gem-Dimethyl­cyclo­propanation of dibenzyl­ideneacetone using triisopropyl sulfoxonium tetra­fluoro­borate

The reaction between dibenzyl­ideneacetone (dba) and tri­isopropyl sulfoxonium tetra­fluoro­borate has been reinvestigated. The stereochemistry of the major diasteromeric bis­(gem-dimethyl­cyclo­propane) adduct has now been assigned as [(1RS,3RS)-2,2-dimethyl-3-phenyl­cyclo­prop­yl][(1SR,3SR)-2,2-dimethyl-3-phenyl­cyclo­prop­yl]methanone, C₂₃H₂₆O, by X-ray crystallographic studies on a twinned crystal. The asymmetric unit contains two mol­ecules of the adduct, the conformations of which differ in the orientation of the phenyl ring relative to the adjacent cyclo­propanated double bond. The carbonyl groups of each adduct are aligned approximately along the a axis and in opposite directions to each other. The mol­ecules pack to give a sinusoidal pattern along the b axis. This is the first acyclic bis­(dimethyl­cyclo­prop­yl) ketone for which an X-ray crystal structure determination has been reported, and is also the first bis-cyclo­propanated dba analogue. The knowledge that the major diastereomer has the meso structure (and therefore the confirmation that the minor isomer is the racemate) will prove invaluable in future studies to utilize bis­(dimethyl­cyclo­prop­yl) ketones as reagents, in rearrangement processes, and as potential ligands and ligand precursors in organometallic chemistry.

S1. Comment

We recently reported the preparation of triisopropyl sulfoxonium tetrafluoroborate, (I), and its use as an isopropylidene transfer reagent for the gem-dimethylcyclopropanation of a range of electron-deficient alkenes (Edwards et al., 2008). Good to excellent yields were obtained with a range of cyclic and acyclic α,β-unsaturated ketones and related systems (see first scheme).

The dimethylcyclopropanation of dienones was also studied. Interestingly, dibenzylideneacetone, (II), gave a mixture of the expected dimethylcyclopropane, (III), together with two inseparable diastereomers of the bis-cyclopropyl adducts, (IV) and (V) (see second scheme). With excess sulfoxonium salt, the bis-adducts (IV) and (V) were formed in 94% yield as an inseparable mixture of diastereomers (2.15:1), but we were unable to assign the structure of the major diastereoisomer.

We have now repeated the bis(dimethylcyclopropanation) of dibenzylideneacetone (II) in order to clarify the stereochemical outcome of this reaction. Repeated recrystallization (ten times) of the (IV)/(V) mixture from ethanol–water, and analysis by ¹H NMR spectroscopy, produced a pure sample of the major diastereomeric product. X-ray crystallographic analysis then confirmed that the major product was the title meso-isomer, (IV) (Fig. 1).

The asymmetric unit contains two molecules of the adduct (IV) with differing conformations. The carbonyl groups of each adduct are aligned approximately along the a axis and in opposite directions to each other. The orientation of the individual molecules is such that there is almost a mirror plane of symmetry along the carbonyl axis, perpendicular to the C8/C9/C10/O1 plane. [From the Co-Editor: Is this also true of the C32/C32/C33/O2 plane?]

The differences between the two conformations are significant, with the r.m.s. best fit for overlap of the heavy atoms being 0.252 Å. Closer inspection reveals that the major difference is in the orientation of the phenyl ring relative to the adjacent cyclopropanated double bond. For one adduct, both rings are twisted with approximately equivalent angles of -15.6 (10) and 16.5 (10)°. In the other, one phenyl ring and bond are almost coplanar, the angles being 2.8 (11) and -13.5 (10)°. This difference is also reflected in the angle between the planes for each pair of cyclopropane and phenyl groups; the angles are 58.8 (6) and 59.2 (6)° for the first adduct and 61.5 (5) and 65.9 (6)° for the second. It is notable that for the second conformer, half of the molecule has an orientation closely similar to that of the first conformer, whilst the remainder is significantly different. This is clearly illustrated in Fig. 2.

The packing of the molecules within the crystal structure also shows some interesting behaviour. Each conformer is arranged to form a sinusoidal pattern orientated along the b axis (Fig. 3). Analysis of the packing shows that there are no intermolecular π–π interactions (neither face-to-face or edge-to-face) as there are no pairs of atoms which are significantly closer (0.2 Å) than the sum of the their van der Waals radii.

A search of the Cambridge Structural Database (Version 5.29 with August 2008 update; Allen, 2002) reveals that only 29 crystal structures have been reported previously which contain the cyclopropyl–carbonyl–cyclopropyl (CyP–CO–CyP) sequence. All but three of these have the (CyP–CO–CyP) moiety as part of a cyclic structure, with the majority being derived from 1,4-benzoquinone. Only two structures are reported which have two dimethylcyclopropyl groups, one being derived from benzoquinone (Edwards et al., 2008) and the other based on tropone (Cetinkaya et al., 1982). Thus, the crystal structure of (IV), with the dimethylcyclopropyl groups and carbonyl in an acyclic arrangement, appears to be the first of its type to be reported.

