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The lupane triterpenoid betulonic aldehyde [also known as betulonal; systematic name: lup-20(29)-en-28-al-3-one, C30H46O2] is a product of betulin oxidation. Crystals were obtained from hexane [form (I)] and dimethyl sulfoxide [form (II)] solutions. Forms (I) and (II) are both ortho­rhom­bic. The molecular geometric parameters in the two forms are similar, but the structures are different with respect to the crystal packing. Polymorph (I) contains two independent mol­ecules in the asymmetric unit, while polymorph (II) contains only one mol­ecule, which has a disordered aldehyde group [the disorder ratio is 0.769 (4):0.231 (4)]. In each mol­ecule, the six-membered rings have chair conformations, whereas the cyclo­pentane ring in each molecule adopts an envelope conformation. All the rings in the lupane nucleus are trans-fused. The extended structures of both polymorphs are stabilized by weak inter­molecular C—H...O and van der Waals inter­actions. Weak intra­molecular C—H...O inter­actions are also observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614017379/ku3132sup1.cif
Contains datablocks I_polymorph, II_polymorph, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614017379/ku3132I_polymorphsup2.hkl
Contains datablock I_polymorph

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614017379/ku3132II_polymorphsup3.hkl
Contains datablock II_polymorph

CCDC references: 1016575; 1016576

Introduction top

Betulonic aldehyde [lup-20 (29)-en-28-al-3-one] (1), also known as betulonal, is a naturally occurring penta­cyclic triterpene of the lupane type. Betulonal was isolated for the first time in 1966 from the white birch bark (Betula pendula) by extraction with cyclo­hexane (Rimpler et al., 1966). Betulonal has already been identified in the outer bark of Betula nigra (Hua et al., 1991), Betula platyphylla (Kochergina et al., 1986), Betula alleghaniensis (Lavoie & Stevanovic, 2005), Betula pubescens (Abyshev et al., 2007), in the root bark of Maytenus cuzcoina (Núñez et al., 2005), in the leaves of Quercus suber (Monaco & Previtera, 1984), in the ground aerial parts of Boronia gracilipes (Ahsan et al., 1995) and in Chios mastic gum (Dabos et al., 2010). The content of betulonic aldehyde in different plant species is rather low and does not exceed 0.05%. Therefore, it seems that a more efficient method for obtaining the compound consists in a synthesis based on betulin oxidation. In the literature one can find several methods, such as Swern, Jones (Barthel et al., 2008), Oppenauer (Krasutsky & Munshi, 2006) oxidation and the application of pyridinium chloro­chromate (PCC; Hata et al., 2002; Sun et al., 1998; Yli-Kauhaluoma et al., 2010) or pyridinium dichromate (PDC; Dabos et al., 2010).

Oxidation of betulin has a great impact on its biological activity. It was stated that the presence of a carbonyl group at carbon C28 is necessary for high cytotoxicity. Moreover, oxidation of the hy­droxy group at carbon C3 also results in a higher cytotoxicity of the derivatives (for atom and ring numbering see Scheme). Oxidation of betulin (position C3 and/or at C28) affects its binding to topoisomerases I/II (Csuk et al., 2012).

Betulone aldehyde shows in vitro cytotoxic activity against different human cancer lines, viz. MCF7 (breast), NCI-H460 (lung), SF-268 (central nervous system, CNS) and bladder (Saxena & Rathnam, 2009). Betulonal causes melanogenesis in mouse B16 2F2 cells assessed as intra­cellular melanin content and inhibited B16 2F2 cell proliferation by induction of apoptosis (Hata et al., 2002). In addition, betulonal shows anti­viral activity against SFV infected in BHK cells, cytotoxicity against human HuH7 cells (Pohjala et al., 2009), anti-HIV activity in acutely infected H9 lymphocytes (Sun et al., 1998), cytotoxicity against human epidermoid carcinoma of the mouth (KB) cell line, cytotoxicity against cultured human melanoma (MEL-2) cell line (Kim et al., 1998) and anti­leishmanial activity against Leishmania donovani axenic amastigotes (Alakurtti et al., 2010).

This work is a continuation of our earlier studies on determination of the structure of betulin derivatives (Boryczka, Michalik et al., 2012; Boryczka, Bębenek et al., 2012; Boryczka et al., 2013). Until now, the crystal structure of betulonal has not been reported. Betulonic aldehyde was obtained by oxidation of naturally occurring betulin using pyridinium chloro­chromate (PCC) (Yli-Kauhaluoma et al., 2010).

Experimental top

Synthesis of betulonic aldehyde, (1) top

Betulonic aldehyde, (1), was synthesized according to the method of Yli-Kauhaluoma et al. (2010). A mixture of betulin (200 mg, 0.45 mmol), pyridinium chloro­chromate (PCC; 585 mg, 2.72 mmol) and dry di­chloro­methane (5 ml) was stirred at room temperature for 2 h. The reaction mixture was dissolved in di­ethyl ether (10 ml) and filtered through alumina. The filtrate was washed with water, 5% hydro­chloric acid, again with water and dried over Na2SO4. The solvent was evaporated in vacuum and the crude product was crystallized from hexane giving 135 mg (68%) of (1). Crystals of (1) suitable for single-crystal X-ray structure analysis were obtained by slow evaporation of hexane [for polymorph (I)] or di­methyl sulfoxide [for polymorph (II)] solution at room temperature.

Analysis of betulonic aldehyde, (1) top

RF = 0.74 (silica gel, di­chloro­methane–ethanol, 20:1 v/v), m.p. 433–435 K (literature 436–439 K; Barthel et al., 2008). 1H NMR (600 MHz, CDCl3): δ 0.93 (s, 3H, CH3, H23), 0.96 (s, 3H, CH3, H24), 0.99 (s, 3H, CH3, H25), 1.02 (s, 3H, CH3, H26), 1.07 (s, 3H, CH3, H27), 1.08–2.11 (22H, CH2, CH), 1.70 (s, 3H, CH3, H30), 2.44 (m, 2H, H2), 2.87 (dt, 1H, H19), 4.63 (br s, 1H, H29), 4.76 (br s, 1H, H29), 9.67 (s, 1H, CHO). 13C NMR (150 MHz, CDCl3): δ 14.19 (C27), 15.73 (C25), 15.95 (C26), 19.01 (C30), 19.61 (C6), 21.02 (C24), 21.28 (C11), 25.55 (C12), 26.61 (C23), 28.80 (C22), 29.15 (C21), 29.86 (C15), 33.17 (C16), 33.64 (C7), 34.12 (C2), 36.90 (C10), 38.76 (C13), 39.64 (C1), 40.78 (C8), 42.61 (C14), 47.32 (C4), 47.48 (C19), 47.98 (C18), 49.83 (C9), 54.97 (C5), 59.31 (C17), 110.20 (C29), 149.65 (C20), 206.49 (C28), 217.94 (C3). IR (KBr, cm-1): ν 3071–2863 (CH2, CH3), 1731 (CO from CHO), 1703 (C O), 1644 (CC), 1451 (CH3), 871 (C—H).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. In polymorph (II), the difference Fourier maps showed the presence of two partially occupied rotamers at atom C28. The PART option in SHELXL (Sheldrick, 2008) was used in order to separate the partially occupied moieties; site-occupation factors for the two alternative positions refined to 0.769 (4) and 0.231 (4). For the disordered part of the molecule, restrained refinement was applied using the SADI and SAME instructions in SHELXL (Sheldrick, 2008). H atoms were treated as riding atoms in geometrically idealized positions fixing the C—H bond lengths at 0.95, 1.00, 0.99, 0.95 and 0.98 Å for aromatic CH, methine CH, methyl­ene CH2, terminal methyl­ene CH2 and methyl CH3 atoms, respectively, and with Uiso(H) = 1.5Ueq(C) for methyl H atoms or 1.2Ueq(C) otherwise.

The structure of betulin contains chiral atoms. Previous studies on other triterpene derivatives of the lupane type have shown that these atoms present the following configurations: C3(S), C5(R), C8(R), C9(S), C10(R), C13(R), C14(R), C17(R) and C19(R) for lupeol (Corrêa et al., 2009), and C3(S), C5(R), C8(R), C9(S), C10(R), C13(R), C14(R), C17(S) and C19(R) for 3-acetyl­betulinic acid (Suleimen et al., 2013). Because of the absence of a heavy atom (>Si), the absolute structure of betulonic aldehyde was determined by comparison as follows: C5(R), C8(R), C9(S), C10(R), C13(R), C14(R), C17(S), C18(R) and C19(R).

Results and discussion top

Polymorphism may be defined as the ability of a compound to exist in various crystalline forms in which the molecules have different arrangements (packing polymorphism) and/or conformations (conformational polymorphism) in the crystal lattice (Grant, 1999). Forms (I) and (II) of Betulonic aldehyde, (1), both crystallize in the orthorhombic P212121 space group. The unit cell of polymorph (I) contains eight molecules of (1) (Z' = 2), while polymorph (II) contains only four molecules (Z' = 1).

The asymmetric unit of polymorph (I) contains two independent molecules, viz. (IA) and (IB) (Fig. 1). A similar crystal arrangement was also observed for betulonic alcohol (Boryczka, Bębenek et al., 2012).

In contrast, the asymmetric unit of polymorph (II) consists of only one type of molecule, as shown in Fig. 2.

These structures have different arrangements in the unit cell and they can be regarded as packing polymorphs. In the polymorph (I), the molecules form two-dimensional (ab plane) layers. Fig. 3 shows schematically a packing diagram of polymorph (I) viewed parallel to the a axis. One may see that the molecules are arranged in an ABAB order along the c axis.

The molecules of polymorph (II) reveal a different alignment to that in form (I) (Fig. 4). In this case, they are packed along the c axis in a zigzag fashion parallel to the bc plane.

The geometric parameters of betulonal in both crystal forms are similar. All bond lengths and angles show typical values. The six-membered rings have chair conformations, while the cyclo­pentane ring adopts an envelope conformation. Atom C17 is displaced from the C18/C19/C21/C22 plane by about 0.665 Å in (IA), 0.652 Å in (IB) and 0.649 Å in (II). The C17—C18—C19—C21 and C19—C21—C22—C17 torsion angles are 27.2 (1) and -26.0 (1)° in (IA), 26.7 (1) and -25.4 (1)° in (IB), and 28.3 (1) and -23.4 (1)° in (II), respectively. This is confirmed by the Cremer and Pople parameters (Table 2; Cremer & Pople, 1975). The appropriate calculations were made using PLATON (Spek, 2009).

All the ring junctions in the lupane nucleus are trans-fused. Similar ring conformations were also described for other derivatives of betulin, for example, 3,28-di­acet­oxy-29-bromo­betulin (Ding et al., 2009), 20 (29)-lupene-3β,28β-di­acetate (Mohamed et al., 2006), betulin ethanol solvate (Drebushchak et al., 2010), betulin DMSO solvate (Boryczka, Michalik et al., 2012) and betulinic acid DMSO solvate (Boryczka, Bębenek et al., 2012). In all molecules, (IA), (IB) and (II), the cyclo­hexanone ring A has a chair conformation, like in crystal structures of betulonic alcohol (Boryczka et al., 2013), but different from betulonic acid DMSO and betulonic acid DMF solvates crystal structures, where it adopts the twisted-boat conformation (Boryczka, Jastrzębska et al., 2012). The methyl groups at atoms C24, C25, C26 and C27 occupy the axial positions, while the methyl group at C23 is equatorial. The selected torsion angles describing molecules conformations of the polymorph (I) and (II) are presented in Table 3.

