Comparative structural analysis of 2,7-dieth­oxy-1,8-bis­(4-phen­oxy­benz­oyl)naphthalene and its homologues: orientation of the 4-phen­oxy­benzoyl groups at the 1- and 8-positions of the naphthalene ring

The title mol­ecule, C₄₀H₃₂O₆, possesses crystallographically imposed twofold symmetry, with the central two C atoms of the naphthalene unit sited on the rotation axis. The two 4-phen­oxy­benzoyl groups in the mol­ecule are twisted away from the attached naphthalene unit, with a torsion angle of 66.76 (15)° between the naphthalene unit and the carbonyl group (C—C—C=O), and are oriented in mutually opposing directions (anti orientation). There is an apparent difference in the conformations of the 4-phen­oxy­benzoyl groups at the 1- and 8-positions of the naphthalene ring between the title mol­ecule and its meth­oxy-bearing homologue [Hijikata et al. (2010). Acta Cryst. E66, o2902–o2903]. Whilst the 4-phen­oxy­benzoyl groups in 2,7-diisoprop­oxy-1,8-bis­(4-phen­oxy­benz­oyl)naphthalene [Yoshiwaka et al. (2013). Acta Cryst. E69, o242] are situated in the same anti orientation as the title mol­ecule, those of 2,7-dimeth­oxy-1,8-bis­(4-phen­oxy­benzo­yl)naphthalene are oriented in the same direction with respect to the naphthalene ring system, i.e. in a syn orientation.

S1. Introduction

Recently, our group found that aroylation reactions of 2,7-di­meth­oxy­naphthalene with arene­carb­oxy­lic acid derivatives selectively afforded peri-aroylated naphthalene derivatives, i.e. 1-aroyl- and 1,8-diaroyl-2,7-di­meth­oxy­naphthalenes, in the presence of a suitable acidic mediator (Okamoto & Yonezawa, 2009; Okamoto et al., 2011). According to X-ray crystal structure studies of these peri-aroyl­naphthalene compounds, the naphthalene ring core and the aroyl group(s) are mutually perpendicular. This non-coplanar nature of peri-aroyl­naphthalene compounds seems to be based on avoidance of inter­nal steric repulsion.

Non-coplanarly accumulated aromatic-ring compounds have attracted increasing attention for use in a wide range of chemical applications. This is because their unique spatial shapes afford useful optical or electronic characteristics. For example, bi­phenyl and bi­naphthyl species have been employed as optically active polymers, catalysts, organic fluorescent dyes and light-emitting diodes (Bulman Page et al., 2012; Kamimura et al., 2014; Seo et al., 2011). Therefore, conformational studies of non-coplanarly accumulated aromatic rings molecules have been actively pursued (Pan et al., 2013).

Under these circumstances, we have investigated the spatial structural study of peri-aroyl­naphthalene compounds, both in the crystalline state and in solution. Here the typically good crystallinity of peri-aroyl­naphthalene compounds has enabled us to develop a systematic structural study by X-ray crystallography. As one perspective, the crystal structures of peri-aroyl­naphthalene compounds are classified into two groups by the orientation of the aroyl groups with respect to the naphthalene ring, i.e. with the aroyl groups lying either in the same direction (syn-orientation) or in opposite directions (anti-orientation). Almost all peri-aroyl­naphthalene compounds have anti-oriented conformations in their crystal structures. However, there are some examples that display syn-orientations, such as 1,8-bis­(4-phen­oxy­benzoyl)-2,7-di­meth­oxy­naphthalene, (2) (Hijikata et al., 2010), {2,7-di­meth­oxy-8-[4-(propan-2-yl­oxy) benzoyl]­naphthalen-1-yl}[4-(propan-2-yl­oxy)phenyl] methanone (Sasagawa et al., 2013) and 1,8-bis­(4-chloro­benzoyl)-7-meth­oxy­naphthalen-2-ol ethanol monosolvate (Mitsui et al., 2010). We regard the 4-phen­oxy­benzoyl group as a candidate entity for affording syn-oriented conformations and have thus designed a series of 2,7-di­alk­oxy-1,8-bis­(4-phen­oxy­benzoyl)­naphthalene homologues, such as 2,7-diisoprop­oxy-1,8-bis­(4-phen­oxy­benzoyl)­naphthalene, (3) (Yoshiwaka et al., 2013).

