Trifluoro­meth­yl derivatives of penta­cyclo­[5.4.0.0^2,6.0^3,10.0^5,9]undeca­ne

Three cage-like polycyclic compounds, viz. exo-8-(trifluoro­meth­yl)­penta­cyclo­[5.4.0.0^2,6.0^3,10.0^5,9]undecan-endo-8-ol, C₁₂H₁₃F₃O, 5-(trifluoro­meth­yl)-4-oxahexa­cyclo­[5.4.1.0^2,6.0^3,10.0^5,9.0^8,11]­dodecan-3-ol, C₁₂H₁₁F₃O₂, and N-[exo-11-(trifluoro­meth­yl)-endo-11-(trimethyl­sil­yl­oxy)­penta­cyclo­[5.4.0.0^2,6.0^3,10.0^5,9]undecan-8-yl­idene]aniline meth­anol solvate, C₂₁H₂₄F₃NOSi·CH₄O, were obtained from the corresponding oxo derivatives by nucleophilic trifluoro­methyl­ation with (tri­fluorometh­yl)trimethyl­silane in 1,2-dimethoxy­ethane solution in the presence of CsF. The crystal structures show that the addition of trifluoro­methanide occurs exclusively from the exo face of the polycyclic ketones. Further examination of the crystal structures, together with that of the starting penta­cyclo­[5.4.0.0^2,6.0^3,10.0^5,9]undecane-8,11-dione, C₁₁H₁₀O₂, showed that increasing substitution at the 8- and/or 11-positions in the cage mol­ecules increases the non-bonded intra­molecular C...C distances at the mouth of the cage and changes the puckering of the five-membered rings involving the 8- and 11-positions from an envelope towards a distorted half-chair conformation. Inter­molecular co-operative O-H...O hydrogen bonds in the endo-8-ol compound link the mol­ecules into tetra­mers.

S1. Comment

Fluorinated organic compounds are of interest because of their modified physico-chemical and biological properties in comparison with their non-fluorinated analogues (Hiyama, 2000; Maienfisch & Hall, 2004). One of the most frequently used methods for the synthesis of fluorinated molecules is trifluoromethylation (Singh & Shreeve, 2000). For nucleophilic trifluoromethylation, (trifluoromethyl)trimethylsilane (CF₃SiMe₃; Ruppert's reagent) has become the reagent of choice (Prakash & Mandal, 2001). In our recent studies, ketones with the pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane skeleton (so called 'cage' ketones; Marchand, 1995) were used as starting materials for the reaction with CF₃SiMe₃ (Romański & Mlostoń, 2005). The addition of trifluoromethanide was expected to occur from the exo face of the cage ketone, analogously to previously reported reactions with other nucleophiles [e.g. Grignard reagents (Marchand et al., 2001), trimethylsilyl cyanide (Bott, Marchand, Vidyanand & Sachleben, 1995) and amines (Bott, Marchand, Kumar et al., 1995)]. Treatment of the ketone pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecan-8-one, (I), with Ruppert's reagent in 1,2-dimethoxyethane (DME) in the presence of CsF led to a single product, which, after acidic hydrolysis, was identified as the trifluoromethylated alcohol, (II), with an exo-oriented trifluoromethyl group. Under the same conditions, the corresponding diketone, (III), was converted to the silylated acetal, (IV), regardless of the ratio of (III) and CF₃SiMe₃ (1:1 or 1:2).

After hydrolysis of compound (IV), the hemiacetal, (V), was obtained as a stable product. Obviously, the addition of trifluoromethanide to one of the carbonyl groups of (III) is followed immediately by ring closure, which results in the subsequent silylation of the second O atom. It is noteworthy that the non-cyclic hexane-2,5-dione reacts with one equivalent of CF₃SiMe₃ to give the corresponding 1:1 adduct without cyclization to the tetrahydrofuran-2-ol derivative (Singh et al., 2001), whereas the reaction with two equivalents of CF₃SiMe₃ leads to the formation of the bistrifluoromethylated diol.

In the case of the iminoketone, (VI), the addition of CF₃SiMe₃ occurred chemoselectively at the keto group, yielding product (VII), again with the CF₃ group in the exo position. In contrast to the reaction with the parent dione, (III), no cyclization via attack of the O atom at the imine C atom was observed and the silylated adduct, (VII), was isolated as the only product. The chemoselectivity observed in this reaction can be explained by the fact that typical imines are much less electrophilic than the corresponding carbonyl compounds and do not undergo trifluoromethylation with CF₃SiMe₃ (Singh & Shreeve, 2000).

The crystal structures of compounds (II), (V) and (VII) were determined in order to confirm the stereochemical outcome of the reactions described above. For comparison, the structure of the parent dione, (III), was also determined. Compound (II) (Fig. 1) crystallizes in a non-centrosymmetric space group, although the presence of glide planes dictates that the compound in the crystal is racemic. The absolute structure has not been determined and the direction of the polar axis was chosen arbitrarily. The asymmetric unit in the structure of compound (VII) contains one molecule of the cage compound plus one disordered methanol molecule. The alternate positions for the methanol molecule are approximately equally occupied, and each arrangement affords an intermolecular O—H···N hydrogen bond with the imine N atom of the same neighbouring cage molecule.

Compound (III) crystallizes with three molecules in the asymmetric unit (molecule A is defined by atoms O1, O2 and C1–C11, molecule B by atoms O21, O22 and C21–C31, and molecule C by atoms O41, O42 and C41–C51) and all have the same molecular conformation (Fig. 2). The weighted r.m.s. fit of the atomic coordinates of the three molecules is 0.030, 0.032 and 0.011 Å for the fit between molecules A and B, A and C, and B and C, respectively. The atomic coordinates of the three molecules were tested carefully for a relationship from a higher-symmetry space group by using the program PLATON (Spek, 2003), but none could be found. Although the compound is racemic because of its internal mirror symmetry, it crystallizes in a polar space group. The absolute structure, and hence the space group P3₁ instead of P3₂, was chosen arbitrarily. The validation routine of PLATON also revealed that the crystal is merohedrally twinned by a twofold rotation about the [100] axis. The twin fraction for the major twin component refined to a value of 0.780 (2). Refinement of the model without allowing for twinning led to a significantly higher R[F² > 2σ(F²)] value of 0.067.

Data for the structures of 137 molecules having the pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane skeleton and a large variety of substituents at various sites are recorded in the Cambridge Structural Database (November 2004 release; Allen, 2002). Of these, 52 are substituted only at the 8- and/or 11-positions, and in 30 of these structures, there is no bridging route through the substituents that links the 8-position to the 11-position, so that these positions form the open mouth of the cage. The cage geometry of representative examples of these compounds has been discussed by Flippen-Anderson et al. (1991), and the cage geometry of compounds (II), (III), (V) and (VII) is generally consistent with those observations. In particular, the cage C9—C10 bond, which lies across from the cyclobutane ring, and is parallel to and immediately adjacent to the C8···C11 axis, is long at around 1.59 Å [excluding compound (V); Table 1]. The long C9—C10 bond is probably a consequence of the stretching strain introduced by the open mouth of the cage formed by the adjacent atoms C8 and C11. When atoms C8 and C11 are held closer together by the oxo-bridge in compound (V), the C9—C10 bond is at its shortest. Interestingly, the C1— C7 bond, which is also immediately adjacent to the C8···C11 axis, is elongated only in compound (III). Flippen-Anderson et al. also remarked that the C—C bonds linking the substituted C atoms to the cyclubutane ring are often unusually short. In the present structures, the corresponding bonds, C7—C8 and C1—C11, are similarly short when the substituent bond involves a π system, as in the dione, (III), and for the imine-substituted C atom of (VII). In most other cases, shortening of these bonds is not observed, although the C7—C8 bond in (II), which involves the substituted C atom, is slightly shorter than the C1—C11 bond, which involves the unsubstituted C atom. The C3—C4—C5 bond angle involving the capping C atom has an average value of 95.3 (5)° across the four structures and is consistent with the observations of Flippen-Anderson et al.

The C8···C11 non-bonded intramolecular distances at the mouth of the cage reflect the congestion caused by various degrees of substitution at these atoms. In compound (V), the oxo-bridge between atoms C8 and C11 holds these atoms together at a distance of 2.172 (2) Å (Fig. 3). In the dione, (III), the environment about atoms C8 and C11 is sp²-planar, so that the steric restraints introduced by the ketone O atoms are small, and the C8···C11 distance ranges from 2.562 (4) to 2.574 (5) Å across the three symmetry-independent molecules. Compound (II) is disubstituted at atom C8 but not substituted at atom C11, and the C8···C11 distance is considerably larger at 2.749 (7) Å. In compound (VII), the C8···C11 distance is only 2.682 (2) Å, even though atom C11 is now also substituted and the trimethylsilyloxy substituent at atom C8 occupies the endo-position (Fig. 4). The shorter distance results from the reduced steric crowding afforded by the sp²-planar character of atom C11 in (VII), compared with the more bulky situation in compound (II), where atom C11 forms part of a tetrahedral methylene group.

The degree and type of substitution at atoms C8 and C11 also affects the puckering of the five-membered rings that form the sides of the cage and in which these atoms reside (Table 2). For five-membered rings, the puckering parameter ϕ₂ ideally has a value of n × 36° for an envelope conformation and (n × 36) + 18° for a half-chair conformation (n is an integer?). In compound (V), which displays the shortest C8···C11 distance and has the constraint of the oxo-bridge, the rings defined by the atom sequences C5—C6—C7—C8—C9 and C1—C2—C3—C10—C11 have almost ideal envelope conformations, puckered on atoms C9 and C10, respectively. In (III), the corresponding rings in molecule A also have similar envelope conformations, but the increase in the C8···C11 distance caused by the opening out of the mouth of the cage has moved atoms C8 and C11 out of the planes of atoms C5, C6 and C7 and atoms C1, C2 and C3, respectively, so that the envelope conformations have become distorted towards half-chair conformations twisted on C8—C9 and C10—C11, respectively. The other two symmetry-independent molecules have almost identical conformations. In (II), the five-membered ring containing the substituted C atom, C8, has an almost ideal half-chair conformation twisted on C8—C9, while the ring containing the unsubstituted C atom can best be described by a half-chair conformation twisted on C10—C11, but distorted somewhat towards an envelope conformation puckered on atom C10. The corresponding five-membered rings in compound (VII) are best described as being distorted half-chairs twisted on C8—C9 and C10—C11, with the puckering distorted to a point almost half way between that of a half-chair and an envelope puckered on atoms C9 and C10, respectively.

A significant feature of the structure of (II) is the O—H···O hydrogen bonding (Table 3). The hydroxy O atom is within hydrogen-bonding distance of the hydroxy O atoms of two neighbouring molecules. Although no obvious positions for the hydroxy H atom could be detected in the peaks lists obtained from any difference Fourier maps, a contoured map showed a hint of residual electron density on opposing sides of the O atom and in positions that would be consistent with O—H···O hydrogen bonds to both neighbouring molecules. Including either one of these positions for the hydroxy H atom in the model generates unreasonably short intermolecular O—H···H—O distances, because the symmetry relationships between adjacent molecules always result in the hydroxy H atoms in these adjacent molecules pointing at one another. Introducing equally occupied disordered sites for the hydroxy H atom, with the O—H vectors pointing in opposite directions and at both neighbouring hydroxy O atoms, alleviates the close contact issue, because neither H-atom site in the H···H contact would need to be occupied simultaneously. The propagation of the interactions leads to a loop of cooperative O—H···O hydrogen bonds, which link four molecules into a tetrameric unit (Fig. 5). The disorder of the H-atom positions represents two alternate directions of the O—H···O pattern around the loop. The hydrogen-bonding pattern can be described by the graph-set motif (Bernstein et al., 1995) of R₄⁴(8).

The hydroxy group in (V) forms an intermolecular hydrogen bond with the oxo O atom of a neighbouring molecule and thereby links pairs of molecules across a centre of inversion into dimers, which can be described by the hydrogen-bonding motif R₂²(8).

