3,3,6,6,9,9-Hexaethyl-1,2,4,5,7,8-hexa­oxacyclo­nonane at 296 K

The title mol­ecule (diethyl ketone triperoxide, DEKTP), C₁₅H₃₀O₆, is a cyclic triperoxide closely related to triacetone triperoxide (TATP), one of the most unstable explosives known. However, the stability of DEKTP is ca 20-50 times greater than that of TATP. DEKTP crystallizes with two mol­ecules in the asymmetric unit, with virtually identical geometry. The cyclo­nonane core is stabilized in a twisted boat-chair conformation (approximate D₃ symmetry), very close to that previously described for TATP. The explanation for the safe thermal behaviour of DEKTP compared with TATP should thus not be sought in the mol­ecular dimensions, but rather in the thermal decomposition kinetics.

S1. Comment

Cyclic gem-peroxides with three peroxidic functions are formed readily from the acid-catalyzed oxidation of carbonyl compounds with hydrogen peroxide to form a mixture of open-chain and cyclic peroxides, the latter arising from the former. The unusual reactivity of peroxides is generally attributed to the weakness of the O—O bond linkage (the reactive site) and hence the ease with which it is homolytically cleaved. Many studies have reported the thermal decomposition rate reaction constants (Cañizo, 2006; Eyler, 2006; Iglesias et al., 2009) for diethyl ketone triperoxide (DEKTP, C₁₅H₃₀O₆) and triacetone triperoxide (TATP, C₉H₁₈O₆). These reports showed that it is possible to compare the thermal solution behaviour for both compounds, and concluded that DEKTP has a higher thermal solution decomposition stability than TATP.

Cyclic peroxide derivatives have been studied mainly for two reasons. Firstly, they are potentially useful radical initiators, for example in the bulk polymerization of styrene (Cerna et al., 2002) or for controlled-rheology polypropylene (Pucci et al., 2004). In this application, their performance is similar to that presented by a multifunctional initiator, giving rise to high molecular weight polystyrene at a high reaction rate. Secondly, some members of this family are also interesting from a conformational point of view, since large rings including only sp³-hybridized atoms can be stabilized in different conformations, sometimes affording separable conformers. A classic example is TATP, a well known peroxide-based explosive material with a power close to that of TNT. A comprehensive study showed that the explosion of this product involves an entropic burst, which is the result of the formation of four gaseous compounds from one molecule of TATP in the solid state (Dubnikova et al., 2005). The X-ray structure of TATP has been established (Groth, 1969; Dubnikova et al., 2005; Jensen et al., 2009), showing that a single conformer is stabilized in the solid state, where the nine-membered cycle adopts a twisted boat–chair conformation with a local symmetry close to D₃. However, some reports claim that two TATP conformers related by a flip-flop interconversion mechanism may exist at room temperature. Computational and experimental evidence supports this claim. For instance, it was found that the C₂-TATP conformer is only 1.85 kcal mol⁻¹ (1 kcal mol⁻¹ = 4.184 kJ mol⁻¹) less stable than the D₃ conformer. On the other hand, the barrier for interconversion, at least in the gas phase, is sufficiently high to allow the two conformers to be separated (Denekamp et al., 2005).

A direct strategy for assessing the conformational flexibility of TATP is to synthesize and characterize closely related compounds. However, very few cyclic triperoxide derivatives bearing a cyclononane core have been X-ray characterized to date (Denekamp et al., 2005; Terent'ev et al., 2007), and all presented a D₃ conformation. The present work deals with the room-temperature solid-state structure of the title compound, DEKTP, (I), where all methyl groups of TATP are formally substituted by ethyl groups. It should be emphasized that, although the compound is difficult to handle at room temperature, low-temperature data collection was not attempted, because the room-temperature structure is the one of interest regarding the relationship with the peculiar properties of the compound. On the other hand, these systems are known to be prone to polymorphism, as recently reported for TATP, for which an exceptional series of five new polymorphs were characterized at T = 180–200 K (Reany et al., 2009).

DEKTP crystallizes as well shaped colourless crystals with a rather low melting point (m.p. 332–333 K) and a strong unpleasant smell. Although the crystals are air-stable for several months, they slowly volatilize in the X-ray beam, as previously observed in the case of TATP (Dubnikova et al., 2005). Depending on the crystal size and power of irradiation, ca 75% diffraction decay is observed after 40 h of data collection. Four partial diffraction patterns with overlapping layers were thus measured, using four crystals, which afforded a complete scaled data set for structure refinement (see Experimental).

The crystal structure of DEKTP has no unexpected features. Molecules display a globular shape with a hydrophobic external surface, and are thus well separated in the crystal. The resulting packing index is rather low, 0.63 (PLATON; Spek, 2003), although no significant voids are detected in the crystal structure.

