Monitoring structural transformations in crystals. 13. On photocyclization in 2,3,4,5,6-penta­methyl­benzophenone, 1,3-diphenyl­butan-1-one and 2,4,6-tri­isopropyl-4'-methoxy­benzophenone

The geometrical parameters governing the potential for the photocyclization reaction occurring in crystals of 2,3,4,5,6-penta­methyl­benzophenone, C₁₈H₂₀O, (I), 1,3-diphenyl­butan-1-one, C₁₆H₁₆O, (II), and 2,4,6-triisopropyl-4'-methoxy­benzo­phenone, C₂₃H₃₀O₂, (IV), have been evaluated. Compound (IV) undergoes photocyclization but (I) and (II) do not, despite the fact that their geometrical parameters appear equally favourable for reaction. The structure of the partially reacted crystal of the photoactive compound, i.e. 2,4,6-triisopropyl-4'-methoxy­benzophenone-3,5-diisopropyl-7-(4-methoxy­phen­yl)-8,8-dimethyl­bicyclo­[4.2.0]octa-1,3,5-trien-7-ol (9/1), 0.90C₂₃H₃₀O₂·0.10C₂₃H₃₀O₂, (III), was also determined, providing structural evidence for the reactivity of the compound. It has been found that the carbonyl group of the photoactive compound reacts with one of the two o-isopropyl groups. The study has shown that the intra­molecular geo­metrical parameters are not the only factors influencing the reactivity of compounds in crystals.

S1. Comment

Compounds containing a carbonyl group and an Hγ atom in their structure can potentially undergo a photocyclization reaction. ortho-Alkylphenyl ketones are an example of such compounds. A mechanism of the above-mentioned reaction is presented in the scheme below.

As can be seen, the reaction leads to formation of a cyclobutane ring from a biradical formed earlier under the influence of UV–vis radiation. However, it was also proposed that the mechanism of formation of benzocyclobutenols can have more complicated character, namely the reaction can proceed not only via a biradical directly but, additionally, via an enol form (Ito et al., 2009). Nevertheless, it was stated that in the case of large substituents and steric crowding, formation of enols in a crystalline state can be neglected (Ito et al., 2009; Moorthy et al., 2004). ortho-Alkylphenyl ketones can also undergo a δ-abstraction reaction (Ito et al., 2009) as follows:

Some 2,4,6-triisopropylbenzophenones are photoactive in a crystalline state and undergo the photocyclization reaction according to Scheme 1 (Fukushima et al., 1998; Ito et al., 2009; Ito, Kano et al., 1998). However, some 2,4,6-triisopropylbenzophenones are photoinert (Fukushima et al., 1998; Ito, Kano et al., 1998; Ito, Yasui et al., 1998). Moreover, 2,4,6-trimethylbenzophenone is photoinert in a crystalline state (Ito et al., 2009) but mesitaldehyde in a solid inclusion compound is photoactive (Moorthy et al., 2001).

In this paper, we present and discuss the structures of the following compounds: 2,3,4,5,6-pentamethylbenzophenone, (I), 1,3-diphenylbutan-1-one, (II), and 2,4,6-triisopropyl-4'-methoxybenzophenone–3,5-diisopropyl-7-(4-methoxyphenyl)-8,8- dimethylbicyclo[4.2.0]octa-1,3,5-trien-7-ol, (III), which is the product of the photocyclization of 2,4,6-triisopropyl-4'-methoxybenzophenone, (IV) (see the first reaction scheme above). The intramolecular photocyclization is one of the reactions monitored by us recently (Turowska-Tyrk, Bąkowicz et al., 2006; Turowska-Tyrk, Bąkowicz et al., 2007; Turowska-Tyrk, Łabęcka et al., 2007; Turowska-Tyrk, Trzop et al., 2006).

There exist geometrical parameters describing conditions that must be fulfilled for a photocyclization reaction to proceed in crystals (Natarajan et al., 2005; Xia et al., 2005). They are as follows (see the scheme below): the (C)O···Hγ distance, d, the (O)C···Cγ distance, D, the deviation of Hγ from the mean plane of the carbonyl group, ω, the C═O···Hγ angle, Δ, and the Cγ—Hγ···O angle, Θ. The ideal and average literature values of these parameters for photoactive compounds are given in Table 1. However, it should be pointed out that good values of these parameters are not the only necessary condition for photocyclization to proceed in crystals (Bąkowicz & Turowska-Tyrk, 2009; Ito, Yasui et al., 1998; Moorthy et al., 2006; Zouev et al., 2006).

One of the reasons for photochemical inactivity of compounds can be the presence of intermolecular π–π interactions. They hinder shifts of atoms and in this manner a whole reaction (Fukushima et al., 1998; Ito et al., 2009). Too small a reaction cavity can be another reason (Fukushima et al., 1998; Ito, Kano et al., 1998; Ito, Yasui et al., 1998; Moorthy et al., 2006; Zouev et al., 2006). In these cases, despite the formation of biradicals, compounds do not cyclize but return to substrates (Ito, Yasui et al., 1998). In order to make molecular and atomic movements easier, reactions were sometimes conducted at elevated temperatures (Fukushima et al., 1998; Ito, Yasui et al., 1998).

Figs. 1 and 2 present the structures of (I) and (II), respectively. The bond lengths in the molecules of both compounds are typical. The dihedral angles between the planes of the two benzene rings are 82.98 (5) and 62.36 (10)° for (I) and (II), respectively. The above-mentioned geometrical parameters influencing the photochemical reaction of the title compounds are given in Table 1. In the case of (I) and (II), only the values for the Hγ atom closer to the carbonyl group are given, but for (IV), the values for both o-isopropyl groups are presented. As can be seen, not all of the geometrical parameters for (I), (II) and (IV) are appropriate for the photocyclization reaction in crystals. For (I), the value of the ω parameter is greater (by 10.5°) than the largest literature value for compounds undergoing the Yang photocyclization (Turowska-Tyrk, Bąkowicz et al., 2007). In the case of (II), D is slightly worse (by 0.02 Å) than the limit known in the literature, but ω is slightly better (by 3.8°). For the first o-isopropyl group of (IV), the d and ω parameters are larger and exceed the literature values (by 0.13 Å and 15.6°, respectively). For the second o-isopropyl group, d, ω and Θ are worse (by 0.05 Å, 10.9° and 0.7°, respectively).

In the case of (I)–(III), there are no π–π interactions between neighbouring naphthalene rings. The lack of π–π stacking can increase the reactivity of compounds (Fukushima et al., 1998; Ito et al., 2009).

However, despite of the above considerations, (I) and (II) are photoinert and (IV) photoactive. Irradiation of crystals of (I) and (II) for periods of 7 and 6 h, respectively, did not cause the photocyclization reaction. We did not observe any changes in the cell constants over the irradiation time and the structures determined after the irradiation revealed only reactant molecules.

In order to make the photoreaction easier, (I) (m.p. 410–411 K) and (II) (m.p. 343–345 K) were irradiated at elevated temperatures: at 373 K for 4 h and at 313 K for 5 h, respectively. Nevertheless, it did not help to induce the photoreaction.

