Crystallographic identification of an unexpected by-product in an Ullman's reaction toward bi­phenyls: 1-(4-hex­yloxy-3-hy­droxy­phen­yl)ethanone

The synthesis of 3,3′-diacet­oxy-4,4′-bis­(hex­yloxy)biphenyl following the nickel-modified Ullmann reaction yielded a by-product which was iden­tified successfully by crystallographic analysis as 1-(4-hex­yloxy-3-hy­droxy­phen­yl)ethanone, C₁₄H₂₀O₃. This unexpected nonbiphenyl by-product exhibited IR, ¹H NMR, ¹³C NMR and COSY (correlation spectroscopy) spectra fully consistent with the proposed structure. The compound crystallized in the orthorombic Pbca space group, with two independent formula units in the asymmetric unit (one of which was slightly disordered), and showed a supra­molecular architecture in which mol­ecules linked by hy­droxy–ethanone O—H...O inter­actions are organized in columns separated by the aliphatic tails.

S1. Introduction

Substituted tri­phenyl­enes are the most extensively studied class of compounds that give rise to columnar liquid crystalline (LC) phases (Pal et al., 2013; Bushby & Kawata, 2011). In this context, we recently proposed a synthetic pathway to tri­phenyl­enes exhibiting terminal functionalizations at the 2 and 7 positions (Zelcer et al., 2013), which allows their incorporation into extended systems like oligomers and polymers (Zelcer et al., 2007, 2013), with the bridging chains attached to the furthest separated positions (2 and 7) at the tri­phenyl­ene units. This synthetic pathway involved substituted 4,4'-di­acet­oxy-3,3'-bis­(hexyl­oxy)bi­phenyl (Zelcer et al., 2013) as a key inter­mediate compound. We then decided to explore the influence of the point of attachment of substituents on the LC properties of such polymers, looking first for materials derived from 3,6-difunctionalized tri­phenyl­enes. In order to synthesize these compounds, our synthetic strategy also involved a key inter­mediate bi­phenyl, in the present case, bearing acet­oxy protecting groups at the 3- and 3'-positions, as shown in the Scheme. The key reaction for the synthesis of bi­phenyl (V) involved a nickel-catalyzed Ullmann reaction (Zembayashi et al., 1977; Hong et al., 2001). The products were fully characterized by ¹H NMR, ¹³C NMR, FT–IR, elemental analysis and HRMS.

During the course of the Ullmann reaction we also isolated a second product and tried to identify it using the same set of techniques. We envisaged different possible substituted bi­phenyls, but none of them could explain the experimental spectra of the product obtained. We then succeeded in crystallizing it and solved its molecular structure. Unexpectedly, the compound was not a substituted bi­phenyl, but a rearranged phenyl product, namely 1-(4-hexyl­oxy-3-hy­droxy­phenyl)­ethanone, (I) (see Scheme). We report herein the crystal and molecular structure of (I), along with its completely assigned ¹H NMR, ¹³C NMR, COSY (correlation spectroscopy) and FT–IR spectra, and suggest a possible mechanism for its formation.

S2. Experimental

All chemical precursors were purchased from Sigma–Aldrich and used without further purification. Operations under an inert atmosphere were carried out using standard Schlenck techniques. ¹H NMR spectra were measured on a Bruker AM500 spectrometer, using CDCl₃ as solvent and its residual peaks as inter­nal references (7.26 p.p.m. for ¹H). Differential scanning calorimetry (DSC) was performed with a Shimadzu DSC-50 apparatus. Elemental analysis was carried out at UMYMFOR, Conicet, & Department of Organic Chemistry – FCEN – UBA.

S2.1. Synthesis and crystallization

S2.1.1. Synthesis of 2-(hexyl­oxy)phenyl acetate, (III)

2-(Hexyl­oxy)phenol, (II) (10 g, 0.05 mol), was acetyl­ated with acetic anhydride (20 ml) and pyridine (20 ml) at room temperature for 16 h. Examination by thin-layer chromatography (TLC; cyclo­hexane/CH₂Cl₂, 1:1 v/v, stain I₂) showed the complete conversion of (II) (RF = 0.46) into a slower moving product (RF = 0.35). The mixture was concentrated and (III) was obtained as an oily syrup (yield 11.4 g, 97%); ¹H NMR (CDCl₃, 500 MHz): δ 7.18 (ddd, 1H, ArH), 7.06 (dd, 1H, J = 7.75, 1.75 Hz, ArH), 6.97 (dd, 1H, J = 8.25, 1.25 Hz, ArH), 6.93 (td, 1H, J = 7.5, 1.5 Hz, ArH), 3.98 (t, 2H, J = 6.5 Hz, CH₂O—), 2.31 (s, 3H, CH₃COO—), 1.78 (m, 2H, CH₂CH₂O—), 1.48 [m, 2H, CH₂(CH₂)₂O—], 1.39–1.36 [m, 4H, (CH₂)₂(CH₂)₂O—], 0.96 [t, 3H, J = 7.0 Hz, —O(CH₂)₅CH₃].

