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The title mol­ecule, 2′-pyrenyl­spiro­[2,3-di­hydro-1H-cyclo­penta­[b]­naphthalene-2,5′-1′,3′-dioxane]-4,9-dione, C32H22O4, contains an electron-donating pyrene group spiro-linked to an electron-accepting naphtho­quinone. The mol­ecules are V-shaped in profile and stack to form columns along b with alternating, approximately coplanar, pyrene and naphtho­quinone fragments. Intermolecular contacts within a column are consistent with some degree of π contact and possible long-range delocalization. Individual columns form a herringbone pattern when the crystal is viewed along b.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012750/bk1564sup1.cif
Contains datablocks I, pfinal

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012750/bk1564Isup2.hkl
Contains datablock I

CCDC reference: 156178

Comment top

As part of a project designed to study the distance dependence of electron transfer, a series of porphyrin-quinone compounds containing oligospirocyclobutane linkers were prepared and studied (Knapp et al., 1991). Theory suggests that the rate of through-bond electron transfer depends on the edge-to-edge porphyrin-to-quinone distance Re according to kET = exp(-bRe), where b is a constant determined experimentally (Wasielewski, 1992; Closs & Miller, 1988). Difficulty in crystallizing the several porphyrin-quinone compounds Ia-d in order to determine Re values prompted us to prepare the title complex (I) in which a bulky tetraarylporphyrin group is replaced by pyrene. We report here the crystal structure of the model compound (I) which, in conjunction with an oligospirocyclobutane model, permitted reasonable estimates of Re for the porphyrin-quinone compounds to be obtained (Knapp et al., 1991). \sch

Compound (II) (Fig. 1) crystallized in space group Pna21 with two molecules per asymmetric unit. The two independent molecules exhibit similar metric parameters (Table 1) and are related by a pseudo-21 screw axis parallel to b at x = 0.633 (4) and z = 0.464 (1). The crystal is pseudocentrosymmetric with inversion centers located at [0.883 (4), −0.006 (5), 0.464 (1)] and related locations (the Z coordinates of the pseudo symmetry elements are consonant with the structural parameters as refined). These observations suggest that the crystal is possibly inversion twinned. Based on Δf'' values of 0.009 and 0.032 for C and O, respectively, anomalous scattering is calculated to be approximately 0.16% of the total, a value too small to produce a significant Flack parameter evaluation. Indeed, refinement of the original structure, the structure inverted through the origin, and the structure inverted through the pseudocenter of symmetry gave identical R(F2), wR(F2) and S values, and Flack parameters of 0.3 (3), 0.7 (3) and 0.3 (3), respectively.

Molecules of (I) may be viewed as containing an electron-donating group (pyrene) separated from an electron-accepting group (naphthoquinone) by a fused cyclopentene ring and a spiro-linked 1,3-dioxane ring. The pyrene fragments (C2—C17) exhibit a maximum atomic deviation from planarity of 0.04 Å while the naphthoquinone fragments (C23—C32, O3, O4) are less planar and show a maximum deviation of 0.08 Å. Deviations of these magnitudes are consistent with those reported for other pyrene- (Kai et al., 1978) and naphthoquinone-containing (Michael et al., 1990) structures. Dihedral angles between the pyrene and naphthoquinone fragments are 71.17 (5) and 70.72 (5)° for the unlettered and "a" molecules, respectively. The five-membered cyclopentene and six-membered dioxane rings are in the expected envelope and chair conformations, respectively. These geometric features, coupled with the torsion angles about C1—C2 and the spiro linkage at C19 (Table 1), combine to give the molecules a V-shaped appearance when viewed approximately in profile (Fig. 1). The largest correlation coefficients, ranging from ±0.71 to ±0.82, are between the Z, U22 or U23 parameters for C3, C9, O2, C20, C17 amd C31, and their pseudo-inversion mates. These values are consistent with the slightly unusual appearance of the displacement ellipsoids of these atoms (Fig. 1).

The crystal contains columns of equally spaced molecules related by the pseudo-21 screw axis parallel to b. Within a column, pyrene and naphthoquinone fragments alternate and are approximately coplanar; the intermolecular P···Qa and Pa···Q dihedral angles are 3.2 (1)° and 4.2 (1)°, respectively, where P and Q refer to the pyrene and naphthoquinone fragments and "a" is used to designate the second molecule in the asymmetric unit. Several short intermolecular P···Q contacts within a column [the shortest is C8···C26a 3.468 (9) Å] are consistent with some degree of π contact between adjacent pyrene and quinone units, while the regular spacing of P—Q units along b suggests the possibility of long-range delocalization in that direction. When the crystal is viewed along b, the columns are seen to pack together in a herringbone arrangement generated by the n and a glide planes.

Experimental top

Pyrene-1-carboxaldehyde dimethylacetal was prepared from commercial pyrene-1-carboxaldehyde by treatment with trimethylorthoformate (Buchler et al., 1988). The pyrene acetal (II) was prepared by acetal exchange (toluene, acetonitrile, pyridinium p-toluenesulfonate, reflux 30 min, 97% yield) of pyrene-1-carboxaldehyde dimethylacetal with a naphthoquinonediol (Albaneze, 1993) as described previously (Knapp et al., 1991; Gentemann et al., 1994). Crystals suitable for X-ray analysis were grown by slow diffusion of pentane vapor into a chloroform/toluene solution of (II) at room temperature. The crystal chosen for study showed sharp extinctions and exhibited orange-yellow dichroism when examined under polarized light.