S2. Experimental

[(1RS,3RS)-2,2-Dimethyl-3-phenylcyclopropyl][(1'SR, 3'SR)-2,2-dimethyl-3-phenylcyclopropyl]methanone, (IV), and [(1RS,3RS)-2,2-dimethyl-3-phenylcyclopropyl][(1'RS,3'RS)-2,2-dimethyl-3-phenylcyclopropyl]methanone, (V), were prepared as follows.

A 25 ml round-bottomed flask with stirrer bar was charged with sodium hydride (60% dispersion in mineral oil, 111 mg, 2.78 mmol, 2.4 equivalents), sealed with a rubber septum and purged with argon. The flask was maintained under argon and anhydrous N,N-dimethylformamide (10 ml) was added. The stirred suspension was cooled to 273 K (ice bath), the septum briefly removed and triisopropyl sulfoxonium tetrafluoroborate (735 mg, 2.78 mmol, 2.4 equivalents) added in a single portion. The mixture was stirred for 5 min before the addition of a solution of dibenzylideneacetone 5 [What is this number?] (272 mg, 1.16 mmol, 1.0 equivalents) in N,N-dimethylformamide (5 ml) dropwise by cannula. The cooling bath was removed and the yellow-coloured solution stirred at room temperature until the reaction was shown to be complete by thin-layer chromatographic analysis (14 h). The reaction was quenched by the addition of saturated aqueous NH₄Cl (15 ml), diluted with water (60 ml) and extracted with Et₂O (3 × 50 ml). The combined organic extracts were dried (Na₂SO₄) and the solvent removed in vacuo. The residue was purified by column chromatography (petrol/Et₂O 19:1 v/v) to afford 350 mg (94%) of a colourless solid, a chromatographically inseparable mixture of diastereoisomers (IV) and (V) (2.15:1) (m.p. 331–333 K). Analysis: R_f = 0.63 (petrol–EtOAc 3:1 v/v; no separation); IR (NaCl, ν, cm^-1): 3027, 2972, 2950, 2919, 2871, 2361, 2338, 1666, 1602, 1579, 1497, 1443, 1422, 1375, 1278, 1103, 1070, 770; MS (ESI): m/z = 341 [M + Na]⁺; HRMS-ESI: m/z [M + Na]⁺ calculated for C₂₃H₂₆NaO: 341.1876; found 341.1882 (1.82 p.p.m. error). Repeated recrystallization (ten times) from EtOH–H₂O (Solvent ratio?) gave a single diastereomer; X-ray analysis identified this as (IV) (m.p. 336–338 K). Analysis: ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 1.03 (s, 6 H, CH₃), 1.29 (s, 6 H, CH₃), 2.54 (d, J = 6.1 Hz, 2 H, CH), 2.93 (d, J = 6.1 Hz, 2 H, CH), 7.17–7.32 (m, 10 H, ArH); ¹³C NMR (125 MHz, CDCl₃, δ, p.p.m.): 20.6 (CH₃), 22.6 (CH₃), 33.7 (C), 38.6 (CH), 42.0 (CH), 126.3 (ArH), 128.1 (ArH), 128.9 (ArH), 138.0 (Ar), 205.2 (C═ O).

S3. Refinement

The crystal was discovered to be non-merohedrally twinned by 180° rotation about the [100] direction. The orientation matrix for each twin component was determined using DIRAX (Duisenberg, 1992), allowing an HKLF 5 file (Software? Reference?) to be prepared. The twin fraction refined to 0.470 (3).

H atoms were placed using a riding model, with C—H = 0.98 (CH₃), 0.95 (aromatic CH) or 1.00 Å (aliphatic CH). They were modelled isotropically with U_iso(H) = 1.5U_eq(C_methyl) and 1.2U_eq(other C).

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); data reduction: DIRAX (Duisenberg, 1992), DENZO (Otwinowski & Minor, 1997), COLLECT (Nonius, 1998) and EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Version 2.02; Farrugia, 1997) and Mercury (Version 1.4.2; Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. A view of the asymmetric unit of compound (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 2. Overlaid crystal structures of the two independent molecules of (IV) (H atoms omitted), highlighting the significant conformational differences of one half of each molecule. In the electronic version of the journal, molecule 1 (atoms C1–C23/O1) is coloured blue and molecule 2 (atoms C24–C46/O2) is coloured red.
	Fig. 3. A packing diagram for (IV), viewed along the a axis. In the electronic version of the journal, the colours denote the two different molecular conformations (cf. Fig. 2).

[(1RS,3RS)-2,2-dimethyl-3- phenylcyclopropyl][(1SR,3SR)-2,2-dimethyl-3- phenylcyclopropyl]methanone

Crystal data

C23H26O	F(000) = 688
Mr = 318.44	Dx = 1.126 Mg m^−3
Monoclinic, P21	Melting point: 336 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 5.7287 (7) Å	Cell parameters from 31108 reflections
b = 27.517 (4) Å	θ = 2.9–27.5°
c = 11.9206 (17) Å	µ = 0.07 mm^−1
β = 91.881 (8)°	T = 120 K
V = 1878.1 (4) Å^3	Plate, colourless
Z = 4	0.28 × 0.24 × 0.02 mm

