(4S,5S,6R,E)-3,5-Dimethyl-6-vinyl­hept-2-ene-1,4,7-triol

Kiedrowski, V. von; Quentin, F.; Golz, C.; Strohmann, C.; Preut, H.; Hiersemann, M.

doi:10.1107/S2414314616006970

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 4| April 2016| x160697

doi:10.1107/S2414314616006970

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(4S,5S,6R,E)-3,5-Dimethyl-6-vinylhept-2-ene-1,4,7-triol

Valeska von Kiedrowski,^a Florian Quentin,^a Christopher Golz,^a Carsten Strohmann,^a Hans Preut ^a ^* and Martin Hiersemann ^a

^aFakultät Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, 44221 Dortmund, Germany
^*Correspondence e-mail: hans.preut@tu-dortmund.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 22 April 2016; accepted 25 April 2016; online 29 April 2016)

The title compound, C₁₁H₂₀O₃, was obtained in the course of the total syntheses of curvicollides A–C and features the same relative configuration for the central lactone moiety as that reported for the latter compounds. In the crystal, molecules are linked via O—H⋯O hydrogen bonds: all of the OH groups act as donors as well as acceptors for these bonds, hence each molecule is bound to six surrounding molecules and a three-dimensional network is formed. The absolute structure was confirmed by refinement of the Flack parameter.

Keywords: crystal structure; curvicollides A–C; hydrogen bonding.

CCDC reference: 1476414

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Chemical scheme

Structure description

As a key precursor in the total synthesis of curvicollides A–C we obtained the title compound (I) (Fig. 1) through reductive cleavage of the benzyl ethers in (4S,5S,6R,E)-1-(benzyloxy)-6-[(benzyloxy)methyl]-3,5-dimethylocta-2,7-dien-4-ol, (II). Background to curvicollides is given by Che et al., (2004 ) and synthetic studies of curvicollides are described by Körner & Hiersemann (2007 ). The stereotriade in the title compound was generated from an enantioselective transformation employing the catalytic asymmetric Gosteli–Claisen rearrangement followed by a diastereoselective reduction. The absolute configuration was determined based on the previously described stereochemical course of the catalytic asymmetric Gosteli–Claisen rearrangement using a modified Evans–Cu{(S,S)-tert-butyl-box}–Lewis acid catalyst. For the synthesis of the Evans–Cu{(S,S)-tert-butyl-box} catalyst, see: Evans et al. (1999 ) and Jaschinski & Hiersemann (2012 ).

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level.

In the crystal, molecules are linked via O—H⋯O hydrogen bonds (Table 1): all of the OH groups act as donors as well as acceptors for these bonds, hence each molecule is bound to six surrounding molecules and a three-dimensional network is formed Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.91 (2)	1.77 (2)	2.6681 (16)	166 (3)
O3—H3⋯O2ⁱⁱ	0.89 (2)	1.83 (2)	2.6983 (16)	166 (2)
O1—H1⋯O3ⁱⁱⁱ	0.92 (2)	1.83 (2)	2.7458 (17)	172 (2)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) x+1, y, z; (iii) x, y-1, z.

Figure 2
The molecular structure of the title compound showing the six hydrogen bonds around the molecule. H atoms on C atoms have been omitted for clarity. [Symmetry codes: (A) x, y − 1, z; (B) $[{1\over 2}]$ + x, y − $[{1\over 2}]$ , 1 − z; (C) x − 1, y, z; (D) x − $[{1\over 2}]$ , $[{1\over 2}]$ − y, 1 − z; (E) x, 1 + y, z; (F) 1 + x, y, z.]

