Head-to-tail square-shaped cyclic hydrogen bonds leading to dimeric aggregates: 1,8-dibenzoyl-2,7-di­hydroxy­naphthalene and a comparison with its analogous benzoyl­naphthalene

The title compound, C₂₄H₁₆O₄, crystallized with two independent mol­ecules in the asymmetric unit. Both carbonyl groups in these mol­ecules form intra­molecular O—H...O=C hydrogen bonds with neighbouring hy­droxy groups, affording six-membered cyclic structures. In the crystal, dimeric aggre­gates arise from two intermolecular O—H...O=C hydrogen bonds between both independent molecules, forming head-to-tail square-shaped cyclic ...O...H...O...H... hydrogen bonds. These dimeric aggregates are connected into layers in the bc plane by inter­molecular (naphthalene)C—H...O=C inter­actions. On the other hand, the analogous compound bearing meth­oxy groups at the 2- and 7-positions of the naph­thal­ene ring, namely 1,8-dibenzoyl-2,7-di­meth­oxy­naph­tha­lene [Nakaema et al. (2008). Acta Cryst. E64, o807], forms a three-dimensional mol­ecular network via C—H...O=C and π–π inter­actions between the benzoyl groups. These results show that the intramolecular O—H...O=C hydrogen bonds in the title compound control the orientations of the benzoyl groups and thus promote the formation of the cyclic intermolecular O—H...O=C interactions involving the same donor and acceptor groups in pairs of molecules.

S1. Introduction

Molecules with noncoplanar aromatic rings, e.g. bi­naphthyl and bi­phenyl compounds, have been in the limelight because of their unique spatial shapes causing characteristic properties and various applications (Alfonso et al., 200; Gasparrini et al., 2008; Zhang et al., 2011). Peri-substituted naphthalenes have also received much attention as characteristic structured aromatic core compounds for a variety of functional materials (Mei et al., 2006; Shinamura et al., 2010; Jiang et al., 2010). Therefore, the structural analyses have been actively performed (Gore et al., 1980; Cohen et al., 2004; Jing et al., 2005). Recently, the authors group has revealed that diaroylation at 1,8-positions of naphthalene proceeds smoothly (Okamoto & Yonezawa, 2009; Okamoto et al., 2011).

According to X-ray crystal studies, the resulting 1,8-diaroylated naphthalene derivatives, such as 1,8-di­benzoyl-2,7-di­meth­oxy­naphthalene (Nakaema et al., 2008), have a noncoplanar organization of the aromatic rings. Herein, the X-ray crystal structure of the title compound, 1,8-di­benzoyl-2,7-di­hydroxy­naphthalene, (I), is reported. The compound has two hy­droxy groups at the 2- and 7-positions of the naphthalene ring in place of the alk­oxy groups of the above-mentioned compound. We report the single-crystal structure and the molecular packing of (I) and discuss the structure-determining factors through comparison with the analogous molecule.

S2. Experimental

S2.1. Synthesis and crystallization

To the solution of 1,8-di­benzoyl-2,7-di­eth­oxy­naphthalene (5.0 mmol, 2.1 g) and toluene (25 ml), AlCl₃ (25.0 mmol, 3.3 g) was added and stirred at 363 K for 1 h. The reaction mixture was poured into 2 M aqueous HCl, and it was extracted with CHCl₃. The combined extracts were washed with brine and dried over anhydrous MgSO₄. The solvent was removed under reduced pressure to give cake. The crude product was purified by recrystallization from toluene (48% isolated yield; m.p. 501.4–502.1 K). ¹H NMR (300 MHz, CDCl₃): δ 7.13 (2H, d, J = 8.9 Hz), 7.19 [4H, d (broad), J = 7.6 Hz], 7.30 (4H t, J = 7.6 Hz), 7.50 (2H, t, J = 7.6 Hz), 7.92 (2H, d, J = 8.9 Hz), 11.24 (2H, s). ¹³C NMR δ (75 MHz, CDCl₃): 115.39, 117.13, 122.16, 128.17, 131.61, 132.82, 133.00, 136.38, 136.49, 161.99, 197.26. IR (KBr, cm^-1): 3441 (O—H), 1661 (C═ O), 1595, 1513, 1451 (Ar, naphthalene). Elemental analysis calculated for C₂₄H₁₆O₄: C 78.25, H 4.38%; found: C 78.10, H 4.41%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms could be located in difference Fourier maps, but were subsequently refined as riding atoms, with O—H = 0.84 Å and U_iso(H) = 1.5U_eq(O) for hy­droxy H atoms, and C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms.

S3. Results and discussion

There are two independent molecules (A and B) in the crystal of (I) with display intra­molecular O—H···O═C hydrogen bonds between the hy­droxy and carbonyl groups (Fig. 1). Each independent molecule has essentially the same noncoplanar organization of aromatic rings, as indicated by a least-squares fit of the two molecules (r.m.s. deviation = 0.003 Å). The dihedral angles between the benzene rings are 9.10 (11) (for molecule A) and 2.37 (10)° (for molecule B), and those between the benzene rings and the naphthalene system are 62.77 (10) and 56.43 (8)° (for molecule A), and 54.68 (8) and 54.74 (9)° (for molecule B).

