 (8)0.047 (3)0.026 (5)0.002 (3)0.001 (6)
C2B0.047 (2)0.072 (3)0.047 (2)0.003 (2)0.0007 (17)0.0059 (19)
S1C0.0773 (16)0.0458 (7)0.0347 (6)0.0054 (7)0.0110 (6)0.0009 (5)
O1C0.125 (5)0.073 (3)0.063 (3)0.016 (3)0.000 (3)0.019 (2)
C1C0.055 (4)0.038 (3)0.045 (3)0.002 (2)0.005 (3)0.002 (3)
C2C0.088 (6)0.140 (8)0.043 (3)0.043 (6)0.003 (4)0.009 (4)
C10.0367 (8)0.0292 (7)0.0173 (6)0.0022 (6)0.0011 (6)0.0014 (5)
C20.0343 (8)0.0304 (7)0.0215 (7)0.0003 (6)0.0003 (6)0.0006 (6)
O20.0329 (6)0.0400 (6)0.0238 (5)0.0003 (5)0.0030 (4)0.0018 (4)
C30.0337 (9)0.0429 (9)0.0353 (9)0.0015 (7)0.0060 (7)0.0008 (7)
O30.0342 (7)0.0709 (9)0.0438 (7)0.0011 (7)0.0026 (6)0.0028 (7)
C40.0395 (10)0.0660 (13)0.0338 (9)0.0025 (9)0.0131 (8)0.0061 (9)
C50.0501 (11)0.0657 (12)0.0262 (9)0.0027 (10)0.0103 (8)0.0093 (8)
C60.0423 (9)0.0421 (9)0.0211 (7)0.0027 (7)0.0066 (7)0.0044 (7)
C70.0490 (10)0.0501 (10)0.0182 (7)0.0006 (8)0.0001 (7)0.0050 (7)
C80.0427 (9)0.0365 (8)0.0235 (7)0.0013 (7)0.0058 (7)0.0015 (6)
C90.0353 (8)0.0318 (7)0.0230 (7)0.0042 (7)0.0022 (6)0.0007 (6)
O90.0312 (6)0.0453 (7)0.0294 (6)0.0031 (5)0.0004 (5)0.0033 (5)
C100.0445 (10)0.0457 (10)0.0305 (8)0.0008 (8)0.0099 (7)0.0005 (7)
C110.0331 (9)0.0475 (10)0.0425 (10)0.0032 (8)0.0078 (7)0.0008 (8)
O120.0381 (6)0.0401 (6)0.0177 (5)0.0059 (5)0.0030 (4)0.0042 (4)
C130.0405 (9)0.0330 (8)0.0176 (6)0.0025 (7)0.0020 (6)0.0019 (6)
C140.0314 (7)0.0311 (7)0.0175 (6)0.0002 (6)0.0001 (5)0.0025 (6)
O140.0370 (6)0.0330 (5)0.0196 (5)0.0033 (5)0.0042 (4)0.0039 (4)
C150.0384 (8)0.0300 (7)0.0166 (7)0.0010 (6)0.0001 (6)0.0016 (6)
C160.0486 (10)0.0383 (9)0.0251 (8)0.0094 (8)0.0052 (7)0.0025 (7)
C170.0503 (10)0.0430 (9)0.0281 (8)0.0096 (9)0.0033 (7)0.0010 (7)
C210.0389 (9)0.0323 (8)0.0227 (7)0.0042 (7)0.0007 (6)0.0068 (6)
C220.0375 (8)0.0283 (8)0.0248 (8)0.0017 (6)0.0004 (6)0.0039 (6)
O220.0370 (6)0.0425 (7)0.0248 (5)0.0015 (5)0.0025 (5)0.0072 (5)
C230.0323 (9)0.0348 (9)0.0407 (10)0.0021 (7)0.0029 (7)0.0053 (7)
O230.0374 (7)0.0582 (8)0.0498 (8)0.0016 (6)0.0018 (6)0.0084 (6)
C240.0507 (11)0.0441 (10)0.0337 (9)0.0014 (8)0.0142 (8)0.0045 (7)
C250.0544 (11)0.0429 (10)0.0266 (8)0.0013 (9)0.0100 (8)0.0018 (7)
C260.0507 (10)0.0289 (8)0.0239 (8)0.0007 (7)0.0061 (7)0.0016 (6)
C270.0573 (11)0.0339 (9)0.0230 (8)0.0017 (8)0.0037 (7)0.0010 (7)
C280.0497 (10)0.0287 (8)0.0298 (8)0.0011 (7)0.0092 (8)0.0034 (6)
C290.0390 (9)0.0316 (8)0.0300 (8)0.0024 (7)0.0005 (7)0.0053 (6)
O290.0370 (7)0.0553 (8)0.0353 (7)0.0001 (6)0.0009 (5)0.0097 (6)
C300.0543 (11)0.0391 (10)0.0395 (10)0.0020 (8)0.0136 (8)0.0017 (8)
C310.0355 (9)0.0481 (11)0.0532 (12)0.0012 (8)0.0081 (8)0.0028 (9)
O320.0366 (6)0.0624 (8)0.0206 (5)0.0095 (6)0.0038 (5)0.0135 (5)
C330.0368 (9)0.0404 (9)0.0218 (7)0.0026 (7)0.0013 (6)0.0071 (6)
O340.0438 (6)0.0347 (6)0.0173 (5)0.0033 (5)0.0044 (4)0.0036 (4)
C340.0306 (8)0.0335 (8)0.0190 (7)0.0012 (6)0.0001 (6)0.0044 (6)
C350.0317 (8)0.0313 (7)0.0215 (7)0.0001 (6)0.0000 (6)0.0043 (6)
C360.0350 (9)0.0389 (9)0.0326 (9)0.0031 (7)0.0006 (7)0.0047 (7)
C370.0441 (10)0.0363 (9)0.0302 (8)0.0033 (7)0.0034 (7)0.0002 (7)
Geometric parameters (Å, º) top
S1A—O1A1.490 (1)C13—H1320.9900
S1A—C2A1.760 (2)C14—O141.418 (2)
S1A—C1A1.762 (3)C14—C151.540 (2)
C1A—H11A0.9800C14—H141.0000
C1A—H12A0.9800O14—C351.443 (2)
C1A—H13A0.9800C15—O341.444 (2)
C2A—H21A0.9800C15—C171.515 (2)
C2A—H22A0.9800C15—C161.515 (2)
C2A—H23A0.9800C16—H1610.9800
S1B—O1B1.491 (3)C16—H1620.9800
S1B—C1B1.768 (6)C16—H1630.9800