Refinement top

Axial photographs revealed mmm reciprocal lattice point symmetry with the cell edges given in the table above. Systematic absences were consistent with space groups Pnma and Pna21; attempts to solve the structure in Pnma using either direct or Patterson methods were unsuccessful. A packing diagram viewed along b revealed that the mirror planes perpendicular to c that are required in space group Pnam, an alternate setting of Pnma, are impossible. H atoms were placed at sp2 or sp3 calculated positions with C—H distances equal to 0.98, 0.97 or 0.93 Å for tertiary, secondary or aromatic C—H linkages, respectively. H atom displacement parameters were set as Uiso(H) = 1.2 Ueq(C) and were treated as riding during refinement.

Computing details top

Data collection: Structure Determination Package (Enraf Nonius, 1985); cell refinement: Structure Determination Package; data reduction: local programs; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1976) and ORTEP-32 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing 30% probability displacement ellipsoids. H atoms are omitted for clarity.
(I) top
Crystal data top
C32H22O4F(000) = 1968
Mr = 470.5Dx = 1.374 Mg m3
Dm = 1.36 (1) Mg m3
Dm measured by flotation
Orthorhombic, Pna21Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2c -2nCell parameters from 25 reflections
a = 16.591 (2) Åθ = 19.6–25.9°
b = 8.8487 (7) ŵ = 0.72 mm1
c = 30.996 (9) ÅT = 295 K
V = 4550.5 (15) Å3Flat rod, gold
Z = 80.50 × 0.18 × 0.05 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
3023 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.055
Graphite monochromatorθmax = 70.0°, θmin = 2.9°
ωθ scansh = 1820
Absorption correction: numerical
SHELX76
k = 1010
Tmin = 0.867, Tmax = 0.964l = 3437
10756 measured reflections3 standard reflections every 180 min
5587 independent reflections intensity decay: 2%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.044 w = 1/[σ2(Fo2) + (0.027P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.085(Δ/σ)max = 0.011
S = 0.99Δρmax = 0.18 e Å3
5587 reflectionsΔρmin = 0.19 e Å3
650 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.00027 (2)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.3 (3)
Crystal data top
C32H22O4V = 4550.5 (15) Å3
Mr = 470.5Z = 8
Orthorhombic, Pna21Cu Kα radiation
a = 16.591 (2) ŵ = 0.72 mm1
b = 8.8487 (7) ÅT = 295 K
c = 30.996 (9) Å0.50 × 0.18 × 0.05 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
3023 reflections with I > 2σ(I)
Absorption correction: numerical
SHELX76
Rint = 0.055
Tmin = 0.867, Tmax = 0.9643 standard reflections every 180 min
10756 measured reflections intensity decay: 2%
5587 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.085Δρmax = 0.18 e Å3
S = 0.99Δρmin = 0.19 e Å3
5587 reflectionsAbsolute structure: Flack (1983)
650 parametersAbsolute structure parameter: 0.3 (3)
1 restraint
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
O10.56963 (19)0.0004 (4)0.47569 (12)0.0467 (10)
O20.5483 (2)0.2567 (4)0.46254 (16)0.0391 (13)
O1A0.69274 (18)0.5000 (4)0.45062 (11)0.0450 (10)
O2A0.7141 (2)0.7567 (4)0.46484 (15)0.0385 (13)
C10.5174 (3)0.1242 (7)0.48347 (17)0.0413 (15)
H10.46290.10150.47320.050*
C1A0.7441 (3)0.6253 (7)0.44365 (18)0.0450 (15)
H1A0.79900.60260.45330.054*
C180.5744 (3)0.0331 (7)0.42988 (17)0.0508 (18)
H18A0.52100.05300.41850.061*
H18B0.60750.12190.42520.061*
C18A0.6887 (3)0.4660 (7)0.49580 (16)0.0456 (17)
H18C0.74240.44550.50670.055*
H18D0.65610.37630.50020.055*