In the polymorph (I), molecules (IA) and (IB) have different orientations of the isopropenyl group (Table 3). The C29—C20—C19—C21 torsion angle describes the orientation of the isopropenyl group and is -99.0 (1)° for (IA) and 93.8 (2)° for (IB). In the case of the molecules in polymorph (II), the orientation of the isopropenyl group is similar to that in molecule (IB). The corresponding torsion angle is 99.5 (1)°.

In all studied cases, the aldehyde group is attached to atom C17 of ring D in an axial orientation. Additionally, in the polymorph (II), two rotamers are observed. The occupancies of the two disordered rotamers are 0.769 (4) and 0.231 (4). Because there is no steric hindrance, the carbonyl group may rotate along the C17—C28 single bond. The values of the torsion angles C18—C17—C28—O2A and C18—C17—C28—O2B in both alternative orientations are -11.7 (2) and +136.5 (4)° for the higher and lower occupancy fragments, respectively. The value of this torsion angle in form (I) is -7.7 (2)° for molecule (IA) and -15.7 (2)° for molecule (IB).

The molecular structure is stabilized only by weak inter­molecular C—H···O hydrogen bonds (Fig. 5) and van der Waals inter­actions. In polymorph (I), weak intra­molecular C—H···O hydrogen bonds are also observed, namely C13—H13···O2 and C19—H19···O2 (Table 4). The absence of such inter­actions in polymorph (II) is associated with the existence of a disorder of axially oriented aldehyde group.

Related literature top

For related literature, see: Abyshev et al. (2007); Ahsan et al. (1995); Alakurtti et al. (2010); Barthel et al. (2008); Boryczka et al. (2013); Boryczka, Bębenek, Jastrzębska, Kusz & Zubko (2012); Boryczka, Jastrzębska, Bębenek, Kusz, Zubko, Kadela & Michalik (2012); Boryczka, Michalik, Jastrzębska, Kusz, Zubko & Bębenek (2012); Corrêa et al. (2009); Cremer & Pople (1975); Csuk et al. (2012); Dabos et al. (2010); Ding et al. (2009); Drebushchak (2010); Grant (1999); Hata et al. (2002); Hua et al. (1991); Kim et al. (1998); Kochergina et al. (1986); Krasutsky & Munshi (2006); Lavoie & Stevanovic (2005); Mohamed (2006); Monaco & Previtera (1984); Núñez et al. (2005); Pohjala et al. (2009); Rimpler et al. (1966); Saxena & Rathnam (2009); Sheldrick (2008); Spek (2009); Suleimen et al. (2013); Sun et al. (1998); Yli-Kauhaluoma, Allakurti, Minkkinen, Sarcerdoti-Sierra, Jaffe & Heiska (2010).

