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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615019919/fn3208sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615019919/fn3208Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615019919/fn3208Isup3.cml
Supplementary material

CCDC reference: 1432541

Introduction top

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.

Experimental top

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.

Synthesis and crystallization top

Synthesis of 2-(hexyl­oxy)phenyl acetate, (III) top

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].

Synthesis of 5-bromo-2-(hexyl­oxy)phenyl acetate, (IV) top

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 (νCaromatic—H), 2958 (νCH3assym), 2931 (νCH2assym), 2872 (νCH3sym), 2859 (νCH2sym), 1776 cm-1 (νCO). Microanalysis found (calculated) for C14H19BrO3 (%): C 54.2 (53.3), H 6.0 (6.0).

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

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 (νCaromatic—H), 2958 (νCH3assym), 2934 (νCH2assym), 2867 (νCH3sym), 2859 (νCH2sym), 1771 cm-1 (νCO). 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, νCaromatic—H), 2953 (νCH3assym), 2927 (νCH2assym), 2873 (νCH3sym), 2859 (νCH2sym), 1666 cm-1 (νCO). 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).

Refinement top

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 Uiso values, while the C—H groups were repositioned in their expected positions and allowed to ride, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for methyl­ene H atoms, and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(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).

Results and discussion top

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 νCaromatic—H band at ca 3100 cm-1 and a νC—Caromatic 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 νCO 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 ···ABAB··· 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 CnH2n+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 top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. The assigned 1H NMR spectrum of (I).
[Figure 3] Fig. 3. The assigned 13C NMR spectrum of (I).
[Figure 4] Fig. 4. The COSY (correlation spectroscopy) analysis for (I).
[Figure 5] Fig. 5. The columnar arrays in the structure of (I), showing (left) the ···ABAB··· sequence along [001] and (right) a single column seen in projection, showing the `shielding' of the potentially interactive core.
[Figure 6] 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 top
Crystal data top
C14H20O3Dx = 1.175 Mg m3
Mr = 236.30Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 2185 reflections