S1B—C2B1.772 (4)C17—H1710.9800
C1B—H11B0.9800C17—H1720.9800
C1B—H12B0.9800C17—H1730.9800
C1B—H13B0.9800C21—O321.359 (2)
C2B—H21B0.9800C21—C221.385 (2)
C2B—H22B0.9800C21—C291.394 (2)
C2B—H23B0.9800C22—O221.373 (2)
S1C—O1C1.489 (4)C22—C261.410 (2)
S1C—C2C1.764 (6)O22—C231.364 (2)
S1C—C1C1.765 (6)C23—O231.209 (2)
C1C—H11C0.9800C23—C241.435 (3)
C1C—H12C0.9800C24—C251.319 (3)
C1C—H13C0.9800C24—H240.9500
C2C—H21C0.9800C25—C261.426 (3)
C2C—H22C0.9800C25—H250.9500
C2C—H23C0.9800C26—C271.388 (3)
C1—O121.364 (2)C27—C281.375 (3)
C1—C91.382 (2)C27—H270.9500
C1—C21.386 (2)C28—C291.401 (2)
C2—O21.369 (2)C28—C301.453 (3)
C2—C61.407 (2)C29—O291.366 (2)
O2—C31.374 (2)O29—C311.378 (2)
C3—O31.202 (2)C30—C311.341 (3)
C3—C41.441 (3)C30—H300.9500
C4—C51.324 (3)C31—H310.9500
C4—H40.9500O32—C331.439 (2)
C5—C61.442 (3)C33—C341.512 (2)
C5—H50.9500C33—H3310.9900
C6—C71.388 (3)C33—H3320.9900
C7—C81.379 (3)O34—C341.415 (2)
C7—H70.9500C34—C351.549 (2)
C8—C91.403 (2)C34—H341.0000
C8—C101.438 (3)C35—C361.516 (2)
C9—O91.364 (2)C35—C371.520 (2)
O9—C111.380 (2)C36—H3610.9800
C10—C111.335 (3)C36—H3620.9800
C10—H100.9500C36—H3630.9800
C11—H110.9500C37—H3710.9800
O12—C131.437 (2)C37—H3720.9800
C13—C141.505 (2)C37—H3730.9800
C13—H1310.9900
O1A—S1A—C2A106.5 (1)C17—C15—C16111.8 (2)
O1A—S1A—C1A106.8 (1)O34—C15—C14108.2 (1)
C2A—S1A—C1A98.6 (2)C17—C15—C14110.2 (1)
S1A—C1A—H11A109.5C16—C15—C14112.4 (1)
S1A—C1A—H12A109.5C15—C16—H161109.5
H11A—C1A—H12A109.5C15—C16—H162109.5
S1A—C1A—H13A109.5H161—C16—H162109.5
H11A—C1A—H13A109.5C15—C16—H163109.5
H12A—C1A—H13A109.5H161—C16—H163109.5
S1A—C2A—H21A109.5H162—C16—H163109.5
S1A—C2A—H22A109.5C15—C17—H171109.5
H21A—C2A—H22A109.5C15—C17—H172109.5
S1A—C2A—H23A109.5H171—C17—H172109.5
H21A—C2A—H23A109.5C15—C17—H173109.5
H22A—C2A—H23A109.5H171—C17—H173109.5
O1B—S1B—C1B106.0 (3)H172—C17—H173109.5
O1B—S1B—C2B106.4 (2)O32—C21—C22117.9 (2)
C1B—S1B—C2B95.6 (3)O32—C21—C29127.4 (2)
O1C—S1C—C2C106.5 (3)C22—C21—C29114.5 (1)
O1C—S1C—C1C106.9 (4)O22—C22—C21116.0 (1)
C2C—S1C—C1C97.7 (4)O22—C22—C26120.6 (2)
S1C—C1C—H11C109.5C21—C22—C26123.3 (2)
S1C—C1C—H12C109.5C23—O22—C22121.8 (1)
H11C—C1C—H12C109.5O23—C23—O22115.5 (2)
S1C—C1C—H13C109.5O23—C23—C24126.9 (2)
H11C—C1C—H13C109.5O22—C23—C24117.6 (2)
H12C—C1C—H13C109.5C25—C24—C23121.3 (2)
S1C—C2C—H21C109.5C25—C24—H24119.3
S1C—C2C—H22C109.5C23—C24—H24119.3
H21C—C2C—H22C109.5C24—C25—C26121.5 (2)
S1C—C2C—H23C109.5C24—C25—H25119.2
H21C—C2C—H23C109.5C26—C25—H25119.2
H22C—C2C—H23C109.5C27—C26—C22119.7 (2)
O12—C1—C9125.8 (1)C27—C26—C25123.4 (2)
O12—C1—C2118.4 (1)C22—C26—C25116.9 (2)
C9—C1—C2115.2 (1)C28—C27—C26118.8 (2)
O2—C2—C1116.1 (1)C28—C27—H27120.6
O2—C2—C6121.3 (1)C26—C27—H27120.6
C1—C2—C6122.6 (2)C27—C28—C29119.8 (2)
C2—O2—C3122.0 (1)C27—C28—C30135.0 (2)
O3—C3—O2116.6 (2)C29—C28—C30105.2 (2)
O3—C3—C4126.3 (2)O29—C29—C21126.0 (1)
O2—C3—C4117.2 (2)O29—C29—C28110.3 (2)
C5—C4—C3121.7 (2)C21—C29—C28123.7 (2)
C5—C4—H4119.1C29—O29—C31106.1 (1)
C3—C4—H4119.1C31—C30—C28106.0 (2)
C4—C5—C6121.2 (2)C31—C30—H30127.0
C4—C5—H5119.4C28—C30—H30127.0
C6—C5—H5119.4C30—C31—O29112.4 (2)
C7—C6—C2120.3 (2)C30—C31—H31123.8
C7—C6—C5123.0 (2)O29—C31—H31123.8
C2—C6—C5116.6 (2)C21—O32—C33119.2 (1)
C8—C7—C6118.4 (1)O32—C33—C34106.6 (1)
C8—C7—H7120.8O32—C33—H331110.4
C6—C7—H7120.8C34—C33—H331110.4
C7—C8—C9119.7 (2)O32—C33—H332110.4
C7—C8—C10135.3 (2)C34—C33—H332110.4
C9—C8—C10104.9 (2)H331—C33—H332108.6
O9—C9—C1125.8 (1)C34—O34—C15114.3 (1)