Computing details top

For both compounds, data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006) and PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Molecular fitting of the two crystallographically independent molecules (IA) and (IB) of polymorph (I) of betulonal.
[Figure 2] Fig. 2. Molecular view of polymorph (II) with only one of the disordered part for the clarity. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. (a) Two-dimensional (ab plane) layers of (IA) and (IB) of polymorph (I) and (b) packing diagram of the polymorph (I) viewed parallel to the a axis.
[Figure 4] Fig. 4. (a) The zig zag chain of molecules of polymorph (II) parallel to the bc plane and (b) packing diagram of the polymorph (II) viewed parallel to the b axis.
[Figure 5] Fig. 5. The C—H···O interaction (dashed line) between two independent molecules in polymorph (I) of betulonal. Displacement ellipsoids are drawn at the 50% probability level.
(I_polymorph) Lup-20 (29)-en-28-al-3-one top
Crystal data top
C30H46O2F(000) = 1936
Mr = 438.67Dx = 1.156 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 27663 reflections
a = 9.3905 (2) Åθ = 2.8–38.4°
b = 19.1080 (3) ŵ = 0.07 mm1
c = 28.0829 (5) ÅT = 100 K
V = 5039.02 (16) Å3Polyhedron, colourless
Z = 80.48 × 0.38 × 0.17 mm
Data collection top
Agilent SuperNova
diffractometer with an Atlas detector
16765 independent reflections
Radiation source: Agilent SuperNova (Mo) X-ray Source15731 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.029
Detector resolution: 10.4498 pixels mm-1θmax = 31.5°, θmin = 2.1°
ω scansh = 913
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
k = 2828
Tmin = 0.757, Tmax = 1.000l = 4141
61016 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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0392P)2 + 1.7207P]
where P = (Fo2 + 2Fc2)/3
16765 reflections(Δ/σ)max = 0.001
589 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C30H46O2V = 5039.02 (16) Å3
Mr = 438.67Z = 8
Orthorhombic, P212121Mo Kα radiation
a = 9.3905 (2) ŵ = 0.07 mm1
b = 19.1080 (3) ÅT = 100 K
c = 28.0829 (5) Å0.48 × 0.38 × 0.17 mm
Data collection top
Agilent SuperNova
diffractometer with an Atlas detector
16765 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
15731 reflections with I > 2σ(I)
Tmin = 0.757, Tmax = 1.000Rint = 0.029
61016 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 1.02Δρmax = 0.30 e Å3
16765 reflectionsΔρmin = 0.20 e Å3
589 parameters
Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.36.32 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
O1A0.85059 (11)0.69260 (6)0.28904 (4)0.0346 (2)
O2A0.12294 (10)0.48113 (5)0.13731 (3)0.02278 (17)
C1A0.48485 (13)0.65916 (6)0.28732 (4)0.0198 (2)
H1A0.39610.67700.30200.024*
H1B0.51290.61620.30470.024*
C2A0.60225 (13)0.71417 (7)0.29323 (5)0.0237 (2)
H2A0.56840.75940.28030.028*
H2B0.62230.72070.32760.028*
C3A0.73772 (13)0.69348 (6)0.26811 (4)0.0209 (2)
C4A0.72473 (12)0.67264 (6)0.21567 (4)0.01625 (19)
C5A0.59916 (11)0.61908 (5)0.21168 (4)0.01348 (17)
H5A0.63170.57770.23060.016*
C6A0.57781 (11)0.59044 (6)0.16118 (4)0.01549 (19)
H6A0.53180.62650.14110.019*
H6B0.67150.57910.14700.019*
C7A0.48485 (11)0.52469 (6)0.16230 (4)0.01528 (18)
H7A0.53600.48760.18000.018*
H7B0.47080.50800.12930.018*
C8A0.33796 (11)0.53582 (5)0.18549 (3)0.01227 (17)
C9A0.35892 (11)0.57281 (5)0.23471 (4)0.01291 (17)
H9A0.41200.53810.25460.015*
C10A0.45470 (11)0.64015 (5)0.23485 (4)0.01393 (18)
C11A0.21573 (12)0.58293 (6)0.26048 (4)0.01634 (19)
H11A0.23400.60180.29270.020*
H11B0.15840.61790.24290.020*
C12A0.12975 (12)0.51523 (6)0.26493 (4)0.01627 (18)
H12A0.17840.48330.28740.020*
H12B0.03450.52610.27810.020*
C13A0.11247 (11)0.47863 (5)0.21695 (4)0.01283 (17)
H13A0.06390.51250.19520.015*
C14A0.26152 (11)0.46257 (5)0.19472 (4)0.01287 (17)
C15A0.24443 (12)0.42091 (6)0.14747 (4)0.01638 (19)
H15A0.20640.45290.12280.020*
H15B0.33980.40530.13680.020*
C16A0.14645 (12)0.35667 (6)0.15068 (4)0.01722 (19)
H16A0.13500.33550.11870.021*
H16B0.18930.32120.17200.021*
C17A0.00108 (12)0.37897 (5)0.16999 (4)0.01492 (18)
C18A0.01897 (11)0.41320 (5)0.21914 (4)0.01384 (17)
H18A0.06970.37860.23980.017*
C19A0.13404 (12)0.41959 (6)0.23861 (4)0.01601 (18)
H19A0.17500.46500.22750.019*
C20A0.15194 (13)0.41507 (6)0.29202 (4)0.0211 (2)
C21A0.21630 (13)0.35836 (6)0.21337 (4)0.0200 (2)
H21A0.25480.32540.23730.024*
H21B0.29650.37710.19440.024*
C22A0.10858 (12)0.32098 (6)0.18079 (4)0.0187 (2)
H22A0.15470.30410.15130.022*
H22B0.06350.28090.19730.022*
C23A0.86466 (12)0.63801 (6)0.20059 (5)0.0215 (2)
H23A0.94400.67010.20670.032*
H23B0.86090.62680.16660.032*
H23C0.87870.59490.21890.032*
C24A0.70647 (13)0.73995 (6)0.18567 (5)0.0212 (2)
H24A0.62670.76740.19820.032*
H24B0.68730.72730.15250.032*
H24C0.79390.76780.18730.032*
C25A0.38168 (12)0.70347 (6)0.21100 (4)0.0190 (2)
H25A0.27940.70250.21800.028*
H25B0.39630.70130.17650.028*
H25C0.42300.74690.22340.028*
C26A0.24841 (12)0.58089 (6)0.15092 (4)0.01676 (19)
H26A0.30800.61820.13760.025*
H26B0.16820.60170.16820.025*
H26C0.21230.55140.12510.025*
C27A0.34952 (12)0.41476 (6)0.22802 (4)0.0179 (2)
H27A0.29530.37210.23490.027*
H27B0.36970.43960.25780.027*
H27C0.43930.40230.21240.027*
C28A0.06833 (12)0.42438 (6)0.13232 (4)0.01764 (19)
H28A0.06890.40590.10090.021*
C29A0.2500 (2)0.45599 (9)0.31380 (6)0.0402 (4)
H29A0.26580.45160.34710.048*
H29B0.30300.48900.29580.048*
C30A0.06771 (19)0.36332 (11)0.31850 (5)0.0431 (4)
H30A0.10030.36170.35160.065*
H30B0.03310.37660.31760.065*
H30C0.07960.31710.30390.065*
O1B0.35987 (14)0.72259 (6)0.03456 (4)0.0390 (3)
O2B0.86757 (13)1.22125 (6)0.08376 (4)0.0392 (3)
C1B0.48022 (14)0.89774 (7)0.04388 (4)0.0225 (2)
H1C0.46210.93880.06450.027*
H1D0.57230.87700.05370.027*
C2B0.36168 (16)0.84372 (7)0.05166 (5)0.0288 (3)
H2C0.26830.86650.04640.035*
H2D0.36480.82740.08510.035*
C3B0.37393 (13)0.78151 (7)0.01910 (5)0.0241 (2)
C4B0.39942 (13)0.79578 (6)0.03374 (5)0.0211 (2)
C5B0.51126 (12)0.85573 (6)0.03949 (4)0.01744 (19)
H5B0.60280.83480.02820.021*
C6B0.54008 (14)0.87601 (7)0.09123 (4)0.0225 (2)
H6C0.54380.83330.11120.027*
H6D0.46170.90590.10310.027*
C7B0.68136 (13)0.91555 (7)0.09522 (4)0.0220 (2)
H7C0.75970.88400.08550.026*
H7D0.69710.92850.12890.026*
C8B0.68740 (12)0.98235 (6)0.06445 (4)0.01613 (19)
C9B0.63310 (11)0.96564 (6)0.01306 (4)0.01476 (18)
H9B0.70810.93460.00080.018*
C10B0.49165 (12)0.92242 (6)0.00828 (4)0.01687 (19)
C11B0.63604 (12)1.03157 (6)0.01820 (4)0.01823 (19)
H11C0.60181.01970.05050.022*
H11D0.57071.06700.00470.022*
C12B0.78629 (12)1.06248 (6)0.02159 (4)0.0175 (2)
H12C0.84901.02940.03880.021*
H12D0.78291.10660.04000.021*
C13B0.84825 (11)1.07692 (6)0.02782 (4)0.01520 (18)
H13B0.78411.11180.04340.018*
C14B0.84699 (12)1.00995 (6)0.05981 (4)0.01564 (18)
C15B0.90957 (13)1.02858 (7)0.10937 (4)0.0221 (2)
H15C0.84131.05940.12610.027*
H15D0.91850.98500.12820.027*
C16B1.05551 (14)1.06508 (7)0.10816 (4)0.0232 (2)
H16C1.08381.07870.14080.028*
H16D1.12831.03250.09550.028*
C17B1.04716 (13)1.12965 (6)0.07683 (4)0.0207 (2)
C18B0.99732 (12)1.10943 (6)0.02674 (4)0.01688 (19)
H18B1.06371.07220.01520.020*
C19B1.02510 (13)1.17460 (6)0.00417 (4)0.0210 (2)
H19B0.93921.20540.00250.025*
C20B1.06024 (13)1.16199 (7)0.05607 (4)0.0233 (2)
C21B1.15153 (16)1.21296 (8)0.02179 (5)0.0314 (3)
H21C1.23521.21650.00050.038*
H21D1.12271.26070.03140.038*
C22B1.18741 (15)1.16837 (8)0.06588 (5)0.0294 (3)
H22C1.21631.19830.09300.035*
H22D1.26501.13490.05880.035*
C23B0.45652 (16)0.72842 (7)0.05665 (5)0.0297 (3)
H23D0.39290.68940.04900.045*
H23E0.46110.73440.09130.045*
H23F0.55200.71850.04430.045*
C24B0.25303 (15)0.81165 (8)0.05645 (6)0.0322 (3)
H24D0.20800.85070.03960.048*
H24E0.26610.82420.09000.048*
H24F0.19220.77010.05420.048*
C25B0.35842 (13)0.96599 (7)0.02002 (5)0.0258 (2)
H25D0.37191.01410.00880.039*
H25E0.34310.96620.05450.039*
H25F0.27530.94540.00420.039*
C26B0.59273 (14)1.03780 (7)0.08953 (4)0.0238 (2)
H26D0.49561.01960.09280.036*
H26E0.59111.08080.07050.036*
H26F0.63161.04800.12120.036*
C27B0.94512 (13)0.95281 (6)0.03836 (4)0.0201 (2)
H27D1.04430.96870.03950.030*
H27E0.91770.94400.00520.030*
H27F0.93540.90950.05680.030*
C28B0.95536 (15)1.18356 (7)0.10169 (5)0.0272 (3)
H28B0.96841.18820.13510.033*
C29B1.11820 (16)1.10286 (8)0.07333 (5)0.0305 (3)
H29C1.14091.09940.10620.037*
H29D1.13651.06460.05260.037*
C30B1.0317 (2)1.22168 (10)0.08822 (6)0.0428 (4)
H30D1.06681.21070.12020.064*
H30E1.08051.26350.07620.064*