C190.6114 (3)0.1032 (6)0.40716 (16)0.0354 (14)
C19A0.6527 (3)0.5960 (6)0.52006 (16)0.0362 (14)
C200.5572 (3)0.2369 (6)0.4172 (2)0.041 (2)
H20A0.58020.32780.40470.049*
H20B0.50470.22080.40420.049*
C20A0.7055 (3)0.7348 (6)0.5108 (2)0.0390 (19)
H20C0.68100.82380.52360.047*
H20D0.75820.72090.52380.047*
C210.6169 (3)0.0796 (7)0.35783 (16)0.0486 (16)
H21A0.62450.02620.35070.058*
H21B0.56910.11700.34330.058*
C21A0.6483 (3)0.5727 (6)0.57002 (15)0.0461 (15)
H21C0.64190.46680.57730.055*
H21D0.69590.61210.58420.055*
C220.6993 (3)0.1321 (6)0.42095 (15)0.0405 (15)
H22A0.70200.20030.44540.049*
H22B0.72660.03850.42820.049*
C22A0.5644 (3)0.6306 (6)0.50667 (16)0.0394 (15)
H22C0.56240.70390.48340.047*
H22D0.53650.53950.49780.047*
O30.6657 (3)0.2031 (6)0.27222 (15)0.0784 (15)
O3A0.6000 (3)0.6858 (6)0.65586 (14)0.0766 (14)
O40.8496 (2)0.3161 (6)0.41055 (14)0.0605 (12)
O4A0.4120 (2)0.8116 (6)0.51921 (13)0.0598 (12)
C20.5162 (3)0.1607 (7)0.53098 (16)0.0403 (15)
C2A0.7434 (3)0.6663 (7)0.39604 (16)0.0357 (14)
C30.4555 (3)0.2535 (6)0.5479 (3)0.037 (2)
C3A0.8033 (3)0.7596 (6)0.3791 (2)0.040 (2)
C40.3920 (3)0.3135 (8)0.52296 (17)0.0460 (15)
H40.38950.28960.49380.055*
C4A0.8703 (3)0.8174 (7)0.40471 (18)0.0453 (15)
H4A0.87430.79140.43370.054*
C50.3345 (3)0.4046 (7)0.53998 (17)0.0535 (17)
H50.29390.44230.52230.064*
C5A0.9263 (3)0.9077 (7)0.38703 (16)0.0519 (17)
H5A0.96820.94300.40420.062*
C60.3353 (3)0.4437 (7)0.58499 (17)0.0410 (16)
C6A0.9235 (3)0.9517 (7)0.34229 (17)0.0454 (16)
C70.3968 (3)0.3824 (7)0.61119 (17)0.0414 (16)
C7A0.8600 (3)0.9002 (6)0.31697 (16)0.0356 (14)
C80.4581 (3)0.2880 (7)0.5919 (2)0.0404 (16)
C8A0.8000 (3)0.8036 (7)0.33439 (19)0.0385 (14)
C90.5216 (4)0.2370 (7)0.6193 (3)0.041 (2)
C9A0.7369 (4)0.7489 (7)0.3091 (3)0.048 (2)
C100.5808 (3)0.1462 (7)0.60063 (18)0.0493 (18)
H100.62270.10920.61750.059*
C10A0.6779 (4)0.6593 (7)0.3273 (2)0.0580 (18)
H10A0.63500.62660.31030.070*
C110.5776 (3)0.1105 (6)0.55678 (19)0.0494 (16)
H110.61810.05120.54480.059*
C11A0.6813 (3)0.6179 (7)0.36969 (18)0.0504 (17)
H11A0.64120.55610.38100.060*
C120.2783 (3)0.5385 (7)0.6042 (2)0.0583 (19)
H120.23770.57920.58710.070*
C12A0.9813 (3)1.0457 (6)0.32420 (18)0.0500 (16)
H12A1.02371.08020.34120.060*
C130.2800 (4)0.5730 (7)0.64662 (19)0.0587 (18)
H130.24090.63600.65840.070*
C13A0.9769 (4)1.0891 (7)0.2811 (2)0.0613 (18)
H13A1.01601.15210.26930.074*
C140.3400 (4)0.5143 (9)0.6723 (2)0.061 (2)
H140.34090.53850.70150.073*
C14A0.9132 (4)1.0370 (8)0.2558 (2)0.0579 (19)
H14A0.90981.06660.22700.069*
C150.3998 (3)0.4187 (7)0.65540 (18)0.0459 (16)
C15A0.8552 (3)0.9421 (7)0.27271 (18)0.0453 (17)
C160.4625 (3)0.3591 (7)0.68125 (18)0.0557 (18)
H160.46300.37840.71070.067*
C16A0.7897 (4)0.8837 (8)0.24735 (19)0.0630 (19)
H16A0.78600.91150.21850.076*
C170.5216 (4)0.2745 (8)0.6635 (3)0.064 (2)
H170.56330.24000.68090.077*
C17A0.7338 (4)0.7908 (9)0.2637 (2)0.0544 (19)
H17A0.69300.75320.24610.065*
C230.7345 (3)0.2027 (8)0.3811 (2)0.0399 (16)
C23A0.5290 (3)0.6942 (7)0.54766 (18)0.0368 (14)
C240.8081 (3)0.2904 (8)0.3789 (2)0.0418 (17)
C24A0.4549 (3)0.7849 (8)0.5511 (2)0.048 (2)
C250.8303 (3)0.3572 (7)0.33582 (19)0.0464 (16)
C25A0.4343 (3)0.8422 (7)0.59478 (18)0.0418 (15)
C260.8961 (4)0.4501 (8)0.3316 (2)0.0623 (19)
H260.92600.47790.35570.075*
C26A0.3679 (3)0.9355 (7)0.5994 (2)0.0555 (18)
H26A0.33800.96350.57530.067*
C270.9178 (4)0.5028 (8)0.2903 (3)0.076 (2)
H270.96310.56390.28730.091*
C27A0.3461 (4)0.9872 (8)0.6401 (2)0.072 (2)
H27A0.30241.05210.64330.086*
C280.8737 (4)0.4657 (9)0.2548 (3)0.074 (2)
