A hydrogen-bonded dimer of 13-hydroxy-13-[(triisopropyl­silyl)­ethynyl]penta­cen-6(13H)-one

The title compound, C₃₃H₃₄O₂Si, has been obtained as a product in the synthesis of 6,13-bis­[(triisopropyl­silyl)ethynyl]-6,13-dihydro­penta­cene-6,13-diol. The solid-state structure reveals a dimer, with strong hydrogen bonds holding the two mol­ecules in a face-to-face arrangement [O...O = 2.746 (2) Å and O—H...O = 173 (2)°]. Within each dimer, the penta­cene units are π-stacked (the distance between the mean least-squares planes of 22 C atoms is 3.60 Å).

S1. Comment

The design of photo- and redox-active systems with potential application as photocatalysts for solar energy conversion is a research imperative for the 21s t century (Eisenberg & Nocera, 2005). With the aim of designing photocatalytic systems involving redox- and photoactive transition metal complexes, we have focused on a modular approach using {M(tpy)₂} metallotectons (tpy is 2,2':6',2''-terpyridine). We have shown that pendant or bridging aromatic units may be used to control energy- and electron-transfer processes (Constable et al., 2005; Figgemeier et al., 2003; Hjelm et al., 2005, and references therein). In the course of our synthetic programme to tune the highest occupied molecular orbital–lowest unoccupied molecular orbital properties and band gap of bridging aromatic moieties, our attention has turned to pentacene units, which have attractive energetic properties (Meng et al., 2005; Sakamoto et al., 2004; Swartz et al., 2005). In this paper, we report the structure of the title compound, (I), a product obtained in the synthesis of 6,13-bis(ethynyl)pentacene.

We required 6,13-bis(ethynyl)pentacene, (V), to introduce it as a spacer between two {M(tpy)₂} units, and used minor variations on the literature procedure to prepare 6,13-bis[(triisopropylsilyl)ethynyl]pentacene, (II) (Anthony et al., 2001, 2002; Payne, Delcamp et al., 2004; Swartz et al., 2005). Pentacene-6,13-dione, (III), was prepared as a yellow solid from the reaction of cyclopentane-1,4-dione with 1,2-benzenedicarboxaldehyde in ethanolic KOH in 95% yield (Ried & Anthöfer, 1953). Reaction of (III) with (triisopropylsilyl)ethynyllithium (TIPSCCLi) in tetrahydrofuran gave a green solid comprising the desired diol, 6,13-bis[(triisopropylsilyl)ethynyl]-6,13-dihydropentacene-6,13-diol, (IV), and a highly fluorescent (λ_em 434 nm) product, characterized as 13-hydroxy-13-[(trisisopropylsilyl)ethynyl]pentacen-6(13H)-one, (I). We have subsequently optimized the yield of orange (I) by reaction of (III) with one equivalent of TIPSCCLi.

We have determined the solid-state crystal structure of compound (I). Fig. 1 shows the structure of a molecule of (I), together with the numbering scheme adopted. The bond distances and angles in (I) are unexceptional; the Si1—C1/C4/C7 distances lie in the range 1.880 (3)–1.883 (3) Å, with Si1—C10 being shorter at 1.837 (2) Å. Five of the C—Si—C bond angles fall in the range 105.9 (1)–110.7 (1)°, while C4—Si1—C7 is larger [115.4 (1)°].

