2,2,3,3-Tetra­fluoro­butane-1,4-diol

Reichvilser, M.M.; Roessner, F.W.; Klüfers, P.

doi:10.1107/S1600536808040555

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o33

doi:10.1107/S1600536808040555

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2,2,3,3-Tetrafluorobutane-1,4-diol

Moritz M. Reichvilser,^a Felix W. Roessner ^a and Peter Klüfers ^a ^*

^aLudwig-Maximilians-Universität, Department Chemie und Biochemie, Butenandtstrasse 5–13 (Haus D), 81377 München, Germany
^*Correspondence e-mail: kluef@cup.uni-muenchen.de

(Received 28 November 2008; accepted 2 December 2008; online 6 December 2008)

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—H⋯F link is also seen.

Related literature

For crystal structures containing 2,2,3,3-tetrafluorobutane-1,4-dioxy units, see: Elias et al. (1994 ); Beşli et al. (2004 , 2005 , 2006 ). For details on graph-set analysis of hydrogen-bond networks, see: Bernstein et al. (1995 ); Etter et al. (1990 ).

Experimental

Crystal data

C₄H₆F₄O₂
M_r = 162.09
Monoclinic, P 2₁ /c
a = 5.4392 (2) Å
b = 8.6935 (3) Å
c = 12.4123 (4) Å
β = 99.768 (2)°
V = 578.42 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 200 (2) K
0.18 × 0.08 × 0.06 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: none
2531 measured reflections
1313 independent reflections
1133 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.085
S = 1.04
1313 reflections
97 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z.

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 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040555/zl2164sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808040555/zl2164Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For crystal structures containing 2,2,3,3-tetrafluorobutane-1,4-dioxy units, see: Elias et al. (1994); Beşli et al. (2004, 2005, 2006). For details on graph-set analysis of hydrogen-bond networks, see: Bernstein et al. (1995); Etter et al. (1990).

Experimental top

The title compound was obtained from Acros Organics. A single-crystal suitable for X-ray diffraction was isolated from the supplied material.

Computing details top

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).

Figures top

	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.
	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.]
	Fig. 3. Newman projections along the bonds of the O1—C1—C2—C3—C4—O2 chain.

2,2,3,3-tetrafluorobutane-1,4-diol top

Crystal data top

C₄H₆F₄O₂	F(000) = 328
M_r = 162.09	D_x = 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

Data collection top

Nonius KappaCCD area-detector diffractometer	1133 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.020
MONTEL, graded multilayered X-ray optics monochromator	θ_max = 27.5°, θ_min = 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 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)] = 0.031	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(F_o²) + (0.0398P)² + 0.2156P] where P = (F_o² + 2F_c²)/3
1313 reflections	(Δ/σ)_max < 0.001
97 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₄H₆F₄O₂	V = 578.42 (3) Å³
M_r = 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)°

Data collection top

Nonius KappaCCD area-detector diffractometer	1133 reflections with I > 2σ(I)
2531 measured reflections	R_int = 0.020
1313 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.38 e Å⁻³
1313 reflections	Δρ_min = −0.25 e Å⁻³
97 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Experimental details

Crystal data
Chemical formula	C₄H₆F₄O₂
M_r	162.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	5.4392 (2), 8.6935 (3), 12.4123 (4)
β (°)	99.768 (2)
V (Å³)	578.42 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.18 × 0.08 × 0.06

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2531, 1313, 1133
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.085, 1.04
No. of reflections	1313
No. of parameters	97
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.25

Computer programs: COLLECT (Hooft, 2004), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

The authors thank Dr Peter Mayer for technical support. MMR thanks the Fonds der Chemischen Industrie (FCI) for a PhD fellowship.

References

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