In the crystal packing, centrosymmetrically related molecules are connected into a supra­molecular dimer via head-to-tail square-shaped cyclic hydrogen bonds involving two intra- and inter­molecular C═O···H hydrogen bonds between the hy­droxy H atoms and the carbonyl O atoms (Table 2 and Fig. 2). The dimeric aggregates are arranged in layers in the bc plane by C—H···O═C hydrogen bonds between the naphthalene rings and the carbonyl groups unrelated with the formation of the square-shaped cyclic hydrogen bonds (C3—H3···O6; Table 2 and Fig. 2). Inter­molecular C—H···O inter­actions between the benzene rings of the benzoyl groups and the hy­droxy groups (C21—H21···O4ⁱⁱⁱ; Table 2 and Fig. 2) contribute to the stability of the molecular alignments along the b axis.

Several years ago, the authors published the crystal structure of a 1,8-di­benzoyl­naphthalene analogue bearing meth­oxy groups at the 2- and 7-positions, namely 1,8-di­benzoyl-2,7-di­meth­oxy­naphthalene, (II) (Nakaema et al., 2008; Fig. 3). The molecules are located on a twofold rotation axis. The molecular packing strikingly differs from that of (I). In the crystal of (II), a three-dimensional molecular network is formed by benzene and methyl C—H···O═C inter­actions and benzene–benzene π–π stacking inter­actions (Fig. 4). The dihedral angle between the benzene ring and the naphthalene system in (II) is larger than that of (I) [80.25 (6)° for (II), 62.77 (10) and 56.43 (8)° for molecule A of (I), and 54.68 (8) and 54.74 (9)° for molecule B of (I)].

The data indicate that intra­molecular O—H···O═C hydrogen bonds fix the benzoyl groups in (I). Intra­molecular O—H···O═C hydrogen bonds might play a key role in the smooth formation of a centrosymmetric dimer via head-to-tail square-shaped cyclic hydrogen bonds between the carbonyl and hy­droxy groups. In other words, the formation of the three-dimensional molecular network requires that benzoyl groups free of strong fixation can change appropriately the situation to make inter­molecular inter­actions, such as C—H···O and π–π.

Related literature

For electrophilic aroylation of naphthalene derivatives, see: Okamoto & Yonezawa (2009); Okamoto et al. (2011). For the structures of closely related compounds, see: Nakaema et al. (2008); Kato et al. (2010), Nagasawa et al. (2010).

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: Il Milione (Burla et al., 2007); 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 title molecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial view of the crystal packing of the title compound, showing the intermolecular O—H···O and C—H···O hydrogen bonds (see Table 1 for details). [Symmetry codes: (i) x-1, -y+1/2, z+1/2; (ii) x+1, -y+1/2, z-1/2; (iii) -x+1, y-1/2, -z+3/2.]
	Fig. 3. The molecular structure of 1,8-dibenzoyl-2,7-dimethoxynaphthalene, showing the atom-labeling scheme and with displacement ellipsoids drawn at the 50% probability level. The symbol "_2" refers to symmetry code (-x, y, -z+1/2). The detail of this molecule is shown in Nagasawa et al. (2010).
	Fig. 4. A partial packing diagram of the title compound, viewed down the b axis. The dashed lines indicate hydrogen bonds.

1,8-Dibenzoyl-2,7-dihydroxynaphthalene

Crystal data

C24H16O4	F(000) = 1536
Mr = 368.37	Dx = 1.385 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 9173 reflections
a = 8.502 (3) Å	θ = 2.0–31.2°
b = 15.446 (5) Å	µ = 0.09 mm^−1
c = 27.071 (10) Å	T = 173 K
β = 96.226 (4)°	Block, colourless
V = 3534 (2) Å^3	0.40 × 0.15 × 0.15 mm
Z = 8

Data collection

Rigaku Saturn70 diffractometer	6159 independent reflections
Radiation source: rotating anode	4828 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 7.314 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ω scans	h = −7→10
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −18→18
Tmin = 0.963, Tmax = 0.986	l = −32→32
23077 measured 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0481P)^2 + 0.7407P] where P = (Fo^2 + 2Fc^2)/3
6159 reflections	(Δ/σ)max < 0.001
509 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

Experimental. Spectroscopic data for the title compound: 1H NMR δ (300 MHz, CDCl3): 7.13 (2H, d, J = 8.9 Hz), 7.19 (4H, d, J=7.6 Hz), 7.30 (4H, t, J = 7.6 Hz), 7.50 (2H, tt, J = 7.6 Hz), 7.92 (2H, d, J = 8.9 Hz), 11.24(2H, s) p.p.m. 13 C NMR δ (75 MHz, CDCl3): 115.39, 117.13, 122.16, 128.17, 131.61, 132.82, 133.00, 136.38, 136.49, 161.99, 197.26 p.p.m. IR (KBr): 3441(–OH), 1661 (Cδb O), 1595, 1513, 1451 (Ar, naphthalene) cm-1. Elemental analysis: Calcd for C24H16O4; C 78.25, H 4.38. Found: C 78.10, H 4.41. m.p. = 501.4–502.1 K.