a = 19.3847 (10) Åθ = 3.9–26.4°
b = 9.0716 (4) ŵ = 0.08 mm1
c = 30.3953 (12) ÅT = 170 K
V = 5345.0 (4) Å3Blocks, colourless
Z = 160.32 × 0.26 × 0.18 mm
F(000) = 2048
Data collection top
CCD Oxford Diffraction Xcalibur (Eos, Gemini)
diffractometer
6210 independent reflections
Radiation source: Enhance (Mo) X-ray Source3357 reflections with I > 2σ(I)
Detector resolution: 16.1158 pixels mm-1Rint = 0.058
thick slices scansθmax = 29.0°, θmin = 3.7°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1825
Tmin = 0.95, Tmax = 0.98k = 1211
18445 measured reflectionsl = 3927
Refinement top
Refinement on F223 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.067H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.189 w = 1/[σ2(Fo2) + (0.0741P)2 + 0.6907P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
6210 reflectionsΔρmax = 0.29 e Å3
365 parametersΔρmin = 0.31 e Å3
Crystal data top
C14H20O3V = 5345.0 (4) Å3
Mr = 236.30Z = 16
Orthorhombic, PbcaMo Kα radiation
a = 19.3847 (10) ŵ = 0.08 mm1
b = 9.0716 (4) ÅT = 170 K
c = 30.3953 (12) Å0.32 × 0.26 × 0.18 mm
Data collection top
CCD Oxford Diffraction Xcalibur (Eos, Gemini)
diffractometer
6210 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
3357 reflections with I > 2σ(I)
Tmin = 0.95, Tmax = 0.98Rint = 0.058
18445 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06723 restraints
wR(F2) = 0.189H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.29 e Å3
6210 reflectionsΔρmin = 0.31 e Å3
365 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
O1A0.66050 (9)0.23557 (17)0.59045 (5)0.0446 (4)
C1A0.68678 (11)0.3851 (2)0.52954 (6)0.0346 (5)
C2A0.72377 (12)0.5033 (3)0.51287 (7)0.0459 (6)
H2A0.74730.56600.53190.055*
C3A0.72574 (13)0.5281 (3)0.46765 (7)0.0523 (7)
H3A0.75180.60560.45650.063*
C4A0.68947 (11)0.4392 (3)0.43964 (7)0.0398 (5)
C5A0.65089 (11)0.3203 (2)0.45608 (7)0.0348 (5)
C6A0.65032 (11)0.2950 (2)0.50085 (7)0.0338 (5)
H6A0.62510.21620.51200.041*
C7A0.68423 (11)0.3532 (3)0.57753 (7)0.0370 (5)
C8A0.70922 (14)0.4665 (3)0.60948 (7)0.0559 (7)
H8AA0.70340.43040.63890.084*
H8AB0.68320.55560.60580.084*
H8AC0.75720.48610.60420.084*
O2A0.61431 (9)0.23021 (17)0.42929 (5)0.0474 (4)
H2OA0.6184 (15)0.253 (3)0.3985 (10)0.078 (9)*
O3A0.68699 (9)0.45456 (19)0.39488 (5)0.0529 (5)0.691 (4)
C9A0.7402 (3)0.5463 (7)0.37586 (14)0.082 (3)0.691 (4)
H9AA0.78500.51500.38660.099*0.691 (4)
H9AB0.73310.64790.38470.099*0.691 (4)
C10A0.7384 (3)0.5354 (7)0.32708 (13)0.0944 (19)0.691 (4)
H10A0.78270.56710.31560.113*0.691 (4)
H10B0.73220.43280.31900.113*0.691 (4)
C11A0.6841 (3)0.6226 (8)0.30612 (15)0.0990 (19)0.691 (4)
H11A0.68460.72170.31820.119*0.691 (4)
H11B0.63960.57910.31280.119*0.691 (4)
C12A0.6936 (3)0.6308 (5)0.25457 (14)0.0882 (15)0.691 (4)