Synthesis and crystallization

The synthesis of the title compound was carried out under the conditions for reductive cleavage of benzyl ethers (Liu et al., 1997 ). To a solution of naphthalene (C₁₀H₈, M = 128.17 g mol⁻¹, 69.5 g, 542.35 mmol, 1.499 equiv.) in THF (300 ml), small pieces of freshly cut lithium metal (Li, M = 6.94 g mol⁻¹, 2.51 g, 361.67 mmol, 1 equiv.) were added at room temperature. Within 30 minutes, the colour of the reaction mixture turned to dark green. The reaction mixture was stirred for a further 3 h in order to completely dissolve the metal. The mixture was then transferred within 45 minutes via a canula to a solution of the benzylether (II) (C₂₅H₃₂O₃, M = 380.52 g mol⁻¹, 5.51 g, 14.48 mmol, 1 equiv) in THF (65 ml) at 195 K. After stirring for 2 h, saturated aqueous ammonium chloride solution (100 ml) was added and the mixture was allowed to reach room temperature. The phases were separated and the aqueous layer was extracted with ethyl acetate (3 × 100 ml). The combined organic phases were dried (MgSO₄), filtered and concentrated under reduced pressure. Purification of the residue by flash chromatography (cyclohexane/ethyl acetate 10/1 to 2/1 to ethyl acetate) delivered the title compound (I) (C₁₁H₂₀O₃, M = 200.27 g mol⁻¹, 2.58 g, 12.88 mmol, 88%) as a pale yellow solid. Single crystals of (I) were obtained by adding n-pentane (6 ml) to a solution of (I) in diethyl ether (0.4 ml). Crystallization was completed by slow evaporation of the solvent over three days and yielded (I) as colourless needles. R_f 0.28 (ethyl acetate); m.p. 335.5–337.5 K; ¹H NMR (CDCl₃, 300 MHz) δ 0.85 (d, J = 7.3 Hz, 3 H, 5-CH₃) 1.59 (s, 3 H, 3-CH₃) 1.96 (quind, J = 7.0, 1.8 Hz, 1 H, 5-H) 2.36–2.48 (m, 1 H, 6-H) 3.43–3.69 (m, 2 H, 7-H₂) 3.84 (d, J = 6.6 Hz, 1 H, 4-H) 3.95 (br s, 1 H, OH) 4.11 (dd, J = 12.8, 5.9 Hz, 1 H, 1-H_a) 4.22 (dd, J = 12.8, 7.3 Hz, 1 H, 1-H_b) 4.94–5.15 (m, 3 H, CH=CH₂, OH) 5.18 (br s, 1 H, OH) 5.58 (t, J = 6.4 Hz, 1H, 2-H) 5.77 (ddd, J = 17.2, 10.4, 8.2 Hz, 1H, CH=CH₂); ¹³C NMR (CDCl₃, 75 MHz) δ 12.38 (3-CH₃) 13.91 (5-CH₃) 38.65 (CH-5) 46.54 (CH-6) 58.86 (CH₂-1) 62.73 (CH₂-7) 78.59 (CH-4) 116.48 (CH=CH₂) 125.75 (CH-2) 137.99 (CH=CH₂) 139.12 (C-3); IR (cm⁻¹): 3334 (br s), 2967 (s), 2880 (s), 1667 (w), 1634 (w), 1455 (m), 1383 (m) 1003 (s) 918 (w), 756 (s), 666 (w); HRMS (ESI) calculated for C₁₁H₂₀O₃Na ([M + Na]⁺): 223.13047, found 223.12963. Analysis calculated for C₁₁H₂₀O₃: C, 65.97; H, 10.07; found: C, 65.7; H, 9.9; [α]_D²⁰ = +46 (c 1, CHCl₃).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₂₀O₃
M_r	200.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	5.8932 (9), 7.1714 (9), 27.347 (4)
V (Å³)	1155.7 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.66
Crystal size (mm)	0.22 × 0.10 × 0.05

Data collection
Diffractometer	Bruker D8 VENTURE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
No. of measured, independent and observed [I > 2σ(I)] reflections	7921, 2189, 2154
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.080, 1.10
No. of reflections	2189
No. of parameters	141
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17
Absolute structure	Flack x determined using 862 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons & Flack, 2004 )
Absolute structure parameter	0.06 (4)
Computer programs: SMART and SAINT (Bruker, 2012), SHELXD, SHELXTL-Plus and SHELXL97 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1476414

Crystal structure: contains datablocks I, b0130. DOI: 10.1107/S2414314616006970/hb4041sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616006970/hb4041Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616006970/hb4041Isup3.cml