Relatively few pentacene derivatives have been structurally characterized to date (Anthony et al., 2001; Borgen, 1966; Campbell et al., 1962; Chan et al., 2005; Dzyabchenko et al., 1979; Holmes et al., 1999; Klarner et al., 2001; Mattheus et al., 2001, 2002; Meng et al., 2005; Miller et al., 2003; Ohkita et al., 2000; Payne, Odom et al., 2004; Sakamoto et al., 2004; Siegrist et al., 2001; Swartz et al., 2005; Uno et al., 2005). As expected on the basis of hydrogen bonding (see later) and the non-aromatic ring structure, the carbonyl C—O bond in (I) is slightly longer [C23—O2 = 1.238 (3) Å] than that in the quinone pentacene-6,13-dione (1.215 Å; Dzyabchenko et al., 1979). Within the pentacene system, the aromatic rings exhibit typical delocalized C—C bond distances in the range 1.358 (4)–1.424 (3) Å, similar to those of the aromatic rings in other pentacenes and 6,13-dihydropentacenes. In the central ring, the C—C bonds to the carbonyl group are a little longer [1.476 (3) and 1.474 (3) Å] and similar in length to those in pentacene-6,13-dione (1.483 Å; Dzyabchenko et al., 1979). The formally single C—C bonds to C12 in the central ring show distances of 1.528 (3) and 1.535 (3) Å, which are similar to, if slightly longer than, those in 6,13-dihydropentacene (1.475 and 1.524 Å; Mattheus et al., 2002). In contrast with 6,13-dihydropentacene, where the least-squares planes through the `naphthalene' units intersect at the sp³ C atoms at an angle of 28° (Mattheus et al., 2002), the pentacene ring system in (I) is nearly planar, with the deviation of the sp³ atom C12 from the least-squares plane of the aromatic rings being only 0.16 Å.

The molecules of (I) form a hydrogen-bonded dimer in the solid state (Fig. 2), in which the hydroxy group of one molecule is strongly hydrogen-bonded to the carbonyl O atom of a second [O1···O2ⁱ = 2.746 (2) Å and O1—H1···O2ⁱ = 173 (2)°; symmetry code:(i) −x, −y, −z]. The consequence of this tight hydrogen bonding is efficient offset face-to-face π-stacking of the two pentacene rings; the distance between least-squares planes, each of 22 C atoms, is 3.60 Å. The dimers are linked along the b axis by hydrogen-bonded interactions [C16—H161···O2ⁱⁱ, with C16···O2ⁱⁱ = 3.447 (3) Å, and C27—H271···O1ⁱⁱⁱ, with C27···O1ⁱⁱⁱ = 3.318 (3) Å; symmetry codes: (ii) ?; (iii) ? Please complete]. When viewed along the b axis (Fig. 3), the solid-state structure reveals packing of the dimers into columns. The dimers are π-stacked with offset face-to-face π-stacking of pentacene rings (the distance between least-squares planes, each of 22 C atoms, is 3.52 Å). The (triisopropyl)silyl (TIPS) substituents are directed outwards from these columns and form an intermeshed assembly between them.

Of the 26 4-hydroxycyclohexa-2,5-dienones present in the Cambridge Structural Database (Version 5.2.7; Allen, 2002; Bruno et al., 2002), the majority exhibit extended or linear hydrogen-bond connectivity, and in only two cases is a dimeric structure related to (I) observed. In the case of 4-ethynyl-4-hydroxy-2,3,5,6-tetramethylcyclohexa-2,5-dienone (Bilton et al., 2000), the monomer unit is related to (I) and the dimer has similar metrical parameters, although the hydrogen bond is significantly weaker [O—H···O = 1.94 (3) and 1.96 (3) Å; O···O = 2.826 (2) and 2.786 (2) Å; O—H···O = 172 (2) and 178 (3)°]. Once again, the hydrogen-bonding facilitates offset face-to-face π-stacking, and the distance between the least-squares planes of the aromatic rings in the dimer is 3.54 Å. The second example is found in 4,5,7-trichloro-3a-hydroxy-1-(4-methylphenyl)-2-(4-methylphenylimino)-2,3,3a,6-tetrahydro-1H-indol-6-one (Doepp et al., 1995), in which strong hydrogen bonds (O···O = 2.722 Å) also support the coplanar arrangement of aromatic rings (the distance between the least-squares planes of the aromatic rings is 3.38 Å), although these are slipped such that there is no direct ring overlap.