S2. Experimental

The starting ketones, (I) and (III), were prepared according to published procedures (Cookson et al., 1964; Romański et al., 2005). Crystals of (III) suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate solution at room temperature (m.p. 413–415 K). Compound (VI) was prepared by heating (III) with aniline in boiling benzene, analogously to a literature protocol (Sasaki et al., 1974), and was used for further reaction without purification. The reactions of ketones (I) and (III), as well as aminoketone (VI), with (trifluoromethyl)trimethylsilane were performed in absolute 1,2-dimethoxyethane (DME) under an argon atmosphere in the presence of catalytic amounts (ca 10 mol%) of caesium fluoride, which had been dried by preheating at 423 K for several hours (Romański & Mlostoń, 2005). After evaporation of the solvent, the residues obtained from ketones (I) and (III) were hydrolyzed by stirring with 4 N HCl to give (II) and (V), respectively. Suitable crystals of these compounds were obtained by slow evaporation of their hexane/dichloromethane and methanol solutions, respectively, at room temperature [m.p. 399–400 and 389–390 K for (II) and (V), respectively]. In the case where (VI) was the starting ketone, the product (VII), obtained after evaporation of DME, was also crystallized by slow evaporation of a methanol solution at room temperature (m.p. 414–415 K).

S3. Refinement

The merohedral twinning in the structure of (III) was treated by employing the twin matrix [1 1 0 / 0 − 1 0 / 0 0 − 1]. The asymmetric unit in the structure of compound (VII) contains one molecule of the cage compound plus one disordered methanol molecule. Two sets of overlapping positions were defined for the atoms of the methanol molecule, and refinement of the site occupation factors led to a value of 0.53 (1) for the major orientation. Similarity restraints were applied to the C—O bond lengths and the atomic displacement parameters of the C and O atoms of each orientation of the methanol molecule.

The hydroxy H atom in compound (V) was located in a difference Fourier map and its position and isotropic displacement parameter were refined. In order to obviate unreasonably short intermolecular O—H···H—O distances in compound (II), the hydroxy H atom must be disordered over two equally occupied sites with the O—H vectors pointing in opposite directions. Both positions for the disordered hydroxy H atom in (II) were initially defined to correspond with the direction that would bring each H atom closest to its nearest hydrogen-bond acceptor. The positions were then constrained to an ideal geometry [O—H = 0.84 Å, with U_iso(H) = 1.5U_eq(O)] and subsequently were allowed to rotate freely about the parent O—C bond. The hydroxy H atoms in the disordered methanol molecule of (VII) were treated in the same way. All methyl H atoms in the structure of (VII) were constrained to an ideal geometry [C—H = 0.98 Å, with U_iso(H) = 1.5U_eq(C)] but were allowed to rotate freely about the parent Si—C or O—C bonds. All other H atoms in the structures were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.95–1.00 Å and U_iso(H) = 1.2U_eq(C).

Compounds (II) and (III) crystallize in non-centrosymmetric space groups. Owing to the absence of any significant anomalous scatterers in these compounds, attempts to confirm the absolute structure by refinement of the Flack (1983) parameter in the presence of 1052 [(for (II)] and 2460 [for (III)] sets of Friedel equivalents led to inconclusive values (Flack & Bernardinelli, 2000) for this parameter [0.3 (14) and 0.4 (9), respectively]. Therefore, the Friedel pairs were merged before the final refinement for (II) and (III), and the absolute structure was assigned arbitrarily. For compounds (II), (III), (V) and (VII), four, one, two and eight low-angle reflections, respectively, were omitted from the final cycles of refinement because their observed intensities were much lower than the calculated values as a result of being partially obscured by the beam stop.

Computing details

For all compounds, data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. View of the molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by circles of arbitrary size and only one of the disordered hydroxy H atoms is shown.
	Fig. 2. View of one of the three symmetry-independent molecules (molecule A) of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size.
	Fig. 3. View of the molecule of (V), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size.
	Fig. 4. View of the molecule of (VII), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size and the disordered methanol molecule has been omitted for clarity.
	Fig. 5. The hydrogen-bonded tetramer in the structure of (II). All H atoms have been omitted for clarity.

(II) exo-8-(trifluoromethyl)pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecan- endo-8-ol

Crystal data

C12H13F3O	Dx = 1.515 Mg m^−3
Mr = 230.23	Melting point: 399 K
Tetragonal, I4c2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I -4 -2c	Cell parameters from 1354 reflections
a = 14.1311 (3) Å	θ = 2.0–27.5°
c = 20.2206 (6) Å	µ = 0.13 mm^−1
V = 4037.81 (17) Å^3	T = 160 K
Z = 16	Block, colourless
F(000) = 1920	0.30 × 0.23 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer	1036 reflections with I > 2σ(I)
Radiation source: Nonius FR590 sealed tube generator	Rint = 0.062
Horizontally mounted graphite crystal monochromator	θmax = 27.5°, θmin = 2.0°
Detector resolution: 9 pixels mm^-1	h = −18→16
ϕ and ω scans with κ offsets	k = −18→16
23516 measured reflections	l = −26→25
1262 independent reflections

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.174	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0974P)^2 + 4.4956P] where P = (Fo^2 + 2Fc^2)/3
1258 reflections	(Δ/σ)max = 0.001
146 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

Experimental. Solvent used: hexane / dichloromethane Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.433 (2) Frames collected: 162 Seconds exposure per frame: 14 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 30.0

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
F1	0.5884 (3)	0.2492 (2)	0.10813 (19)	0.0783 (11)
F2	0.5033 (2)	0.1522 (2)	0.16398 (15)	0.0728 (9)
F3	0.63411 (19)	0.2029 (2)	0.20297 (14)	0.0637 (9)
O1	0.5751 (2)	0.0591 (2)	0.06563 (14)	0.0508 (8)
H1A	0.5248	0.0429	0.0846	0.076*	0.50
H1B	0.5939	0.0746	0.0277	0.076*	0.50
C1	0.7176 (4)	−0.0725 (3)	0.1315 (3)	0.0624 (14)
H1	0.6952	−0.1355	0.1476	0.075*
C2	0.8137 (4)	−0.0390 (3)	0.1603 (3)	0.0575 (13)
H2	0.8484	−0.0834	0.1903	0.069*
C3	0.8679 (3)	0.0030 (5)	0.1027 (2)	0.0606 (13)
H3	0.9198	−0.0378	0.0850	0.073*
C4	0.8990 (3)	0.0989 (4)	0.1269 (3)	0.0567 (12)
H41	0.9264	0.1386	0.0913	0.068*
H42	0.9430	0.0953	0.1649	0.068*
C5	0.8001 (3)	0.1302 (3)	0.1468 (2)	0.0442 (10)
H5	0.7964	0.1949	0.1666	0.053*
C6	0.7666 (3)	0.0503 (3)	0.1920 (2)	0.0422 (10)
H6	0.7725	0.0593	0.2409	0.051*
C7	0.6689 (3)	0.0141 (3)	0.16370 (19)	0.0428 (9)
H7	0.6195	−0.0009	0.1975	0.051*
C8	0.6417 (3)	0.0890 (3)	0.11330 (17)	0.0319 (8)
C9	0.7381 (3)	0.1151 (3)	0.08444 (19)	0.0388 (9)
H9	0.7362	0.1713	0.0544	0.047*
C10	0.7871 (3)	0.0254 (4)	0.0525 (2)	0.0568 (14)
H10	0.8115	0.0380	0.0069	0.068*
C11	0.7300 (4)	−0.0642 (4)	0.0566 (3)	0.0660 (16)
H111	0.7650	−0.1189	0.0382	0.079*
H112	0.6684	−0.0579	0.0337	0.079*
C12	0.5932 (3)	0.1719 (3)	0.1472 (2)	0.0443 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.086 (2)	0.0557 (17)	0.093 (2)	0.0283 (16)	0.006 (2)	0.0158 (17)
F2	0.0392 (14)	0.097 (2)	0.0825 (19)	−0.0057 (16)	0.0170 (15)	−0.0316 (17)
F3	0.0522 (16)	0.0742 (19)	0.0648 (16)	0.0068 (13)	−0.0047 (13)	−0.0382 (15)
O1	0.0428 (17)	0.068 (2)	0.0413 (14)	−0.0014 (14)	−0.0144 (13)	−0.0143 (15)
C1	0.062 (3)	0.035 (2)	0.090 (4)	0.003 (2)	−0.020 (3)	−0.003 (2)
C2	0.056 (3)	0.042 (2)	0.074 (3)	0.0053 (19)	−0.018 (3)	0.003 (2)
C3	0.033 (2)	0.076 (3)	0.073 (3)	0.011 (2)	−0.004 (2)	−0.029 (3)
C4	0.039 (2)	0.067 (3)	0.064 (3)	−0.002 (2)	0.001 (2)	−0.004 (3)
C5	0.036 (2)	0.039 (2)	0.058 (3)	−0.0048 (16)	−0.0084 (19)	−0.0054 (18)
C6	0.038 (2)	0.054 (3)	0.0350 (19)	0.0012 (17)	−0.0086 (17)	−0.0002 (18)
C7	0.049 (2)	0.038 (2)	0.0409 (19)	−0.0070 (17)	−0.0116 (19)	0.0045 (17)
C8	0.0298 (17)	0.0392 (19)	0.0268 (16)	−0.0067 (14)	−0.0068 (14)	−0.0034 (15)
C9	0.035 (2)	0.043 (2)	0.0382 (19)	−0.0039 (16)	0.0033 (16)	−0.0029 (17)
C10	0.041 (2)	0.077 (4)	0.053 (2)	0.008 (2)	0.002 (2)	−0.027 (2)
C11	0.058 (3)	0.059 (3)	0.082 (4)	0.015 (2)	−0.016 (3)	−0.040 (3)
C12	0.040 (2)	0.046 (2)	0.047 (2)	0.0020 (17)	0.0024 (18)	−0.006 (2)

Geometric parameters (Å, º)