O9—C9—C8110.4 (2)O34—C34—C33107.1 (1)
C1—C9—C8123.8 (2)O34—C34—C35109.7 (1)
C9—O9—C11105.8 (1)C33—C34—C35112.6 (1)
C11—C10—C8106.9 (2)O34—C34—H34109.1
C11—C10—H10126.6C33—C34—H34109.1
C8—C10—H10126.6C35—C34—H34109.1
C10—C11—O9112.0 (2)O14—C35—C36104.5 (1)
C10—C11—H11124.0O14—C35—C37108.6 (1)
O9—C11—H11124.0C36—C35—C37111.8 (1)
C1—O12—C13117.1 (1)O14—C35—C34108.6 (1)
O12—C13—C14106.8 (1)C36—C35—C34112.5 (1)
O12—C13—H131110.4C37—C35—C34110.6 (1)
C14—C13—H131110.4C35—C36—H361109.5
O12—C13—H132110.4C35—C36—H362109.5
C14—C13—H132110.4H361—C36—H362109.5
H131—C13—H132108.6C35—C36—H363109.5
O14—C14—C13107.6 (1)H361—C36—H363109.5
O14—C14—C15109.9 (1)H362—C36—H363109.5
C13—C14—C15113.0 (1)C35—C37—H371109.5
O14—C14—H14108.7C35—C37—H372109.5
C13—C14—H14108.7H371—C37—H372109.5
C15—C14—H14108.7C35—C37—H373109.5
C14—O14—C35113.5 (1)H371—C37—H373109.5
O34—C15—C17109.6 (1)H372—C37—H373109.5
O34—C15—C16104.4 (1)
O12—C1—C2—O26.4 (2)C29—C21—C22—C262.7 (2)
C9—C1—C2—O2178.6 (1)C21—C22—O22—C23176.0 (2)
O12—C1—C2—C6171.9 (2)C26—C22—O22—C233.6 (2)
C9—C1—C2—C60.3 (2)C22—O22—C23—O23174.5 (2)
C1—C2—O2—C3176.5 (1)C22—O22—C23—C245.8 (2)
C6—C2—O2—C31.8 (2)O23—C23—C24—C25176.0 (2)
C2—O2—C3—O3179.1 (2)O22—C23—C24—C254.3 (3)
C2—O2—C3—C41.3 (2)C23—C24—C25—C260.6 (3)
O3—C3—C4—C5179.5 (2)O22—C22—C26—C27178.3 (2)
O2—C3—C4—C50.0 (3)C21—C22—C26—C271.2 (3)
C3—C4—C5—C60.8 (3)O22—C22—C26—C250.3 (2)
O2—C2—C6—C7178.5 (2)C21—C22—C26—C25179.8 (2)
C1—C2—C6—C70.3 (3)C24—C25—C26—C27176.9 (2)
O2—C2—C6—C51.0 (3)C24—C25—C26—C221.7 (3)
C1—C2—C6—C5177.3 (2)C22—C26—C27—C281.3 (3)
C4—C5—C6—C7177.1 (2)C25—C26—C27—C28177.2 (2)
C4—C5—C6—C20.3 (3)C26—C27—C28—C292.0 (2)
C2—C6—C7—C80.3 (3)C26—C27—C28—C30176.9 (2)
C5—C6—C7—C8177.1 (2)O32—C21—C29—O297.3 (3)
C6—C7—C8—C90.3 (3)C22—C21—C29—O29177.0 (2)
C6—C7—C8—C10175.6 (2)O32—C21—C29—C28173.6 (2)
O12—C1—C9—O95.5 (3)C22—C21—C29—C282.0 (2)
C2—C1—C9—O9177.0 (2)C27—C28—C29—O29179.5 (2)
O12—C1—C9—C8171.2 (2)C30—C28—C29—O290.3 (2)
C2—C1—C9—C80.4 (2)C27—C28—C29—C210.3 (3)
C7—C8—C9—O9177.5 (2)C30—C28—C29—C21178.9 (2)
C10—C8—C9—O90.5 (2)C21—C29—O29—C31178.7 (2)
C7—C8—C9—C10.4 (3)C28—C29—O29—C310.5 (2)
C10—C8—C9—C1176.7 (2)C27—C28—C30—C31178.9 (2)
C1—C9—O9—C11176.2 (2)C29—C28—C30—C310.0 (2)
C8—C9—O9—C110.9 (2)C28—C30—C31—O290.4 (2)
C7—C8—C10—C11176.2 (2)C29—O29—C31—C300.6 (2)
C9—C8—C10—C110.1 (2)C22—C21—O32—C33146.1 (2)
C8—C10—C11—O90.7 (2)C29—C21—O32—C3338.4 (3)
C9—O9—C11—C101.0 (2)C21—O32—C33—C34164.1 (2)
C9—C1—O12—C1351.1 (2)C17—C15—O34—C3493.7 (2)
C2—C1—O12—C13137.6 (2)C16—C15—O34—C34146.5 (1)
C1—O12—C13—C14170.7 (1)C14—C15—O34—C3426.5 (2)
O12—C13—C14—O1479.4 (2)C15—O34—C34—C33171.4 (1)
O12—C13—C14—C15159.1 (1)C15—O34—C34—C3566.1 (2)
C13—C14—O14—C35169.0 (1)O32—C33—C34—O3475.0 (2)
C15—C14—O14—C3567.6 (2)O32—C33—C34—C35164.3 (1)
O14—C14—C15—O3438.0 (2)C14—O14—C35—C36147.9 (1)
C13—C14—C15—O34158.2 (1)C14—O14—C35—C3792.8 (2)
O14—C14—C15—C17157.8 (1)C14—O14—C35—C3427.6 (2)
C13—C14—C15—C1782.0 (2)O34—C34—C35—O1436.4 (2)
O14—C14—C15—C1676.8 (2)C33—C34—C35—O14155.5 (1)
C13—C14—C15—C1643.4 (2)O34—C34—C35—C3678.8 (2)
O32—C21—C22—O227.1 (2)C33—C34—C35—C3640.4 (2)
C29—C21—C22—O22176.8 (1)O34—C34—C35—C37155.4 (1)
O32—C21—C22—C26173.4 (2)C33—C34—C35—C3785.5 (2)
(II) 9,9'-(1,4-dioxane-2,5-diyldimethylenedioxy)di(7H-furo[3,2-g]chromen-7-one) dimethylformamide solvate top
Crystal data top
C32H28O10·C3H7NOF(000) = 680
Mr = 645.64Dx = 1.393 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 7355 reflections