S2. Experimental

Pentacene-6,13-dione (5.00 g, 16.2 mmol) was dissolved in freshly distilled diethyl ether (50 ml) and the solution was added to a mixture of (triisopropylsilyl)ethyne (6.00 ml, 4.88 g, 26.7 mmol) and n-BuLi (5 ml, 1.6 M in tetrahydrofuran, 8 mmol) in tetrahydrofuran (10 ml). The mixture was stirred at room temperature under nitrogen for 24 h, and then the solvent was removed in vacuo and the residue purified by chromatography over silica gel (hexanes–CHCl₃ 1:1) to give 13-hydroxy-13-[(triisopropylsilyl)ethynyl]pentacen-6(13H)-one, (I), as a green solid (5.50 g, 69.2%; m.p. > 673 K), together with some 6,13-bis[(triisopropylsilyl)ethynyl]pentacene (1.26 g, 11.7%). Spectroscopic analysis: ¹H NMR (250 MHz, CDCl₃, 297 K, δ, p.p.m.): 8.811 (H^P5,7, s, 2H), 8.722 (H^P12,14, s, 2H), 8.03 (H^P4,8, d, 2H, J = 8.2 Hz), 7.92 (H^P1,11, d, 2H, J = 8.2 Hz), 7.62 (H^P2,10, d, 2H, J = 8.2, 6.8 and 1.3 Hz), 7.60 (H^P3,9, d, 2H, J = 8.2, 6.8 and 1.3 Hz), 1.78 (H^TIPS, m, 3H), 1.15 (H^TIPS, m, 18H); ¹³C NMR (CDCl₃, 62.5 MHz, 297 K, δ, p.p.m.): 206.9, 138.8, 135.6, 132.8, 129.7, 129.6, 128.9, 128.6, 128.2, 127.3, 127.2, 108.2, 90.0, 68.6, 18.6, 11.2; EIMS: m/z 474.1 [M+H]⁺; UV–VIS (nm): 266, 276, 320, 356; Emission (nm): 434 (λ_ex 356 nm).

S3. Refinement

Hydroxy atom H1 was located in a difference map and refined freely. All other H atoms were treated as riding, with C—H distances of 1.00 Å and with U_iso(H) = 1.5U_eq(C). [Please check added text]

Computing details

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CRYSTALS.

Figures

	Fig. 1. A view of a single molecule of (I), showing the numbering scheme adopted. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The dimeric assembly of two molecules of (I) in the crystal structure. H atoms other than those involved in hydrogen bonding have been omitted, as have the (triisopropyl)silyl groups. [Symmetry code: (i) −x, −y, −z.]
	Fig. 3. A space-filling diagram of (I), viewed down the b axis, showing the packing of the dimers into columns, between which lie the (triisopropyl)silyl groups.

13-hydroxy-13-[(triisopropylsilyl)ethynyl]pentacen-6(13H)-one

Crystal data

C33H34O2Si	Z = 2
Mr = 490.72	F(000) = 524
Triclinic, P1	Dx = 1.201 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8875 (3) Å	Cell parameters from 5830 reflections
b = 8.9910 (3) Å	θ = 1–27°
c = 17.6023 (7) Å	µ = 0.11 mm^−1
α = 90.406 (2)°	T = 173 K
β = 92.2227 (19)°	Plate, colourless
γ = 105.032 (2)°	0.40 × 0.34 × 0.02 mm
V = 1357.19 (9) Å^3

Data collection

Nonius Kappa area-detector CCD diffractometer	3673 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.015
ϕ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997)	h = −11→11
Tmin = 0.96, Tmax = 1.00	k = −11→11
11207 measured reflections	l = −22→22
6138 independent reflections

Refinement

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.064	w = 1/[σ(F) + 0.04P] where P = [max(Fo,0) + 2Fc]/3
S = 1.07	(Δ/σ)max = 0.000204
3673 reflections	Δρmax = 0.30 e Å^−3
329 parameters	Δρmin = −0.22 e Å^−3
2 restraints