The structure of (IV) before irradiation, i.e. containing only reactant molecules, has been reported previously (Fukushima et al., 1998). Nevertheless, we redetermined it in order to have confidence that we have the proper structure for further experiments. The molecular geometries for both structures were very similar. The information that (IV) undergoes the photocyclization reaction according to Scheme 1 was also given (Fukushima et al., 1998; Ito & Matsura, 1988), but structural evidence, i.e. a structure of a crystal containing product molecules, was not supplied. The photoreaction of (IV) does not proceed in a single-crystal-to-single-crystal manner. Crystals under prolonged influence of UV–vis radiation lose their diffracting properties. Nevertheless, we were able to determine the crystal structure containing 89.6 (7)% of reactant and 10.4 (7)% of product molecules. The structure is presented in Fig. 3. It is very interesting that the carbonyl group reacts with one of two o-isopropyl groups, at least at the beginning of the photoreaction. Unfortunately, because the crystal loses its diffracting properties, it is not possible to see teh behaviour of the compound during the rest of the photoreaction.

In many cases, intramolecular parameters describing geometrical demands for a chemical reaction work very well. In the scientific literature many such examples are known (for instance, Chen et al., 2005; Ihmels & Scheffer, 1999; Leibovitch et al., 1998; Natarajan et al., 2005; Turowska-Tyrk, Bąkowicz et al., 2007; Turowska-Tyrk, Łabęcka et al., 2007; Turowska-Tyrk & Trzop, 2003; Vishnumurthy et al., 2002; Xia et al., 2005). However, there are also situations where predictions about reactivity on the basis of such parameters fail (for instance, Fukushima et al., 1998; Ito, Kano et al., 1998;). Such a situation concerns also the title compounds.

Related literature

For related literature, see: Bąkowicz & Turowska-Tyrk (2009); Chen et al. (2005); Fukushima et al. (1998); Ihmels & Scheffer (1999); Ito & Matsura (1988); Ito et al. (2009); Ito, Kano & Nakamura (1998); Ito, Yasui, Yamauchi, Ohba & Kano (1998); Leibovitch et al. (1998); Moorthy et al. (2001, 2004, 2006); Natarajan et al. (2005); Sheldrick (2008); Turowska-Tyrk & Trzop (2003); Turowska-Tyrk, Bąkowicz & Scheffer (2007); Turowska-Tyrk, Bąkowicz, Scheffer & Xia (2006); Turowska-Tyrk, Trzop, Scheffer & Chen (2006); Turowska-Tyrk, Łabęcka, Scheffer & Xia (2007); Vishnumurthy et al. (2002); Xia et al. (2005); Zouev et al. (2006).

S2. Experimental

Compounds (I) and (II) were purchased from Alfa Aesar and compound (IV) from Sigma-Aldrich. Compounds (I) and (II) were recrystallized from acetone and ethanol, respectively; (IV) was not recrystallized.

S3. Refinement

H atoms of all –CH₃ groups of (I) and –C23H₃ of (III) were located in difference Fourier maps and refined as part of rigid rotating groups. The remaining H atoms of (I) and (III) and all H atoms of (II) were positioned geometrically and treated as riding. C—H distances were fixed at 0.93–0.98 Å and U_iso(H) values at 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) for other H atoms.

The crystal of (IV) was irradiated for 4 h using a 100 W Hg lamp equipped with a water filter. For (III), the first atoms of the minor component (product) were found in a difference Fourier map and the remaining atoms were located geometrically. The difference peaks were seen near one o-isopropyl group and not near the other. The major component (reactant) was refined anisotropically and the minor component isotropically. H atoms in groups –OH and –OCH₃ of the minor component were omitted. The percentage of product molecules was determined by refinement of the site occupation factor. The R₁ value improved from 0.075 to 0.066 after inclusion of the minor component. Owing to a reactant–product disorder, which is always a feature of partly reacted crystals, the following weak restraints from SHELXL97 (Sheldrick, 2008) were applied for the minor component: DFIX, DANG, FLAT and SIMU. The DFIX and DANG commands restrained bond lengths and valence angles to target values. The target values were taken from the structures of the pure reactant (IV) and the pure photoproduct of a similar compound. FLAT restrained some atoms to be coplanar. SIMU restrained the displacement parameters of atoms of the photoproduct.

Computing details

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis CCD (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. An ORTEP (Farrugia, 1997) view of the molecule of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. An ORTEP (Farrugia, 1997) view of the molecule of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. An ORTEP (Farrugia, 1997) view of the photoproduct molecule (empty bonds) superimposed on the reactant molecule (filled bonds) for the crystal of (III). H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 10% probability level.

(I) 2,3,4,5,6-pentamethylbenzophenone

Crystal data

C18H20O	F(000) = 544
Mr = 252.34	Dx = 1.150 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1312 reflections
a = 6.3784 (15) Å	θ = 2.8–20.7°
b = 12.793 (2) Å	µ = 0.07 mm^−1
c = 18.014 (5) Å	T = 299 K
β = 97.28 (2)°	Block, colourless
V = 1458.1 (6) Å^3	0.60 × 0.30 × 0.13 mm
Z = 4

Data collection

Kuma KM-4 CCD diffractometer	1751 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
Graphite monochromator	θmax = 25.0°, θmin = 3.2°
ω scans	h = −3→7
7742 measured reflections	k = −14→15
2553 independent reflections	l = −21→20

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.177	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.1124P)^2] where P = (Fo^2 + 2Fc^2)/3
2553 reflections	(Δ/σ)max < 0.001
177 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

