5,5'-Di-tert-butyl-2,2'-di­hydroxy-3,3'-methyl­enedibenz­aldehyde and 6,6'-di-tert-butyl-8,8'-methyl­ene­bis­(spiro­[4H-1,3-benzodioxin-2,1'-cyclo­hexane])

Two related compounds containing p-tert-butyl-o-methyl­ene-linked phenol or phenol-derived subunits are described, namely 5,5'-di-tert-butyl-2,2'-di­hydroxy-3,3'-methyl­ene­di­benz­aldehyde, C₂₃H₂₈O₄, (I), and 6,6'-di-tert-butyl-8,8'-methyl­ene­bis­(spiro­[4H-1,3-benzo­di­oxin-2,1'-cyclo­hexane]), C₃₅H₄₈O₄, (II). Both compounds adopt a `butterfly' shape, with the two phenol or phenol-derived O atoms in distal positions. Phenol and aldehyde groups in (I) are involved in intramolecular hydrogen bonds and the two dioxin rings in (II) are in distorted half-chair conformations.

S1. Comment

In the course of our studies on homooxacalixarenes and related compounds, we obtained single crystals of two species containing two equivalent p-tert-butyl-o-methylene linked phenol or phenol-derived subunits, ortho formyl groups being also present in compound (I) and spiro systems involving 1,3-benzodioxin and cyclohexane being featured in compound (II), which is the diacetal compound obtained by condensation of a bis(hydroxymethyl)diphenol with cyclohexanone.

The asymmetric unit in (I) contains half a molecule, with methylene atom C12 located on a binary axis. The two aromatic rings define a dihedral angle of 61.68 (4)°, similar to that in 2,2'-methylenebisphenol [61.81 (8)°] and somewhat lower than the values generally observed in uncomplexed diphenols in `butterfly' conformation (Thuéry et al., 2000, and references therein) [C2—C3—C12—C3ⁱ = 101.23 (16)°; symmetry code: (i) 2 − x, 1.5–y, z]. However, in contrast to the previously reported diphenol, the phenol O atoms in (I) are in distal positions; this conformation can be ascribed to the absence of a hydrogen bond between the two phenol O atoms, as is frequently observed in diphenols. The two intramolecular hydrogen bonds in (I) involve the phenol and aldehyde groups in each half-molecule. Atoms O2 and H1 are displaced only 0.053 (3) and 0.022 (3) Å from the plane of the aromatic ring. The latter and the O1—H1···O2—C7—C1—C2 six-membered ring are thus nearly coplanar. The packing does not involve intermolecular hydrogen bonds, or π–π or CH–π interactions, in contrast to the situation that is frequently observed in such compounds (Masci et al., 2002), but instead is effected by normal van der Waals forces.

Compound (II) possesses a pseudo-binary axis only, as does the related compound 2,2,2',2',6,6'-hexamethyl-8,8'-methylenebis(4H-1,3-benzodioxin), (III) (Masci et al., 2002). Each half-molecule contains a cyclic acetal group in the form of a heterocyclic 1,3-dioxin ring, which is fused to an aromatic ring, giving the 1,3-benzodioxin moiety. Compound (II) differs from (III)? by replacement of the 6-methyl group by 6-tert-butyl substituents and of the 2,2-dimethyl substituents by the pentamethylene unit, giving rise to the spiro system. A `butterfly' conformation, with the dioxin rings in distal positions, is observed in both (I) and (II)?. The dihedral angle between the two aromatic rings in (II) is 65.67 (6)°, slightly larger than that in (I) and smaller than that in (III) [72.17 (8)°]. The C2—C3—C18—C19 and C3—C18—C19—C20 torsion angles in (II) are 82.0 (3) and 81.2 (3)°, respectively, close to the values in (III)? and in 6,6',7,7'-tetrachloro-8,8'-methylenebis(4H-1,3-benzodioxin) (88.2°; Ferguson et al., 1989). As in the previous benzodioxin derivatives, the 1,3-dioxin rings in (II) are in distorted half-chair conformations. In the first ring, atoms O1 and C12 are −0.340 (4) and 0.373 (4) Å from the mean plane defined by atoms O2, C1, C2 and C11 (r.m.s. deviation 0.004 Å) and, in the second ring, atoms O4 and C30 are at 0.201 (4) and −0.505 (4) Å from the mean plane defined by atoms O3, C20, C21 and C29 (r.m.s. deviation 0.0008 Å). It has been noted previously that the single C—O bonds in such compounds are not of equal length, the bonds analogous to O1—C12 in (II) being shorter by about 0.03–0.05 Å than those analogous to O1—C11 (and possibly also O2—C12) (Hamada et al., 1987; Ferguson et al., 1989; Irving & Irving, 1989a,b). The same trend seems to apply to the 1,3-benzodioxin compounds we reported recently (Masci et al., 2002) and to (II), in spite of the different substituents present, with an overall mean value of 1.415 (9) Å for the O1—C12 bond and its counterparts, and 1.436 (8) Å for the O1—C11 and O2—C12 bonds and their counterparts [for (II), O1—C12 = 1.422 (3) Å, O1—C11 = 1.432 (3) Å, O2—C12 = 1.439 (3) Å, O4—C30 = 1.420 (3) Å, O4—C29 = 1.430 (3) Å and O3–C30 1.436 (3) Å]. The C12—C17 and C30–C35 rings are both in chair conformations, although with a difference in their linking to the 1,3-dioxin ring; the C12–C17 ring is bound in such a way that the alcohol-derived atom O1 is in an equatorial position, whereas the C30–C35 ring has phenol-derived atom O3 in an equatorial position. This difference is not surprising, since there is no size difference between these two groups and hence no increase in stability is expected upon location of one or the other in an equatorial position. No significant π–π interaction is present in the packing and only two very weak CH–π interactions may be noted, both of them involving tert-butyl H atoms [H9A···Cg1<sup>i</sup> = 2.88 Å and C9–H9A···Cg1<sup>i</sup> = 163°, and H28C···Cg2<sup>ii</sup> = 2.73 Å and C28–H28C···Cg2<sup>ii</sup> 143°; Cg1 and Cg2 are the centroids of the C1–C6 and C19–C24 rings; symmetry codes: (i) −x, 2 − y, –z; (ii) 1 − x, 1 − y, −z]. The latter interaction corresponds to the formation of loosely associated dimers, with the tert-butyl group containing atom C28 in each molecule included in the `cup' formed by the other ?tert-butyl group?.