a = 8.2000 (7) Åθ = 2.2–28.1°
b = 16.2132 (14) ŵ = 0.10 mm1
c = 11.6706 (10) ÅT = 200 K
β = 97.244 (1)°Plate, colourless
V = 1539.2 (2) Å30.50 × 0.40 × 0.04 mm
Z = 2
Data collection top
Bruker SMART APEX area-detector
diffractometer
3516 independent reflections
Radiation source: MacScience, M18XCE rotating anode3381 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
Detector resolution: 8.366 pixels mm-1θmax = 27.1°, θmin = 2.2°
ω scanh = 1010
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 2020
Tmin = 0.932, Tmax = 1.0l = 1414
13520 measured reflections
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0757P)2 + 0.3442P]
where P = (Fo2 + 2Fc2)/3
3516 reflections(Δ/σ)max < 0.001
430 parametersΔρmax = 0.67 e Å3
3 restraintsΔρmin = 0.38 e Å3
Crystal data top
C32H28O10·C3H7NOV = 1539.2 (2) Å3
Mr = 645.64Z = 2
Monoclinic, P21Mo Kα radiation
a = 8.2000 (7) ŵ = 0.10 mm1
b = 16.2132 (14) ÅT = 200 K
c = 11.6706 (10) Å0.50 × 0.40 × 0.04 mm
β = 97.244 (1)°
Data collection top
Bruker SMART APEX area-detector
diffractometer
3516 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
3381 reflections with I > 2σ(I)
Tmin = 0.932, Tmax = 1.0Rint = 0.017
13520 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0423 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.04Δρmax = 0.67 e Å3
3516 reflectionsΔρmin = 0.38 e Å3
430 parameters
Special details top

Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

− 1.6136 (0.0048) x + 4.9254 (0.0096) y − 10.5029 (0.0041) z = 7.4050 (0.0059)

* −0.0559 (0.0022) C21 * −0.0162 (0.0025) C22 * 0.0332 (0.0021) O22 * 0.0584 (0.0027) C23 * 0.0121 (0.0028) C24 * −0.0214 (0.0026) C25 * −0.0133 (0.0026) C26 * −0.0310 (0.0026) C27 * −0.0246 (0.0026) C28 * −0.0534 (0.0025) C29 * 0.0550 (0.0027) C30 * 0.0633 (0.0027) C31 * −0.0063 (0.0020) O29

Rms deviation of fitted atoms = 0.0394

− 1.2969 (0.0049) x − 0.8595 (0.0107) y + 11.6480 (0.0011) z = 2.8726 (0.0072)

Angle to previous plane (with approximate e.s.d.) = 25.30 (0.04)

* −0.0456 (0.0024) C1 * −0.0521 (0.0025) C2 * −0.0044 (0.0021) O2 * 0.0685 (0.0027) C3 * 0.0512 (0.0030) C4 * −0.0184 (0.0028) C5 * −0.0470 (0.0027) C6 * −0.0274 (0.0028) C7 * −0.0050 (0.0029) C8 * −0.0182 (0.0026) C9 * 0.0323 (0.0031) C10 * 0.0454 (0.0032) C11 * 0.0207 (0.0022) O9

Rms deviation of fitted atoms = 0.0385

Refinement. In the absence of significant anomalous scattering effects, Friedel pairs were merged, and the absolute configuration is assumed from that of the crystal structure obtained from dimethylsulfoxide solution.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2453 (4)0.77989 (18)0.3276 (2)0.0327 (6)
C20.4125 (4)0.79808 (19)0.3469 (2)0.0349 (6)
O20.4540 (2)0.87951 (15)0.36168 (18)0.0389 (5)
C30.6158 (4)0.9053 (3)0.3879 (3)0.0495 (9)
O30.6368 (4)0.9778 (2)0.4010 (3)0.0691 (9)
C40.7386 (4)0.8414 (4)0.3953 (3)0.0631 (12)
H40.85100.85640.41240.076*
C50.7015 (5)0.7631 (3)0.3794 (3)0.0577 (11)
H50.78770.72370.38340.069*
C60.5334 (4)0.7354 (2)0.3562 (2)0.0460 (8)
C70.4877 (5)0.6528 (2)0.3467 (3)0.0555 (10)
H70.56880.61070.35250.067*
C80.3219 (5)0.6329 (2)0.3287 (3)0.0509 (9)
C90.2051 (4)0.69606 (19)0.3192 (2)0.0396 (7)
O90.0498 (3)0.66622 (15)0.3031 (2)0.0492 (6)
C100.2238 (8)0.5581 (3)0.3155 (3)0.0698 (14)
H100.26420.50320.31700.084*
C110.0670 (7)0.5810 (2)0.3008 (3)0.0636 (12)
H110.02280.54360.29010.076*
O120.1233 (2)0.83701 (13)0.33009 (17)0.0335 (4)