H12A0.73990.66510.24800.106*0.691 (4)
H12B0.68860.53270.24230.106*0.691 (4)
C13A0.6455 (3)0.7257 (6)0.23440 (13)0.0829 (16)0.691 (4)
H13A0.65380.82600.24410.099*0.691 (4)
H13B0.59930.69810.24350.099*0.691 (4)
C14A0.6503 (2)0.7191 (4)0.18381 (9)0.0906 (11)0.691 (4)
H14A0.61610.78300.17120.136*0.691 (4)
H14B0.64230.61980.17410.136*0.691 (4)
H14C0.69540.75030.17460.136*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)
H9C0.76290.58540.37470.078*0.309 (4)
H9D0.69620.67170.38880.078*0.309 (4)
C10'0.6901 (5)0.5904 (14)0.3267 (2)0.065 (3)0.309 (4)
H10C0.64110.61260.32560.078*0.309 (4)
H10D0.69710.49460.31330.078*0.309 (4)
C11'0.7281 (6)0.7021 (13)0.3016 (2)0.099 (2)0.309 (4)
H11C0.73720.78550.32070.119*0.309 (4)
H11D0.77230.66100.29300.119*0.309 (4)
C12'0.6905 (6)0.7593 (9)0.2593 (2)0.0888 (16)0.309 (4)
H12C0.64490.79370.26750.107*0.309 (4)
H12D0.71580.84310.24780.107*0.309 (4)
C13'0.6837 (8)0.6543 (13)0.2259 (2)0.128 (7)0.309 (4)
H13C0.65570.57320.23660.153*0.309 (4)
H13D0.72890.61540.21870.153*0.309 (4)
C14'0.6503 (2)0.7191 (4)0.18381 (9)0.0906 (11)0.309 (4)
H14D0.64660.64340.16190.136*0.309 (4)
H14E0.60510.75590.19070.136*0.309 (4)
H14F0.67840.79800.17280.136*0.309 (4)
O1B0.60177 (9)0.23252 (19)0.33965 (5)0.0522 (5)
C1B0.56349 (11)0.1185 (2)0.27495 (7)0.0378 (5)
C2B0.52063 (13)0.0158 (3)0.25549 (8)0.0479 (6)
H2B0.49720.05170.27300.057*
C3B0.51213 (13)0.0121 (3)0.21008 (7)0.0457 (6)
H3B0.48290.05710.19740.055*
C4B0.54704 (11)0.1109 (2)0.18399 (7)0.0361 (5)
C5B0.59232 (11)0.2134 (2)0.20315 (7)0.0353 (5)
C6B0.59926 (11)0.2174 (2)0.24814 (7)0.0358 (5)
H6B0.62820.28700.26090.043*
C7B0.57128 (12)0.1276 (3)0.32316 (7)0.0416 (6)
C8B0.54339 (15)0.0076 (3)0.35173 (8)0.0631 (8)
H8BA0.55770.02380.38160.095*
H8BB0.56060.08580.34180.095*
H8BC0.49390.00760.35020.095*
O2B0.62791 (9)0.31252 (18)0.17830 (5)0.0486 (5)
H2OB0.6302 (15)0.282 (3)0.1493 (10)0.074 (9)*
O3B0.54257 (8)0.11987 (17)0.13942 (4)0.0410 (4)
C9B0.49771 (12)0.0171 (3)0.11721 (7)0.0442 (6)
H9BA0.45190.02060.13010.053*
H9BB0.51540.08240.12040.053*
C10B0.49432 (12)0.0580 (3)0.06956 (7)0.0430 (6)
H10E0.46920.01820.05390.052*
H10F0.54090.06010.05780.052*
C11B0.46042 (13)0.2049 (3)0.06046 (7)0.0482 (6)
H11E0.48950.28350.07170.058*
H11F0.41650.20950.07570.058*
C12B0.44862 (13)0.2275 (3)0.01119 (7)0.0488 (6)
H12E0.49300.22650.00350.059*
H12F0.42220.14460.00010.059*
C13B0.41190 (15)0.3665 (3)0.00099 (9)0.0654 (8)
H13E0.43800.45040.00980.078*
H13F0.36700.36810.01310.078*
C14B0.40268 (18)0.3804 (4)0.05076 (9)0.0767 (9)
H14G0.38000.47170.05740.115*
H14H0.37520.29970.06130.115*
H14I0.44700.37840.06480.115*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0620 (11)0.0419 (9)0.0300 (7)0.0026 (8)0.0001 (8)0.0012 (7)