S2. Experimental

Compound (I) was obtained as reported previously (Barreira Fontecha et al., 2002) and recrystallized from methanol. Compound (II) was obtained from 5,5'-di-tert-butyl-2,2'-dihydroxy-3,3'-methanediyldibenzyl alcohol and cyclohexanone in the presence of p-toluenesulfonic acid. The compound was recrystallized from acetone (m.p. 427.5–429 K). Spectroscopic analysis, ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 1.22 (s, 18H), 1.36–1.50 (m, 2H), 1.54–1.64 (m, 4H), 1.69–1.79 (m, 2H), 1.80–1.90 (m, 2H), 3.89 (s, 2H), 4.82 (s, 2H), 6.77 (d, J = 1.8 Hz, 2H), 7.08 (d, J = 1.8 Hz, 2H).

S3. Refinement

The hydroxy H atom in (I) was found in a difference Fourier map and introduced as a riding atom, with an isotropic displacement parameter equal to 1.2 times that of the parent atom. All other H atoms in both compounds were introduced at calculated positions as riding atoms, with C—H bond lengths of 0.93 (CH), 0.97 (CH₂) and 0.96 Å (CH₃) and an isotropic displacement parameter equal to 1.2 (CH and CH₂) or 1.5 (CH₃) times that of the parent atom.

Computing details

For both compounds, data collection: KappaCCD Server Software (Nonius, 1998); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997). Data reduction: DENZO–SMN for (I); DENZO–SMN (Otwinowski & Minor, 1997) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2000).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as small spheres of arbitrary radii. [Symmetry code: ' 2 − x, 1.5–y, z.]
	Fig. 2. A view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as small spheres of arbitrary radii.

(I) 5,5'-Di-tert-butyl-2,2'-dihydroxy-3,3'-methylenedibenzaldehyde

Crystal data

C23H28O4	Dx = 1.246 Mg m^−3
Mr = 368.45	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 15112 reflections
Hall symbol: -I 4ad	θ = 2.8–25.7°
a = 12.7655 (5) Å	µ = 0.08 mm^−1
c = 24.1122 (11) Å	T = 100 K
V = 3929.3 (3) Å^3	Irregular, colourless
Z = 8	0.40 × 0.35 × 0.30 mm
F(000) = 1584

Data collection

Nonius KappaCCD diffractometer	1437 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.066
Graphite monochromator	θmax = 25.7°, θmin = 2.8°
ϕ scans	h = 0→15
15112 measured reflections	k = −10→11
1874 independent reflections	l = 0→29

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0774P)^2 + 2.6466P] where P = (Fo^2 + 2Fc^2)/3
1874 reflections	(Δ/σ)max < 0.001
126 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Experimental. crystal-to-detector distance 28 mm

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. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The H atom bound to O1 was found on a Fourier-difference map and all the other ones were introduced at calculated positions. All H atoms were treated as riding atoms with an isotropic displacement parameter equal to 1.2 (OH, CH, CH₂) or 1.5