H280.88790.50290.22780.089*
C28A0.3894 (4)0.9416 (8)0.6758 (2)0.072 (2)
H28A0.37290.97170.70310.086*
C290.8077 (4)0.3725 (8)0.2594 (2)0.070 (2)
H290.77810.34610.23500.085*
C29A0.4570 (4)0.8520 (8)0.6715 (2)0.0663 (19)
H29A0.48740.82440.69540.080*
C300.7843 (4)0.3171 (8)0.2994 (2)0.0539 (17)
C30A0.4781 (4)0.8047 (8)0.6308 (2)0.0475 (16)
C310.7105 (4)0.2281 (8)0.3025 (3)0.056 (2)
C31A0.5537 (4)0.7134 (8)0.6251 (2)0.0506 (19)
C320.6898 (3)0.1713 (7)0.34626 (18)0.0441 (16)
C32A0.5748 (3)0.6619 (6)0.58173 (18)0.0374 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.062 (2)0.029 (3)0.049 (3)0.006 (2)0.005 (2)0.006 (2)
O20.052 (2)0.021 (3)0.044 (3)0.0034 (18)0.010 (2)0.0019 (17)
O1A0.053 (2)0.039 (3)0.042 (2)0.008 (2)0.0090 (19)0.001 (2)
O2A0.047 (2)0.040 (4)0.028 (3)0.0019 (18)0.001 (2)0.0019 (18)
C10.050 (4)0.026 (4)0.048 (4)0.005 (3)0.001 (3)0.001 (3)
C1A0.039 (3)0.043 (5)0.053 (4)0.001 (3)0.013 (3)0.006 (4)
C180.068 (4)0.037 (5)0.047 (4)0.001 (3)0.008 (3)0.014 (3)
C18A0.047 (3)0.047 (5)0.043 (4)0.003 (3)0.005 (3)0.003 (3)
C190.041 (3)0.027 (4)0.038 (3)0.003 (3)0.003 (3)0.004 (3)
C19A0.039 (3)0.030 (4)0.039 (3)0.004 (3)0.000 (3)0.001 (3)
C200.046 (4)0.046 (5)0.030 (4)0.004 (3)0.003 (3)0.002 (3)
C20A0.046 (3)0.034 (5)0.037 (5)0.000 (3)0.004 (3)0.002 (3)
C210.052 (4)0.047 (4)0.047 (4)0.012 (3)0.011 (3)0.013 (3)
C21A0.049 (4)0.053 (4)0.036 (3)0.000 (3)0.003 (3)0.007 (3)
C220.045 (3)0.043 (4)0.033 (3)0.007 (3)0.000 (3)0.001 (3)
C22A0.037 (3)0.039 (4)0.043 (3)0.010 (3)0.001 (3)0.003 (3)
O30.072 (3)0.121 (4)0.042 (3)0.001 (3)0.010 (2)0.001 (3)
O3A0.090 (3)0.105 (4)0.035 (3)0.013 (3)0.001 (2)0.016 (3)
O40.046 (2)0.077 (3)0.058 (3)0.002 (2)0.004 (2)0.003 (3)
O4A0.041 (2)0.090 (3)0.049 (3)0.007 (3)0.006 (2)0.005 (3)
C20.044 (4)0.044 (5)0.033 (4)0.001 (3)0.001 (3)0.003 (3)
C2A0.044 (4)0.028 (4)0.035 (4)0.005 (3)0.005 (3)0.005 (3)
C30.042 (4)0.034 (5)0.036 (5)0.000 (3)0.003 (3)0.011 (3)
C3A0.042 (4)0.046 (6)0.032 (5)0.001 (3)0.001 (3)0.005 (3)
C40.053 (4)0.058 (4)0.027 (3)0.001 (4)0.002 (3)0.006 (4)
C4A0.048 (4)0.046 (4)0.042 (4)0.013 (3)0.002 (3)0.003 (4)
C50.047 (4)0.066 (5)0.048 (4)0.010 (4)0.001 (3)0.001 (4)
C5A0.064 (4)0.057 (5)0.035 (4)0.013 (4)0.004 (3)0.000 (3)
C60.045 (4)0.039 (4)0.039 (4)0.003 (3)0.006 (3)0.003 (3)
C6A0.044 (4)0.050 (5)0.042 (4)0.004 (3)0.001 (3)0.001 (3)
C70.044 (4)0.044 (4)0.036 (4)0.004 (3)0.005 (3)0.007 (3)
C7A0.042 (4)0.032 (4)0.033 (3)0.011 (3)0.009 (3)0.000 (3)
C80.036 (3)0.048 (4)0.038 (4)0.004 (3)0.002 (3)0.009 (4)
C8A0.048 (4)0.036 (4)0.031 (4)0.001 (3)0.005 (3)0.000 (4)
C90.047 (4)0.030 (5)0.046 (5)0.004 (3)0.008 (3)0.002 (3)
C9A0.050 (4)0.058 (7)0.036 (5)0.003 (3)0.003 (3)0.002 (3)
C100.053 (4)0.050 (5)0.045 (4)0.011 (3)0.005 (3)0.007 (3)
C10A0.062 (4)0.054 (5)0.057 (5)0.000 (4)0.018 (4)0.005 (4)
C110.052 (4)0.037 (4)0.060 (4)0.001 (3)0.005 (3)0.001 (3)
C11A0.050 (4)0.054 (5)0.047 (4)0.014 (3)0.007 (3)0.005 (3)
C120.057 (4)0.067 (5)0.051 (4)0.020 (4)0.012 (3)0.000 (4)
C12A0.047 (4)0.053 (5)0.050 (4)0.003 (3)0.003 (3)0.005 (4)
C130.067 (4)0.068 (5)0.041 (4)0.017 (4)0.003 (3)0.002 (4)
C13A0.065 (4)0.054 (5)0.065 (5)0.004 (4)0.019 (4)0.013 (4)
C140.072 (4)0.075 (5)0.035 (4)0.007 (4)0.003 (4)0.012 (4)
C14A0.058 (4)0.067 (5)0.048 (4)0.015 (4)0.006 (3)0.004 (4)
C150.052 (4)0.046 (4)0.039 (4)0.004 (3)0.006 (3)0.003 (3)
C15A0.045 (4)0.056 (5)0.036 (4)0.008 (3)0.004 (3)0.001 (3)
C160.055 (4)0.071 (5)0.041 (4)0.005 (4)0.004 (3)0.008 (3)
C16A0.066 (4)0.082 (6)0.041 (4)0.009 (4)0.012 (3)0.005 (4)