Data collection

Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer	4341 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3685 reflections with I > 2σ(I)
10cm confocal mirrors monochromator	Rint = 0.072
Detector resolution: 66.06 pixels mm^-1	θmax = 27.5°, θmin = 3.4°
ϕ & ω scans	h = −7→7
Absorption correction: multi-scan (TWINABS; Sheldrick, 2007)	k = −35→35
Tmin = 0.454, Tmax = 0.999	l = −15→15
6207 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.087	H-atom parameters constrained
wR(F^2) = 0.186	w = 1/[σ^2(Fo^2) + (0.025P)^2 + 2.6539P] where P = (Fo^2 + 2Fc^2)/3
S = 1.24	(Δ/σ)max = 0.001
4341 reflections	Δρmax = 0.38 e Å^−3
442 parameters	Δρmin = −0.36 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 3 (5)

Special details

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. The uncertainty on the value of the Flack parameter is so large as to make assignment of the absolute stereochemistry impossible. The chirality arises as a function of the packing. We assume that the handedness in this structure is random and that other crystals will have the enantiomeric arrangement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.9241 (13)	0.2555 (3)	0.6841 (6)	0.0305 (16)
H1	0.9749	0.2882	0.6763	0.037*
C2	1.0482 (13)	0.2186 (3)	0.6358 (6)	0.0319 (16)
H2	1.1841	0.2261	0.5956	0.038*
C3	0.9779 (15)	0.1710 (3)	0.6449 (6)	0.0381 (18)
H3	1.0625	0.1457	0.6101	0.046*
C4	0.7830 (15)	0.1604 (3)	0.7051 (7)	0.0392 (19)
H4	0.7360	0.1276	0.7139	0.047*
C5	0.6542 (14)	0.1975 (3)	0.7534 (6)	0.0305 (16)
H5	0.5173	0.1900	0.7927	0.037*
C6	0.7264 (12)	0.2458 (2)	0.7438 (5)	0.0234 (14)
C7	0.5830 (12)	0.2845 (2)	0.7963 (5)	0.0240 (14)
H7	0.4137	0.2835	0.7732	0.029*
C8	0.6792 (12)	0.3358 (2)	0.8125 (5)	0.0231 (14)
H8	0.8476	0.3403	0.7956	0.028*
C9	0.5224 (12)	0.3767 (2)	0.7808 (5)	0.0250 (14)
C10	0.6435 (12)	0.4233 (2)	0.7563 (5)	0.0223 (14)
H10	0.8127	0.4204	0.7393	0.027*
C11	0.5097 (12)	0.4620 (2)	0.6905 (5)	0.0250 (14)
H11	0.3411	0.4541	0.6757	0.030*
C12	0.6203 (13)	0.4881 (2)	0.5979 (6)	0.0261 (15)
C13	0.8184 (12)	0.4727 (3)	0.5465 (6)	0.0290 (15)
H13	0.8902	0.4434	0.5718	0.035*
C14	0.9188 (15)	0.4979 (3)	0.4594 (6)	0.0395 (18)
H14	1.0601	0.4868	0.4287	0.047*
C15	0.8106 (15)	0.5393 (3)	0.4180 (6)	0.0357 (18)
H15	0.8749	0.5565	0.3572	0.043*
C16	0.6079 (17)	0.5556 (3)	0.4656 (7)	0.0402 (19)
H16	0.5325	0.5840	0.4372	0.048*
C17	0.5146 (14)	0.5308 (2)	0.5541 (6)	0.0320 (16)
H17	0.3763	0.5426	0.5864	0.038*
C18	0.6286 (12)	0.3023 (2)	0.9137 (5)	0.0239 (14)
C19	0.8379 (12)	0.2821 (3)	0.9771 (6)	0.0314 (15)
H19A	0.7932	0.2525	1.0167	0.047*
H19B	0.8965	0.3063	1.0316	0.047*
H19C	0.9604	0.2745	0.9245	0.047*
C20	0.4285 (13)	0.3153 (3)	0.9868 (6)	0.0351 (17)
H20A	0.2988	0.3282	0.9400	0.053*
H20B	0.4796	0.3400	1.0415	0.053*
H20C	0.3768	0.2862	1.0264	0.053*
