(±)-syn-Isopropyl 4-(1,1,1,3,3,3-hexa-fluoro-propan-2-yl-oxy)-1-hydr-oxy-3-methyl-2-(prop-1-yn-yl)cyclo-pent-2-ene-carboxyl-ate.

The title compound, C(16)H(18)F(6)O(4), was obtained through an unprecedented one-pot reaction sequence involving a Gosteli-Claisen rearrangement and a cyclo-isomerization. The constitution and relative configuration were determined by single-crystal X-ray diffraction analysis. In the crystal, mol-ecules 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 = 388.30

Triclinic,

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 ▶) 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[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.106

S = 0.96

3175 reflections

240 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.29 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); 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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H18F6O4	Z = 2
Mr = 388.30	F(000) = 400
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0599P)2] where P = (Fo2 + 2Fc2)/3
3175 reflections	(Δ/σ)max < 0.001
240 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .