Crystal structure of 3-hy­droxy-2-(4-hy­droxy-3-meth­oxy­phenyl­methyl)-5,5-di­methyl­cyclo­hex-2-enone

Stikute, A.; Skestere, K.; Mierina, I.; Mishnev, A.; Jure, M.

doi:10.1107/S2056989018006941

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Volume 74| Part 6| June 2018| Pages 796-798

https://doi.org/10.1107/S2056989018006941

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Crystal structure of 3-hydroxy-2-(4-hydroxy-3-methoxyphenylmethyl)-5,5-dimethylcyclohex-2-enone

Agnese Stikute,^a Karina Skestere,^a Inese Mierina,^a Anatoly Mishnev ^b ^* and Mara Jure ^a ^*

^aInstitute of Technology of Organic Chemistry, Faculty of Materials Science and Applied Chemistry, Riga Technical University, P. Valdena Str. 3/7, Riga, LV-1048, Latvia, and ^bLatvian Institute of Organic Synthesis, Aizkraukles Str. 21, Riga, LV-1006, Latvia
^*Correspondence e-mail: mishnevs@osi.lv, Mara.Jure@rtu.lv

Edited by H. Ishida, Okayama University, Japan (Received 13 April 2018; accepted 7 May 2018; online 15 May 2018)

In the title compound, C₁₆H₂₀O₄, a new starting compound for the synthesis of various heterocycles, the partially saturated six-membered ring adopts a sofa conformation. An intramolecular O—H⋯O hydrogen bond is observed in the guaiacol residue. In the crystal, molecules are assembled into a sheet structure parallel to the ab plane via O—H⋯O hydrogen bonds. The hydrogen-bond pattern is described by an R₄⁴(28) graph-set motif. The sheets are further linked by C—H⋯O hydrogen bonds into a three-dimensional network.

Keywords: crystal structure; arylmethyl dimedone; arylmethyl 1,3-cyclohexanedione; arylmethyl 3-hydroxycyclohex-2-enone.

CCDC reference: 1841730

1. Chemical context

Cyclic 2-arylmethyl-1,3-diketones attract interest as valuable intermediates for organic chemistry. A few of the latest examples of these cyclohexanedione derivatives have been used as starting compounds for the synthesis of various heterocycles [e.g. tetrahydrobenzofuranones (Yoshida et al., 2010 ) or tetrahydro-1H-xanthen-1-ones (Sudheendran et al., 2012 )], as well as carbocycles, e.g. analogues of Wieland–Miesher and Hajos–Parrish ketones (Xu et al., 2013 ).

2. Structural commentary

Fig. 1 shows the molecular structure of the title compound, which exhibits an intramolecular O—H⋯O hydrogen bond (Table 1). In crystalline state, the molecules assume the enol tautomeric form, 1a. In the dimedone fragment, the bond distances reflect the effect of conjugation in the flat fragment O1=C3—C4=C5—O2. The double bonds, O1=C3 and C4=C5, are elongated [1.246 (2) and 1.357 (3) Å, respectively], while the single bond C3—C4 is shortened [1.447 (3) Å] as compared with standard double and single bonds (Allen et al., 1987 ). The general shape of the molecule is characterized by the torsion angles C3—C4—C7—C8 = −62.8 (2)° and C4—C7—C8—C9 = 152.2 (2)°, thus exhibiting an extended conformation. The partially saturated C1–C6 ring adopts a sofa conformation. The distance of atom C1 from the mean plane formed by atoms C2–C6 is 0.612 (3) Å. The dihedral angle between the mean plane of the C1–C6 ring and the C8–C13 benzene ring is 75.69 (6)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O4ⁱ	0.97	2.49	3.417 (3)	161
C14—H14C⋯O1ⁱⁱ	0.96	2.49	3.247 (3)	136
O2—H2⋯O1ⁱⁱⁱ	0.88 (3)	1.74 (3)	2.586 (2)	161 (3)
O4—H4⋯O3	0.94 (4)	2.10 (4)	2.638 (2)	115 (3)
O4—H4⋯O2^iv	0.94 (4)	2.11 (4)	2.919 (2)	142 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Figure 1
The molecular structure of the title compound, with the atom-numbering scheme and 50% probability displacement ellipsoids. The intramolecular hydrogen bond is shown as a double-dashed line.