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

Refinement. 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	0.1217 (3)	0.48343 (12)	0.23147 (10)	0.0904 (6)
C1	0.2385 (3)	0.47419 (14)	0.18363 (11)	0.0530 (5)
C2	0.2922 (3)	0.36765 (14)	0.15748 (10)	0.0444 (5)
C3	0.4785 (3)	0.31976 (14)	0.19035 (10)	0.0468 (5)
C4	0.5255 (3)	0.21971 (14)	0.16754 (11)	0.0509 (5)
C5	0.3858 (3)	0.16787 (15)	0.11418 (10)	0.0536 (5)
C6	0.2003 (3)	0.21668 (15)	0.08186 (10)	0.0549 (5)
C7	0.1537 (3)	0.31763 (15)	0.10326 (11)	0.0502 (5)
C8	0.6199 (3)	0.37545 (19)	0.25120 (13)	0.0691 (6)
H8A	0.6419	0.3319	0.2949	0.104*
H8B	0.5544	0.4397	0.2634	0.104*
H8C	0.7533	0.3903	0.2341	0.104*
C9	0.7268 (3)	0.16752 (19)	0.20307 (14)	0.0751 (7)
H9A	0.8384	0.2182	0.2102	0.113*
H9B	0.7649	0.1127	0.1710	0.113*
H9C	0.7044	0.1386	0.2506	0.113*
C10	0.4354 (5)	0.05735 (19)	0.09262 (15)	0.0874 (8)
H10A	0.5479	0.0582	0.0619	0.131*
H10B	0.3119	0.0264	0.0652	0.131*
H10C	0.4777	0.0172	0.1370	0.131*
C11	0.0473 (4)	0.1600 (2)	0.02402 (14)	0.0895 (8)
H11A	−0.0805	0.2000	0.0138	0.134*
H11B	0.0153	0.0925	0.0429	0.134*
H11C	0.1104	0.1518	−0.0213	0.134*
C12	−0.0445 (3)	0.3729 (2)	0.06800 (14)	0.0760 (7)
H12A	−0.0510	0.4413	0.0894	0.114*
H12B	−0.1665	0.3333	0.0772	0.114*
H12C	−0.0415	0.3789	0.0150	0.114*
C13	0.3258 (3)	0.56766 (14)	0.14940 (10)	0.0454 (5)
C14	0.4642 (3)	0.55909 (16)	0.09658 (10)	0.0535 (5)
H14	0.5038	0.4934	0.0812	0.064*
C15	0.5438 (3)	0.64792 (18)	0.06656 (12)	0.0658 (6)
H15	0.6359	0.6421	0.0307	0.079*
C16	0.4867 (3)	0.74431 (17)	0.08979 (12)	0.0664 (6)
H16	0.5409	0.8040	0.0697	0.080*
C17	0.3507 (3)	0.75374 (16)	0.14225 (12)	0.0674 (6)
H17	0.3121	0.8197	0.1575	0.081*
C18	0.2710 (3)	0.66603 (15)	0.17239 (11)	0.0577 (5)
H18	0.1797	0.6727	0.2085	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.1211 (13)	0.0590 (11)	0.1075 (13)	−0.0012 (9)	0.0778 (12)	−0.0023 (9)
C1	0.0575 (11)	0.0453 (12)	0.0599 (12)	0.0011 (8)	0.0222 (9)	0.0010 (9)
C2	0.0504 (9)	0.0355 (10)	0.0498 (11)	−0.0027 (7)	0.0162 (8)	0.0040 (7)
C3	0.0509 (10)	0.0428 (11)	0.0479 (11)	−0.0069 (8)	0.0104 (8)	0.0034 (8)
C4	0.0563 (10)	0.0433 (11)	0.0560 (12)	0.0040 (8)	0.0189 (9)	0.0089 (9)
C5	0.0754 (13)	0.0398 (11)	0.0499 (12)	−0.0038 (9)	0.0252 (10)	−0.0005 (8)
C6	0.0693 (12)	0.0498 (12)	0.0472 (11)	−0.0152 (9)	0.0137 (9)	−0.0029 (9)
C7	0.0517 (10)	0.0496 (12)	0.0505 (11)	−0.0052 (8)	0.0103 (8)	0.0069 (9)
C8	0.0662 (13)	0.0648 (15)	0.0730 (15)	−0.0097 (10)	−0.0033 (11)	−0.0050 (11)
C9	0.0731 (14)	0.0665 (15)	0.0871 (17)	0.0209 (11)	0.0161 (12)	0.0145 (12)
C10	0.138 (2)	0.0485 (14)	0.0824 (16)	0.0058 (14)	0.0389 (15)	−0.0098 (12)
C11	0.0996 (19)	0.0904 (19)	0.0757 (17)	−0.0299 (15)	0.0001 (14)	−0.0200 (14)
C12	0.0610 (12)	0.0882 (18)	0.0764 (15)	0.0044 (11)	−0.0006 (11)	0.0132 (13)
C13	0.0506 (9)	0.0398 (10)	0.0463 (10)	0.0016 (8)	0.0083 (8)	0.0001 (8)
C14	0.0629 (11)	0.0455 (11)	0.0551 (11)	−0.0026 (9)	0.0188 (9)	−0.0023 (9)
C15	0.0772 (14)	0.0618 (15)	0.0628 (13)	−0.0121 (11)	0.0261 (11)	0.0015 (10)
C16	0.0814 (14)	0.0496 (13)	0.0682 (14)	−0.0133 (11)	0.0096 (11)	0.0096 (10)
C17	0.0847 (15)	0.0384 (12)	0.0791 (15)	0.0013 (10)	0.0104 (12)	−0.0008 (10)
C18	0.0689 (12)	0.0440 (12)	0.0630 (13)	0.0036 (9)	0.0191 (10)	−0.0026 (9)

Geometric parameters (Å, º)

O1—C1	1.214 (2)	C10—H10A	0.9600
C1—C13	1.486 (2)	C10—H10B	0.9600
C1—C2	1.496 (2)	C10—H10C	0.9600
C2—C7	1.387 (3)	C11—H11A	0.9600
C2—C3	1.400 (2)	C11—H11B	0.9600
C3—C4	1.389 (3)	C11—H11C	0.9600
C3—C8	1.507 (3)	C12—H12A	0.9600
C4—C5	1.393 (3)	C12—H12B	0.9600
C4—C9	1.515 (3)	C12—H12C	0.9600
C5—C6	1.398 (3)	C13—C14	1.382 (3)
C5—C10	1.510 (3)	C13—C18	1.384 (3)
C6—C7	1.391 (3)	C14—C15	1.383 (3)
C6—C11	1.518 (3)	C14—H14	0.9300
C7—C12	1.516 (3)	C15—C16	1.366 (3)
C8—H8A	0.9600	C15—H15	0.9300
C8—H8B	0.9600	C16—C17	1.367 (3)
C8—H8C	0.9600	C16—H16	0.9300
C9—H9A	0.9600	C17—C18	1.372 (3)
C9—H9B	0.9600	C17—H17	0.9300
C9—H9C	0.9600	C18—H18	0.9300
O1—C1—C13	120.82 (17)	H10A—C10—H10B	109.5
O1—C1—C2	119.85 (17)	C5—C10—H10C	109.5
C13—C1—C2	119.32 (15)	H10A—C10—H10C	109.5
C7—C2—C3	121.77 (17)	H10B—C10—H10C	109.5
C7—C2—C1	119.42 (16)	C6—C11—H11A	109.5
C3—C2—C1	118.78 (16)	C6—C11—H11B	109.5
C4—C3—C2	118.78 (16)	H11A—C11—H11B	109.5
C4—C3—C8	121.31 (17)	C6—C11—H11C	109.5
C2—C3—C8	119.88 (17)	H11A—C11—H11C	109.5
C3—C4—C5	120.01 (17)	H11B—C11—H11C	109.5
C3—C4—C9	118.95 (18)	C7—C12—H12A	109.5
C5—C4—C9	121.02 (19)	C7—C12—H12B	109.5
C4—C5—C6	120.55 (18)	H12A—C12—H12B	109.5
C4—C5—C10	119.14 (19)	C7—C12—H12C	109.5
C6—C5—C10	120.31 (19)	H12A—C12—H12C	109.5
C7—C6—C5	119.91 (17)	H12B—C12—H12C	109.5
C7—C6—C11	119.5 (2)	C14—C13—C18	119.08 (17)
C5—C6—C11	120.6 (2)	C14—C13—C1	121.86 (17)
C2—C7—C6	118.95 (17)	C18—C13—C1	119.05 (16)
C2—C7—C12	120.18 (19)	C13—C14—C15	120.17 (19)
C6—C7—C12	120.86 (19)	C13—C14—H14	119.9
C3—C8—H8A	109.5	C15—C14—H14	119.9
C3—C8—H8B	109.5	C16—C15—C14	119.8 (2)
H8A—C8—H8B	109.5	C16—C15—H15	120.1
C3—C8—H8C	109.5	C14—C15—H15	120.1
H8A—C8—H8C	109.5	C15—C16—C17	120.6 (2)
H8B—C8—H8C	109.5	C15—C16—H16	119.7
C4—C9—H9A	109.5	C17—C16—H16	119.7
C4—C9—H9B	109.5	C16—C17—C18	120.1 (2)
H9A—C9—H9B	109.5	C16—C17—H17	120.0
C4—C9—H9C	109.5	C18—C17—H17	120.0
H9A—C9—H9C	109.5	C17—C18—C13	120.34 (19)
H9B—C9—H9C	109.5	C17—C18—H18	119.8
C5—C10—H10A	109.5	C13—C18—H18	119.8
C5—C10—H10B	109.5