C21	0.5715 (12)	0.4718 (2)	0.8104 (6)	0.0255 (14)
C22	0.3819 (13)	0.4717 (3)	0.8966 (7)	0.0370 (18)
H22A	0.3063	0.5037	0.8976	0.055*
H22B	0.4517	0.4647	0.9710	0.055*
H22C	0.2656	0.4468	0.8769	0.055*
C23	0.7676 (14)	0.5067 (3)	0.8386 (6)	0.0333 (17)
H23A	0.7054	0.5399	0.8422	0.050*
H23B	0.8846	0.5050	0.7806	0.050*
H23C	0.8403	0.4980	0.9114	0.050*
O1	0.3116 (8)	0.37286 (18)	0.7726 (4)	0.0308 (11)
C24	0.2532 (13)	0.1695 (3)	0.0332 (6)	0.0327 (16)
H24	0.1532	0.1951	0.0552	0.039*
C25	0.1880 (17)	0.1415 (4)	−0.0582 (7)	0.049 (2)
H25	0.0428	0.1469	−0.0969	0.059*
C26	0.3394 (17)	0.1045 (3)	−0.0938 (7)	0.045 (2)
H26	0.3008	0.0856	−0.1583	0.054*
C27	0.5426 (17)	0.0966 (3)	−0.0334 (6)	0.039 (2)
H27	0.6426	0.0709	−0.0549	0.047*
C28	0.6064 (14)	0.1249 (2)	0.0582 (6)	0.0319 (17)
H28	0.7514	0.1196	0.0972	0.038*
C29	0.4559 (13)	0.1618 (2)	0.0932 (5)	0.0245 (14)
C30	0.5358 (11)	0.1906 (2)	0.1929 (5)	0.0232 (14)
H30	0.7071	0.1976	0.1948	0.028*
C31	0.3921 (12)	0.2309 (2)	0.2417 (6)	0.0241 (14)
H31	0.2307	0.2348	0.2084	0.029*
C32	0.5165 (12)	0.2769 (2)	0.2732 (5)	0.0240 (14)
C33	0.3582 (12)	0.3180 (2)	0.3029 (5)	0.0228 (13)
H33	0.1903	0.3143	0.2787	0.027*
C34	0.4585 (11)	0.3695 (2)	0.2971 (5)	0.0221 (13)
H34	0.6285	0.3706	0.2807	0.026*
C35	0.3206 (12)	0.4103 (2)	0.2472 (5)	0.0213 (13)
C36	0.4072 (13)	0.4575 (3)	0.2663 (6)	0.0295 (16)
H36	0.5474	0.4626	0.3095	0.035*
C37	0.2826 (16)	0.4967 (3)	0.2203 (6)	0.0383 (19)
H37	0.3403	0.5287	0.2322	0.046*
C38	0.0797 (16)	0.4902 (3)	0.1584 (6)	0.0374 (19)
H38	−0.0026	0.5175	0.1286	0.045*
C39	−0.0055 (13)	0.4436 (3)	0.1394 (6)	0.0328 (17)
H39	−0.1464	0.4387	0.0967	0.039*
C40	0.1191 (12)	0.4043 (3)	0.1839 (6)	0.0271 (15)
H40	0.0624	0.3724	0.1699	0.033*
C41	0.4367 (12)	0.1843 (2)	0.3088 (5)	0.0242 (14)
C42	0.6060 (12)	0.1844 (3)	0.4075 (6)	0.0285 (15)
H42A	0.6652	0.1514	0.4204	0.043*
H42B	0.5268	0.1957	0.4743	0.043*
H42C	0.7365	0.2062	0.3923	0.043*
C43	0.2280 (13)	0.1513 (3)	0.3208 (6)	0.0323 (17)
H43A	0.1268	0.1535	0.2531	0.048*
H43B	0.1405	0.1613	0.3862	0.048*
H43C	0.2813	0.1177	0.3309	0.048*
C44	0.4066 (12)	0.3478 (2)	0.4100 (6)	0.0237 (14)
C45	0.6020 (12)	0.3336 (3)	0.4910 (6)	0.0293 (15)
H45A	0.6484	0.3618	0.5367	0.044*
H45B	0.7358	0.3223	0.4492	0.044*
H45C	0.5489	0.3075	0.5401	0.044*
C46	0.1921 (12)	0.3669 (3)	0.4677 (6)	0.0309 (16)
H46A	0.2336	0.3962	0.5105	0.046*
H46B	0.1344	0.3420	0.5187	0.046*
H46C	0.0700	0.3747	0.4111	0.046*
O2	0.7276 (8)	0.28059 (18)	0.2757 (4)	0.0284 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.037 (4)	0.024 (3)	0.030 (4)	0.005 (3)	0.001 (3)	0.004 (3)
C2	0.027 (4)	0.032 (4)	0.036 (4)	0.005 (3)	0.002 (3)	−0.002 (3)
C3	0.056 (5)	0.029 (4)	0.028 (4)	0.014 (4)	−0.010 (4)	−0.002 (3)
C4	0.059 (5)	0.025 (4)	0.032 (4)	0.000 (4)	−0.012 (4)	−0.002 (3)
C5	0.039 (4)	0.029 (4)	0.024 (4)	0.001 (3)	−0.004 (3)	0.005 (3)