S2.1.2. Synthesis of 5-bromo-2-(hexyl­oxy)phenyl acetate, (IV)

Compound (III) (3.0 g, 0.013 mol) was placed in a round-bottomed two-necked flask equipped with a pressure-compensed funnel and CH₂Cl₂ (7.5 ml) was added. The flask was cooled to 273 K and a vessel bubbler with a Na₂CO₃ solution, was placed in the remaining neck. Then a solution of Br₂ (0.75 ml, 0.015 mol) in CH₂Cl₂ (2.8 ml) was introduced into the funnel and added dropwise under continuous stirring over a period of 90 min, resulting in a red solution. The ice bath was removed and the solution stirred until it remained colourless. When TLC (cyclo­hexane–di­chloro­methane, 1:1 v/v, UV and FeCl₃ stain) showed the complete conversion of the starting material (RF = 0.48) into a faster moving spot (RF = 0.55), di­chloro­methane (50 ml) was added to the mixture and the organic phase was washed with NaHCO₃(ss) and water, then dried over Na₂SO₄, filtered and evaporated under reduced pressure. The product was purified by chromatographic column [cyclo­hexane → cyclo­hexane: CH₂Cl₂ (95:5)]. Compound (II) was a colourless oil (yield 2.9 g, 71%); ¹H NMR (500 MHz, CDCl₃): δ 7.28 (dd, 1H, J = 8.7, 2.4 Hz, ArH), 7.17 (d, 1H, J = 2.4 Hz, ArH), 6.81 (d, 1H, J = 8.8 Hz, ArH), 3.94 (t, 2H, J = 6.5 Hz, CH₂O—), 2.29 (s, 3H, CH₃COO—), 1.75 (m, 2H, CH₂CH₂O—), 1.45–1.30 [m, 6H, O(CH₂)₂(CH₂)₃CH₃], 0.90 [t, 3H, J = 7.0 Hz, O(CH₂)₅CH₃]; ¹³C NMR (CDCl₃, 125.7 MHz): δ 168.7 (—OCOCH₃), 150.2, 140.8, 129.7, 126.1, 114.7, 111.9 (Ar), 69.1 (OCH₂), 31.6, 29.2, 25.7, 22.7 [OCH₂(CH₂)₄CH₃], 20.6 (—OCOCH₃), 14.1 [OCH₂(CH₂)₄CH₃]. FT–IR diagnostic bands: 3074 cm^-1 (νC_aromatic—H), 2958 (νCH₃^assym), 2931 (νCH₂^assym), 2872 (νCH₃^sym), 2859 (νCH₂^sym), 1776 cm^-1 (νC═O). Microanalysis found (calculated) for C₁₄H₁₉BrO₃ (%): C 54.2 (53.3), H 6.0 (6.0).

S2.1.3. Synthesis of 3,3'-di­acet­oxy-4,4'-bis­(hexyl­oxy)bi­phenyl, (V), and 1-(4-hexyl­oxy-3-hy­droxy­phenyl)­ethanone, (I)

In a Schlenk round-bottomed flask, NiCl₂[P(Ph)₃]₂ (0.55 g, 0.84 mmol) and N(CH₂CH₃)4I (0.23 g, 0.89 mmol) were added, dried and degassed applying three cycles of vacuum/argon. Then, under an argon atmosphere, a suspension of Zn dust (1.1 g, 17 mmol) in dried and de­oxy­genated THF (2 ml) was added. The mixture was stirred for 30 min. In another Schlenck flask, a solution of de­oxy­genated (IV) (2.5 g, 7.8 mmol) in THF (11 ml) was added to the first flask and the reaction mixture was stirred at 329 K for 20 h under an argon atmosphere. When TLC (cyclo­hexane–AcOEt 10:1 v/v, FeCl₃ stain) showed complete consumption of (IV) (RF = 0.43) and the formation of a new spot that corresponds to (V) (RF = 0.23), the reaction was stopped. Finally, the suspension was filtered through compacted silica, washed with ethyl ether and the filtrate concentrated in vacuo. The resulting solid was purified by column chromatography (silica, cyclo­hexane/ethyl acetate up to 20:1 v/v), to give a white solid (yield 550 mg, 30%). Analysis found (calculated) for C₂₈H₃₈O₆ (%): C 70.6 (71.4), H 7.7 (8.1). ¹H NMR (500 MHz, CDCl₃): δ 7.35 (dd, 2H, J = 7.7, 2.3 Hz, ArH), 7.23 (d, 2H, J = 2.3 Hz, ArH), 7.00 (d, 2H, J = 8.0 Hz, ArH), 4.05 (t, J = 6.5 Hz, 4H, CH₂O—), 2.34 (s, 6H, —OCOCH₃), 1.80 (m, 4H, CH₂CH₂O—), 1.50–1.30 [m, 12H, O(CH₂)₂(CH₂)₃CH₃], 0.94 [t, 6H, J = 7.1 Hz, O(CH₂)₅CH₃]; ¹³C NMR (125.7 MHz, CDCl₃): δ 169.1 (—OCOCH₃), 149.9, 140.4, 133.1, 125.0, 121.2, 113.7 (Ar), 69.0 (OCH₂), 31.6, 29.3, 25.7, 22.7 [OCH₂(CH₂)₄CH₃], 20.7 (—OCOCH₃), 14.1 [OCH₂(CH₂)₄CH₃]; FT–IR diagnostic bands: 3045 cm^-1 (νC_aromatic—H), 2958 (νCH₃^assym), 2934 (νCH₂^assym), 2867 (νCH₃^sym), 2859 (νCH₂^sym), 1771 cm^-1 (νC═O). A second set of fractions was collected and evaporated to dryness, yielding (I) as a white solid. Single crystals of (I) were grown by slow evaporation from CHCl₃ solutions. Crystallographic analysis allowed us to establish the nature of (I) as 1-(4-hexyl­oxy-3-hy­droxy­phenyl)­ethanone (see below) [yield 100 mg, 10%; m.p. 368 K (Fisher–Jones)]. Thermal data from DSC runs: Cr 340 K (6, 8 kJ mol^-1), Cr' 366K (28 kJ mol^-1). FT–IR diagnostic bands: 3308 cm^-1 (br, νO—H), 3099 (sh, νC_aromatic—H), 2953 (νCH₃^assym), 2927 (νCH₂^assym), 2873 (νCH₃^sym), 2859 (νCH₂^sym), 1666 cm^-1 (νC═O). Analysis found (calculated) for C₁₄H₂₀O₃ (%): C 70.7 (71.1 ), H 8.4 (8.5). ¹H NMR (500 MHz, CDCl₃): δ 7.53 (d, 1H, J = 2.0 Hz, ArH-2), 7.51 (dd, 1H, J = 8.3, 2.1 Hz, ArH-6), 6.86 (d, 1H, J = 8.3 Hz, ArH-5), 5.79 (s, 1H, OH), 4.10 (t, J = 6.6 Hz, 2H, CH₂O—), 2.53 (s, 1H, CH₃CO—), 1.84 (m, 2H, CH₂CH₂O—), 1.46–1.32 [m, 6H, O(CH₂)₂(CH₂)₃CH₃], 0.90 [t, 3H, J = 7.0 Hz, O(CH₂)₅CH₃]; ¹³C NMR (CDCl₃, 125.7 MHz): δ 197.1 (—COCH3), 150.2, 145.6, 130.9, 121.9, 114.5, 110.7 (Ar), 69.2 (OCH₂), 31.6, 29.1, 26.5, 25.7 [OCH₂(CH₂)₄CH₃], 22.7 (—COCH₃), 14.1 (OCH₂(CH₂)₄CH₃). For a complete assignment of the ¹H NMR and ¹³C NMR spectra, see Results and discussion (section 3).