(II) 1,3-diphenylbutan-1-one

Crystal data

C16H16O	F(000) = 480
Mr = 224.29	Dx = 1.181 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1527 reflections
a = 10.7926 (18) Å	θ = 2.4–18.8°
b = 14.931 (2) Å	µ = 0.07 mm^−1
c = 7.8275 (11) Å	T = 299 K
V = 1261.4 (3) Å^3	Block, colourless
Z = 4	0.30 × 0.15 × 0.10 mm

Data collection

Kuma KM-4 CCD diffractometer	1050 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 25.0°, θmin = 3.3°
ω scans	h = −12→12
6471 measured reflections	k = −17→17
1201 independent reflections	l = −9→6

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.038	w = 1/[σ^2(Fo^2) + (0.0774P)^2 + 0.0454P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.115	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.11 e Å^−3
1201 reflections	Δρmin = −0.11 e Å^−3
155 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.020 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Absolute configuration is unknown. An arbitrary choice of enantiomer has been made.
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0 (10)

Special details

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

Refinement. 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
C1	0.84728 (19)	0.37590 (18)	0.3329 (3)	0.0651 (6)
C2	0.9337 (2)	0.31572 (16)	0.4293 (4)	0.0643 (6)
H2A	0.9234	0.3270	0.5505	0.077*
H2B	1.0182	0.3316	0.3995	0.077*
C3	0.9158 (2)	0.21544 (17)	0.3968 (4)	0.0685 (7)
H3	0.8270	0.2029	0.4065	0.082*
C4	0.9807 (2)	0.16110 (17)	0.5316 (4)	0.0663 (7)
C5	0.9146 (3)	0.1214 (2)	0.6621 (4)	0.0855 (8)
H5	0.8289	0.1276	0.6657	0.103*
C6	0.9745 (5)	0.0721 (2)	0.7883 (5)	0.1053 (12)
H6	0.9287	0.0455	0.8753	0.126*
C7	1.0997 (5)	0.0626 (2)	0.7850 (6)	0.1054 (12)
H7	1.1394	0.0293	0.8692	0.126*
C8	1.1668 (3)	0.1016 (2)	0.6589 (5)	0.0956 (10)
H8	1.2525	0.0955	0.6575	0.115*
C9	1.1087 (3)	0.1502 (2)	0.5334 (4)	0.0799 (8)
H9	1.1560	0.1764	0.4476	0.096*
C10	0.8673 (2)	0.47472 (17)	0.3403 (3)	0.0591 (6)
C11	0.7825 (2)	0.53073 (18)	0.2608 (3)	0.0708 (7)
H11	0.7138	0.5064	0.2061	0.085*
C12	0.7994 (2)	0.6219 (2)	0.2622 (4)	0.0810 (8)
H12	0.7429	0.6588	0.2067	0.097*
C13	0.8985 (3)	0.6588 (2)	0.3445 (4)	0.0779 (8)
H13	0.9088	0.7206	0.3463	0.093*
C14	0.9828 (3)	0.60445 (18)	0.4246 (4)	0.0747 (7)
H14	1.0509	0.6295	0.4795	0.090*
C15	0.9669 (2)	0.51246 (17)	0.4242 (3)	0.0635 (6)
H15	1.0236	0.4760	0.4806	0.076*
C16	0.9553 (3)	0.1904 (2)	0.2156 (4)	0.0902 (10)
H16A	0.9111	0.2268	0.1350	0.135*
H16B	0.9369	0.1284	0.1952	0.135*
H16C	1.0427	0.2002	0.2029	0.135*
O1	0.7610 (2)	0.34564 (12)	0.2529 (4)	0.0981 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0546 (11)	0.0782 (16)	0.0625 (13)	0.0024 (11)	−0.0028 (12)	−0.0104 (13)
C2	0.0601 (12)	0.0685 (14)	0.0644 (15)	0.0000 (10)	−0.0008 (12)	−0.0103 (13)
C3	0.0734 (14)	0.0683 (15)	0.0638 (14)	−0.0108 (11)	0.0020 (13)	−0.0050 (13)
C4	0.0813 (17)	0.0572 (13)	0.0604 (14)	−0.0065 (12)	0.0062 (13)	−0.0101 (11)
C5	0.100 (2)	0.0788 (17)	0.0773 (19)	−0.0131 (16)	0.0167 (17)	0.0021 (16)
C6	0.161 (4)	0.082 (2)	0.072 (2)	−0.024 (2)	0.008 (2)	0.0136 (17)
C7	0.153 (4)	0.072 (2)	0.091 (2)	−0.001 (2)	−0.033 (2)	−0.0026 (18)
C8	0.107 (2)	0.0812 (19)	0.099 (2)	0.0123 (17)	−0.021 (2)	−0.0159 (19)
C9	0.0845 (17)	0.0824 (18)	0.0728 (17)	−0.0026 (14)	0.0019 (15)	−0.0088 (14)
C10	0.0547 (10)	0.0734 (15)	0.0491 (11)	0.0062 (10)	0.0032 (10)	−0.0027 (12)
C11	0.0592 (14)	0.0940 (17)	0.0593 (15)	0.0114 (12)	−0.0051 (12)	−0.0003 (15)
C12	0.0839 (17)	0.0929 (19)	0.0661 (16)	0.0268 (15)	−0.0005 (16)	0.0100 (16)
C13	0.0918 (18)	0.0726 (17)	0.0694 (17)	0.0093 (14)	0.0088 (17)	0.0076 (14)
C14	0.0752 (15)	0.0756 (16)	0.0734 (16)	−0.0033 (13)	−0.0015 (14)	−0.0032 (16)
C15	0.0595 (13)	0.0728 (15)	0.0582 (13)	0.0049 (11)	−0.0044 (11)	−0.0010 (13)
C16	0.136 (3)	0.0687 (15)	0.0662 (17)	−0.0006 (17)	0.0029 (17)	−0.0103 (14)
O1	0.0753 (11)	0.0993 (13)	0.1199 (18)	−0.0029 (11)	−0.0354 (13)	−0.0174 (14)

Geometric parameters (Å, º)