In contrast with TATP, the title peroxide has two molecules in the asymmetric unit, both located on general positions (Figs. 1 and 2). The two independent molecules have quite similar conformations: an overlay (Macrae et al., 2006) between both molecules computed with all non-H atoms affords an r.m.s. deviation of 0.115 Å. The largest differences arise from the peripheral ethyl groups, which are potentially free to rotate about their σ C—C bonds, providing that the C atoms in the cyclononane rings retain a tetrahedral geometry (Fig. 2, inset). The largest deviation of 0.348 Å corresponds to the pair of fitted atoms C10/C30. Each molecule displays the same twisted boat–chair conformation, similar to that found for TATP. Total puckering amplitudes (Cremer & Pople, 1975) are similar in both independent molecules, 1.3232 (13) and 1.3220 (13) Å for the O1- and O21-rings, respectively. Departures from ideal D₃ symmetry for the cyclononane cores are small, as reflected in the range of the C—O—O—C torsion angles in the cycles, −134.54 (14)– −136.54 (14)°. The bond lengths for the O—O groups also span a very narrow range, 1.4711 (16)–1.4775 (17) Å, and compare well with those found in TATP [average 1.470 (2) Å at 180 K].

In conclusion, a comparison between the molecular structures of TATP and DEKTP clearly shows that substitution of methyl by ethyl groups does not introduce additional strain in the cyclononane ring system. Assuming a similar thermal decomposition pathway for both molecules, we can then suggest that DEKTP is not as sensitive to impact or temperature changes as TATP is, because some products of the decomposition process have higher molecular weights. For instance, acetone, the main product of TATP decomposition, should be diethylketone in the case of DEKTP decomposition. In the same way, methyl acetate as a product of decomposition of TATP is replaced by ethyl propanoate for DEKTP (see scheme 2 in Dubnikova et al., 2005).

S2. Experimental

DEKTP was obtained in a simple and efficient one-step procedure using the acid-catalyzed oxidation reaction of diethylketone by hydrogen peroxide (Eyler et al., 1993). Over a period of 1 h, diethylketone (50 mmol, 5.6 ml) was added constantly [Dropwise?] to a mixture of hydrogen peroxide (4.6 ml) and sulfuric acid (7.3 ml, 70% v/v). The reaction is exothermic and was conducted at low temperature (263 K). After addition, the slurry was stirred for 2 h at low temperature. Subsequently, the organic and aqueous phases were allowed to separate. The organic layer was isolated, neutralized with a saturated ammonium sulfate aqueous solution, and re-extracted with petroleum ether (333 K). This phase was dried over anhydrous sodium sulfate for 12 h, filtered, and the solvent removed under reduced pressure. The crude product was crystallized from methanol, affording colourless crystals of DEKTP, (I) (m.p. 332–333 K; yield 80%).

S3. Refinement

Because of the intrinsic instability of DEKTP under X-ray irradiation, four crystals of quite similar sizes were used for data collection. In order to minimize damage, the beam shutter was left closed during dead times, ensuring non-continuous irradiation. Different parts of reciprocal space were measured for each crystal, with a common layer in each pair of crystals. Raw data were corrected for crystal decay, using the intensity of three standard reflections. The index range and decay for each crystal were as follows. Crystal 1: h − 12 → 3, decay 1 → 0.23; crystal 2: h − 12 → −6, decay 1 → 0.66; crystal 3: h − 1 → −3, decay 1 → 0.72; crystal 4: h − 3 → 5, decay 1 → 0.65. Finally, a dataset scaling by least-squares fitting of common reflections was used to produce a suitable intensities file (XPREP; Bruker, 1997). Scale factor and R_int indices for each contributing crystal in the final data set were as follows. Crystal 1: K = 1, R_int = 0.066; crystal 2: K = 0.09, R_int = 0.061; crystal 3: K = 0.60, R_int = 0.041; crystal 4: K = 0.34, R_int = 0.025.

Methylene H atoms were placed in idealized positions and refined as riding on their parent C atoms, with C—H = 0.97 Å. Methyl H atoms were placed in calculated positions, with C—H = 0.96 Å, and the CH₃ groups considered as rigid groups free to rotate about their C—C bonds. For all H atoms, U_iso(H) = 1.2U_eq(C) for methylene groups or 1.5U_eq(C) for methyl groups.