S2.2. Refinement

Crystal data, data collection and structure refinement details for (I) are summarized in Table 1. All H atoms were originally found in difference maps, but were treated differently in the refinement. The O—H groups were refined freely with free U_iso values, while the C—H groups were repositioned in their expected positions and allowed to ride, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methyl­ene H atoms, and C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms. The hexyl tail in one of the independent molecules appeared disordered over two positions. A split model was refined with restained geometry and displacement parameters and the refined occupancies were 0.691 (4) and 0.309 (4).

S3. Results and discussion

The title compound, (I), crystallizes in the orthorhombic space group Pbca and the asymmetric unit consists of two independent molecules (Fig. 1), one of which is disordered (see Refinement, section 2.2). Unexpectedly, these moieties do not correspond to any kind of substituted bi­phenyl, but to 1-(4-hexyl­oxy-3-hy­droxy­phenyl)­ethanone.

Once the chemical nature of (I) was established crystallographically, further evidence was obtained from spectral data. Indeed, the IR spectrum of (I) shows the expected νCH₂ and νCH₃ bands in the 2850–2950 cm^-1 region, a νC_aromatic—H band at ca 3100 cm^-1 and a νC—C_aromatic band at ca 1600 cm^-1, all of which are already present in the starting material 5-bromo-2-(hexyl­oxy)phenyl acetate, (IV). In agreement with the lack of an acet­oxy group and the presence of a ketone moiety, the νC═O band shifted from 1776 cm^-1 in (IV) to 1666 cm^-1 in (I), an identical value to that found in benzo­phenone. Compound (I) also exhibits an additional broad band at 3308 cm^-1, assigned to the new phenolic O—H group. ¹H NMR, ¹³C NMR and COSY spectra are shown on Figs. 2, 3 and 4, respectively, which also contain the assignment of each detected signal. The ¹H NMR spectrum of (I) shows the characteristic signals of the aromatic ring at about 7.0 p.p.m. The multiplicities of the different signals are in agreement with the substitution pattern observed, and as it could be expected, the aromatic H-2 atom was the more unprotected (at low fields) due to the neighbouring effect of the OH and ketone groups. This assignment was confirmed by the coupling constant observed, i.e. J = 2.0 Hz, a typical value for a meta-coupling. The aromatic H-6 atom was found at 7.50 p.p.m. as a doublet of doublets with J = 8.3 Hz, typical of ortho-coupling and J = 2.0 Hz due to meta-coupling with H-2. Aromatic H-5 was found at 6.86 p.p.m. as a doublet with the same ortho-coupling. Other diagnostic signals were that of the phenolic H atom, detected as a singlet at 5.79 p.p.m., that of the α-methyl­ene of the hexyl­oxy tail, detected at 4.10 p.p.m. (the other signals corresponding to this hydro­carbon chain appeared in the range 1.86–0.89 p.p.m.) and the singlet of the methyl group of the ketone group at 2.53 p.p.m. The COSY spectrum showed both the correlation between the aromatic H atoms and the lack of inter­actions for the signal at 5.79 p.p.m., as expected for the phenol H atom. The most distinctive signal in the ¹³C NMR spectrum of (I) is that at 197.1 p.p.m., which corresponds to the ketone C atom; all other observed signals are in agreement with the proposed structure.

Since the molecular structure of (I) does not depart from expected values, the discussion of the structure will be restricted to the supra­molecular architecure.

Inter­molecular inter­actions are dominated by the hy­droxy–ethanone O—H···O hydrogen bonds (Table 2) which link molecules into columnar arrays built up by the c-glide plane in a ···A—B—A—B··· sequence along [001] (Fig. 5, left). The inter­active part in the columns (O atoms and π rings), are in turn `shielded' from external inter­actions by the hexyl tails wrapping the around the columns (Fig. 5, right). Thus, inter­column inter­actions are attained solely through weaker van der Waals forces (Fig. 6). Irrespective of this fact, the structure appears well packed, with no room for eventual solvates and a Kitajgorodskij packing index of 0.67% (PLATON; Spek, 2009).

