(S)-6-{[(S)-2,2-Dimethyl-1,3-dioxolan-4-yl]meth-yl}-5,5-difluoro-5,6-dihydro-2H-pyran-2-one.

The title compound, C(11)H(14)F(2)O(4), is a γ,γ-gem-difluorinated α,β-unsaturated δ-lactone. The dioxolane five-membered ring and the lactone ring adopt half-chair conformations. There are two inter-molecular C-H⋯O inter-actions involving the carbonyl group as an acceptor which stabilize the crystal structure.

Related literature

For related synthetic procedures, see: Borjesson & Welch (1992 ▶); Dardonville & Gilbert (2003 ▶); Gaunt et al. (2003 ▶); Saito et al. (1992 ▶); You et al. (2006 ▶).

Experimental

Crystal data

C11H14F2O4

M = 248.22

Orthorhombic,

a = 5.8003 (8) Å

b = 7.8135 (11) Å

c = 25.977 (4) Å

V = 1177.3 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 293 K

0.51 × 0.48 × 0.26 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.761, T max = 1.000 (expected range = 0.736–0.968)

6682 measured reflections

1455 independent reflections

1261 reflections with I > 2σ(I)

R int = 0.131

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.134

S = 1.00

1455 reflections

173 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.32 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028256/gk2220sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028256/gk2220Isup2.hkl

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

C11H14F2O4	Dx = 1.400 Mg m−3
Mr = 248.22	Melting point: 351 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2723 reflections
a = 5.8003 (8) Å	θ = 2.7–27.7°
b = 7.8135 (11) Å	µ = 0.13 mm−1
c = 25.977 (4) Å	T = 293 K
V = 1177.3 (3) Å3	Prismatic, colorless
Z = 4	0.51 × 0.48 × 0.26 mm
F(000) = 520

Bruker SMART APEX CCD area-detector diffractometer	1455 independent reflections
Radiation source: fine-focus sealed tube	1261 reflections with I > 2σ(I)
graphite	Rint = 0.131
Detector resolution: 0 pixels mm-1	θmax = 26.5°, θmin = 1.6°
φ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −9→9
Tmin = 0.761, Tmax = 1.000	l = −22→32
6682 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.134	w = 1/[σ2(Fo2) + (0.0757P)2 + 0.0067P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
1455 reflections	Δρmax = 0.25 e Å−3
173 parameters	Δρmin = −0.32 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (5)

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
O1	0.3246 (5)	0.3829 (4)	1.04388 (8)	0.0741 (7)
O2	0.3476 (3)	0.4190 (2)	0.96034 (7)	0.0476 (5)
O3	0.3431 (4)	0.1554 (3)	0.85332 (9)	0.0639 (7)
O4	0.1373 (4)	0.1699 (3)	0.78051 (8)	0.0644 (6)
F1	0.5404 (4)	0.7375 (2)	0.92182 (8)	0.0666 (6)
F2	0.8095 (3)	0.5889 (3)	0.88536 (7)	0.0720 (6)
C1	0.4418 (5)	0.4245 (4)	1.00830 (11)	0.0517 (7)
C2	0.6747 (6)	0.4915 (4)	1.01335 (13)	0.0570 (8)
C3	0.7764 (5)	0.5731 (4)	0.97527 (13)	0.0559 (8)
C5	0.6553 (4)	0.5857 (4)	0.92469 (11)	0.0473 (6)
C6	0.4949 (4)	0.4373 (3)	0.91582 (10)	0.0393 (6)
C7	0.3425 (5)	0.4559 (3)	0.86946 (11)	0.0436 (6)
H7A	0.4376	0.4761	0.8394	0.052*
H7B	0.2433	0.5546	0.8741	0.052*
C8	0.1945 (5)	0.2985 (4)	0.86032 (11)	0.0468 (6)
C9	0.0516 (6)	0.3041 (4)	0.81085 (13)	0.0612 (8)
H9A	−0.1107	0.2872	0.8183	0.073*
H9B	0.0706	0.4131	0.7935	0.073*
C10	0.2494 (5)	0.0526 (4)	0.81349 (11)	0.0529 (7)
C11	0.0790 (8)	−0.0735 (4)	0.83574 (15)	0.0712 (9)
H11A	0.0221	−0.1464	0.8088	0.107*
H11B	−0.0473	−0.0124	0.8510	0.107*
H11C	0.1539	−0.1418	0.8615	0.107*
C12	0.4412 (7)	−0.0334 (6)	0.7860 (2)	0.0917 (14)
H12A	0.5456	0.0512	0.7728	0.137*
H12B	0.3803	−0.0998	0.7581	0.137*
H12C	0.5218	−0.1073	0.8094	0.137*
H2	0.758 (6)	0.483 (5)	1.0503 (15)	0.070 (10)*
H3	0.936 (7)	0.614 (5)	0.9775 (14)	0.070 (10)*
H6	0.588 (4)	0.335 (3)	0.9143 (11)	0.038 (7)*
H8	0.084 (5)	0.278 (3)	0.8868 (12)	0.039 (7)*