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Version 2.0; Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1. The structure of the first independent molecule of DEKTP, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Fig. 2. The structure of the second independent molecule of DEKTP, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The inset is an overlay of the non-H atoms between the two molecules; red denotes the O1-molecule and green the O21-molecule. [Colours will not be distinguishable in greyscale in the printed journal - please revise]

3,3,6,6,9,9-Hexaethyl-1,2,4,5,7,8-hexaoxacyclononane

Crystal data

C15H30O6	F(000) = 1344
Mr = 306.39	Dx = 1.115 Mg m^−3
Monoclinic, P21/c	Melting point = 332–333 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.4545 (12) Å	Cell parameters from 68 reflections
b = 10.859 (3) Å	θ = 4.7–12.5°
c = 32.168 (5) Å	µ = 0.09 mm^−1
β = 91.796 (10)°	T = 296 K
V = 3650.0 (12) Å^3	Needle, colourless
Z = 8	0.6 × 0.4 × 0.3 mm

Data collection

Siemens P4 diffractometer	Rint = 0.045
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.0°
Graphite monochromator	h = −12→5
ω scans	k = −11→12
17260 measured reflections	l = −38→38
6424 independent reflections	3 standard reflections every 97 reflections
4356 reflections with I > 2σ(I)	intensity decay: >50%

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)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 0.5376P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
6424 reflections	Δρmax = 0.15 e Å^−3
392 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0046 (4)

