(±)-syn-Isopropyl 4-(1,1,1,3,3,3-hexa­fluoro­propan-2-yl­oxy)-1-hydr­oxy-3-methyl-2-(prop-1-yn­yl)cyclo­pent-2-ene­carboxyl­ate

Gille, A.; Schürmann, M.; Preut, H.; Hiersemann, M.

doi:10.1107/S1600536809023162

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1660

doi:10.1107/S1600536809023162

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(±)-syn-Isopropyl 4-(1,1,1,3,3,3-hexafluoropropan-2-yloxy)-1-hydroxy-3-methyl-2-(prop-1-ynyl)cyclopent-2-enecarboxylate

Annika Gille,^a Markus Schürmann,^a Hans Preut ^a ^* and Martin Hiersemann ^a

^aFakultät Chemie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, 44221 Dortmund, Germany
^*Correspondence e-mail: hans.preut@udo.edu

(Received 5 June 2009; accepted 16 June 2009; online 20 June 2009)

The title compound, C₁₆H₁₈F₆O₄, was obtained through an unprecedented one-pot reaction sequence involving a Gosteli–Claisen rearrangement and a cycloisomerization. The constitution and relative configuration were determined by single-crystal X-ray diffraction analysis. In the crystal, molecules are connected via O—H ⋯ O hydrogen bonds.

Related literature

For the preparation, see: Neises & Steglich (1978 ); Hiersemann (2000 ). For details of the Gosteli–Claisen rearrangement, see: Gosteli (1972 ); Landor & Black (1965 ).

Experimental

Crystal data

C₁₆H₁₈F₆O₄
M_r = 388.30
Triclinic, $[P \overline 1]$
a = 6.0166 (4) Å
b = 11.9075 (6) Å
c = 13.2798 (8) Å
α = 104.600 (5)°
β = 91.775 (5)°
γ = 96.955 (5)°
V = 912.03 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 173 K
0.42 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur S CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.944, T_max = 0.975
7349 measured reflections
3175 independent reflections
2089 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.106
S = 0.96
3175 reflections
240 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.84	2.10	2.8431 (17)	148
Symmetry code: (i) -x, -y, -z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023162/hg2521sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809023162/hg2521Isup2.hkl

checkCIF report

Comment top

For the preparation of the title compound (±)-(I) a propargyl vinyl ether (II) was synthesized from 2-butin-1-ol using an etherification with bromoacetic acid, an esterification under Steglich's conditions (Neises & Steglich, 1978) and an aldol condensation (Hiersemann, 2000). An unprecedented one-pot reaction sequence involving an uncatalyzed Gosteli-Claisen rearrangement (Gosteli, 1972) of the propargyl vinyl ether (II) (Landor & Black, 1965) and a cycloisomerization under incorporation of a solvent molecule provided (I) as a colourless solid. Fig. 1 depicts the constitution and relative configuration of the isolated diastereomer (I).

Related literature top

For related literature concerning the synthesis, see: Gosteli (1972); Hiersemann (2000); Landor & Black (1965); Neises & Steglich (1978).