F1—C12	1.350 (5)	C4—H41	0.9900
F2—C12	1.343 (5)	C4—H42	0.9900
F3—C12	1.341 (5)	C5—C6	1.527 (6)
O1—C8	1.412 (4)	C5—C9	1.551 (6)
O1—H1A	0.8400	C5—H5	1.0000
O1—H1B	0.8400	C6—C7	1.580 (5)
C1—C7	1.548 (7)	C6—H6	1.0000
C1—C11	1.530 (9)	C7—C8	1.518 (5)
C1—C2	1.551 (7)	C7—H7	1.0000
C1—H1	1.0000	C8—C12	1.520 (5)
C2—C3	1.514 (8)	C8—C9	1.527 (5)
C2—C6	1.565 (6)	C9—C10	1.582 (6)
C2—H2	1.0000	C9—H9	1.0000
C3—C4	1.507 (8)	C10—C11	1.504 (8)
C3—C10	1.560 (7)	C10—H10	1.0000
C3—H3	1.0000	C11—H111	0.9900
C4—C5	1.519 (6)	C11—H112	0.9900
C8—O1—H1A	109.5	C7—C6—H6	118.1
C8—O1—H1B	109.5	C8—C7—C1	112.4 (4)
C11—C1—C7	114.0 (4)	C8—C7—C6	103.8 (3)
C11—C1—C2	104.4 (5)	C1—C7—C6	91.1 (3)
C7—C1—C2	89.5 (4)	C8—C7—H7	115.5
C11—C1—H1	115.2	C1—C7—H7	115.5
C7—C1—H1	115.2	C6—C7—H7	115.5
C2—C1—H1	115.2	O1—C8—C7	114.7 (3)
C3—C2—C1	105.9 (4)	O1—C8—C12	103.7 (3)
C3—C2—C6	102.3 (4)	C7—C8—C12	110.4 (3)
C1—C2—C6	91.5 (4)	O1—C8—C9	114.0 (3)
C3—C2—H2	117.7	C7—C8—C9	101.5 (3)
C1—C2—H2	117.7	C12—C8—C9	112.9 (3)
C6—C2—H2	117.7	C8—C9—C5	103.1 (3)
C4—C3—C2	104.5 (4)	C8—C9—C10	110.7 (3)
C4—C3—C10	104.0 (5)	C5—C9—C10	101.2 (3)
C2—C3—C10	102.2 (4)	C8—C9—H9	113.6
C4—C3—H3	114.9	C5—C9—H9	113.6
C2—C3—H3	114.9	C10—C9—H9	113.6
C10—C3—H3	114.9	C11—C10—C3	100.7 (5)
C3—C4—C5	94.6 (4)	C11—C10—C9	114.7 (4)
C3—C4—H41	112.8	C3—C10—C9	102.5 (3)
C5—C4—H41	112.8	C11—C10—H10	112.6
C3—C4—H42	112.8	C3—C10—H10	112.6
C5—C4—H42	112.8	C9—C10—H10	112.6
H41—C4—H42	110.3	C10—C11—C1	100.4 (4)
C4—C5—C6	103.2 (4)	C10—C11—H111	111.7
C4—C5—C9	105.3 (4)	C1—C11—H111	111.7
C6—C5—C9	102.1 (3)	C10—C11—H112	111.7
C4—C5—H5	114.9	C1—C11—H112	111.7
C6—C5—H5	114.9	H111—C11—H112	109.5
C9—C5—H5	114.9	F3—C12—F2	105.2 (3)
C5—C6—C2	102.7 (3)	F3—C12—F1	104.4 (4)
C5—C6—C7	107.1 (3)	F2—C12—F1	105.5 (4)
C2—C6—C7	87.8 (3)	F3—C12—C8	115.9 (4)
C5—C6—H6	118.1	F2—C12—C8	112.4 (3)
C2—C6—H6	118.1	F1—C12—C8	112.5 (3)
C11—C1—C2—C3	10.2 (5)	C6—C7—C8—C9	36.3 (4)
C7—C1—C2—C3	−104.5 (4)	O1—C8—C9—C5	−171.9 (3)
C11—C1—C2—C6	113.5 (4)	C7—C8—C9—C5	−48.0 (4)
C7—C1—C2—C6	−1.2 (4)	C12—C8—C9—C5	70.1 (4)
C1—C2—C3—C4	128.7 (4)	O1—C8—C9—C10	−64.4 (4)
C6—C2—C3—C4	33.5 (4)	C7—C8—C9—C10	59.5 (4)
C1—C2—C3—C10	20.6 (5)	C12—C8—C9—C10	177.6 (3)
C6—C2—C3—C10	−74.6 (4)	C4—C5—C9—C8	147.4 (3)
C2—C3—C4—C5	−53.5 (4)	C6—C5—C9—C8	39.8 (4)
C10—C3—C4—C5	53.3 (4)	C4—C5—C9—C10	32.8 (5)
C3—C4—C5—C6	53.3 (4)	C6—C5—C9—C10	−74.7 (4)
C3—C4—C5—C9	−53.4 (4)	C4—C3—C10—C11	−153.3 (4)
C4—C5—C6—C2	−34.3 (4)	C2—C3—C10—C11	−44.7 (5)
C9—C5—C6—C2	74.8 (4)	C4—C3—C10—C9	−34.8 (5)
C4—C5—C6—C7	−125.9 (4)	C2—C3—C10—C9	73.8 (5)
C9—C5—C6—C7	−16.8 (4)	C8—C9—C10—C11	0.4 (6)
C3—C2—C6—C5	0.8 (4)	C5—C9—C10—C11	109.2 (5)
C1—C2—C6—C5	−105.8 (4)	C8—C9—C10—C3	−107.7 (4)
C3—C2—C6—C7	107.8 (4)	C5—C9—C10—C3	1.1 (5)
C1—C2—C6—C7	1.2 (4)	C3—C10—C11—C1	50.9 (4)
C11—C1—C7—C8	1.1 (6)	C9—C10—C11—C1	−58.4 (5)
C2—C1—C7—C8	106.6 (4)	C7—C1—C11—C10	57.9 (5)
C11—C1—C7—C6	−104.3 (5)	C2—C1—C11—C10	−38.1 (4)
C2—C1—C7—C6	1.2 (4)	O1—C8—C12—F3	168.3 (3)
C5—C6—C7—C8	−12.0 (4)	C7—C8—C12—F3	44.9 (4)
C2—C6—C7—C8	−114.6 (4)	C9—C8—C12—F3	−67.9 (4)
C5—C6—C7—C1	101.4 (4)	O1—C8—C12—F2	47.2 (4)
C2—C6—C7—C1	−1.2 (4)	C7—C8—C12—F2	−76.2 (4)
C1—C7—C8—O1	62.6 (5)	C9—C8—C12—F2	171.1 (3)
C6—C7—C8—O1	159.7 (3)	O1—C8—C12—F1	−71.7 (4)
C1—C7—C8—C12	179.4 (4)	C7—C8—C12—F1	164.9 (3)
C6—C7—C8—C12	−83.6 (4)	C9—C8—C12—F1	52.1 (5)
C1—C7—C8—C9	−60.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O1^i	0.84	2.05	2.701 (6)	133
O1—H1B···O1^ii	0.84	1.95	2.673 (6)	144

Symmetry codes: (i) −x+1, −y, z; (ii) y+1/2, x−1/2, −z.

(III) pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane-8,11-dione

Crystal data

C11H10O2	Dx = 1.427 Mg m^−3
Mr = 174.20	Melting point: 414 K
Trigonal, P31	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 31	Cell parameters from 3543 reflections
a = 18.0861 (4) Å	θ = 2.0–30.0°
c = 6.4388 (1) Å	µ = 0.10 mm^−1
V = 1824.00 (6) Å^3	T = 160 K
Z = 9	Block, colourless
F(000) = 828	0.35 × 0.30 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer	3128 reflections with I > 2σ(I)
Radiation source: Nonius FR590 sealed tube generator	Rint = 0.054
Horizontally mounted graphite crystal monochromator	θmax = 30.0°, θmin = 2.6°
Detector resolution: 9 pixels mm^-1	h = −25→25
ϕ and ω scans with κ offsets	k = −25→25
28695 measured reflections	l = −8→9
3543 independent reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0544P)^2 + 0.1521P] where P = (Fo^2 + 2Fc^2)/3
3542 reflections	(Δ/σ)max = 0.001
353 parameters	Δρmax = 0.28 e Å^−3
1 restraint	Δρmin = −0.21 e Å^−3

Special details

Experimental. Solvent used: ethyl acetate Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.438 (1) Frames collected: 209 Seconds exposure per frame: 14 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 30.0