(CH₃) times that of the parent atom. 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.90097 (9)	0.55453 (10)	0.11413 (5)	0.0344 (3)
H1	0.8849	0.4900	0.1071	0.041*
O2	0.91448 (10)	0.36120 (10)	0.07521 (6)	0.0381 (4)
C1	1.05128 (13)	0.48629 (13)	0.06526 (7)	0.0271 (4)
C2	0.99934 (13)	0.56736 (13)	0.09356 (7)	0.0268 (4)
C3	1.05006 (13)	0.66344 (13)	0.10155 (7)	0.0253 (4)
C4	1.15015 (13)	0.67559 (13)	0.07997 (7)	0.0257 (4)
H4	1.1839	0.7393	0.0856	0.031*
C5	1.20360 (12)	0.59754 (12)	0.05017 (7)	0.0248 (4)
C6	1.15240 (13)	0.50240 (13)	0.04414 (7)	0.0275 (4)
H6	1.1859	0.4480	0.0256	0.033*
C7	1.00212 (14)	0.38433 (14)	0.05800 (8)	0.0329 (4)
H7	1.0396	0.3332	0.0390	0.040*
C8	1.31466 (13)	0.61727 (13)	0.02885 (7)	0.0281 (4)
C9	1.34553 (15)	0.53959 (15)	−0.01677 (8)	0.0399 (5)
H9A	1.3459	0.4698	−0.0019	0.060*
H9B	1.4141	0.5566	−0.0304	0.060*
H9C	1.2959	0.5436	−0.0466	0.060*
C10	1.39148 (15)	0.60534 (17)	0.07746 (8)	0.0399 (5)
H10A	1.3855	0.5362	0.0927	0.060*
H10B	1.3752	0.6561	0.1055	0.060*
H10C	1.4617	0.6163	0.0645	0.060*
C11	1.32389 (15)	0.72815 (15)	0.00509 (9)	0.0409 (5)
H11A	1.3943	0.7398	−0.0075	0.061*
H11B	1.3068	0.7783	0.0333	0.061*
H11C	1.2764	0.7358	−0.0255	0.061*
C12	1.0000	0.7500	0.13521 (10)	0.0276 (5)
H12A	1.0525	0.7804	0.1587	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0245 (7)	0.0340 (7)	0.0447 (8)	−0.0031 (5)	0.0040 (5)	0.0010 (6)
O2	0.0338 (7)	0.0323 (7)	0.0484 (8)	−0.0079 (5)	−0.0023 (6)	0.0063 (6)
C1	0.0268 (9)	0.0241 (9)	0.0305 (9)	−0.0008 (6)	−0.0032 (7)	0.0048 (7)
C2	0.0214 (8)	0.0299 (9)	0.0290 (8)	0.0009 (7)	−0.0013 (7)	0.0043 (7)
C3	0.0245 (8)	0.0255 (9)	0.0258 (8)	0.0033 (6)	−0.0013 (7)	0.0028 (6)
C4	0.0261 (9)	0.0224 (8)	0.0286 (9)	−0.0001 (7)	−0.0025 (7)	0.0014 (7)
C5	0.0255 (9)	0.0225 (8)	0.0263 (8)	0.0015 (6)	−0.0023 (7)	0.0028 (7)
C6	0.0279 (9)	0.0234 (9)	0.0311 (9)	0.0027 (7)	−0.0002 (7)	0.0013 (7)
C7	0.0332 (10)	0.0263 (9)	0.0393 (10)	−0.0021 (7)	−0.0025 (8)	0.0048 (8)
C8	0.0255 (8)	0.0238 (9)	0.0349 (9)	0.0016 (6)	0.0025 (7)	−0.0003 (7)
C9	0.0324 (10)	0.0385 (11)	0.0489 (12)	−0.0014 (8)	0.0099 (9)	−0.0109 (9)
C10	0.0271 (10)	0.0490 (12)	0.0434 (11)	0.0004 (8)	−0.0025 (8)	0.0010 (9)
C11	0.0380 (11)	0.0302 (10)	0.0545 (12)	0.0009 (8)	0.0187 (9)	0.0087 (9)
C12	0.0251 (12)	0.0294 (13)	0.0283 (12)	0.0016 (9)	0.000	0.000

Geometric parameters (Å, º)