As is common practice when dealing with compounds containing alkyl C_nH_2n+1 tails, we looked in the Cambridge Structural Database (CSD, Version 5.3, updated May 2015; Groom & Allen, 2014) for other members of the series, viz. of the 1-(4-(n-yl­oxy)-3-hy­droxy­phenyl)­ethanone type (n ≠ 6), for comparison purposes. To our surprise, we found that no further members of the family have been reported. In fact, even the parent (3-hy­droxy­phenyl)­ethanone skeleton is rare, with only two structures including this molecule (CSD refcodes JIVREL and HALYOI; Byrn et al., 1991, 1993), and not in isolation, but as part of a complex, and thus not suitable for comparison with (I), with a C(7) synthon generated by O—H···O hydrogen bonding and responsible of the chain structure. [reworded; is this clear enough?] More frequently observed is the (2-hy­droxy­phenyl)­ethanone skeleton, with both substitutents in neighbouring sites. This disposition, however, largely promotes an intra­molecular O—H···O synthon defining an inter­nal R₁¹(6) loop, and comparisons are again precluded. Thus, against this background, the present structure (I) could be considered as `novel'.

From a chemical point of view, it is well known (Matsumoto et al., 1983; Sperotto et al., 2010) that the Ni-modified Ullmann reaction involves in a first step a reduction of Ni²⁺ to Ni⁰, and it is Ni⁰ that reacts, in our case, via an oxidative addition of a molecule of (IV). This complex then reacts with another molecule of (IV) to give an inter­mediate in which nickel is oxidized to Ni⁴⁺. The last step in the formation of the bi­aryl product involves a reductive elimination which reconstitutes the nickel catalyst. We think that a plausible explanation for the formation of (I) could involve a cleavage of the O—C linkage of the acet­oxy group which suffers an intra­molecular rearrangement to give product (I), in which the acyl group substitutes the Br atom.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 40% probability level. Single broken lines represent hydrogen bonds and double broken lines (and empty ellipsoids) correspond to the (unlabelled) minor fraction of the disordered hexyl group.
	Fig. 2. The assigned ^1H NMR spectrum of (I).
	Fig. 3. The assigned ^13C NMR spectrum of (I).
	Fig. 4. The COSY (correlation spectroscopy) analysis for (I).
	Fig. 5. The columnar arrays in the structure of (I), showing (left) the ···A—B—A—B··· sequence along [001] and (right) a single column seen in projection, showing the `shielding' of the potentially interactive core.
	Fig. 6. A packing view drawn along the column direction. Neighbouring columns are shown arbitrarily in light and dark for clarity.

1-(4-Hexyloxy-3-hydroxyphenyl)ethanone

Crystal data

C14H20O3	Dx = 1.175 Mg m^−3
Mr = 236.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 2185 reflections
a = 19.3847 (10) Å	θ = 3.9–26.4°
b = 9.0716 (4) Å	µ = 0.08 mm^−1
c = 30.3953 (12) Å	T = 170 K
V = 5345.0 (4) Å^3	Blocks, colourless
Z = 16	0.32 × 0.26 × 0.18 mm
F(000) = 2048

Data collection

CCD Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer	6210 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3357 reflections with I > 2σ(I)
Detector resolution: 16.1158 pixels mm^-1	Rint = 0.058
thick slices scans	θmax = 29.0°, θmin = 3.7°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −18→25
Tmin = 0.95, Tmax = 0.98	k = −12→11
18445 measured reflections	l = −39→27