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	0.59530 (16)	0.00535 (9)	0.56238 (5)	0.0397 (4)
O2	0.33352 (16)	0.08096 (8)	0.70315 (5)	0.0354 (3)
O3	0.70450 (18)	0.12871 (10)	0.50841 (5)	0.0454 (4)
H3A	0.6979	0.0774	0.5182	0.068*
O4	0.28594 (17)	0.24410 (9)	0.72288 (5)	0.0379 (4)
H4A	0.2677	0.1908	0.7248	0.057*
O5	1.16664 (16)	0.38740 (8)	0.29072 (5)	0.0343 (3)
O6	0.88873 (16)	0.33585 (9)	0.43501 (5)	0.0383 (4)
O7	1.23369 (16)	0.54805 (8)	0.26784 (5)	0.0342 (3)
H7A	1.2436	0.4940	0.2662	0.051*
O8	0.78121 (16)	0.46528 (9)	0.47975 (5)	0.0388 (4)
H8A	0.7869	0.4129	0.4717	0.058*
C1	0.5552 (2)	0.15430 (12)	0.57795 (7)	0.0261 (4)
C2	0.6448 (2)	0.18248 (13)	0.54094 (7)	0.0317 (5)
C3	0.6704 (3)	0.27101 (14)	0.53296 (8)	0.0402 (5)
H3	0.7307	0.2890	0.5072	0.048*
C4	0.6088 (3)	0.33053 (14)	0.56218 (8)	0.0403 (5)
H4	0.6211	0.3903	0.5553	0.048*
C5	0.4711 (2)	0.36949 (13)	0.63416 (8)	0.0374 (5)
H5	0.4903	0.4289	0.6281	0.045*
C6	0.3910 (2)	0.34717 (13)	0.67298 (8)	0.0375 (5)
H6	0.3509	0.3908	0.6930	0.045*
C7	0.3676 (2)	0.25929 (12)	0.68344 (7)	0.0301 (4)
C8	0.4339 (2)	0.19376 (11)	0.65670 (7)	0.0251 (4)
C9	0.5044 (2)	0.21635 (11)	0.61254 (7)	0.0262 (4)
C10	0.5268 (2)	0.30588 (12)	0.60257 (7)	0.0304 (4)
C11	0.5047 (2)	0.06209 (12)	0.57486 (7)	0.0281 (4)
C12	0.3372 (2)	0.03860 (12)	0.57922 (7)	0.0307 (4)
C13	0.3004 (3)	−0.04404 (14)	0.59417 (8)	0.0394 (5)
H13	0.3828	−0.0838	0.6043	0.047*
C14	0.1447 (3)	−0.06876 (18)	0.59444 (9)	0.0546 (7)
H14	0.1201	−0.1250	0.6055	0.066*
C15	0.0249 (3)	−0.01195 (19)	0.57867 (10)	0.0622 (8)
H15	−0.0824	−0.0291	0.5787	0.075*
C16	0.0608 (3)	0.07032 (18)	0.56283 (11)	0.0634 (8)
H16	−0.0219	0.1092	0.5515	0.076*
C17	0.2165 (3)	0.09592 (15)	0.56354 (9)	0.0452 (6)
H17	0.2410	0.1527	0.5533	0.054*
C18	0.4434 (2)	0.10713 (11)	0.68058 (7)	0.0266 (4)
C19	0.5934 (2)	0.05592 (11)	0.68426 (6)	0.0256 (4)
C20	0.5880 (2)	−0.03217 (12)	0.69564 (7)	0.0312 (4)
H20	0.4893	−0.0591	0.6992	0.037*
C21	0.7257 (3)	−0.08031 (13)	0.70180 (7)	0.0372 (5)
H21	0.7212	−0.1405	0.7088	0.045*
C22	0.8705 (3)	−0.04107 (13)	0.69773 (8)	0.0387 (5)
H22	0.9650	−0.0744	0.7018	0.046*
C23	0.8772 (2)	0.04705 (13)	0.68771 (7)	0.0342 (5)
H23	0.9764	0.0743	0.6856	0.041*
C24	0.7395 (2)	0.09493 (12)	0.68081 (7)	0.0281 (4)
H24	0.7445	0.1550	0.6736	0.034*
C25	1.0770 (2)	0.50749 (11)	0.33412 (7)	0.0239 (4)
C26	1.1526 (2)	0.56839 (12)	0.30663 (7)	0.0270 (4)
C27	1.1424 (2)	0.65782 (12)	0.31597 (7)	0.0319 (5)
H27	1.1923	0.6982	0.2963	0.038*
C28	1.0614 (2)	0.68587 (12)	0.35303 (7)	0.0320 (5)
H28	1.0491	0.7463	0.3578	0.038*
C29	0.9136 (2)	0.65890 (13)	0.42445 (7)	0.0324 (5)
H29	0.9099	0.7195	0.4301	0.039*
C30	0.8418 (2)	0.60489 (13)	0.45416 (7)	0.0329 (5)
H30	0.7822	0.6275	0.4789	0.039*