O1—C2	1.360 (2)	C8—C9	1.533 (2)
O1—H1	0.8660	C8—C11	1.532 (2)
O2—C7	1.229 (2)	C8—C10	1.536 (3)
C1—C6	1.403 (2)	C9—H9A	0.9600
C1—C2	1.406 (2)	C9—H9B	0.9600
C1—C7	1.455 (2)	C9—H9C	0.9600
C2—C3	1.400 (2)	C10—H10A	0.9600
C3—C4	1.388 (2)	C10—H10B	0.9600
C3—C12	1.513 (2)	C10—H10C	0.9600
C4—C5	1.405 (2)	C11—H11A	0.9600
C4—H4	0.9300	C11—H11B	0.9600
C5—C6	1.387 (2)	C11—H11C	0.9600
C5—C8	1.529 (2)	C12—C3^i	1.513 (2)
C6—H6	0.9300	C12—H12A	0.9600
C7—H7	0.9300
C2—O1—H1	105.2	C5—C8—C10	108.61 (15)
C6—C1—C2	120.15 (15)	C9—C8—C10	108.63 (15)
C6—C1—C7	118.96 (16)	C11—C8—C10	109.15 (16)
C2—C1—C7	120.88 (16)	C8—C9—H9A	109.5
O1—C2—C3	118.83 (15)	C8—C9—H9B	109.5
O1—C2—C1	121.59 (15)	H9A—C9—H9B	109.5
C3—C2—C1	119.57 (15)	C8—C9—H9C	109.5
C4—C3—C2	118.15 (15)	H9A—C9—H9C	109.5
C4—C3—C12	120.56 (13)	H9B—C9—H9C	109.5
C2—C3—C12	121.22 (13)	C8—C10—H10A	109.5
C3—C4—C5	124.01 (15)	C8—C10—H10B	109.5
C3—C4—H4	118.0	H10A—C10—H10B	109.5
C5—C4—H4	118.0	C8—C10—H10C	109.5
C6—C5—C4	116.47 (15)	H10A—C10—H10C	109.5
C6—C5—C8	123.09 (15)	H10B—C10—H10C	109.5
C4—C5—C8	120.36 (14)	C8—C11—H11A	109.5
C5—C6—C1	121.60 (16)	C8—C11—H11B	109.5
C5—C6—H6	119.2	H11A—C11—H11B	109.5
C1—C6—H6	119.2	C8—C11—H11C	109.5
O2—C7—C1	124.52 (17)	H11A—C11—H11C	109.5
O2—C7—H7	117.7	H11B—C11—H11C	109.5
C1—C7—H7	117.7	C3—C12—C3^i	115.1 (2)
C5—C8—C9	111.91 (14)	C3—C12—H12A	108.5
C5—C8—C11	110.45 (13)	C3^i—C12—H12A	108.5
C9—C8—C11	108.03 (15)

Symmetry code: (i) −x+2, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.87	1.85	2.6461 (18)	151

(II) 6,6'-di-tert-butyl-8,8'-methylenebis(spiro[4H-1,3-benzodioxine-2,1'- cyclohexane])

Crystal data

C35H48O4	F(000) = 1160
Mr = 532.73	Dx = 1.189 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 22732 reflections
a = 12.7635 (10) Å	θ = 3.0–25.7°
b = 10.0278 (9) Å	µ = 0.08 mm^−1
c = 23.2629 (13) Å	T = 100 K
β = 91.496 (5)°	Irregular, colourless
V = 2976.4 (4) Å^3	0.18 × 0.15 × 0.09 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3467 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.063
Graphite monochromator	θmax = 25.7°, θmin = 3.0°
ϕ scans	h = 0→15
22732 measured reflections	k = 0→12
5621 independent reflections	l = −28→28

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.147	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0648P)^2 + 0.6047P] where P = (Fo^2 + 2Fc^2)/3
5621 reflections	(Δ/σ)max = 0.001
358 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Experimental. 'crystal-to-detector distance 28 mm'