Herein, we report the crystal structure of 2,7-dieth­oxy-1,8-bis­(4-phen­oxy­benzoyl)­naphthalene, (1), and discuss the factors that determine the orientations of the 4-phen­oxy­benzoyl groups. This is done through comparison of the title compound, (1), with its meth­oxy-bearing [(2)] and isoprop­oxy-bearing [(3)] homologues.

S2. Experimental

S2.1. Synthesis and crystallization

To a solution of 2,7-di­eth­oxy-1,8-bis­(4-fluoro­benzoyl)­naphthalene (1.0 mmol, 432 mg) in di­methyl­acetamide (2.5 ml), K₂CO₃ (5.0 mmol, 691 mg) was added and the resulting solution stirred at 423 K for 6 h. The reaction mixture was poured into aqueous 2 M HCl and the mixture was extracted with ethyl acetate several times. The combined extracts were washed with water and brine and the organic layer was dried over anhydrous MgSO₄. The solvent was removed under reduced pressure to give a cake of the crude material. The crude product was purified by recrystallization from chloro­form–methanol (1:1 v/v). Single crystals of (1) suitable for X-ray diffraction were obtained by crystallization from methanol (64% isolated yield; m.p. 422.6–424.2 K). Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 7.89 (2H, d, J = 9.0 Hz), 7.68 (4H, d, J = 8.1 Hz), 7.37 (4H, t, J = 7.8 Hz), 7.10–7.19 (3H, m), 7.09 (4H, d, J = 7.8 Hz), 6.88 (4H, d, J = 8.1 Hz), 3.99 (4H, q, J = 6.9 Hz), 1.02 (6H, t, J = 6.9 Hz); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 14.52, 64.96, 112.25, 116.70, 120.15, 121.92, 124.24, 125.47, 129.87, 131.28, 131.84, 134.02, 155.58, 155.68, 161.26, 195.66; IR (KBr, ν, cm^-1): 1661 (C═O), 1584, 1511, 1487 (Ar), 1267 (C—O—C). Analysis, calculated for C₄₀H₃₂O₆: C 78.93, H 5.30%; found: C 78.64, H 5.30%.

S2.2. Refinement

All H atoms could be located by difference Fourier synthesis, but were subsequently refined in optimized positions and in riding modes, with C—H = 0.95 (aromatic), 0.98 (methyl) and 0.99 (methyl­ene) Å, and with U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

The molecule of (1) is situated on crystallographic two-fold axis so that the asymmetric unit contains one-half of the molecule, Z' = 0.5. Thus, the two 4-phen­oxy­benzoyl groups are situated in an anti-orientation (Fig. 1). The molecules exhibit axial chirality, with either two S,S or two R,R stereogenic axes. The dihedral angle between the inter­nal benzene ring of the 4-phen­oxy­benzoyl group (C10–C15) and the naphthalene ring system (C1–C6) is 74.13 (5)° [torsion angle C2—C1—C9—O1 = 66.76 (15)°]. The dihedral angle between the inter­nal benzene ring and the terminal benzene ring (C16–C21) of the 4-phen­oxy­benzoyl group is 82.94 (7)°. The dihedral angle between the naphthalene ring system (C1–C6) and the terminal benzene ring of the 4-phen­oxy­benzoyl group is 10.03 (6)°.

In the crystal structure, the R,R and S,S-isomers are arranged alternately in all directions (Figs. 2 and 3). Three kinds of C—H···O═C hydrogen bonds, all with similar distances [C19—H19···O1ⁱ = 2.68 Å, C18—H18···O1ⁱ = 2.66 Å and C12—H12···O1ⁱⁱ = 2.64 Å; symmetry codes: (i) 1/2 - x, 1/2 - y, 1/2 + z, (ii) x, 1 - y, 1/2 + z] are observed, together with a C—H···π inter­action that has distance longer than 3 Å [C18—H18···Cg3 = 3.17 Å; Cg3 is the centroid of the C10–C15 ring generated by symmetry code (i)]. Given these geometries, the significance of these inter­actions as structure-directing inter­actions is likely to be rather subsidiary.