3. Supramolecular features

In the crystal, the molecules are assembled into a sheet structure parallel to the ab plane via O—H⋯O hydrogen bonds (Table 1). The hydrogen-bonding pattern in the sheet is described by an R₄⁴(28) graph-set motif (Fig. 2). Furthermore, weak C—H⋯O hydrogen bonds join the sheets into a three-dimensional network (Table 1).

Figure 2
A packing diagram of the title compound, viewed along the c axis. O—H⋯O hydrogen bonds are shown as dashed lines. For clarity weak C—H⋯O bonds are not depicted.

4. Database survey

A search of the Cambridge Structural Database (Version 5.39, last update February 2018; Groom et al., 2016 ) gave 76 structures of 3-hydroxy-5,5-dimethylcyclohex-2-enone derivatives. The closest structures are 2-(naphthalen-1-ylmethyl)- and 2-(3-chlorophenyl)methyl-substituted dimedones (NIHTEE and NIHTII, respectively; Ramachary & Kishor, 2007 ).

5. Antiradical activity against free radicals

Compound 1 demonstrates notable antiradical activity against free radicals. Free radical tests were realized according to the procedures described previously (Mierina et al., 2017 ). 1,1-Diphenyl-2-picrylhydrazyl test: inhibition, when molar ratio of the compound and free radical is 1:1, was 93.3±2.5%; IC₅₀ was 23.0±0.6 µM (starting concentration of free radical was 100 µM). Galvinoxyl test: inhibition was 82.3±1.0% and IC₅₀ – 20.3±2.0 µM.

6. Synthesis and crystallization

3-Hydroxy-2-(4-hydroxy-3-methoxyphenylmethyl)-5,5-dimethylcyclohex-2-enone (1a) was synthesized according to the reaction scheme in Fig. 3. Formic acid (3.6 ml) was added to a solution of dimedone 2 (500 mg, 3.6 mmol) and vanillin 3 (543 mg, 3.6 mmol) in triethylamine (5.5 ml) while cooling in an ice-bath. The reaction mixture was then heated at 413 K for 5 h, followed by cooling to room temperature, pouring into ice (700–800 ml) and filtering the formed solid. The solid material was purified by crystallization from chloroform leading to the target compound 1a (615 mg, 62%) with m.p. 466–468 K. Single crystals were obtained from a methanol solution. IR (KBr) ν, cm⁻¹: 3470, 2935, 2645, 1580, 1515, 1375, 1250, 1230, 1200, 1040.

Figure 3
Reaction scheme for the title compound (1a) and its tautomer (1 b).

The enol form, 1a, was observed exclusively in a DMSO solution. ¹H NMR for compound 1a (300 MHz, DMSO-d₆) δ, ppm: 10.71–10.08 (1H, brs, OH), 8.68–8.37 (1H, brs, OH), 6.68 (1H, s, H^Ar), 6.59 (1H, d, J = 7.7 Hz, H^Ar), 6.50 (1H, d, J = 7.7 Hz, H^Ar), 3.68 (3H, s, OMe), 3.41 (2H, brs, CH₂Ar, overlapping with H₂O signal), 2.34–2.13 (4H, brs, 2CH₂), 0.98 (6H, s, 2Me). ¹³C NMR for compound 1a (75 MHz, DMSO-d₆) δ, ppm: 147.1, 144.1, 132.7, 120.2, 115.0, 113.3, 112.5, 55.5, 31.7, 28.0, 26.5. Mixture of keto–enol tautomers (1a and 1b) was observed in a chloroform solution. The ratio of enol 1a and ketone 1b was 1.35:1 (at room temperature). ¹H NMR for compound 1a (300 MHz, CDCl₃) δ, ppm: 6.84–6.63 (3H, m, H^Ar), (2H, brs, 2OH), 3.82 (3H, s, OMe), 3.61 (2H, s, CH₂Ar), 2.33–2.29 (4H, brs, 2CH₂), 1.07 (6H, s, 2Me). ¹H NMR for compound 1b (300 MHz, CDCl₃) δ, ppm: 6.84–6.63 (3H, m, H^Ar), 5.62–5.68 (1H, brs, OH), 3.86 (3H, s, OMe), 3.56 (1H, t, J = 5.4 Hz, CHCH₂), 3.11 (2H, d, J = 5.4 Hz, CHCH₂), 2.65 (2H, d, J = 13.4 Hz, H^a from CH₂), 2.44 (2H, d, J = 13.4 Hz, H^b from CH₂), 1.16 (3H, s, Me), 0.82 (3H, s, Me).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms bonded to O atoms were refined freely. Other H atoms were included in the refinement at geometrically calculated positions with C—H = 0.93–0.97 Å and treated as riding with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C-methyl).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₂₀O₄
M_r	276.32
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	190
a, b, c (Å)	9.3504 (3), 13.6265 (4), 22.8790 (9)
V (Å³)	2915.09 (17)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.32 × 0.17 × 0.12

Data collection
Diffractometer	Bruker KappaCCD
No. of measured, independent and observed [I > 2σ(I)] reflections	6082, 3295, 2149
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.131, 1.04
No. of reflections	3295
No. of parameters	192
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19
Computer programs: COLLECT (Bruker, 2001 ), SCALEPACK (Otwinowski & Minor, 1997 ), DENZO (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2005 ), SHELXL2017 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1841730

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018006941/is5495sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018006941/is5495Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018006941/is5495Isup3.cml

checkCIF report

Computing details top

Data collection: COLLECT (Bruker, 2001); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

3-Hydroxy-2-(4-hydroxy-3-methoxyphenylmethyl)-5,5-dimethylcyclohex-2-enone top

Crystal data top

C₁₆H₂₀O₄	D_x = 1.259 Mg m⁻³
M_r = 276.32	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 32401 reflections
a = 9.3504 (3) Å	θ = 1.0–27.5°
b = 13.6265 (4) Å	µ = 0.09 mm⁻¹
c = 22.8790 (9) Å	T = 190 K
V = 2915.09 (17) Å³	Block, colourless
Z = 8	0.32 × 0.17 × 0.12 mm
F(000) = 1184

Data collection top

Bruker KappaCCD diffractometer	R_int = 0.057
CCD scans	θ_max = 27.5°, θ_min = 2.8°
6082 measured reflections	h = −12→12
3295 independent reflections	k = −17→17
2149 reflections with I > 2σ(I)	l = −29→29

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.131	w = 1/[σ²(F_o²) + (0.0489P)² + 1.0327P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.006
3295 reflections	Δρ_max = 0.21 e Å⁻³
192 parameters	Δρ_min = −0.19 e Å⁻³