C130.1077 (3)0.89826 (16)0.2396 (2)0.0315 (5)
H1310.21820.92020.23100.038*
H1320.04020.94460.26270.038*
C140.0306 (3)0.86529 (15)0.1246 (2)0.0267 (5)
H140.09070.81480.10430.032*
O140.1350 (2)0.84472 (12)0.13681 (16)0.0305 (4)
C150.0321 (3)0.93058 (16)0.0279 (2)0.0302 (5)
C160.1916 (4)0.9253 (2)0.0256 (3)0.0422 (7)
H1610.18800.96450.08990.063*
H1620.20530.86930.05420.063*
H1630.28430.93890.03290.063*
C170.0007 (4)1.01791 (18)0.0679 (3)0.0425 (7)
H1710.09441.01790.11100.064*
H1720.02151.05420.00050.064*
H1730.09771.03790.11780.064*
C210.0944 (3)0.78052 (18)0.3192 (2)0.0318 (5)
C220.0645 (3)0.80042 (19)0.3381 (2)0.0342 (6)
O220.1137 (3)0.87989 (15)0.3130 (2)0.0419 (5)
C230.2697 (4)0.9076 (3)0.3264 (3)0.0510 (9)
O230.2993 (4)0.9785 (2)0.3024 (3)0.0695 (8)
C240.3799 (4)0.8473 (3)0.3672 (3)0.0581 (11)
H240.48910.86350.37580.070*
C250.3336 (4)0.7710 (3)0.3927 (3)0.0522 (10)
H250.41000.73360.41910.063*
C260.1701 (4)0.7430 (2)0.3815 (2)0.0418 (7)
C270.1158 (4)0.6634 (2)0.4088 (3)0.0476 (8)
H270.18710.62410.43660.057*
C280.0433 (5)0.6424 (2)0.3948 (3)0.0432 (7)
C290.1445 (4)0.70026 (19)0.3494 (2)0.0353 (6)
O290.2978 (3)0.66946 (14)0.34475 (18)0.0413 (5)
C300.1474 (6)0.5715 (2)0.4196 (3)0.0533 (9)
H300.11690.52080.45180.064*
C310.2955 (5)0.5901 (2)0.3890 (3)0.0499 (8)
H310.38690.55360.39650.060*
O320.1958 (2)0.83920 (13)0.28315 (16)0.0338 (4)
C330.2680 (3)0.82090 (18)0.1791 (2)0.0321 (5)
H3310.31100.76380.18370.038*
H3320.36170.85860.17400.038*
C340.1458 (3)0.82979 (16)0.0711 (2)0.0272 (5)
H340.04460.79720.08010.033*
O340.1050 (2)0.91437 (11)0.05982 (17)0.0312 (4)
C350.2179 (3)0.80034 (16)0.0393 (2)0.0290 (5)
C360.1919 (4)0.70822 (19)0.0567 (3)0.0411 (7)
H3610.23110.69140.12910.062*
H3620.07450.69550.06020.062*
H3630.25320.67830.00790.062*
C370.3979 (3)0.8233 (2)0.0392 (3)0.0389 (6)
H3710.41210.88250.02420.058*
H3720.43220.81010.11450.058*
H3730.46530.79210.02130.058*
N1D0.6127 (3)0.61071 (17)0.0546 (3)0.0440 (6)
C2D0.5685 (5)0.5730 (3)0.0546 (3)0.0584 (9)
H21D0.64380.52720.06400.088*
H22D0.57530.61370.11590.088*
H23D0.45580.55190.05940.088*
C3D0.5601 (7)0.5724 (4)0.1535 (4)0.0828 (15)
H31D0.61190.60000.22350.124*
H32D0.59200.51410.15560.124*
H33D0.44030.57680.14950.124*
C4D0.7181 (5)0.6721 (3)0.0736 (6)0.0862 (18)
H4D0.74450.68590.15290.103*
O4D0.7842 (5)0.7121 (3)0.0125 (6)0.133 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0371 (14)0.0372 (14)0.0236 (12)0.0088 (11)0.0034 (10)0.0023 (10)
C20.0354 (13)0.0443 (16)0.0254 (12)0.0132 (12)0.0051 (10)0.0045 (11)
O20.0287 (9)0.0523 (13)0.0349 (10)0.0046 (9)0.0009 (8)0.0074 (9)
C30.0324 (15)0.079 (3)0.0362 (15)0.0046 (16)0.0010 (12)0.0173 (16)
O30.0482 (15)0.078 (2)0.0766 (19)0.0194 (14)0.0091 (13)0.0220 (17)
C40.0280 (14)0.114 (4)0.0474 (19)0.011 (2)0.0055 (13)0.026 (2)
C50.0402 (17)0.099 (3)0.0350 (16)0.035 (2)0.0108 (13)0.0166 (18)
C60.0443 (16)0.069 (2)0.0263 (13)0.0318 (16)0.0090 (11)0.0073 (13)
C70.078 (3)0.059 (2)0.0299 (14)0.045 (2)0.0083 (15)0.0049 (14)
C80.085 (3)0.0391 (17)0.0282 (14)0.0214 (17)0.0050 (15)0.0006 (12)
C90.0543 (17)0.0383 (15)0.0259 (13)0.0046 (13)0.0041 (12)0.0007 (11)
O90.0656 (15)0.0415 (12)0.0386 (11)0.0059 (11)0.0003 (10)0.0008 (10)
C100.134 (5)0.0350 (17)0.0402 (19)0.015 (2)0.011 (2)0.0002 (14)
C110.108 (4)0.0385 (19)0.0425 (19)0.012 (2)0.005 (2)0.0029 (15)
O120.0292 (9)0.0375 (10)0.0333 (9)0.0067 (8)0.0020 (7)0.0034 (8)
C130.0297 (12)0.0243 (11)0.0385 (14)0.0035 (10)0.0034 (10)0.0002 (10)