C170.052 (5)0.088 (7)0.053 (5)0.003 (4)0.017 (4)0.010 (4)
C17A0.061 (5)0.063 (5)0.039 (5)0.006 (4)0.006 (3)0.002 (4)
C230.041 (3)0.048 (4)0.030 (4)0.006 (3)0.007 (3)0.003 (4)
C23A0.031 (3)0.038 (4)0.041 (4)0.009 (3)0.003 (3)0.002 (4)
C240.037 (3)0.057 (4)0.032 (4)0.009 (3)0.006 (3)0.002 (4)
C24A0.038 (4)0.053 (5)0.053 (5)0.013 (4)0.003 (4)0.001 (4)
C250.034 (3)0.053 (5)0.053 (4)0.017 (3)0.001 (3)0.008 (4)
C25A0.038 (3)0.044 (4)0.043 (4)0.002 (3)0.009 (3)0.002 (3)
C260.049 (4)0.069 (5)0.069 (5)0.017 (4)0.017 (3)0.019 (4)
C26A0.043 (4)0.061 (5)0.062 (5)0.003 (4)0.005 (3)0.006 (4)
C270.053 (4)0.062 (6)0.112 (7)0.023 (4)0.034 (5)0.039 (5)
C27A0.063 (5)0.077 (6)0.076 (6)0.002 (4)0.017 (4)0.012 (5)
C280.068 (5)0.081 (6)0.074 (6)0.023 (5)0.019 (4)0.041 (5)
C28A0.089 (5)0.070 (6)0.055 (5)0.013 (5)0.030 (4)0.011 (4)
C290.070 (5)0.096 (6)0.046 (4)0.013 (4)0.009 (3)0.022 (4)
C29A0.084 (5)0.069 (6)0.046 (4)0.024 (4)0.018 (4)0.006 (4)
C300.042 (4)0.070 (5)0.049 (4)0.025 (4)0.010 (3)0.007 (4)
C30A0.052 (4)0.053 (4)0.037 (4)0.005 (4)0.015 (3)0.002 (4)
C310.062 (5)0.071 (6)0.035 (5)0.023 (4)0.004 (4)0.002 (4)
C31A0.052 (4)0.066 (5)0.034 (4)0.019 (4)0.004 (3)0.010 (4)
C320.040 (3)0.052 (5)0.041 (4)0.006 (3)0.003 (3)0.002 (3)
C32A0.041 (3)0.037 (4)0.034 (3)0.010 (3)0.006 (3)0.012 (3)
Geometric parameters (Å, º) top
O1—C11.417 (5)C7—C81.446 (7)
O1A—C1A1.415 (6)C7A—C8A1.420 (7)
O2—C11.434 (6)C7A—C15A1.423 (7)
O2A—C1A1.424 (6)C8—C91.426 (9)
O1—C181.453 (5)C8A—C9A1.394 (8)
O2—C201.425 (7)C9—C101.393 (8)
O1A—C18A1.434 (5)C9—C171.411 (11)
O2A—C20A1.445 (8)C9A—C10A1.380 (8)
C1—C21.508 (6)C9A—C17A1.455 (11)
C1A—C2A1.519 (7)C10—C111.396 (6)
C18—C191.525 (6)C10A—C11A1.366 (6)
C18A—C19A1.498 (6)C12—C131.350 (7)
C19—C201.518 (6)C12A—C13A1.393 (7)
C19A—C20A1.535 (7)C13—C141.375 (8)
C19—C211.546 (6)C13A—C14A1.394 (8)
C19A—C21A1.564 (6)C14—C151.405 (8)
C19—C221.541 (6)C14A—C15A1.381 (8)
C19A—C22A1.553 (6)C15—C161.415 (7)
C21—C321.500 (6)C15A—C16A1.437 (7)
C21A—C32A1.497 (6)C16—C171.351 (8)
C22—C231.501 (7)C16A—C17A1.340 (8)
C22A—C23A1.509 (7)C23—C321.340 (7)
O3—C311.217 (8)C23—C241.448 (8)
O3A—C31A1.250 (7)C23A—C32A1.332 (7)
O4—C241.221 (6)C23A—C24A1.472 (8)
O4A—C24A1.240 (7)C24—C251.505 (8)
C2—C31.400 (8)C24A—C25A1.487 (8)
C2A—C3A1.396 (7)C25—C261.373 (7)
C2—C111.370 (7)C25—C301.409 (8)
C2A—C11A1.382 (6)C25A—C30A1.371 (7)
C3—C81.397 (9)C25A—C26A1.384 (7)
C3—C41.411 (8)C26—C271.409 (8)
C3A—C8A1.441 (8)C26A—C27A1.391 (8)
C3A—C4A1.458 (8)C27—C281.362 (10)
C4—C51.356 (7)C27A—C28A1.379 (9)
C4A—C5A1.341 (6)C28—C291.378 (9)
C5—C61.437 (7)C28A—C29A1.380 (8)
C5A—C6A1.441 (7)C29—C301.389 (7)
C6—C121.398 (7)C29A—C30A1.375 (8)
C6—C71.412 (7)C30—C311.459 (9)
C6A—C12A1.387 (7)C30A—C31A1.502 (9)
C6A—C7A1.391 (7)C31—C321.487 (9)
C7—C151.408 (7)C31A—C32A1.461 (8)
C1—O1—C18110.9 (4)C10A—C9A—C8A120.1 (7)
C20—O2—C1112.6 (4)C10A—C9A—C17A121.0 (6)
C1A—O1A—C18A110.0 (4)C8A—C9A—C17A118.8 (7)
C1A—O2A—C20A112.3 (4)C9—C10—C11120.5 (6)
O1—C1—O2109.7 (4)C11A—C10A—C9A121.2 (6)
O1A—C1A—O2A111.0 (4)C2—C11—C10121.5 (5)
O1—C1—C2109.9 (5)C10A—C11A—C2A121.1 (5)
O1A—C1A—C2A109.3 (5)C13—C12—C6122.5 (6)
O2—C1—C2105.8 (5)C6A—C12A—C13A121.1 (6)
O2A—C1A—C2A104.5 (5)C12—C13—C14119.5 (6)
O1—C18—C19108.2 (4)C12A—C13A—C14A119.3 (6)
O1A—C18A—C19A110.4 (5)C13—C14—C15121.6 (6)
C18—C19—C20106.5 (4)C15A—C14A—C13A121.0 (6)
C18A—C19A—C20A107.1 (4)C7—C15—C14118.3 (6)
C20—C19—C22112.0 (4)C7—C15—C16119.5 (6)
C20A—C19A—C22A109.2 (4)C14—C15—C16122.2 (6)
C18—C19—C22112.6 (4)C14A—C15A—C7A119.1 (6)
C18A—C19A—C22A113.1 (4)C14A—C15A—C16A122.5 (6)