Experimental top

The title compound (I) was synthesized according to the following procedure. A solution of (II) (0.044 g, 0.2 mmol) in dry hexafluoroisopropanol (0.6 ml) was stirred at 333 K for 23 h. The solvent was removed under reduced pressure. Flash chromatography (isohexane/ethyl acetate 100/1 to 50/1 to 20/1) afforded (I) as a single diastereomer (0.026 g, 0.07 mmol, 34%) and 37% of the starting material (II). Single crystals of (I) were obtained by vapor diffusion recrystallization technique from isohexane and ethyl acetate to yield colorless cuboids: mp 385 K; R_f 0.32 (cyclohexane/ethyl acetate 5/1); ¹H NMR (CDCl₃, 400 MHz, δ): 1.23 (d, J = 6.3 Hz, 3H, 8-H), 1.26 (d, J = 6.3 Hz, 3H, 8-H), 1.91 (s, 3H, 12-H), 2.01 (s, 3H, 11-H), 2.03 (dd, J = 13.6, 5.9 Hz, 1H, 5-H), 2.86 (dd, J = 13.6, 7.0 Hz, 1H, 5-H), 3.76 (br.s, 1H, –OH), 4.23 (sep, J = 5.9 Hz, 1H, 13-H), 4.67 (t, J = 5.9 Hz, 1H, 4-H), 5.06 (sep, J = 6.3 Hz, 1H, 7-H); ¹⁹F NMR (CDCl₃, 282 MHz, δ): (-77.0)-(-76.7) (m, 6 F); ¹³C NMR (CDCl₃, 101 MHz, δ): 4.8 (11-CH₃), 13.3 (12-CH₃), 21.7 (8-CH₃), 21.8 (8-CH₃), 42.7 (5-CH₂), 70.6 (7-CH), 71.6 (9-C), 76.0 (sep, J = 32.6 Hz, 13-CH), 83.1 (1-C), 88.9 (4-CH), 94.5 (10-C), 121.2 (q, J = 283.0 Hz, 14-C), 121.8 (q, J = 283.0 Hz, 14-C), 126.5 (2-C), 146.9 (3-C), 173.6 (6-C); IR (cm^-1): 3485(br,s) (ν O—H, OH in H-bridges), 2990(m) 2940(m) 2920(m) (ν_as,s C—H, CH₂, CH₃, CH), 2230(w) (ν C≡C), 1715(s) (ν C=O, ester), 1635(m) (ν C=C), 1380(m) (δ_s C—H, CH₃), 1295(s) (ν C—O, ester), 1240(s) 1230(s) 1220(s) (ν C—F), 1185(s) 1120(s) 1105(s) (ν C—O, ether); Anal. Calcd. for C₁₆H₁₈F₆O₄: C,49.5; H, 4.7; Found: C, 49.1; H, 4.7; M = 388.30 g/mol.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); 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 (I) with displacement ellipsoids shown at the 30% probability level.

(±)-syn-Isopropyl 4-(1,1,1,3,3,3-hexafluoropropan-2-yloxy)-1-hydroxy- 3-methyl-2-(prop-1-ynyl)cyclopent-2-enecarboxylate top

Crystal data top

C₁₆H₁₈F₆O₄	Z = 2
M_r = 388.30	F(000) = 400
Triclinic, P1	D_x = 1.414 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0166 (4) Å	Cell parameters from 3408 reflections
b = 11.9075 (6) Å	θ = 2.7–25.0°
c = 13.2798 (8) Å	µ = 0.14 mm⁻¹
α = 104.600 (5)°	T = 173 K
β = 91.775 (5)°	Block, colourless
γ = 96.955 (5)°	0.42 × 0.20 × 0.18 mm
V = 912.03 (10) Å³

Data collection top

Oxford Diffraction Xcalibur S CCD diffractometer	3175 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2089 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 16.0560 pixels mm^-1	θ_max = 25.0°, θ_min = 2.7°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −13→14
T_min = 0.944, T_max = 0.975	l = −15→11
7349 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0599P)²] where P = (F_o² + 2F_c²)/3
3175 reflections	(Δ/σ)_max < 0.001
240 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₆H₁₈F₆O₄	γ = 96.955 (5)°
M_r = 388.30	V = 912.03 (10) Å³
Triclinic, P1	Z = 2
a = 6.0166 (4) Å	Mo Kα radiation
b = 11.9075 (6) Å	µ = 0.14 mm⁻¹
c = 13.2798 (8) Å	T = 173 K
α = 104.600 (5)°	0.42 × 0.20 × 0.18 mm
β = 91.775 (5)°

Data collection top

Oxford Diffraction Xcalibur S CCD diffractometer	3175 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	2089 reflections with I > 2σ(I)
T_min = 0.944, T_max = 0.975	R_int = 0.026
7349 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 0.96	Δρ_max = 0.27 e Å⁻³
3175 reflections	Δρ_min = −0.29 e Å⁻³
240 parameters