C140.0227 (10)0.0222 (11)0.0345 (13)0.0026 (8)0.0013 (9)0.0001 (9)
O140.0258 (8)0.0327 (10)0.0327 (9)0.0036 (7)0.0027 (7)0.0041 (8)
C150.0249 (11)0.0254 (12)0.0385 (14)0.0020 (9)0.0032 (10)0.0026 (10)
C160.0278 (13)0.0506 (18)0.0473 (16)0.0063 (12)0.0016 (12)0.0065 (14)
C170.0453 (16)0.0232 (12)0.0554 (18)0.0015 (11)0.0081 (14)0.0012 (12)
C210.0336 (13)0.0367 (14)0.0247 (12)0.0059 (11)0.0023 (10)0.0025 (10)
C220.0327 (13)0.0433 (15)0.0264 (12)0.0060 (11)0.0031 (10)0.0047 (11)
O220.0341 (10)0.0499 (13)0.0425 (11)0.0051 (9)0.0079 (8)0.0026 (10)
C230.0403 (16)0.075 (3)0.0379 (16)0.0147 (16)0.0059 (13)0.0115 (16)
O230.0622 (17)0.077 (2)0.0711 (18)0.0298 (16)0.0146 (14)0.0066 (16)
C240.0305 (14)0.112 (4)0.0320 (15)0.0002 (18)0.0057 (12)0.0136 (18)
C250.0360 (16)0.092 (3)0.0292 (14)0.0179 (18)0.0067 (12)0.0096 (16)
C260.0367 (14)0.065 (2)0.0243 (12)0.0163 (14)0.0058 (10)0.0075 (13)
C270.0554 (19)0.060 (2)0.0283 (14)0.0278 (16)0.0079 (12)0.0033 (13)
C280.0623 (19)0.0410 (16)0.0258 (13)0.0161 (14)0.0031 (12)0.0040 (11)
C290.0420 (15)0.0372 (14)0.0259 (12)0.0055 (12)0.0011 (11)0.0042 (11)
O290.0486 (12)0.0383 (11)0.0367 (11)0.0042 (9)0.0036 (9)0.0000 (9)
C300.088 (3)0.0370 (16)0.0334 (15)0.0096 (17)0.0019 (16)0.0022 (12)
C310.074 (2)0.0352 (15)0.0385 (16)0.0046 (16)0.0007 (15)0.0036 (13)
O320.0320 (9)0.0362 (10)0.0334 (10)0.0044 (8)0.0050 (7)0.0019 (8)
C330.0253 (11)0.0395 (14)0.0312 (12)0.0010 (10)0.0030 (9)0.0020 (11)
C340.0216 (10)0.0274 (12)0.0323 (12)0.0018 (9)0.0021 (9)0.0020 (10)
O340.0262 (9)0.0290 (10)0.0366 (10)0.0001 (7)0.0035 (7)0.0043 (7)
C350.0246 (11)0.0289 (12)0.0333 (12)0.0028 (9)0.0028 (9)0.0024 (10)
C360.0467 (16)0.0296 (14)0.0458 (16)0.0062 (12)0.0019 (13)0.0000 (12)
C370.0243 (11)0.0529 (17)0.0402 (14)0.0045 (12)0.0074 (10)0.0043 (13)
N1D0.0378 (13)0.0369 (13)0.0572 (16)0.0002 (11)0.0058 (11)0.0051 (12)
C2D0.063 (2)0.070 (3)0.0417 (18)0.0123 (19)0.0071 (16)0.0037 (17)
C3D0.091 (3)0.120 (5)0.039 (2)0.000 (3)0.013 (2)0.007 (2)
C4D0.045 (2)0.043 (2)0.169 (6)0.0021 (18)0.010 (3)0.009 (3)
O4D0.058 (2)0.064 (2)0.277 (7)0.0061 (17)0.024 (3)0.060 (3)
Geometric parameters (Å, º) top
C1—O121.366 (3)O22—C231.383 (4)
C1—C21.392 (4)C23—O231.200 (5)
C1—C91.399 (4)C23—C241.452 (6)
C2—O21.369 (4)C24—C251.318 (7)
C2—C61.415 (4)C24—H240.9500
O2—C31.388 (4)C25—C261.437 (5)
C3—O31.195 (5)C25—H250.9500
C3—C41.440 (6)C26—C271.390 (6)
C4—C51.312 (8)C27—C281.377 (5)
C4—H40.9500C27—H270.9500
C5—C61.443 (6)C28—C291.400 (4)
C5—H50.9500C28—C301.440 (5)
C6—C71.391 (6)C29—O291.360 (4)
C7—C81.387 (6)O29—C311.387 (4)
C7—H70.9500C30—C311.343 (6)
C8—C91.397 (5)C30—H300.9500
C8—C101.452 (7)C31—H310.9500
C9—O91.353 (4)O32—C331.447 (3)
O9—C111.389 (5)C33—C341.516 (3)
C10—C111.329 (8)C33—H3310.9900
C10—H100.9500C33—H3320.9900
C11—H110.9500C34—O341.414 (3)
O12—C131.443 (3)C34—C351.559 (4)
C13—C141.508 (4)C34—H341.0000
C13—H1310.9900C35—C361.519 (4)
C13—H1320.9900C35—C371.522 (3)
C14—O141.422 (3)C36—H3610.9800
C14—C151.548 (4)C36—H3620.9800
C14—H141.0000C36—H3630.9800
O14—C351.442 (3)C37—H3710.9800
C15—O341.445 (3)C37—H3720.9800
C15—C161.521 (4)C37—H3730.9800
C15—C171.523 (4)N1D—C4D1.319 (5)
C16—H1610.9800N1D—C2D1.419 (5)
C16—H1620.9800N1D—C3D1.424 (6)
C16—H1630.9800C2D—H21D0.9800
C17—H1710.9800C2D—H22D0.9800
C17—H1720.9800C2D—H23D0.9800
C17—H1730.9800C3D—H31D0.9800
C21—O321.364 (3)C3D—H32D0.9800
C21—C221.387 (4)C3D—H33D0.9800
C21—C291.396 (4)C4D—O4D1.149 (5)
C22—O221.371 (4)C4D—H4D0.9500