C1A0.0330 (11)0.0417 (12)0.0289 (10)0.0050 (10)0.0012 (10)0.0020 (10)
C2A0.0444 (13)0.0527 (14)0.0406 (12)0.0118 (11)0.0068 (11)0.0009 (12)
C3A0.0468 (14)0.0654 (16)0.0447 (13)0.0223 (13)0.0028 (12)0.0127 (13)
C4A0.0370 (12)0.0521 (14)0.0304 (11)0.0013 (10)0.0028 (10)0.0051 (11)
C5A0.0343 (12)0.0382 (12)0.0319 (10)0.0024 (9)0.0034 (10)0.0019 (10)
C6A0.0366 (12)0.0335 (11)0.0313 (10)0.0025 (9)0.0008 (10)0.0014 (10)
C7A0.0345 (12)0.0428 (13)0.0336 (11)0.0068 (10)0.0021 (10)0.0014 (11)
C8A0.0708 (18)0.0616 (17)0.0354 (12)0.0131 (14)0.0033 (13)0.0061 (13)
O2A0.0681 (12)0.0454 (9)0.0286 (8)0.0104 (8)0.0061 (8)0.0008 (8)
O3A0.0593 (11)0.0687 (12)0.0307 (8)0.0116 (9)0.0007 (8)0.0101 (8)
C9A0.086 (5)0.115 (6)0.045 (3)0.033 (4)0.003 (3)0.028 (3)
C10A0.081 (4)0.154 (6)0.048 (2)0.019 (4)0.004 (3)0.033 (3)
C11A0.115 (5)0.120 (5)0.062 (3)0.045 (3)0.029 (3)0.017 (3)
C12A0.129 (4)0.063 (2)0.073 (3)0.019 (3)0.030 (3)0.013 (3)
C13A0.104 (4)0.092 (4)0.052 (3)0.001 (3)0.002 (3)0.001 (3)
C14A0.123 (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)
O1B0.0753 (12)0.0512 (10)0.0300 (8)0.0076 (9)0.0045 (8)0.0008 (8)
C1B0.0417 (13)0.0400 (12)0.0316 (11)0.0018 (10)0.0017 (10)0.0007 (10)
C2B0.0550 (15)0.0503 (14)0.0383 (12)0.0120 (12)0.0020 (12)0.0017 (12)
C3B0.0505 (14)0.0506 (14)0.0362 (12)0.0122 (11)0.0018 (12)0.0043 (12)
C4B0.0390 (12)0.0403 (12)0.0290 (10)0.0003 (10)0.0002 (10)0.0027 (10)
C5B0.0399 (12)0.0324 (11)0.0337 (11)0.0012 (9)0.0002 (10)0.0029 (10)
C6B0.0381 (12)0.0364 (11)0.0330 (11)0.0010 (9)0.0028 (10)0.0063 (10)
C7B0.0494 (14)0.0414 (13)0.0339 (11)0.0045 (11)0.0003 (11)0.0016 (11)
C8B0.088 (2)0.0647 (18)0.0368 (12)0.0158 (15)0.0003 (14)0.0072 (13)
O2B0.0676 (12)0.0491 (10)0.0291 (8)0.0192 (8)0.0032 (8)0.0042 (8)
O3B0.0461 (9)0.0476 (9)0.0292 (7)0.0124 (7)0.0015 (7)0.0046 (7)
C9B0.0422 (13)0.0512 (14)0.0393 (12)0.0109 (11)0.0023 (11)0.0082 (12)
C10B0.0402 (13)0.0542 (14)0.0346 (11)0.0050 (11)0.0027 (11)0.0107 (11)
C11B0.0485 (15)0.0583 (16)0.0378 (12)0.0018 (12)0.0008 (12)0.0098 (12)
C12B0.0482 (15)0.0570 (15)0.0413 (13)0.0029 (12)0.0001 (12)0.0064 (12)
C13B0.072 (2)0.0632 (19)0.0611 (17)0.0143 (15)0.0031 (16)0.0058 (15)
C14B0.094 (2)0.079 (2)0.0569 (17)0.0228 (18)0.0088 (17)0.0122 (17)
Geometric parameters (Å, º) top
O1A—C7A1.227 (3)C11'—H11D0.9700
C1A—C2A1.386 (3)C12'—C13'1.398 (7)
C1A—C6A1.389 (3)C12'—H12C0.9700
C1A—C7A1.488 (3)C12'—H12D0.9700
C2A—C3A1.393 (3)C13'—C14'1.551 (6)
C2A—H2A0.9300C13'—H13C0.9700
C3A—C4A1.368 (3)C13'—H13D0.9700
C3A—H3A0.9300C14'—H14D0.9600
C4A—O3'1.368 (2)C14'—H14E0.9600
C4A—O3A1.368 (2)C14'—H14F0.9600
C4A—C5A1.405 (3)O1B—C7B1.228 (3)
C5A—O2A1.354 (2)C1B—C2B1.381 (3)
C5A—C6A1.380 (3)C1B—C6B1.396 (3)
C6A—H6A0.9300C1B—C7B1.475 (3)
C7A—C8A1.494 (3)C2B—C3B1.390 (3)