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

	x	y	z	Uiso*/Ueq
Si1	0.67081 (8)	0.77144 (8)	0.34415 (4)	0.0337
O1	1.05215 (18)	0.75981 (18)	0.13917 (10)	0.0347
O2	0.8191 (2)	0.23865 (19)	0.00023 (10)	0.0411
C1	0.7094 (3)	0.6404 (3)	0.42131 (15)	0.0482
C2	0.6365 (5)	0.4710 (4)	0.4004 (2)	0.0794
C3	0.8841 (4)	0.6686 (5)	0.4409 (2)	0.0775
C4	0.7663 (3)	0.9783 (3)	0.37053 (16)	0.0464
C5	0.7399 (4)	1.0248 (4)	0.45210 (19)	0.0643
C6	0.7254 (4)	1.0935 (3)	0.31480 (19)	0.0573
C7	0.4566 (3)	0.7267 (3)	0.31777 (14)	0.0339
C8	0.3618 (3)	0.7656 (3)	0.38301 (16)	0.0445
C9	0.4186 (3)	0.8003 (3)	0.24335 (15)	0.0437
C10	0.7644 (3)	0.7220 (3)	0.25978 (14)	0.0346
C11	0.8276 (3)	0.6826 (3)	0.20661 (14)	0.0325
C12	0.9130 (3)	0.6359 (3)	0.14352 (13)	0.0309
C13	0.8160 (3)	0.6219 (3)	0.06896 (14)	0.0325
C14	0.7609 (3)	0.7449 (3)	0.04626 (14)	0.0359
C15	0.6725 (3)	0.7404 (3)	−0.02269 (14)	0.0358
C16	0.6140 (3)	0.8663 (3)	−0.04628 (16)	0.0449
C17	0.5245 (3)	0.8552 (3)	−0.11228 (16)	0.0481
C18	0.4908 (3)	0.7209 (3)	−0.15789 (16)	0.0495
C19	0.5461 (3)	0.5987 (3)	−0.13749 (15)	0.0430
C20	0.6382 (3)	0.6051 (3)	−0.06913 (14)	0.0364
C21	0.6963 (3)	0.4807 (3)	−0.04522 (14)	0.0352
C22	0.7836 (3)	0.4872 (3)	0.02178 (13)	0.0318
C23	0.8420 (3)	0.3531 (3)	0.04289 (14)	0.0331
C24	0.9284 (3)	0.3572 (3)	0.11640 (14)	0.0317
C25	0.9820 (3)	0.2311 (3)	0.13689 (15)	0.0354
C26	1.0618 (3)	0.2265 (3)	0.20697 (15)	0.0360
C27	1.1146 (3)	0.0965 (3)	0.22980 (17)	0.0427
C28	1.1856 (3)	0.0943 (3)	0.29933 (18)	0.0486
C29	1.2097 (3)	0.2221 (3)	0.34961 (17)	0.0477
C30	1.1623 (3)	0.3492 (3)	0.32941 (16)	0.0432
C31	1.0875 (3)	0.3559 (3)	0.25764 (15)	0.0363
C32	1.0347 (3)	0.4851 (3)	0.23450 (14)	0.0347
C33	0.9578 (3)	0.4879 (3)	0.16589 (14)	0.0314
H1	1.097 (3)	0.752 (3)	0.0919 (9)	0.058 (7)*
H11	0.6590	0.6645	0.4680	0.0608*
H21	0.6592	0.4050	0.4426	0.0972*
H22	0.6817	0.4443	0.3526	0.0972*
H23	0.5211	0.4528	0.3924	0.0972*
H31	0.9000	0.5972	0.4819	0.0980*
H32	0.9279	0.7776	0.4588	0.0980*
H33	0.9385	0.6492	0.3946	0.0980*
H41	0.8811	0.9911	0.3677	0.0539*
H51	0.7943	1.1359	0.4615	0.0746*
H52	0.7822	0.9603	0.4890	0.0746*
H53	0.6256	1.0085	0.4589	0.0746*
H61	0.7801	1.2008	0.3321	0.0668*
H62	0.6101	1.0809	0.3130	0.0668*
H63	0.7591	1.0741	0.2629	0.0668*
H71	0.4205	0.6127	0.3092	0.0404*
H81	0.2489	0.7401	0.3666	0.0538*
H82	0.3992	0.8778	0.3962	0.0538*
H83	0.3758	0.7038	0.4285	0.0538*
H91	0.3031	0.7716	0.2330	0.0526*
H92	0.4577	0.9148	0.2482	0.0526*
H93	0.4701	0.7624	0.2005	0.0526*
H141	0.7841	0.8397	0.0793	0.0412*
H161	0.6381	0.9629	−0.0145	0.0519*
H171	0.4830	0.9440	−0.1282	0.0567*
H181	0.4255	0.7149	−0.2059	0.0566*
H191	0.5214	0.5039	−0.1706	0.0492*
H211	0.6733	0.3850	−0.0777	0.0398*
H251	0.9628	0.1408	0.1010	0.0415*
H271	1.0987	0.0057	0.1945	0.0520*
H281	1.2213	0.0019	0.3150	0.0580*
H291	1.2625	0.2194	0.4006	0.0562*