checkCIF report

Experimental top

The synthesis of the title compound was carried out under the conditions for reductive cleavage of benzyl ethers (Liu et al., 1997). To a solution of naphthalene (C₁₀H₈, M = 128.17 g mol^-1, 69.5 g, 542.35 mmol, 1.499 equiv.) in THF (300 ml), small pieces of freshly cut lithium metal (Li, M = 6.94 g mol^-1, 2.51 g, 361.67 mmol, 1 equiv.) were added at room temperature. Within 30 minutes, the colour of the reaction mixture turned to dark green. The reaction mixture was stirred for a further 3 h in order to completely dissolve the metal. The mixture was then transferred within 45 minutes via a canula to a solution of the benzylether (II) (C₂₅H₃₂O₃, M = 380.52 g mol^-1, 5.51 g, 14.48 mmol, 1 equiv) in THF (65 ml) at 195 K. After stirring for 2 h, saturated aqueous ammonium chloride solution (100 ml) was added and the mixture was allowed to reach room temperature. The phases were separated and the aqueous layer was extracted with ethyl acetate (3 × 100 ml). The combined organic phases were dried (MgSO₄), filtered and concentrated under reduced pressure. Purification of the residue by flash chromatography (cyclohexane/ethyl acetate 10/1 to 2/1 to ethyl acetate) delivered the title compound (I) (C₁₁H₂₀O₃, M = 200.27 g mol^-1, 2.58 g, 12.88 mmol, 88%) as a pale yellow solid. Single crystals of (I) were obtained by adding n-pentane (6 ml) to a solution of (I) in diethyl ether (0.4 ml). Crystallization was completed by slow evaporation of the solvent over three days and yielded (I) as colourless needles. R_f 0.28 (ethyl acetate); m.p. 335.5–337.5 K; ¹H NMR (CDCl₃, 300 MHz) δ 0.85 (d, J = 7.3 Hz, 3 H, 5-CH₃) 1.59 (s, 3 H, 3-CH₃) 1.96 (quind, J = 7.0, 1.8 Hz, 1 H, 5-H) 2.36–2.48 (m, 1 H, 6-H) 3.43–3.69 (m, 2 H, 7-H₂) 3.84 (d, J = 6.6 Hz, 1 H, 4-H) 3.95 (br s, 1 H, OH) 4.11 (dd, J = 12.8, 5.9 Hz, 1 H, 1-H_a) 4.22 (dd, J = 12.8, 7.3 Hz, 1 H, 1-H_b) 4.94–5.15 (m, 3 H, CH═CH₂, OH) 5.18 (br s, 1 H, OH) 5.58 (t, J = 6.4 Hz, 1H, 2-H) 5.77 (ddd, J = 17.2, 10.4, 8.2 Hz, 1H, CH═CH₂); ¹³C NMR (CDCl₃, 75 MHz) δ 12.38 (3-CH₃) 13.91 (5-CH₃) 38.65 (CH-5) 46.54 (CH-6) 58.86 (CH₂-1) 62.73 (CH₂-7) 78.59 (CH-4) 116.48 (CH═CH₂) 125.75 (CH-2) 137.99 (CH═CH₂) 139.12 (C-3); IR (cm^-1): 3334 (br s), 2967 (s), 2880 (s), 1667 (w), 1634 (w), 1455 (m), 1383 (m) 1003 (s) 918 (w), 756 (s), 666 (w); HRMS (ESI) calculated for C₁₁H₂₀O₃Na ([M + Na]⁺): 223.13047, found 223.12963. Analysis calculated for C₁₁H₂₀O₃: C, 65.97; H, 10.07; found: C, 65.7; H, 9.9; [α]_D²⁰ = +46 (c 1, CHCl₃).

Structure description top

As a key precursor in the total synthesis of curvicollides A–C we obtained the title compound (I) (Fig. 1) through reductive cleavage of the benzyl ethers in (4S,5S,6R,E)-1-(benzyloxy)-6-[(benzyloxy)methyl]-3,5-dimethylocta-2,7-dien-4-ol, (II). Background to curvicollides is given by Che et al., (2004) and synthetic studies of curvicollides are described by Körner & Hiersemann (2007). The stereotriade in the title compound was generated from an enantioselective transformation employing the catalytic asymmetric Gosteli–Claisen rearrangement followed by a diastereoselective reduction. The absolute configuration was determined based on the previously described stereochemical course of the catalytic asymmetric Gosteli–Claisen rearrangement using a modified Evans–Cu{(S,S)-tert-butyl-box}–Lewis acid catalyst. For the synthesis of the Evans–Cu{(S,S)-tert-butyl-box} catalyst, see: Evans et al. (1999) and Jaschinski & Hiersemann (2012).

In the crystal, molecules are linked via O—H···O hydrogen bonds (Table 1): all of the OH groups act as donors as well as acceptors for these bonds, hence each molecule is bound to six surrounding molecules and a three-dimensional network is formed Fig. 2).