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1	0.77113 (17)	0.71933 (15)	0.1055 (4)	0.0425 (6)
O2	0.92397 (14)	0.72917 (14)	0.5467 (4)	0.0373 (5)
C1	0.89022 (18)	0.62783 (17)	0.2635 (4)	0.0237 (5)
H1	0.9512	0.6501	0.2241	0.028*
C2	0.83414 (18)	0.52974 (17)	0.2976 (4)	0.0255 (6)
H2	0.8625	0.4947	0.2814	0.031*
C3	0.78075 (18)	0.51589 (19)	0.4978 (4)	0.0288 (6)
H3	0.8006	0.4983	0.6236	0.035*
C4	0.69002 (19)	0.4534 (2)	0.4273 (5)	0.0342 (7)
H41	0.6467	0.4455	0.5325	0.041*
H42	0.6826	0.3974	0.3856	0.041*
C5	0.69094 (19)	0.5066 (2)	0.2421 (5)	0.0315 (7)
H5	0.6373	0.4810	0.1580	0.038*
C6	0.77256 (18)	0.52392 (18)	0.1220 (4)	0.0266 (6)
H6	0.7649	0.4857	0.0019	0.032*
C7	0.8271 (2)	0.62167 (19)	0.0846 (4)	0.0273 (6)
H7	0.8523	0.6404	−0.0572	0.033*
C8	0.77205 (19)	0.6563 (2)	0.1637 (5)	0.0281 (6)
C9	0.71889 (18)	0.5954 (2)	0.3353 (4)	0.0269 (6)
H9	0.6704	0.6029	0.3833	0.032*
C10	0.78204 (18)	0.60212 (19)	0.5160 (4)	0.0261 (6)
H10	0.7657	0.6128	0.6565	0.031*
C11	0.87358 (18)	0.66511 (18)	0.4552 (4)	0.0234 (5)
O21	0.46342 (15)	1.06201 (15)	0.1120 (4)	0.0371 (5)
O22	0.60382 (15)	1.05719 (15)	0.5569 (4)	0.0370 (5)
C21	0.57026 (18)	0.95649 (18)	0.2704 (4)	0.0243 (5)
H21	0.6312	0.9758	0.2361	0.029*
C22	0.50915 (17)	0.85917 (18)	0.2924 (4)	0.0253 (6)
H22	0.5342	0.8213	0.2738	0.030*
C23	0.45281 (19)	0.84396 (19)	0.4873 (4)	0.0285 (6)
H23	0.4681	0.8211	0.6115	0.034*
C24	0.36244 (19)	0.78793 (19)	0.4057 (5)	0.0324 (7)
H241	0.3183	0.7805	0.5078	0.039*
H242	0.3519	0.7316	0.3566	0.039*
C25	0.37094 (18)	0.84745 (19)	0.2275 (5)	0.0287 (6)
H25	0.3192	0.8271	0.1380	0.034*
C26	0.45236 (18)	0.86103 (18)	0.1140 (4)	0.0259 (6)
H26	0.4441	0.8243	−0.0098	0.031*
C27	0.51229 (19)	0.95882 (18)	0.0873 (4)	0.0255 (6)
H27	0.5401	0.9791	−0.0513	0.031*
C28	0.46089 (17)	0.99713 (19)	0.1682 (4)	0.0239 (5)
C29	0.40282 (18)	0.93527 (19)	0.3324 (4)	0.0261 (6)
H29	0.3561	0.9457	0.3791	0.031*
C30	0.46075 (18)	0.93279 (19)	0.5169 (4)	0.0253 (6)
H30	0.4435	0.9419	0.6579	0.030*
C31	0.55392 (18)	0.99339 (18)	0.4644 (4)	0.0239 (6)
O41	0.27325 (14)	0.39197 (14)	0.4981 (4)	0.0377 (6)
O42	0.12602 (15)	0.39195 (14)	0.0593 (3)	0.0358 (5)
C41	0.05919 (18)	0.29318 (18)	0.3491 (4)	0.0233 (5)
H411	0.0194	0.3146	0.3850	0.028*
C42	0.01970 (17)	0.19496 (17)	0.3295 (4)	0.0236 (5)
H421	−0.0433	0.1589	0.3516	0.028*
C43	0.05755 (19)	0.17740 (19)	0.1305 (4)	0.0266 (6)
H43	0.0182	0.1552	0.0083	0.032*
C44	0.0903 (2)	0.11933 (19)	0.2110 (5)	0.0319 (6)
H441	0.0437	0.0637	0.2617	0.038*
H442	0.1253	0.1102	0.1071	0.038*
C45	0.14349 (19)	0.17801 (18)	0.3865 (5)	0.0271 (6)
H45	0.1746	0.1566	0.4737	0.033*
C46	0.07882 (18)	0.19550 (18)	0.5050 (4)	0.0249 (6)
H46	0.0507	0.1598	0.6304	0.030*
C47	0.11962 (18)	0.29416 (18)	0.5285 (4)	0.0235 (5)
H47	0.1144	0.3160	0.6672	0.028*
C48	0.20857 (18)	0.32850 (18)	0.4431 (4)	0.0245 (6)
C49	0.20045 (18)	0.26551 (18)	0.2791 (4)	0.0239 (5)
H49	0.2564	0.2739	0.2285	0.029*
C50	0.13975 (18)	0.26486 (18)	0.0986 (4)	0.0246 (6)
H50	0.1649	0.2729	−0.0436	0.030*
C51	0.11133 (18)	0.32791 (18)	0.1529 (4)	0.0243 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0497 (15)	0.0364 (13)	0.0499 (14)	0.0279 (11)	−0.0061 (11)	0.0081 (11)
O2	0.0326 (12)	0.0335 (12)	0.0460 (12)	0.0167 (10)	−0.0126 (10)	−0.0171 (10)
C1	0.0254 (13)	0.0236 (13)	0.0248 (13)	0.0142 (12)	−0.0011 (10)	−0.0016 (10)
C2	0.0232 (13)	0.0197 (12)	0.0337 (15)	0.0110 (11)	0.0016 (11)	0.0011 (11)
C3	0.0262 (14)	0.0291 (15)	0.0294 (14)	0.0125 (12)	0.0055 (11)	0.0088 (11)
C4	0.0272 (15)	0.0284 (15)	0.0413 (17)	0.0096 (13)	0.0067 (13)	0.0072 (12)
C5	0.0224 (13)	0.0347 (16)	0.0365 (16)	0.0135 (12)	−0.0037 (12)	−0.0021 (13)
C6	0.0265 (14)	0.0256 (13)	0.0260 (13)	0.0119 (11)	−0.0023 (10)	−0.0058 (10)
C7	0.0296 (14)	0.0313 (15)	0.0223 (12)	0.0162 (12)	−0.0028 (11)	0.0002 (11)
C8	0.0260 (14)	0.0325 (15)	0.0277 (14)	0.0161 (13)	−0.0083 (11)	−0.0016 (12)
C9	0.0206 (13)	0.0354 (16)	0.0280 (14)	0.0163 (12)	−0.0023 (11)	−0.0005 (12)
C10	0.0259 (14)	0.0350 (15)	0.0184 (12)	0.0161 (12)	0.0010 (10)	−0.0021 (11)
C11	0.0260 (14)	0.0251 (14)	0.0227 (12)	0.0154 (12)	−0.0030 (10)	−0.0036 (10)
O21	0.0397 (13)	0.0343 (12)	0.0442 (13)	0.0238 (11)	−0.0012 (10)	0.0087 (10)
O22	0.0352 (12)	0.0336 (12)	0.0356 (12)	0.0124 (10)	−0.0142 (9)	−0.0092 (9)
C21	0.0210 (12)	0.0255 (14)	0.0270 (13)	0.0121 (11)	0.0006 (10)	0.0007 (11)
C22	0.0230 (13)	0.0235 (13)	0.0313 (14)	0.0131 (11)	0.0000 (11)	−0.0013 (11)
C23	0.0291 (15)	0.0285 (15)	0.0278 (14)	0.0144 (12)	0.0030 (11)	0.0058 (11)
C24	0.0274 (15)	0.0271 (15)	0.0371 (16)	0.0093 (12)	0.0070 (12)	0.0043 (12)
C25	0.0205 (13)	0.0291 (15)	0.0328 (15)	0.0096 (12)	−0.0002 (11)	−0.0008 (12)
C26	0.0241 (13)	0.0246 (14)	0.0257 (14)	0.0096 (11)	−0.0005 (11)	−0.0051 (11)
C27	0.0261 (14)	0.0274 (14)	0.0236 (13)	0.0138 (12)	0.0006 (10)	0.0020 (11)
C28	0.0213 (13)	0.0269 (14)	0.0233 (13)	0.0118 (11)	−0.0054 (11)	−0.0008 (11)
C29	0.0236 (14)	0.0302 (15)	0.0276 (14)	0.0158 (12)	0.0000 (11)	0.0019 (11)
C30	0.0240 (14)	0.0312 (15)	0.0195 (13)	0.0128 (12)	0.0012 (10)	0.0001 (11)
C31	0.0239 (14)	0.0268 (14)	0.0234 (13)	0.0145 (12)	−0.0041 (10)	0.0003 (11)
O41	0.0262 (11)	0.0334 (12)	0.0477 (14)	0.0105 (10)	−0.0089 (10)	−0.0069 (10)
O42	0.0377 (12)	0.0323 (12)	0.0386 (13)	0.0184 (10)	0.0006 (10)	0.0118 (10)
C41	0.0232 (13)	0.0264 (13)	0.0240 (13)	0.0152 (12)	0.0005 (10)	0.0005 (11)
C42	0.0213 (13)	0.0229 (13)	0.0273 (13)	0.0117 (11)	0.0001 (11)	0.0001 (11)
C43	0.0241 (14)	0.0291 (14)	0.0261 (14)	0.0129 (12)	−0.0020 (11)	−0.0055 (11)
C44	0.0310 (16)	0.0242 (14)	0.0423 (17)	0.0150 (13)	0.0040 (13)	−0.0060 (13)
C45	0.0300 (14)	0.0267 (14)	0.0306 (14)	0.0187 (12)	0.0007 (12)	0.0038 (12)
C46	0.0257 (14)	0.0242 (13)	0.0247 (14)	0.0125 (11)	0.0042 (11)	0.0035 (11)
C47	0.0269 (14)	0.0261 (14)	0.0203 (12)	0.0154 (12)	0.0003 (10)	−0.0021 (10)
C48	0.0234 (13)	0.0252 (13)	0.0257 (13)	0.0129 (11)	−0.0040 (10)	0.0015 (11)
C49	0.0226 (13)	0.0283 (14)	0.0248 (13)	0.0158 (11)	−0.0002 (10)	0.0009 (11)
C50	0.0248 (13)	0.0288 (14)	0.0200 (13)	0.0132 (12)	0.0011 (10)	0.0001 (11)
C51	0.0226 (13)	0.0263 (14)	0.0239 (13)	0.0121 (11)	−0.0044 (10)	0.0018 (11)

Geometric parameters (Å, º)

