2,2,3,3-Tetra­fluoro­butane-1,4-diol

Abstract

In the title compound, C₄H₆F₄O₂, a partially fluorinated aliphatic diol, cooperative O—H⋯O hydrogen bonds form R ₂ ²(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,

• a = 5.4392 (2) Å

• b = 8.6935 (3) Å

• c = 12.4123 (4) Å

• β = 99.768 (2)°

• V = 578.42 (3) ų

• 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[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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

Refinement

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 [U_iso(H) = 1.2U_eq(C)]. Coordinates of O-bonded H atoms and O—H distances were refined freely [U_iso(H) = 1.5U_eq(O)].

Figures

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.

Crystal data

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

Data collection

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

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

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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, °)

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, °)

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.