C1—O1	1.210 (3)	C8—C9	1.373 (5)
C1—C10	1.492 (3)	C8—H8	0.9300
C1—C2	1.499 (4)	C9—H9	0.9300
C2—C3	1.531 (4)	C10—C15	1.381 (3)
C2—H2A	0.9700	C10—C11	1.387 (3)
C2—H2B	0.9700	C11—C12	1.374 (4)
C3—C4	1.504 (4)	C11—H11	0.9300
C3—C16	1.527 (4)	C12—C13	1.365 (4)
C3—H3	0.9800	C12—H12	0.9300
C4—C5	1.379 (4)	C13—C14	1.371 (4)
C4—C9	1.391 (4)	C13—H13	0.9300
C5—C6	1.392 (5)	C14—C15	1.384 (4)
C5—H5	0.9300	C14—H14	0.9300
C6—C7	1.358 (6)	C15—H15	0.9300
C6—H6	0.9300	C16—H16A	0.9600
C7—C8	1.356 (6)	C16—H16B	0.9600
C7—H7	0.9300	C16—H16C	0.9600
O1—C1—C10	120.0 (2)	C9—C8—H8	119.9
O1—C1—C2	121.1 (2)	C8—C9—C4	121.5 (3)
C10—C1—C2	118.9 (2)	C8—C9—H9	119.2
C1—C2—C3	115.1 (2)	C4—C9—H9	119.2
C1—C2—H2A	108.5	C15—C10—C11	118.8 (2)
C3—C2—H2A	108.5	C15—C10—C1	122.3 (2)
C1—C2—H2B	108.5	C11—C10—C1	118.9 (2)
C3—C2—H2B	108.5	C12—C11—C10	120.4 (2)
H2A—C2—H2B	107.5	C12—C11—H11	119.8
C4—C3—C16	112.9 (2)	C10—C11—H11	119.8
C4—C3—C2	110.6 (2)	C13—C12—C11	120.5 (2)
C16—C3—C2	111.0 (2)	C13—C12—H12	119.7
C4—C3—H3	107.3	C11—C12—H12	119.7
C16—C3—H3	107.3	C12—C13—C14	119.8 (3)
C2—C3—H3	107.3	C12—C13—H13	120.1
C5—C4—C9	117.1 (3)	C14—C13—H13	120.1
C5—C4—C3	120.7 (3)	C13—C14—C15	120.3 (3)
C9—C4—C3	122.2 (3)	C13—C14—H14	119.9
C4—C5—C6	120.9 (3)	C15—C14—H14	119.9
C4—C5—H5	119.6	C10—C15—C14	120.1 (2)
C6—C5—H5	119.6	C10—C15—H15	119.9
C7—C6—C5	120.2 (3)	C14—C15—H15	119.9
C7—C6—H6	119.9	C3—C16—H16A	109.5
C5—C6—H6	119.9	C3—C16—H16B	109.5
C8—C7—C6	120.0 (4)	H16A—C16—H16B	109.5
C8—C7—H7	120.0	C3—C16—H16C	109.5
C6—C7—H7	120.0	H16A—C16—H16C	109.5
C7—C8—C9	120.3 (3)	H16B—C16—H16C	109.5
C7—C8—H8	119.9

(III) 2,4,6-triisopropyl-4'-methoxybenzophenone– 3,5-diisopropyl-7-(4-methoxyphenyl)-8,8-dimethylbicyclo[4.2.0]octa-1,3,5- trien-7-ol (9/1)

Crystal data

0.90C23H30O2·0.10C23H30O2	F(000) = 736
Mr = 338.47	Dx = 1.074 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1000 reflections
a = 9.2288 (10) Å	θ = 3.7–17.9°
b = 12.0541 (14) Å	µ = 0.07 mm^−1
c = 18.821 (2) Å	T = 299 K
β = 90.021 (9)°	Block, colourless
V = 2093.7 (4) Å^3	0.40 × 0.30 × 0.15 mm
Z = 4

Data collection

Kuma KM-4 CCD diffractometer	1609 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 25.0°, θmin = 4.0°
ω scans	h = −10→10
9964 measured reflections	k = −10→14
3564 independent reflections	l = −22→21

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.232	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.1192P)^2] where P = (Fo^2 + 2Fc^2)/3
3564 reflections	(Δ/σ)max < 0.001
328 parameters	Δρmax = 0.26 e Å^−3
224 restraints	Δρmin = −0.15 e Å^−3