Computing details top

Data collection: SMART (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXD (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level.
	Fig. 2. The molecular structure of the title compound showing the six hydrogen bonds around the molecule. H atoms on C atoms have been omitted for clarity. [Symmetry codes: (A) x, y - 1, z; (B) 1/2 + x, y - 1/2, 1 - z; (C) x - 1, y, z; (D) x - 1/2, 1/2 - y, 1 - z; (E) x, 1 + y, z; (F) 1 + x, y, z.]

(4S,5S,6R,E)-3,5-Dimethyl-6-vinylhept-2-ene-1,4,7-triol top

Crystal data top

C₁₁H₂₀O₃	D_x = 1.151 Mg m⁻³
M_r = 200.27	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 7854 reflections
a = 5.8932 (9) Å	θ = 3.2–70.2°
b = 7.1714 (9) Å	µ = 0.66 mm⁻¹
c = 27.347 (4) Å	T = 100 K
V = 1155.7 (3) Å³	Plate, colourless-yellow
Z = 4	0.22 × 0.10 × 0.05 mm
F(000) = 440

Data collection top

Bruker D8 VENTURE CCD diffractometer	2189 independent reflections
Radiation source: microfocus sealed X-ray tube	2154 reflections with I > 2σ(I)
Detector resolution: 7.9 pixels mm^-1	R_int = 0.025
ω and φ scans	θ_max = 70.2°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −7→7
	k = −8→8
7921 measured reflections	l = −27→33

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0446P)² + 0.1631P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2189 reflections	Δρ_max = 0.19 e Å⁻³
141 parameters	Δρ_min = −0.17 e Å⁻³
3 restraints	Absolute structure: Flack x determined using 862 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons & Flack, 2004)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (4)

Crystal data top

C₁₁H₂₀O₃	V = 1155.7 (3) Å³
M_r = 200.27	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 5.8932 (9) Å	µ = 0.66 mm⁻¹
b = 7.1714 (9) Å	T = 100 K
c = 27.347 (4) Å	0.22 × 0.10 × 0.05 mm

Data collection top

Bruker D8 VENTURE CCD diffractometer	2189 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	2154 reflections with I > 2σ(I)
	R_int = 0.025
7921 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.080	Δρ_max = 0.19 e Å⁻³
S = 1.10	Δρ_min = −0.17 e Å⁻³
2189 reflections	Absolute structure: Flack x determined using 862 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons & Flack, 2004)
141 parameters	Absolute structure parameter: 0.06 (4)
3 restraints

Special details top

Experimental. A total of 1956 frames were collected. The total exposure time was 43.62 hours. The frames were integrated with the Bruker SAINT software package using a narrow-frame algorithm. The integration of the data yielded a total of 7921 reflections to maximum angle of 70.22° (0.82 Å resolution), of which 2189 were independent (completeness 99.5%).