C20—C19—C21110.0 (5)C7A—C15A—C16A118.4 (6)
C20A—C19A—C21A108.5 (5)C17—C16—C15120.6 (6)
C18—C19—C21112.0 (4)C17A—C16A—C15A122.5 (6)
C18A—C19A—C21A114.5 (4)C16—C17—C9121.8 (6)
C21—C19—C22103.9 (4)C16A—C17A—C9A119.8 (6)
C21A—C19A—C22A104.2 (4)C32—C23—C24122.6 (6)
O2—C20—C19111.0 (4)C32—C23—C22111.2 (5)
O2A—C20A—C19A110.3 (5)C24—C23—C22126.2 (5)
C32—C21—C19102.2 (4)C32A—C23A—C24A122.4 (6)
C32A—C21A—C19A102.1 (4)C32A—C23A—C22A111.5 (5)
C23—C22—C19102.1 (4)C24A—C23A—C22A126.1 (5)
C23A—C22A—C19A102.5 (4)O4—C24—C23122.4 (6)
C3—C2—C11120.4 (6)O4—C24—C25120.1 (6)
C3A—C2A—C11A119.5 (5)C23—C24—C25117.4 (5)
C1—C2—C11119.3 (5)O4A—C24A—C23A121.7 (6)
C1A—C2A—C11A120.4 (5)O4A—C24A—C25A121.9 (6)
C1—C2—C3120.1 (5)C23A—C24A—C25A116.3 (6)
C1A—C2A—C3A120.1 (5)C26—C25—C30120.3 (6)
C8—C3—C2118.1 (6)C26—C25—C24121.0 (5)
C8—C3—C4118.4 (6)C30—C25—C24118.6 (6)
C2—C3—C4123.5 (7)C30A—C25A—C26A118.8 (6)
C2A—C3A—C8A119.6 (5)C30A—C25A—C24A122.4 (6)
C2A—C3A—C4A123.1 (6)C26A—C25A—C24A118.7 (6)
C8A—C3A—C4A117.3 (6)C25—C26—C27119.3 (6)
C5—C4—C3122.4 (5)C25A—C26A—C27A119.8 (6)
C5A—C4A—C3A120.9 (6)C28—C27—C26121.1 (7)
C4—C5—C6120.9 (5)C28A—C27A—C26A119.7 (6)
C4A—C5A—C6A122.1 (5)C27—C28—C29119.3 (7)
C12—C6—C7118.3 (5)C27A—C28A—C29A121.0 (7)
C12—C6—C5123.4 (5)C28—C29—C30121.6 (7)
C7—C6—C5118.3 (5)C30A—C29A—C28A118.0 (7)
C12A—C6A—C7A119.5 (5)C29—C30—C25118.4 (6)
C12A—C6A—C5A122.0 (5)C29—C30—C31119.0 (6)
C7A—C6A—C5A118.6 (5)C25—C30—C31122.5 (6)
C15—C7—C6119.9 (6)C29A—C30A—C25A122.5 (6)
C15—C7—C8120.6 (5)C29A—C30A—C31A118.9 (6)
C6—C7—C8119.5 (5)C25A—C30A—C31A118.5 (6)
C6A—C7A—C8A121.0 (5)O3—C31—C30124.0 (7)
C6A—C7A—C15A120.1 (5)O3—C31—C32120.0 (6)
C8A—C7A—C15A119.0 (5)C30—C31—C32115.9 (6)
C3—C8—C9122.2 (6)O3A—C31A—C32A119.6 (6)
C3—C8—C7120.6 (5)O3A—C31A—C30A122.0 (7)
C9—C8—C7117.2 (6)C32A—C31A—C30A118.4 (6)
C9A—C8A—C7A121.5 (6)C23—C32—C31122.5 (6)
C9A—C8A—C3A118.5 (6)C23—C32—C21111.4 (5)
C7A—C8A—C3A120.1 (5)C31—C32—C21126.0 (5)
C10—C9—C17122.6 (7)C23A—C32A—C31A121.7 (5)
C10—C9—C8117.2 (7)C23A—C32A—C21A112.7 (5)
C17—C9—C8120.2 (7)C31A—C32A—C21A125.6 (5)
C18—O1—C1—O261.8 (5)C3A—C2A—C11A—C10A0.3 (9)
C18—O1—C1—C2177.7 (4)C1A—C2A—C11A—C10A177.1 (5)
C20—O2—C1—O158.4 (5)C7—C6—C12—C130.0 (9)
C20—O2—C1—C2176.9 (4)C5—C6—C12—C13179.6 (6)
C18A—O1A—C1A—O2A61.5 (6)C7A—C6A—C12A—C13A0.1 (8)
C18A—O1A—C1A—C2A176.3 (4)C5A—C6A—C12A—C13A178.9 (5)
C20A—O2A—C1A—O1A58.5 (6)C6—C12—C13—C140.4 (10)
C20A—O2A—C1A—C2A176.2 (4)C6A—C12A—C13A—C14A0.0 (9)
C1—O1—C18—C1963.3 (5)C12—C13—C14—C150.0 (10)
C1A—O1A—C18A—C19A62.7 (5)C12A—C13A—C14A—C15A0.7 (9)
O1—C18—C19—C2058.2 (5)C6—C7—C15—C140.9 (9)
O1—C18—C19—C2264.8 (5)C8—C7—C15—C14178.3 (5)
O1—C18—C19—C21178.5 (4)C6—C7—C15—C16178.8 (5)
O1A—C18A—C19A—C20A57.7 (5)C8—C7—C15—C161.5 (9)
O1A—C18A—C19A—C22A62.8 (5)C13—C14—C15—C70.6 (9)
O1A—C18A—C19A—C21A178.0 (4)C13—C14—C15—C16179.1 (6)
C1—O2—C20—C1956.9 (6)C13A—C14A—C15A—C7A1.4 (9)
C18—C19—C20—O255.8 (5)C13A—C14A—C15A—C16A178.7 (6)
C22—C19—C20—O267.6 (6)C6A—C7A—C15A—C14A1.5 (9)
C21—C19—C20—O2177.4 (4)C8A—C7A—C15A—C14A179.5 (5)
C1A—O2A—C20A—C19A54.8 (5)C6A—C7A—C15A—C16A178.5 (5)
C18A—C19A—C20A—O2A53.4 (5)C8A—C7A—C15A—C16A0.4 (8)
C22A—C19A—C20A—O2A69.4 (5)C7—C15—C16—C173.5 (9)
C21A—C19A—C20A—O2A177.5 (4)C14—C15—C16—C17176.3 (6)
C20—C19—C21—C3292.0 (5)C14A—C15A—C16A—C17A179.5 (6)
C18—C19—C21—C32149.8 (4)C7A—C15A—C16A—C17A0.6 (9)
C22—C19—C21—C3228.1 (6)C15—C16—C17—C92.6 (10)
C18A—C19A—C21A—C32A149.1 (4)C10—C9—C17—C16178.1 (6)
C20A—C19A—C21A—C32A91.3 (5)C8—C9—C17—C160.2 (10)