We have previously reported the crystal structures of compounds analogous to (1). These have meth­oxy and isoprop­oxy groups at the 2- and 7-positions of the naphthalene ring instead of eth­oxy groups, namely 2,7-di­meth­oxy-1,8-bis­(4-phen­oxy­benzoyl)­naphthalene, (2) (Hijikata et al., 2010), and 2,7-diisoprop­oxy-1,8-bis­(4-phen­oxy­benzoyl)­naphthalene, (3) (Yoshiwaka et al., 2013). The isoprop­oxy-bearing homologue, (3), shows the same C₂ symmetry as (1). This naturally means that the two 4-phen­oxy­benzoyl groups of homologue (3) are thus oriented in an anti-orientation. On the other hand, the spatial organization of the meth­oxy-bearing homologue, (2), is apparently different from those of (1) and (3), in that the two 4-phen­oxy­benzoyl groups in (2) are oriented in the same direction (syn-conformation).

In the molecules of (1) and homologue (3), the terminal benzene ring, the inter­nal benzene ring and the naphthalene ring are situated in a crankshaft fashion. As described above, compound (1) apparently has no effective inter­molecular inter­actions. Therefore, the crankshaft structure plausibly originates from the avoidance of otherwise large inter­nal steric repulsions in this type of molecule. On the other hand, two more significant kinds of inter­molecular inter­action are observed for both homologues (2) and (3). These are a C—H···π inter­action between an H atom of the terminal benzene ring and the π-system of the inter­nal benzene ring of the 4-phen­oxy­benzoyl group, and a C—H···O═C hydrogen bond between an aromatic ring and the carbonyl group [the aromatic ring is the naphthalene ring for homologue (2), and the inter­nal benzene ring of the 4-phen­oxy­benzoyl group for homologue (3)] (Table 2; Figs. 4 and 5). The inter­molecular C—H···O═C hydrogen bond observed in homologue (2) is the same length as that in homologue (3) [2.44 Å for both (2) and (3)]. However, the inter­molecular C—H···π inter­action in homologue (2) is shorter than that in homologue (3) [2.78 Å for homologue (2); 2.97 Å for homologue (3)]. In consequence of this, it would seem that the C—H···π inter­actions between 4-phen­oxy­benzoyl groups in homologue (2) lead to the dimeric aggregate of syn-conformers that is observed.

In the crystal structures of these compounds, the molecular conformations are mainly determined by the balance between the strong C—H···π inter­action and the molecular packing density. The effects of these factors can be correlated with the volume of the alk­oxy groups. The most effective inter­action observed is the C—H···π inter­action between the terminal phen­oxy group and the phenyl­ene ring of the phen­oxy­benzoyl group of an adjacent molecule for the 2,7-meth­oxy-bearing homologue, (2). As two molecules of (2) form a dimeric structure, each such centrosymmetric unit has two such strong inter­actions. In consequence of this, each of the molecules of (2) adopts a syn-conformation, for which the small volume of the methyl­oxy groups on the 2,7-positions probably allows a satisfactory packing density. On the other hand, the 2,7-eth­oxy- and 2,7-isoprop­oxy-bearing homologues, (1) and (3), display crankshaft molecular features, i.e. molecules with anti-conformations. These homologues display C₂ symmetry of the single molecule. In the crystal structure, the isoprop­oxy-bearing homologue, (3), thus shows two sets of effective C—H···π inter­actions, between the terminal phen­oxy group and the inter­nal benzene ring of the 4-phen­oxy­benzoyl group of an adjacent molecule, and vice versa the same inter­actions with the other adjacent molecule. Although eth­oxy homologue (1) shows no effective inter­actions concerning the 4-phen­oxy­benzoyl groups, the spatial organization of (1) is essentially the same as that of the isoprop­oxy-bearing homologue, (3). Consequently, the inter­actions between the 4-phen­oxy­benzoyl groups of isoprop­oxy-bearing homologue (3) are plausibly smaller than the corresponding inter­action observed in homologue (2). As eth­oxy and isoprop­oxy groups have significantly larger volumes than a meth­oxy group, it is suggested that this prevents sufficient packing density being obtained in the syn-conformation, resulting in the formation of the alternative crankshaft-like anti-conformation.