O1—C8	1.207 (4)	C24—H242	0.9900
O2—C11	1.210 (3)	C25—C29	1.548 (4)
C1—C2	1.557 (4)	C25—C26	1.549 (4)
C1—C7	1.585 (4)	C25—H25	1.0000
C1—C11	1.508 (4)	C26—C27	1.554 (4)
C1—H1	1.0000	C26—H26	1.0000
C2—C6	1.553 (4)	C27—C28	1.503 (4)
C2—C3	1.554 (4)	C27—H27	1.0000
C2—H2	1.0000	C28—C29	1.516 (4)
C3—C4	1.523 (4)	C29—C30	1.599 (4)
C3—C10	1.553 (4)	C29—H29	1.0000
C3—H3	1.0000	C30—C31	1.519 (4)
C4—C5	1.527 (4)	C30—H30	1.0000
C4—H41	0.9900	O41—C48	1.212 (3)
C4—H42	0.9900	O42—C51	1.212 (3)
C5—C9	1.544 (4)	C41—C42	1.553 (4)
C5—C6	1.553 (4)	C41—C47	1.584 (4)
C5—H5	1.0000	C41—C51	1.512 (4)
C6—C7	1.553 (4)	C41—H411	1.0000
C6—H6	1.0000	C42—C46	1.552 (4)
C7—C8	1.507 (4)	C42—C43	1.558 (4)
C7—H7	1.0000	C42—H421	1.0000
C8—C9	1.517 (4)	C43—C44	1.531 (4)
C9—C10	1.592 (4)	C43—C50	1.550 (4)
C9—H9	1.0000	C43—H43	1.0000
C10—C11	1.519 (4)	C44—C45	1.519 (4)
C10—H10	1.0000	C44—H441	0.9900
O21—C28	1.207 (4)	C44—H442	0.9900
O22—C31	1.208 (4)	C45—C49	1.554 (4)
C21—C22	1.547 (4)	C45—C46	1.555 (4)
C21—C27	1.592 (4)	C45—H45	1.0000
C21—C31	1.513 (4)	C46—C47	1.560 (4)
C21—H21	1.0000	C46—H46	1.0000
C22—C23	1.552 (4)	C47—C48	1.509 (4)
C22—C26	1.553 (4)	C47—H47	1.0000
C22—H22	1.0000	C48—C49	1.506 (4)
C23—C24	1.523 (4)	C49—C50	1.595 (4)
C23—C30	1.552 (4)	C49—H49	1.0000
C23—H23	1.0000	C50—C51	1.508 (4)
C24—C25	1.528 (4)	C50—H50	1.0000
C24—H241	0.9900
C11—C1—C2	103.4 (2)	C25—C26—C22	103.6 (2)
C11—C1—C7	109.2 (2)	C25—C26—C27	107.4 (2)
C2—C1—C7	89.2 (2)	C22—C26—C27	90.8 (2)
C11—C1—H1	117.0	C25—C26—H26	117.1
C2—C1—H1	117.0	C22—C26—H26	117.1
C7—C1—H1	117.0	C27—C26—H26	117.1
C6—C2—C3	103.1 (2)	C28—C27—C26	104.2 (2)
C6—C2—C1	90.6 (2)	C28—C27—C21	108.8 (2)
C3—C2—C1	107.4 (2)	C26—C27—C21	89.0 (2)
C6—C2—H2	117.3	C28—C27—H27	117.0
C3—C2—H2	117.3	C26—C27—H27	117.0
C1—C2—H2	117.3	C21—C27—H27	117.0
C4—C3—C10	103.7 (2)	O21—C28—C27	127.8 (3)
C4—C3—C2	103.0 (2)	O21—C28—C29	127.0 (3)
C10—C3—C2	101.8 (2)	C27—C28—C29	105.2 (2)
C4—C3—H3	115.5	C28—C29—C25	102.6 (2)
C10—C3—H3	115.5	C28—C29—C30	108.5 (2)
C2—C3—H3	115.5	C25—C29—C30	102.0 (2)
C3—C4—C5	95.6 (2)	C28—C29—H29	114.2
C3—C4—H41	112.6	C25—C29—H29	114.2
C5—C4—H41	112.6	C30—C29—H29	114.2
C3—C4—H42	112.6	C31—C30—C23	102.4 (2)
C5—C4—H42	112.6	C31—C30—C29	108.7 (2)
H41—C4—H42	110.1	C23—C30—C29	102.4 (2)
C4—C5—C9	104.2 (2)	C31—C30—H30	114.0
C4—C5—C6	103.1 (2)	C23—C30—H30	114.0
C9—C5—C6	101.5 (2)	C29—C30—H30	114.0
C4—C5—H5	115.4	O22—C31—C21	127.7 (3)
C9—C5—H5	115.4	O22—C31—C30	127.5 (3)
C6—C5—H5	115.4	C21—C31—C30	104.8 (2)
C5—C6—C7	107.8 (2)	C51—C41—C42	104.0 (2)
C5—C6—C2	103.2 (2)	C51—C41—C47	108.7 (2)
C7—C6—C2	90.6 (2)	C42—C41—C47	89.6 (2)
C5—C6—H6	117.2	C51—C41—H411	116.9
C7—C6—H6	117.2	C42—C41—H411	116.9
C2—C6—H6	117.2	C47—C41—H411	116.9
C8—C7—C6	104.2 (2)	C46—C42—C41	90.7 (2)
C8—C7—C1	109.1 (2)	C46—C42—C43	103.2 (2)
C6—C7—C1	89.6 (2)	C41—C42—C43	107.6 (2)
C8—C7—H7	116.8	C46—C42—H421	117.2
C6—C7—H7	116.8	C41—C42—H421	117.2
C1—C7—H7	116.8	C43—C42—H421	117.2
O1—C8—C7	127.7 (3)	C44—C43—C50	104.0 (2)
O1—C8—C9	127.5 (3)	C44—C43—C42	102.8 (2)
C7—C8—C9	104.8 (2)	C50—C43—C42	101.3 (2)
C8—C9—C5	103.4 (2)	C44—C43—H43	115.6
C8—C9—C10	107.9 (2)	C50—C43—H43	115.6
C5—C9—C10	102.3 (2)	C42—C43—H43	115.6
C8—C9—H9	114.0	C43—C44—C45	95.7 (2)
C5—C9—H9	114.0	C45—C44—H441	112.6
C10—C9—H9	114.0	C43—C44—H441	112.6
C11—C10—C3	101.4 (2)	C45—C44—H442	112.6
C11—C10—C9	109.9 (2)	C43—C44—H442	112.6
C3—C10—C9	102.6 (2)	H441—C44—H442	110.1
C11—C10—H10	113.9	C44—C45—C49	104.2 (2)
C3—C10—H10	113.9	C44—C45—C46	103.2 (2)
C9—C10—H10	113.9	C49—C45—C46	101.2 (2)
O2—C11—C1	127.1 (3)	C44—C45—H45	115.4
O2—C11—C10	127.6 (3)	C49—C45—H45	115.4
C1—C11—C10	105.2 (2)	C46—C45—H45	115.4
C31—C21—C22	103.9 (2)	C42—C46—C45	103.2 (2)
C31—C21—C27	108.8 (2)	C42—C46—C47	90.5 (2)
C22—C21—C27	89.6 (2)	C45—C46—C47	107.8 (2)
C31—C21—H21	116.9	C42—C46—H46	117.2
C22—C21—H21	116.9	C45—C46—H46	117.2
C27—C21—H21	116.9	C47—C46—H46	117.2
C21—C22—C23	107.9 (2)	C48—C47—C46	103.4 (2)
C21—C22—C26	90.7 (2)	C48—C47—C41	109.1 (2)
C23—C22—C26	102.7 (2)	C46—C47—C41	89.3 (2)
C21—C22—H22	117.2	C48—C47—H47	117.0
C23—C22—H22	117.2	C46—C47—H47	117.0
C26—C22—H22	117.2	C41—C47—H47	117.0
C24—C23—C30	104.1 (2)	O41—C48—C49	127.2 (3)
C24—C23—C22	103.3 (2)	O41—C48—C47	127.5 (3)
C30—C23—C22	101.7 (2)	C49—C48—C47	105.3 (2)
C24—C23—H23	115.3	C48—C49—C45	102.8 (2)
C30—C23—H23	115.3	C48—C49—C50	108.8 (2)
C22—C23—H23	115.3	C45—C49—C50	102.3 (2)
C23—C24—C25	95.4 (2)	C48—C49—H49	113.9
C23—C24—H241	112.7	C45—C49—H49	113.9
C25—C24—H241	112.7	C50—C49—H49	113.9
C23—C24—H242	112.7	C51—C50—C43	103.0 (2)
C25—C24—H242	112.7	C51—C50—C49	108.6 (2)
H241—C24—H242	110.2	C43—C50—C49	102.5 (2)
C24—C25—C29	104.5 (2)	C51—C50—H50	113.9
C24—C25—C26	102.6 (2)	C43—C50—H50	113.9
C29—C25—C26	101.9 (2)	C49—C50—H50	113.9
C24—C25—H25	115.3	O42—C51—C50	127.8 (3)
C29—C25—H25	115.3	O42—C51—C41	127.3 (3)
C26—C25—H25	115.3	C50—C51—C41	104.9 (2)
C11—C1—C2—C6	109.7 (2)	C26—C27—C28—O21	−148.7 (3)
C7—C1—C2—C6	0.1 (2)	C21—C27—C28—O21	117.4 (3)
C11—C1—C2—C3	5.8 (3)	C26—C27—C28—C29	29.7 (3)
C7—C1—C2—C3	−103.8 (2)	C21—C27—C28—C29	−64.2 (3)
C6—C2—C3—C4	33.9 (3)	O21—C28—C29—C25	134.8 (3)
C1—C2—C3—C4	128.7 (2)	C27—C28—C29—C25	−43.6 (3)
C6—C2—C3—C10	−73.4 (3)	O21—C28—C29—C30	−117.7 (3)
C1—C2—C3—C10	21.5 (3)	C27—C28—C29—C30	63.9 (3)
C10—C3—C4—C5	52.7 (3)	C24—C25—C29—C28	145.4 (2)
C2—C3—C4—C5	−53.1 (3)	C26—C25—C29—C28	38.9 (3)
C3—C4—C5—C9	−52.9 (3)	C24—C25—C29—C30	33.1 (3)
C3—C4—C5—C6	52.8 (3)	C26—C25—C29—C30	−73.5 (2)
C4—C5—C6—C7	−127.9 (3)	C24—C23—C30—C31	−146.0 (2)
C9—C5—C6—C7	−20.1 (3)	C22—C23—C30—C31	−38.9 (3)
C4—C5—C6—C2	−32.9 (3)	C24—C23—C30—C29	−33.4 (3)
C9—C5—C6—C2	74.8 (3)	C22—C23—C30—C29	73.7 (2)
C3—C2—C6—C5	−0.5 (3)	C28—C29—C30—C31	0.1 (3)
C1—C2—C6—C5	−108.6 (2)	C25—C29—C30—C31	108.0 (3)
C3—C2—C6—C7	107.9 (2)	C28—C29—C30—C23	−107.7 (2)
C1—C2—C6—C7	−0.1 (2)	C25—C29—C30—C23	0.1 (3)
C5—C6—C7—C8	−5.5 (3)	C22—C21—C31—O22	149.5 (3)
C2—C6—C7—C8	−109.5 (2)	C27—C21—C31—O22	−116.1 (3)
C5—C6—C7—C1	104.1 (2)	C22—C21—C31—C30	−30.8 (3)
C2—C6—C7—C1	0.1 (2)	C27—C21—C31—C30	63.6 (3)
C11—C1—C7—C8	0.9 (3)	C23—C30—C31—O22	−136.0 (3)
C2—C1—C7—C8	104.8 (3)	C29—C30—C31—O22	116.2 (3)
C11—C1—C7—C6	−104.0 (2)	C23—C30—C31—C21	44.3 (3)
C2—C1—C7—C6	−0.1 (2)	C29—C30—C31—C21	−63.6 (3)
C6—C7—C8—O1	−151.1 (3)	C51—C41—C42—C46	109.1 (2)
C1—C7—C8—O1	114.3 (3)	C47—C41—C42—C46	−0.08 (19)
C6—C7—C8—C9	29.8 (3)	C51—C41—C42—C43	5.0 (3)
C1—C7—C8—C9	−64.8 (3)	C47—C41—C42—C43	−104.2 (2)
O1—C8—C9—C5	137.4 (3)	C46—C42—C43—C44	33.3 (3)
C7—C8—C9—C5	−43.5 (3)	C41—C42—C43—C44	128.3 (2)
O1—C8—C9—C10	−114.7 (3)	C46—C42—C43—C50	−74.1 (2)
C7—C8—C9—C10	64.4 (3)	C41—C42—C43—C50	20.9 (3)
C4—C5—C9—C8	145.1 (2)	C50—C43—C44—C45	52.5 (3)
C6—C5—C9—C8	38.2 (3)	C42—C43—C44—C45	−52.8 (3)
C4—C5—C9—C10	33.0 (3)	C43—C44—C45—C49	−52.5 (3)
C6—C5—C9—C10	−73.8 (3)	C43—C44—C45—C46	52.9 (3)
C4—C3—C10—C11	−147.0 (2)	C41—C42—C46—C45	−108.4 (2)
C2—C3—C10—C11	−40.3 (2)	C43—C42—C46—C45	−0.1 (3)
C4—C3—C10—C9	−33.4 (3)	C41—C42—C46—C47	0.1 (2)
C2—C3—C10—C9	73.3 (2)	C43—C42—C46—C47	108.3 (2)
C8—C9—C10—C11	−1.2 (3)	C44—C45—C46—C42	−33.4 (3)
C5—C9—C10—C11	107.4 (3)	C49—C45—C46—C42	74.3 (3)
C8—C9—C10—C3	−108.4 (3)	C44—C45—C46—C47	−128.2 (2)
C5—C9—C10—C3	0.2 (3)	C49—C45—C46—C47	−20.5 (3)
C2—C1—C11—O2	144.6 (3)	C42—C46—C47—C48	−109.5 (2)
C7—C1—C11—O2	−121.5 (3)	C45—C46—C47—C48	−5.5 (3)
C2—C1—C11—C10	−31.9 (3)	C42—C46—C47—C41	−0.07 (19)
C7—C1—C11—C10	62.0 (3)	C45—C46—C47—C41	103.9 (2)
C3—C10—C11—O2	−130.5 (3)	C51—C41—C47—C48	−0.6 (3)
C9—C10—C11—O2	121.5 (3)	C42—C41—C47—C48	104.1 (2)
C3—C10—C11—C1	46.0 (3)	C51—C41—C47—C46	−104.6 (2)
C9—C10—C11—C1	−62.0 (3)	C42—C41—C47—C46	0.07 (19)
C31—C21—C22—C23	5.8 (3)	C46—C47—C48—O41	−147.5 (3)
C27—C21—C22—C23	−103.5 (2)	C41—C47—C48—O41	118.6 (3)
C31—C21—C22—C26	109.3 (2)	C46—C47—C48—C49	30.8 (3)
C27—C21—C22—C26	0.0 (2)	C41—C47—C48—C49	−63.2 (3)
C21—C22—C23—C24	128.2 (2)	O41—C48—C49—C45	133.5 (3)
C26—C22—C23—C24	33.4 (3)	C47—C48—C49—C45	−44.8 (3)
C21—C22—C23—C30	20.5 (3)	O41—C48—C49—C50	−118.5 (3)
C26—C22—C23—C30	−74.4 (2)	C47—C48—C49—C50	63.2 (3)
C30—C23—C24—C25	52.7 (3)	C44—C45—C49—C48	146.0 (2)
C22—C23—C24—C25	−53.2 (3)	C46—C45—C49—C48	39.1 (3)
C23—C24—C25—C29	−52.8 (3)	C44—C45—C49—C50	33.1 (3)
C23—C24—C25—C26	53.2 (3)	C46—C45—C49—C50	−73.8 (2)
C24—C25—C26—C22	−33.9 (3)	C44—C43—C50—C51	−145.7 (2)
C29—C25—C26—C22	74.1 (3)	C42—C43—C50—C51	−39.3 (3)
C24—C25—C26—C27	−129.1 (2)	C44—C43—C50—C49	−32.9 (3)
C29—C25—C26—C27	−21.1 (3)	C42—C43—C50—C49	73.5 (2)
C21—C22—C26—C25	−108.1 (2)	C48—C49—C50—C51	0.3 (3)
C23—C22—C26—C25	0.4 (3)	C45—C49—C50—C51	108.6 (3)
C21—C22—C26—C27	0.0 (2)	C48—C49—C50—C43	−108.3 (2)
C23—C22—C26—C27	108.6 (2)	C45—C49—C50—C43	0.1 (3)
C25—C26—C27—C28	−4.7 (3)	C43—C50—C51—O42	−134.9 (3)
C22—C26—C27—C28	−109.2 (2)	C49—C50—C51—O42	116.9 (3)
C25—C26—C27—C21	104.5 (2)	C43—C50—C51—C41	44.3 (3)
C22—C26—C27—C21	0.0 (2)	C49—C50—C51—C41	−63.9 (3)
C31—C21—C27—C28	0.2 (3)	C42—C41—C51—O42	149.0 (3)
C22—C21—C27—C28	104.7 (2)	C47—C41—C51—O42	−116.6 (3)
C31—C21—C27—C26	−104.5 (2)	C42—C41—C51—C50	−30.2 (3)
C22—C21—C27—C26	0.0 (2)	C47—C41—C51—C50	64.2 (3)

(V) 5-(trifluoromethyl)-4- oxahexacyclo[5.4.1.0^2,6.0^3,10.0^5,9.0^8,11]dodecan-3-ol

Crystal data

C12H11F3O2	F(000) = 504
Mr = 244.21	Dx = 1.642 Mg m^−3
Monoclinic, P21/c	Melting point: 389 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.4499 (3) Å	Cell parameters from 2379 reflections
b = 12.0228 (5) Å	θ = 2.0–27.5°
c = 11.6047 (3) Å	µ = 0.15 mm^−1
β = 108.082 (2)°	T = 160 K
V = 988.08 (6) Å^3	Block, colourless
Z = 4	0.25 × 0.22 × 0.12 mm