H30F0.92901.23050.08950.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0277 (5)0.0455 (6)0.0307 (5)0.0028 (4)0.0097 (4)0.0107 (4)
O2A0.0255 (4)0.0208 (4)0.0221 (4)0.0010 (3)0.0042 (3)0.0000 (3)
C1A0.0213 (5)0.0216 (5)0.0165 (5)0.0062 (4)0.0021 (4)0.0066 (4)
C2A0.0243 (5)0.0244 (5)0.0224 (5)0.0076 (5)0.0020 (4)0.0097 (4)
C3A0.0218 (5)0.0182 (5)0.0227 (5)0.0054 (4)0.0016 (4)0.0041 (4)
C4A0.0150 (4)0.0142 (4)0.0196 (5)0.0017 (4)0.0001 (4)0.0024 (4)
C5A0.0132 (4)0.0126 (4)0.0146 (4)0.0004 (3)0.0007 (3)0.0007 (3)
C6A0.0152 (4)0.0162 (4)0.0150 (4)0.0020 (4)0.0030 (4)0.0017 (3)
C7A0.0150 (4)0.0155 (4)0.0153 (4)0.0016 (4)0.0036 (4)0.0041 (3)
C8A0.0134 (4)0.0128 (4)0.0106 (4)0.0003 (3)0.0003 (3)0.0009 (3)
C9A0.0146 (4)0.0126 (4)0.0116 (4)0.0005 (3)0.0010 (3)0.0017 (3)
C10A0.0149 (4)0.0131 (4)0.0139 (4)0.0007 (3)0.0015 (3)0.0028 (3)
C11A0.0169 (4)0.0166 (4)0.0155 (4)0.0024 (4)0.0039 (4)0.0058 (4)
C12A0.0181 (5)0.0185 (5)0.0121 (4)0.0037 (4)0.0028 (4)0.0032 (3)
C13A0.0141 (4)0.0130 (4)0.0113 (4)0.0015 (3)0.0019 (3)0.0014 (3)
C14A0.0150 (4)0.0115 (4)0.0121 (4)0.0003 (3)0.0009 (3)0.0016 (3)
C15A0.0170 (5)0.0159 (4)0.0163 (4)0.0017 (4)0.0037 (4)0.0057 (4)
C16A0.0183 (5)0.0148 (4)0.0186 (5)0.0016 (4)0.0030 (4)0.0062 (4)
C17A0.0164 (4)0.0134 (4)0.0149 (4)0.0020 (4)0.0017 (4)0.0026 (3)
C18A0.0153 (4)0.0131 (4)0.0131 (4)0.0011 (3)0.0019 (3)0.0008 (3)
C19A0.0163 (4)0.0150 (4)0.0167 (4)0.0026 (4)0.0036 (4)0.0012 (4)
C20A0.0223 (5)0.0237 (5)0.0175 (5)0.0084 (4)0.0056 (4)0.0020 (4)
C21A0.0192 (5)0.0205 (5)0.0204 (5)0.0059 (4)0.0044 (4)0.0035 (4)
C22A0.0204 (5)0.0152 (4)0.0206 (5)0.0038 (4)0.0019 (4)0.0034 (4)
C23A0.0139 (5)0.0207 (5)0.0299 (6)0.0004 (4)0.0005 (4)0.0037 (4)
C24A0.0199 (5)0.0166 (5)0.0271 (6)0.0015 (4)0.0013 (4)0.0023 (4)
C25A0.0179 (5)0.0139 (4)0.0251 (5)0.0016 (4)0.0020 (4)0.0011 (4)
C26A0.0189 (5)0.0165 (4)0.0148 (4)0.0015 (4)0.0028 (4)0.0022 (4)
C27A0.0186 (5)0.0140 (4)0.0211 (5)0.0010 (4)0.0015 (4)0.0020 (4)
C28A0.0179 (5)0.0209 (5)0.0141 (4)0.0033 (4)0.0001 (4)0.0010 (4)
C29A0.0548 (10)0.0387 (8)0.0273 (7)0.0072 (7)0.0195 (7)0.0083 (6)
C30A0.0405 (8)0.0677 (12)0.0212 (6)0.0057 (8)0.0040 (6)0.0151 (7)
O1B0.0471 (6)0.0281 (5)0.0418 (6)0.0068 (5)0.0093 (5)0.0029 (4)
O2B0.0459 (6)0.0415 (6)0.0302 (5)0.0197 (5)0.0122 (5)0.0171 (4)
C1B0.0245 (6)0.0249 (5)0.0180 (5)0.0071 (5)0.0041 (4)0.0042 (4)
C2B0.0302 (6)0.0302 (6)0.0261 (6)0.0115 (5)0.0087 (5)0.0055 (5)
C3B0.0169 (5)0.0260 (6)0.0294 (6)0.0040 (4)0.0004 (5)0.0034 (5)
C4B0.0176 (5)0.0212 (5)0.0246 (6)0.0002 (4)0.0037 (4)0.0058 (4)
C5B0.0155 (5)0.0196 (5)0.0172 (5)0.0020 (4)0.0023 (4)0.0033 (4)
C6B0.0248 (6)0.0266 (6)0.0162 (5)0.0000 (5)0.0048 (4)0.0057 (4)
C7B0.0247 (5)0.0284 (6)0.0127 (4)0.0012 (5)0.0010 (4)0.0045 (4)
C8B0.0170 (4)0.0208 (5)0.0106 (4)0.0025 (4)0.0018 (3)0.0002 (4)
C9B0.0140 (4)0.0194 (5)0.0109 (4)0.0013 (4)0.0004 (3)0.0012 (3)
C10B0.0144 (4)0.0196 (5)0.0165 (4)0.0012 (4)0.0003 (4)0.0030 (4)
C11B0.0174 (5)0.0224 (5)0.0149 (4)0.0019 (4)0.0037 (4)0.0038 (4)
C12B0.0179 (5)0.0222 (5)0.0122 (4)0.0031 (4)0.0024 (4)0.0004 (4)
C13B0.0160 (4)0.0189 (5)0.0107 (4)0.0015 (4)0.0018 (3)0.0014 (3)
C14B0.0166 (4)0.0194 (5)0.0109 (4)0.0028 (4)0.0015 (3)0.0016 (3)
C15B0.0252 (6)0.0296 (6)0.0116 (4)0.0021 (5)0.0049 (4)0.0009 (4)
C16B0.0239 (5)0.0284 (6)0.0173 (5)0.0031 (5)0.0083 (4)0.0032 (4)
C17B0.0215 (5)0.0239 (5)0.0167 (5)0.0010 (4)0.0057 (4)0.0063 (4)
C18B0.0170 (5)0.0191 (5)0.0146 (4)0.0008 (4)0.0025 (4)0.0039 (4)
C19B0.0212 (5)0.0205 (5)0.0213 (5)0.0022 (4)0.0034 (4)0.0016 (4)
C20B0.0168 (5)0.0325 (6)0.0205 (5)0.0062 (5)0.0031 (4)0.0032 (5)
C21B0.0343 (7)0.0314 (7)0.0286 (6)0.0133 (6)0.0070 (5)0.0040 (5)
C22B0.0247 (6)0.0328 (7)0.0307 (7)0.0054 (5)0.0099 (5)0.0075 (5)
C23B0.0305 (6)0.0238 (6)0.0349 (7)0.0007 (5)0.0001 (6)0.0100 (5)
C24B0.0207 (6)0.0321 (7)0.0437 (8)0.0026 (5)0.0120 (6)0.0042 (6)
C25B0.0157 (5)0.0252 (6)0.0366 (7)0.0040 (4)0.0013 (5)0.0052 (5)
C26B0.0227 (5)0.0282 (6)0.0207 (5)0.0032 (5)0.0068 (4)0.0054 (4)
C27B0.0173 (5)0.0201 (5)0.0229 (5)0.0027 (4)0.0003 (4)0.0022 (4)
C28B0.0329 (6)0.0286 (6)0.0200 (5)0.0030 (5)0.0063 (5)0.0105 (5)
C29B0.0311 (7)0.0378 (7)0.0227 (6)0.0018 (6)0.0081 (5)0.0018 (5)
C30B0.0465 (9)0.0514 (10)0.0304 (7)0.0128 (8)0.0004 (7)0.0126 (7)
Geometric parameters (Å, º) top
O1A—C3A1.2122 (16)O1B—C3B1.2140 (17)
O2A—C28A1.2077 (14)O2B—C28B1.2049 (17)
C1A—C2A1.5322 (16)C1B—C2B1.5336 (18)
C1A—C10A1.5438 (15)C1B—C10B1.5426 (16)
C1A—H1A0.9900C1B—H1C0.9900
C1A—H1B0.9900C1B—H1D0.9900
C2A—C3A1.5074 (17)C2B—C3B1.5041 (18)
C2A—H2A0.9900C2B—H2C0.9900
C2A—H2B0.9900C2B—H2D0.9900
C3A—C4A1.5302 (16)C3B—C4B1.5278 (18)
C4A—C23A1.5310 (16)C4B—C23B1.5355 (17)
C4A—C24A1.5472 (16)C4B—C24B1.5455 (18)
C4A—C5A1.5653 (14)C4B—C5B1.5625 (17)
C5A—C6A1.5334 (15)C5B—C6B1.5278 (17)
C5A—C10A1.5574 (14)C5B—C10B1.5576 (15)
C5A—H5A1.0000C5B—H5B1.0000
C6A—C7A1.5301 (15)C6B—C7B1.5308 (18)
C6A—H6A0.9900C6B—H6C0.9900
C6A—H6B0.9900C6B—H6D0.9900
C7A—C8A1.5402 (14)C7B—C8B1.5426 (16)
C7A—H7A0.9900C7B—H7C0.9900
C7A—H7B0.9900C7B—H7D0.9900
C8A—C26A1.5465 (15)C8B—C26B1.5520 (16)
C8A—C9A1.5647 (14)C8B—C9B1.5634 (15)
C8A—C14A1.5943 (14)C8B—C14B1.5940 (16)
C9A—C11A1.5392 (15)C9B—C11B1.5358 (15)
C9A—C10A1.5700 (14)C9B—C10B1.5698 (15)
C9A—H9A1.0000C9B—H9B1.0000
C10A—C25A1.5436 (15)C10B—C25B1.5385 (16)
C11A—C12A1.5300 (15)C11B—C12B1.5325 (16)
C11A—H11A0.9900C11B—H11C0.9900
C11A—H11B0.9900C11B—H11D0.9900
C12A—C13A1.5267 (14)C12B—C13B1.5298 (14)
C12A—H12A0.9900C12B—H12C0.9900
C12A—H12B0.9900C12B—H12D0.9900
C13A—C18A1.5290 (14)C13B—C18B1.5318 (16)
C13A—C14A1.5629 (14)C13B—C14B1.5636 (15)
C13A—H13A1.0000C13B—H13B1.0000
C14A—C27A1.5466 (15)C14B—C27B1.5505 (15)
C14A—C15A1.5558 (14)C14B—C15B1.5521 (15)
C15A—C16A1.5366 (15)C15B—C16B1.5380 (18)
C15A—H15A0.9900C15B—H15C0.9900
C15A—H15B0.9900C15B—H15D0.9900
C16A—C17A1.5293 (15)C16B—C17B1.5174 (18)
C16A—H16A0.9900C16B—H16C0.9900
C16A—H16B0.9900C16B—H16D0.9900
C17A—C28A1.5156 (16)C17B—C28B1.5139 (18)
C17A—C18A1.5367 (14)C17B—C18B1.5321 (15)
C17A—C22A1.5428 (15)C17B—C22B1.5416 (19)
C18A—C19A1.5422 (15)C18B—C19B1.5401 (16)
C18A—H18A1.0000C18B—H18B1.0000
C19A—C20A1.5117 (16)C19B—C20B1.5138 (18)
C19A—C21A1.5709 (15)C19B—C21B1.5743 (17)
C19A—H19A1.0000C19B—H19B1.0000
C20A—C29A1.354 (2)C20B—C29B1.344 (2)
C20A—C30A1.469 (2)C20B—C30B1.479 (2)
C21A—C22A1.5396 (16)C21B—C22B1.540 (2)
C21A—H21A0.9900C21B—H21C0.9900
C21A—H21B0.9900C21B—H21D0.9900
C22A—H22A0.9900C22B—H22C0.9900
C22A—H22B0.9900C22B—H22D0.9900
C23A—H23A0.9800C23B—H23D0.9800
C23A—H23B0.9800C23B—H23E0.9800
C23A—H23C0.9800C23B—H23F0.9800
C24A—H24A0.9800C24B—H24D0.9800
C24A—H24B0.9800C24B—H24E0.9800
C24A—H24C0.9800C24B—H24F0.9800
C25A—H25A0.9800C25B—H25D0.9800
C25A—H25B0.9800C25B—H25E0.9800
C25A—H25C0.9800C25B—H25F0.9800
C26A—H26A0.9800C26B—H26D0.9800
C26A—H26B0.9800C26B—H26E0.9800
C26A—H26C0.9800C26B—H26F0.9800
C27A—H27A0.9800C27B—H27D0.9800
C27A—H27B0.9800C27B—H27E0.9800
C27A—H27C0.9800C27B—H27F0.9800
C28A—H28A0.9500C28B—H28B0.9500
C29A—H29A0.9500C29B—H29C0.9500
C29A—H29B0.9500C29B—H29D0.9500
C30A—H30A0.9800C30B—H30D0.9800
C30A—H30B0.9800C30B—H30E0.9800
C30A—H30C0.9800C30B—H30F0.9800
C2A—C1A—C10A113.38 (9)C2B—C1B—C10B113.06 (10)
C2A—C1A—H1A108.9C2B—C1B—H1C109.0
C10A—C1A—H1A108.9C10B—C1B—H1C109.0
C2A—C1A—H1B108.9C2B—C1B—H1D109.0
C10A—C1A—H1B108.9C10B—C1B—H1D109.0
H1A—C1A—H1B107.7H1C—C1B—H1D107.8
C3A—C2A—C1A112.12 (10)C3B—C2B—C1B112.94 (11)
C3A—C2A—H2A109.2C3B—C2B—H2C109.0
C1A—C2A—H2A109.2C1B—C2B—H2C109.0
C3A—C2A—H2B109.2C3B—C2B—H2D109.0
C1A—C2A—H2B109.2C1B—C2B—H2D109.0
H2A—C2A—H2B107.9H2C—C2B—H2D107.8
O1A—C3A—C2A120.96 (12)O1B—C3B—C2B120.49 (13)
O1A—C3A—C4A122.19 (12)O1B—C3B—C4B122.00 (12)
C2A—C3A—C4A116.83 (10)C2B—C3B—C4B117.48 (11)
C3A—C4A—C23A108.08 (10)C3B—C4B—C23B108.19 (11)
C3A—C4A—C24A108.44 (9)C3B—C4B—C24B107.24 (11)
C23A—C4A—C24A107.68 (10)C23B—C4B—C24B107.59 (11)
C3A—C4A—C5A107.41 (9)C3B—C4B—C5B109.66 (9)
C23A—C4A—C5A110.14 (9)C23B—C4B—C5B109.67 (10)
C24A—C4A—C5A114.90 (9)C24B—C4B—C5B114.29 (10)
C6A—C5A—C10A111.40 (8)C6B—C5B—C10B110.40 (9)
C6A—C5A—C4A113.46 (8)C6B—C5B—C4B113.78 (9)
C10A—C5A—C4A117.21 (8)C10B—C5B—C4B117.53 (9)
C6A—C5A—H5A104.4C6B—C5B—H5B104.5
C10A—C5A—H5A104.4C10B—C5B—H5B104.5
C4A—C5A—H5A104.4C4B—C5B—H5B104.5
C7A—C6A—C5A110.41 (9)C5B—C6B—C7B110.38 (9)
C7A—C6A—H6A109.6C5B—C6B—H6C109.6
C5A—C6A—H6A109.6C7B—C6B—H6C109.6
C7A—C6A—H6B109.6C5B—C6B—H6D109.6
C5A—C6A—H6B109.6C7B—C6B—H6D109.6
H6A—C6A—H6B108.1H6C—C6B—H6D108.1
C6A—C7A—C8A113.97 (8)C6B—C7B—C8B113.53 (10)