Related literature

For related literature, see: Hijikata et al. (2010); Kamimura et al. (2014); Mitsui et al. (2010); Okamoto & Yonezawa (2009); Okamoto et al. (2011); Bulman Page et al. (2012); Pan et al. (2013); Sasagawa et al. (2013); Seo et al. (2011); Yoshiwaka et al. (2013).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998; data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (1), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Atoms C2 and C3 lie on a crystallographic two-fold axis, with the symmetry operation (-x, y, -z + 1/2) generating the atoms without labels.
	Fig. 2. The crystal packing structure of (1).
	Fig. 3. The weak non-bonding molecular interactions in (1) (dashed lines). As described in the text, all contact distances are longer than the sum of the van der Waals radii.
	Fig. 4. The intermolecular interactions of the methoxy-bearing homologue, (2). Dashed lines indicate C—H···π and C—H···O═C interactions.
	Fig. 5. The intermolecular interactions of the isopropoxy-bearing homologue, (3). Dashed lines indicate C—H···π and C—H···O═C interactions.

2,7-diethoxy-1,8-bis(4-phenoxybenzoyl)naphthalene

Crystal data

C40H32O6	F(000) = 1280
Mr = 608.66	Dx = 1.275 Mg m^−3
Orthorhombic, Pbcn	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2n 2ab	Cell parameters from 37024 reflections
a = 10.27720 (19) Å	θ = 3.6–68.2°
b = 19.3360 (4) Å	µ = 0.69 mm^−1
c = 15.9587 (3) Å	T = 193 K
V = 3171.31 (10) Å^3	Block, colourless
Z = 4	0.70 × 0.40 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	2912 independent reflections
Radiation source: fine-focus sealed tube	2693 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 10.000 pixels mm^-1	θmax = 68.2°, θmin = 4.6°
ω scans	h = −12→12
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −23→23
Tmin = 0.645, Tmax = 0.875	l = −19→19
53303 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.105	w = 1/[σ^2(Fo^2) + (0.0545P)^2 + 0.9251P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
2912 reflections	Δρmax = 0.24 e Å^−3
211 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0037 (2)