C31	0.8562 (2)	0.51460 (13)	0.44808 (7)	0.0284 (4)
C32	0.9476 (2)	0.47933 (12)	0.41317 (6)	0.0249 (4)
C33	1.0070 (2)	0.53647 (11)	0.37722 (6)	0.0236 (4)
C34	0.9944 (2)	0.62724 (12)	0.38497 (7)	0.0269 (4)
C35	1.0602 (2)	0.41899 (11)	0.31273 (7)	0.0253 (4)
C36	0.9068 (2)	0.37078 (11)	0.31184 (6)	0.0253 (4)
C37	0.9079 (2)	0.28096 (12)	0.30647 (7)	0.0311 (4)
H37	1.0052	0.2513	0.3050	0.037*
C38	0.7674 (3)	0.23492 (13)	0.30334 (8)	0.0390 (5)
H38	0.7686	0.1736	0.3006	0.047*
C39	0.6254 (3)	0.27830 (14)	0.30416 (8)	0.0409 (5)
H39	0.5290	0.2467	0.3019	0.049*
C40	0.6233 (2)	0.36775 (14)	0.30822 (7)	0.0369 (5)
H40	0.5255	0.3975	0.3082	0.044*
C41	0.7638 (2)	0.41366 (12)	0.31236 (7)	0.0291 (4)
H41	0.7623	0.4749	0.3156	0.035*
C42	0.9873 (2)	0.38596 (12)	0.41975 (7)	0.0272 (4)
C43	1.1500 (2)	0.35211 (12)	0.41585 (7)	0.0267 (4)
C44	1.1717 (3)	0.26267 (13)	0.41421 (8)	0.0389 (5)
H44	1.0824	0.2254	0.4128	0.047*
C45	1.3211 (3)	0.22773 (14)	0.41467 (9)	0.0474 (6)
H45	1.3345	0.1668	0.4132	0.057*
C46	1.4513 (3)	0.28168 (15)	0.41724 (8)	0.0431 (5)
H46	1.5543	0.2579	0.4172	0.052*
C47	1.4317 (2)	0.37000 (14)	0.41985 (8)	0.0384 (5)
H47	1.5216	0.4069	0.4221	0.046*
C48	1.2822 (2)	0.40531 (12)	0.41925 (7)	0.0300 (4)
H48	1.2698	0.4663	0.4212	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0404 (8)	0.0342 (8)	0.0473 (9)	0.0026 (7)	0.0166 (7)	−0.0063 (7)
O2	0.0376 (8)	0.0319 (8)	0.0399 (8)	−0.0025 (6)	0.0186 (7)	0.0004 (6)
O3	0.0493 (9)	0.0543 (10)	0.0355 (8)	−0.0099 (8)	0.0185 (7)	−0.0065 (7)
O4	0.0443 (9)	0.0315 (8)	0.0401 (8)	0.0052 (7)	0.0137 (7)	−0.0053 (7)
O5	0.0375 (8)	0.0308 (8)	0.0373 (8)	0.0012 (6)	0.0161 (7)	−0.0012 (6)
O6	0.0404 (8)	0.0361 (8)	0.0402 (8)	−0.0111 (7)	0.0132 (7)	0.0051 (7)
O7	0.0421 (8)	0.0287 (7)	0.0347 (8)	−0.0034 (6)	0.0170 (6)	0.0011 (6)
O8	0.0374 (8)	0.0478 (9)	0.0336 (8)	−0.0054 (7)	0.0153 (6)	0.0011 (7)
C1	0.0256 (10)	0.0285 (10)	0.0239 (9)	−0.0021 (8)	0.0016 (8)	0.0009 (8)
C2	0.0307 (10)	0.0401 (12)	0.0242 (10)	−0.0066 (9)	0.0022 (8)	−0.0001 (9)
C3	0.0469 (13)	0.0453 (13)	0.0285 (11)	−0.0149 (10)	0.0050 (10)	0.0080 (10)
C4	0.0502 (13)	0.0329 (12)	0.0357 (12)	−0.0131 (10)	−0.0050 (10)	0.0111 (10)
C5	0.0480 (13)	0.0216 (10)	0.0397 (12)	−0.0003 (9)	−0.0093 (10)	0.0038 (9)
C6	0.0468 (13)	0.0255 (11)	0.0389 (12)	0.0077 (9)	−0.0018 (10)	−0.0049 (9)
C7	0.0294 (10)	0.0311 (11)	0.0293 (10)	0.0032 (8)	0.0012 (8)	−0.0011 (8)
C8	0.0254 (9)	0.0217 (9)	0.0282 (10)	0.0000 (8)	0.0025 (8)	−0.0009 (8)
C9	0.0245 (9)	0.0244 (10)	0.0284 (10)	−0.0010 (8)	−0.0021 (8)	0.0029 (8)
C10	0.0340 (11)	0.0254 (10)	0.0297 (10)	−0.0032 (8)	−0.0057 (9)	0.0020 (8)
C11	0.0325 (11)	0.0284 (10)	0.0241 (10)	0.0006 (9)	0.0066 (8)	−0.0012 (8)
C12	0.0331 (11)	0.0311 (11)	0.0289 (10)	−0.0048 (9)	0.0076 (8)	−0.0112 (9)