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

	x	y	z	Uiso*/Ueq
O1	0.57682 (11)	0.42338 (11)	0.67141 (4)	0.0569 (3)
O2	0.64392 (11)	0.30702 (11)	0.68168 (4)	0.0580 (3)
O3	0.67111 (10)	0.37723 (11)	0.75086 (4)	0.0575 (3)
O4	0.57335 (10)	0.28663 (11)	0.76263 (4)	0.0566 (3)
O5	0.41644 (11)	0.42489 (11)	0.73694 (3)	0.0560 (3)
O6	0.39324 (11)	0.34037 (11)	0.70158 (3)	0.0572 (3)
C1	0.44428 (16)	0.39613 (17)	0.66591 (5)	0.0536 (4)
C2	0.41999 (19)	0.29785 (19)	0.63246 (5)	0.0679 (5)
H2A	0.4582	0.2209	0.6419	0.081*
H2B	0.3285	0.2847	0.6290	0.081*
C3	0.4734 (3)	0.3313 (2)	0.59054 (6)	0.0929 (7)
H3A	0.4630	0.2628	0.5718	0.139*
H3B	0.5627	0.3507	0.5940	0.139*
H3C	0.4283	0.4014	0.5793	0.139*
C4	0.38639 (17)	0.52195 (18)	0.65660 (6)	0.0625 (5)
H4A	0.4094	0.5774	0.6793	0.075*
H4B	0.4233	0.5543	0.6316	0.075*
C5	0.24196 (19)	0.5203 (2)	0.65079 (7)	0.0838 (7)
H5A	0.2112	0.6030	0.6470	0.126*
H5B	0.2046	0.4850	0.6749	0.126*
H5C	0.2186	0.4720	0.6268	0.126*
C6	0.73208 (15)	0.33097 (17)	0.71521 (5)	0.0549 (4)
C7	0.82448 (18)	0.4350 (2)	0.70541 (6)	0.0697 (5)
H7A	0.7769	0.5116	0.7033	0.084*
H7B	0.8865	0.4432	0.7283	0.084*
C8	0.8955 (2)	0.4155 (3)	0.66541 (8)	0.1025 (8)
H8A	0.9405	0.4894	0.6585	0.154*
H8B	0.8354	0.3954	0.6433	0.154*
H8C	0.9556	0.3492	0.6692	0.154*
C9	0.79281 (18)	0.20506 (19)	0.72283 (6)	0.0666 (5)
H9A	0.7258	0.1463	0.7286	0.080*
H9B	0.8334	0.1787	0.6976	0.080*
C10	0.8909 (2)	0.2024 (3)	0.75826 (8)	0.1013 (8)
H10A	0.9168	0.1189	0.7635	0.152*
H10B	0.8542	0.2362	0.7828	0.152*
H10C	0.9640	0.2504	0.7510	0.152*
C11	0.46000 (15)	0.35313 (17)	0.77143 (5)	0.0527 (4)
C12	0.48267 (18)	0.45023 (18)	0.80509 (5)	0.0621 (5)
H12A	0.5406	0.5122	0.7948	0.075*
H12B	0.4021	0.4904	0.8105	0.075*
C13	0.5383 (2)	0.3983 (2)	0.84564 (6)	0.0881 (7)
H13A	0.5527	0.4642	0.8652	0.132*
H13B	0.6180	0.3579	0.8405	0.132*
H13C	0.4794	0.3402	0.8568	0.132*
C14	0.36694 (16)	0.25044 (18)	0.78204 (6)	0.0622 (5)
H14A	0.3626	0.1919	0.7593	0.075*
H14B	0.3994	0.2073	0.8066	0.075*
C15	0.23330 (19)	0.2970 (2)	0.78999 (9)	0.0988 (8)
H15A	0.1775	0.2283	0.7944	0.148*
H15B	0.2022	0.3436	0.7664	0.148*
H15C	0.2355	0.3486	0.8142	0.148*
O21	0.81301 (11)	0.12670 (12)	0.41802 (3)	0.0573 (3)
O22	0.89907 (11)	0.02031 (11)	0.42479 (3)	0.0563 (3)
O23	1.06812 (12)	0.14682 (12)	0.40392 (4)	0.0637 (3)
O24	1.11347 (11)	0.15049 (11)	0.44775 (4)	0.0602 (3)
O25	0.95525 (11)	0.29950 (11)	0.46059 (4)	0.0604 (3)
O26	0.88545 (11)	0.20421 (11)	0.48317 (3)	0.0551 (3)
C21	0.77720 (15)	0.16837 (17)	0.45789 (5)	0.0514 (4)
C22	0.71799 (17)	0.06752 (17)	0.48385 (5)	0.0573 (5)
H22A	0.7851	0.0122	0.4938	0.069*
H22B	0.6800	0.1046	0.5079	0.069*
C23	0.6164 (2)	−0.0068 (2)	0.46017 (6)	0.0794 (6)
H23A	0.5857	−0.0712	0.4777	0.119*
H23B	0.6527	−0.0423	0.4359	0.119*
H23C	0.5466	0.0462	0.4520	0.119*
C24	0.68985 (18)	0.27793 (19)	0.44725 (6)	0.0661 (5)
H24A	0.7358	0.3350	0.4300	0.079*
H24B	0.6161	0.2485	0.4311	0.079*
C25	0.6436 (2)	0.3463 (2)	0.48475 (7)	0.0888 (7)
H25A	0.6009	0.4205	0.4759	0.133*
H25B	0.7154	0.3666	0.5028	0.133*
H25C	0.5852	0.2952	0.4994	0.133*
C26	1.00319 (17)	0.03319 (18)	0.39764 (5)	0.0572 (5)
C27	0.9592 (2)	0.0418 (2)	0.35197 (5)	0.0730 (6)
H27A	0.9153	0.1197	0.3475	0.088*
H27B	1.0339	0.0417	0.3349	0.088*
C28	0.8708 (2)	−0.0618 (2)	0.33774 (7)	0.0902 (7)
H28A	0.8429	−0.0478	0.3094	0.135*
H28B	0.7979	−0.0644	0.3551	0.135*
H28C	0.9158	−0.1387	0.3397	0.135*
C29	1.08606 (18)	−0.07766 (19)	0.40901 (6)	0.0659 (5)
H29A	1.0897	−0.0864	0.4390	0.079*
H29B	1.0458	−0.1511	0.3975	0.079*
C30	1.2219 (2)	−0.0698 (2)	0.39369 (7)	0.0892 (7)
H30A	1.2651	−0.1465	0.3990	0.134*
H30B	1.2668	−0.0047	0.4081	0.134*
H30C	1.2195	−0.0533	0.3644	0.134*
C31	1.08821 (17)	0.26987 (17)	0.46351 (6)	0.0608 (5)
