Acta Cryst. (2009). E65, o33 [ doi:10.1107/S1600536808040555 ]
In the title compound, C4H6F4O2, a partially fluorinated aliphatic diol, cooperative O-H
O hydrogen bonds form R22(14) rings, which are connected into infinite layers parallel to the (100) plane by C(7) chains. A C-HF link is also seen.
The title compound was obtained from Acros Organics. A single-crystal suitable for X-ray diffraction was isolated from the supplied material.
All H atoms were found in difference maps. C-bonded H atoms were positioned geometrically (C—H = 0.99 Å) and treated as riding on their parent atoms [Uiso(H) = 1.2Ueq(C)]. Coordinates of O-bonded H atoms and O—H distances were refined freely [Uiso(H) = 1.5Ueq(O)].
Data collection: COLLECT (Hooft, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).
![[Figure 1]](./zl2164fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms. |
![[Figure 2]](./zl2164fig2thm.gif)
| Fig. 2. Hydrogen bonding in (I). [Symmetry codes: (i) x, 1/2-y, 1/2+z; (ii) 1-x, -y, -z; (iii) 1-x, 1/2+y, 1/2-z.] |
![[Figure 3]](./zl2164fig3thm.gif)
| Fig. 3. Newman projections along the bonds of the O1—C1—C2—C3—C4—O2 chain. |
| C4H6F4O2 | F(000) = 328 |
| Mr = 162.09 | Dx = 1.861 (1) Mg m−3 |
| Monoclinic, P21/c | Melting point = 355.3–356.3 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 5.4392 (2) Å | Cell parameters from 7007 reflections |
| b = 8.6935 (3) Å | θ = 3.1–27.5° |
| c = 12.4123 (4) Å | µ = 0.22 mm−1 |
| β = 99.768 (2)° | T = 200 K |
| V = 578.42 (3) Å3 | Block, colourless |
| Z = 4 | 0.18 × 0.08 × 0.06 mm |
| Nonius KappaCCD area-detector diffractometer | 1133 reflections with I > 2σ(I) |
| Radiation source: rotating anode | Rint = 0.020 |
| MONTEL, graded multilayered X-ray optics | θmax = 27.5°, θmin = 3.3° |
| Detector resolution: 9 pixels mm-1 | h = −7→7 |
| φ and ω scans | k = −11→11 |
| 2531 measured reflections | l = −16→16 |
| 1313 independent 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)] = 0.031 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0398P)2 + 0.2156P] where P = (Fo2 + 2Fc2)/3 |
| 1313 reflections | (Δ/σ)max < 0.001 |
| 97 parameters | Δρmax = 0.38 e Å−3 |
| 0 restraints | Δρmin = −0.25 e Å−3 |
| C4H6F4O2 | V = 578.42 (3) Å3 |
| Mr = 162.09 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 5.4392 (2) Å | µ = 0.22 mm−1 |
| b = 8.6935 (3) Å | T = 200 K |
| c = 12.4123 (4) Å | 0.18 × 0.08 × 0.06 mm |
| β = 99.768 (2)° |
| Nonius KappaCCD area-detector diffractometer | 1133 reflections with I > 2σ(I) |
| 2531 measured reflections | Rint = 0.020 |
| 1313 independent reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.085 | Δρmax = 0.38 e Å−3 |
| S = 1.04 | Δρmin = −0.25 e Å−3 |
| 1313 reflections | Absolute structure: ? |
| 97 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 > 2σ(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 | 0.70269 (17) | 0.39078 (9) | 0.15846 (6) | 0.0318 (2) | |
| F2 | 1.07701 (15) | 0.32375 (11) | 0.13418 (7) | 0.0343 (2) | |
| F3 | 0.81808 (17) | 0.38903 (11) | −0.05076 (6) | 0.0349 (2) | |
| F4 | 0.86586 (15) | 0.14104 (11) | −0.03922 (6) | 0.0328 (2) | |
| O1 | 0.58505 (19) | 0.07917 (11) | 0.18952 (8) | 0.0256 (2) | |
| H1 | 0.528 (4) | 0.125 (2) | 0.2357 (16) | 0.038* | |
| O2 | 0.41094 (18) | 0.23464 (12) | −0.15572 (7) | 0.0253 (2) | |
| H2 | 0.431 (3) | 0.143 (2) | −0.1751 (15) | 0.038* | |
| C1 | 0.8308 (3) | 0.13254 (16) | 0.19011 (10) | 0.0246 (3) | |
| H1A | 0.9293 | 0.0505 | 0.1621 | 0.030* | |
| H1B | 0.9099 | 0.1556 | 0.2662 | 0.030* | |
| C2 | 0.8355 (2) | 0.27521 (15) | 0.12090 (10) | 0.0216 (3) | |
| C3 | 0.7415 (2) | 0.26145 (14) | −0.00258 (10) | 0.0202 (3) | |
| C4 | 0.4637 (2) | 0.24221 (16) | −0.04003 (10) | 0.0227 (3) | |
| H4A | 0.4061 | 0.1468 | −0.0086 | 0.027* | |
| H4B | 0.3737 | 0.3302 | −0.0142 | 0.027* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| F1 | 0.0491 (5) | 0.0227 (4) | 0.0240 (4) | 0.0031 (4) | 0.0075 (4) | −0.0057 (3) |