Data collection

Nonius KappaCCD area-detector diffractometer	1725 reflections with I > 2σ(I)
Radiation source: Nonius FR590 sealed tube generator	Rint = 0.051
Horizontally mounted graphite crystal monochromator	θmax = 27.5°, θmin = 2.5°
Detector resolution: 9 pixels mm^-1	h = −9→9
ϕ and ω scans with κ offsets	k = −15→15
20424 measured reflections	l = −15→15
2271 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom & difmap
R[F^2 > 2σ(F^2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0675P)^2 + 0.3171P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2269 reflections	Δρmax = 0.30 e Å^−3
159 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (4)

Special details

Experimental. Solvent used: MeOH Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.561 (2) Frames collected: 289 Seconds exposure per frame: 20 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 30.0

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
F1	0.82609 (16)	−0.12252 (9)	0.62247 (11)	0.0465 (4)
F2	1.07758 (14)	−0.02507 (9)	0.69292 (10)	0.0375 (3)
F3	0.84692 (17)	0.03763 (10)	0.54448 (10)	0.0454 (4)
O1	0.85151 (16)	−0.02203 (10)	0.84613 (10)	0.0273 (3)
O2	0.76337 (19)	0.01404 (12)	1.02054 (12)	0.0361 (4)
H2	0.881 (4)	0.025 (2)	1.069 (3)	0.069 (8)*
C1	0.8328 (2)	0.16799 (15)	0.89491 (15)	0.0292 (4)
H1	0.9370	0.1970	0.9654	0.035*
C2	0.6620 (2)	0.24580 (15)	0.83654 (16)	0.0331 (4)
H21	0.6665	0.3220	0.8719	0.040*
C3	0.4787 (2)	0.17864 (16)	0.81762 (16)	0.0322 (4)
H3	0.4078	0.1948	0.8761	0.039*
C4	0.3707 (2)	0.20080 (16)	0.68370 (17)	0.0345 (4)
H41	0.2573	0.1534	0.6529	0.041*
H42	0.3365	0.2801	0.6671	0.041*
C5	0.5327 (2)	0.16474 (15)	0.63651 (16)	0.0298 (4)
H5	0.5055	0.1688	0.5466	0.036*
C6	0.6992 (2)	0.23636 (14)	0.71173 (16)	0.0310 (4)
H6	0.7251	0.3069	0.6741	0.037*
C7	0.8693 (2)	0.15917 (14)	0.77014 (15)	0.0274 (4)
H7	0.9959	0.1822	0.7657	0.033*
C8	0.8043 (2)	0.03833 (13)	0.73445 (14)	0.0238 (4)
C9	0.5872 (2)	0.04910 (14)	0.69322 (15)	0.0253 (4)
H9	0.5191	−0.0138	0.6416	0.030*
C10	0.5506 (2)	0.05874 (14)	0.81889 (15)	0.0275 (4)
H10	0.4632	0.0010	0.8330	0.033*
C11	0.7505 (2)	0.05343 (15)	0.90730 (15)	0.0277 (4)
C12	0.8887 (2)	−0.01859 (15)	0.64949 (16)	0.0295 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0482 (7)	0.0399 (7)	0.0499 (7)	0.0017 (5)	0.0130 (6)	−0.0184 (5)
F2	0.0284 (6)	0.0504 (7)	0.0345 (6)	0.0101 (5)	0.0110 (5)	0.0001 (5)
F3	0.0505 (7)	0.0654 (8)	0.0241 (6)	0.0227 (6)	0.0173 (5)	0.0099 (5)
O1	0.0270 (6)	0.0317 (7)	0.0231 (6)	0.0021 (5)	0.0074 (5)	0.0040 (5)
O2	0.0299 (7)	0.0572 (9)	0.0222 (7)	0.0007 (6)	0.0094 (6)	0.0071 (6)
C1	0.0258 (9)	0.0352 (9)	0.0258 (8)	−0.0032 (7)	0.0067 (7)	−0.0077 (7)
C2	0.0336 (10)	0.0285 (10)	0.0370 (10)	0.0009 (7)	0.0107 (8)	−0.0087 (8)
C3	0.0263 (9)	0.0398 (10)	0.0313 (9)	0.0031 (8)	0.0100 (7)	−0.0030 (8)
C4	0.0291 (9)	0.0369 (10)	0.0365 (10)	0.0044 (8)	0.0087 (8)	0.0006 (8)
C5	0.0292 (9)	0.0325 (9)	0.0260 (9)	0.0023 (7)	0.0060 (7)	0.0030 (7)
C6	0.0333 (10)	0.0257 (9)	0.0355 (10)	−0.0014 (7)	0.0127 (8)	0.0021 (7)
C7	0.0250 (8)	0.0300 (9)	0.0281 (9)	−0.0042 (7)	0.0095 (7)	−0.0021 (7)
C8	0.0250 (9)	0.0289 (9)	0.0178 (8)	0.0007 (7)	0.0070 (7)	0.0008 (6)
C9	0.0248 (9)	0.0285 (9)	0.0219 (8)	−0.0029 (7)	0.0062 (7)	−0.0023 (7)
C10	0.0236 (9)	0.0342 (9)	0.0251 (8)	−0.0030 (7)	0.0080 (7)	0.0009 (7)
C11	0.0259 (9)	0.0369 (10)	0.0211 (8)	0.0015 (7)	0.0084 (7)	0.0007 (7)
C12	0.0287 (9)	0.0341 (10)	0.0237 (9)	0.0056 (7)	0.0053 (7)	0.0015 (7)

Geometric parameters (Å, º)

F1—C12	1.337 (2)	C4—C5	1.535 (2)
F2—C12	1.341 (2)	C4—H41	0.9900
F3—C12	1.343 (2)	C4—H42	0.9900
O1—C8	1.4308 (19)	C5—C9	1.538 (2)
O1—C11	1.492 (2)	C5—C6	1.539 (2)
O2—C11	1.372 (2)	C5—H5	1.0000
O2—H2	0.89 (3)	C6—C7	1.547 (2)
C1—C2	1.555 (2)	C6—H6	1.0000
C1—C7	1.557 (2)	C7—C8	1.547 (2)
C1—C11	1.532 (3)	C7—H7	1.0000
C1—H1	1.0000	C8—C12	1.490 (2)
C2—C3	1.542 (3)	C8—C9	1.543 (2)
C2—C6	1.561 (3)	C9—C10	1.569 (2)
C2—H21	1.0000	C9—H9	1.0000
C3—C4	1.535 (3)	C10—C11	1.525 (2)
C3—C10	1.536 (3)	C10—H10	1.0000
C3—H3	1.0000
C8—O1—C11	95.97 (11)	C2—C6—H6	117.2
C11—O2—H2	108.4 (18)	C8—C7—C6	107.49 (13)
C11—C1—C2	106.52 (13)	C8—C7—C1	100.51 (13)
C11—C1—C7	102.50 (13)	C6—C7—C1	90.64 (13)
C2—C1—C7	89.50 (13)	C8—C7—H7	117.9
C11—C1—H1	118.0	C6—C7—H7	117.9
C2—C1—H1	118.0	C1—C7—H7	117.9
C7—C1—H1	118.0	O1—C8—C12	109.31 (13)
C3—C2—C1	108.40 (15)	O1—C8—C9	105.24 (12)
C3—C2—C6	103.55 (14)	C12—C8—C9	116.77 (14)
C1—C2—C6	90.19 (13)	O1—C8—C7	105.38 (12)
C3—C2—H21	117.0	C12—C8—C7	116.56 (14)
C1—C2—H21	117.0	C9—C8—C7	102.42 (13)
C6—C2—H21	117.0	C5—C9—C8	108.69 (14)
C4—C3—C10	104.13 (14)	C5—C9—C10	103.42 (13)
C4—C3—C2	102.47 (15)	C8—C9—C10	100.71 (12)
C10—C3—C2	101.50 (13)	C5—C9—H9	114.2
C4—C3—H3	115.6	C8—C9—H9	114.2
C10—C3—H3	115.6	C10—C9—H9	114.2
C2—C3—H3	115.6	C11—C10—C3	108.08 (14)
C3—C4—C5	95.11 (13)	C11—C10—C9	101.96 (13)
C5—C4—H41	112.7	C3—C10—C9	102.77 (13)
C3—C4—H41	112.7	C11—C10—H10	114.2
C5—C4—H42	112.7	C3—C10—H10	114.2
C3—C4—H42	112.7	C9—C10—H10	114.2
H41—C4—H42	110.2	O2—C11—O1	110.50 (14)
C4—C5—C9	103.59 (14)	O2—C11—C10	114.98 (14)
C4—C5—C6	102.95 (14)	O1—C11—C10	103.70 (13)
C9—C5—C6	101.77 (13)	O2—C11—C1	119.28 (15)
C4—C5—H5	115.5	O1—C11—C1	103.07 (12)
C9—C5—H5	115.5	C10—C11—C1	103.58 (14)
C6—C5—H5	115.5	F1—C12—F2	106.43 (14)
C5—C6—C7	108.60 (14)	F1—C12—F3	106.97 (14)
C5—C6—C2	102.87 (14)	F2—C12—F3	106.91 (14)
C7—C6—C2	89.67 (13)	F1—C12—C8	113.34 (15)
C5—C6—H6	117.2	F2—C12—C8	112.77 (14)
C7—C6—H6	117.2	F3—C12—C8	110.03 (14)
C11—C1—C2—C3	1.56 (17)	C6—C5—C9—C10	73.28 (15)
C7—C1—C2—C3	104.46 (14)	O1—C8—C9—C5	141.98 (13)
C11—C1—C2—C6	−102.80 (14)	C12—C8—C9—C5	−96.60 (17)
C7—C1—C2—C6	0.10 (13)	C7—C8—C9—C5	32.01 (16)
C1—C2—C3—C4	−128.60 (15)	O1—C8—C9—C10	33.72 (15)
C6—C2—C3—C4	−33.80 (17)	C12—C8—C9—C10	155.14 (14)
C1—C2—C3—C10	−21.13 (17)	C7—C8—C9—C10	−76.25 (14)
C6—C2—C3—C10	73.67 (15)	C4—C3—C10—C11	140.18 (14)
C10—C3—C4—C5	−52.06 (16)	C2—C3—C10—C11	34.01 (17)
C2—C3—C4—C5	53.38 (16)	C4—C3—C10—C9	32.87 (16)
C3—C4—C5—C9	51.95 (16)	C2—C3—C10—C9	−73.30 (15)
C3—C4—C5—C6	−53.77 (16)	C5—C9—C10—C11	−111.61 (14)
C4—C5—C6—C7	128.07 (15)	C8—C9—C10—C11	0.75 (16)
C9—C5—C6—C7	20.96 (17)	C5—C9—C10—C3	0.31 (16)
C4—C5—C6—C2	34.01 (17)	C8—C9—C10—C3	112.67 (14)
C9—C5—C6—C2	−73.10 (15)	C8—O1—C11—O2	177.60 (13)
C3—C2—C6—C5	−0.07 (17)	C8—O1—C11—C10	53.88 (14)
C1—C2—C6—C5	108.92 (14)	C8—O1—C11—C1	−53.87 (14)
C3—C2—C6—C7	−109.09 (14)	C3—C10—C11—O2	98.18 (17)
C1—C2—C6—C7	−0.10 (13)	C9—C10—C11—O2	−153.95 (15)
C5—C6—C7—C8	−2.15 (18)	C3—C10—C11—O1	−141.08 (13)
C2—C6—C7—C8	101.34 (14)	C9—C10—C11—O1	−33.20 (15)
C5—C6—C7—C1	−103.38 (14)	C3—C10—C11—C1	−33.71 (17)
C2—C6—C7—C1	0.10 (13)	C9—C10—C11—C1	74.16 (15)
C11—C1—C7—C8	−1.21 (15)	C2—C1—C11—O2	−110.32 (17)
C2—C1—C7—C8	−108.02 (13)	C7—C1—C11—O2	156.45 (15)
C11—C1—C7—C6	106.72 (13)	C2—C1—C11—O1	126.83 (13)
C2—C1—C7—C6	−0.10 (13)	C7—C1—C11—O1	33.60 (15)
C11—O1—C8—C12	179.97 (13)	C2—C1—C11—C10	19.00 (16)
C11—O1—C8—C9	−53.86 (14)	C7—C1—C11—C10	−74.23 (15)
C11—O1—C8—C7	53.97 (14)	O1—C8—C12—F1	60.80 (19)
C6—C7—C8—O1	−127.46 (13)	C9—C8—C12—F1	−58.5 (2)
C1—C7—C8—O1	−33.42 (15)	C7—C8—C12—F1	−179.90 (13)
C6—C7—C8—C12	111.14 (16)	O1—C8—C12—F2	−60.22 (18)
C1—C7—C8—C12	−154.82 (14)	C9—C8—C12—F2	−179.48 (13)
C6—C7—C8—C9	−17.60 (16)	C7—C8—C12—F2	59.1 (2)
C1—C7—C8—C9	76.44 (14)	O1—C8—C12—F3	−179.49 (12)
C4—C5—C9—C8	−139.73 (14)	C9—C8—C12—F3	61.3 (2)
C6—C5—C9—C8	−33.12 (17)	C7—C8—C12—F3	−60.2 (2)
C4—C5—C9—C10	−33.33 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1^i	0.89 (3)	1.93 (3)	2.8070 (18)	167 (3)

Symmetry code: (i) −x+2, −y, −z+2.