C32	1.1474 (2)	0.3720 (2)	0.43788 (8)	0.0834 (6)
H32A	1.0998	0.3791	0.4116	0.100*
H32B	1.1389	0.4495	0.4526	0.100*
C33	1.2877 (2)	0.3512 (3)	0.42913 (11)	0.1209 (10)
H33A	1.3173	0.4155	0.4114	0.181*
H33B	1.2976	0.2730	0.4157	0.181*
H33C	1.3369	0.3518	0.4548	0.181*
C34	1.1376 (2)	0.2585 (2)	0.50854 (6)	0.0724 (6)
H34A	1.1070	0.1816	0.5199	0.087*
H34B	1.2303	0.2550	0.5089	0.087*
C35	1.0968 (3)	0.3636 (2)	0.53648 (8)	0.1039 (8)
H35A	1.1301	0.3499	0.5643	0.156*
H35B	1.0051	0.3674	0.5367	0.156*
H35C	1.1296	0.4399	0.5262	0.156*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0466 (6)	0.0605 (8)	0.0632 (7)	−0.0059 (6)	−0.0027 (5)	0.0021 (6)
O2	0.0488 (7)	0.0614 (8)	0.0634 (7)	0.0007 (6)	−0.0021 (5)	−0.0084 (6)
O3	0.0437 (6)	0.0659 (8)	0.0630 (7)	−0.0043 (6)	0.0026 (5)	−0.0111 (6)
O4	0.0437 (6)	0.0611 (8)	0.0652 (7)	0.0021 (6)	0.0054 (5)	0.0027 (6)
O5	0.0572 (7)	0.0604 (7)	0.0501 (6)	0.0046 (6)	−0.0022 (5)	0.0003 (6)
O6	0.0515 (7)	0.0659 (8)	0.0538 (6)	−0.0101 (6)	−0.0039 (5)	0.0010 (6)
C1	0.0449 (9)	0.0652 (11)	0.0502 (9)	−0.0105 (9)	−0.0038 (7)	0.0030 (8)
C2	0.0675 (12)	0.0724 (13)	0.0631 (11)	−0.0157 (11)	−0.0080 (9)	−0.0065 (10)
C3	0.1160 (19)	0.1025 (18)	0.0605 (12)	−0.0188 (16)	0.0064 (12)	−0.0127 (12)
C4	0.0566 (11)	0.0717 (13)	0.0588 (10)	−0.0050 (10)	−0.0053 (9)	0.0063 (9)
C5	0.0595 (12)	0.1072 (18)	0.0838 (14)	0.0070 (13)	−0.0094 (10)	0.0049 (13)
C6	0.0392 (9)	0.0662 (12)	0.0593 (10)	−0.0025 (9)	0.0011 (8)	−0.0108 (9)
C7	0.0464 (10)	0.0764 (14)	0.0864 (13)	−0.0105 (10)	0.0015 (9)	−0.0042 (11)
C8	0.0722 (15)	0.124 (2)	0.1131 (19)	−0.0179 (15)	0.0302 (14)	0.0068 (16)
C9	0.0509 (10)	0.0697 (13)	0.0794 (12)	0.0055 (10)	0.0041 (9)	−0.0089 (10)
C10	0.0781 (15)	0.1055 (19)	0.1185 (19)	0.0120 (15)	−0.0265 (14)	0.0067 (16)
C11	0.0432 (9)	0.0624 (11)	0.0526 (9)	0.0099 (9)	0.0017 (7)	0.0057 (8)
C12	0.0601 (11)	0.0719 (13)	0.0544 (10)	0.0084 (10)	0.0037 (8)	−0.0024 (9)
C13	0.0981 (17)	0.1066 (18)	0.0586 (11)	0.0051 (15)	−0.0128 (11)	−0.0002 (12)
C14	0.0489 (10)	0.0698 (13)	0.0682 (11)	0.0047 (9)	0.0067 (9)	0.0101 (10)
C15	0.0503 (12)	0.0942 (18)	0.153 (2)	0.0072 (12)	0.0198 (13)	0.0153 (17)
O21	0.0551 (7)	0.0730 (8)	0.0439 (6)	0.0043 (6)	0.0028 (5)	0.0060 (6)
O22	0.0588 (7)	0.0610 (8)	0.0497 (6)	0.0004 (6)	0.0121 (5)	0.0028 (6)
O23	0.0653 (8)	0.0710 (9)	0.0550 (7)	−0.0093 (7)	0.0072 (6)	0.0069 (6)
O24	0.0581 (7)	0.0587 (8)	0.0632 (7)	0.0003 (6)	−0.0053 (6)	−0.0006 (6)
O25	0.0538 (7)	0.0539 (7)	0.0730 (8)	−0.0018 (6)	−0.0023 (6)	0.0096 (6)
O26	0.0531 (7)	0.0609 (7)	0.0512 (6)	−0.0030 (6)	−0.0023 (5)	0.0064 (5)
C21	0.0459 (9)	0.0632 (11)	0.0451 (8)	0.0011 (8)	0.0002 (7)	0.0012 (8)
C22	0.0574 (10)	0.0682 (12)	0.0465 (9)	0.0005 (9)	0.0072 (8)	0.0017 (8)
C23	0.0714 (13)	0.0970 (16)	0.0704 (12)	−0.0254 (13)	0.0101 (10)	−0.0040 (12)
C24	0.0551 (11)	0.0772 (13)	0.0656 (11)	0.0078 (10)	−0.0028 (9)	0.0112 (10)
C25	0.0859 (16)	0.0854 (16)	0.0954 (16)	0.0253 (13)	0.0076 (13)	−0.0028 (13)
C26	0.0574 (11)	0.0660 (12)	0.0488 (9)	−0.0059 (10)	0.0118 (8)	0.0000 (9)
C27	0.0690 (12)	0.1032 (17)	0.0475 (10)	−0.0046 (12)	0.0102 (9)	0.0028 (11)
C28	0.0816 (15)	0.119 (2)	0.0690 (13)	−0.0025 (15)	−0.0068 (11)	−0.0193 (13)
C29	0.0688 (12)	0.0685 (13)	0.0607 (11)	0.0018 (10)	0.0070 (9)	−0.0068 (9)
C30	0.0720 (14)	0.1096 (19)	0.0871 (15)	0.0168 (14)	0.0183 (12)	−0.0120 (14)
C31	0.0486 (10)	0.0554 (11)	0.0779 (12)	−0.0039 (9)	−0.0049 (9)	0.0003 (9)
C32	0.0706 (14)	0.0654 (14)	0.1144 (17)	−0.0134 (11)	0.0081 (12)	0.0102 (12)
C33	0.0766 (17)	0.109 (2)	0.178 (3)	−0.0214 (16)	0.0296 (17)	0.015 (2)
C34	0.0637 (12)	0.0676 (13)	0.0848 (13)	0.0020 (10)	−0.0151 (10)	−0.0094 (11)
C35	0.124 (2)	0.0822 (17)	0.1031 (18)	0.0079 (16)	−0.0277 (16)	−0.0281 (14)