Refinement

Refinement on F^2	23 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.067	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.189	w = 1/[σ^2(Fo^2) + (0.0741P)^2 + 0.6907P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
6210 reflections	Δρmax = 0.29 e Å^−3
365 parameters	Δρmin = −0.31 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1A	0.66050 (9)	0.23557 (17)	0.59045 (5)	0.0446 (4)
C1A	0.68678 (11)	0.3851 (2)	0.52954 (6)	0.0346 (5)
C2A	0.72377 (12)	0.5033 (3)	0.51287 (7)	0.0459 (6)
H2A	0.7473	0.5660	0.5319	0.055*
C3A	0.72574 (13)	0.5281 (3)	0.46765 (7)	0.0523 (7)
H3A	0.7518	0.6056	0.4565	0.063*
C4A	0.68947 (11)	0.4392 (3)	0.43964 (7)	0.0398 (5)
C5A	0.65089 (11)	0.3203 (2)	0.45608 (7)	0.0348 (5)
C6A	0.65032 (11)	0.2950 (2)	0.50085 (7)	0.0338 (5)
H6A	0.6251	0.2162	0.5120	0.041*
C7A	0.68423 (11)	0.3532 (3)	0.57753 (7)	0.0370 (5)
C8A	0.70922 (14)	0.4665 (3)	0.60948 (7)	0.0559 (7)
H8AA	0.7034	0.4304	0.6389	0.084*
H8AB	0.6832	0.5556	0.6058	0.084*
H8AC	0.7572	0.4861	0.6042	0.084*
O2A	0.61431 (9)	0.23021 (17)	0.42929 (5)	0.0474 (4)
H2OA	0.6184 (15)	0.253 (3)	0.3985 (10)	0.078 (9)*
O3A	0.68699 (9)	0.45456 (19)	0.39488 (5)	0.0529 (5)	0.691 (4)
C9A	0.7402 (3)	0.5463 (7)	0.37586 (14)	0.082 (3)	0.691 (4)
H9AA	0.7850	0.5150	0.3866	0.099*	0.691 (4)
H9AB	0.7331	0.6479	0.3847	0.099*	0.691 (4)
C10A	0.7384 (3)	0.5354 (7)	0.32708 (13)	0.0944 (19)	0.691 (4)
H10A	0.7827	0.5671	0.3156	0.113*	0.691 (4)
H10B	0.7322	0.4328	0.3190	0.113*	0.691 (4)
C11A	0.6841 (3)	0.6226 (8)	0.30612 (15)	0.0990 (19)	0.691 (4)
H11A	0.6846	0.7217	0.3182	0.119*	0.691 (4)
H11B	0.6396	0.5791	0.3128	0.119*	0.691 (4)
C12A	0.6936 (3)	0.6308 (5)	0.25457 (14)	0.0882 (15)	0.691 (4)
H12A	0.7399	0.6651	0.2480	0.106*	0.691 (4)
H12B	0.6886	0.5327	0.2423	0.106*	0.691 (4)
C13A	0.6455 (3)	0.7257 (6)	0.23440 (13)	0.0829 (16)	0.691 (4)
H13A	0.6538	0.8260	0.2441	0.099*	0.691 (4)
H13B	0.5993	0.6981	0.2435	0.099*	0.691 (4)
C14A	0.6503 (2)	0.7191 (4)	0.18381 (9)	0.0906 (11)	0.691 (4)
H14A	0.6161	0.7830	0.1712	0.136*	0.691 (4)
H14B	0.6423	0.6198	0.1741	0.136*	0.691 (4)
H14C	0.6954	0.7503	0.1746	0.136*	0.691 (4)
O3'	0.68699 (9)	0.45456 (19)	0.39488 (5)	0.0529 (5)	0.309 (4)
C9'	0.7129 (7)	0.5850 (12)	0.3735 (2)	0.065 (4)	0.309 (4)
H9C	0.7629	0.5854	0.3747	0.078*	0.309 (4)
H9D	0.6962	0.6717	0.3888	0.078*	0.309 (4)
C10'	0.6901 (5)	0.5904 (14)	0.3267 (2)	0.065 (3)	0.309 (4)
H10C	0.6411	0.6126	0.3256	0.078*	0.309 (4)
H10D	0.6971	0.4946	0.3133	0.078*	0.309 (4)
C11'	0.7281 (6)	0.7021 (13)	0.3016 (2)	0.099 (2)	0.309 (4)
H11C	0.7372	0.7855	0.3207	0.119*	0.309 (4)
H11D	0.7723	0.6610	0.2930	0.119*	0.309 (4)
C12'	0.6905 (6)	0.7593 (9)	0.2593 (2)	0.0888 (16)	0.309 (4)
H12C	0.6449	0.7937	0.2675	0.107*	0.309 (4)
H12D	0.7158	0.8431	0.2478	0.107*	0.309 (4)
C13'	0.6837 (8)	0.6543 (13)	0.2259 (2)	0.128 (7)	0.309 (4)
H13C	0.6557	0.5732	0.2366	0.153*	0.309 (4)
H13D	0.7289	0.6154	0.2187	0.153*	0.309 (4)
C14'	0.6503 (2)	0.7191 (4)	0.18381 (9)	0.0906 (11)	0.309 (4)
H14D	0.6466	0.6434	0.1619	0.136*	0.309 (4)
H14E	0.6051	0.7559	0.1907	0.136*	0.309 (4)
H14F	0.6784	0.7980	0.1728	0.136*	0.309 (4)
O1B	0.60177 (9)	0.23252 (19)	0.33965 (5)	0.0522 (5)
C1B	0.56349 (11)	0.1185 (2)	0.27495 (7)	0.0378 (5)
C2B	0.52063 (13)	0.0158 (3)	0.25549 (8)	0.0479 (6)
H2B	0.4972	−0.0517	0.2730	0.057*
C3B	0.51213 (13)	0.0121 (3)	0.21008 (7)	0.0457 (6)
H3B	0.4829	−0.0571	0.1974	0.055*
C4B	0.54704 (11)	0.1109 (2)	0.18399 (7)	0.0361 (5)
C5B	0.59232 (11)	0.2134 (2)	0.20315 (7)	0.0353 (5)
C6B	0.59926 (11)	0.2174 (2)	0.24814 (7)	0.0358 (5)
H6B	0.6282	0.2870	0.2609	0.043*
C7B	0.57128 (12)	0.1276 (3)	0.32316 (7)	0.0416 (6)
C8B	0.54339 (15)	0.0076 (3)	0.35173 (8)	0.0631 (8)
H8BA	0.5577	0.0238	0.3816	0.095*
H8BB	0.5606	−0.0858	0.3418	0.095*
H8BC	0.4939	0.0076	0.3502	0.095*
O2B	0.62791 (9)	0.31252 (18)	0.17830 (5)	0.0486 (5)
H2OB	0.6302 (15)	0.282 (3)	0.1493 (10)	0.074 (9)*
O3B	0.54257 (8)	0.11987 (17)	0.13942 (4)	0.0410 (4)
C9B	0.49771 (12)	0.0171 (3)	0.11721 (7)	0.0442 (6)
H9BA	0.4519	0.0206	0.1301	0.053*
H9BB	0.5154	−0.0824	0.1204	0.053*
C10B	0.49432 (12)	0.0580 (3)	0.06956 (7)	0.0430 (6)
H10E	0.4692	−0.0182	0.0539	0.052*
H10F	0.5409	0.0601	0.0578	0.052*
C11B	0.46042 (13)	0.2049 (3)	0.06046 (7)	0.0482 (6)
H11E	0.4895	0.2835	0.0717	0.058*
H11F	0.4165	0.2095	0.0757	0.058*
C12B	0.44862 (13)	0.2275 (3)	0.01119 (7)	0.0488 (6)
H12E	0.4930	0.2265	−0.0035	0.059*
H12F	0.4222	0.1446	0.0001	0.059*
C13B	0.41190 (15)	0.3665 (3)	−0.00099 (9)	0.0654 (8)
H13E	0.4380	0.4504	0.0098	0.078*
H13F	0.3670	0.3681	0.0131	0.078*
C14B	0.40268 (18)	0.3804 (4)	−0.05076 (9)	0.0767 (9)
H14G	0.3800	0.4717	−0.0574	0.115*
H14H	0.3752	0.2997	−0.0613	0.115*
H14I	0.4470	0.3784	−0.0648	0.115*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0620 (11)	0.0419 (9)	0.0300 (7)	0.0026 (8)	−0.0001 (8)	0.0012 (7)
C1A	0.0330 (11)	0.0417 (12)	0.0289 (10)	0.0050 (10)	−0.0012 (10)	−0.0020 (10)
C2A	0.0444 (13)	0.0527 (14)	0.0406 (12)	−0.0118 (11)	−0.0068 (11)	−0.0009 (12)
C3A	0.0468 (14)	0.0654 (16)	0.0447 (13)	−0.0223 (13)	−0.0028 (12)	0.0127 (13)
C4A	0.0370 (12)	0.0521 (14)	0.0304 (11)	−0.0013 (10)	−0.0028 (10)	0.0051 (11)
C5A	0.0343 (12)	0.0382 (12)	0.0319 (10)	0.0024 (9)	−0.0034 (10)	−0.0019 (10)
C6A	0.0366 (12)	0.0335 (11)	0.0313 (10)	0.0025 (9)	0.0008 (10)	0.0014 (10)
C7A	0.0345 (12)	0.0428 (13)	0.0336 (11)	0.0068 (10)	−0.0021 (10)	−0.0014 (11)
C8A	0.0708 (18)	0.0616 (17)	0.0354 (12)	−0.0131 (14)	−0.0033 (13)	−0.0061 (13)
O2A	0.0681 (12)	0.0454 (9)	0.0286 (8)	−0.0104 (8)	−0.0061 (8)	−0.0008 (8)
O3A	0.0593 (11)	0.0687 (12)	0.0307 (8)	−0.0116 (9)	0.0007 (8)	0.0101 (8)
C9A	0.086 (5)	0.115 (6)	0.045 (3)	−0.033 (4)	0.003 (3)	0.028 (3)
C10A	0.081 (4)	0.154 (6)	0.048 (2)	−0.019 (4)	0.004 (3)	0.033 (3)
C11A	0.115 (5)	0.120 (5)	0.062 (3)	−0.045 (3)	−0.029 (3)	0.017 (3)
C12A	0.129 (4)	0.063 (2)	0.073 (3)	−0.019 (3)	−0.030 (3)	0.013 (3)
C13A	0.104 (4)	0.092 (4)	0.052 (3)	0.001 (3)	−0.002 (3)	−0.001 (3)
C14A	0.123 (3)	0.094 (3)	0.0552 (18)	0.009 (2)	0.0003 (19)	0.0209 (19)
O3'	0.0593 (11)	0.0687 (12)	0.0307 (8)	−0.0116 (9)	0.0007 (8)	0.0101 (8)
C9'	0.075 (10)	0.064 (7)	0.056 (7)	−0.018 (7)	0.014 (6)	0.022 (6)
C10'	0.039 (5)	0.121 (10)	0.035 (5)	−0.008 (6)	−0.015 (5)	0.020 (6)
C11'	0.114 (5)	0.120 (5)	0.062 (3)	−0.046 (4)	−0.028 (3)	0.018 (3)
C12'	0.129 (4)	0.063 (3)	0.074 (3)	−0.019 (3)	−0.030 (3)	0.013 (3)
C13'	0.147 (15)	0.188 (19)	0.048 (6)	0.047 (13)	0.017 (9)	−0.008 (9)
C14'	0.123 (3)	0.094 (3)	0.0552 (18)	0.009 (2)	0.0003 (19)	0.0209 (19)
O1B	0.0753 (12)	0.0512 (10)	0.0300 (8)	−0.0076 (9)	−0.0045 (8)	−0.0008 (8)
C1B	0.0417 (13)	0.0400 (12)	0.0316 (11)	0.0018 (10)	0.0017 (10)	−0.0007 (10)
C2B	0.0550 (15)	0.0503 (14)	0.0383 (12)	−0.0120 (12)	0.0020 (12)	0.0017 (12)
C3B	0.0505 (14)	0.0506 (14)	0.0362 (12)	−0.0122 (11)	−0.0018 (12)	−0.0043 (12)
C4B	0.0390 (12)	0.0403 (12)	0.0290 (10)	0.0003 (10)	0.0002 (10)	−0.0027 (10)
C5B	0.0399 (12)	0.0324 (11)	0.0337 (11)	0.0012 (9)	0.0002 (10)	−0.0029 (10)
C6B	0.0381 (12)	0.0364 (11)	0.0330 (11)	−0.0010 (9)	−0.0028 (10)	−0.0063 (10)
C7B	0.0494 (14)	0.0414 (13)	0.0339 (11)	0.0045 (11)	0.0003 (11)	0.0016 (11)
C8B	0.088 (2)	0.0647 (18)	0.0368 (12)	−0.0158 (15)	0.0003 (14)	0.0072 (13)
O2B	0.0676 (12)	0.0491 (10)	0.0291 (8)	−0.0192 (8)	0.0032 (8)	−0.0042 (8)
O3B	0.0461 (9)	0.0476 (9)	0.0292 (7)	−0.0124 (7)	−0.0015 (7)	−0.0046 (7)
C9B	0.0422 (13)	0.0512 (14)	0.0393 (12)	−0.0109 (11)	−0.0023 (11)	−0.0082 (12)
C10B	0.0402 (13)	0.0542 (14)	0.0346 (11)	−0.0050 (11)	−0.0027 (11)	−0.0107 (11)
C11B	0.0485 (15)	0.0583 (16)	0.0378 (12)	−0.0018 (12)	−0.0008 (12)	−0.0098 (12)
C12B	0.0482 (15)	0.0570 (15)	0.0413 (13)	0.0029 (12)	0.0001 (12)	−0.0064 (12)
C13B	0.072 (2)	0.0632 (19)	0.0611 (17)	0.0143 (15)	−0.0031 (16)	−0.0058 (15)
C14B	0.094 (2)	0.079 (2)	0.0569 (17)	0.0228 (18)	−0.0088 (17)	0.0122 (17)