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.75371 (16)	0.50507 (9)	0.63597 (7)	0.0331 (4)
O2	0.62541 (15)	0.83466 (10)	0.63025 (7)	0.0287 (4)
O3	0.16966 (16)	0.39470 (10)	0.68561 (7)	0.0367 (4)
O4	0.13650 (15)	0.39579 (10)	0.57111 (7)	0.0319 (4)
C1	0.9683 (2)	0.71070 (12)	0.58699 (9)	0.0224 (4)
C2	0.8992 (2)	0.60988 (13)	0.57748 (9)	0.0256 (5)
H2A	0.864618	0.605845	0.537577	0.031*
H2B	0.971321	0.559458	0.582589	0.031*
C3	0.7777 (2)	0.58996 (13)	0.61829 (9)	0.0230 (5)
C4	0.6838 (2)	0.66925 (13)	0.63552 (9)	0.0213 (4)
C5	0.7173 (2)	0.76168 (13)	0.61827 (9)	0.0216 (4)
C6	0.8495 (2)	0.78837 (13)	0.58489 (9)	0.0243 (5)
H6A	0.886941	0.849470	0.600375	0.029*
H6B	0.823687	0.799694	0.544389	0.029*
C7	0.5558 (2)	0.64569 (13)	0.67303 (10)	0.0277 (5)
H7A	0.508367	0.706600	0.683286	0.033*
H7B	0.589063	0.615710	0.709003	0.033*
C8	0.4470 (2)	0.57763 (13)	0.64472 (9)	0.0232 (5)
C9	0.3616 (2)	0.51732 (13)	0.68030 (9)	0.0258 (5)
H9	0.374309	0.517992	0.720617	0.031*
C10	0.2589 (2)	0.45705 (13)	0.65589 (9)	0.0252 (5)
C11	0.2391 (2)	0.45584 (13)	0.59560 (9)	0.0244 (5)
C12	0.3230 (2)	0.51344 (15)	0.56037 (10)	0.0300 (5)
H12	0.310764	0.512153	0.520037	0.036*
C13	0.4265 (2)	0.57391 (14)	0.58529 (10)	0.0287 (5)
H13	0.483160	0.612663	0.561127	0.034*
C14	0.1966 (3)	0.37943 (17)	0.74571 (11)	0.0469 (7)
H14A	0.293311	0.357396	0.750859	0.070*
H14B	0.131964	0.330679	0.760536	0.070*
H14C	0.182851	0.439830	0.766563	0.070*
C15	1.0448 (2)	0.71292 (14)	0.64588 (10)	0.0317 (5)
H15A	0.977325	0.700158	0.676564	0.048*
H15B	1.087200	0.776352	0.651680	0.048*
H15C	1.118201	0.663631	0.646450	0.048*
C16	1.0760 (2)	0.73067 (15)	0.53816 (10)	0.0345 (5)
H16A	1.115861	0.795077	0.543051	0.052*
H16B	1.028672	0.726735	0.500998	0.052*
H16C	1.151155	0.682745	0.539763	0.052*
H2	0.664 (3)	0.892 (2)	0.6238 (13)	0.079 (10)*
H4	0.085 (4)	0.368 (3)	0.6024 (16)	0.114 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0372 (8)	0.0110 (6)	0.0510 (10)	−0.0009 (6)	0.0078 (8)	0.0033 (6)
O2	0.0240 (8)	0.0128 (7)	0.0493 (10)	0.0022 (6)	−0.0014 (7)	0.0001 (6)
O3	0.0393 (9)	0.0406 (9)	0.0304 (9)	−0.0196 (7)	0.0011 (7)	0.0042 (7)
O4	0.0283 (8)	0.0362 (8)	0.0312 (9)	−0.0096 (7)	−0.0035 (7)	−0.0033 (7)
C1	0.0241 (10)	0.0168 (9)	0.0262 (11)	−0.0004 (8)	0.0006 (9)	0.0004 (8)
C2	0.0287 (11)	0.0172 (9)	0.0308 (12)	0.0006 (8)	0.0033 (9)	−0.0035 (8)
C3	0.0253 (11)	0.0149 (9)	0.0288 (12)	−0.0019 (8)	−0.0012 (9)	−0.0016 (8)
C4	0.0199 (10)	0.0145 (9)	0.0297 (12)	−0.0023 (8)	−0.0019 (9)	−0.0035 (8)
C5	0.0207 (11)	0.0163 (9)	0.0278 (12)	0.0010 (8)	−0.0047 (8)	−0.0014 (8)
C6	0.0241 (10)	0.0151 (9)	0.0336 (12)	−0.0028 (8)	−0.0038 (9)	0.0029 (8)
C7	0.0306 (12)	0.0160 (9)	0.0366 (14)	−0.0026 (9)	0.0042 (10)	−0.0034 (8)
C8	0.0222 (10)	0.0164 (9)	0.0310 (12)	0.0031 (8)	0.0031 (9)	0.0003 (8)
C9	0.0283 (11)	0.0233 (10)	0.0260 (12)	0.0005 (9)	0.0014 (9)	0.0000 (8)
C10	0.0236 (10)	0.0198 (9)	0.0322 (12)	−0.0023 (9)	0.0060 (9)	0.0024 (8)
C11	0.0207 (10)	0.0197 (9)	0.0328 (12)	0.0011 (8)	−0.0013 (9)	−0.0003 (9)
C12	0.0330 (12)	0.0300 (11)	0.0271 (13)	−0.0028 (10)	−0.0005 (10)	0.0037 (9)
C13	0.0279 (11)	0.0222 (10)	0.0359 (13)	−0.0035 (9)	0.0038 (10)	0.0061 (9)
C14	0.0604 (17)	0.0503 (14)	0.0300 (14)	−0.0262 (13)	0.0077 (12)	0.0032 (11)
C15	0.0263 (11)	0.0273 (11)	0.0414 (14)	0.0024 (9)	−0.0045 (10)	−0.0003 (10)
C16	0.0333 (12)	0.0270 (11)	0.0432 (15)	−0.0024 (10)	0.0077 (10)	0.0000 (10)