C8A—H8AA0.9600C2B—H2B0.9300
C8A—H8AB0.9600C3B—C4B1.375 (3)
C8A—H8AC0.9600C3B—H3B0.9300
O2A—H2OA0.96 (3)C4B—O3B1.360 (2)
O3A—C9A1.445 (4)C4B—C5B1.406 (3)
C9A—C10A1.486 (5)C5B—O2B1.362 (3)
C9A—H9AA0.9700C5B—C6B1.374 (3)
C9A—H9AB0.9700C6B—H6B0.9300
C10A—C11A1.463 (7)C7B—C8B1.494 (3)
C10A—H10A0.9700C8B—H8BA0.9600
C10A—H10B0.9700C8B—H8BB0.9600
C11A—C12A1.580 (6)C8B—H8BC0.9600
C11A—H11A0.9700O2B—H2OB0.92 (3)
C11A—H11B0.9700O3B—C9B1.443 (2)
C12A—C13A1.409 (6)C9B—C10B1.496 (3)
C12A—H12A0.9700C9B—H9BA0.9700
C12A—H12B0.9700C9B—H9BB0.9700
C13A—C14A1.542 (4)C10B—C11B1.511 (3)
C13A—H13A0.9700C10B—H10E0.9700
C13A—H13B0.9700C10B—H10F0.9700
C14A—H14A0.9600C11B—C12B1.529 (3)
C14A—H14B0.9600C11B—H11E0.9700
C14A—H14C0.9600C11B—H11F0.9700
O3'—C9'1.440 (5)C12B—C13B1.495 (3)
C9'—C10'1.490 (6)C12B—H12E0.9700
C9'—H9C0.9700C12B—H12F0.9700
C9'—H9D0.9700C13B—C14B1.529 (3)
C10'—C11'1.467 (7)C13B—H13E0.9700
C10'—H10C0.9700C13B—H13F0.9700
C10'—H10D0.9700C14B—H14G0.9600
C11'—C12'1.566 (7)C14B—H14H0.9600
C11'—H11C0.9700C14B—H14I0.9600
C2A—C1A—C6A119.29 (19)H11C—C11'—H11D107.5
C2A—C1A—C7A121.7 (2)C13'—C12'—C11'114.4 (6)
C6A—C1A—C7A118.96 (19)C13'—C12'—H12C108.6
C1A—C2A—C3A120.0 (2)C11'—C12'—H12C108.6
C1A—C2A—H2A120.0C13'—C12'—H12D108.6
C3A—C2A—H2A120.0C11'—C12'—H12D108.6
C4A—C3A—C2A120.3 (2)H12C—C12'—H12D107.6
C4A—C3A—H3A119.8C12'—C13'—C14'112.4 (6)
C2A—C3A—H3A119.8C12'—C13'—H13C109.1
C3A—C4A—O3'125.2 (2)C14'—C13'—H13C109.1
C3A—C4A—O3A125.2 (2)C12'—C13'—H13D109.1
C3A—C4A—C5A120.36 (19)C14'—C13'—H13D109.1
O3'—C4A—C5A114.4 (2)H13C—C13'—H13D107.9
O3A—C4A—C5A114.4 (2)C13'—C14'—H14D109.5
O2A—C5A—C6A119.2 (2)C13'—C14'—H14E109.5
O2A—C5A—C4A121.90 (19)H14D—C14'—H14E109.5
C6A—C5A—C4A118.9 (2)C13'—C14'—H14F109.5
C5A—C6A—C1A121.1 (2)H14D—C14'—H14F109.5
C5A—C6A—H6A119.4H14E—C14'—H14F109.5
C1A—C6A—H6A119.4C2B—C1B—C6B118.83 (19)
O1A—C7A—C1A119.7 (2)C2B—C1B—C7B121.6 (2)
O1A—C7A—C8A120.8 (2)C6B—C1B—C7B119.5 (2)
C1A—C7A—C8A119.5 (2)C1B—C2B—C3B120.8 (2)
C7A—C8A—H8AA109.5C1B—C2B—H2B119.6
C7A—C8A—H8AB109.5C3B—C2B—H2B119.6
H8AA—C8A—H8AB109.5C4B—C3B—C2B119.9 (2)
C7A—C8A—H8AC109.5C4B—C3B—H3B120.1
H8AA—C8A—H8AC109.5C2B—C3B—H3B120.1
H8AB—C8A—H8AC109.5O3B—C4B—C3B125.6 (2)
C5A—O2A—H2OA114.2 (17)O3B—C4B—C5B114.38 (19)
C4A—O3A—C9A115.5 (2)C3B—C4B—C5B120.00 (19)
O3A—C9A—C10A110.2 (4)O2B—C5B—C6B119.00 (19)
O3A—C9A—H9AA109.6O2B—C5B—C4B121.58 (18)
C10A—C9A—H9AA109.6C6B—C5B—C4B119.4 (2)
O3A—C9A—H9AB109.6C5B—C6B—C1B121.0 (2)
C10A—C9A—H9AB109.6C5B—C6B—H6B119.5
H9AA—C9A—H9AB108.1C1B—C6B—H6B119.5
C11A—C10A—C9A114.5 (5)O1B—C7B—C1B119.9 (2)
C11A—C10A—H10A108.6O1B—C7B—C8B120.1 (2)
C9A—C10A—H10A108.6C1B—C7B—C8B120.0 (2)
C11A—C10A—H10B108.6C7B—C8B—H8BA109.5
C9A—C10A—H10B108.6C7B—C8B—H8BB109.5
H10A—C10A—H10B107.6H8BA—C8B—H8BB109.5
C10A—C11A—C12A111.9 (5)C7B—C8B—H8BC109.5