C13	0.0475 (13)	0.0382 (12)	0.0333 (11)	−0.0131 (10)	0.0079 (10)	−0.0061 (9)
C14	0.0574 (16)	0.0649 (17)	0.0429 (14)	−0.0318 (14)	0.0114 (12)	−0.0089 (12)
C15	0.0408 (14)	0.086 (2)	0.0621 (17)	−0.0305 (15)	0.0159 (13)	−0.0271 (15)
C16	0.0314 (13)	0.0724 (19)	0.085 (2)	−0.0024 (12)	0.0013 (13)	−0.0304 (16)
C17	0.0357 (12)	0.0396 (13)	0.0596 (15)	−0.0046 (10)	0.0021 (11)	−0.0127 (11)
C18	0.0322 (10)	0.0234 (10)	0.0249 (10)	−0.0032 (8)	0.0061 (8)	−0.0060 (8)
C19	0.0341 (10)	0.0236 (10)	0.0197 (9)	−0.0007 (8)	0.0058 (8)	−0.0008 (7)
C20	0.0390 (11)	0.0259 (10)	0.0297 (10)	−0.0018 (9)	0.0090 (9)	0.0017 (8)
C21	0.0522 (14)	0.0248 (10)	0.0350 (11)	0.0057 (10)	0.0065 (10)	0.0043 (9)
C22	0.0414 (12)	0.0375 (12)	0.0369 (12)	0.0125 (10)	0.0034 (10)	0.0018 (10)
C23	0.0313 (11)	0.0406 (12)	0.0306 (11)	−0.0017 (9)	0.0032 (9)	0.0001 (9)
C24	0.0340 (11)	0.0270 (10)	0.0233 (10)	−0.0006 (8)	0.0036 (8)	0.0002 (8)
C25	0.0232 (9)	0.0229 (9)	0.0257 (9)	−0.0006 (7)	0.0031 (8)	0.0002 (8)
C26	0.0270 (10)	0.0288 (10)	0.0255 (10)	−0.0001 (8)	0.0047 (8)	0.0000 (8)
C27	0.0390 (11)	0.0249 (10)	0.0326 (11)	−0.0068 (9)	0.0074 (9)	0.0034 (8)
C28	0.0383 (11)	0.0236 (10)	0.0337 (11)	−0.0003 (8)	0.0024 (9)	−0.0013 (8)
C29	0.0353 (11)	0.0313 (11)	0.0302 (10)	0.0058 (9)	0.0010 (9)	−0.0065 (9)
C30	0.0291 (10)	0.0433 (12)	0.0269 (10)	0.0052 (9)	0.0059 (9)	−0.0053 (9)
C31	0.0235 (10)	0.0389 (12)	0.0227 (9)	−0.0020 (8)	0.0021 (8)	0.0008 (8)
C32	0.0218 (9)	0.0284 (10)	0.0247 (9)	−0.0020 (8)	0.0026 (8)	−0.0010 (8)
C33	0.0199 (9)	0.0269 (10)	0.0235 (9)	−0.0013 (8)	0.0003 (7)	−0.0006 (8)
C34	0.0254 (10)	0.0269 (10)	0.0280 (10)	0.0000 (8)	0.0014 (8)	−0.0016 (8)
C35	0.0299 (10)	0.0245 (10)	0.0219 (9)	0.0003 (8)	0.0051 (8)	0.0028 (8)
C36	0.0315 (10)	0.0248 (10)	0.0201 (9)	−0.0031 (8)	0.0048 (8)	−0.0017 (8)
C37	0.0376 (11)	0.0290 (10)	0.0272 (10)	−0.0035 (9)	0.0056 (9)	−0.0045 (8)
C38	0.0509 (14)	0.0320 (11)	0.0346 (11)	−0.0110 (10)	0.0067 (10)	−0.0033 (9)
C39	0.0427 (13)	0.0467 (13)	0.0327 (11)	−0.0183 (10)	0.0008 (10)	−0.0042 (10)
C40	0.0311 (11)	0.0493 (13)	0.0301 (11)	−0.0018 (10)	0.0028 (9)	−0.0019 (10)
C41	0.0323 (11)	0.0297 (10)	0.0247 (10)	−0.0013 (8)	0.0009 (8)	0.0001 (8)
C42	0.0321 (10)	0.0302 (10)	0.0196 (9)	−0.0077 (8)	0.0041 (8)	−0.0009 (8)
C43	0.0317 (10)	0.0259 (10)	0.0225 (9)	−0.0014 (8)	0.0024 (8)	0.0023 (8)
C44	0.0428 (13)	0.0294 (11)	0.0431 (13)	−0.0040 (9)	−0.0017 (10)	−0.0005 (9)
C45	0.0534 (15)	0.0327 (12)	0.0543 (15)	0.0080 (11)	−0.0019 (12)	−0.0057 (10)
C46	0.0385 (12)	0.0498 (14)	0.0401 (13)	0.0137 (11)	−0.0006 (10)	−0.0028 (10)
C47	0.0289 (11)	0.0469 (13)	0.0389 (12)	−0.0005 (9)	0.0011 (9)	0.0032 (10)
C48	0.0346 (11)	0.0271 (10)	0.0278 (10)	−0.0027 (8)	0.0006 (9)	0.0016 (8)