C6	0.031 (4)	0.021 (3)	0.017 (3)	0.003 (3)	−0.011 (3)	−0.003 (3)
C7	0.028 (3)	0.021 (3)	0.023 (3)	−0.004 (3)	0.000 (3)	0.002 (3)
C8	0.029 (3)	0.020 (3)	0.020 (3)	0.000 (3)	0.001 (3)	0.004 (3)
C9	0.035 (4)	0.023 (3)	0.016 (3)	0.001 (3)	−0.003 (3)	−0.003 (3)
C10	0.028 (3)	0.016 (3)	0.024 (3)	0.001 (3)	0.005 (3)	0.001 (2)
C11	0.029 (4)	0.025 (3)	0.021 (3)	0.003 (3)	−0.001 (3)	−0.004 (3)
C12	0.035 (4)	0.022 (3)	0.021 (3)	−0.002 (3)	−0.006 (3)	0.000 (3)
C13	0.033 (4)	0.030 (3)	0.024 (3)	−0.003 (3)	−0.003 (3)	0.005 (3)
C14	0.050 (5)	0.040 (4)	0.028 (4)	−0.010 (4)	0.004 (3)	−0.001 (3)
C15	0.061 (5)	0.026 (3)	0.020 (3)	−0.016 (4)	−0.002 (3)	−0.002 (3)
C16	0.070 (6)	0.018 (3)	0.032 (4)	0.004 (4)	−0.010 (4)	0.005 (3)
C17	0.046 (5)	0.026 (4)	0.023 (4)	0.005 (3)	−0.005 (3)	−0.002 (3)
C18	0.036 (4)	0.022 (3)	0.014 (3)	−0.005 (3)	−0.003 (3)	0.001 (2)
C19	0.032 (4)	0.034 (4)	0.027 (4)	−0.005 (3)	−0.006 (3)	0.004 (3)
C20	0.033 (4)	0.041 (4)	0.032 (4)	0.002 (3)	0.009 (3)	0.005 (3)
C21	0.030 (3)	0.024 (3)	0.023 (3)	0.003 (3)	−0.002 (3)	−0.002 (3)
C22	0.035 (4)	0.040 (4)	0.036 (4)	0.008 (4)	0.005 (3)	−0.003 (3)
C23	0.041 (4)	0.030 (4)	0.028 (4)	0.005 (3)	−0.006 (3)	−0.005 (3)
O1	0.025 (2)	0.030 (3)	0.037 (3)	−0.001 (2)	−0.001 (2)	−0.001 (2)
C24	0.033 (4)	0.039 (4)	0.026 (4)	0.000 (3)	−0.002 (3)	−0.001 (3)
C25	0.053 (5)	0.068 (6)	0.026 (4)	−0.025 (5)	−0.005 (4)	−0.003 (4)
C26	0.073 (6)	0.040 (4)	0.022 (4)	−0.031 (5)	0.002 (4)	−0.004 (3)
C27	0.071 (6)	0.025 (4)	0.023 (4)	0.001 (4)	0.008 (4)	−0.002 (3)
C28	0.048 (4)	0.025 (3)	0.022 (4)	−0.004 (3)	0.001 (3)	−0.003 (3)
C29	0.042 (4)	0.018 (3)	0.014 (3)	0.001 (3)	0.004 (3)	0.001 (2)
C30	0.021 (3)	0.025 (3)	0.023 (3)	0.003 (3)	0.001 (3)	0.000 (3)
C31	0.022 (3)	0.024 (3)	0.026 (4)	0.004 (3)	−0.006 (3)	0.000 (3)
C32	0.037 (4)	0.022 (3)	0.013 (3)	0.003 (3)	−0.004 (3)	−0.002 (2)
C33	0.027 (3)	0.019 (3)	0.022 (3)	0.002 (3)	−0.003 (3)	0.002 (2)
C34	0.021 (3)	0.022 (3)	0.023 (3)	0.003 (3)	−0.002 (3)	0.001 (3)
C35	0.025 (3)	0.026 (3)	0.013 (3)	−0.001 (3)	−0.001 (2)	0.001 (2)
C36	0.039 (4)	0.028 (4)	0.022 (3)	0.001 (3)	−0.003 (3)	−0.001 (3)
C37	0.067 (6)	0.026 (4)	0.021 (4)	0.003 (4)	0.004 (4)	0.005 (3)
C38	0.062 (5)	0.029 (4)	0.022 (4)	0.015 (4)	0.006 (4)	0.005 (3)
C39	0.025 (4)	0.044 (4)	0.030 (4)	0.012 (3)	−0.002 (3)	0.007 (3)
C40	0.027 (4)	0.025 (3)	0.029 (4)	0.001 (3)	−0.001 (3)	0.003 (3)
C41	0.029 (3)	0.024 (3)	0.019 (3)	0.007 (3)	−0.002 (3)	0.004 (3)
C42	0.028 (4)	0.030 (4)	0.027 (4)	−0.001 (3)	−0.004 (3)	0.000 (3)
C43	0.035 (4)	0.036 (4)	0.026 (4)	0.001 (3)	−0.001 (3)	0.004 (3)
C44	0.022 (3)	0.020 (3)	0.029 (4)	0.001 (3)	−0.003 (3)	−0.004 (3)
C45	0.031 (4)	0.031 (4)	0.025 (4)	−0.001 (3)	−0.004 (3)	−0.002 (3)
C46	0.030 (4)	0.039 (4)	0.024 (4)	0.004 (3)	0.003 (3)	−0.002 (3)
O2	0.027 (3)	0.026 (2)	0.032 (3)	0.001 (2)	0.001 (2)	−0.007 (2)