| F2 | 0.0285 (4) | 0.0452 (5) | 0.0273 (4) | −0.0150 (4) | −0.0012 (3) | 0.0044 (4) |
| F3 | 0.0445 (5) | 0.0363 (5) | 0.0227 (4) | −0.0187 (4) | 0.0026 (3) | 0.0077 (3) |
| F4 | 0.0305 (5) | 0.0407 (5) | 0.0275 (4) | 0.0102 (4) | 0.0059 (3) | −0.0101 (4) |
| O1 | 0.0327 (5) | 0.0239 (5) | 0.0217 (5) | −0.0053 (4) | 0.0091 (4) | −0.0022 (4) |
| O2 | 0.0325 (5) | 0.0252 (5) | 0.0169 (4) | −0.0018 (4) | 0.0000 (4) | −0.0003 (4) |
| C1 | 0.0278 (7) | 0.0261 (7) | 0.0203 (6) | 0.0001 (5) | 0.0051 (5) | 0.0028 (5) |
| C2 | 0.0226 (6) | 0.0231 (6) | 0.0189 (6) | −0.0036 (5) | 0.0035 (5) | −0.0021 (5) |
| C3 | 0.0252 (6) | 0.0193 (6) | 0.0171 (6) | −0.0024 (5) | 0.0068 (5) | −0.0004 (5) |
| C4 | 0.0238 (6) | 0.0274 (7) | 0.0165 (6) | −0.0005 (5) | 0.0024 (5) | 0.0001 (5) |
| F1—C2 | 1.3651 (15) | C1—C2 | 1.5114 (18) |
| F2—C2 | 1.3626 (15) | C1—H1A | 0.9900 |
| F3—C3 | 1.3587 (14) | C1—H1B | 0.9900 |
| F4—C3 | 1.3656 (14) | C2—C3 | 1.5360 (17) |
| O1—C1 | 1.4135 (17) | C3—C4 | 1.5128 (17) |
| O1—H1 | 0.80 (2) | C4—H4A | 0.9900 |
| O2—C4 | 1.4173 (15) | C4—H4B | 0.9900 |
| O2—H2 | 0.84 (2) | ||
| C1—O1—H1 | 108.0 (14) | C1—C2—C3 | 117.92 (11) |
| C4—O2—H2 | 108.6 (13) | F3—C3—F4 | 105.84 (9) |
| O1—C1—C2 | 111.96 (11) | F3—C3—C4 | 108.66 (10) |
| O1—C1—H1A | 109.2 | F4—C3—C4 | 109.78 (10) |
| C2—C1—H1A | 109.2 | F3—C3—C2 | 107.49 (10) |
| O1—C1—H1B | 109.2 | F4—C3—C2 | 106.97 (10) |
| C2—C1—H1B | 109.2 | C4—C3—C2 | 117.48 (10) |
| H1A—C1—H1B | 107.9 | O2—C4—C3 | 109.65 (10) |
| F2—C2—F1 | 106.61 (10) | O2—C4—H4A | 109.7 |
| F2—C2—C1 | 107.13 (10) | C3—C4—H4A | 109.7 |
| F1—C2—C1 | 110.41 (10) | O2—C4—H4B | 109.7 |
| F2—C2—C3 | 107.21 (9) | C3—C4—H4B | 109.7 |
| F1—C2—C3 | 106.98 (10) | H4A—C4—H4B | 108.2 |
| O1—C1—C2—F2 | 175.17 (10) | C1—C2—C3—F4 | −52.09 (14) |
| O1—C1—C2—F1 | 59.45 (14) | F2—C2—C3—C4 | −167.32 (11) |
| O1—C1—C2—C3 | −63.91 (14) | F1—C2—C3—C4 | −53.27 (14) |
| F2—C2—C3—F3 | −44.50 (13) | C1—C2—C3—C4 | 71.80 (15) |
| F1—C2—C3—F3 | 69.55 (12) | F3—C3—C4—O2 | 56.60 (13) |
| C1—C2—C3—F3 | −165.38 (11) | F4—C3—C4—O2 | −58.71 (13) |
| F2—C2—C3—F4 | 68.79 (12) | C2—C3—C4—O2 | 178.82 (11) |
| F1—C2—C3—F4 | −177.16 (9) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2i | 0.80 (2) | 2.001 (19) | 2.7972 (14) | 171.9 (18) |
| O2—H2···O1ii | 0.845 (17) | 1.940 (17) | 2.7608 (14) | 163.6 (17) |
| C1—H1B···F3i | 0.99 | 2.44 | 3.2343 (15) | 137 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2i | 0.80 (2) | 2.001 (19) | 2.7972 (14) | 171.9 (18) |
| O2—H2···O1ii | 0.845 (17) | 1.940 (17) | 2.7608 (14) | 163.6 (17) |
| C1—H1B···F3i | 0.99 | 2.44 | 3.2343 (15) | 137 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z. |
The authors thank Dr Peter Mayer for technical support. MMR thanks the Fonds der Chemischen Industrie (FCI) for a PhD fellowship.
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The asymmetric unit of the title compound contains one complete molecule, which is shown in Figure 1.
The molecular packing is dominated by two O—H···O hydrogen bonds. According to graph set theory [Bernstein et al. (1995), Etter et al. (1990)] the descriptors C(7) and R22(14) can be assigned. Together with one C—H···F hydrogen bond [motif C(5)] the first-level (unitary) graph set N1 = C(5)C(7)R22(14) is obtained.
Figure 2 shows a cutout of the layers parallel to the (100) plane which are generated by the O—H···O hydrogen bond framework. The C—H···F bonds which are located within these layers are omitted for clarity.
Due to packing effects and the specific hydrogen bonding interactions the O1—C1—C2—C3—C4—O2 chain adopts a somewhat unusual conformation. The substituents at the C2—C3 fragment are staggered with the CH2OH moieties being gauche to each other. For Newman projections see Fig. 3.