	U11	U22	U33	U12	U13	U23
O1	0.0934 (15)	0.0921 (17)	0.0369 (11)	−0.0240 (15)	0.0040 (11)	0.0066 (13)
O2	0.0503 (9)	0.0605 (11)	0.0319 (9)	−0.0088 (9)	−0.0024 (7)	0.0022 (9)
O3	0.0785 (13)	0.0511 (11)	0.0622 (14)	0.0125 (11)	−0.0381 (12)	−0.0168 (12)
O4	0.0925 (15)	0.0675 (13)	0.0331 (10)	0.0026 (13)	−0.0193 (11)	0.0025 (11)
F1	0.0884 (12)	0.0420 (8)	0.0694 (13)	0.0005 (8)	−0.0035 (10)	−0.0024 (10)
F2	0.0613 (10)	0.0915 (13)	0.0633 (12)	−0.0178 (10)	0.0215 (9)	−0.0051 (11)
C1	0.0662 (15)	0.0513 (15)	0.0377 (14)	−0.0059 (14)	−0.0075 (13)	0.0004 (14)
C2	0.0676 (17)	0.0553 (15)	0.0481 (16)	−0.0037 (15)	−0.0169 (15)	−0.0088 (15)
C3	0.0468 (14)	0.0617 (17)	0.0591 (18)	−0.0077 (13)	−0.0064 (13)	−0.0158 (16)
C5	0.0487 (12)	0.0468 (14)	0.0465 (15)	−0.0032 (12)	0.0073 (12)	−0.0055 (13)
C6	0.0424 (12)	0.0418 (13)	0.0336 (13)	0.0014 (10)	0.0024 (10)	−0.0028 (12)
C7	0.0532 (13)	0.0448 (13)	0.0328 (12)	0.0013 (11)	−0.0011 (11)	0.0044 (11)
C8	0.0569 (14)	0.0484 (14)	0.0352 (13)	0.0006 (12)	−0.0093 (13)	0.0018 (13)
C9	0.0747 (17)	0.0619 (18)	0.0470 (17)	0.0064 (15)	−0.0250 (16)	−0.0014 (16)
C10	0.0641 (15)	0.0534 (16)	0.0414 (15)	0.0008 (13)	−0.0142 (13)	−0.0082 (14)
C11	0.096 (2)	0.0593 (19)	0.058 (2)	−0.0092 (18)	−0.0136 (18)	−0.0016 (18)
C12	0.084 (2)	0.094 (3)	0.098 (3)	0.008 (2)	0.006 (2)	−0.031 (3)

O1—C1	1.193 (4)	C6—H6	0.96 (3)
O2—C1	1.361 (3)	C7—C8	1.518 (4)
O2—C6	1.445 (3)	C7—H7A	0.9700
O3—C10	1.418 (3)	C7—H7B	0.9700
O3—C8	1.424 (4)	C8—C9	1.530 (4)
O4—C9	1.402 (4)	C8—H8	0.95 (3)
O4—C10	1.414 (4)	C9—H9A	0.9700
F1—C5	1.362 (3)	C9—H9B	0.9700
F2—C5	1.358 (3)	C10—C12	1.482 (5)
C1—C2	1.455 (5)	C10—C11	1.511 (5)
C2—C3	1.316 (5)	C11—H11A	0.9600
C2—H2	1.08 (4)	C11—H11B	0.9600
C3—C5	1.493 (4)	C11—H11C	0.9600
C3—H3	0.98 (4)	C12—H12A	0.9600
C5—C6	1.505 (3)	C12—H12B	0.9600
C6—C7	1.501 (4)	C12—H12C	0.9600
C1—O2—C6	119.5 (2)	O3—C8—C7	108.3 (2)
C10—O3—C8	107.82 (19)	O3—C8—C9	104.1 (2)
C9—O4—C10	107.9 (2)	C7—C8—C9	114.5 (2)
O1—C1—O2	118.2 (3)	O3—C8—H8	111.6 (17)
O1—C1—C2	123.9 (3)	C7—C8—H8	113.8 (17)
O2—C1—C2	117.8 (3)	C9—C8—H8	104.2 (17)
C3—C2—C1	121.5 (3)	O4—C9—C8	105.0 (2)
C3—C2—H2	120 (2)	O4—C9—H9A	110.7
C1—C2—H2	118 (2)	C8—C9—H9A	110.7
C2—C3—C5	118.9 (3)	O4—C9—H9B	110.7
C2—C3—H3	122 (2)	C8—C9—H9B	110.7
C5—C3—H3	118 (2)	H9A—C9—H9B	108.8
F2—C5—F1	105.4 (2)	O4—C10—O3	104.5 (2)
F2—C5—C3	110.7 (2)	O4—C10—C12	110.3 (3)
F1—C5—C3	109.6 (3)	O3—C10—C12	108.7 (3)
F2—C5—C6	107.8 (2)	O4—C10—C11	110.7 (3)
F1—C5—C6	111.1 (2)	O3—C10—C11	109.9 (3)
C3—C5—C6	112.0 (3)	C12—C10—C11	112.3 (3)
O2—C6—C7	107.65 (18)	C10—C11—H11A	109.5
O2—C6—C5	108.6 (2)	C10—C11—H11B	109.5
C7—C6—C5	114.4 (2)	H11A—C11—H11B	109.5
O2—C6—H6	106.4 (16)	C10—C11—H11C	109.5
C7—C6—H6	112.1 (17)	H11A—C11—H11C	109.5
C5—C6—H6	107.4 (16)	H11B—C11—H11C	109.5
C6—C7—C8	112.3 (2)	C10—C12—H12A	109.5
C6—C7—H7A	109.1	C10—C12—H12B	109.5
C8—C7—H7A	109.1	H12A—C12—H12B	109.5
C6—C7—H7B	109.1	C10—C12—H12C	109.5
C8—C7—H7B	109.1	H12A—C12—H12C	109.5
H7A—C7—H7B	107.9	H12B—C12—H12C	109.5
C6—O2—C1—O1	−168.5 (3)	O2—C6—C7—C8	−62.7 (3)
C6—O2—C1—C2	15.5 (4)	C5—C6—C7—C8	176.5 (2)
O1—C1—C2—C3	−163.5 (3)	C10—O3—C8—C7	−140.1 (2)
O2—C1—C2—C3	12.3 (5)	C10—O3—C8—C9	−17.9 (3)
C1—C2—C3—C5	−4.4 (5)	C6—C7—C8—O3	−59.2 (3)
C2—C3—C5—F2	−148.5 (3)	C6—C7—C8—C9	−174.8 (2)
C2—C3—C5—F1	95.6 (3)	C10—O4—C9—C8	21.3 (3)
C2—C3—C5—C6	−28.1 (4)	O3—C8—C9—O4	−2.0 (3)
C1—O2—C6—C7	−170.7 (2)	C7—C8—C9—O4	116.0 (3)
C1—O2—C6—C5	−46.3 (3)	C9—O4—C10—O3	−32.7 (3)
F2—C5—C6—O2	173.1 (2)	C9—O4—C10—C12	−149.4 (3)
F1—C5—C6—O2	−71.9 (3)	C9—O4—C10—C11	85.6 (3)
C3—C5—C6—O2	51.1 (3)	C8—O3—C10—O4	31.3 (3)
F2—C5—C6—C7	−66.6 (3)	C8—O3—C10—C12	149.1 (3)
F1—C5—C6—C7	48.3 (3)	C8—O3—C10—C11	−87.6 (3)
C3—C5—C6—C7	171.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1i	0.95 (3)	2.66 (3)	3.578 (4)	161 (2)
C6—H6···O1ii	0.96 (3)	2.44 (3)	3.318 (4)	151 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O1i	0.95 (3)	2.66 (3)	3.578 (4)	161 (2)
C6—H6⋯O1ii	0.96 (3)	2.44 (3)	3.318 (4)	151 (2)

Symmetry codes: (i) ; (ii) .