C10A—C11A—H11A109.2H8BA—C8B—H8BC109.5
C12A—C11A—H11A109.2H8BB—C8B—H8BC109.5
C10A—C11A—H11B109.2C5B—O2B—H2OB111.0 (18)
C12A—C11A—H11B109.2C4B—O3B—C9B117.76 (17)
H11A—C11A—H11B107.9O3B—C9B—C10B108.61 (18)
C13A—C12A—C11A112.5 (5)O3B—C9B—H9BA110.0
C13A—C12A—H12A109.1C10B—C9B—H9BA110.0
C11A—C12A—H12A109.1O3B—C9B—H9BB110.0
C13A—C12A—H12B109.1C10B—C9B—H9BB110.0
C11A—C12A—H12B109.1H9BA—C9B—H9BB108.3
H12A—C12A—H12B107.8C9B—C10B—C11B114.51 (19)
C12A—C13A—C14A111.7 (4)C9B—C10B—H10E108.6
C12A—C13A—H13A109.3C11B—C10B—H10E108.6
C14A—C13A—H13A109.3C9B—C10B—H10F108.6
C12A—C13A—H13B109.3C11B—C10B—H10F108.6
C14A—C13A—H13B109.3H10E—C10B—H10F107.6
H13A—C13A—H13B107.9C10B—C11B—C12B111.25 (19)
C13A—C14A—H14A109.5C10B—C11B—H11E109.4
C13A—C14A—H14B109.5C12B—C11B—H11E109.4
H14A—C14A—H14B109.5C10B—C11B—H11F109.4
C13A—C14A—H14C109.5C12B—C11B—H11F109.4
H14A—C14A—H14C109.5H11E—C11B—H11F108.0
H14B—C14A—H14C109.5C13B—C12B—C11B115.3 (2)
C4A—O3'—C9'121.4 (4)C13B—C12B—H12E108.5
O3'—C9'—C10'110.8 (5)C11B—C12B—H12E108.5
O3'—C9'—H9C109.5C13B—C12B—H12F108.5
C10'—C9'—H9C109.5C11B—C12B—H12F108.5
O3'—C9'—H9D109.5H12E—C12B—H12F107.5
C10'—C9'—H9D109.5C12B—C13B—C14B111.7 (2)
H9C—C9'—H9D108.1C12B—C13B—H13E109.3
C9'—C10'—C11'111.7 (6)C14B—C13B—H13E109.3
C9'—C10'—H10C109.3C12B—C13B—H13F109.3
C11'—C10'—H10C109.3C14B—C13B—H13F109.3
C9'—C10'—H10D109.3H13E—C13B—H13F107.9
C11'—C10'—H10D109.3C13B—C14B—H14G109.5
H10C—C10'—H10D107.9C13B—C14B—H14H109.5
C12'—C11'—C10'114.9 (6)H14G—C14B—H14H109.5
C12'—C11'—H11C108.5C13B—C14B—H14I109.5
C10'—C11'—H11C108.5H14G—C14B—H14I109.5
C12'—C11'—H11D108.5H14H—C14B—H14I109.5
C10'—C11'—H11D108.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2A—H2OA···O1B0.96 (3)1.83 (3)2.735 (2)156 (3)
O2B—H2OB···O1Ai0.92 (3)1.89 (3)2.779 (2)161 (3)
Symmetry code: (i) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC14H20O3
Mr236.30
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)170
a, b, c (Å)19.3847 (10), 9.0716 (4), 30.3953 (12)
V3)5345.0 (4)
Z16
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.32 × 0.26 × 0.18
Data collection
DiffractometerCCD Oxford Diffraction Xcalibur (Eos, Gemini)
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.95, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections
18445, 6210, 3357
Rint0.058
(sin θ/λ)max1)0.683
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.189, 1.02
No. of reflections6210
No. of parameters365
No. of restraints23
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.29, 0.31

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2A—H2OA···O1B0.96 (3)1.83 (3)2.735 (2)156 (3)
O2B—H2OB···O1Ai0.92 (3)1.89 (3)2.779 (2)161 (3)
Symmetry code: (i) x, y+1/2, z1/2.
 

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