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. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The H atoms were introduced at calculated positions and were treated as riding atoms with an isotropic displacement parameter equal to 1.2 (CH, CH₂) or 1.5 (CH₃) times that of the parent atom. 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.16627 (14)	0.55834 (16)	−0.11191 (7)	0.0334 (4)
O2	0.27551 (13)	0.73692 (15)	−0.08596 (6)	0.0254 (4)
O3	0.41987 (13)	0.92047 (15)	0.10763 (6)	0.0271 (4)
O4	0.54067 (13)	0.87491 (16)	0.18227 (6)	0.0291 (4)
C1	0.11568 (19)	0.7044 (2)	−0.03450 (9)	0.0249 (5)
C2	0.21211 (18)	0.7668 (2)	−0.04065 (9)	0.0225 (5)
C3	0.24865 (18)	0.8606 (2)	−0.00088 (9)	0.0230 (5)
C4	0.18655 (19)	0.8897 (2)	0.04579 (9)	0.0240 (5)
H4	0.2110	0.9511	0.0729	0.029*
C5	0.08878 (19)	0.8302 (2)	0.05351 (9)	0.0245 (5)
C6	0.05557 (19)	0.7372 (2)	0.01237 (9)	0.0266 (5)
H6	−0.0090	0.6957	0.0165	0.032*
C7	0.0207 (2)	0.8616 (2)	0.10515 (9)	0.0286 (6)
C8	0.0209 (3)	0.7409 (3)	0.14524 (12)	0.0624 (10)
H8A	−0.0100	0.6660	0.1255	0.094*
H8B	−0.0190	0.7611	0.1786	0.094*
H8C	0.0917	0.7198	0.1569	0.094*
C9	−0.0911 (2)	0.8942 (4)	0.08515 (13)	0.0609 (10)
H9A	−0.0904	0.9694	0.0596	0.091*
H9B	−0.1324	0.9151	0.1179	0.091*
H9C	−0.1210	0.8187	0.0654	0.091*
C10	0.0622 (2)	0.9799 (3)	0.13991 (12)	0.0456 (7)
H10A	0.1315	0.9603	0.1545	0.068*
H10B	0.0169	0.9966	0.1714	0.068*
H10C	0.0643	1.0573	0.1157	0.068*
C11	0.0809 (2)	0.6003 (2)	−0.07752 (10)	0.0325 (6)
H11A	0.0529	0.5240	−0.0574	0.039*
H11B	0.0255	0.6365	−0.1022	0.039*
C12	0.22567 (19)	0.6667 (2)	−0.13319 (9)	0.0283 (6)
C13	0.3135 (2)	0.6069 (2)	−0.16699 (10)	0.0331 (6)
H13A	0.2840	0.5486	−0.1965	0.040*
H13B	0.3576	0.5533	−0.1415	0.040*
C14	0.3805 (2)	0.7139 (3)	−0.19525 (10)	0.0341 (6)
H14A	0.4179	0.7643	−0.1656	0.041*
H14B	0.4320	0.6712	−0.2191	0.041*
C15	0.3136 (2)	0.8092 (3)	−0.23222 (10)	0.0392 (7)
H15A	0.3574	0.8797	−0.2470	0.047*
H15B	0.2828	0.7611	−0.2647	0.047*
C16	0.2271 (2)	0.8698 (3)	−0.19672 (11)	0.0389 (7)
H16A	0.1831	0.9259	−0.2213	0.047*
H16B	0.2583	0.9255	−0.1668	0.047*
C17	0.1594 (2)	0.7634 (3)	−0.16919 (10)	0.0324 (6)
H17A	0.1085	0.8060	−0.1450	0.039*
H17B	0.1214	0.7144	−0.1990	0.039*
C18	0.35272 (18)	0.9293 (2)	−0.00902 (9)	0.0250 (5)
H18A	0.3596	0.9494	−0.0495	0.030*
H18B	0.3523	1.0134	0.0116	0.030*
C19	0.44745 (19)	0.8499 (2)	0.01115 (9)	0.0236 (5)
C20	0.47819 (18)	0.8472 (2)	0.06929 (9)	0.0242 (5)
C21	0.56665 (18)	0.7762 (2)	0.08793 (9)	0.0242 (5)
C22	0.62343 (19)	0.7048 (2)	0.04841 (9)	0.0252 (5)
H22	0.6814	0.6560	0.0613	0.030*
C23	0.59633 (19)	0.7038 (2)	−0.01019 (9)	0.0243 (5)
C24	0.50765 (18)	0.7783 (2)	−0.02726 (9)	0.0236 (5)
H24	0.4882	0.7798	−0.0661	0.028*
C25	0.66167 (18)	0.6231 (2)	−0.05205 (9)	0.0247 (5)
C26	0.7762 (2)	0.6694 (3)	−0.04815 (12)	0.0468 (7)
H26A	0.7799	0.7623	−0.0578	0.070*
H26B	0.8169	0.6188	−0.0745	0.070*
H26C	0.8033	0.6561	−0.0097	0.070*
C27	0.6223 (2)	0.6374 (3)	−0.11444 (9)	0.0339 (6)
H27A	0.5511	0.6070	−0.1178	0.051*
H27B	0.6653	0.5849	−0.1390	0.051*
H27C	0.6257	0.7294	−0.1257	0.051*
C28	0.6570 (2)	0.4756 (2)	−0.03569 (10)	0.0372 (7)
H28A	0.6819	0.4645	0.0033	0.056*
H28B	0.7003	0.4250	−0.0608	0.056*
H28C	0.5860	0.4447	−0.0393	0.056*
C29	0.5994 (2)	0.7797 (2)	0.15068 (9)	0.0297 (6)
H29A	0.5898	0.6919	0.1672	0.036*
H29B	0.6733	0.8016	0.1541	0.036*
C30	0.43254 (19)	0.8772 (2)	0.16626 (9)	0.0266 (5)
C31	0.3838 (2)	0.9826 (2)	0.20331 (10)	0.0316 (6)
H31A	0.3128	1.0000	0.1893	0.038*
H31B	0.4234	1.0647	0.2003	0.038*