H301	1.1805	0.4387	0.3657	0.0505*
H321	1.0546	0.5769	0.2694	0.0406*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0307 (4)	0.0414 (4)	0.0299 (4)	0.0107 (3)	0.0037 (3)	−0.0042 (3)
O1	0.0320 (9)	0.0325 (9)	0.0343 (10)	−0.0012 (7)	0.0047 (7)	−0.0081 (7)
O2	0.0432 (10)	0.0371 (10)	0.0391 (11)	0.0029 (8)	0.0069 (8)	−0.0140 (8)
C1	0.0516 (17)	0.0682 (19)	0.0318 (15)	0.0278 (14)	0.0047 (12)	0.0054 (13)
C2	0.111 (3)	0.063 (2)	0.071 (2)	0.034 (2)	−0.001 (2)	0.0235 (18)
C3	0.065 (2)	0.127 (3)	0.054 (2)	0.051 (2)	−0.0079 (17)	0.007 (2)
C4	0.0334 (14)	0.0525 (17)	0.0494 (17)	0.0042 (12)	0.0066 (12)	−0.0162 (13)
C5	0.065 (2)	0.065 (2)	0.056 (2)	0.0065 (16)	0.0051 (16)	−0.0272 (16)
C6	0.0535 (18)	0.0390 (16)	0.074 (2)	−0.0006 (13)	0.0164 (16)	−0.0026 (15)
C7	0.0309 (12)	0.0355 (13)	0.0351 (14)	0.0078 (10)	0.0041 (10)	−0.0012 (10)
C8	0.0355 (14)	0.0529 (16)	0.0471 (17)	0.0140 (12)	0.0099 (12)	0.0001 (13)
C9	0.0377 (14)	0.0531 (16)	0.0405 (16)	0.0125 (12)	−0.0015 (12)	0.0004 (12)
C10	0.0294 (12)	0.0394 (14)	0.0356 (15)	0.0098 (10)	0.0035 (11)	−0.0035 (11)
C11	0.0298 (12)	0.0320 (12)	0.0340 (14)	0.0054 (10)	−0.0003 (10)	−0.0030 (10)
C12	0.0264 (11)	0.0306 (12)	0.0324 (13)	0.0015 (9)	0.0039 (10)	−0.0073 (10)
C13	0.0273 (12)	0.0320 (13)	0.0340 (14)	0.0000 (9)	0.0054 (10)	−0.0055 (10)
C14	0.0362 (13)	0.0350 (13)	0.0328 (14)	0.0026 (10)	0.0037 (11)	−0.0070 (10)
C15	0.0305 (12)	0.0392 (14)	0.0336 (14)	0.0008 (10)	0.0073 (10)	0.0007 (11)
C16	0.0472 (16)	0.0421 (15)	0.0423 (16)	0.0056 (12)	0.0028 (13)	0.0014 (12)
C17	0.0484 (16)	0.0511 (17)	0.0427 (17)	0.0088 (13)	0.0022 (13)	0.0103 (13)
C18	0.0416 (16)	0.0652 (19)	0.0361 (16)	0.0039 (13)	−0.0005 (12)	0.0070 (14)
C19	0.0372 (14)	0.0512 (16)	0.0353 (15)	0.0019 (12)	0.0044 (12)	−0.0022 (12)
C20	0.0287 (12)	0.0406 (14)	0.0334 (14)	−0.0032 (10)	0.0067 (10)	−0.0022 (11)
C21	0.0296 (12)	0.0397 (13)	0.0309 (14)	−0.0015 (10)	0.0073 (10)	−0.0087 (10)
C22	0.0250 (12)	0.0347 (13)	0.0307 (13)	−0.0017 (9)	0.0073 (10)	−0.0074 (10)
C23	0.0277 (12)	0.0327 (13)	0.0343 (14)	−0.0015 (9)	0.0115 (10)	−0.0082 (10)
C24	0.0245 (11)	0.0314 (12)	0.0353 (14)	−0.0008 (9)	0.0102 (10)	−0.0063 (10)
C25	0.0311 (12)	0.0296 (13)	0.0423 (15)	0.0012 (10)	0.0097 (11)	−0.0100 (11)
C26	0.0276 (12)	0.0308 (13)	0.0465 (16)	0.0011 (10)	0.0099 (11)	−0.0051 (11)
C27	0.0380 (14)	0.0309 (13)	0.0588 (19)	0.0073 (11)	0.0108 (13)	−0.0042 (12)
C28	0.0459 (16)	0.0393 (15)	0.062 (2)	0.0135 (12)	0.0036 (14)	0.0067 (13)
C29	0.0471 (16)	0.0432 (16)	0.0513 (18)	0.0096 (12)	−0.0024 (13)	0.0034 (13)
C30	0.0439 (15)	0.0377 (14)	0.0456 (17)	0.0067 (11)	0.0004 (12)	−0.0049 (12)
C31	0.0307 (13)	0.0323 (13)	0.0435 (15)	0.0036 (10)	0.0054 (11)	−0.0034 (11)
C32	0.0340 (13)	0.0290 (12)	0.0388 (15)	0.0045 (10)	0.0013 (11)	−0.0086 (10)
C33	0.0258 (12)	0.0307 (12)	0.0353 (14)	0.0024 (9)	0.0072 (10)	−0.0071 (10)