Geometric parameters (Å, º)

O1—C11	1.238 (2)	C21—H21	0.9500
O2—C18	1.238 (2)	C22—C23	1.390 (3)
O3—C2	1.349 (2)	C22—H22	0.9500
O3—H3A	0.8400	C23—C24	1.380 (3)
O4—C7	1.356 (2)	C23—H23	0.9500
O4—H4A	0.8400	C24—H24	0.9500
O5—C35	1.237 (2)	C25—C26	1.399 (3)
O6—C42	1.244 (2)	C25—C33	1.437 (2)
O7—C26	1.354 (2)	C25—C35	1.486 (2)
O7—H7A	0.8400	C26—C27	1.409 (3)
O8—C31	1.357 (2)	C27—C28	1.349 (3)
O8—H8A	0.8400	C27—H27	0.9500
C1—C2	1.392 (3)	C28—C34	1.414 (3)
C1—C9	1.439 (3)	C28—H28	0.9500
C1—C11	1.488 (3)	C29—C30	1.350 (3)
C2—C3	1.405 (3)	C29—C34	1.419 (3)
C3—C4	1.355 (3)	C29—H29	0.9500
C3—H3	0.9500	C30—C31	1.411 (3)
C4—C10	1.412 (3)	C30—H30	0.9500
C4—H4	0.9500	C31—C32	1.397 (3)
C5—C6	1.358 (3)	C32—C33	1.445 (2)
C5—C10	1.417 (3)	C32—C42	1.488 (3)
C5—H5	0.9500	C33—C34	1.424 (3)
C6—C7	1.405 (3)	C35—C36	1.500 (3)
C6—H6	0.9500	C36—C41	1.386 (3)
C7—C8	1.398 (3)	C36—C37	1.395 (3)
C8—C9	1.437 (3)	C37—C38	1.385 (3)
C8—C18	1.485 (3)	C37—H37	0.9500
C9—C10	1.426 (3)	C38—C39	1.383 (3)
C11—C12	1.487 (3)	C38—H38	0.9500
C12—C13	1.385 (3)	C39—C40	1.386 (3)
C12—C17	1.386 (3)	C39—H39	0.9500
C13—C14	1.379 (3)	C40—C41	1.383 (3)
C13—H13	0.9500	C40—H40	0.9500
C14—C15	1.377 (4)	C41—H41	0.9500
C14—H14	0.9500	C42—C43	1.493 (3)
C15—C16	1.386 (4)	C43—C48	1.387 (3)
C15—H15	0.9500	C43—C44	1.395 (3)
C16—C17	1.380 (3)	C44—C45	1.379 (3)
C16—H16	0.9500	C44—H44	0.9500
C17—H17	0.9500	C45—C46	1.381 (3)
C18—C19	1.495 (3)	C45—H45	0.9500
C19—C24	1.393 (3)	C46—C47	1.377 (3)
C19—C20	1.397 (3)	C46—H46	0.9500
C20—C21	1.381 (3)	C47—C48	1.382 (3)
C20—H20	0.9500	C47—H47	0.9500
C21—C22	1.388 (3)	C48—H48	0.9500
C2—O3—H3A	109.5	C23—C24—H24	119.7
C7—O4—H4A	109.5	C19—C24—H24	119.7
C26—O7—H7A	109.5	C26—C25—C33	118.50 (16)
C31—O8—H8A	109.5	C26—C25—C35	116.21 (16)
C2—C1—C9	119.10 (17)	C33—C25—C35	124.92 (16)
C2—C1—C11	115.86 (16)	O7—C26—C25	123.97 (17)
C9—C1—C11	124.69 (16)	O7—C26—C27	114.41 (16)
O3—C2—C1	123.45 (18)	C25—C26—C27	121.54 (17)
O3—C2—C3	115.02 (17)	C28—C27—C26	119.67 (17)
C1—C2—C3	121.41 (18)	C28—C27—H27	120.2
C4—C3—C2	119.62 (19)	C26—C27—H27	120.2
C4—C3—H3	120.2	C27—C28—C34	121.43 (18)
C2—C3—H3	120.2	C27—C28—H28	119.3
C3—C4—C10	121.60 (19)	C34—C28—H28	119.3
C3—C4—H4	119.2	C30—C29—C34	121.54 (18)
C10—C4—H4	119.2	C30—C29—H29	119.2
C6—C5—C10	121.30 (18)	C34—C29—H29	119.2
C6—C5—H5	119.3	C29—C30—C31	119.41 (18)
C10—C5—H5	119.4	C29—C30—H30	120.3
C5—C6—C7	119.68 (19)	C31—C30—H30	120.3
C5—C6—H6	120.2	O8—C31—C32	122.84 (18)
C7—C6—H6	120.2	O8—C31—C30	115.40 (17)
O4—C7—C8	123.51 (17)	C32—C31—C30	121.71 (17)
O4—C7—C6	114.94 (17)	C31—C32—C33	118.57 (17)
C8—C7—C6	121.41 (18)	C31—C32—C42	115.64 (16)
C7—C8—C9	118.88 (17)	C33—C32—C42	125.53 (16)
C7—C8—C18	115.65 (16)	C34—C33—C25	118.09 (16)
C9—C8—C18	124.97 (16)	C34—C33—C32	117.69 (16)
C10—C9—C8	117.98 (17)	C25—C33—C32	124.22 (16)