C32	0.3814 (2)	0.9400 (3)	0.26660 (10)	0.0374 (6)
H32A	0.4525	0.9364	0.2823	0.045*
H32B	0.3432	1.0060	0.2882	0.045*
C33	0.3296 (2)	0.8040 (3)	0.27383 (10)	0.0412 (7)
H33A	0.2558	0.8105	0.2633	0.049*
H33B	0.3353	0.7772	0.3139	0.049*
C34	0.3811 (2)	0.6987 (3)	0.23651 (10)	0.0362 (6)
H34A	0.3440	0.6148	0.2400	0.043*
H34B	0.4530	0.6851	0.2498	0.043*
C35	0.3794 (2)	0.7425 (2)	0.17354 (10)	0.0310 (6)
H35A	0.4150	0.6762	0.1508	0.037*
H35B	0.3074	0.7482	0.1594	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0343 (11)	0.0309 (9)	0.0354 (9)	−0.0073 (8)	0.0086 (8)	−0.0078 (7)
O2	0.0250 (9)	0.0301 (9)	0.0212 (7)	−0.0013 (7)	0.0008 (7)	−0.0037 (7)
O3	0.0287 (10)	0.0291 (9)	0.0237 (8)	0.0031 (7)	0.0010 (7)	−0.0002 (7)
O4	0.0263 (10)	0.0336 (9)	0.0271 (8)	0.0022 (8)	−0.0033 (7)	−0.0042 (7)
C1	0.0280 (14)	0.0231 (12)	0.0237 (11)	−0.0008 (10)	0.0011 (10)	0.0001 (9)
C2	0.0229 (13)	0.0224 (12)	0.0224 (11)	0.0023 (10)	0.0032 (9)	0.0009 (9)
C3	0.0248 (14)	0.0201 (11)	0.0240 (11)	0.0022 (10)	−0.0036 (10)	0.0016 (9)
C4	0.0276 (14)	0.0207 (11)	0.0234 (11)	0.0023 (10)	−0.0047 (10)	−0.0018 (9)
C5	0.0241 (14)	0.0243 (12)	0.0250 (11)	0.0006 (11)	−0.0006 (10)	0.0005 (10)
C6	0.0235 (14)	0.0284 (13)	0.0280 (12)	−0.0030 (11)	0.0012 (10)	0.0010 (10)
C7	0.0285 (15)	0.0320 (13)	0.0252 (12)	−0.0001 (11)	0.0023 (10)	−0.0020 (10)
C8	0.100 (3)	0.0462 (18)	0.0427 (17)	0.0051 (19)	0.0346 (18)	0.0069 (14)
C9	0.0315 (18)	0.099 (3)	0.0517 (17)	0.0113 (18)	−0.0005 (14)	−0.0370 (18)
C10	0.0392 (18)	0.0531 (18)	0.0452 (16)	−0.0064 (15)	0.0109 (13)	−0.0180 (14)
C11	0.0299 (15)	0.0358 (14)	0.0321 (12)	−0.0064 (12)	0.0068 (11)	−0.0082 (11)
C12	0.0290 (15)	0.0302 (13)	0.0258 (12)	−0.0052 (11)	−0.0005 (10)	−0.0061 (10)
C13	0.0333 (16)	0.0354 (14)	0.0308 (13)	0.0033 (12)	0.0032 (11)	−0.0085 (11)
C14	0.0292 (15)	0.0482 (16)	0.0250 (12)	0.0061 (12)	0.0024 (10)	−0.0019 (11)
C15	0.0322 (16)	0.0588 (18)	0.0266 (12)	0.0039 (14)	0.0016 (11)	0.0069 (12)
C16	0.0360 (17)	0.0488 (16)	0.0319 (13)	0.0127 (13)	0.0026 (12)	0.0104 (12)
C17	0.0261 (14)	0.0461 (15)	0.0250 (12)	0.0016 (12)	0.0000 (10)	−0.0002 (11)
C18	0.0241 (14)	0.0243 (12)	0.0265 (12)	−0.0011 (10)	−0.0006 (10)	0.0003 (10)
C19	0.0224 (13)	0.0217 (12)	0.0266 (11)	−0.0043 (10)	0.0001 (10)	0.0013 (10)
C20	0.0242 (14)	0.0210 (12)	0.0274 (12)	−0.0016 (10)	0.0019 (10)	−0.0005 (9)
C21	0.0237 (14)	0.0243 (12)	0.0246 (11)	−0.0030 (10)	−0.0009 (10)	0.0017 (10)
C22	0.0235 (14)	0.0233 (12)	0.0288 (12)	0.0015 (10)	0.0011 (10)	0.0013 (10)
C23	0.0234 (13)	0.0216 (12)	0.0280 (12)	−0.0047 (10)	0.0006 (10)	0.0009 (9)
C24	0.0225 (13)	0.0247 (12)	0.0235 (11)	−0.0020 (10)	−0.0002 (10)	−0.0003 (10)
C25	0.0201 (13)	0.0273 (12)	0.0270 (12)	−0.0009 (10)	0.0027 (10)	−0.0004 (10)
C26	0.0294 (16)	0.0586 (19)	0.0530 (17)	−0.0065 (14)	0.0092 (13)	−0.0207 (15)
C27	0.0392 (17)	0.0357 (14)	0.0271 (12)	0.0062 (12)	0.0053 (11)	0.0013 (11)
C28	0.0498 (19)	0.0313 (14)	0.0305 (13)	0.0052 (13)	0.0007 (12)	0.0008 (11)
C29	0.0302 (15)	0.0336 (14)	0.0253 (12)	0.0036 (11)	−0.0005 (10)	−0.0007 (10)
C30	0.0254 (14)	0.0316 (13)	0.0226 (11)	0.0004 (11)	−0.0019 (10)	0.0012 (10)
C31	0.0324 (16)	0.0323 (13)	0.0301 (13)	0.0042 (12)	−0.0015 (11)	−0.0056 (11)
C32	0.0371 (17)	0.0468 (16)	0.0285 (13)	0.0059 (13)	0.0021 (11)	−0.0076 (12)
C33	0.0428 (18)	0.0532 (17)	0.0277 (13)	−0.0014 (14)	0.0055 (12)	0.0004 (12)
C34	0.0438 (17)	0.0376 (15)	0.0272 (12)	−0.0048 (13)	0.0004 (11)	0.0024 (11)
C35	0.0337 (16)	0.0316 (13)	0.0278 (12)	−0.0014 (11)	0.0002 (11)	−0.0007 (10)