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	0.13283 (9)	0.46898 (4)	0.19937 (5)	0.0397 (2)
O2	0.21433 (13)	0.34782 (5)	0.56600 (6)	0.0600 (3)
O3	0.33768 (9)	0.57468 (5)	0.30505 (6)	0.0449 (3)
C1	0.11827 (12)	0.57505 (6)	0.27148 (7)	0.0317 (3)
C2	0.0000	0.60930 (8)	0.2500	0.0313 (4)
C3	0.0000	0.68332 (8)	0.2500	0.0358 (4)
C4	0.11515 (14)	0.71924 (6)	0.27090 (8)	0.0416 (3)
H4	0.1144	0.7684	0.2710	0.050*
C5	0.22693 (13)	0.68565 (7)	0.29084 (8)	0.0415 (3)
H5	0.3033	0.7109	0.3045	0.050*
C6	0.22789 (12)	0.61281 (6)	0.29091 (7)	0.0365 (3)
C7	0.43662 (15)	0.60159 (9)	0.35856 (10)	0.0579 (4)
H7A	0.3972	0.6248	0.4077	0.069*
H7B	0.4907	0.6356	0.3280	0.069*
C8	0.51758 (17)	0.54145 (11)	0.38592 (12)	0.0726 (5)
H8A	0.5567	0.5194	0.3367	0.087*
H8B	0.4626	0.5079	0.4154	0.087*
H8C	0.5865	0.5576	0.4236	0.087*
C9	0.13528 (11)	0.49754 (6)	0.26737 (7)	0.0321 (3)
C10	0.15593 (11)	0.45828 (6)	0.34619 (7)	0.0323 (3)
C11	0.14385 (12)	0.48891 (6)	0.42496 (7)	0.0344 (3)
H11	0.1232	0.5367	0.4288	0.041*
C12	0.16128 (13)	0.45109 (6)	0.49740 (8)	0.0374 (3)
H12	0.1524	0.4725	0.5507	0.045*
C13	0.19186 (13)	0.38145 (7)	0.49138 (8)	0.0402 (3)
C14	0.20423 (14)	0.34955 (7)	0.41393 (8)	0.0437 (3)
H14	0.2252	0.3018	0.4104	0.052*
C15	0.18572 (13)	0.38808 (6)	0.34184 (8)	0.0382 (3)
H15	0.1934	0.3664	0.2887	0.046*
C16	0.20790 (16)	0.27600 (7)	0.56803 (8)	0.0463 (3)
C17	0.32062 (15)	0.23955 (8)	0.58386 (9)	0.0500 (4)
H17	0.4017	0.2628	0.5883	0.060*
C18	0.31364 (16)	0.16863 (8)	0.59322 (11)	0.0550 (4)
H18	0.3907	0.1428	0.6036	0.066*
C19	0.19545 (16)	0.13497 (8)	0.58764 (10)	0.0544 (4)
H19	0.1911	0.0863	0.5949	0.065*
C20	0.08421 (16)	0.17198 (9)	0.57157 (9)	0.0551 (4)
H20	0.0031	0.1487	0.5672	0.066*
C21	0.08986 (16)	0.24321 (8)	0.56170 (9)	0.0530 (4)
H21	0.0130	0.2690	0.5507	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0523 (5)	0.0367 (5)	0.0300 (4)	0.0042 (4)	−0.0024 (4)	−0.0048 (4)
O2	0.1093 (10)	0.0380 (5)	0.0327 (5)	0.0096 (5)	−0.0134 (5)	0.0023 (4)
O3	0.0355 (5)	0.0485 (5)	0.0506 (6)	0.0000 (4)	−0.0096 (4)	−0.0048 (4)
C1	0.0375 (6)	0.0318 (6)	0.0257 (6)	0.0001 (5)	−0.0013 (5)	−0.0009 (4)
C2	0.0391 (9)	0.0307 (8)	0.0242 (7)	0.000	−0.0011 (6)	0.000
C3	0.0473 (10)	0.0300 (8)	0.0301 (8)	0.000	0.0004 (7)	0.000
C4	0.0559 (8)	0.0300 (6)	0.0389 (7)	−0.0055 (5)	0.0000 (6)	−0.0028 (5)
C5	0.0457 (7)	0.0397 (7)	0.0390 (7)	−0.0105 (6)	−0.0029 (6)	−0.0044 (5)
C6	0.0386 (7)	0.0404 (7)	0.0305 (6)	−0.0006 (5)	−0.0023 (5)	−0.0019 (5)
C7	0.0460 (8)	0.0733 (10)	0.0543 (9)	−0.0046 (7)	−0.0164 (7)	−0.0063 (8)
C8	0.0520 (10)	0.1006 (14)	0.0650 (10)	0.0036 (9)	−0.0208 (8)	0.0123 (10)
C9	0.0308 (6)	0.0343 (6)	0.0313 (6)	0.0017 (5)	−0.0013 (5)	−0.0025 (5)
C10	0.0316 (6)	0.0335 (6)	0.0316 (6)	0.0030 (5)	−0.0024 (5)	−0.0014 (5)
C11	0.0380 (6)	0.0316 (6)	0.0337 (6)	0.0047 (5)	−0.0023 (5)	−0.0033 (5)
C12	0.0435 (7)	0.0387 (6)	0.0298 (6)	0.0038 (5)	−0.0025 (5)	−0.0049 (5)
C13	0.0504 (8)	0.0388 (7)	0.0313 (6)	0.0046 (6)	−0.0052 (5)	0.0022 (5)
C14	0.0606 (9)	0.0326 (6)	0.0378 (7)	0.0104 (6)	−0.0037 (6)	−0.0020 (5)
C15	0.0479 (7)	0.0361 (6)	0.0305 (6)	0.0064 (5)	−0.0014 (5)	−0.0047 (5)
C16	0.0683 (10)	0.0416 (7)	0.0291 (6)	0.0069 (6)	−0.0020 (6)	0.0033 (5)
C17	0.0511 (8)	0.0509 (8)	0.0480 (8)	−0.0025 (6)	0.0044 (6)	0.0074 (6)
C18	0.0526 (9)	0.0488 (8)	0.0634 (10)	0.0098 (7)	0.0031 (7)	0.0122 (7)
C19	0.0650 (10)	0.0433 (8)	0.0549 (9)	−0.0013 (7)	−0.0020 (7)	0.0105 (6)
C20	0.0521 (9)	0.0625 (9)	0.0508 (9)	−0.0059 (7)	−0.0017 (7)	−0.0017 (7)
C21	0.0567 (9)	0.0606 (9)	0.0418 (7)	0.0156 (7)	−0.0101 (6)	−0.0038 (6)