Special details top

Experimental. CrysAlis RED (Oxford Diffraction 2008) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
F1	0.8004 (4)	0.56391 (17)	0.16252 (16)	0.1130 (8)
F2	1.0918 (3)	0.49063 (18)	0.10772 (12)	0.1036 (7)
F3	0.7665 (3)	0.39187 (15)	0.06173 (11)	0.0842 (6)
F4	1.0556 (2)	0.43622 (12)	0.40071 (10)	0.0537 (4)
F5	0.9672 (2)	0.59099 (11)	0.36511 (11)	0.0631 (5)
F6	1.2566 (2)	0.51846 (13)	0.30212 (11)	0.0608 (4)
O1	0.0648 (2)	0.15814 (11)	0.13523 (10)	0.0286 (4)
H1	0.0264	0.1079	0.0786	0.043*
O2	0.6874 (2)	0.38842 (11)	0.26452 (11)	0.0310 (4)
O3	0.1934 (2)	−0.05252 (12)	0.05543 (11)	0.0406 (4)
O4	0.4173 (2)	−0.03491 (12)	0.19701 (11)	0.0391 (4)
C1	0.6115 (3)	0.26537 (16)	0.25431 (15)	0.0243 (5)
H1A	0.7429	0.2231	0.2609	0.029*
C2	0.4539 (3)	0.25339 (16)	0.33674 (15)	0.0243 (5)
C3	0.2714 (3)	0.17686 (16)	0.29615 (15)	0.0231 (4)
C4	0.2677 (3)	0.13463 (16)	0.17825 (14)	0.0227 (4)
C5	0.4762 (3)	0.20733 (17)	0.15116 (15)	0.0293 (5)
H5A	0.5661	0.1562	0.1028	0.035*
H5B	0.4311	0.2673	0.1177	0.035*
C6	0.9030 (3)	0.41341 (17)	0.23280 (16)	0.0299 (5)
H6	0.9684	0.3384	0.2098	0.036*
C7	0.8883 (5)	0.4666 (2)	0.1413 (2)	0.0605 (8)
C8	1.0461 (4)	0.4918 (2)	0.32484 (18)	0.0397 (6)
C9	0.5107 (3)	0.31553 (18)	0.44862 (15)	0.0367 (6)
H9A	0.3943	0.2902	0.4912	0.055*
H9B	0.5193	0.4002	0.4574	0.055*
H9C	0.6557	0.2970	0.4708	0.055*
C10	0.0936 (3)	0.13487 (17)	0.35228 (15)	0.0256 (5)
C11	−0.0581 (3)	0.09773 (18)	0.39548 (16)	0.0318 (5)
C12	−0.2433 (4)	0.0527 (2)	0.44912 (19)	0.0486 (6)
H12A	−0.2256	−0.0270	0.4525	0.073*
H12B	−0.3858	0.0518	0.4109	0.073*
H12C	−0.2428	0.1032	0.5200	0.073*
C13	0.2847 (3)	0.00474 (17)	0.13700 (15)	0.0237 (5)
C14	0.4642 (4)	−0.15683 (18)	0.16071 (17)	0.0392 (6)
H14	0.3778	−0.1949	0.0926	0.047*
C15	0.7079 (4)	−0.1520 (2)	0.1452 (2)	0.0602 (8)
H15A	0.7475	−0.1045	0.0963	0.090*
H15B	0.7441	−0.2315	0.1168	0.090*
H15C	0.7929	−0.1168	0.2121	0.090*
C16	0.3840 (5)	−0.2186 (2)	0.2411 (2)	0.0710 (9)
H16A	0.4691	−0.1819	0.3078	0.107*
H16B	0.4064	−0.3011	0.2184	0.107*