Geometric parameters (Å, º)

Si1—C1	1.883 (3)	C12—C33	1.535 (3)
Si1—C4	1.880 (3)	C13—C14	1.376 (3)
Si1—C7	1.880 (2)	C13—C22	1.424 (3)
Si1—C10	1.837 (2)	C14—C15	1.415 (3)
O1—C12	1.439 (3)	C14—H141	1.000
O1—H1	0.944 (10)	C15—C16	1.421 (4)
O2—C23	1.238 (3)	C15—C20	1.420 (3)
C1—C2	1.529 (5)	C16—C17	1.370 (4)
C1—C3	1.532 (4)	C16—H161	1.000
C1—H11	1.000	C17—C18	1.405 (4)
C2—H21	1.000	C17—H171	1.000
C2—H22	1.000	C18—C19	1.359 (4)
C2—H23	1.000	C18—H181	1.000
C3—H31	1.000	C19—C20	1.421 (4)
C3—H32	1.000	C19—H191	1.000
C3—H33	1.000	C20—C21	1.409 (4)
C4—C5	1.536 (4)	C21—C22	1.379 (3)
C4—C6	1.533 (4)	C21—H211	1.000
C4—H41	1.000	C22—C23	1.476 (3)
C5—H51	1.000	C23—C24	1.474 (3)
C5—H52	1.000	C24—C25	1.384 (3)
C5—H53	1.000	C24—C33	1.420 (3)
C6—H61	1.000	C25—C26	1.405 (4)
C6—H62	1.000	C25—H251	1.000
C6—H63	1.000	C26—C27	1.422 (3)
C7—C8	1.540 (3)	C26—C31	1.426 (3)
C7—C9	1.536 (3)	C27—C28	1.358 (4)
C7—H71	1.000	C27—H271	1.000
C8—H81	1.000	C28—C29	1.412 (4)
C8—H82	1.000	C28—H281	1.000
C8—H83	1.000	C29—C30	1.361 (4)
C9—H91	1.000	C29—H291	1.000
C9—H92	1.000	C30—C31	1.413 (4)
C9—H93	1.000	C30—H301	1.000
C10—C11	1.206 (3)	C31—C32	1.418 (3)
C11—C12	1.486 (3)	C32—C33	1.368 (3)
C12—C13	1.528 (3)	C32—H321	1.000
C1—Si1—C4	110.52 (14)	C11—C12—C33	108.54 (19)
C1—Si1—C7	110.67 (12)	O1—C12—C33	109.28 (18)
C4—Si1—C7	115.38 (12)	C13—C12—C33	114.05 (18)
C1—Si1—C10	105.87 (12)	C12—C13—C14	118.7 (2)
C4—Si1—C10	107.88 (11)	C12—C13—C22	122.1 (2)
C7—Si1—C10	105.95 (11)	C14—C13—C22	119.2 (2)
C12—O1—H1	108.5 (18)	C13—C14—C15	121.6 (2)
Si1—C1—C2	111.6 (2)	C13—C14—H141	119.2
Si1—C1—C3	111.7 (2)	C15—C14—H141	119.2
C2—C1—C3	110.7 (3)	C14—C15—C16	122.0 (2)
Si1—C1—H11	107.6	C14—C15—C20	119.2 (2)
C2—C1—H11	107.5	C16—C15—C20	118.8 (2)
C3—C1—H11	107.5	C15—C16—C17	120.1 (3)
C1—C2—H21	109.4	C15—C16—H161	119.8
C1—C2—H22	109.4	C17—C16—H161	120.1
H21—C2—H22	109.5	C16—C17—C18	120.8 (3)
C1—C2—H23	109.6	C16—C17—H171	119.5
H21—C2—H23	109.5	C18—C17—H171	119.7