Geometric parameters (Å, º) top

O1—C3	1.246 (2)	C7—H7A	0.9700
O2—C5	1.342 (2)	C7—H7B	0.9700
O2—H2	0.88 (3)	C8—C13	1.374 (3)
O3—C10	1.371 (2)	C8—C9	1.406 (3)
O3—C14	1.413 (3)	C9—C10	1.381 (3)
O4—C11	1.380 (2)	C9—H9	0.9300
O4—H4	0.94 (4)	C10—C11	1.392 (3)
C1—C15	1.526 (3)	C11—C12	1.371 (3)
C1—C16	1.529 (3)	C12—C13	1.394 (3)
C1—C2	1.534 (3)	C12—H12	0.9300
C1—C6	1.534 (3)	C13—H13	0.9300
C2—C3	1.495 (3)	C14—H14A	0.9600
C2—H2A	0.9700	C14—H14B	0.9600
C2—H2B	0.9700	C14—H14C	0.9600
C3—C4	1.447 (3)	C15—H15A	0.9600
C4—C5	1.357 (3)	C15—H15B	0.9600
C4—C7	1.507 (3)	C15—H15C	0.9600
C5—C6	1.498 (3)	C16—H16A	0.9600
C6—H6A	0.9700	C16—H16B	0.9600
C6—H6B	0.9700	C16—H16C	0.9600
C7—C8	1.521 (3)

C5—O2—H2	111 (2)	C13—C8—C9	118.18 (18)
C10—O3—C14	117.73 (17)	C13—C8—C7	122.47 (18)
C11—O4—H4	107 (2)	C9—C8—C7	119.33 (19)
C15—C1—C16	109.41 (17)	C10—C9—C8	120.5 (2)
C15—C1—C2	109.91 (16)	C10—C9—H9	119.7
C16—C1—C2	109.48 (16)	C8—C9—H9	119.7
C15—C1—C6	110.69 (16)	O3—C10—C9	126.20 (19)
C16—C1—C6	109.34 (16)	O3—C10—C11	113.78 (17)
C2—C1—C6	107.99 (16)	C9—C10—C11	120.02 (18)
C3—C2—C1	113.20 (15)	C12—C11—O4	119.9 (2)
C3—C2—H2A	108.9	C12—C11—C10	119.98 (19)
C1—C2—H2A	108.9	O4—C11—C10	120.14 (18)
C3—C2—H2B	108.9	C11—C12—C13	119.7 (2)
C1—C2—H2B	108.9	C11—C12—H12	120.2
H2A—C2—H2B	107.8	C13—C12—H12	120.2
O1—C3—C4	119.70 (18)	C8—C13—C12	121.57 (19)
O1—C3—C2	120.54 (17)	C8—C13—H13	119.2
C4—C3—C2	119.71 (16)	C12—C13—H13	119.2
C5—C4—C3	118.27 (18)	O3—C14—H14A	109.5
C5—C4—C7	123.16 (17)	O3—C14—H14B	109.5
C3—C4—C7	118.55 (16)	H14A—C14—H14B	109.5
O2—C5—C4	118.71 (17)	O3—C14—H14C	109.5
O2—C5—C6	116.90 (15)	H14A—C14—H14C	109.5
C4—C5—C6	124.37 (17)	H14B—C14—H14C	109.5
C5—C6—C1	114.44 (15)	C1—C15—H15A	109.5
C5—C6—H6A	108.7	C1—C15—H15B	109.5
C1—C6—H6A	108.7	H15A—C15—H15B	109.5
C5—C6—H6B	108.7	C1—C15—H15C	109.5
C1—C6—H6B	108.7	H15A—C15—H15C	109.5
H6A—C6—H6B	107.6	H15B—C15—H15C	109.5
C4—C7—C8	114.73 (17)	C1—C16—H16A	109.5
C4—C7—H7A	108.6	C1—C16—H16B	109.5
C8—C7—H7A	108.6	H16A—C16—H16B	109.5
C4—C7—H7B	108.6	C1—C16—H16C	109.5
C8—C7—H7B	108.6	H16A—C16—H16C	109.5
H7A—C7—H7B	107.6	H16B—C16—H16C	109.5