H16C	0.2241	−0.2131	0.2495	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.179 (2)	0.0561 (12)	0.1164 (16)	0.0058 (12)	−0.0384 (15)	0.0547 (11)
F2	0.1085 (14)	0.1364 (17)	0.0573 (11)	−0.0682 (13)	0.0018 (10)	0.0494 (11)
F3	0.1084 (12)	0.0924 (13)	0.0418 (9)	−0.0499 (10)	−0.0191 (9)	0.0316 (8)
F4	0.0516 (8)	0.0668 (10)	0.0425 (8)	−0.0019 (7)	−0.0024 (6)	0.0191 (7)
F5	0.0721 (9)	0.0333 (8)	0.0679 (10)	0.0027 (7)	0.0029 (8)	−0.0145 (7)
F6	0.0357 (8)	0.0757 (10)	0.0675 (10)	−0.0151 (7)	0.0060 (7)	0.0220 (8)
O1	0.0311 (7)	0.0296 (8)	0.0227 (8)	0.0091 (6)	−0.0052 (6)	0.0008 (6)
O2	0.0303 (8)	0.0201 (7)	0.0417 (9)	0.0021 (6)	0.0045 (6)	0.0069 (6)
O3	0.0513 (9)	0.0306 (8)	0.0333 (9)	0.0110 (7)	−0.0156 (8)	−0.0043 (7)
O4	0.0503 (9)	0.0288 (8)	0.0346 (9)	0.0142 (7)	−0.0144 (7)	−0.0006 (7)
C1	0.0238 (10)	0.0183 (10)	0.0301 (11)	0.0032 (8)	0.0018 (9)	0.0050 (8)
C2	0.0275 (10)	0.0239 (10)	0.0219 (11)	0.0061 (8)	0.0003 (9)	0.0058 (8)
C3	0.0251 (10)	0.0231 (10)	0.0214 (10)	0.0055 (8)	0.0020 (8)	0.0051 (8)
C4	0.0215 (10)	0.0265 (10)	0.0198 (10)	0.0046 (8)	0.0000 (8)	0.0050 (8)
C5	0.0327 (11)	0.0312 (11)	0.0228 (11)	−0.0001 (9)	0.0052 (9)	0.0065 (9)
C6	0.0355 (11)	0.0199 (10)	0.0337 (12)	−0.0011 (8)	0.0092 (10)	0.0073 (9)
C7	0.0795 (19)	0.0498 (18)	0.0488 (17)	−0.0232 (15)	−0.0063 (15)	0.0228 (14)
C8	0.0365 (13)	0.0399 (14)	0.0404 (14)	−0.0015 (10)	0.0045 (11)	0.0089 (11)
C9	0.0404 (12)	0.0375 (13)	0.0276 (12)	0.0012 (10)	−0.0024 (10)	0.0022 (10)
C10	0.0291 (11)	0.0266 (11)	0.0219 (11)	0.0053 (9)	−0.0001 (9)	0.0070 (9)
C11	0.0309 (12)	0.0387 (13)	0.0294 (12)	0.0042 (10)	0.0011 (10)	0.0157 (10)
C12	0.0402 (13)	0.0657 (17)	0.0502 (16)	0.0040 (12)	0.0107 (12)	0.0342 (13)
C13	0.0183 (9)	0.0294 (11)	0.0221 (11)	0.0012 (8)	0.0025 (9)	0.0052 (9)
C14	0.0536 (14)	0.0256 (12)	0.0372 (13)	0.0147 (10)	−0.0072 (11)	0.0026 (10)
C15	0.0656 (17)	0.0441 (15)	0.078 (2)	0.0211 (13)	0.0294 (15)	0.0188 (14)
C16	0.079 (2)	0.0405 (15)	0.100 (2)	0.0080 (14)	0.0324 (18)	0.0276 (16)