Special details

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

Refinement. 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)
O1R	0.5854 (6)	0.1056 (4)	0.2805 (2)	0.1133 (19)	0.897 (7)
O2R	0.137 (2)	0.4210 (8)	0.4257 (8)	0.098 (3)	0.897 (7)
C1R	0.5076 (7)	0.2158 (6)	0.1267 (4)	0.0831 (19)	0.897 (7)
C2R	0.5588 (7)	0.2554 (7)	0.0623 (3)	0.093 (2)	0.897 (7)
H2R	0.5055	0.2411	0.0214	0.111*	0.897 (7)
C3R	0.6847 (9)	0.3147 (8)	0.0566 (4)	0.097 (2)	0.897 (7)
C4R	0.7598 (9)	0.3357 (10)	0.1178 (5)	0.102 (3)	0.897 (7)
H4R	0.8459	0.3756	0.1148	0.123*	0.897 (7)
C5R	0.7138 (8)	0.3003 (8)	0.1840 (4)	0.090 (3)	0.897 (7)
C6R	0.5882 (7)	0.2373 (7)	0.1887 (4)	0.081 (2)	0.897 (7)
C7R	0.5367 (7)	0.1921 (5)	0.2578 (3)	0.0802 (18)	0.897 (7)
C8R	0.4263 (6)	0.2524 (5)	0.2999 (3)	0.0710 (16)	0.897 (7)
C9R	0.3586 (7)	0.2031 (5)	0.3565 (3)	0.0814 (17)	0.897 (7)
H9R	0.3797	0.1298	0.3678	0.098*	0.897 (7)
C10R	0.2612 (7)	0.2600 (5)	0.3963 (3)	0.0812 (18)	0.897 (7)
H10R	0.2141	0.2246	0.4336	0.097*	0.897 (7)
C11R	0.2315 (8)	0.3696 (6)	0.3820 (4)	0.075 (2)	0.897 (7)
C12R	0.2971 (9)	0.4196 (6)	0.3254 (4)	0.080 (2)	0.897 (7)
H12R	0.2771	0.4934	0.3147	0.096*	0.897 (7)
C13R	0.3930 (8)	0.3602 (5)	0.2842 (4)	0.080 (2)	0.897 (7)
H13R	0.4358	0.3940	0.2450	0.096*	0.897 (7)
C14R	0.3670 (8)	0.1533 (7)	0.1286 (4)	0.101 (2)	0.897 (7)
H14R	0.3528	0.1274	0.1774	0.121*	0.897 (7)
C15R	0.2397 (8)	0.2265 (9)	0.1102 (5)	0.136 (3)	0.897 (7)
H15A	0.1518	0.1842	0.1133	0.203*	0.897 (7)
H15B	0.2509	0.2542	0.0627	0.203*	0.897 (7)
H15C	0.2354	0.2876	0.1428	0.203*	0.897 (7)
C16R	0.3719 (11)	0.0510 (8)	0.0809 (5)	0.130 (3)	0.897 (7)
H16A	0.2819	0.0116	0.0845	0.195*	0.897 (7)
H16B	0.4499	0.0036	0.0957	0.195*	0.897 (7)
H16C	0.3871	0.0736	0.0326	0.195*	0.897 (7)
C17R	0.7386 (9)	0.3554 (7)	−0.0150 (4)	0.124 (3)	0.897 (7)
H17R	0.6652	0.3251	−0.0473	0.149*	0.897 (7)
C18R	0.8645 (16)	0.3034 (12)	−0.0395 (6)	0.237 (7)	0.897 (7)
H18A	0.8585	0.2252	−0.0304	0.355*	0.897 (7)
H18B	0.9471	0.3336	−0.0152	0.355*	0.897 (7)
H18C	0.8744	0.3157	−0.0896	0.355*	0.897 (7)
C19R	0.7199 (17)	0.4720 (10)	−0.0249 (6)	0.224 (6)	0.897 (7)
H19A	0.6282	0.4944	−0.0055	0.336*	0.897 (7)
H19B	0.7223	0.4889	−0.0747	0.336*	0.897 (7)
H19C	0.7964	0.5111	−0.0011	0.336*	0.897 (7)
C20R	0.8038 (9)	0.3209 (7)	0.2497 (4)	0.115 (3)	0.897 (7)
H20R	0.7396	0.3116	0.2907	0.138*	0.897 (7)
C21R	0.8653 (13)	0.4363 (9)	0.2538 (6)	0.182 (4)	0.897 (7)
H21A	0.9206	0.4440	0.2967	0.273*	0.897 (7)
H21B	0.7876	0.4893	0.2537	0.273*	0.897 (7)
H21C	0.9269	0.4492	0.2135	0.273*	0.897 (7)
C22R	0.9242 (12)	0.2334 (14)	0.2564 (7)	0.160 (4)	0.897 (7)
H22A	0.8824	0.1606	0.2542	0.239*	0.897 (7)
H22B	0.9734	0.2426	0.3009	0.239*	0.897 (7)
H22C	0.9921	0.2423	0.2181	0.239*	0.897 (7)
C23R	0.1219 (14)	0.5379 (7)	0.4203 (5)	0.109 (3)	0.897 (7)
H23A	0.2151	0.5722	0.4258	0.164*	0.897 (7)
H23B	0.0579	0.5639	0.4569	0.164*	0.897 (7)
H23C	0.0827	0.5565	0.3746	0.164*	0.897 (7)
O1P	0.499 (4)	0.087 (3)	0.242 (2)	0.114 (12)*	0.103 (7)
O2P	0.12 (2)	0.424 (6)	0.417 (8)	0.098 (10)*	0.103 (7)
C1P	0.520 (5)	0.249 (5)	0.113 (2)	0.090 (17)*	0.103 (7)
C2P	0.585 (6)	0.299 (5)	0.056 (2)	0.094 (17)*	0.103 (7)
H2P	0.5385	0.3055	0.0123	0.112*	0.103 (7)
C3P	0.724 (6)	0.340 (6)	0.067 (2)	0.098 (17)*	0.103 (7)
C4P	0.792 (6)	0.327 (8)	0.130 (3)	0.104 (17)*	0.103 (7)
H4P	0.8863	0.3535	0.1348	0.125*	0.103 (7)
C5P	0.728 (5)	0.275 (6)	0.189 (2)	0.081 (17)*	0.103 (7)
C6P	0.583 (4)	0.249 (5)	0.1774 (19)	0.089 (17)*	0.103 (7)
C7P	0.458 (4)	0.192 (3)	0.2148 (17)	0.098 (13)*	0.103 (7)
C8P	0.386 (4)	0.260 (3)	0.2734 (19)	0.062 (13)*	0.103 (7)