C10—C9—C1	117.86 (17)	C28—C34—C29	120.01 (17)
C8—C9—C1	124.16 (16)	C28—C34—C33	119.92 (17)
C4—C10—C5	120.37 (18)	C29—C34—C33	120.06 (17)
C4—C10—C9	119.71 (18)	O5—C35—C25	120.45 (16)
C5—C10—C9	119.88 (18)	O5—C35—C36	118.50 (16)
O1—C11—C12	118.62 (17)	C25—C35—C36	120.63 (16)
O1—C11—C1	120.57 (17)	C41—C36—C37	119.49 (17)
C12—C11—C1	120.18 (16)	C41—C36—C35	121.66 (16)
C13—C12—C17	119.67 (19)	C37—C36—C35	118.66 (17)
C13—C12—C11	119.78 (18)	C38—C37—C36	120.10 (19)
C17—C12—C11	120.21 (18)	C38—C37—H37	119.9
C14—C13—C12	120.3 (2)	C36—C37—H37	119.9
C14—C13—H13	119.9	C39—C38—C37	119.92 (19)
C12—C13—H13	119.9	C39—C38—H38	120.0
C15—C14—C13	120.0 (2)	C37—C38—H38	120.0
C15—C14—H14	120.0	C38—C39—C40	120.19 (19)
C13—C14—H14	120.0	C38—C39—H39	119.9
C14—C15—C16	120.0 (2)	C40—C39—H39	119.9
C14—C15—H15	120.0	C41—C40—C39	119.93 (19)
C16—C15—H15	120.0	C41—C40—H40	120.0
C17—C16—C15	120.1 (2)	C39—C40—H40	120.0
C17—C16—H16	119.9	C40—C41—C36	120.32 (18)
C15—C16—H16	119.9	C40—C41—H41	119.8
C16—C17—C12	119.9 (2)	C36—C41—H41	119.8
C16—C17—H17	120.1	O6—C42—C32	119.38 (17)
C12—C17—H17	120.1	O6—C42—C43	117.92 (17)
O2—C18—C8	120.07 (17)	C32—C42—C43	122.08 (15)
O2—C18—C19	118.57 (16)	C48—C43—C44	118.68 (18)
C8—C18—C19	120.77 (16)	C48—C43—C42	122.54 (17)
C24—C19—C20	119.16 (17)	C44—C43—C42	118.39 (17)
C24—C19—C18	121.83 (16)	C45—C44—C43	120.8 (2)
C20—C19—C18	118.79 (17)	C45—C44—H44	119.6
C21—C20—C19	120.20 (19)	C43—C44—H44	119.6
C21—C20—H20	119.9	C44—C45—C46	119.8 (2)
C19—C20—H20	119.9	C44—C45—H45	120.1
C20—C21—C22	120.19 (19)	C46—C45—H45	120.1
C20—C21—H21	119.9	C47—C46—C45	120.0 (2)
C22—C21—H21	119.9	C47—C46—H46	120.0
C21—C22—C23	119.90 (19)	C45—C46—H46	120.0
C21—C22—H22	120.0	C46—C47—C48	120.4 (2)
C23—C22—H22	120.0	C46—C47—H47	119.8
C24—C23—C22	119.95 (19)	C48—C47—H47	119.8
C24—C23—H23	120.0	C47—C48—C43	120.31 (19)
C22—C23—H23	120.0	C47—C48—H48	119.8
C23—C24—C19	120.56 (18)	C43—C48—H48	119.8
C9—C1—C2—O3	176.55 (17)	C33—C25—C26—O7	174.45 (16)
C11—C1—C2—O3	−9.9 (3)	C35—C25—C26—O7	−12.2 (3)
C9—C1—C2—C3	−7.7 (3)	C33—C25—C26—C27	−9.1 (3)
C11—C1—C2—C3	165.83 (18)	C35—C25—C26—C27	164.32 (17)
O3—C2—C3—C4	176.95 (19)	O7—C26—C27—C28	178.54 (18)
C1—C2—C3—C4	0.9 (3)	C25—C26—C27—C28	1.7 (3)
C2—C3—C4—C10	3.8 (3)	C26—C27—C28—C34	4.0 (3)
C10—C5—C6—C7	2.5 (3)	C34—C29—C30—C31	4.3 (3)
C5—C6—C7—O4	−179.88 (18)	C29—C30—C31—O8	179.54 (17)
C5—C6—C7—C8	4.2 (3)	C29—C30—C31—C32	2.3 (3)
O4—C7—C8—C9	173.87 (17)	O8—C31—C32—C33	172.72 (16)
C6—C7—C8—C9	−10.5 (3)	C30—C31—C32—C33	−10.2 (3)
O4—C7—C8—C18	−13.8 (3)	O8—C31—C32—C42	−12.8 (3)
C6—C7—C8—C18	161.77 (18)	C30—C31—C32—C42	164.26 (17)
C7—C8—C9—C10	10.1 (3)	C26—C25—C33—C34	10.5 (3)
C18—C8—C9—C10	−161.39 (17)	C35—C25—C33—C34	−162.23 (17)
C7—C8—C9—C1	−170.43 (17)	C26—C25—C33—C32	−169.88 (17)