Geometric parameters (Å, º) top

F1—C7	1.302 (3)	C5—H5A	0.9900
F2—C7	1.339 (3)	C5—H5B	0.9900
F3—C7	1.329 (3)	C6—C8	1.507 (3)
F4—C8	1.341 (3)	C6—C7	1.510 (3)
F5—C8	1.319 (2)	C6—H6	1.0000
F6—C8	1.330 (2)	C9—H9A	0.9800
O1—C4	1.419 (2)	C9—H9B	0.9800
O1—H1	0.8400	C9—H9C	0.9800
O2—C6	1.397 (2)	C10—C11	1.192 (3)
O2—C1	1.452 (2)	C11—C12	1.461 (3)
O3—C13	1.200 (2)	C12—H12A	0.9800
O4—C13	1.318 (2)	C12—H12B	0.9800
O4—C14	1.474 (2)	C12—H12C	0.9800
C1—C2	1.492 (3)	C14—C15	1.483 (3)
C1—C5	1.528 (3)	C14—C16	1.502 (4)
C1—H1A	1.0000	C14—H14	1.0000
C2—C3	1.342 (2)	C15—H15A	0.9800
C2—C9	1.492 (3)	C15—H15B	0.9800
C3—C10	1.434 (3)	C15—H15C	0.9800
C3—C4	1.517 (3)	C16—H16A	0.9800
C4—C13	1.522 (3)	C16—H16B	0.9800
C4—C5	1.541 (3)	C16—H16C	0.9800

C4—O1—H1	109.5	F5—C8—F4	106.86 (19)
C6—O2—C1	115.42 (14)	F6—C8—F4	106.70 (18)
C13—O4—C14	118.33 (14)	F5—C8—C6	113.48 (18)
O2—C1—C2	109.65 (14)	F6—C8—C6	112.73 (19)
O2—C1—C5	112.11 (17)	F4—C8—C6	109.13 (18)
C2—C1—C5	105.10 (14)	C2—C9—H9A	109.5
O2—C1—H1A	110.0	C2—C9—H9B	109.5
C2—C1—H1A	110.0	H9A—C9—H9B	109.5
C5—C1—H1A	110.0	C2—C9—H9C	109.5
C3—C2—C9	127.42 (19)	H9A—C9—H9C	109.5
C3—C2—C1	110.79 (16)	H9B—C9—H9C	109.5
C9—C2—C1	121.69 (16)	C11—C10—C3	177.6 (2)
C2—C3—C10	126.87 (18)	C10—C11—C12	179.6 (2)
C2—C3—C4	112.41 (17)	C11—C12—H12A	109.5
C10—C3—C4	120.72 (15)	C11—C12—H12B	109.5
O1—C4—C3	108.58 (14)	H12A—C12—H12B	109.5
O1—C4—C13	108.35 (13)	C11—C12—H12C	109.5
C3—C4—C13	114.56 (17)	H12A—C12—H12C	109.5
O1—C4—C5	112.55 (16)	H12B—C12—H12C	109.5
C3—C4—C5	103.23 (14)	O3—C13—O4	124.56 (18)
C13—C4—C5	109.61 (15)	O3—C13—C4	122.24 (17)
C1—C5—C4	106.17 (16)	O4—C13—C4	113.11 (15)
C1—C5—H5A	110.5	O4—C14—C15	107.02 (18)
C4—C5—H5A	110.5	O4—C14—C16	106.87 (18)
C1—C5—H5B	110.5	C15—C14—C16	115.0 (2)
C4—C5—H5B	110.5	O4—C14—H14	109.3
H5A—C5—H5B	108.7	C15—C14—H14	109.3
O2—C6—C8	108.60 (17)	C16—C14—H14	109.3
O2—C6—C7	109.24 (18)	C14—C15—H15A	109.5
C8—C6—C7	113.26 (19)	C14—C15—H15B	109.5
O2—C6—H6	108.5	H15A—C15—H15B	109.5
C8—C6—H6	108.5	C14—C15—H15C	109.5
C7—C6—H6	108.5	H15A—C15—H15C	109.5
F1—C7—F3	108.0 (2)	H15B—C15—H15C	109.5
F1—C7—F2	106.8 (2)	C14—C16—H16A	109.5
F3—C7—F2	106.9 (2)	C14—C16—H16B	109.5
F1—C7—C6	113.5 (2)	H16A—C16—H16B	109.5
F3—C7—C6	110.3 (2)	C14—C16—H16C	109.5
F2—C7—C6	111.1 (2)	H16A—C16—H16C	109.5
F5—C8—F6	107.57 (18)	H16B—C16—H16C	109.5