Geometric parameters (Å, º)

O1—C1	1.4224 (19)	O21—C21	1.4211 (19)
O1—O2	1.4775 (17)	O21—O22	1.4762 (17)
O2—C6	1.4207 (19)	O22—C26	1.424 (2)
O3—C6	1.421 (2)	O23—C26	1.420 (2)
O3—O4	1.4765 (16)	O23—O24	1.4739 (16)
O4—C11	1.424 (2)	O24—C31	1.420 (2)
O5—C11	1.4190 (19)	O25—C31	1.427 (2)
O5—O6	1.4757 (16)	O25—O26	1.4711 (16)
O6—C1	1.416 (2)	O26—C21	1.4269 (19)
C1—C4	1.520 (3)	C21—C22	1.521 (2)
C1—C2	1.531 (2)	C21—C24	1.532 (3)
C2—C3	1.519 (3)	C22—C23	1.519 (3)
C2—H2A	0.9700	C22—H22A	0.9700
C2—H2B	0.9700	C22—H22B	0.9700
C3—H3A	0.9600	C23—H23A	0.9600
C3—H3B	0.9600	C23—H23B	0.9600
C3—H3C	0.9600	C23—H23C	0.9600
C4—C5	1.516 (3)	C24—C25	1.509 (3)
C4—H4A	0.9700	C24—H24A	0.9700
C4—H4B	0.9700	C24—H24B	0.9700
C5—H5A	0.9600	C25—H25A	0.9600
C5—H5B	0.9600	C25—H25B	0.9600
C5—H5C	0.9600	C25—H25C	0.9600
C6—C9	1.524 (3)	C26—C29	1.521 (3)
C6—C7	1.526 (3)	C26—C27	1.529 (2)
C7—C8	1.521 (3)	C27—C28	1.517 (3)
C7—H7A	0.9700	C27—H27A	0.9700
C7—H7B	0.9700	C27—H27B	0.9700
C8—H8A	0.9600	C28—H28A	0.9600
C8—H8B	0.9600	C28—H28B	0.9600
C8—H8C	0.9600	C28—H28C	0.9600
C9—C10	1.509 (3)	C29—C30	1.520 (3)
C9—H9A	0.9700	C29—H29A	0.9700
C9—H9B	0.9700	C29—H29B	0.9700
C10—H10A	0.9600	C30—H30A	0.9600
C10—H10B	0.9600	C30—H30B	0.9600
C10—H10C	0.9600	C30—H30C	0.9600
C11—C12	1.524 (2)	C31—C32	1.525 (3)
C11—C14	1.525 (3)	C31—C34	1.527 (3)
C12—C13	1.520 (3)	C32—C33	1.519 (3)
C12—H12A	0.9700	C32—H32A	0.9700
C12—H12B	0.9700	C32—H32B	0.9700
C13—H13A	0.9600	C33—H33A	0.9600
C13—H13B	0.9600	C33—H33B	0.9600
C13—H13C	0.9600	C33—H33C	0.9600
C14—C15	1.515 (3)	C34—C35	1.522 (3)
C14—H14A	0.9700	C34—H34A	0.9700
C14—H14B	0.9700	C34—H34B	0.9700
C15—H15A	0.9600	C35—H35A	0.9600
C15—H15B	0.9600	C35—H35B	0.9600
C15—H15C	0.9600	C35—H35C	0.9600
C1—O1—O2	107.68 (12)	C21—O21—O22	107.01 (10)
C6—O2—O1	107.78 (11)	C26—O22—O21	107.87 (12)
C6—O3—O4	107.64 (11)	C26—O23—O24	107.33 (11)
C11—O4—O3	107.47 (12)	C31—O24—O23	107.96 (12)
C11—O5—O6	107.58 (12)	C31—O25—O26	107.83 (11)
C1—O6—O5	107.55 (11)	C21—O26—O25	107.89 (11)
O6—C1—O1	112.24 (12)	O21—C21—O26	112.00 (13)
O6—C1—C4	112.70 (15)	O21—C21—C22	112.93 (14)
O1—C1—C4	102.58 (14)	O26—C21—C22	102.28 (12)
O6—C1—C2	102.30 (14)	O21—C21—C24	102.57 (13)
O1—C1—C2	111.83 (15)	O26—C21—C24	111.84 (15)
C4—C1—C2	115.58 (15)	C22—C21—C24	115.59 (15)
C3—C2—C1	113.57 (17)	C23—C22—C21	113.41 (15)
C3—C2—H2A	108.9	C23—C22—H22A	108.9
C1—C2—H2A	108.9	C21—C22—H22A	108.9
C3—C2—H2B	108.9	C23—C22—H22B	108.9
C1—C2—H2B	108.9	C21—C22—H22B	108.9
H2A—C2—H2B	107.7	H22A—C22—H22B	107.7
C2—C3—H3A	109.5	C22—C23—H23A	109.5