Geometric parameters (Å, º)

O1—C9	1.2179 (14)	C9—C10	1.4844 (16)
O2—C13	1.3762 (15)	C10—C15	1.3932 (17)
O2—C16	1.3908 (17)	C10—C11	1.3951 (16)
O3—C6	1.3666 (15)	C11—C12	1.3796 (17)
O3—C7	1.4261 (16)	C11—H11	0.9500
C1—C6	1.3779 (17)	C12—C13	1.3861 (18)
C1—C2	1.4260 (14)	C12—H12	0.9500
C1—C9	1.5102 (16)	C13—C14	1.3873 (18)
C2—C1^i	1.4260 (14)	C14—C15	1.3836 (18)
C2—C3	1.431 (2)	C14—H14	0.9500
C3—C4	1.4122 (15)	C15—H15	0.9500
C3—C4^i	1.4123 (15)	C16—C21	1.372 (2)
C4—C5	1.3575 (19)	C16—C17	1.379 (2)
C4—H4	0.9500	C17—C18	1.381 (2)
C5—C6	1.4085 (18)	C17—H17	0.9500
C5—H5	0.9500	C18—C19	1.381 (2)
C7—C8	1.495 (2)	C18—H18	0.9500
C7—H7A	0.9900	C19—C20	1.373 (2)
C7—H7B	0.9900	C19—H19	0.9500
C8—H8A	0.9800	C20—C21	1.387 (2)
C8—H8B	0.9800	C20—H20	0.9500
C8—H8C	0.9800	C21—H21	0.9500
C13—O2—C16	118.94 (10)	C15—C10—C9	119.18 (10)
C6—O3—C7	119.39 (11)	C11—C10—C9	122.25 (10)
C6—C1—C2	120.33 (11)	C12—C11—C10	121.22 (11)
C6—C1—C9	116.16 (10)	C12—C11—H11	119.4
C2—C1—C9	123.31 (10)	C10—C11—H11	119.4
C1—C2—C1^i	124.65 (14)	C11—C12—C13	119.10 (11)
C1—C2—C3	117.67 (7)	C11—C12—H12	120.4
C1^i—C2—C3	117.67 (7)	C13—C12—H12	120.4
C4—C3—C4^i	121.06 (15)	O2—C13—C12	115.91 (11)
C4—C3—C2	119.47 (8)	O2—C13—C14	123.07 (11)
C4^i—C3—C2	119.47 (8)	C12—C13—C14	120.96 (11)
C5—C4—C3	121.94 (12)	C15—C14—C13	119.26 (12)
C5—C4—H4	119.0	C15—C14—H14	120.4
C3—C4—H4	119.0	C13—C14—H14	120.4
C4—C5—C6	118.99 (12)	C14—C15—C10	120.89 (11)
C4—C5—H5	120.5	C14—C15—H15	119.6
C6—C5—H5	120.5	C10—C15—H15	119.6
O3—C6—C1	115.24 (11)	C21—C16—C17	121.32 (13)
O3—C6—C5	123.05 (11)	C21—C16—O2	120.11 (13)
C1—C6—C5	121.60 (12)	C17—C16—O2	118.33 (14)
O3—C7—C8	106.74 (13)	C16—C17—C18	118.91 (14)
O3—C7—H7A	110.4	C16—C17—H17	120.5
C8—C7—H7A	110.4	C18—C17—H17	120.5