H22—C2—H23	109.5	C17—C18—C19	120.8 (3)
C1—C3—H31	109.4	C17—C18—H181	119.7
C1—C3—H32	109.6	C19—C18—H181	119.6
H31—C3—H32	109.5	C18—C19—C20	120.2 (3)
C1—C3—H33	109.4	C18—C19—H191	119.9
H31—C3—H33	109.5	C20—C19—H191	119.9
H32—C3—H33	109.5	C19—C20—C15	119.4 (2)
Si1—C4—C5	114.6 (2)	C19—C20—C21	122.2 (2)
Si1—C4—C6	113.70 (19)	C15—C20—C21	118.4 (2)
C5—C4—C6	109.5 (2)	C20—C21—C22	121.7 (2)
Si1—C4—H41	106.1	C20—C21—H211	119.1
C5—C4—H41	106.1	C22—C21—H211	119.2
C6—C4—H41	106.2	C13—C22—C21	119.9 (2)
C4—C5—H51	109.5	C13—C22—C23	121.4 (2)
C4—C5—H52	109.6	C21—C22—C23	118.8 (2)
H51—C5—H52	109.5	C22—C23—O2	121.2 (2)
C4—C5—H53	109.3	C22—C23—C24	118.7 (2)
H51—C5—H53	109.5	O2—C23—C24	120.2 (2)
H52—C5—H53	109.5	C23—C24—C25	118.9 (2)
C4—C6—H61	109.5	C23—C24—C33	121.2 (2)
C4—C6—H62	109.4	C25—C24—C33	119.8 (2)
H61—C6—H62	109.5	C24—C25—C26	121.7 (2)
C4—C6—H63	109.5	C24—C25—H251	119.1
H61—C6—H63	109.5	C26—C25—H251	119.2
H62—C6—H63	109.5	C25—C26—C27	122.5 (2)
Si1—C7—C8	112.09 (17)	C25—C26—C31	118.5 (2)
Si1—C7—C9	113.94 (17)	C27—C26—C31	119.0 (2)
C8—C7—C9	110.9 (2)	C26—C27—C28	120.6 (2)
Si1—C7—H71	106.4	C26—C27—H271	119.7
C8—C7—H71	106.5	C28—C27—H271	119.7
C9—C7—H71	106.4	C27—C28—C29	120.3 (2)
C7—C8—H81	109.5	C27—C28—H281	119.9
C7—C8—H82	109.5	C29—C28—H281	119.8
H81—C8—H82	109.5	C28—C29—C30	120.8 (3)
C7—C8—H83	109.4	C28—C29—H291	119.6
H81—C8—H83	109.5	C30—C29—H291	119.6
H82—C8—H83	109.5	C29—C30—C31	120.7 (2)
C7—C9—H91	109.5	C29—C30—H301	119.7
C7—C9—H92	109.4	C31—C30—H301	119.7
H91—C9—H92	109.5	C26—C31—C30	118.7 (2)
C7—C9—H93	109.5	C26—C31—C32	118.7 (2)
H91—C9—H93	109.5	C30—C31—C32	122.6 (2)
H92—C9—H93	109.5	C31—C32—C33	122.0 (2)
Si1—C10—C11	176.3 (2)	C31—C32—H321	118.9
C10—C11—C12	177.1 (2)	C33—C32—H321	119.1
C11—C12—O1	104.51 (17)	C12—C33—C24	122.2 (2)
C11—C12—C13	110.18 (18)	C12—C33—C32	118.50 (19)
O1—C12—C13	109.83 (19)	C24—C33—C32	119.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.94 (2)	1.81 (2)	2.746 (2)	173 (?)

Symmetry code: (i) −x+2, −y+1, −z.