Geometric parameters (Å, º)

C1—C2	1.376 (10)	C24—C29	1.361 (10)
C1—C6	1.383 (10)	C24—C25	1.376 (11)
C1—H1	0.9500	C24—H24	0.9500
C2—C3	1.377 (11)	C25—C26	1.410 (13)
C2—H2	0.9500	C25—H25	0.9500
C3—C4	1.378 (12)	C26—C27	1.366 (13)
C3—H3	0.9500	C26—H26	0.9500
C4—C5	1.395 (11)	C27—C28	1.382 (10)
C4—H4	0.9500	C27—H27	0.9500
C5—C6	1.395 (10)	C28—C29	1.403 (10)
C5—H5	0.9500	C28—H28	0.9500
C6—C7	1.496 (9)	C29—C30	1.489 (9)
C7—C18	1.497 (9)	C30—C31	1.509 (9)
C7—C8	1.525 (9)	C30—C41	1.521 (9)
C7—H7	1.0000	C30—H30	1.0000
C8—C9	1.481 (9)	C31—C32	1.495 (9)
C8—C18	1.553 (8)	C31—C41	1.527 (9)
C8—H8	1.0000	C31—H31	1.0000
C9—O1	1.213 (8)	C32—O2	1.213 (8)
C9—C10	1.491 (9)	C32—C33	1.499 (9)
C10—C11	1.516 (9)	C33—C34	1.531 (9)
C10—C21	1.543 (9)	C33—C44	1.535 (9)
C10—H10	1.0000	C33—H33	1.0000
C11—C12	1.477 (10)	C34—C35	1.485 (9)
C11—C21	1.485 (9)	C34—C44	1.511 (9)
C11—H11	1.0000	C34—H34	1.0000
C12—C13	1.374 (10)	C35—C40	1.368 (10)
C12—C17	1.413 (9)	C35—C36	1.407 (10)
C13—C14	1.389 (10)	C36—C37	1.395 (10)
C13—H13	0.9500	C36—H36	0.9500
C14—C15	1.381 (11)	C37—C38	1.367 (12)
C14—H14	0.9500	C37—H37	0.9500
C15—C16	1.384 (12)	C38—C39	1.387 (11)
C15—H15	0.9500	C38—H38	0.9500
C16—C17	1.379 (11)	C39—C40	1.391 (9)
C16—H16	0.9500	C39—H39	0.9500
C17—H17	0.9500	C40—H40	0.9500
C18—C19	1.503 (10)	C41—C42	1.500 (9)
C18—C20	1.506 (10)	C41—C43	1.512 (10)
C19—H19A	0.9800	C42—H42A	0.9800
C19—H19B	0.9800	C42—H42B	0.9800
C19—H19C	0.9800	C42—H42C	0.9800
C20—H20A	0.9800	C43—H43A	0.9800
C20—H20B	0.9800	C43—H43B	0.9800
C20—H20C	0.9800	C43—H43C	0.9800
C21—C23	1.509 (10)	C44—C45	1.505 (9)
C21—C22	1.520 (10)	C44—C46	1.522 (9)
C22—H22A	0.9800	C45—H45A	0.9800
C22—H22B	0.9800	C45—H45B	0.9800
C22—H22C	0.9800	C45—H45C	0.9800
C23—H23A	0.9800	C46—H46A	0.9800
C23—H23B	0.9800	C46—H46B	0.9800
C23—H23C	0.9800	C46—H46C	0.9800
C2—C1—C6	121.0 (7)	C29—C24—C25	122.2 (8)
C2—C1—H1	119.5	C29—C24—H24	118.9
C6—C1—H1	119.5	C25—C24—H24	118.9
C1—C2—C3	120.8 (7)	C24—C25—C26	119.2 (8)
C1—C2—H2	119.6	C24—C25—H25	120.4
C3—C2—H2	119.6	C26—C25—H25	120.4
C2—C3—C4	119.1 (7)	C27—C26—C25	118.6 (7)
C2—C3—H3	120.5	C27—C26—H26	120.7
C4—C3—H3	120.5	C25—C26—H26	120.7
C3—C4—C5	120.6 (7)	C26—C27—C28	121.6 (8)
C3—C4—H4	119.7	C26—C27—H27	119.2
C5—C4—H4	119.7	C28—C27—H27	119.2
C4—C5—C6	120.0 (7)	C27—C28—C29	119.6 (8)
C4—C5—H5	120.0	C27—C28—H28	120.2
C6—C5—H5	120.0	C29—C28—H28	120.2
C1—C6—C5	118.4 (7)	C24—C29—C28	118.6 (7)
C1—C6—C7	123.2 (6)	C24—C29—C30	124.8 (6)
C5—C6—C7	118.4 (6)	C28—C29—C30	116.5 (6)
C6—C7—C18	122.9 (6)	C29—C30—C31	122.9 (6)
C6—C7—C8	120.8 (6)	C29—C30—C41	123.4 (6)
C18—C7—C8	61.8 (4)	C31—C30—C41	60.6 (4)
C6—C7—H7	113.9	C29—C30—H30	113.4
C18—C7—H7	113.9	C31—C30—H30	113.4
C8—C7—H7	113.9	C41—C30—H30	113.4
C9—C8—C7	117.3 (6)	C32—C31—C30	117.2 (6)
C9—C8—C18	121.5 (6)	C32—C31—C41	120.6 (6)
C7—C8—C18	58.2 (4)	C30—C31—C41	60.1 (4)
C9—C8—H8	115.8	C32—C31—H31	115.8
C7—C8—H8	115.8	C30—C31—H31	115.8