C2—C3—H3B	109.5	C22—C23—H23B	109.5
H3A—C3—H3B	109.5	H23A—C23—H23B	109.5
C2—C3—H3C	109.5	C22—C23—H23C	109.5
H3A—C3—H3C	109.5	H23A—C23—H23C	109.5
H3B—C3—H3C	109.5	H23B—C23—H23C	109.5
C5—C4—C1	113.75 (17)	C25—C24—C21	114.02 (16)
C5—C4—H4A	108.8	C25—C24—H24A	108.7
C1—C4—H4A	108.8	C21—C24—H24A	108.7
C5—C4—H4B	108.8	C25—C24—H24B	108.7
C1—C4—H4B	108.8	C21—C24—H24B	108.7
H4A—C4—H4B	107.7	H24A—C24—H24B	107.6
C4—C5—H5A	109.5	C24—C25—H25A	109.5
C4—C5—H5B	109.5	C24—C25—H25B	109.5
H5A—C5—H5B	109.5	H25A—C25—H25B	109.5
C4—C5—H5C	109.5	C24—C25—H25C	109.5
H5A—C5—H5C	109.5	H25A—C25—H25C	109.5
H5B—C5—H5C	109.5	H25B—C25—H25C	109.5
O2—C6—O3	112.38 (13)	O23—C26—O22	111.68 (14)
O2—C6—C9	102.42 (14)	O23—C26—C29	112.79 (15)
O3—C6—C9	112.48 (15)	O22—C26—C29	102.44 (14)
O2—C6—C7	112.24 (15)	O23—C26—C27	102.23 (14)
O3—C6—C7	102.00 (14)	O22—C26—C27	112.50 (15)
C9—C6—C7	115.73 (15)	C29—C26—C27	115.59 (16)
C8—C7—C6	113.62 (18)	C28—C27—C26	113.99 (17)
C8—C7—H7A	108.8	C28—C27—H27A	108.8
C6—C7—H7A	108.8	C26—C27—H27A	108.8
C8—C7—H7B	108.8	C28—C27—H27B	108.8
C6—C7—H7B	108.8	C26—C27—H27B	108.8
H7A—C7—H7B	107.7	H27A—C27—H27B	107.6
C7—C8—H8A	109.5	C27—C28—H28A	109.5
C7—C8—H8B	109.5	C27—C28—H28B	109.5
H8A—C8—H8B	109.5	H28A—C28—H28B	109.5
C7—C8—H8C	109.5	C27—C28—H28C	109.5
H8A—C8—H8C	109.5	H28A—C28—H28C	109.5
H8B—C8—H8C	109.5	H28B—C28—H28C	109.5
C10—C9—C6	114.12 (17)	C30—C29—C26	114.11 (18)
C10—C9—H9A	108.7	C30—C29—H29A	108.7
C6—C9—H9A	108.7	C26—C29—H29A	108.7
C10—C9—H9B	108.7	C30—C29—H29B	108.7
C6—C9—H9B	108.7	C26—C29—H29B	108.7
H9A—C9—H9B	107.6	H29A—C29—H29B	107.6
C9—C10—H10A	109.5	C29—C30—H30A	109.5
C9—C10—H10B	109.5	C29—C30—H30B	109.5
H10A—C10—H10B	109.5	H30A—C30—H30B	109.5
C9—C10—H10C	109.5	C29—C30—H30C	109.5
H10A—C10—H10C	109.5	H30A—C30—H30C	109.5
H10B—C10—H10C	109.5	H30B—C30—H30C	109.5
O5—C11—O4	111.83 (13)	O24—C31—O25	111.97 (14)
O5—C11—C12	102.38 (14)	O24—C31—C32	112.83 (16)
O4—C11—C12	112.34 (14)	O25—C31—C32	102.20 (15)
O5—C11—C14	112.64 (14)	O24—C31—C34	101.76 (14)
O4—C11—C14	102.38 (14)	O25—C31—C34	112.34 (16)
C12—C11—C14	115.64 (15)	C32—C31—C34	116.14 (17)
C13—C12—C11	113.58 (17)	C33—C32—C31	113.7 (2)
C13—C12—H12A	108.8	C33—C32—H32A	108.8
C11—C12—H12A	108.8	C31—C32—H32A	108.8
C13—C12—H12B	108.8	C33—C32—H32B	108.8
C11—C12—H12B	108.8	C31—C32—H32B	108.8
H12A—C12—H12B	107.7	H32A—C32—H32B	107.7
C12—C13—H13A	109.5	C32—C33—H33A	109.5
C12—C13—H13B	109.5	C32—C33—H33B	109.5
H13A—C13—H13B	109.5	H33A—C33—H33B	109.5
C12—C13—H13C	109.5	C32—C33—H33C	109.5
H13A—C13—H13C	109.5	H33A—C33—H33C	109.5