(VII) N-phenyl-[exo-11-(trifluoromethyl)-endo-11- (trimethylsilyloxy)pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecan- 8-yliden]amine methanol solvate

Crystal data

C21H24F3NOSi·CH4O	Z = 2
Mr = 423.54	F(000) = 448
Triclinic, P1	Dx = 1.366 Mg m^−3
Hall symbol: -P 1	Melting point: 414 K
a = 8.8352 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3775 (3) Å	Cell parameters from 5859 reflections
c = 12.6843 (5) Å	θ = 2.0–30.0°
α = 100.2675 (15)°	µ = 0.16 mm^−1
β = 91.417 (2)°	T = 160 K
γ = 94.652 (2)°	Tablet, colourless
V = 1029.86 (6) Å^3	0.22 × 0.20 × 0.10 mm

Data collection

Nonius KappaCCD area-detector diffractometer	4581 reflections with I > 2σ(I)
Radiation source: Nonius FR590 sealed tube generator	Rint = 0.046
Horizontally mounted graphite crystal monochromator	θmax = 30.1°, θmin = 3.3°
Detector resolution: 9 pixels mm^-1	h = −12→12
ϕ and ω scans with κ offsets	k = −13→13
26283 measured reflections	l = −17→17
6025 independent reflections

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.054P)^2 + 0.529P] where P = (Fo^2 + 2Fc^2)/3
6017 reflections	(Δ/σ)max = 0.001
288 parameters	Δρmax = 0.63 e Å^−3
37 restraints	Δρmin = −0.31 e Å^−3

Special details

Experimental. Solvent used: MeOH Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.648 (2) Frames collected: 385 Seconds exposure per frame: 30 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 33.0

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Si1	0.43810 (5)	0.57671 (5)	0.71828 (3)	0.02294 (12)
F1	0.46186 (12)	0.25079 (12)	0.54106 (8)	0.0384 (3)
F2	0.35857 (11)	0.23194 (12)	0.68990 (9)	0.0378 (3)
F3	0.52424 (13)	0.08612 (11)	0.62628 (10)	0.0443 (3)
O1	0.58168 (12)	0.47446 (11)	0.68663 (9)	0.0213 (2)
N1	0.86584 (15)	0.66237 (15)	0.81984 (11)	0.0266 (3)
C1	0.90044 (18)	0.41446 (18)	0.70807 (14)	0.0280 (3)
H1	0.9736	0.4537	0.6592	0.034*
C2	0.9579 (2)	0.2965 (2)	0.76997 (15)	0.0334 (4)
H2	1.0647	0.2704	0.7595	0.040*
C3	0.9059 (2)	0.3361 (2)	0.88700 (15)	0.0334 (4)
H3	0.9878	0.3816	0.9413	0.040*
C4	0.8269 (2)	0.1929 (2)	0.90645 (15)	0.0362 (4)
H41	0.7721	0.2039	0.9742	0.043*
H42	0.8970	0.1152	0.9039	0.043*
C5	0.7198 (2)	0.17055 (19)	0.80748 (14)	0.0305 (4)
H5	0.6483	0.0804	0.7966	0.037*
C6	0.82742 (19)	0.18345 (18)	0.71588 (14)	0.0287 (4)
H6	0.8573	0.0909	0.6724	0.034*
C7	0.77079 (18)	0.29957 (17)	0.65348 (14)	0.0257 (3)
H7	0.7719	0.2739	0.5735	0.031*
C8	0.61632 (17)	0.33428 (16)	0.69971 (13)	0.0224 (3)
C9	0.64358 (18)	0.31595 (18)	0.81659 (13)	0.0250 (3)
H9	0.5486	0.3165	0.8579	0.030*
C10	0.77445 (19)	0.43266 (18)	0.87252 (13)	0.0271 (3)
H10	0.7446	0.4915	0.9414	0.033*
C11	0.84287 (17)	0.52368 (18)	0.79644 (13)	0.0257 (3)
C12	0.49128 (19)	0.22469 (18)	0.63973 (14)	0.0282 (3)
C13	0.3562 (2)	0.5500 (2)	0.84789 (15)	0.0372 (4)
H131	0.3157	0.4484	0.8423	0.056*
H132	0.2743	0.6139	0.8645	0.056*
H133	0.4357	0.5737	0.9051	0.056*
C14	0.29071 (19)	0.5363 (2)	0.60790 (15)	0.0320 (4)
H141	0.3387	0.5386	0.5393	0.048*
H142	0.2167	0.6094	0.6192	0.048*
H143	0.2388	0.4396	0.6068	0.048*
C15	0.5216 (2)	0.76670 (18)	0.72946 (14)	0.0300 (4)
H151	0.6075	0.7847	0.7819	0.045*
H152	0.4444	0.8336	0.7530	0.045*
H153	0.5571	0.7823	0.6595	0.045*
C16	0.93928 (18)	0.74087 (18)	0.74621 (13)	0.0252 (3)
C17	1.05351 (19)	0.84948 (19)	0.78664 (15)	0.0308 (4)
H17	1.0807	0.8689	0.8611	0.037*
C18	1.1277 (2)	0.9295 (2)	0.71799 (16)	0.0347 (4)
H18	1.2070	1.0021	0.7456	0.042*
C19	1.0869 (2)	0.90418 (19)	0.60970 (16)	0.0328 (4)
H19	1.1392	0.9579	0.5629	0.039*
C20	0.9693 (2)	0.80004 (19)	0.57011 (14)	0.0300 (4)
H20	0.9391	0.7845	0.4963	0.036*
C21	0.89529 (18)	0.71808 (18)	0.63767 (13)	0.0273 (3)
H21	0.8149	0.6467	0.6100	0.033*
O22A	0.7893 (9)	0.8216 (12)	1.0294 (5)	0.0721 (18)	0.534 (15)
H22A	0.8137	0.7801	0.9687	0.108*	0.534 (15)
C22A	0.6528 (19)	0.8799 (19)	1.0202 (15)	0.046 (2)	0.534 (15)
H221	0.6298	0.9372	1.0895	0.069*	0.534 (15)
H222	0.5721	0.8012	0.9984	0.069*	0.534 (15)
H223	0.6591	0.9428	0.9662	0.069*	0.534 (15)
O22B	0.7341 (12)	0.7649 (9)	1.0246 (6)	0.0570 (17)	0.466 (15)
H22B	0.7007	0.7004	0.9728	0.086*	0.466 (15)
C22B	0.650 (2)	0.883 (2)	1.0307 (18)	0.047 (2)	0.466 (15)
H224	0.6118	0.9072	1.1029	0.071*	0.466 (15)
H225	0.5644	0.8601	0.9782	0.071*	0.466 (15)
H226	0.7145	0.9665	1.0151	0.071*	0.466 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0223 (2)	0.0230 (2)	0.0239 (2)	0.00251 (16)	0.00323 (16)	0.00476 (17)
F1	0.0444 (6)	0.0391 (6)	0.0284 (5)	−0.0066 (5)	−0.0064 (4)	0.0028 (5)
F2	0.0270 (5)	0.0413 (6)	0.0425 (6)	−0.0099 (4)	0.0038 (4)	0.0061 (5)
F3	0.0499 (7)	0.0217 (5)	0.0578 (7)	−0.0008 (5)	−0.0116 (6)	0.0017 (5)
O1	0.0212 (5)	0.0191 (5)	0.0245 (5)	0.0013 (4)	0.0026 (4)	0.0064 (4)
N1	0.0238 (7)	0.0294 (7)	0.0260 (7)	−0.0026 (5)	−0.0014 (5)	0.0063 (6)
C1	0.0215 (8)	0.0281 (8)	0.0357 (9)	0.0016 (6)	0.0048 (6)	0.0089 (7)
C2	0.0253 (8)	0.0347 (10)	0.0411 (10)	0.0049 (7)	0.0019 (7)	0.0082 (8)
C3	0.0355 (9)	0.0301 (9)	0.0344 (9)	0.0013 (7)	−0.0088 (7)	0.0077 (7)
C4	0.0441 (11)	0.0332 (9)	0.0334 (9)	0.0083 (8)	−0.0021 (8)	0.0104 (8)
C5	0.0339 (9)	0.0259 (8)	0.0339 (9)	0.0040 (7)	0.0025 (7)	0.0105 (7)
C6	0.0287 (8)	0.0222 (8)	0.0356 (9)	0.0059 (6)	0.0012 (7)	0.0044 (7)
C7	0.0259 (8)	0.0225 (8)	0.0293 (8)	0.0038 (6)	0.0051 (6)	0.0047 (6)
C8	0.0231 (7)	0.0187 (7)	0.0258 (8)	0.0009 (6)	0.0022 (6)	0.0058 (6)
C9	0.0245 (8)	0.0257 (8)	0.0261 (8)	−0.0008 (6)	0.0025 (6)	0.0095 (6)
C10	0.0296 (8)	0.0260 (8)	0.0258 (8)	−0.0008 (6)	−0.0001 (6)	0.0065 (6)
C11	0.0206 (7)	0.0294 (8)	0.0275 (8)	−0.0019 (6)	−0.0020 (6)	0.0083 (7)
C12	0.0279 (8)	0.0237 (8)	0.0330 (9)	0.0000 (6)	0.0005 (6)	0.0062 (7)
C13	0.0432 (11)	0.0378 (10)	0.0323 (9)	0.0083 (8)	0.0145 (8)	0.0070 (8)
C14	0.0235 (8)	0.0336 (9)	0.0390 (10)	0.0030 (7)	−0.0019 (7)	0.0072 (8)
C15	0.0317 (9)	0.0248 (8)	0.0337 (9)	0.0043 (6)	0.0003 (7)	0.0054 (7)
C16	0.0215 (7)	0.0251 (8)	0.0294 (8)	0.0008 (6)	0.0012 (6)	0.0061 (6)
C17	0.0285 (8)	0.0270 (8)	0.0371 (9)	−0.0024 (6)	−0.0056 (7)	0.0090 (7)
C18	0.0255 (8)	0.0276 (9)	0.0521 (11)	−0.0026 (7)	−0.0028 (7)	0.0131 (8)
C19	0.0301 (9)	0.0274 (9)	0.0450 (10)	0.0059 (7)	0.0099 (7)	0.0148 (8)
C20	0.0323 (9)	0.0287 (9)	0.0300 (9)	0.0060 (7)	0.0062 (7)	0.0057 (7)
C21	0.0245 (8)	0.0274 (8)	0.0294 (8)	−0.0001 (6)	0.0019 (6)	0.0042 (7)
O22A	0.071 (3)	0.089 (4)	0.050 (2)	0.028 (3)	−0.018 (2)	−0.013 (3)
C22A	0.055 (3)	0.044 (3)	0.034 (4)	0.002 (3)	0.007 (3)	−0.006 (3)
O22B	0.088 (4)	0.052 (3)	0.042 (2)	0.030 (3)	0.023 (2)	0.022 (2)
C22B	0.056 (4)	0.046 (4)	0.039 (4)	−0.002 (3)	0.005 (3)	0.009 (4)