C6A—C7A—H7A108.8C6B—C7B—H7C108.9
C8A—C7A—H7A108.8C8B—C7B—H7C108.9
C6A—C7A—H7B108.8C6B—C7B—H7D108.9
C8A—C7A—H7B108.8C8B—C7B—H7D108.9
H7A—C7A—H7B107.7H7C—C7B—H7D107.7
C7A—C8A—C26A107.36 (8)C7B—C8B—C26B106.83 (9)
C7A—C8A—C9A108.86 (8)C7B—C8B—C9B109.64 (9)
C26A—C8A—C9A111.80 (8)C26B—C8B—C9B111.81 (9)
C7A—C8A—C14A110.54 (8)C7B—C8B—C14B110.74 (9)
C26A—C8A—C14A110.25 (8)C26B—C8B—C14B110.47 (9)
C9A—C8A—C14A108.03 (8)C9B—C8B—C14B107.39 (8)
C11A—C9A—C8A111.23 (8)C11B—C9B—C8B110.75 (9)
C11A—C9A—C10A113.35 (8)C11B—C9B—C10B113.44 (9)
C8A—C9A—C10A116.39 (8)C8B—C9B—C10B117.54 (9)
C11A—C9A—H9A104.9C11B—C9B—H9B104.5
C8A—C9A—H9A104.9C8B—C9B—H9B104.5
C10A—C9A—H9A104.9C10B—C9B—H9B104.5
C25A—C10A—C1A108.14 (9)C25B—C10B—C1B108.20 (10)
C25A—C10A—C5A114.09 (9)C25B—C10B—C5B114.72 (9)
C1A—C10A—C5A107.45 (9)C1B—C10B—C5B107.00 (9)
C25A—C10A—C9A112.75 (9)C25B—C10B—C9B112.65 (9)
C1A—C10A—C9A107.48 (8)C1B—C10B—C9B107.52 (9)
C5A—C10A—C9A106.63 (8)C5B—C10B—C9B106.40 (8)
C12A—C11A—C9A113.15 (9)C12B—C11B—C9B111.60 (9)
C12A—C11A—H11A108.9C12B—C11B—H11C109.3
C9A—C11A—H11A108.9C9B—C11B—H11C109.3
C12A—C11A—H11B108.9C12B—C11B—H11D109.3
C9A—C11A—H11B108.9C9B—C11B—H11D109.3
H11A—C11A—H11B107.8H11C—C11B—H11D108.0
C13A—C12A—C11A111.78 (8)C13B—C12B—C11B111.31 (9)
C13A—C12A—H12A109.3C13B—C12B—H12C109.4
C11A—C12A—H12A109.3C11B—C12B—H12C109.4
C13A—C12A—H12B109.3C13B—C12B—H12D109.4
C11A—C12A—H12B109.3C11B—C12B—H12D109.4
H12A—C12A—H12B107.9H12C—C12B—H12D108.0
C12A—C13A—C18A113.58 (8)C12B—C13B—C18B113.75 (9)
C12A—C13A—C14A110.32 (8)C12B—C13B—C14B111.75 (9)
C18A—C13A—C14A111.70 (8)C18B—C13B—C14B110.50 (9)
C12A—C13A—H13A107.0C12B—C13B—H13B106.8
C18A—C13A—H13A107.0C18B—C13B—H13B106.8
C14A—C13A—H13A107.0C14B—C13B—H13B106.8
C27A—C14A—C15A105.59 (8)C27B—C14B—C15B106.55 (9)
C27A—C14A—C13A110.67 (8)C27B—C14B—C13B110.40 (9)
C15A—C14A—C13A110.41 (8)C15B—C14B—C13B108.94 (9)
C27A—C14A—C8A112.10 (8)C27B—C14B—C8B110.95 (9)
C15A—C14A—C8A110.91 (8)C15B—C14B—C8B111.01 (9)
C13A—C14A—C8A107.20 (8)C13B—C14B—C8B108.95 (8)
C16A—C15A—C14A114.85 (9)C16B—C15B—C14B114.93 (10)
C16A—C15A—H15A108.6C16B—C15B—H15C108.5
C14A—C15A—H15A108.6C14B—C15B—H15C108.5
C16A—C15A—H15B108.6C16B—C15B—H15D108.5
C14A—C15A—H15B108.6C14B—C15B—H15D108.5
H15A—C15A—H15B107.5H15C—C15B—H15D107.5
C17A—C16A—C15A109.44 (9)C17B—C16B—C15B109.60 (10)
C17A—C16A—H16A109.8C17B—C16B—H16C109.8
C15A—C16A—H16A109.8C15B—C16B—H16C109.8
C17A—C16A—H16B109.8C17B—C16B—H16D109.8
C15A—C16A—H16B109.8C15B—C16B—H16D109.8
H16A—C16A—H16B108.2H16C—C16B—H16D108.2
C28A—C17A—C16A107.20 (9)C28B—C17B—C16B108.38 (11)
C28A—C17A—C18A115.49 (9)C28B—C17B—C18B114.90 (10)
C16A—C17A—C18A109.84 (9)C16B—C17B—C18B110.07 (9)
C28A—C17A—C22A105.15 (9)C28B—C17B—C22B104.59 (10)
C16A—C17A—C22A117.74 (9)C16B—C17B—C22B117.51 (11)
C18A—C17A—C22A101.66 (8)C18B—C17B—C22B101.47 (10)
C13A—C18A—C17A112.01 (8)C13B—C18B—C17B111.30 (9)
C13A—C18A—C19A118.99 (8)C13B—C18B—C19B119.59 (9)
C17A—C18A—C19A104.49 (8)C17B—C18B—C19B105.18 (9)
C13A—C18A—H18A106.9C13B—C18B—H18B106.7
C17A—C18A—H18A106.9C17B—C18B—H18B106.7
C19A—C18A—H18A106.9C19B—C18B—H18B106.7
C20A—C19A—C18A116.79 (10)C20B—C19B—C18B116.80 (10)
C20A—C19A—C21A110.52 (9)C20B—C19B—C21B110.83 (10)
C18A—C19A—C21A103.84 (8)C18B—C19B—C21B104.08 (10)
C20A—C19A—H19A108.5C20B—C19B—H19B108.3
C18A—C19A—H19A108.5C18B—C19B—H19B108.3
C21A—C19A—H19A108.5C21B—C19B—H19B108.3
C29A—C20A—C30A121.76 (13)C29B—C20B—C30B120.09 (13)
C29A—C20A—C19A119.39 (13)C29B—C20B—C19B124.68 (12)
C30A—C20A—C19A118.75 (11)C30B—C20B—C19B115.18 (13)
C22A—C21A—C19A106.90 (9)C22B—C21B—C19B106.24 (11)
C22A—C21A—H21A110.3C22B—C21B—H21C110.5
C19A—C21A—H21A110.3C19B—C21B—H21C110.5
C22A—C21A—H21B110.3C22B—C21B—H21D110.5
C19A—C21A—H21B110.3C19B—C21B—H21D110.5
H21A—C21A—H21B108.6H21C—C21B—H21D108.7
C21A—C22A—C17A102.83 (8)C21B—C22B—C17B103.83 (10)
C21A—C22A—H22A111.2C21B—C22B—H22C111.0
C17A—C22A—H22A111.2C17B—C22B—H22C111.0
C21A—C22A—H22B111.2C21B—C22B—H22D111.0
C17A—C22A—H22B111.2C17B—C22B—H22D111.0
H22A—C22A—H22B109.1H22C—C22B—H22D109.0
C4A—C23A—H23A109.5C4B—C23B—H23D109.5
C4A—C23A—H23B109.5C4B—C23B—H23E109.5
H23A—C23A—H23B109.5H23D—C23B—H23E109.5
C4A—C23A—H23C109.5C4B—C23B—H23F109.5
H23A—C23A—H23C109.5H23D—C23B—H23F109.5
H23B—C23A—H23C109.5H23E—C23B—H23F109.5
C4A—C24A—H24A109.5C4B—C24B—H24D109.5
C4A—C24A—H24B109.5C4B—C24B—H24E109.5
H24A—C24A—H24B109.5H24D—C24B—H24E109.5
C4A—C24A—H24C109.5C4B—C24B—H24F109.5
H24A—C24A—H24C109.5H24D—C24B—H24F109.5
H24B—C24A—H24C109.5H24E—C24B—H24F109.5
C10A—C25A—H25A109.5C10B—C25B—H25D109.5
C10A—C25A—H25B109.5C10B—C25B—H25E109.5
H25A—C25A—H25B109.5H25D—C25B—H25E109.5
C10A—C25A—H25C109.5C10B—C25B—H25F109.5
H25A—C25A—H25C109.5H25D—C25B—H25F109.5
H25B—C25A—H25C109.5H25E—C25B—H25F109.5
C8A—C26A—H26A109.5C8B—C26B—H26D109.5
C8A—C26A—H26B109.5C8B—C26B—H26E109.5
H26A—C26A—H26B109.5H26D—C26B—H26E109.5
C8A—C26A—H26C109.5C8B—C26B—H26F109.5
H26A—C26A—H26C109.5H26D—C26B—H26F109.5
H26B—C26A—H26C109.5H26E—C26B—H26F109.5
C14A—C27A—H27A109.5C14B—C27B—H27D109.5
C14A—C27A—H27B109.5C14B—C27B—H27E109.5
H27A—C27A—H27B109.5H27D—C27B—H27E109.5
C14A—C27A—H27C109.5C14B—C27B—H27F109.5
H27A—C27A—H27C109.5H27D—C27B—H27F109.5
H27B—C27A—H27C109.5H27E—C27B—H27F109.5
O2A—C28A—C17A128.00 (10)O2B—C28B—C17B127.14 (12)
O2A—C28A—H28A116.0O2B—C28B—H28B116.4
C17A—C28A—H28A116.0C17B—C28B—H28B116.4
C20A—C29A—H29A120.0C20B—C29B—H29C120.0
C20A—C29A—H29B120.0C20B—C29B—H29D120.0
H29A—C29A—H29B120.0H29C—C29B—H29D120.0
C20A—C30A—H30A109.5C20B—C30B—H30D109.5
C20A—C30A—H30B109.5C20B—C30B—H30E109.5
H30A—C30A—H30B109.5H30D—C30B—H30E109.5
C20A—C30A—H30C109.5C20B—C30B—H30F109.5
H30A—C30A—H30C109.5H30D—C30B—H30F109.5
H30B—C30A—H30C109.5H30E—C30B—H30F109.5
C10A—C1A—C2A—C3A53.72 (14)C10B—C1B—C2B—C3B54.38 (16)
C1A—C2A—C3A—O1A127.02 (13)C1B—C2B—C3B—O1B134.51 (14)
C1A—C2A—C3A—C4A51.89 (15)C1B—C2B—C3B—C4B47.49 (17)
O1A—C3A—C4A—C23A11.74 (16)O1B—C3B—C4B—C23B20.42 (17)
C2A—C3A—C4A—C23A167.16 (10)C2B—C3B—C4B—C23B161.61 (12)
O1A—C3A—C4A—C24A104.73 (14)O1B—C3B—C4B—C24B95.37 (15)
C2A—C3A—C4A—C24A76.37 (12)C2B—C3B—C4B—C24B82.60 (14)
O1A—C3A—C4A—C5A130.55 (12)O1B—C3B—C4B—C5B140.00 (13)
C2A—C3A—C4A—C5A48.35 (13)C2B—C3B—C4B—C5B42.03 (14)
C3A—C4A—C5A—C6A177.14 (9)C3B—C4B—C5B—C6B177.75 (10)
C23A—C4A—C5A—C6A59.66 (12)C23B—C4B—C5B—C6B63.58 (13)
C24A—C4A—C5A—C6A62.13 (12)C24B—C4B—C5B—C6B57.32 (14)
C3A—C4A—C5A—C10A50.77 (12)C3B—C4B—C5B—C10B46.50 (13)
C23A—C4A—C5A—C10A168.24 (9)C23B—C4B—C5B—C10B165.17 (10)
C24A—C4A—C5A—C10A69.97 (12)C24B—C4B—C5B—C10B73.94 (14)
C10A—C5A—C6A—C7A61.19 (11)C10B—C5B—C6B—C7B64.26 (12)
C4A—C5A—C6A—C7A163.94 (9)C4B—C5B—C6B—C7B161.08 (10)
C5A—C6A—C7A—C8A57.11 (12)C5B—C6B—C7B—C8B58.00 (13)
C6A—C7A—C8A—C26A71.19 (11)C6B—C7B—C8B—C26B74.00 (12)
C6A—C7A—C8A—C9A50.00 (11)C6B—C7B—C8B—C9B47.33 (13)
C6A—C7A—C8A—C14A168.51 (8)C6B—C7B—C8B—C14B165.65 (9)
C7A—C8A—C9A—C11A177.93 (8)C7B—C8B—C9B—C11B179.22 (9)
C26A—C8A—C9A—C11A63.63 (11)C26B—C8B—C9B—C11B60.93 (12)
C14A—C8A—C9A—C11A57.85 (10)C14B—C8B—C9B—C11B60.40 (11)
C7A—C8A—C9A—C10A50.20 (11)C7B—C8B—C9B—C10B46.59 (12)
C26A—C8A—C9A—C10A68.24 (11)C26B—C8B—C9B—C10B71.70 (12)
C14A—C8A—C9A—C10A170.28 (8)C14B—C8B—C9B—C10B166.97 (9)
C2A—C1A—C10A—C25A70.27 (12)C2B—C1B—C10B—C25B68.67 (13)
C2A—C1A—C10A—C5A53.32 (12)C2B—C1B—C10B—C5B55.44 (13)
C2A—C1A—C10A—C9A167.74 (9)C2B—C1B—C10B—C9B169.40 (10)
C6A—C5A—C10A—C25A67.26 (11)C6B—C5B—C10B—C25B66.26 (13)
C4A—C5A—C10A—C25A65.77 (12)C4B—C5B—C10B—C25B66.51 (14)
C6A—C5A—C10A—C1A172.88 (8)C6B—C5B—C10B—C1B173.72 (10)
C4A—C5A—C10A—C1A54.10 (12)C4B—C5B—C10B—C1B53.51 (12)
C6A—C5A—C10A—C9A57.89 (11)C6B—C5B—C10B—C9B59.00 (11)
C4A—C5A—C10A—C9A169.09 (9)C4B—C5B—C10B—C9B168.22 (9)
C11A—C9A—C10A—C25A59.02 (12)C11B—C9B—C10B—C25B57.10 (12)
C8A—C9A—C10A—C25A71.87 (11)C8B—C9B—C10B—C25B74.32 (12)
C11A—C9A—C10A—C1A60.06 (11)C11B—C9B—C10B—C1B62.02 (12)
C8A—C9A—C10A—C1A169.06 (9)C8B—C9B—C10B—C1B166.56 (9)
C11A—C9A—C10A—C5A175.03 (8)C11B—C9B—C10B—C5B176.38 (9)
C8A—C9A—C10A—C5A54.09 (11)C8B—C9B—C10B—C5B52.20 (12)
C8A—C9A—C11A—C12A52.78 (12)C8B—C9B—C11B—C12B58.67 (12)
C10A—C9A—C11A—C12A173.82 (9)C10B—C9B—C11B—C12B166.65 (9)
C9A—C11A—C12A—C13A52.00 (12)C9B—C11B—C12B—C13B54.95 (12)
C11A—C12A—C13A—C18A176.23 (9)C11B—C12B—C13B—C18B178.73 (9)
C11A—C12A—C13A—C14A57.49 (11)C11B—C12B—C13B—C14B55.29 (12)
C12A—C13A—C14A—C27A59.71 (11)C12B—C13B—C14B—C27B63.93 (11)
C18A—C13A—C14A—C27A67.62 (11)C18B—C13B—C14B—C27B63.82 (11)
C12A—C13A—C14A—C15A176.25 (9)C12B—C13B—C14B—C15B179.39 (9)
C18A—C13A—C14A—C15A48.92 (11)C18B—C13B—C14B—C15B52.86 (11)