C22A—C19A—C21A—C32A25.0 (6)C15A—C16A—C17A—C9A1.7 (10)
C20—C19—C22—C2389.7 (5)C10A—C9A—C17A—C16A176.8 (6)
C18—C19—C22—C23150.4 (5)C8A—C9A—C17A—C16A1.8 (10)
C21—C19—C22—C2329.0 (6)C19—C22—C23—C3219.9 (7)
C18A—C19A—C22A—C23A150.2 (5)C19—C22—C23—C24161.8 (6)
C20A—C19A—C22A—C23A90.6 (5)C19A—C22A—C23A—C32A16.6 (6)
C21A—C19A—C22A—C23A25.2 (6)C19A—C22A—C23A—C24A161.7 (6)
O1—C1—C2—C1119.3 (8)C32—C23—C24—O4178.3 (6)
O1A—C1A—C2A—C11A19.4 (7)C22—C23—C24—O40.3 (11)
O2—C1—C2—C1199.0 (6)C32—C23—C24—C254.8 (10)
O2A—C1A—C2A—C11A99.5 (6)C22—C23—C24—C25177.2 (5)
O1—C1—C2—C3164.8 (5)C32A—C23A—C24A—O4A178.6 (6)
O1A—C1A—C2A—C3A163.9 (5)C22A—C23A—C24A—O4A3.4 (10)
O2—C1—C2—C376.9 (6)C32A—C23A—C24A—C25A1.3 (9)
O2A—C1A—C2A—C3A77.2 (6)C22A—C23A—C24A—C25A176.7 (5)
C11—C2—C3—C82.3 (8)O4—C24—C25—C261.4 (9)
C1—C2—C3—C8178.1 (5)C23—C24—C25—C26175.6 (6)
C11—C2—C3—C4177.8 (6)O4—C24—C25—C30175.8 (6)
C1—C2—C3—C42.0 (8)C23—C24—C25—C307.3 (8)
C11A—C2A—C3A—C8A0.3 (8)O4A—C24A—C25A—C30A175.3 (6)
C1A—C2A—C3A—C8A177.1 (5)C23A—C24A—C25A—C30A4.6 (9)
C11A—C2A—C3A—C4A179.2 (5)O4A—C24A—C25A—C26A3.8 (10)
C1A—C2A—C3A—C4A2.4 (8)C23A—C24A—C25A—C26A176.3 (5)
C8—C3—C4—C51.0 (9)C30—C25—C26—C271.0 (9)
C2—C3—C4—C5179.2 (6)C24—C25—C26—C27176.1 (5)
C2A—C3A—C4A—C5A179.6 (6)C30A—C25A—C26A—C27A1.0 (9)
C8A—C3A—C4A—C5A0.1 (9)C24A—C25A—C26A—C27A178.2 (6)
C3—C4—C5—C60.5 (9)C25—C26—C27—C281.4 (10)
C3A—C4A—C5A—C6A0.2 (9)C25A—C26A—C27A—C28A1.8 (10)
C4—C5—C6—C12179.2 (6)C26—C27—C28—C291.4 (11)
C4—C5—C6—C71.2 (9)C26A—C27A—C28A—C29A3.6 (10)
C4A—C5A—C6A—C12A179.7 (5)C27—C28—C29—C301.0 (11)
C4A—C5A—C6A—C7A0.9 (9)C27A—C28A—C29A—C30A2.4 (10)
C12—C6—C7—C150.6 (8)C28—C29—C30—C250.6 (10)
C5—C6—C7—C15179.7 (5)C28—C29—C30—C31175.5 (6)
C12—C6—C7—C8178.0 (5)C26—C25—C30—C290.6 (9)
C5—C6—C7—C82.3 (8)C24—C25—C30—C29176.5 (5)
C12A—C6A—C7A—C8A179.8 (5)C26—C25—C30—C31175.3 (6)
C5A—C6A—C7A—C8A1.4 (8)C24—C25—C30—C317.5 (9)
C12A—C6A—C7A—C15A0.9 (8)C28A—C29A—C30A—C25A0.6 (10)
C5A—C6A—C7A—C15A179.7 (5)C28A—C29A—C30A—C31A177.1 (6)
C2—C3—C8—C92.5 (9)C26A—C25A—C30A—C29A2.3 (10)
C4—C3—C8—C9177.7 (5)C24A—C25A—C30A—C29A176.9 (6)
C2—C3—C8—C7179.6 (5)C26A—C25A—C30A—C31A175.4 (6)
C4—C3—C8—C70.3 (9)C24A—C25A—C30A—C31A5.5 (9)
C15—C7—C8—C3179.3 (5)C29—C30—C31—O32.7 (11)
C6—C7—C8—C31.9 (9)C25—C30—C31—O3173.2 (6)
C15—C7—C8—C91.2 (9)C29—C30—C31—C32179.4 (6)
C6—C7—C8—C9176.1 (5)C25—C30—C31—C324.7 (9)
C6A—C7A—C8A—C9A178.7 (6)C29A—C30A—C31A—O3A3.8 (10)
C15A—C7A—C8A—C9A0.2 (8)C25A—C30A—C31A—O3A174.0 (6)
C6A—C7A—C8A—C3A1.2 (8)C29A—C30A—C31A—C32A179.0 (5)
C15A—C7A—C8A—C3A179.9 (5)C25A—C30A—C31A—C32A3.2 (9)
C2A—C3A—C8A—C9A1.0 (9)C24—C23—C32—C312.2 (10)
C4A—C3A—C8A—C9A179.5 (5)C22—C23—C32—C31179.5 (5)
C2A—C3A—C8A—C7A179.1 (5)C24—C23—C32—C21179.8 (6)
C4A—C3A—C8A—C7A0.4 (8)C22—C23—C32—C211.9 (7)
C3—C8—C9—C101.9 (9)O3—C31—C32—C23176.1 (6)
C7—C8—C9—C10179.9 (5)C30—C31—C32—C231.9 (9)
C3—C8—C9—C17179.9 (6)O3—C31—C32—C211.1 (10)
C7—C8—C9—C172.1 (9)C30—C31—C32—C21179.1 (6)
C7A—C8A—C9A—C10A177.8 (5)C19—C21—C32—C2316.9 (7)
C3A—C8A—C9A—C10A2.4 (9)C19—C21—C32—C31160.6 (6)
C7A—C8A—C9A—C17A0.8 (9)C24A—C23A—C32A—C31A0.7 (9)
C3A—C8A—C9A—C17A179.0 (5)C22A—C23A—C32A—C31A179.0 (5)
C17—C9—C10—C11179.1 (6)C24A—C23A—C32A—C21A178.1 (5)
C8—C9—C10—C111.1 (9)C22A—C23A—C32A—C21A0.2 (7)
C8A—C9A—C10A—C11A2.4 (9)O3A—C31A—C32A—C23A177.1 (6)
C17A—C9A—C10A—C11A179.0 (6)C30A—C31A—C32A—C23A0.2 (9)
C3—C2—C11—C101.7 (9)O3A—C31A—C32A—C21A1.5 (9)
C1—C2—C11—C10177.5 (5)C30A—C31A—C32A—C21A178.8 (5)
C9—C10—C11—C21.1 (9)C19A—C21A—C32A—C23A16.1 (6)
C9A—C10A—C11A—C2A1.0 (9)C19A—C21A—C32A—C31A162.6 (5)