Geometric parameters (Å, º)

O1—C12	1.422 (3)	C16—H16B	0.9700
O1—C11	1.432 (3)	C17—H17A	0.9700
O2—C2	1.379 (3)	C17—H17B	0.9700
O2—C12	1.439 (3)	C18—C19	1.512 (3)
O3—C20	1.387 (3)	C18—H18A	0.9700
O3—C30	1.436 (3)	C18—H18B	0.9700
O4—C30	1.420 (3)	C19—C24	1.393 (3)
O4—C29	1.430 (3)	C19—C20	1.399 (3)
C1—C6	1.389 (3)	C20—C21	1.395 (3)
C1—C2	1.392 (3)	C21—C22	1.385 (3)
C1—C11	1.505 (3)	C21—C29	1.508 (3)
C2—C3	1.391 (3)	C22—C23	1.398 (3)
C3—C4	1.392 (3)	C22—H22	0.9300
C3—C18	1.513 (3)	C23—C24	1.404 (3)
C4—C5	1.399 (3)	C23—C25	1.530 (3)
C4—H4	0.9300	C24—H24	0.9300
C5—C6	1.395 (3)	C25—C28	1.529 (3)
C5—C7	1.534 (3)	C25—C27	1.530 (3)
C6—H6	0.9300	C25—C26	1.534 (3)
C7—C10	1.523 (3)	C26—H26A	0.9600
C7—C9	1.525 (4)	C26—H26B	0.9600
C7—C8	1.528 (4)	C26—H26C	0.9600
C8—H8A	0.9600	C27—H27A	0.9600
C8—H8B	0.9600	C27—H27B	0.9600
C8—H8C	0.9600	C27—H27C	0.9600
C9—H9A	0.9600	C28—H28A	0.9600
C9—H9B	0.9600	C28—H28B	0.9600
C9—H9C	0.9600	C28—H28C	0.9600
C10—H10A	0.9600	C29—H29A	0.9700
C10—H10B	0.9600	C29—H29B	0.9700
C10—H10C	0.9600	C30—C31	1.509 (3)
C11—H11A	0.9700	C30—C35	1.523 (3)
C11—H11B	0.9700	C31—C32	1.534 (3)
C12—C13	1.510 (3)	C31—H31A	0.9700
C12—C17	1.523 (3)	C31—H31B	0.9700
C13—C14	1.531 (4)	C32—C33	1.526 (4)
C13—H13A	0.9700	C32—H32A	0.9700
C13—H13B	0.9700	C32—H32B	0.9700
C14—C15	1.531 (3)	C33—C34	1.526 (4)
C14—H14A	0.9700	C33—H33A	0.9700
C14—H14B	0.9700	C33—H33B	0.9700
C15—C16	1.522 (4)	C34—C35	1.529 (3)
C15—H15A	0.9700	C34—H34A	0.9700
C15—H15B	0.9700	C34—H34B	0.9700
C16—C17	1.524 (4)	C35—H35A	0.9700
C16—H16A	0.9700	C35—H35B	0.9700
C12—O1—C11	112.97 (18)	C19—C18—H18A	108.6
C2—O2—C12	115.70 (18)	C3—C18—H18A	108.6
C20—O3—C30	113.68 (17)	C19—C18—H18B	108.6
C30—O4—C29	113.28 (17)	C3—C18—H18B	108.6
C6—C1—C2	118.8 (2)	H18A—C18—H18B	107.6
C6—C1—C11	121.8 (2)	C24—C19—C20	117.7 (2)
C2—C1—C11	119.3 (2)	C24—C19—C18	121.50 (19)
O2—C2—C3	117.5 (2)	C20—C19—C18	120.8 (2)
O2—C2—C1	121.28 (19)	O3—C20—C21	120.96 (19)
C3—C2—C1	121.2 (2)	O3—C20—C19	118.0 (2)
C2—C3—C4	118.2 (2)	C21—C20—C19	121.0 (2)
C2—C3—C18	120.3 (2)	C22—C21—C20	119.4 (2)
C4—C3—C18	121.4 (2)	C22—C21—C29	121.2 (2)
C3—C4—C5	122.6 (2)	C20—C21—C29	119.4 (2)
C3—C4—H4	118.7	C21—C22—C23	122.1 (2)
C5—C4—H4	118.7	C21—C22—H22	119.0
C6—C5—C4	117.0 (2)	C23—C22—H22	119.0
C6—C5—C7	120.4 (2)	C22—C23—C24	116.7 (2)
C4—C5—C7	122.6 (2)	C22—C23—C25	120.0 (2)
C1—C6—C5	122.2 (2)	C24—C23—C25	123.36 (19)
C1—C6—H6	118.9	C19—C24—C23	123.1 (2)
C5—C6—H6	118.9	C19—C24—H24	118.4
C10—C7—C9	107.8 (2)	C23—C24—H24	118.4
C10—C7—C8	107.3 (2)	C28—C25—C27	108.25 (19)
C9—C7—C8	110.1 (3)	C28—C25—C23	109.16 (19)