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	0.4533 (2)	−0.10535 (18)	0.51945 (4)	0.0343 (3)
H1	0.510 (4)	−0.150 (3)	0.5486 (7)	0.046 (6)*
O2	0.0463 (2)	0.60420 (16)	0.57604 (4)	0.0248 (3)
H2	0.038 (5)	0.598 (4)	0.5427 (7)	0.060 (8)*
O3	0.63256 (19)	0.73206 (19)	0.60174 (4)	0.0297 (3)
H3	0.771 (4)	0.686 (4)	0.5986 (9)	0.053 (7)*
C1	0.2461 (3)	−0.0061 (2)	0.52644 (6)	0.0286 (4)
H1A	0.1479	−0.0769	0.5492	0.034*
H1B	0.1656	0.0039	0.4948	0.034*
C2	0.2851 (3)	0.1850 (2)	0.54652 (5)	0.0221 (3)
H2A	0.4186	0.2471	0.5359	0.026*
C3	0.1529 (2)	0.2779 (2)	0.57773 (5)	0.0207 (3)
C4	0.2178 (2)	0.4751 (2)	0.59199 (5)	0.0195 (3)
H4	0.3642	0.5077	0.5756	0.023*
C5	0.2444 (3)	0.5057 (2)	0.64742 (5)	0.0201 (3)
H5	0.0904	0.4887	0.6621	0.024*
C6	0.3197 (3)	0.7081 (2)	0.65976 (5)	0.0216 (3)
H6	0.2309	0.7949	0.6385	0.026*
C7	0.2623 (3)	0.7525 (2)	0.71240 (5)	0.0275 (4)
H7	0.3363	0.6821	0.7371	0.033*
C8	0.1175 (3)	0.8815 (3)	0.72652 (6)	0.0362 (4)
H8A	0.0401	0.9548	0.7029	0.043*
H8B	0.0903	0.9013	0.7604	0.043*
C9	−0.0663 (3)	0.2043 (3)	0.59807 (6)	0.0302 (4)
H9A	−0.0627	0.2113	0.6339	0.045*
H9B	−0.0863	0.0743	0.5879	0.045*
H9C	−0.1928	0.2794	0.5857	0.045*
C10	0.3971 (3)	0.3580 (2)	0.67028 (6)	0.0291 (4)
H10A	0.3264	0.2350	0.6667	0.044*
H10B	0.4183	0.3856	0.7051	0.044*
H10C	0.5447	0.3583	0.6538	0.044*
C11	0.5714 (3)	0.7499 (3)	0.65208 (5)	0.0275 (3)
H11A	0.6048	0.8782	0.6633	0.033*
H11B	0.6634	0.6626	0.6719	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0504 (7)	0.0307 (6)	0.0219 (5)	0.0196 (6)	0.0061 (5)	0.0026 (5)
O2	0.0329 (6)	0.0235 (6)	0.0181 (5)	0.0067 (5)	−0.0054 (4)	−0.0018 (4)
O3	0.0228 (5)	0.0433 (7)	0.0229 (5)	−0.0026 (5)	0.0006 (4)	0.0048 (5)
C1	0.0370 (9)	0.0214 (7)	0.0274 (8)	0.0039 (7)	0.0020 (7)	−0.0028 (6)
C2	0.0257 (7)	0.0207 (7)	0.0198 (6)	0.0006 (6)	0.0006 (6)	0.0013 (6)
C3	0.0227 (7)	0.0212 (7)	0.0183 (6)	0.0001 (6)	−0.0008 (5)	0.0011 (6)
C4	0.0208 (7)	0.0205 (7)	0.0173 (6)	0.0018 (6)	0.0013 (5)	−0.0002 (5)
C5	0.0207 (7)	0.0232 (7)	0.0164 (7)	0.0014 (6)	0.0012 (5)	0.0002 (5)
C6	0.0244 (7)	0.0238 (8)	0.0165 (6)	0.0001 (6)	−0.0016 (5)	−0.0018 (6)
C7	0.0331 (8)	0.0311 (8)	0.0182 (7)	−0.0041 (8)	−0.0017 (6)	−0.0040 (6)
C8	0.0409 (9)	0.0404 (10)	0.0272 (8)	0.0006 (9)	0.0044 (7)	−0.0115 (7)
C9	0.0279 (8)	0.0274 (8)	0.0352 (8)	−0.0061 (7)	0.0073 (7)	−0.0055 (7)
C10	0.0343 (9)	0.0284 (8)	0.0245 (7)	0.0073 (8)	−0.0053 (7)	0.0009 (6)
C11	0.0274 (7)	0.0343 (9)	0.0207 (7)	−0.0060 (7)	−0.0032 (6)	−0.0008 (6)

Geometric parameters (Å, º) top

O1—C1	1.426 (2)	C5—H5	1.0000
O1—H1	0.922 (19)	C6—C7	1.5125 (19)
O2—C4	1.4380 (18)	C6—C11	1.528 (2)
O2—H2	0.914 (19)	C6—H6	1.0000
O3—C11	1.4288 (18)	C7—C8	1.317 (3)
O3—H3	0.89 (2)	C7—H7	0.9500
C1—C2	1.494 (2)	C8—H8A	0.9500
C1—H1A	0.9900	C8—H8B	0.9500
C1—H1B	0.9900	C9—H9A	0.9800
C2—C3	1.334 (2)	C9—H9B	0.9800
C2—H2A	0.9500	C9—H9C	0.9800
C3—C9	1.502 (2)	C10—H10A	0.9800
C3—C4	1.516 (2)	C10—H10B	0.9800
C4—C5	1.5398 (19)	C10—H10C	0.9800
C4—H4	1.0000	C11—H11A	0.9900
C5—C10	1.524 (2)	C11—H11B	0.9900
C5—C6	1.555 (2)