H13B—C13—H13C	109.5	H33B—C33—H33C	109.5
C15—C14—C11	113.07 (17)	C35—C34—C31	114.02 (17)
C15—C14—H14A	109.0	C35—C34—H34A	108.7
C11—C14—H14A	109.0	C31—C34—H34A	108.7
C15—C14—H14B	109.0	C35—C34—H34B	108.7
C11—C14—H14B	109.0	C31—C34—H34B	108.7
H14A—C14—H14B	107.8	H34A—C34—H34B	107.6
C14—C15—H15A	109.5	C34—C35—H35A	109.5
C14—C15—H15B	109.5	C34—C35—H35B	109.5
H15A—C15—H15B	109.5	H35A—C35—H35B	109.5
C14—C15—H15C	109.5	C34—C35—H35C	109.5
H15A—C15—H15C	109.5	H35A—C35—H35C	109.5
H15B—C15—H15C	109.5	H35B—C35—H35C	109.5
C1—O1—O2—C6	−135.40 (13)	C21—O21—O22—C26	−136.54 (13)
C6—O3—O4—C11	−135.28 (13)	C26—O23—O24—C31	−136.54 (14)
C11—O5—O6—C1	−136.30 (13)	C31—O25—O26—C21	−134.54 (14)
O5—O6—C1—O1	57.42 (16)	O22—O21—C21—O26	59.57 (16)
O5—O6—C1—C4	−57.80 (15)	O22—O21—C21—C22	−55.26 (16)
O5—O6—C1—C2	177.44 (12)	O22—O21—C21—C24	179.66 (12)
O2—O1—C1—O6	57.54 (16)	O25—O26—C21—O21	56.61 (16)
O2—O1—C1—C4	178.77 (12)	O25—O26—C21—C22	177.80 (12)
O2—O1—C1—C2	−56.77 (16)	O25—O26—C21—C24	−57.91 (16)
O6—C1—C2—C3	−176.63 (17)	O21—C21—C22—C23	−47.0 (2)
O1—C1—C2—C3	−56.3 (2)	O26—C21—C22—C23	−167.56 (16)
C4—C1—C2—C3	60.5 (2)	C24—C21—C22—C23	70.7 (2)
O6—C1—C4—C5	−57.0 (2)	O21—C21—C24—C25	−176.27 (17)
O1—C1—C4—C5	−177.93 (15)	O26—C21—C24—C25	−56.1 (2)
C2—C1—C4—C5	60.1 (2)	C22—C21—C24—C25	60.4 (2)
O1—O2—C6—O3	58.51 (17)	O24—O23—C26—O22	58.39 (16)
O1—O2—C6—C9	179.45 (12)	O24—O23—C26—C29	−56.34 (16)
O1—O2—C6—C7	−55.78 (16)	O24—O23—C26—C27	178.88 (13)
O4—O3—C6—O2	56.96 (17)	O21—O22—C26—O23	56.67 (16)
O4—O3—C6—C9	−58.01 (16)	O21—O22—C26—C29	177.63 (12)
O4—O3—C6—C7	177.36 (12)	O21—O22—C26—C27	−57.62 (18)
O2—C6—C7—C8	−54.1 (2)	O23—C26—C27—C28	−172.48 (17)
O3—C6—C7—C8	−174.60 (18)	O22—C26—C27—C28	−52.6 (2)
C9—C6—C7—C8	63.0 (2)	C29—C26—C27—C28	64.6 (2)
O2—C6—C9—C10	−178.82 (17)	O23—C26—C29—C30	−43.7 (2)
O3—C6—C9—C10	−57.9 (2)	O22—C26—C29—C30	−163.93 (16)
C7—C6—C9—C10	58.7 (2)	C27—C26—C29—C30	73.4 (2)
O6—O5—C11—O4	58.43 (16)	O23—O24—C31—O25	58.89 (17)
O6—O5—C11—C12	178.90 (12)	O23—O24—C31—C32	−55.75 (18)
O6—O5—C11—C14	−56.24 (16)	O23—O24—C31—C34	179.07 (13)
O3—O4—C11—O5	57.93 (16)	O26—O25—C31—O24	57.09 (17)
O3—O4—C11—C12	−56.54 (16)	O26—O25—C31—C32	178.11 (13)
O3—O4—C11—C14	178.76 (11)	O26—O25—C31—C34	−56.71 (18)
O5—C11—C12—C13	−176.61 (16)	O24—C31—C32—C33	−49.3 (3)
O4—C11—C12—C13	−56.5 (2)	O25—C31—C32—C33	−169.8 (2)
C14—C11—C12—C13	60.5 (2)	C34—C31—C32—C33	67.6 (3)
O5—C11—C14—C15	−55.8 (2)	O24—C31—C34—C35	−167.02 (18)
O4—C11—C14—C15	−176.08 (17)	O25—C31—C34—C35	−47.1 (2)
C12—C11—C14—C15	61.4 (2)	C32—C31—C34—C35	70.0 (3)