C12A—C13A—C14A—C8A62.82 (10)C12B—C13B—C14B—C8B58.15 (11)
C18A—C13A—C14A—C8A169.85 (8)C18B—C13B—C14B—C8B174.11 (8)
C7A—C8A—C14A—C27A59.81 (11)C7B—C8B—C14B—C27B57.46 (12)
C26A—C8A—C14A—C27A178.35 (9)C26B—C8B—C14B—C27B175.62 (9)
C9A—C8A—C14A—C27A59.21 (10)C9B—C8B—C14B—C27B62.22 (11)
C7A—C8A—C14A—C15A57.95 (11)C7B—C8B—C14B—C15B60.82 (12)
C26A—C8A—C14A—C15A60.60 (11)C26B—C8B—C14B—C15B57.33 (12)
C9A—C8A—C14A—C15A176.96 (8)C9B—C8B—C14B—C15B179.50 (9)
C7A—C8A—C14A—C13A178.55 (8)C7B—C8B—C14B—C13B179.20 (9)
C26A—C8A—C14A—C13A60.01 (10)C26B—C8B—C14B—C13B62.64 (11)
C9A—C8A—C14A—C13A62.43 (10)C9B—C8B—C14B—C13B59.53 (11)
C27A—C14A—C15A—C16A69.90 (11)C27B—C14B—C15B—C16B67.05 (13)
C13A—C14A—C15A—C16A49.76 (12)C13B—C14B—C15B—C16B52.06 (13)
C8A—C14A—C15A—C16A168.44 (9)C8B—C14B—C15B—C16B172.04 (10)
C14A—C15A—C16A—C17A54.84 (12)C14B—C15B—C16B—C17B54.64 (13)
C15A—C16A—C17A—C28A67.87 (11)C15B—C16B—C17B—C28B69.38 (12)
C15A—C16A—C17A—C18A58.33 (11)C15B—C16B—C17B—C18B57.04 (13)
C15A—C16A—C17A—C22A173.96 (9)C15B—C16B—C17B—C22B172.44 (10)
C12A—C13A—C18A—C17A178.55 (9)C12B—C13B—C18B—C17B174.10 (10)
C14A—C13A—C18A—C17A55.90 (11)C14B—C13B—C18B—C17B59.26 (12)
C12A—C13A—C18A—C19A56.38 (12)C12B—C13B—C18B—C19B51.11 (13)
C14A—C13A—C18A—C19A178.07 (9)C14B—C13B—C18B—C19B177.75 (9)
C28A—C17A—C18A—C13A60.62 (12)C28B—C17B—C18B—C13B61.25 (14)
C16A—C17A—C18A—C13A60.74 (11)C16B—C17B—C18B—C13B61.42 (12)
C22A—C17A—C18A—C13A173.83 (9)C22B—C17B—C18B—C13B173.42 (10)
C28A—C17A—C18A—C19A69.49 (11)C28B—C17B—C18B—C19B69.67 (13)
C16A—C17A—C18A—C19A169.15 (9)C16B—C17B—C18B—C19B167.67 (10)
C22A—C17A—C18A—C19A43.72 (10)C22B—C17B—C18B—C19B42.51 (12)
C13A—C18A—C19A—C20A85.01 (12)C13B—C18B—C19B—C20B84.91 (13)
C17A—C18A—C19A—C20A149.15 (9)C17B—C18B—C19B—C20B149.16 (10)
C13A—C18A—C19A—C21A153.06 (9)C13B—C18B—C19B—C21B152.58 (10)
C17A—C18A—C19A—C21A27.22 (10)C17B—C18B—C19B—C21B26.65 (12)
C18A—C19A—C20A—C29A142.65 (12)C18B—C19B—C20B—C29B25.16 (18)
C21A—C19A—C20A—C29A98.98 (14)C21B—C19B—C20B—C29B93.76 (15)
C18A—C19A—C20A—C30A40.80 (16)C18B—C19B—C20B—C30B157.26 (12)
C21A—C19A—C20A—C30A77.58 (14)C21B—C19B—C20B—C30B83.81 (15)
C20A—C19A—C21A—C22A126.59 (11)C20B—C19B—C21B—C22B126.91 (12)
C18A—C19A—C21A—C22A0.58 (12)C18B—C19B—C21B—C22B0.55 (14)
C19A—C21A—C22A—C17A25.95 (12)C19B—C21B—C22B—C17B25.39 (14)
C28A—C17A—C22A—C21A78.26 (10)C28B—C17B—C22B—C21B78.30 (12)
C16A—C17A—C22A—C21A162.49 (10)C16B—C17B—C22B—C21B161.51 (11)
C18A—C17A—C22A—C21A42.48 (11)C18B—C17B—C22B—C21B41.48 (13)
C16A—C17A—C28A—O2A130.43 (12)C16B—C17B—C28B—O2B139.26 (16)
C18A—C17A—C28A—O2A7.66 (17)C18B—C17B—C28B—O2B15.7 (2)
C22A—C17A—C28A—O2A103.51 (13)C22B—C17B—C28B—O2B94.63 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13A—H13A···O2A1.002.473.1452 (13)125
C13B—H13B···O2B1.002.503.1792 (15)125
C19A—H19A···O2A1.002.603.0801 (14)110
C19B—H19B···O2B1.002.533.0134 (17)109
C22A—H22A···O2Bi0.992.483.3325 (15)144
Symmetry code: (i) x1, y1, z.
(II_polymorph) Lup-20 (29)-en-28-al-3-one top
Crystal data top
C30H46O2F(000) = 968
Mr = 438.67Dx = 1.178 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 15750 reflections
a = 10.3987 (2) Åθ = 2.5–38.4°
b = 13.8559 (3) ŵ = 0.07 mm1
c = 17.1632 (2) ÅT = 100 K
V = 2472.93 (8) Å3Plate, colourless
Z = 40.30 × 0.26 × 0.10 mm
Data collection top
Agilent SuperNova
diffractometer with an Atlas detector
7855 independent reflections
Radiation source: SuperNova (Mo) X-ray Source7535 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.020
Detector resolution: 10.4498 pixels mm-1θmax = 31.0°, θmin = 2.3°
ω scansh = 1415
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
k = 1920
Tmin = 0.917, Tmax = 1.000l = 2224
24511 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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0426P)2 + 0.7618P]
where P = (Fo2 + 2Fc2)/3
7855 reflections(Δ/σ)max = 0.001
305 parametersΔρmax = 0.35 e Å3
2 restraintsΔρmin = 0.21 e Å3
Crystal data top
C30H46O2V = 2472.93 (8) Å3
Mr = 438.67Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 10.3987 (2) ŵ = 0.07 mm1
b = 13.8559 (3) ÅT = 100 K
c = 17.1632 (2) Å0.30 × 0.26 × 0.10 mm
Data collection top
Agilent SuperNova
diffractometer with an Atlas detector
7855 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
7535 reflections with I > 2σ(I)
Tmin = 0.917, Tmax = 1.000Rint = 0.020
24511 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0362 restraints
wR(F2) = 0.094H-atom parameters constrained
S = 1.02Δρmax = 0.35 e Å3
7855 reflectionsΔρmin = 0.21 e Å3
305 parameters
Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.36.32 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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)
O10.58894 (10)0.03494 (8)1.14232 (6)0.0364 (2)
C10.74851 (11)0.16505 (8)1.06364 (6)0.01888 (19)
H1A0.80840.21661.08030.023*
H1B0.66110.19321.06170.023*
C20.75044 (12)0.08385 (9)1.12463 (6)0.0228 (2)
H2A0.84030.06271.13310.027*
H2B0.71710.10901.17470.027*
C30.67054 (12)0.00148 (9)1.09977 (6)0.0222 (2)
C40.69646 (11)0.04233 (8)1.01828 (6)0.01937 (19)
C50.69810 (10)0.04404 (7)0.95983 (5)0.01485 (17)
H50.60870.07050.96110.018*
C60.71914 (11)0.01291 (7)0.87504 (6)0.01699 (18)
H6A0.81050.00490.86730.020*
H6B0.66580.04460.86360.020*
C70.68320 (10)0.09459 (7)0.81931 (5)0.01604 (18)
H7A0.58980.10730.82390.019*
H7B0.70020.07320.76520.019*
C80.75668 (9)0.18961 (7)0.83405 (5)0.01263 (16)
C90.75119 (10)0.21465 (7)0.92288 (5)0.01345 (16)
H90.65850.22880.93340.016*
C100.78640 (10)0.13146 (7)0.98091 (5)0.01434 (17)
C110.82145 (11)0.31032 (7)0.93930 (6)0.01823 (19)
H11A0.81210.32660.99520.022*
H11B0.91420.30190.92840.022*
C120.76985 (11)0.39402 (7)0.89024 (6)0.01748 (18)
H12A0.68100.40930.90700.021*
H12B0.82360.45190.89930.021*
C130.76983 (9)0.37005 (7)0.80322 (6)0.01386 (16)
H130.86110.35680.78830.017*
C140.69209 (9)0.27551 (7)0.78683 (5)0.01271 (16)
C150.69300 (10)0.25305 (7)0.69814 (6)0.01672 (18)
H15A0.78090.23320.68290.020*
H15B0.63490.19780.68820.020*
C160.65136 (11)0.33790 (8)0.64658 (6)0.01951 (19)
H16A0.66040.32010.59100.023*
H16B0.55990.35340.65660.023*
C170.73431 (10)0.42539 (7)0.66427 (6)0.01795 (18)
C180.72268 (10)0.45247 (7)0.75083 (6)0.01516 (17)
H180.62900.46110.76190.018*
C190.78504 (10)0.55314 (7)0.75692 (6)0.01768 (18)
H190.87960.54470.76520.021*
C200.73410 (11)0.62069 (8)0.81885 (7)0.0216 (2)
C210.76329 (11)0.59846 (8)0.67393 (7)0.0216 (2)
H21A0.70830.65660.67770.026*
H21B0.84660.61720.65040.026*
C220.69701 (12)0.52073 (8)0.62404 (7)0.0226 (2)
H22A0.72880.52240.56970.027*
H22B0.60260.52970.62390.027*
C230.58740 (13)0.11220 (9)0.99805 (7)0.0267 (2)
H23A0.57820.15991.03980.040*
H23B0.60730.14520.94900.040*
H23C0.50690.07620.99240.040*
C240.82287 (12)0.10070 (8)1.02012 (7)0.0245 (2)
H24A0.80970.16031.04980.037*
H24B0.89040.06211.04500.037*
H24C0.84880.11670.96680.037*
C250.93129 (10)0.10783 (8)0.98129 (6)0.01824 (19)
H25A0.98060.16700.97210.027*
H25B0.95020.06090.94010.027*
H25C0.95520.08051.03190.027*
C260.89673 (10)0.17365 (8)0.80668 (6)0.01716 (18)
H26A0.92780.11140.82610.026*
H26B0.95140.22550.82700.026*
H26C0.89980.17390.74960.026*
C270.54934 (10)0.28884 (8)0.80948 (6)0.01746 (18)
H27A0.51620.34820.78580.026*
H27B0.54190.29320.86630.026*
H27C0.49940.23360.79070.026*
C280.87024 (12)0.40434 (9)0.63657 (7)0.0274 (2)
C290.62078 (12)0.61221 (9)0.85442 (8)0.0276 (2)
H29A0.59360.66010.89040.033*
H29B0.56720.55830.84380.033*
C300.82068 (14)0.70538 (10)0.83473 (10)0.0352 (3)
H30A0.78010.74790.87320.053*
H30B0.83510.74120.78630.053*
H30C0.90320.68220.85500.053*
O2A0.96717 (11)0.41684 (9)0.66528 (7)0.0267 (3)0.769 (3)
H2AO0.86620.37630.57700.032*0.769 (3)
O2B0.92433 (18)0.3506 (3)0.5993 (2)0.0393 (13)0.231 (3)
H2BO0.92910.44580.67740.047*0.231 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0393 (6)0.0459 (6)0.0240 (4)0.0136 (5)0.0046 (4)0.0053 (4)
C10.0242 (5)0.0204 (4)0.0120 (4)0.0002 (4)0.0007 (4)0.0024 (3)
C20.0300 (6)0.0259 (5)0.0125 (4)0.0026 (4)0.0023 (4)0.0002 (4)
C30.0248 (5)0.0261 (5)0.0158 (4)0.0019 (4)0.0033 (4)0.0052 (4)
C40.0240 (5)0.0189 (4)0.0152 (4)0.0037 (4)0.0042 (4)0.0038 (3)
C50.0174 (4)0.0151 (4)0.0120 (4)0.0020 (3)0.0026 (3)0.0009 (3)
C60.0238 (5)0.0135 (4)0.0136 (4)0.0013 (4)0.0030 (3)0.0002 (3)
C70.0220 (5)0.0139 (4)0.0122 (4)0.0021 (3)0.0034 (3)0.0001 (3)
C80.0141 (4)0.0128 (4)0.0111 (3)0.0005 (3)0.0002 (3)0.0010 (3)
C90.0156 (4)0.0133 (4)0.0115 (4)0.0003 (3)0.0006 (3)0.0013 (3)
C100.0172 (4)0.0146 (4)0.0112 (4)0.0004 (3)0.0017 (3)0.0012 (3)