C22—C261.408 (4)
O12—C1—C2124.2 (3)O22—C23—C24116.2 (4)
O12—C1—C9119.5 (3)C25—C24—C23122.2 (3)
C2—C1—C9115.8 (3)C25—C24—H24118.9
O2—C2—C1116.7 (2)C23—C24—H24118.9
O2—C2—C6121.5 (3)C24—C25—C26121.4 (3)
C1—C2—C6121.8 (3)C24—C25—H25119.3
C2—O2—C3122.3 (3)C26—C25—H25119.3
O3—C3—O2116.3 (3)C27—C26—C22120.2 (3)
O3—C3—C4127.7 (4)C27—C26—C25123.2 (3)
O2—C3—C4116.0 (4)C22—C26—C25116.6 (3)
C5—C4—C3122.7 (3)C28—C27—C26118.9 (3)
C5—C4—H4118.7C28—C27—H27120.5
C3—C4—H4118.7C26—C27—H27120.5
C4—C5—C6121.8 (3)C27—C28—C29119.6 (3)
C4—C5—H5119.1C27—C28—C30136.0 (3)
C6—C5—H5119.1C29—C28—C30104.3 (3)
C7—C6—C2120.4 (3)O29—C29—C21125.2 (3)
C7—C6—C5123.8 (3)O29—C29—C28111.3 (3)
C2—C6—C5115.7 (4)C21—C29—C28123.4 (3)
C8—C7—C6119.0 (3)C29—O29—C31105.6 (3)
C8—C7—H7120.5C31—C30—C28107.4 (3)
C6—C7—H7120.5C31—C30—H30126.3
C7—C8—C9119.4 (3)C28—C30—H30126.3
C7—C8—C10136.8 (4)C30—C31—O29111.3 (3)
C9—C8—C10103.8 (4)C30—C31—H31124.4
O9—C9—C8111.9 (3)O29—C31—H31124.4
O9—C9—C1124.5 (3)C21—O32—C33116.4 (2)
C8—C9—C1123.6 (3)O32—C33—C34112.4 (2)
C9—O9—C11105.2 (3)O32—C33—H331109.1
C11—C10—C8107.1 (4)C34—C33—H331109.1
C11—C10—H10126.4O32—C33—H332109.1
C8—C10—H10126.4C34—C33—H332109.1
C10—C11—O9112.0 (4)H331—C33—H332107.9
C10—C11—H11124.0O34—C34—C33107.1 (2)
O9—C11—H11124.0O34—C34—C35109.3 (2)
C1—O12—C13116.6 (2)C33—C34—C35112.3 (2)
O12—C13—C14113.3 (2)O34—C34—H34109.4
O12—C13—H131108.9C33—C34—H34109.4
C14—C13—H131108.9C35—C34—H34109.4
O12—C13—H132108.9C34—O34—C15113.32 (18)
C14—C13—H132108.9O14—C35—C36109.9 (2)
H131—C13—H132107.7O14—C35—C37103.9 (2)
O14—C14—C13107.0 (2)C36—C35—C37111.1 (2)
O14—C14—C15109.19 (19)O14—C35—C34108.0 (2)
C13—C14—C15111.4 (2)C36—C35—C34110.5 (2)
O14—C14—H14109.7C37—C35—C34113.2 (2)
C13—C14—H14109.7C35—C36—H361109.5
C15—C14—H14109.7C35—C36—H362109.5
C14—O14—C35113.52 (19)H361—C36—H362109.5
O34—C15—C16109.3 (2)C35—C36—H363109.5
O34—C15—C17103.9 (2)H361—C36—H363109.5
C16—C15—C17111.4 (3)H362—C36—H363109.5
O34—C15—C14108.4 (2)C35—C37—H371109.5
C16—C15—C14110.3 (2)C35—C37—H372109.5
C17—C15—C14113.3 (2)H371—C37—H372109.5
C15—C16—H161109.5C35—C37—H373109.5
C15—C16—H162109.5H371—C37—H373109.5
H161—C16—H162109.5H372—C37—H373109.5
C15—C16—H163109.5C4D—N1D—C2D124.3 (4)
H161—C16—H163109.5C4D—N1D—C3D116.8 (4)
H162—C16—H163109.5C2D—N1D—C3D118.1 (4)
C15—C17—H171109.5N1D—C2D—H21D109.5
C15—C17—H172109.5N1D—C2D—H22D109.5
H171—C17—H172109.5H21D—C2D—H22D109.5
C15—C17—H173109.5N1D—C2D—H23D109.5
H171—C17—H173109.5H21D—C2D—H23D109.5
H172—C17—H173109.5H22D—C2D—H23D109.5
O32—C21—C22120.5 (3)N1D—C3D—H31D109.5
O32—C21—C29123.8 (3)N1D—C3D—H32D109.5
C22—C21—C29115.4 (3)H31D—C3D—H32D109.5
O22—C22—C21116.2 (3)N1D—C3D—H33D109.5
O22—C22—C26121.3 (3)H31D—C3D—H33D109.5
C21—C22—C26122.4 (3)H32D—C3D—H33D109.5
C22—O22—C23122.2 (3)O4D—C4D—N1D132.2 (6)
O23—C23—O22116.6 (4)O4D—C4D—H4D113.9
O23—C23—C24127.2 (4)N1D—C4D—H4D113.9
O12—C1—C2—O24.5 (4)C21—C22—O22—C23179.1 (3)
C9—C1—C2—O2176.5 (2)C26—C22—O22—C231.5 (4)
O12—C1—C2—C6172.7 (2)C22—O22—C23—O23179.7 (3)
C9—C1—C2—C60.7 (4)C22—O22—C23—C240.8 (4)
C1—C2—O2—C3176.4 (3)O23—C23—C24—C25179.0 (4)
C6—C2—O2—C30.8 (4)O22—C23—C24—C251.5 (5)
C2—O2—C3—O3178.5 (3)C23—C24—C25—C260.0 (5)
C2—O2—C3—C41.8 (4)O22—C22—C26—C27178.4 (3)
O3—C3—C4—C5179.8 (4)C21—C22—C26—C271.0 (4)
O2—C3—C4—C50.5 (5)O22—C22—C26—C252.9 (4)
C3—C4—C5—C61.7 (5)C21—C22—C26—C25177.7 (3)
O2—C2—C6—C7176.7 (3)C24—C25—C26—C27179.2 (3)
C1—C2—C6—C70.4 (4)C24—C25—C26—C222.2 (4)