C18—C8—C9—C1	18.0 (3)	C35—C25—C33—C32	17.4 (3)
C2—C1—C9—C10	9.7 (3)	C31—C32—C33—C34	11.4 (2)
C11—C1—C9—C10	−163.18 (17)	C42—C32—C33—C34	−162.44 (17)
C2—C1—C9—C8	−169.70 (17)	C31—C32—C33—C25	−168.17 (17)
C11—C1—C9—C8	17.4 (3)	C42—C32—C33—C25	18.0 (3)
C3—C4—C10—C5	176.50 (19)	C27—C28—C34—C29	178.29 (18)
C3—C4—C10—C9	−1.5 (3)	C27—C28—C34—C33	−2.2 (3)
C6—C5—C10—C4	179.50 (19)	C30—C29—C34—C28	176.80 (18)
C6—C5—C10—C9	−2.6 (3)	C30—C29—C34—C33	−2.7 (3)
C8—C9—C10—C4	174.14 (17)	C25—C33—C34—C28	−5.1 (3)
C1—C9—C10—C4	−5.3 (3)	C32—C33—C34—C28	175.24 (17)
C8—C9—C10—C5	−3.8 (3)	C25—C33—C34—C29	174.34 (17)
C1—C9—C10—C5	176.71 (17)	C32—C33—C34—C29	−5.3 (3)
C2—C1—C11—O1	39.0 (3)	C26—C25—C35—O5	37.0 (3)
C9—C1—C11—O1	−147.85 (19)	C33—C25—C35—O5	−150.10 (18)
C2—C1—C11—C12	−131.72 (18)	C26—C25—C35—C36	−135.40 (17)
C9—C1—C11—C12	41.4 (3)	C33—C25—C35—C36	37.5 (3)
O1—C11—C12—C13	32.3 (3)	O5—C35—C36—C41	−147.62 (18)
C1—C11—C12—C13	−156.76 (17)	C25—C35—C36—C41	24.9 (3)
O1—C11—C12—C17	−141.0 (2)	O5—C35—C36—C37	27.4 (2)
C1—C11—C12—C17	29.9 (3)	C25—C35—C36—C37	−160.11 (17)
C17—C12—C13—C14	−1.3 (3)	C41—C36—C37—C38	−2.1 (3)
C11—C12—C13—C14	−174.66 (19)	C35—C36—C37—C38	−177.20 (17)
C12—C13—C14—C15	1.6 (3)	C36—C37—C38—C39	1.8 (3)
C13—C14—C15—C16	−0.4 (4)	C37—C38—C39—C40	−0.1 (3)
C14—C15—C16—C17	−1.0 (4)	C38—C39—C40—C41	−1.2 (3)
C15—C16—C17—C12	1.3 (4)	C39—C40—C41—C36	0.8 (3)
C13—C12—C17—C16	−0.1 (3)	C37—C36—C41—C40	0.8 (3)
C11—C12—C17—C16	173.2 (2)	C35—C36—C41—C40	175.74 (17)
C7—C8—C18—O2	39.3 (3)	C31—C32—C42—O6	35.6 (2)
C9—C8—C18—O2	−148.98 (18)	C33—C32—C42—O6	−150.32 (18)
C7—C8—C18—C19	−131.77 (18)	C31—C32—C42—C43	−135.17 (18)
C9—C8—C18—C19	40.0 (3)	C33—C32—C42—C43	38.9 (3)
O2—C18—C19—C24	−150.29 (18)	O6—C42—C43—C48	−153.20 (18)
C8—C18—C19—C24	20.9 (3)	C32—C42—C43—C48	17.7 (3)
O2—C18—C19—C20	24.2 (3)	O6—C42—C43—C44	19.6 (3)
C8—C18—C19—C20	−164.63 (17)	C32—C42—C43—C44	−169.47 (17)
C24—C19—C20—C21	−2.0 (3)	C48—C43—C44—C45	−1.6 (3)
C18—C19—C20—C21	−176.70 (17)	C42—C43—C44—C45	−174.72 (19)
C19—C20—C21—C22	1.3 (3)	C43—C44—C45—C46	0.6 (3)
C20—C21—C22—C23	0.4 (3)	C44—C45—C46—C47	0.7 (3)
C21—C22—C23—C24	−1.3 (3)	C45—C46—C47—C48	−0.9 (3)
C22—C23—C24—C19	0.6 (3)	C46—C47—C48—C43	−0.2 (3)
C20—C19—C24—C23	1.1 (3)	C44—C43—C48—C47	1.4 (3)
C18—C19—C24—C23	175.56 (16)	C42—C43—C48—C47	174.21 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1	0.84	1.91	2.631 (2)	143
O4—H4A···O2	0.84	1.90	2.616 (2)	142
O4—H4A···O5^i	0.84	2.39	2.989 (2)	129
O7—H7A···O2^ii	0.84	2.26	2.843 (2)	126
O7—H7A···O5	0.84	1.92	2.635 (2)	143
O8—H8A···O6	0.84	1.83	2.557 (2)	144
C3—H3···O6	0.95	2.59	3.542 (3)	178
C21—H21···O4^iii	0.95	2.57	3.401 (3)	146

Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) x+1, −y+1/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2.