C18—C8—H8	115.8	C41—C31—H31	115.8
O1—C9—C8	123.2 (7)	O2—C32—C31	122.9 (6)
O1—C9—C10	121.9 (6)	O2—C32—C33	122.8 (6)
C8—C9—C10	114.9 (6)	C31—C32—C33	114.3 (6)
C9—C10—C11	118.4 (6)	C32—C33—C34	117.2 (6)
C9—C10—C21	121.9 (6)	C32—C33—C44	120.3 (6)
C11—C10—C21	58.1 (4)	C34—C33—C44	59.1 (4)
C9—C10—H10	115.4	C32—C33—H33	116.1
C11—C10—H10	115.4	C34—C33—H33	116.1
C21—C10—H10	115.4	C44—C33—H33	116.1
C12—C11—C21	122.5 (6)	C35—C34—C44	122.5 (6)
C12—C11—C10	120.4 (6)	C35—C34—C33	121.4 (6)
C21—C11—C10	61.9 (4)	C44—C34—C33	60.6 (4)
C12—C11—H11	114.1	C35—C34—H34	114.0
C21—C11—H11	114.1	C44—C34—H34	114.0
C10—C11—H11	114.1	C33—C34—H34	114.0
C13—C12—C17	116.2 (7)	C40—C35—C36	119.1 (6)
C13—C12—C11	124.3 (6)	C40—C35—C34	124.0 (6)
C17—C12—C11	119.4 (7)	C36—C35—C34	116.9 (6)
C12—C13—C14	123.2 (7)	C37—C36—C35	118.5 (7)
C12—C13—H13	118.4	C37—C36—H36	120.8
C14—C13—H13	118.4	C35—C36—H36	120.8
C15—C14—C13	119.2 (8)	C38—C37—C36	121.8 (8)
C15—C14—H14	120.4	C38—C37—H37	119.1
C13—C14—H14	120.4	C36—C37—H37	119.1
C14—C15—C16	119.6 (7)	C37—C38—C39	119.8 (7)
C14—C15—H15	120.2	C37—C38—H38	120.1
C16—C15—H15	120.2	C39—C38—H38	120.1
C17—C16—C15	120.3 (7)	C38—C39—C40	118.8 (7)
C17—C16—H16	119.8	C38—C39—H39	120.6
C15—C16—H16	119.8	C40—C39—H39	120.6
C16—C17—C12	121.5 (7)	C35—C40—C39	122.1 (7)
C16—C17—H17	119.3	C35—C40—H40	119.0
C12—C17—H17	119.3	C39—C40—H40	119.0
C7—C18—C19	117.5 (6)	C42—C41—C43	114.8 (6)
C7—C18—C20	120.4 (6)	C42—C41—C30	117.5 (6)
C19—C18—C20	114.0 (6)	C43—C41—C30	118.3 (6)
C7—C18—C8	60.0 (4)	C42—C41—C31	120.1 (6)
C19—C18—C8	116.4 (6)	C43—C41—C31	115.7 (6)
C20—C18—C8	118.3 (6)	C30—C41—C31	59.3 (4)
C18—C19—H19A	109.5	C41—C42—H42A	109.5
C18—C19—H19B	109.5	C41—C42—H42B	109.5
H19A—C19—H19B	109.5	H42A—C42—H42B	109.5
C18—C19—H19C	109.5	C41—C42—H42C	109.5
H19A—C19—H19C	109.5	H42A—C42—H42C	109.5
H19B—C19—H19C	109.5	H42B—C42—H42C	109.5
C18—C20—H20A	109.5	C41—C43—H43A	109.5
C18—C20—H20B	109.5	C41—C43—H43B	109.5
H20A—C20—H20B	109.5	H43A—C43—H43B	109.5
C18—C20—H20C	109.5	C41—C43—H43C	109.5
H20A—C20—H20C	109.5	H43A—C43—H43C	109.5
H20B—C20—H20C	109.5	H43B—C43—H43C	109.5
C11—C21—C23	118.8 (6)	C45—C44—C34	120.7 (6)
C11—C21—C22	119.9 (6)	C45—C44—C46	113.2 (6)
C23—C21—C22	113.1 (6)	C34—C44—C46	116.9 (6)
C11—C21—C10	60.1 (4)	C45—C44—C33	120.4 (6)
C23—C21—C10	115.9 (6)	C34—C44—C33	60.3 (4)
C22—C21—C10	119.2 (6)	C46—C44—C33	115.7 (6)
C21—C22—H22A	109.5	C44—C45—H45A	109.5
C21—C22—H22B	109.5	C44—C45—H45B	109.5
H22A—C22—H22B	109.5	H45A—C45—H45B	109.5
C21—C22—H22C	109.5	C44—C45—H45C	109.5
H22A—C22—H22C	109.5	H45A—C45—H45C	109.5
H22B—C22—H22C	109.5	H45B—C45—H45C	109.5
C21—C23—H23A	109.5	C44—C46—H46A	109.5
C21—C23—H23B	109.5	C44—C46—H46B	109.5
H23A—C23—H23B	109.5	H46A—C46—H46B	109.5
C21—C23—H23C	109.5	C44—C46—H46C	109.5
H23A—C23—H23C	109.5	H46A—C46—H46C	109.5
H23B—C23—H23C	109.5	H46B—C46—H46C	109.5
C6—C1—C2—C3	0.5 (11)	C29—C24—C25—C26	−2.2 (12)