O2—C2—C6—C51.3 (4)C22—C26—C27—C281.3 (4)
C1—C2—C6—C5178.4 (3)C25—C26—C27—C28179.8 (3)
C4—C5—C6—C7175.4 (3)C26—C27—C28—C292.5 (4)
C4—C5—C6—C22.6 (5)C26—C27—C28—C30174.7 (3)
C2—C6—C7—C80.4 (4)O32—C21—C29—O291.5 (4)
C5—C6—C7—C8177.5 (3)C22—C21—C29—O29175.8 (2)
C6—C7—C8—C90.7 (5)O32—C21—C29—C28174.8 (3)
C6—C7—C8—C10179.3 (4)C22—C21—C29—C280.5 (4)
C7—C8—C9—O9179.4 (3)C27—C28—C29—O29178.4 (3)
C10—C8—C9—O90.6 (3)C30—C28—C29—O290.4 (3)
C7—C8—C9—C10.4 (5)C27—C28—C29—C211.6 (4)
C10—C8—C9—C1179.6 (3)C30—C28—C29—C21176.4 (3)
O12—C1—C9—O96.1 (4)C21—C29—O29—C31176.3 (3)
C2—C1—C9—O9178.5 (3)C28—C29—O29—C310.4 (3)
O12—C1—C9—C8172.8 (3)C27—C28—C30—C31177.7 (4)
C2—C1—C9—C80.3 (4)C29—C28—C30—C310.2 (3)
C8—C9—O9—C110.6 (4)C28—C30—C31—O290.0 (4)
C1—C9—O9—C11179.6 (3)C29—O29—C31—C300.2 (3)
C7—C8—C10—C11179.6 (4)C22—C21—O32—C33125.4 (3)
C9—C8—C10—C110.3 (4)C29—C21—O32—C3360.6 (3)
C8—C10—C11—O90.0 (4)C21—O32—C33—C3475.2 (3)
C9—O9—C11—C100.4 (4)O32—C33—C34—O3466.7 (3)
C2—C1—O12—C1367.4 (3)O32—C33—C34—C35173.4 (2)
C9—C1—O12—C13120.8 (3)C33—C34—O34—C15169.7 (2)
C1—O12—C13—C1475.1 (3)C35—C34—O34—C1568.4 (2)
O12—C13—C14—O1466.3 (3)C16—C15—O34—C3488.9 (3)
O12—C13—C14—C15174.4 (2)C17—C15—O34—C34152.1 (2)
C13—C14—O14—C35170.9 (2)C14—C15—O34—C3431.4 (3)
C15—C14—O14—C3568.4 (3)C14—O14—C35—C3689.2 (3)
O14—C14—C15—O3434.2 (3)C14—O14—C35—C37151.8 (2)
C13—C14—C15—O34152.2 (2)C14—O14—C35—C3431.4 (3)
O14—C14—C15—C16153.8 (2)O34—C34—C35—O1434.3 (3)
C13—C14—C15—C1688.2 (3)C33—C34—C35—O14152.9 (2)
O14—C14—C15—C1780.5 (3)O34—C34—C35—C36154.5 (2)
C13—C14—C15—C1737.5 (3)C33—C34—C35—C3686.8 (3)
O32—C21—C22—O223.1 (4)O34—C34—C35—C3780.1 (3)
C29—C21—C22—O22177.6 (2)C33—C34—C35—C3738.5 (3)
O32—C21—C22—C26176.3 (2)C2D—N1D—C4D—O4D7.3 (8)
C29—C21—C22—C261.8 (4)C3D—N1D—C4D—O4D177.4 (6)

Experimental details

(I)(II)
Crystal data
Chemical formulaC32H28O10·2C2H6OSC32H28O10·C3H7NO
Mr728.80645.64
Crystal system, space groupOrthorhombic, P212121Monoclinic, P21
Temperature (K)200200
a, b, c (Å)10.903 (2), 13.068 (2), 24.400 (4)8.2000 (7), 16.2132 (14), 11.6706 (10)
α, β, γ (°)90, 90, 9090, 97.244 (1), 90
V3)3476.5 (11)1539.2 (2)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.220.10
Crystal size (mm)0.50 × 0.20 × 0.040.50 × 0.40 × 0.04
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Bruker SMART APEX area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.913, 1.00.932, 1.0
No. of measured, independent and
observed [I > 2σ(I)] reflections
30564, 7659, 7041 13520, 3516, 3381
Rint0.0260.017
(sin θ/λ)max1)0.6410.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.099, 0.90 0.042, 0.116, 1.04
No. of reflections76593516
No. of parameters498430
No. of restraints183
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.190.67, 0.38
Absolute structureFlack (1983), 3379 Friedel pairs?
Absolute structure parameter0.04 (6)?

Computer programs: SMART (Bruker, 1998), SMART, SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2001).

Selected torsion angles (°). top
DMSO formDMF form
Dioxane ring
C35O14C14C1567.6 (2)68.4 (3)
O14C14C15O34-38.0 (2)-34.2 (3)
C14C15O34C34-26.5 (2)-31.4 (3)
C15O34C34C3566.1 (2)68.4 (2)
O34C34C35O14-36.4 (2)-34.3 (3)
C34C35O14C14-27.6 (2)-31.4 (3)
Ether linkage
C2C1O12C13-137.6 (2)67.4 (3)
C1O12C13C14-170.7 (1)75.1 (3)
O12C13C14O1479.4 (2)66.3 (3)
C22C21O32C33-146.1 (2)-125.4 (2)
C21O32C33C34-164.1 (2)75.2 (3)
O32C33C34O3475.0 (2)66.7 (3)
 

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