Experimental details

Crystal data
Chemical formulaC32H22O4
Mr470.5
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)295
a, b, c (Å)16.591 (2), 8.8487 (7), 30.996 (9)
V3)4550.5 (15)
Z8
Radiation typeCu Kα
µ (mm1)0.72
Crystal size (mm)0.50 × 0.18 × 0.05
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionNumerical
SHELX76
Tmin, Tmax0.867, 0.964
No. of measured, independent and
observed [I > 2σ(I)] reflections
10756, 5587, 3023
Rint0.055
(sin θ/λ)max1)0.610
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.085, 0.99
No. of reflections5587
No. of parameters650
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.19
Absolute structureFlack (1983)
Absolute structure parameter0.3 (3)

Computer programs: Structure Determination Package (Enraf Nonius, 1985), Structure Determination Package, local programs, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1976) and ORTEP-32 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
O1—C11.417 (5)C19A—C20A1.535 (7)
O1A—C1A1.415 (6)C19—C211.546 (6)
O2—C11.434 (6)C19A—C21A1.564 (6)
O2A—C1A1.424 (6)C19—C221.541 (6)
C1—C21.508 (6)C19A—C22A1.553 (6)
C1A—C2A1.519 (7)C2—C31.400 (8)
C18—C191.525 (6)C2A—C3A1.396 (7)
C18A—C19A1.498 (6)C2—C111.370 (7)
C19—C201.518 (6)C2A—C11A1.382 (6)
O1—C1—O2109.7 (4)C20—C19—C21110.0 (5)
O1A—C1A—O2A111.0 (4)C20A—C19A—C21A108.5 (5)
O1—C1—C2109.9 (5)C18—C19—C21112.0 (4)
O1A—C1A—C2A109.3 (5)C18A—C19A—C21A114.5 (4)
O2—C1—C2105.8 (5)C21—C19—C22103.9 (4)
O2A—C1A—C2A104.5 (5)C21A—C19A—C22A104.2 (4)
C18—C19—C20106.5 (4)C3—C2—C11120.4 (6)
C18A—C19A—C20A107.1 (4)C3A—C2A—C11A119.5 (5)
C20—C19—C22112.0 (4)C1—C2—C11119.3 (5)
C20A—C19A—C22A109.2 (4)C1A—C2A—C11A120.4 (5)
C18—C19—C22112.6 (4)C1—C2—C3120.1 (5)
C18A—C19A—C22A113.1 (4)C1A—C2A—C3A120.1 (5)
O1—C1—C2—C1119.3 (8)O1—C1—C2—C3164.8 (5)
O1A—C1A—C2A—C11A19.4 (7)O1A—C1A—C2A—C3A163.9 (5)
O2—C1—C2—C1199.0 (6)O2—C1—C2—C376.9 (6)
O2A—C1A—C2A—C11A99.5 (6)O2A—C1A—C2A—C3A77.2 (6)
 

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