C1—O1—H1	111.6 (16)	C11—C6—C5	115.48 (13)
C4—O2—H2	107.9 (17)	C7—C6—H6	107.8
C11—O3—H3	111.0 (16)	C11—C6—H6	107.8
O1—C1—C2	112.06 (14)	C5—C6—H6	107.8
O1—C1—H1A	109.2	C8—C7—C6	124.90 (16)
C2—C1—H1A	109.2	C8—C7—H7	117.6
O1—C1—H1B	109.2	C6—C7—H7	117.6
C2—C1—H1B	109.2	C7—C8—H8A	120.0
H1A—C1—H1B	107.9	C7—C8—H8B	120.0
C3—C2—C1	127.14 (15)	H8A—C8—H8B	120.0
C3—C2—H2A	116.4	C3—C9—H9A	109.5
C1—C2—H2A	116.4	C3—C9—H9B	109.5
C2—C3—C9	124.29 (15)	H9A—C9—H9B	109.5
C2—C3—C4	118.91 (14)	C3—C9—H9C	109.5
C9—C3—C4	116.71 (13)	H9A—C9—H9C	109.5
O2—C4—C3	110.20 (11)	H9B—C9—H9C	109.5
O2—C4—C5	106.17 (11)	C5—C10—H10A	109.5
C3—C4—C5	114.31 (12)	C5—C10—H10B	109.5
O2—C4—H4	108.7	H10A—C10—H10B	109.5
C3—C4—H4	108.7	C5—C10—H10C	109.5
C5—C4—H4	108.7	H10A—C10—H10C	109.5
C10—C5—C4	111.40 (12)	H10B—C10—H10C	109.5
C10—C5—C6	113.05 (12)	O3—C11—C6	111.09 (12)
C4—C5—C6	112.07 (11)	O3—C11—H11A	109.4
C10—C5—H5	106.6	C6—C11—H11A	109.4
C4—C5—H5	106.6	O3—C11—H11B	109.4
C6—C5—H5	106.6	C6—C11—H11B	109.4
C7—C6—C11	107.85 (12)	H11A—C11—H11B	108.0
C7—C6—C5	109.84 (13)

O1—C1—C2—C3	−145.42 (16)	C3—C4—C5—C6	177.87 (12)
C1—C2—C3—C9	−0.9 (2)	C10—C5—C6—C7	−73.56 (16)
C1—C2—C3—C4	−177.31 (14)	C4—C5—C6—C7	159.53 (12)
C2—C3—C4—O2	116.83 (15)	C10—C5—C6—C11	48.64 (17)
C9—C3—C4—O2	−59.86 (16)	C4—C5—C6—C11	−78.26 (15)
C2—C3—C4—C5	−123.71 (15)	C11—C6—C7—C8	117.18 (19)
C9—C3—C4—C5	59.60 (17)	C5—C6—C7—C8	−116.18 (19)
O2—C4—C5—C10	171.78 (13)	C7—C6—C11—O3	−173.22 (14)
C3—C4—C5—C10	50.08 (17)	C5—C6—C11—O3	63.52 (17)
O2—C4—C5—C6	−60.43 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.91 (2)	1.77 (2)	2.6681 (16)	166 (3)
O3—H3···O2ⁱⁱ	0.89 (2)	1.83 (2)	2.6983 (16)	166 (2)
O1—H1···O3ⁱⁱⁱ	0.92 (2)	1.83 (2)	2.7458 (17)	172 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.914 (19)	1.77 (2)	2.6681 (16)	166 (3)
O3—H3···O2ⁱⁱ	0.89 (2)	1.83 (2)	2.6983 (16)	166 (2)
O1—H1···O3ⁱⁱⁱ	0.922 (19)	1.830 (19)	2.7458 (17)	172 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₂₀O₃
M_r	200.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	5.8932 (9), 7.1714 (9), 27.347 (4)
V (Å³)	1155.7 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.22 × 0.10 × 0.05

Data collection
Diffractometer	Bruker D8 VENTURE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012)
No. of measured, independent and observed [I > 2σ(I)] reflections	7921, 2189, 2154
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.080, 1.10
No. of reflections	2189
No. of parameters	141
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17
Absolute structure	Flack x determined using 862 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons & Flack, 2004)
Absolute structure parameter	0.06 (4)

Computer programs: SMART (Bruker, 2012), SAINT (Bruker, 2012), SHELXD (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2015), SHELXTL-Plus (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

Financial support by the Fonds der Chemischen Industrie (FCI) and the TU Dortmund is gratefully acknowledged.

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