Geometric parameters (Å, º)

Si1—O1	1.6659 (11)	C9—H9	1.0000
Si1—C15	1.8520 (18)	C10—C11	1.505 (2)
Si1—C14	1.8547 (17)	C10—H10	1.0000
Si1—C13	1.8614 (18)	C13—H131	0.9800
F1—C12	1.341 (2)	C13—H132	0.9800
F2—C12	1.349 (2)	C13—H133	0.9800
F3—C12	1.337 (2)	C14—H141	0.9800
O1—C8	1.4105 (18)	C14—H142	0.9800
N1—C11	1.280 (2)	C14—H143	0.9800
N1—C16	1.426 (2)	C15—H151	0.9800
C1—C7	1.564 (2)	C15—H152	0.9800
C1—C11	1.506 (2)	C15—H153	0.9800
C1—C2	1.575 (2)	C16—C17	1.393 (2)
C1—H1	1.0000	C16—C21	1.395 (2)
C2—C3	1.555 (3)	C17—C18	1.390 (3)
C2—C6	1.558 (2)	C17—H17	0.9500
C2—H2	1.0000	C18—C19	1.385 (3)
C3—C4	1.525 (3)	C18—H18	0.9500
C3—C10	1.556 (2)	C19—C20	1.386 (3)
C3—H3	1.0000	C19—H19	0.9500
C4—C5	1.526 (2)	C20—C21	1.391 (2)
C4—H41	0.9900	C20—H20	0.9500
C4—H42	0.9900	C21—H21	0.9500
C5—C6	1.534 (2)	O22A—C22A	1.375 (8)
C5—C9	1.557 (2)	O22A—H22A	0.8400
C5—H5	1.0000	C22A—H221	0.9800
C6—C7	1.562 (2)	C22A—H222	0.9800
C6—H6	1.0000	C22A—H223	0.9800
C7—C8	1.535 (2)	O22B—C22B	1.376 (8)
C7—H7	1.0000	O22B—H22B	0.8400
C8—C12	1.533 (2)	C22B—H224	0.9800
C8—C9	1.538 (2)	C22B—H225	0.9800
C9—C10	1.586 (2)	C22B—H226	0.9800
O1—Si1—C15	105.05 (7)	C5—C9—H9	113.1
O1—Si1—C14	109.36 (7)	C10—C9—H9	113.1
C15—Si1—C14	109.36 (8)	C11—C10—C3	100.91 (13)
O1—Si1—C13	112.04 (7)	C11—C10—C9	112.47 (13)
C15—Si1—C13	109.84 (9)	C3—C10—C9	102.08 (13)
C14—Si1—C13	111.00 (9)	C11—C10—H10	113.4
C8—O1—Si1	135.40 (10)	C3—C10—H10	113.4
C11—N1—C16	119.88 (14)	C9—C10—H10	113.4
C11—C1—C7	111.98 (13)	N1—C11—C10	122.96 (15)
C11—C1—C2	102.80 (14)	N1—C11—C1	131.72 (15)
C7—C1—C2	88.74 (12)	C10—C11—C1	104.13 (14)
C11—C1—H1	116.5	F3—C12—F1	105.79 (14)
C7—C1—H1	116.5	F3—C12—F2	106.88 (14)
C2—C1—H1	116.5	F1—C12—F2	105.89 (13)
C3—C2—C6	102.58 (14)	F3—C12—C8	114.34 (14)
C3—C2—C1	106.52 (14)	F1—C12—C8	111.49 (13)
C6—C2—C1	90.78 (13)	F2—C12—C8	111.89 (14)
C3—C2—H2	117.6	Si1—C13—H131	109.5
C6—C2—H2	117.6	Si1—C13—H132	109.5
C1—C2—H2	117.6	H131—C13—H132	109.5
C4—C3—C2	102.83 (15)	Si1—C13—H133	109.5
C4—C3—C10	104.78 (14)	H131—C13—H133	109.5
C2—C3—C10	101.41 (13)	H132—C13—H133	109.5
C4—C3—H3	115.3	Si1—C14—H141	109.5
C2—C3—H3	115.3	Si1—C14—H142	109.5
C10—C3—H3	115.3	H141—C14—H142	109.5
C3—C4—C5	95.16 (14)	Si1—C14—H143	109.5
C3—C4—H41	112.7	H141—C14—H143	109.5
C5—C4—H41	112.7	H142—C14—H143	109.5
C3—C4—H42	112.7	Si1—C15—H151	109.5
C5—C4—H42	112.7	Si1—C15—H152	109.5
H41—C4—H42	110.2	H151—C15—H152	109.5
C4—C5—C6	103.48 (14)	Si1—C15—H153	109.5
C4—C5—C9	104.40 (14)	H151—C15—H153	109.5
C6—C5—C9	100.88 (13)	H152—C15—H153	109.5
C4—C5—H5	115.4	C17—C16—C21	119.52 (15)
C6—C5—H5	115.4	C17—C16—N1	117.89 (15)
C9—C5—H5	115.4	C21—C16—N1	122.50 (14)
C5—C6—C2	103.43 (14)	C18—C17—C16	119.94 (17)
C5—C6—C7	108.08 (13)	C18—C17—H17	120.0
C2—C6—C7	89.46 (13)	C16—C17—H17	120.0
C5—C6—H6	117.3	C19—C18—C17	120.52 (16)
C2—C6—H6	117.3	C19—C18—H18	119.7
C7—C6—H6	117.3	C17—C18—H18	119.7
C8—C7—C6	104.98 (13)	C18—C19—C20	119.57 (16)
C8—C7—C1	111.08 (13)	C18—C19—H19	120.2
C6—C7—C1	91.01 (12)	C20—C19—H19	120.2
C8—C7—H7	115.6	C19—C20—C21	120.48 (17)
C6—C7—H7	115.6	C19—C20—H20	119.8
C1—C7—H7	115.6	C21—C20—H20	119.8
O1—C8—C12	107.68 (12)	C20—C21—C16	119.88 (16)
O1—C8—C7	110.91 (12)	C20—C21—H21	120.1
C12—C8—C7	109.47 (13)	C16—C21—H21	120.1
O1—C8—C9	114.97 (13)	C22B—O22B—H22B	109.5
C12—C8—C9	112.95 (13)	O22B—C22B—H224	109.5
C7—C8—C9	100.69 (12)	O22B—C22B—H225	109.5
C8—C9—C5	104.37 (13)	H224—C22B—H225	109.5
C8—C9—C10	109.71 (12)	O22B—C22B—H226	109.5
C5—C9—C10	102.65 (13)	H224—C22B—H226	109.5
C8—C9—H9	113.1	H225—C22B—H226	109.5
C15—Si1—O1—C8	154.52 (14)	C12—C8—C9—C10	179.82 (13)
C14—Si1—O1—C8	−88.20 (15)	C7—C8—C9—C10	63.19 (15)
C13—Si1—O1—C8	35.31 (16)	C4—C5—C9—C8	147.53 (13)
C11—C1—C2—C3	8.42 (17)	C6—C5—C9—C8	40.41 (16)
C7—C1—C2—C3	−103.84 (14)	C4—C5—C9—C10	33.06 (16)
C11—C1—C2—C6	111.79 (13)	C6—C5—C9—C10	−74.07 (14)
C7—C1—C2—C6	−0.48 (13)	C4—C3—C10—C11	−149.14 (14)
C6—C2—C3—C4	34.39 (16)	C2—C3—C10—C11	−42.42 (16)
C1—C2—C3—C4	129.01 (14)	C4—C3—C10—C9	−33.07 (17)
C6—C2—C3—C10	−73.85 (15)	C2—C3—C10—C9	73.64 (15)
C1—C2—C3—C10	20.78 (17)	C8—C9—C10—C11	−3.23 (19)
C2—C3—C4—C5	−53.36 (16)	C5—C9—C10—C11	107.29 (15)
C10—C3—C4—C5	52.30 (16)	C8—C9—C10—C3	−110.56 (14)
C3—C4—C5—C6	53.10 (16)	C5—C9—C10—C3	−0.04 (16)
C3—C4—C5—C9	−52.09 (16)	C16—N1—C11—C10	176.34 (14)
C4—C5—C6—C2	−32.97 (16)	C16—N1—C11—C1	10.9 (3)
C9—C5—C6—C2	74.88 (15)	C3—C10—C11—N1	−118.96 (17)
C4—C5—C6—C7	−126.86 (14)	C9—C10—C11—N1	132.95 (16)
C9—C5—C6—C7	−19.01 (17)	C3—C10—C11—C1	49.91 (15)
C3—C2—C6—C5	−0.87 (16)	C9—C10—C11—C1	−58.17 (16)
C1—C2—C6—C5	−107.99 (14)	C7—C1—C11—N1	−134.60 (18)
C3—C2—C6—C7	107.60 (14)	C2—C1—C11—N1	131.54 (18)
C1—C2—C6—C7	0.48 (13)	C7—C1—C11—C10	57.93 (16)
C5—C6—C7—C8	−8.67 (17)	C2—C1—C11—C10	−35.94 (15)
C2—C6—C7—C8	−112.63 (13)	O1—C8—C12—F3	166.96 (13)
C5—C6—C7—C1	103.48 (14)	C7—C8—C12—F3	46.29 (19)
C2—C6—C7—C1	−0.48 (13)	C9—C8—C12—F3	−65.01 (18)
C11—C1—C7—C8	3.66 (19)	O1—C8—C12—F1	47.02 (17)
C2—C1—C7—C8	106.96 (14)	C7—C8—C12—F1	−73.65 (17)
C11—C1—C7—C6	−102.83 (15)	C9—C8—C12—F1	175.05 (13)
C2—C1—C7—C6	0.48 (13)	O1—C8—C12—F2	−71.36 (16)
Si1—O1—C8—C12	60.79 (18)	C7—C8—C12—F2	167.97 (13)
Si1—O1—C8—C7	−179.46 (11)	C9—C8—C12—F2	56.67 (18)
Si1—O1—C8—C9	−66.07 (18)	C11—N1—C16—C17	−134.67 (17)
C6—C7—C8—O1	155.08 (13)	C11—N1—C16—C21	48.9 (2)
C1—C7—C8—O1	58.03 (17)	C21—C16—C17—C18	−3.1 (3)
C6—C7—C8—C12	−86.24 (15)	N1—C16—C17—C18	−179.62 (15)
C1—C7—C8—C12	176.71 (13)	C16—C17—C18—C19	1.3 (3)
C6—C7—C8—C9	32.93 (15)	C17—C18—C19—C20	1.2 (3)
C1—C7—C8—C9	−64.12 (15)	C18—C19—C20—C21	−1.9 (3)
O1—C8—C9—C5	−165.45 (13)	C19—C20—C21—C16	0.1 (3)
C12—C8—C9—C5	70.43 (16)	C17—C16—C21—C20	2.4 (2)
C7—C8—C9—C5	−46.20 (15)	N1—C16—C21—C20	178.73 (15)
O1—C8—C9—C10	−56.06 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O22A—H22A···N1	0.84	2.09	2.931 (6)	176
O22B—H22B···N1	0.84	2.45	2.910 (6)	115