Geometric parameters (Å, º)

O1A—C7A	1.227 (3)	C11'—H11D	0.9700
C1A—C2A	1.386 (3)	C12'—C13'	1.398 (7)
C1A—C6A	1.389 (3)	C12'—H12C	0.9700
C1A—C7A	1.488 (3)	C12'—H12D	0.9700
C2A—C3A	1.393 (3)	C13'—C14'	1.551 (6)
C2A—H2A	0.9300	C13'—H13C	0.9700
C3A—C4A	1.368 (3)	C13'—H13D	0.9700
C3A—H3A	0.9300	C14'—H14D	0.9600
C4A—O3'	1.368 (2)	C14'—H14E	0.9600
C4A—O3A	1.368 (2)	C14'—H14F	0.9600
C4A—C5A	1.405 (3)	O1B—C7B	1.228 (3)
C5A—O2A	1.354 (2)	C1B—C2B	1.381 (3)
C5A—C6A	1.380 (3)	C1B—C6B	1.396 (3)
C6A—H6A	0.9300	C1B—C7B	1.475 (3)
C7A—C8A	1.494 (3)	C2B—C3B	1.390 (3)
C8A—H8AA	0.9600	C2B—H2B	0.9300
C8A—H8AB	0.9600	C3B—C4B	1.375 (3)
C8A—H8AC	0.9600	C3B—H3B	0.9300
O2A—H2OA	0.96 (3)	C4B—O3B	1.360 (2)
O3A—C9A	1.445 (4)	C4B—C5B	1.406 (3)
C9A—C10A	1.486 (5)	C5B—O2B	1.362 (3)
C9A—H9AA	0.9700	C5B—C6B	1.374 (3)
C9A—H9AB	0.9700	C6B—H6B	0.9300
C10A—C11A	1.463 (7)	C7B—C8B	1.494 (3)
C10A—H10A	0.9700	C8B—H8BA	0.9600
C10A—H10B	0.9700	C8B—H8BB	0.9600
C11A—C12A	1.580 (6)	C8B—H8BC	0.9600
C11A—H11A	0.9700	O2B—H2OB	0.92 (3)
C11A—H11B	0.9700	O3B—C9B	1.443 (2)
C12A—C13A	1.409 (6)	C9B—C10B	1.496 (3)
C12A—H12A	0.9700	C9B—H9BA	0.9700
C12A—H12B	0.9700	C9B—H9BB	0.9700
C13A—C14A	1.542 (4)	C10B—C11B	1.511 (3)
C13A—H13A	0.9700	C10B—H10E	0.9700
C13A—H13B	0.9700	C10B—H10F	0.9700
C14A—H14A	0.9600	C11B—C12B	1.529 (3)
C14A—H14B	0.9600	C11B—H11E	0.9700
C14A—H14C	0.9600	C11B—H11F	0.9700
O3'—C9'	1.440 (5)	C12B—C13B	1.495 (3)
C9'—C10'	1.490 (6)	C12B—H12E	0.9700
C9'—H9C	0.9700	C12B—H12F	0.9700
C9'—H9D	0.9700	C13B—C14B	1.529 (3)
C10'—C11'	1.467 (7)	C13B—H13E	0.9700
C10'—H10C	0.9700	C13B—H13F	0.9700
C10'—H10D	0.9700	C14B—H14G	0.9600
C11'—C12'	1.566 (7)	C14B—H14H	0.9600
C11'—H11C	0.9700	C14B—H14I	0.9600
C2A—C1A—C6A	119.29 (19)	H11C—C11'—H11D	107.5
C2A—C1A—C7A	121.7 (2)	C13'—C12'—C11'	114.4 (6)
C6A—C1A—C7A	118.96 (19)	C13'—C12'—H12C	108.6
C1A—C2A—C3A	120.0 (2)	C11'—C12'—H12C	108.6
C1A—C2A—H2A	120.0	C13'—C12'—H12D	108.6
C3A—C2A—H2A	120.0	C11'—C12'—H12D	108.6
C4A—C3A—C2A	120.3 (2)	H12C—C12'—H12D	107.6
C4A—C3A—H3A	119.8	C12'—C13'—C14'	112.4 (6)
C2A—C3A—H3A	119.8	C12'—C13'—H13C	109.1
C3A—C4A—O3'	125.2 (2)	C14'—C13'—H13C	109.1
C3A—C4A—O3A	125.2 (2)	C12'—C13'—H13D	109.1
C3A—C4A—C5A	120.36 (19)	C14'—C13'—H13D	109.1
O3'—C4A—C5A	114.4 (2)	H13C—C13'—H13D	107.9
O3A—C4A—C5A	114.4 (2)	C13'—C14'—H14D	109.5
O2A—C5A—C6A	119.2 (2)	C13'—C14'—H14E	109.5
O2A—C5A—C4A	121.90 (19)	H14D—C14'—H14E	109.5
C6A—C5A—C4A	118.9 (2)	C13'—C14'—H14F	109.5
C5A—C6A—C1A	121.1 (2)	H14D—C14'—H14F	109.5
C5A—C6A—H6A	119.4	H14E—C14'—H14F	109.5
C1A—C6A—H6A	119.4	C2B—C1B—C6B	118.83 (19)
O1A—C7A—C1A	119.7 (2)	C2B—C1B—C7B	121.6 (2)
O1A—C7A—C8A	120.8 (2)	C6B—C1B—C7B	119.5 (2)
C1A—C7A—C8A	119.5 (2)	C1B—C2B—C3B	120.8 (2)
C7A—C8A—H8AA	109.5	C1B—C2B—H2B	119.6
C7A—C8A—H8AB	109.5	C3B—C2B—H2B	119.6