C10—C7—C5	112.3 (2)	C27—C25—C23	112.50 (19)
C9—C7—C5	110.5 (2)	C28—C25—C26	108.7 (2)
C8—C7—C5	108.9 (2)	C27—C25—C26	108.5 (2)
C7—C8—H8A	109.5	C23—C25—C26	109.65 (19)
C7—C8—H8B	109.5	C25—C26—H26A	109.5
H8A—C8—H8B	109.5	C25—C26—H26B	109.5
C7—C8—H8C	109.5	H26A—C26—H26B	109.5
H8A—C8—H8C	109.5	C25—C26—H26C	109.5
H8B—C8—H8C	109.5	H26A—C26—H26C	109.5
C7—C9—H9A	109.5	H26B—C26—H26C	109.5
C7—C9—H9B	109.5	C25—C27—H27A	109.5
H9A—C9—H9B	109.5	C25—C27—H27B	109.5
C7—C9—H9C	109.5	H27A—C27—H27B	109.5
H9A—C9—H9C	109.5	C25—C27—H27C	109.5
H9B—C9—H9C	109.5	H27A—C27—H27C	109.5
C7—C10—H10A	109.5	H27B—C27—H27C	109.5
C7—C10—H10B	109.5	C25—C28—H28A	109.5
H10A—C10—H10B	109.5	C25—C28—H28B	109.5
C7—C10—H10C	109.5	H28A—C28—H28B	109.5
H10A—C10—H10C	109.5	C25—C28—H28C	109.5
H10B—C10—H10C	109.5	H28A—C28—H28C	109.5
O1—C11—C1	111.1 (2)	H28B—C28—H28C	109.5
O1—C11—H11A	109.4	O4—C29—C21	112.14 (19)
C1—C11—H11A	109.4	O4—C29—H29A	109.2
O1—C11—H11B	109.4	C21—C29—H29A	109.2
C1—C11—H11B	109.4	O4—C29—H29B	109.2
H11A—C11—H11B	108.0	C21—C29—H29B	109.2
O1—C12—O2	109.71 (17)	H29A—C29—H29B	107.9
O1—C12—C13	106.70 (19)	O4—C30—O3	109.78 (19)
O2—C12—C13	105.82 (19)	O4—C30—C31	105.91 (18)
O1—C12—C17	112.6 (2)	O3—C30—C31	107.03 (18)
O2—C12—C17	109.66 (19)	O4—C30—C35	112.90 (19)
C13—C12—C17	112.06 (19)	O3—C30—C35	109.52 (18)
C12—C13—C14	112.1 (2)	C31—C30—C35	111.5 (2)
C12—C13—H13A	109.2	C30—C31—C32	111.8 (2)
C14—C13—H13A	109.2	C30—C31—H31A	109.3
C12—C13—H13B	109.2	C32—C31—H31A	109.3
C14—C13—H13B	109.2	C30—C31—H31B	109.3
H13A—C13—H13B	107.9	C32—C31—H31B	109.3
C15—C14—C13	111.6 (2)	H31A—C31—H31B	107.9
C15—C14—H14A	109.3	C33—C32—C31	112.0 (2)
C13—C14—H14A	109.3	C33—C32—H32A	109.2
C15—C14—H14B	109.3	C31—C32—H32A	109.2
C13—C14—H14B	109.3	C33—C32—H32B	109.2
H14A—C14—H14B	108.0	C31—C32—H32B	109.2
C16—C15—C14	110.3 (2)	H32A—C32—H32B	107.9
C16—C15—H15A	109.6	C32—C33—C34	111.2 (2)
C14—C15—H15A	109.6	C32—C33—H33A	109.4
C16—C15—H15B	109.6	C34—C33—H33A	109.4
C14—C15—H15B	109.6	C32—C33—H33B	109.4
H15A—C15—H15B	108.1	C34—C33—H33B	109.4
C15—C16—C17	112.1 (2)	H33A—C33—H33B	108.0
C15—C16—H16A	109.2	C33—C34—C35	110.6 (2)
C17—C16—H16A	109.2	C33—C34—H34A	109.5
C15—C16—H16B	109.2	C35—C34—H34A	109.5
C17—C16—H16B	109.2	C33—C34—H34B	109.5
H16A—C16—H16B	107.9	C35—C34—H34B	109.5
C12—C17—C16	111.4 (2)	H34A—C34—H34B	108.1
C12—C17—H17A	109.4	C30—C35—C34	111.46 (19)
C16—C17—H17A	109.4	C30—C35—H35A	109.3
C12—C17—H17B	109.4	C34—C35—H35A	109.3
C16—C17—H17B	109.4	C30—C35—H35B	109.3
H17A—C17—H17B	108.0	C34—C35—H35B	109.3
C19—C18—C3	114.76 (18)	H35A—C35—H35B	108.0