O3—C7—H7B	110.4	C19—C18—C17	120.43 (14)
C8—C7—H7B	110.4	C19—C18—H18	119.8
H7A—C7—H7B	108.6	C17—C18—H18	119.8
C7—C8—H8A	109.5	C20—C19—C18	119.93 (14)
C7—C8—H8B	109.5	C20—C19—H19	120.0
H8A—C8—H8B	109.5	C18—C19—H19	120.0
C7—C8—H8C	109.5	C19—C20—C21	120.25 (15)
H8A—C8—H8C	109.5	C19—C20—H20	119.9
H8B—C8—H8C	109.5	C21—C20—H20	119.9
O1—C9—C10	121.74 (11)	C16—C21—C20	119.16 (14)
O1—C9—C1	119.09 (10)	C16—C21—H21	120.4
C10—C9—C1	119.16 (9)	C20—C21—H21	120.4
C15—C10—C11	118.56 (11)
C6—C1—C2—C1^i	179.65 (11)	C1—C9—C10—C15	−173.06 (11)
C9—C1—C2—C1^i	5.02 (8)	O1—C9—C10—C11	−172.33 (12)
C6—C1—C2—C3	−0.35 (11)	C1—C9—C10—C11	8.33 (17)
C9—C1—C2—C3	−174.98 (8)	C15—C10—C11—C12	0.23 (19)
C1—C2—C3—C4	0.01 (8)	C9—C10—C11—C12	178.86 (11)
C1^i—C2—C3—C4	−179.99 (8)	C10—C11—C12—C13	0.3 (2)
C1—C2—C3—C4^i	−179.99 (8)	C16—O2—C13—C12	161.46 (13)
C1^i—C2—C3—C4^i	0.01 (8)	C16—O2—C13—C14	−21.4 (2)
C4^i—C3—C4—C5	−179.74 (14)	C11—C12—C13—O2	176.82 (12)
C2—C3—C4—C5	0.26 (14)	C11—C12—C13—C14	−0.4 (2)
C3—C4—C5—C6	−0.19 (18)	O2—C13—C14—C15	−176.99 (13)
C7—O3—C6—C1	−152.93 (12)	C12—C13—C14—C15	0.0 (2)
C7—O3—C6—C5	30.86 (18)	C13—C14—C15—C10	0.5 (2)
C2—C1—C6—O3	−175.83 (9)	C11—C10—C15—C14	−0.62 (19)
C9—C1—C6—O3	−0.83 (15)	C9—C10—C15—C14	−179.28 (12)
C2—C1—C6—C5	0.44 (17)	C13—O2—C16—C21	−71.80 (18)
C9—C1—C6—C5	175.43 (11)	C13—O2—C16—C17	113.82 (15)
C4—C5—C6—O3	175.81 (11)	C21—C16—C17—C18	0.2 (2)
C4—C5—C6—C1	−0.16 (19)	O2—C16—C17—C18	174.48 (13)
C6—O3—C7—C8	160.39 (13)	C16—C17—C18—C19	−0.7 (2)
C6—C1—C9—O1	−108.07 (13)	C17—C18—C19—C20	0.9 (2)
C2—C1—C9—O1	66.76 (15)	C18—C19—C20—C21	−0.6 (2)
C6—C1—C9—C10	71.29 (14)	C17—C16—C21—C20	0.1 (2)
C2—C1—C9—C10	−113.88 (11)	O2—C16—C21—C20	−174.12 (12)
O1—C9—C10—C15	6.28 (18)	C19—C20—C21—C16	0.1 (2)

Symmetry code: (i) −x, y, −z+1/2.