1,1,1,5,5,5-Hexafluoro-2,4-dimeth­oxy­pentane-2,4-diol

Koen, R.; Roodt, A.; Visser, H.G.; Muller, T.J.

doi:10.1107/S1600536811044813

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3155

https://doi.org/10.1107/S1600536811044813

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1,1,1,5,5,5-Hexafluoro-2,4-dimethoxypentane-2,4-diol

Renier Koen,^a ^* Andreas Roodt,^a Hendrik G. Visser ^a and Theunis J. Muller ^a

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9300, South Africa
^*Correspondence e-mail: koen.renier87@gmail.com

(Received 18 October 2011; accepted 26 October 2011; online 2 November 2011)

The title compound, C₇H₁₀F₆O₄, was isolated as an unexpected product from a reaction of tantalum(V) methoxide with hexafluoroacetylacetone in a methanol solution. The asymmetric unit consists of one half-molecule with the middle C atom lying on a twofold axis. The crystal structure is stabilized by O—H⋯O and an array of C—H⋯F hydrogen-bonding interactions. These interactions link the molecules into a stable supramolecular three-dimensional network. The molecules pack in a ribbon-like form in the ac plane as a result of these interactions.

Related literature

For metal complexes with acetylacetone derivatives, see: Viljoen et al. (2010 ); Steyn et al. (2008 ); Cole et al. (2005 ).

Experimental

Crystal data

C₇H₁₀F₆O₄
M_r = 272.15
Monoclinic, C 2/c
a = 17.829 (5) Å
b = 6.713 (5) Å
c = 9.347 (5) Å
β = 109.509 (5)°
V = 1054.5 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 100 K
0.75 × 0.28 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.936, T_max = 0.963
5850 measured reflections
1277 independent reflections
1049 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.079
S = 1.05
1277 reflections
98 parameters
All H-atom parameters refined
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.835 (17)	1.935 (17)	2.6648 (14)	145.4 (16)
O2—H2⋯O2ⁱⁱ	0.835 (17)	2.640 (17)	3.073 (2)	113.7 (14)
C4—H4A⋯F3ⁱⁱⁱ	0.954 (17)	2.741 (17)	3.644 (2)	158.4 (13)
C3—H3⋯F2^iv	0.945 (13)	2.663 (13)	3.4022 (17)	135.5 (10)
C4—H4A⋯F1^v	0.954 (17)	2.853 (17)	3.383 (3)	116.1 (11)
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iv) -x+1, -y, -z; (v) x, y+1, z.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811044813/pv2464sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811044813/pv2464Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811044813/pv2464Isup3.cml

checkCIF report

Comment top

In continuation of our research on the formation kinetics of complexes derived from metals like hafnium, zirconium, etc., with different bidentate ligands (Viljoen et al., 2010; Steyn et al., 2008), an unexpected product, the title compound, was isolated after reacting tantalum(V) methoxide with hexafluoroacetylacetone in a methanol reaction solution.

The asymmetric unit of the title compound consists of a half molecule with C3 lying on a twofold axis (Figure 1). The bond angles and bond distances in the title compound are in accord with corresponding bond angles and distances reported for hexafluoroacetylacetone like derivatives (Cole et al., 2005).

The crystal structure is stabilized by O—H···O (O···O separation 2.6648 (14) and 3.073 (2) Å) and an array of C—H···F (C···F separation in the range 3.383 (2)-3.644 (2)Å) hydrogen bonding interactions. All of these interactions serve to link the molecules into a stable supramolecular three-dimensional network. In the ac plane, the molecules pack in a ribbon-like formation as a result of these interactions (Figure 2).

Related literature top

For metal complexes with acetylacetone derivatives, see: Viljoen et al. (2010); Steyn et al. (2008); Cole et al. (2005).

Experimental top

The reaction was performed under modified Schlenk conditions under a nitrogen atmosphere. To a solution of Ta(OMe)₅ (0.5010 g, 1.40 x 10 ^-3 mol), a solution of hexafluoroacetylacetone (0.2912 g, 1.40 x 10 ^-3 mol) was added and was placed in a sonic bath for 1 h. The resultant mixture was then stored at 252 K. After two days colourless crystals of the title compound were formed.

Structure description top

For metal complexes with acetylacetone derivatives, see: Viljoen et al. (2010); Steyn et al. (2008); Cole et al. (2005).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. An ORTEP view of the title compound, showing the numbering scheme and displacement ellipsoids (50% probability). Symmetry code: ⁱ: 1 - x, y, 1/2 - z.
	Fig. 2. A partial packing diagram of the unit cell showing selected hydrogen bonding interactions of the title compound illustrating the ribbon-like formation across the ac plane.