H8AA—C8A—H8AB	109.5	C4B—C3B—C2B	119.9 (2)
C7A—C8A—H8AC	109.5	C4B—C3B—H3B	120.1
H8AA—C8A—H8AC	109.5	C2B—C3B—H3B	120.1
H8AB—C8A—H8AC	109.5	O3B—C4B—C3B	125.6 (2)
C5A—O2A—H2OA	114.2 (17)	O3B—C4B—C5B	114.38 (19)
C4A—O3A—C9A	115.5 (2)	C3B—C4B—C5B	120.00 (19)
O3A—C9A—C10A	110.2 (4)	O2B—C5B—C6B	119.00 (19)
O3A—C9A—H9AA	109.6	O2B—C5B—C4B	121.58 (18)
C10A—C9A—H9AA	109.6	C6B—C5B—C4B	119.4 (2)
O3A—C9A—H9AB	109.6	C5B—C6B—C1B	121.0 (2)
C10A—C9A—H9AB	109.6	C5B—C6B—H6B	119.5
H9AA—C9A—H9AB	108.1	C1B—C6B—H6B	119.5
C11A—C10A—C9A	114.5 (5)	O1B—C7B—C1B	119.9 (2)
C11A—C10A—H10A	108.6	O1B—C7B—C8B	120.1 (2)
C9A—C10A—H10A	108.6	C1B—C7B—C8B	120.0 (2)
C11A—C10A—H10B	108.6	C7B—C8B—H8BA	109.5
C9A—C10A—H10B	108.6	C7B—C8B—H8BB	109.5
H10A—C10A—H10B	107.6	H8BA—C8B—H8BB	109.5
C10A—C11A—C12A	111.9 (5)	C7B—C8B—H8BC	109.5
C10A—C11A—H11A	109.2	H8BA—C8B—H8BC	109.5
C12A—C11A—H11A	109.2	H8BB—C8B—H8BC	109.5
C10A—C11A—H11B	109.2	C5B—O2B—H2OB	111.0 (18)
C12A—C11A—H11B	109.2	C4B—O3B—C9B	117.76 (17)
H11A—C11A—H11B	107.9	O3B—C9B—C10B	108.61 (18)
C13A—C12A—C11A	112.5 (5)	O3B—C9B—H9BA	110.0
C13A—C12A—H12A	109.1	C10B—C9B—H9BA	110.0
C11A—C12A—H12A	109.1	O3B—C9B—H9BB	110.0
C13A—C12A—H12B	109.1	C10B—C9B—H9BB	110.0
C11A—C12A—H12B	109.1	H9BA—C9B—H9BB	108.3
H12A—C12A—H12B	107.8	C9B—C10B—C11B	114.51 (19)
C12A—C13A—C14A	111.7 (4)	C9B—C10B—H10E	108.6
C12A—C13A—H13A	109.3	C11B—C10B—H10E	108.6
C14A—C13A—H13A	109.3	C9B—C10B—H10F	108.6
C12A—C13A—H13B	109.3	C11B—C10B—H10F	108.6
C14A—C13A—H13B	109.3	H10E—C10B—H10F	107.6
H13A—C13A—H13B	107.9	C10B—C11B—C12B	111.25 (19)
C13A—C14A—H14A	109.5	C10B—C11B—H11E	109.4
C13A—C14A—H14B	109.5	C12B—C11B—H11E	109.4
H14A—C14A—H14B	109.5	C10B—C11B—H11F	109.4
C13A—C14A—H14C	109.5	C12B—C11B—H11F	109.4
H14A—C14A—H14C	109.5	H11E—C11B—H11F	108.0
H14B—C14A—H14C	109.5	C13B—C12B—C11B	115.3 (2)
C4A—O3'—C9'	121.4 (4)	C13B—C12B—H12E	108.5
O3'—C9'—C10'	110.8 (5)	C11B—C12B—H12E	108.5
O3'—C9'—H9C	109.5	C13B—C12B—H12F	108.5
C10'—C9'—H9C	109.5	C11B—C12B—H12F	108.5
O3'—C9'—H9D	109.5	H12E—C12B—H12F	107.5
C10'—C9'—H9D	109.5	C12B—C13B—C14B	111.7 (2)
H9C—C9'—H9D	108.1	C12B—C13B—H13E	109.3
C9'—C10'—C11'	111.7 (6)	C14B—C13B—H13E	109.3
C9'—C10'—H10C	109.3	C12B—C13B—H13F	109.3
C11'—C10'—H10C	109.3	C14B—C13B—H13F	109.3
C9'—C10'—H10D	109.3	H13E—C13B—H13F	107.9
C11'—C10'—H10D	109.3	C13B—C14B—H14G	109.5
H10C—C10'—H10D	107.9	C13B—C14B—H14H	109.5
C12'—C11'—C10'	114.9 (6)	H14G—C14B—H14H	109.5
C12'—C11'—H11C	108.5	C13B—C14B—H14I	109.5
C10'—C11'—H11C	108.5	H14G—C14B—H14I	109.5
C12'—C11'—H11D	108.5	H14H—C14B—H14I	109.5
C10'—C11'—H11D	108.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2OA···O1B	0.96 (3)	1.83 (3)	2.735 (2)	156 (3)
O2B—H2OB···O1A^i	0.92 (3)	1.89 (3)	2.779 (2)	161 (3)

Symmetry code: (i) x, −y+1/2, z−1/2.