C9P	0.316 (5)	0.206 (3)	0.327 (2)	0.082 (14)*	0.103 (7)
H9P	0.3297	0.1301	0.3330	0.098*	0.103 (7)
C10P	0.224 (6)	0.263 (4)	0.372 (2)	0.095 (17)*	0.103 (7)
H10P	0.1747	0.2238	0.4073	0.114*	0.103 (7)
C11P	0.205 (8)	0.375 (4)	0.366 (3)	0.074 (17)*	0.103 (7)
C12P	0.270 (8)	0.428 (4)	0.310 (3)	0.075 (16)*	0.103 (7)
H12P	0.2487	0.5020	0.3010	0.090*	0.103 (7)
C13P	0.365 (8)	0.373 (3)	0.267 (3)	0.083 (17)*	0.103 (7)
H13P	0.4167	0.4121	0.2334	0.100*	0.103 (7)
C14P	0.385 (4)	0.185 (4)	0.135 (2)	0.099 (9)*	0.103 (7)
C15P	0.247 (6)	0.255 (8)	0.129 (4)	0.140 (18)*	0.103 (7)
H15D	0.2631	0.3261	0.1506	0.210*	0.103 (7)
H15E	0.1697	0.2176	0.1538	0.210*	0.103 (7)
H15F	0.2215	0.2640	0.0803	0.210*	0.103 (7)
C16P	0.365 (10)	0.074 (5)	0.101 (4)	0.129 (18)*	0.103 (7)
H16D	0.4508	0.0308	0.1070	0.193*	0.103 (7)
H16E	0.3454	0.0838	0.0511	0.193*	0.103 (7)
H16F	0.2842	0.0370	0.1228	0.193*	0.103 (7)
C17P	0.789 (6)	0.415 (5)	0.008 (3)	0.125 (10)*	0.103 (7)
H17P	0.8069	0.4875	0.0297	0.150*	0.103 (7)
C18P	0.928 (8)	0.373 (10)	−0.017 (5)	0.23 (2)*	0.103 (7)
H18D	0.9845	0.3469	0.0224	0.346*	0.103 (7)
H18E	0.9796	0.4308	−0.0412	0.346*	0.103 (7)
H18F	0.9120	0.3122	−0.0496	0.346*	0.103 (7)
C19P	0.682 (9)	0.431 (12)	−0.049 (5)	0.22 (2)*	0.103 (7)
H19D	0.6005	0.4710	−0.0303	0.332*	0.103 (7)
H19E	0.6513	0.3603	−0.0662	0.332*	0.103 (7)
H19F	0.7258	0.4728	−0.0865	0.332*	0.103 (7)
C20P	0.790 (6)	0.284 (5)	0.264 (2)	0.114 (10)*	0.103 (7)
H20P	0.7338	0.2353	0.2950	0.137*	0.103 (7)
C21P	0.775 (11)	0.402 (6)	0.291 (4)	0.183 (18)*	0.103 (7)
H21D	0.6758	0.4250	0.2874	0.274*	0.103 (7)
H21E	0.8347	0.4503	0.2628	0.274*	0.103 (7)
H21F	0.8056	0.4049	0.3396	0.274*	0.103 (7)
C22P	0.946 (9)	0.250 (11)	0.267 (6)	0.163 (18)*	0.103 (7)
H22D	0.9584	0.1798	0.2446	0.244*	0.103 (7)
H22E	0.9754	0.2450	0.3162	0.244*	0.103 (7)
H22F	1.0046	0.3049	0.2437	0.244*	0.103 (7)
C23P	0.118 (15)	0.537 (6)	0.396 (5)	0.117 (18)*	0.103 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1R	0.151 (5)	0.101 (3)	0.088 (3)	0.036 (3)	0.024 (3)	0.003 (2)
O2R	0.091 (6)	0.109 (4)	0.095 (6)	0.004 (2)	0.031 (6)	−0.004 (3)
C1R	0.074 (4)	0.095 (5)	0.081 (4)	−0.007 (3)	0.010 (3)	0.004 (3)
C2R	0.084 (4)	0.115 (6)	0.079 (4)	−0.006 (4)	0.003 (3)	0.005 (4)
C3R	0.082 (5)	0.114 (6)	0.096 (5)	−0.003 (4)	0.019 (4)	−0.001 (4)
C4R	0.083 (5)	0.116 (6)	0.108 (6)	−0.019 (5)	0.025 (4)	−0.016 (5)
C5R	0.079 (4)	0.102 (6)	0.090 (5)	−0.003 (4)	0.011 (4)	−0.021 (4)
C6R	0.077 (4)	0.087 (4)	0.077 (4)	0.000 (3)	0.012 (3)	−0.007 (3)
C7R	0.096 (4)	0.080 (4)	0.065 (3)	0.005 (3)	0.003 (3)	−0.007 (3)
C8R	0.081 (4)	0.073 (4)	0.059 (3)	−0.004 (3)	0.001 (3)	0.002 (3)
C9R	0.097 (4)	0.081 (4)	0.067 (4)	0.002 (3)	0.001 (4)	0.007 (3)
C10R	0.082 (4)	0.091 (4)	0.070 (4)	−0.005 (3)	0.011 (4)	0.010 (3)
C11R	0.062 (4)	0.093 (5)	0.069 (4)	−0.006 (3)	0.004 (4)	−0.001 (3)
C12R	0.079 (5)	0.078 (4)	0.085 (5)	0.003 (3)	0.008 (5)	0.003 (3)
C13R	0.086 (5)	0.080 (4)	0.074 (4)	−0.010 (3)	0.018 (4)	0.003 (3)
C14R	0.099 (5)	0.123 (6)	0.080 (4)	−0.029 (4)	0.006 (3)	−0.009 (4)
C15R	0.079 (5)	0.176 (9)	0.152 (8)	−0.013 (5)	0.020 (5)	−0.034 (6)
C16R	0.118 (6)	0.147 (7)	0.125 (7)	−0.028 (5)	−0.010 (5)	−0.029 (5)
C17R	0.129 (6)	0.128 (6)	0.115 (5)	−0.005 (5)	0.045 (5)	0.025 (5)
C18R	0.272 (13)	0.276 (14)	0.163 (9)	0.094 (12)	0.133 (10)	0.066 (9)
C19R	0.327 (15)	0.158 (11)	0.187 (10)	0.032 (10)	0.109 (10)	0.061 (9)
C20R	0.096 (5)	0.146 (7)	0.103 (5)	−0.015 (5)	0.008 (4)	−0.038 (5)
C21R	0.188 (9)	0.178 (9)	0.180 (9)	−0.059 (8)	−0.010 (7)	−0.077 (7)
C22R	0.128 (7)	0.231 (11)	0.120 (7)	0.014 (8)	−0.032 (5)	−0.043 (6)
C23R	0.118 (5)	0.102 (5)	0.108 (7)	0.022 (4)	0.031 (7)	−0.007 (4)