C6—O2—C1—C2	149.56 (16)	O2—C6—C7—F1	60.4 (2)
C6—O2—C1—C5	−94.11 (18)	C8—C6—C7—F1	−60.8 (3)
O2—C1—C2—C3	133.92 (16)	O2—C6—C7—F3	−60.9 (3)
C5—C1—C2—C3	13.2 (2)	C8—C6—C7—F3	177.9 (2)
O2—C1—C2—C9	−49.5 (2)	O2—C6—C7—F2	−179.27 (18)
C5—C1—C2—C9	−170.23 (17)	C8—C6—C7—F2	59.6 (3)
C9—C2—C3—C10	−2.3 (3)	O2—C6—C8—F5	−58.6 (2)
C1—C2—C3—C10	173.99 (18)	C7—C6—C8—F5	63.0 (3)
C9—C2—C3—C4	178.06 (18)	O2—C6—C8—F6	178.82 (17)
C1—C2—C3—C4	−5.6 (2)	C7—C6—C8—F6	−59.6 (3)
C2—C3—C4—O1	−123.92 (17)	O2—C6—C8—F4	60.5 (2)
C10—C3—C4—O1	56.4 (2)	C7—C6—C8—F4	−178.0 (2)
C2—C3—C4—C13	114.83 (18)	C14—O4—C13—O3	2.1 (3)
C10—C3—C4—C13	−64.8 (2)	C14—O4—C13—C4	−174.52 (16)
C2—C3—C4—C5	−4.3 (2)	O1—C4—C13—O3	25.9 (2)
C10—C3—C4—C5	176.06 (16)	C3—C4—C13—O3	147.25 (18)
O2—C1—C5—C4	−134.32 (16)	C5—C4—C13—O3	−97.3 (2)
C2—C1—C5—C4	−15.27 (19)	O1—C4—C13—O4	−157.37 (16)
O1—C4—C5—C1	128.89 (16)	C3—C4—C13—O4	−36.0 (2)
C3—C4—C5—C1	12.02 (18)	C5—C4—C13—O4	79.5 (2)
C13—C4—C5—C1	−110.46 (17)	C13—O4—C14—C15	115.9 (2)
C1—O2—C6—C8	−119.38 (18)	C13—O4—C14—C16	−120.4 (2)
C1—O2—C6—C7	116.65 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.84	2.10	2.8431 (17)	148

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈F₆O₄
M_r	388.30
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	6.0166 (4), 11.9075 (6), 13.2798 (8)
α, β, γ (°)	104.600 (5), 91.775 (5), 96.955 (5)
V (Å³)	912.03 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.42 × 0.20 × 0.18

Data collection
Diffractometer	Oxford Diffraction Xcalibur S CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.944, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	7349, 3175, 2089
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.106, 0.96
No. of reflections	3175
No. of parameters	240
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.29

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.84	2.10	2.8431 (17)	147.5

Symmetry code: (i) −x, −y, −z.

References

Gosteli, J. (1972). Helv. Chim. Acta, 55, 451–460. CrossRef CAS PubMed Web of Science Google Scholar
Hiersemann, M. (2000). Synthesis, pp. 1279–1290. CrossRef Google Scholar
Landor, S. R. & Black, D. K. (1965). J. Chem. Soc. pp. 6784–6788. Google Scholar
Neises, B. & Steglich, W. (1978). Angew. Chem. 90, 556–557. CrossRef CAS Google Scholar
Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 65| Part 7| July 2009| Page o1660

doi:10.1107/S1600536809023162

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(±)-syn-Iso­propyl 4-(1,1,1,3,3,3-hexa­fluoro­propan-2-yl­­oxy)-1-hydr­­oxy-3-methyl-2-(prop-1-yn­yl)cyclo­pent-2-ene­carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

(±)-syn-Isopropyl 4-(1,1,1,3,3,3-hexafluoropropan-2-yloxy)-1-hydroxy-3-methyl-2-(prop-1-ynyl)cyclopent-2-enecarboxylate