C1—C2—C3—C4	−1.2 (11)	C24—C25—C26—C27	2.4 (12)
C2—C3—C4—C5	2.0 (11)	C25—C26—C27—C28	−2.6 (12)
C3—C4—C5—C6	−2.0 (11)	C26—C27—C28—C29	2.4 (11)
C2—C1—C6—C5	−0.5 (11)	C25—C24—C29—C28	2.0 (11)
C2—C1—C6—C7	−178.9 (7)	C25—C24—C29—C30	−179.8 (7)
C4—C5—C6—C1	1.2 (10)	C27—C28—C29—C24	−2.1 (10)
C4—C5—C6—C7	179.8 (6)	C27—C28—C29—C30	179.6 (6)
C1—C6—C7—C18	−90.0 (9)	C24—C29—C30—C31	2.8 (11)
C5—C6—C7—C18	91.5 (8)	C28—C29—C30—C31	−179.0 (6)
C1—C6—C7—C8	−15.6 (10)	C24—C29—C30—C41	76.8 (9)
C5—C6—C7—C8	165.9 (6)	C28—C29—C30—C41	−105.0 (7)
C6—C7—C8—C9	134.8 (6)	C29—C30—C31—C32	−135.8 (6)
C18—C7—C8—C9	−111.8 (7)	C41—C30—C31—C32	111.4 (6)
C6—C7—C8—C18	−113.4 (7)	C29—C30—C31—C41	112.8 (7)
C7—C8—C9—O1	20.5 (10)	C30—C31—C32—O2	−10.4 (10)
C18—C8—C9—O1	−47.2 (9)	C41—C31—C32—O2	59.3 (9)
C7—C8—C9—C10	−157.8 (6)	C30—C31—C32—C33	170.3 (6)
C18—C8—C9—C10	134.5 (6)	C41—C31—C32—C33	−120.0 (7)
O1—C9—C10—C11	−16.6 (10)	O2—C32—C33—C34	20.9 (9)
C8—C9—C10—C11	161.7 (6)	C31—C32—C33—C34	−159.8 (6)
O1—C9—C10—C21	51.6 (10)	O2—C32—C33—C44	−47.5 (9)
C8—C9—C10—C21	−130.1 (7)	C31—C32—C33—C44	131.9 (6)
C9—C10—C11—C12	−135.1 (6)	C32—C33—C34—C35	137.0 (6)
C21—C10—C11—C12	113.1 (7)	C44—C33—C34—C35	−112.3 (7)
C9—C10—C11—C21	111.8 (7)	C32—C33—C34—C44	−110.7 (6)
C21—C11—C12—C13	90.6 (9)	C44—C34—C35—C40	−86.4 (9)
C10—C11—C12—C13	16.5 (10)	C33—C34—C35—C40	−13.5 (10)
C21—C11—C12—C17	−92.1 (8)	C44—C34—C35—C36	94.3 (8)
C10—C11—C12—C17	−166.2 (6)	C33—C34—C35—C36	167.3 (6)
C17—C12—C13—C14	2.6 (10)	C40—C35—C36—C37	0.4 (10)
C11—C12—C13—C14	179.9 (7)	C34—C35—C36—C37	179.8 (6)
C12—C13—C14—C15	−3.1 (12)	C35—C36—C37—C38	0.4 (11)
C13—C14—C15—C16	1.6 (11)	C36—C37—C38—C39	−0.6 (12)
C14—C15—C16—C17	0.2 (11)	C37—C38—C39—C40	−0.1 (11)
C15—C16—C17—C12	−0.7 (12)	C36—C35—C40—C39	−1.2 (11)
C13—C12—C17—C16	−0.7 (10)	C34—C35—C40—C39	179.5 (6)
C11—C12—C17—C16	−178.2 (7)	C38—C39—C40—C35	1.0 (11)
C6—C7—C18—C19	4.1 (9)	C29—C30—C41—C42	137.6 (7)
C8—C7—C18—C19	−106.1 (7)	C31—C30—C41—C42	−110.5 (7)
C6—C7—C18—C20	−142.6 (7)	C29—C30—C41—C43	−7.3 (9)
C8—C7—C18—C20	107.2 (7)	C31—C30—C41—C43	104.7 (7)
C6—C7—C18—C8	110.2 (7)	C29—C30—C41—C31	−112.0 (7)
C9—C8—C18—C7	104.6 (7)	C32—C31—C41—C42	0.2 (10)
C9—C8—C18—C19	−147.4 (7)	C30—C31—C41—C42	106.0 (7)
C7—C8—C18—C19	108.0 (7)	C32—C31—C41—C43	145.1 (6)
C9—C8—C18—C20	−6.0 (9)	C30—C31—C41—C43	−109.1 (7)
C7—C8—C18—C20	−110.6 (7)	C32—C31—C41—C30	−105.9 (7)
C12—C11—C21—C23	−4.9 (10)	C35—C34—C44—C45	−139.6 (7)
C10—C11—C21—C23	105.0 (7)	C33—C34—C44—C45	109.8 (7)
C12—C11—C21—C22	141.5 (7)	C35—C34—C44—C46	4.8 (9)
C10—C11—C21—C22	−108.6 (7)	C33—C34—C44—C46	−105.7 (7)
C12—C11—C21—C10	−109.9 (7)	C35—C34—C44—C33	110.5 (7)
C9—C10—C21—C11	−105.7 (7)	C32—C33—C44—C45	−4.8 (10)
C9—C10—C21—C23	144.4 (7)	C34—C33—C44—C45	−110.3 (7)
C11—C10—C21—C23	−109.8 (7)	C32—C33—C44—C34	105.4 (7)
C9—C10—C21—C22	3.9 (10)	C32—C33—C44—C46	−146.9 (7)
C11—C10—C21—C22	109.6 (7)	C34—C33—C44—C46	107.6 (7)