C15—C1—C2—C3	67.9 (2)	C3—C4—C7—C8	−62.8 (2)
C16—C1—C2—C3	−171.93 (17)	C4—C7—C8—C13	−29.1 (3)
C6—C1—C2—C3	−53.0 (2)	C4—C7—C8—C9	152.22 (17)
C1—C2—C3—O1	−146.67 (19)	C13—C8—C9—C10	−0.8 (3)
C1—C2—C3—C4	35.9 (3)	C7—C8—C9—C10	177.99 (17)
O1—C3—C4—C5	176.34 (19)	C14—O3—C10—C9	−9.4 (3)
C2—C3—C4—C5	−6.2 (3)	C14—O3—C10—C11	170.34 (19)
O1—C3—C4—C7	−2.0 (3)	C8—C9—C10—O3	179.63 (18)
C2—C3—C4—C7	175.47 (18)	C8—C9—C10—C11	−0.1 (3)
C3—C4—C5—O2	175.08 (17)	O3—C10—C11—C12	−178.86 (17)
C7—C4—C5—O2	−6.6 (3)	C9—C10—C11—C12	0.9 (3)
C3—C4—C5—C6	−3.2 (3)	O3—C10—C11—O4	0.3 (3)
C7—C4—C5—C6	175.11 (19)	C9—C10—C11—O4	−179.93 (16)
O2—C5—C6—C1	163.97 (17)	O4—C11—C12—C13	−179.95 (17)
C4—C5—C6—C1	−17.7 (3)	C10—C11—C12—C13	−0.8 (3)
C15—C1—C6—C5	−76.1 (2)	C9—C8—C13—C12	0.9 (3)
C16—C1—C6—C5	163.26 (17)	C7—C8—C13—C12	−177.81 (18)
C2—C1—C6—C5	44.2 (2)	C11—C12—C13—C8	−0.1 (3)
C5—C4—C7—C8	118.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O4ⁱ	0.97	2.49	3.417 (3)	161
C14—H14C···O1ⁱⁱ	0.96	2.49	3.247 (3)	136
O2—H2···O1ⁱⁱⁱ	0.88 (3)	1.74 (3)	2.586 (2)	161 (3)
O4—H4···O3	0.94 (4)	2.10 (4)	2.638 (2)	115 (3)
O4—H4···O2^iv	0.94 (4)	2.11 (4)	2.919 (2)	142 (3)

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

Funding information

Funding for this research was provided by: European Regional Development Fund, Operational Programme `Growth and Employment' within the Activity `Post-doctoral Research Aid' (grant No. 1.1.1.2/VIAA/1/16/039).

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