C110.0233 (5)0.0155 (4)0.0159 (4)0.0026 (4)0.0040 (4)0.0020 (3)
C120.0221 (5)0.0134 (4)0.0169 (4)0.0020 (4)0.0004 (3)0.0020 (3)
C130.0141 (4)0.0121 (4)0.0153 (4)0.0006 (3)0.0003 (3)0.0002 (3)
C140.0126 (4)0.0124 (4)0.0131 (4)0.0006 (3)0.0002 (3)0.0003 (3)
C150.0207 (4)0.0158 (4)0.0137 (4)0.0014 (4)0.0014 (4)0.0000 (3)
C160.0252 (5)0.0181 (4)0.0153 (4)0.0025 (4)0.0029 (4)0.0011 (3)
C170.0196 (5)0.0168 (4)0.0175 (4)0.0028 (4)0.0018 (4)0.0027 (3)
C180.0139 (4)0.0132 (4)0.0183 (4)0.0010 (3)0.0005 (3)0.0014 (3)
C190.0151 (4)0.0141 (4)0.0239 (5)0.0000 (3)0.0008 (4)0.0025 (3)
C200.0211 (5)0.0150 (4)0.0285 (5)0.0013 (4)0.0005 (4)0.0009 (4)
C210.0202 (5)0.0175 (4)0.0272 (5)0.0006 (4)0.0001 (4)0.0067 (4)
C220.0270 (6)0.0188 (4)0.0221 (5)0.0029 (4)0.0011 (4)0.0058 (4)
C230.0321 (6)0.0246 (5)0.0233 (5)0.0109 (5)0.0060 (4)0.0068 (4)
C240.0305 (6)0.0196 (5)0.0234 (5)0.0009 (4)0.0080 (4)0.0038 (4)
C250.0166 (4)0.0199 (5)0.0182 (4)0.0002 (4)0.0034 (3)0.0001 (4)
C260.0155 (4)0.0203 (5)0.0157 (4)0.0045 (3)0.0022 (3)0.0013 (3)
C270.0132 (4)0.0175 (4)0.0217 (4)0.0010 (3)0.0010 (3)0.0007 (4)
C280.0278 (6)0.0217 (5)0.0325 (6)0.0061 (4)0.0128 (5)0.0076 (5)
C290.0261 (6)0.0197 (5)0.0369 (6)0.0006 (4)0.0068 (5)0.0046 (5)
C300.0308 (6)0.0257 (6)0.0490 (8)0.0048 (5)0.0039 (6)0.0127 (6)
O2A0.0210 (5)0.0291 (6)0.0300 (6)0.0004 (4)0.0052 (4)0.0005 (5)
O2B0.038 (3)0.041 (3)0.039 (3)0.008 (2)0.0146 (19)0.000 (2)
Geometric parameters (Å, º) top
O1—C31.2117 (15)C16—H16A0.9900
C1—C21.5370 (15)C16—H16B0.9900
C1—C101.5452 (14)C17—C281.5196 (16)
C1—H1A0.9900C17—C181.5370 (14)
C1—H1B0.9900C17—C221.5403 (15)
C2—C31.5068 (17)C18—C191.5418 (14)
C2—H2A0.9900C18—H181.0000
C2—H2B0.9900C19—C201.5121 (15)
C3—C41.5326 (15)C19—C211.5730 (15)
C4—C231.5310 (16)C19—H191.0000
C4—C241.5436 (17)C20—C291.3324 (17)
C4—C51.5617 (14)C20—C301.5039 (17)
C5—C61.5335 (14)C21—C221.5388 (16)
C5—C101.5625 (14)C21—H21A0.9900
C5—H51.0000C21—H21B0.9900
C6—C71.5282 (13)C22—H22A0.9900
C6—H6A0.9900C22—H22B0.9900
C6—H6B0.9900C23—H23A0.9800
C7—C81.5431 (13)C23—H23B0.9800
C7—H7A0.9900C23—H23C0.9800
C7—H7B0.9900C24—H24A0.9800
C8—C261.5461 (14)C24—H24B0.9800
C8—C91.5646 (13)C24—H24C0.9800
C8—C141.5889 (13)C25—H25A0.9800
C9—C111.5395 (14)C25—H25B0.9800
C9—C101.5668 (13)C25—H25C0.9800
C9—H91.0000C26—H26A0.9800
C10—C251.5419 (15)C26—H26B0.9800
C11—C121.5304 (15)C26—H26C0.9800
C11—H11A0.9900C27—H27A0.9800
C11—H11B0.9900C27—H27B0.9800
C12—C131.5300 (14)C27—H27C0.9800
C12—H12A0.9900C28—O2B1.1320 (19)
C12—H12B0.9900C28—O2A1.1353 (17)
C13—C181.5341 (13)C28—H2AO1.0937
C13—C141.5648 (13)C28—H2BO1.0937
C13—H131.0000C29—H29A0.9500
C14—C271.5455 (14)C29—H29B0.9500
C14—C151.5537 (13)C30—H30A0.9800
C15—C161.5339 (14)C30—H30B0.9800
C15—H15A0.9900C30—H30C0.9800
C15—H15B0.9900O2A—H2BO0.6003
C16—C171.5185 (15)O2B—H2AO0.7987
C2—C1—C10113.70 (9)C17—C16—H16A109.7
C2—C1—H1A108.8C15—C16—H16A109.7
C10—C1—H1A108.8C17—C16—H16B109.7
C2—C1—H1B108.8C15—C16—H16B109.7
C10—C1—H1B108.8H16A—C16—H16B108.2
H1A—C1—H1B107.7C16—C17—C28108.22 (9)
C3—C2—C1111.98 (9)C16—C17—C18110.09 (8)
C3—C2—H2A109.2C28—C17—C18114.99 (9)
C1—C2—H2A109.2C16—C17—C22116.87 (9)
C3—C2—H2B109.2C28—C17—C22104.98 (9)
C1—C2—H2B109.2C18—C17—C22101.77 (8)
H2A—C2—H2B107.9C13—C18—C17111.08 (8)
O1—C3—C2121.04 (11)C13—C18—C19119.95 (8)
O1—C3—C4122.13 (11)C17—C18—C19104.68 (8)
C2—C3—C4116.82 (9)C13—C18—H18106.8
C23—C4—C3108.07 (10)C17—C18—H18106.8
C23—C4—C24107.70 (9)C19—C18—H18106.8
C3—C4—C24108.94 (9)C20—C19—C18117.41 (9)
C23—C4—C5110.30 (8)C20—C19—C21109.82 (9)
C3—C4—C5107.77 (9)C18—C19—C21103.84 (8)
C24—C4—C5113.91 (9)C20—C19—H19108.5
C6—C5—C4113.31 (8)C18—C19—H19108.5
C6—C5—C10110.73 (8)C21—C19—H19108.5
C4—C5—C10116.85 (8)C29—C20—C30121.01 (11)
C6—C5—H5104.9C29—C20—C19125.27 (10)
C4—C5—H5104.9C30—C20—C19113.62 (10)
C10—C5—H5104.9C22—C21—C19106.79 (8)
C7—C6—C5110.54 (8)C22—C21—H21A110.4
C7—C6—H6A109.5C19—C21—H21A110.4
C5—C6—H6A109.5C22—C21—H21B110.4
C7—C6—H6B109.5C19—C21—H21B110.4
C5—C6—H6B109.5H21A—C21—H21B108.6
H6A—C6—H6B108.1C21—C22—C17103.77 (9)
C6—C7—C8114.09 (8)C21—C22—H22A111.0
C6—C7—H7A108.7C17—C22—H22A111.0
C8—C7—H7A108.7C21—C22—H22B111.0
C6—C7—H7B108.7C17—C22—H22B111.0
C8—C7—H7B108.7H22A—C22—H22B109.0
H7A—C7—H7B107.6C4—C23—H23A109.5
C7—C8—C26107.13 (8)C4—C23—H23B109.5
C7—C8—C9109.33 (7)H23A—C23—H23B109.5
C26—C8—C9111.23 (8)C4—C23—H23C109.5
C7—C8—C14110.25 (7)H23A—C23—H23C109.5
C26—C8—C14110.51 (7)H23B—C23—H23C109.5
C9—C8—C14108.39 (7)C4—C24—H24A109.5
C11—C9—C8110.61 (8)C4—C24—H24B109.5
C11—C9—C10113.96 (8)H24A—C24—H24B109.5
C8—C9—C10116.60 (7)C4—C24—H24C109.5
C11—C9—H9104.8H24A—C24—H24C109.5
C8—C9—H9104.8H24B—C24—H24C109.5
C10—C9—H9104.8C10—C25—H25A109.5
C25—C10—C1108.01 (8)C10—C25—H25B109.5
C25—C10—C5114.24 (8)H25A—C25—H25B109.5
C1—C10—C5107.25 (8)C10—C25—H25C109.5
C25—C10—C9112.78 (8)H25A—C25—H25C109.5
C1—C10—C9107.64 (8)H25B—C25—H25C109.5
C5—C10—C9106.61 (7)C8—C26—H26A109.5
C12—C11—C9112.67 (8)C8—C26—H26B109.5
C12—C11—H11A109.1H26A—C26—H26B109.5
C9—C11—H11A109.1C8—C26—H26C109.5
C12—C11—H11B109.1H26A—C26—H26C109.5
C9—C11—H11B109.1H26B—C26—H26C109.5
H11A—C11—H11B107.8C14—C27—H27A109.5
C13—C12—C11111.87 (8)C14—C27—H27B109.5
C13—C12—H12A109.2H27A—C27—H27B109.5
C11—C12—H12A109.2C14—C27—H27C109.5
C13—C12—H12B109.2H27A—C27—H27C109.5
C11—C12—H12B109.2H27B—C27—H27C109.5
H12A—C12—H12B107.9O2B—C28—O2A84.54 (16)
C12—C13—C18114.24 (8)O2B—C28—C17139.95 (13)
C12—C13—C14110.94 (8)O2A—C28—C17131.36 (11)
C18—C13—C14110.65 (8)O2A—C28—H2AO119.6
C12—C13—H13106.9C17—C28—H2AO109.0
C18—C13—H13106.9O2B—C28—H2BO115.4
C14—C13—H13106.9C17—C28—H2BO102.7
C27—C14—C15106.04 (8)H2AO—C28—H2BO143.7
C27—C14—C13110.54 (8)C20—C29—H29A120.0
C15—C14—C13109.92 (8)C20—C29—H29B120.0
C27—C14—C8111.54 (8)H29A—C29—H29B120.0
C15—C14—C8110.31 (7)C20—C30—H30A109.5
C13—C14—C8108.48 (7)C20—C30—H30B109.5
C16—C15—C14114.21 (8)H30A—C30—H30B109.5
C16—C15—H15A108.7C20—C30—H30C109.5
C14—C15—H15A108.7H30A—C30—H30C109.5
C16—C15—H15B108.7H30B—C30—H30C109.5
C14—C15—H15B108.7C28—O2A—H2BO70.6
H15A—C15—H15B107.6C28—O2B—H2AO66.4
C17—C16—C15109.64 (9)
C10—C1—C2—C353.38 (13)C18—C13—C14—C1551.86 (10)
C1—C2—C3—O1127.94 (12)C12—C13—C14—C859.58 (10)
C1—C2—C3—C451.27 (14)C18—C13—C14—C8172.54 (8)
O1—C3—C4—C2311.49 (16)C7—C8—C14—C2758.23 (10)
C2—C3—C4—C23167.70 (10)C26—C8—C14—C27176.47 (8)
O1—C3—C4—C24105.26 (13)C9—C8—C14—C2761.40 (10)
C2—C3—C4—C2475.54 (12)C7—C8—C14—C1559.34 (10)
O1—C3—C4—C5130.68 (12)C26—C8—C14—C1558.90 (10)
C2—C3—C4—C548.51 (13)C9—C8—C14—C15178.97 (8)
C23—C4—C5—C660.46 (12)C7—C8—C14—C13179.78 (8)
C3—C4—C5—C6178.22 (9)C26—C8—C14—C1361.54 (9)
C24—C4—C5—C660.78 (12)C9—C8—C14—C1360.59 (9)
C23—C4—C5—C10168.98 (9)C27—C14—C15—C1667.83 (11)
C3—C4—C5—C1051.22 (12)C13—C14—C15—C1651.68 (11)
C24—C4—C5—C1069.78 (12)C8—C14—C15—C16171.26 (8)
C4—C5—C6—C7164.34 (9)C14—C15—C16—C1755.20 (12)
C10—C5—C6—C762.11 (11)C15—C16—C17—C2868.06 (11)
C5—C6—C7—C856.80 (11)C15—C16—C17—C1858.38 (11)
C6—C7—C8—C2672.23 (10)C15—C16—C17—C22173.78 (9)
C6—C7—C8—C948.42 (11)C12—C13—C18—C17176.08 (9)
C6—C7—C8—C14167.47 (8)C14—C13—C18—C1757.87 (10)
C7—C8—C9—C11178.86 (8)C12—C13—C18—C1953.70 (12)
C26—C8—C9—C1163.03 (10)C14—C13—C18—C19179.75 (8)
C14—C8—C9—C1158.66 (10)C16—C17—C18—C1361.43 (11)
C7—C8—C9—C1048.79 (11)C28—C17—C18—C1361.10 (11)
C26—C8—C9—C1069.32 (11)C22—C17—C18—C13173.96 (8)
C14—C8—C9—C10168.99 (8)C16—C17—C18—C19167.72 (8)
C2—C1—C10—C2570.17 (11)C28—C17—C18—C1969.75 (10)
C2—C1—C10—C553.41 (11)C22—C17—C18—C1943.11 (10)
C2—C1—C10—C9167.78 (9)C13—C18—C19—C2084.84 (12)
C6—C5—C10—C2566.47 (10)C17—C18—C19—C20149.70 (9)
C4—C5—C10—C2565.28 (11)C13—C18—C19—C21153.75 (9)
C6—C5—C10—C1173.87 (8)C17—C18—C19—C2128.30 (10)
C4—C5—C10—C154.38 (11)C18—C19—C20—C2918.72 (17)
C6—C5—C10—C958.80 (10)C21—C19—C20—C2999.53 (13)
C4—C5—C10—C9169.45 (8)C18—C19—C20—C30164.97 (10)
C11—C9—C10—C2558.61 (11)C21—C19—C20—C3076.78 (13)
C8—C9—C10—C2572.20 (11)C20—C19—C21—C22129.22 (10)
C11—C9—C10—C160.44 (11)C18—C19—C21—C222.87 (11)
C8—C9—C10—C1168.76 (8)C19—C21—C22—C1723.41 (11)
C11—C9—C10—C5175.24 (8)C16—C17—C22—C21160.53 (9)
C8—C9—C10—C553.95 (11)C28—C17—C22—C2179.58 (10)
C8—C9—C11—C1255.36 (11)C18—C17—C22—C2140.59 (10)
C10—C9—C11—C12170.96 (8)C16—C17—C28—O2B13.0 (4)
C9—C11—C12—C1353.50 (12)C18—C17—C28—O2B136.5 (4)
C11—C12—C13—C18178.32 (9)C22—C17—C28—O2B112.5 (4)
C11—C12—C13—C1455.78 (11)C16—C17—C28—O2A135.26 (15)
C12—C13—C14—C2763.02 (10)C18—C17—C28—O2A11.72 (19)
C18—C13—C14—C2764.86 (10)C22—C17—C28—O2A99.24 (16)
C12—C13—C14—C15179.73 (8)