Geometric parameters (Å, º)

O1R—C7R	1.213 (6)	C23R—H23C	0.9600
O2R—C11R	1.351 (7)	O1P—C7P	1.416 (16)
O2R—C23R	1.419 (8)	O2P—C11P	1.359 (8)
C1R—C2R	1.385 (9)	O2P—C23P	1.420 (9)
C1R—C6R	1.408 (8)	C1P—C6P	1.352 (15)
C1R—C14R	1.501 (9)	C1P—C2P	1.362 (15)
C2R—C3R	1.369 (10)	C1P—C14P	1.522 (15)
C2R—H2R	0.9300	C2P—C3P	1.385 (15)
C3R—C4R	1.368 (11)	C2P—H2P	0.9300
C3R—C17R	1.519 (9)	C3P—C4P	1.363 (15)
C4R—C5R	1.384 (9)	C3P—C17P	1.545 (16)
C4R—H4R	0.9300	C4P—C5P	1.405 (16)
C5R—C6R	1.389 (8)	C4P—H4P	0.9300
C5R—C20R	1.509 (9)	C5P—C6P	1.387 (15)
C6R—C7R	1.488 (8)	C5P—C20P	1.519 (16)
C7R—C8R	1.481 (7)	C6P—C7P	1.516 (15)
C8R—C13R	1.367 (8)	C7P—C8P	1.525 (15)
C8R—C9R	1.372 (7)	C7P—C14P	1.652 (16)
C9R—C10R	1.356 (7)	C8P—C9P	1.363 (15)
C9R—H9R	0.9300	C8P—C13P	1.380 (15)
C10R—C11R	1.375 (8)	C9P—C10P	1.381 (16)
C10R—H10R	0.9300	C9P—H9P	0.9300
C11R—C12R	1.367 (8)	C10P—C11P	1.368 (15)
C12R—C13R	1.378 (7)	C10P—H10P	0.9300
C12R—H12R	0.9300	C11P—C12P	1.373 (15)
C13R—H13R	0.9300	C12P—C13P	1.362 (16)
C14R—C15R	1.509 (10)	C12P—H12P	0.9300
C14R—C16R	1.525 (10)	C13P—H13P	0.9300
C14R—H14R	0.9800	C14P—C16P	1.496 (16)
C15R—H15A	0.9600	C14P—C15P	1.527 (16)
C15R—H15B	0.9600	C15P—H15D	0.9600
C15R—H15C	0.9600	C15P—H15E	0.9600
C16R—H16A	0.9600	C15P—H15F	0.9600
C16R—H16B	0.9600	C16P—H16D	0.9600
C16R—H16C	0.9600	C16P—H16E	0.9600
C17R—C18R	1.398 (12)	C16P—H16F	0.9600
C17R—C19R	1.429 (13)	C17P—C19P	1.464 (17)
C17R—H17R	0.9800	C17P—C18P	1.465 (17)
C18R—H18A	0.9600	C17P—H17P	0.9800
C18R—H18B	0.9600	C18P—H18D	0.9600
C18R—H18C	0.9600	C18P—H18E	0.9600
C19R—H19A	0.9600	C18P—H18F	0.9600
C19R—H19B	0.9600	C19P—H19D	0.9600
C19R—H19C	0.9600	C19P—H19E	0.9600
C20R—C21R	1.504 (12)	C19P—H19F	0.9600
C20R—C22R	1.538 (12)	C20P—C22P	1.503 (17)
C20R—H20R	0.9800	C20P—C21P	1.513 (17)
C21R—H21A	0.9600	C20P—H20P	0.9800
C21R—H21B	0.9600	C21P—H21D	0.9600
C21R—H21C	0.9600	C21P—H21E	0.9600
C22R—H22A	0.9600	C21P—H21F	0.9600
C22R—H22B	0.9600	C22P—H22D	0.9600
C22R—H22C	0.9600	C22P—H22E	0.9600
C23R—H23A	0.9600	C22P—H22F	0.9600
C23R—H23B	0.9600
C11R—O2R—C23R	118.3 (6)	C6P—C1P—C14P	95.9 (14)
C2R—C1R—C6R	118.8 (6)	C2P—C1P—C14P	143 (2)
C2R—C1R—C14R	119.2 (6)	C1P—C2P—C3P	117 (2)
C6R—C1R—C14R	122.0 (6)	C1P—C2P—H2P	121.6
C3R—C2R—C1R	122.6 (6)	C3P—C2P—H2P	121.6
C3R—C2R—H2R	118.7	C4P—C3P—C2P	121.0 (18)
C1R—C2R—H2R	118.7	C4P—C3P—C17P	121 (2)
C4R—C3R—C2R	117.4 (6)	C2P—C3P—C17P	118 (2)
C4R—C3R—C17R	121.5 (7)	C3P—C4P—C5P	123 (2)
C2R—C3R—C17R	121.1 (7)	C3P—C4P—H4P	118.4
C3R—C4R—C5R	123.1 (7)	C5P—C4P—H4P	118.4
C3R—C4R—H4R	118.5	C6P—C5P—C4P	112.6 (19)
C5R—C4R—H4R	118.5	C6P—C5P—C20P	122 (2)
C4R—C5R—C6R	118.8 (7)	C4P—C5P—C20P	123 (2)
C4R—C5R—C20R	121.2 (7)	C1P—C6P—C5P	123.9 (18)
C6R—C5R—C20R	119.8 (7)	C1P—C6P—C7P	95.3 (14)
C5R—C6R—C1R	119.3 (6)	C5P—C6P—C7P	139 (2)
C5R—C6R—C7R	121.5 (6)	O1P—C7P—C6P	112 (2)
C1R—C6R—C7R	119.3 (6)	O1P—C7P—C8P	109.4 (18)
O1R—C7R—C8R	119.3 (5)	C6P—C7P—C8P	115 (2)
O1R—C7R—C6R	120.2 (6)	O1P—C7P—C14P	113 (2)
C8R—C7R—C6R	120.5 (6)	C6P—C7P—C14P	84.8 (12)
C13R—C8R—C9R	118.5 (5)	C8P—C7P—C14P	120 (3)
C13R—C8R—C7R	120.4 (5)	C9P—C8P—C13P	117.5 (18)
C9R—C8R—C7R	121.1 (5)	C9P—C8P—C7P	119.1 (19)
C10R—C9R—C8R	120.8 (6)	C13P—C8P—C7P	122 (2)
C10R—C9R—H9R	119.6	C8P—C9P—C10P	121 (2)
C8R—C9R—H9R	119.6	C8P—C9P—H9P	119.6
C9R—C10R—C11R	120.7 (5)	C10P—C9P—H9P	119.6
C9R—C10R—H10R	119.7	C11P—C10P—C9P	121 (2)
C11R—C10R—H10R	119.7	C11P—C10P—H10P	119.4
O2R—C11R—C12R	124.0 (6)	C9P—C10P—H10P	119.4
O2R—C11R—C10R	116.8 (6)	O2P—C11P—C10P	117 (2)
C12R—C11R—C10R	119.2 (5)	O2P—C11P—C12P	125 (2)
C11R—C12R—C13R	119.6 (6)	C10P—C11P—C12P	117.9 (18)
C11R—C12R—H12R	120.2	C13P—C12P—C11P	120 (2)
C13R—C12R—H12R	120.2	C13P—C12P—H12P	119.8
C8R—C13R—C12R	121.1 (6)	C11P—C12P—H12P	119.8
C8R—C13R—H13R	119.4	C12P—C13P—C8P	122 (2)
C12R—C13R—H13R	119.4	C12P—C13P—H13P	119.1
C1R—C14R—C15R	112.0 (6)	C8P—C13P—H13P	119.1
C1R—C14R—C16R	111.5 (6)	C16P—C14P—C1P	116 (2)
C15R—C14R—C16R	111.1 (6)	C16P—C14P—C15P	111 (2)
C1R—C14R—H14R	107.3	C1P—C14P—C15P	113 (2)
C15R—C14R—H14R	107.3	C16P—C14P—C7P	119 (2)
C16R—C14R—H14R	107.3	C1P—C14P—C7P	83.8 (12)
C14R—C15R—H15A	109.5	C15P—C14P—C7P	112 (2)
C14R—C15R—H15B	109.5	C14P—C15P—H15D	109.5
H15A—C15R—H15B	109.5	C14P—C15P—H15E	109.5
C14R—C15R—H15C	109.5	H15D—C15P—H15E	109.5
H15A—C15R—H15C	109.5	C14P—C15P—H15F	109.5
H15B—C15R—H15C	109.5	H15D—C15P—H15F	109.5
C14R—C16R—H16A	109.5	H15E—C15P—H15F	109.5
C14R—C16R—H16B	109.5	C14P—C16P—H16D	109.5
H16A—C16R—H16B	109.5	C14P—C16P—H16E	109.5
C14R—C16R—H16C	109.5	H16D—C16P—H16E	109.5
H16A—C16R—H16C	109.5	C14P—C16P—H16F	109.5
H16B—C16R—H16C	109.5	H16D—C16P—H16F	109.5
C18R—C17R—C19R	119.9 (9)	H16E—C16P—H16F	109.5
C18R—C17R—C3R	114.8 (8)	C19P—C17P—C18P	113 (3)
C19R—C17R—C3R	113.2 (8)	C19P—C17P—C3P	110 (2)
C18R—C17R—H17R	101.7	C18P—C17P—C3P	112 (3)
C19R—C17R—H17R	101.7	C19P—C17P—H17P	107.2
C3R—C17R—H17R	101.7	C18P—C17P—H17P	107.2
C17R—C18R—H18A	109.5	C3P—C17P—H17P	107.2
C17R—C18R—H18B	109.5	C17P—C18P—H18D	109.5
H18A—C18R—H18B	109.5	C17P—C18P—H18E	109.5
C17R—C18R—H18C	109.5	H18D—C18P—H18E	109.5
H18A—C18R—H18C	109.5	C17P—C18P—H18F	109.5
H18B—C18R—H18C	109.5	H18D—C18P—H18F	109.5
C17R—C19R—H19A	109.5	H18E—C18P—H18F	109.5
C17R—C19R—H19B	109.5	C17P—C19P—H19D	109.5
H19A—C19R—H19B	109.5	C17P—C19P—H19E	109.5
C17R—C19R—H19C	109.5	H19D—C19P—H19E	109.5
H19A—C19R—H19C	109.5	C17P—C19P—H19F	109.5
H19B—C19R—H19C	109.5	H19D—C19P—H19F	109.5
C21R—C20R—C5R	113.7 (8)	H19E—C19P—H19F	109.5
C21R—C20R—C22R	110.9 (8)	C22P—C20P—C21P	109 (2)
C5R—C20R—C22R	110.6 (6)	C22P—C20P—C5P	113 (3)
C21R—C20R—H20R	107.1	C21P—C20P—C5P	110 (2)
C5R—C20R—H20R	107.1	C22P—C20P—H20P	108.3
C22R—C20R—H20R	107.1	C21P—C20P—H20P	108.3
C20R—C21R—H21A	109.5	C5P—C20P—H20P	108.3
C20R—C21R—H21B	109.5	C20P—C21P—H21D	109.5
H21A—C21R—H21B	109.5	C20P—C21P—H21E	109.5
C20R—C21R—H21C	109.5	H21D—C21P—H21E	109.5
H21A—C21R—H21C	109.5	C20P—C21P—H21F	109.5
H21B—C21R—H21C	109.5	H21D—C21P—H21F	109.5
C20R—C22R—H22A	109.5	H21E—C21P—H21F	109.5
C20R—C22R—H22B	109.5	C20P—C22P—H22D	109.5
H22A—C22R—H22B	109.5	C20P—C22P—H22E	109.5
C20R—C22R—H22C	109.5	H22D—C22P—H22E	109.5
H22A—C22R—H22C	109.5	C20P—C22P—H22F	109.5
H22B—C22R—H22C	109.5	H22D—C22P—H22F	109.5
C11P—O2P—C23P	104.3 (8)	H22E—C22P—H22F	109.5
C6P—C1P—C2P	121.1 (19)