Experimental details

(I_polymorph)(II_polymorph)
Crystal data
Chemical formulaC30H46O2C30H46O2
Mr438.67438.67
Crystal system, space groupOrthorhombic, P212121Orthorhombic, P212121
Temperature (K)100100
a, b, c (Å)9.3905 (2), 19.1080 (3), 28.0829 (5)10.3987 (2), 13.8559 (3), 17.1632 (2)
V3)5039.02 (16)2472.93 (8)
Z84
Radiation typeMo KαMo Kα
µ (mm1)0.070.07
Crystal size (mm)0.48 × 0.38 × 0.170.30 × 0.26 × 0.10
Data collection
DiffractometerAgilent SuperNova
diffractometer with an Atlas detector
Agilent SuperNova
diffractometer with an Atlas detector
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2013)
Multi-scan
(CrysAlis PRO; Agilent, 2013)
Tmin, Tmax0.757, 1.0000.917, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
61016, 16765, 15731 24511, 7855, 7535
Rint0.0290.020
(sin θ/λ)max1)0.7350.725
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.098, 1.02 0.036, 0.094, 1.02
No. of reflections167657855
No. of parameters589305
No. of restraints02
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.200.35, 0.21

Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006) and PLATON (Spek, 2009), publCIF (Westrip, 2010).

Cremer–Pople puckering parameters for polymorphs (I) and (II) of betulonal top
RingMoleculeCremer–Pople parameters
A(IA)Q = 0.5309 Å, θ = 4.71°, φ = 313.17°
(IB)Q = 0.5129 Å, θ = 10.86°, φ = 326.34°
(II)Q = 0.5307 Å, θ = 4.74°, φ = 311.5°
B(IA)Q = 0.5738 Å, θ = 7.43°, φ = 3.96°
(IB)Q = 0.5737 Å, θ = 11.24°, φ = 12.07°
(II)Q = 0.5738 Å, θ = 8.83°, φ = 2.3°
C(IA)Q = 0.6142 Å, θ = 9.69°, φ = 309.15°
(IB)Q = 0.6108 Å, θ = 5.99°, φ = 352.32°
(II)Q = 0.6039 Å, θ = 6.65°, φ = 330.0°
D(IA)Q = 0.5695 Å, θ = 172.95°, φ = 65.23°
(IB)Q = 0.5829 Å, θ = 174.9°, φ = 102.06°
(II)Q = 0.5828 Å, θ = 174.38°, φ = 77.8°
E(IA)q2 = 0.4392 Å, φ2 = 1.25°
(IB)q2 = 0.4880 Å, φ2 = 0.73°
(II)q2 = 0.4279 (15) Å, φ2 = 4.3 (2)°
Selected torsion angles for polymorphs (I) [molecules (IA) and (IB)] and (II) of betulonal top
(IA)(IB)(II)
O1—C3—C4—C5130.55 (12)140.00 (13)130.68 (12)
O1—C3—C4—C23-104.7 (2)-95.5 (2)-105.3 (2)
C18—C19—C20—C29142.65 (12)-25.16 (18)-18.72 (17)
C21—C19—C20—C29-98.98 (14)93.76 (15)99.53 (13)
C18—C19—C20—C30-40.80 (16)157.26 (12)164.97 (10)
C21—C19—C20—C3077.58 (14)-83.81 (15)-76.78 (13)
C16—C17—C28—O2-130.43 (12)-139.26 (16)-135.26 (15) (O2A), 13.0 (4) (O2B)
C22—C17—C28—O2103.51 (13)94.63 (17)99.24 (16) (O2A), -112.5 (4) (O2B)
C18—C17—C28—O2-7.66 (17)-15.7 (2)-11.72 (19) (O2A), 136.5 (4) (O2B)
C2—C1—C10—C553.32 (12)55.44 (13)53.41 (11)
C4—C5—C10—C1-54.10 (12)-53.51 (12)-54.38 (11)
C2—C3—C4—C5-48.35 (13)-42.03 (14)-48.51 (13)
C1—C2—C3—C451.89 (15)47.49 (17)51.27 (14)
C17—C18—C19—C2127.22 (10)26.65 (12)28.30 (10)
C19—C21—C22—C17-25.95 (12)-25.39 (14)-23.41 (11)
Hydrogen-bond geometry (Å, º) for (I_polymorph) top
D—H···AD—HH···AD···AD—H···A
C13A—H13A···O2A1.002.473.1452 (13)124.8
C13B—H13B···O2B1.002.503.1792 (15)124.5
C19A—H19A···O2A1.002.603.0801 (14)109.6
C19B—H19B···O2B1.002.533.0134 (17)109.2
C22A—H22A···O2Bi0.992.483.3325 (15)144.3
Symmetry code: (i) x1, y1, z.
 

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