1,1,1,5,5,5-Hexafluoro-2,4-dimethoxypentane-2,4-diol top

Crystal data top

C₇H₁₀F₆O₄	F(000) = 552
M_r = 272.15	D_x = 1.714 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.829 (5) Å	Cell parameters from 2123 reflections
b = 6.713 (5) Å	θ = 3.3–28.1°
c = 9.347 (5) Å	µ = 0.20 mm⁻¹
β = 109.509 (5)°	T = 100 K
V = 1054.5 (10) Å³	Needle, colourless
Z = 4	0.75 × 0.28 × 0.19 mm

Data collection top

Bruker APEXII CCD diffractometer	1049 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 28°, θ_min = 3.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −23→21
T_min = 0.936, T_max = 0.963	k = −8→8
5850 measured reflections	l = −11→12
1277 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	All H-atom parameters refined
S = 1.05	w = 1/[σ²(F_o²) + (0.0386P)² + 0.4659P] where P = (F_o² + 2F_c²)/3
1277 reflections	(Δ/σ)_max < 0.001
98 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₇H₁₀F₆O₄	V = 1054.5 (10) Å³
M_r = 272.15	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.829 (5) Å	µ = 0.20 mm⁻¹
b = 6.713 (5) Å	T = 100 K
c = 9.347 (5) Å	0.75 × 0.28 × 0.19 mm
β = 109.509 (5)°

Data collection top

Bruker APEXII CCD diffractometer	1277 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1049 reflections with I > 2σ(I)
T_min = 0.936, T_max = 0.963	R_int = 0.025
5850 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.079	All H-atom parameters refined
S = 1.05	Δρ_max = 0.39 e Å⁻³
1277 reflections	Δρ_min = −0.24 e Å⁻³
98 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.67222 (4)	0.00201 (11)	0.36009 (8)	0.0251 (2)
F2	0.61085 (5)	−0.06716 (11)	0.12475 (8)	0.0263 (2)
F3	0.69105 (4)	0.18291 (12)	0.18451 (9)	0.0286 (2)
O1	0.59145 (5)	0.34897 (12)	0.35035 (9)	0.0176 (2)
O2	0.54269 (5)	0.31437 (13)	0.08511 (9)	0.0192 (2)
C1	0.63589 (7)	0.08280 (19)	0.22390 (13)	0.0192 (3)
C2	0.56606 (7)	0.21774 (18)	0.22550 (12)	0.0153 (3)
C3	0.5	0.0899 (2)	0.25	0.0150 (3)
C4	0.64796 (10)	0.5018 (2)	0.34926 (19)	0.0311 (3)
H3	0.4785 (8)	0.008 (2)	0.1636 (14)	0.016 (3)*
H4A	0.6446 (9)	0.598 (3)	0.4222 (18)	0.032 (4)*
H4B	0.6369 (10)	0.559 (3)	0.251 (2)	0.043 (5)*
H4C	0.7027 (13)	0.450 (3)	0.383 (2)	0.056 (6)*
H2	0.4960 (10)	0.351 (3)	0.0706 (18)	0.036 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0227 (4)	0.0299 (4)	0.0202 (4)	0.0092 (3)	0.0038 (3)	0.0038 (3)
F2	0.0285 (4)	0.0259 (4)	0.0241 (4)	0.0068 (3)	0.0083 (3)	−0.0070 (3)
F3	0.0198 (4)	0.0341 (5)	0.0382 (5)	0.0039 (3)	0.0179 (3)	0.0044 (3)
O1	0.0171 (4)	0.0168 (4)	0.0207 (4)	−0.0048 (3)	0.0085 (3)	−0.0045 (3)
O2	0.0164 (5)	0.0238 (5)	0.0187 (4)	0.0031 (4)	0.0076 (3)	0.0064 (3)
C1	0.0181 (6)	0.0226 (6)	0.0171 (6)	0.0024 (5)	0.0062 (5)	−0.0007 (4)
C2	0.0159 (6)	0.0162 (5)	0.0143 (6)	0.0011 (4)	0.0057 (4)	0.0001 (4)
C3	0.0149 (8)	0.0148 (8)	0.0152 (8)	0	0.0049 (6)	0
C4	0.0336 (8)	0.0291 (8)	0.0342 (8)	−0.0165 (6)	0.0159 (7)	−0.0074 (6)

Geometric parameters (Å, º) top

F1—C1	1.3354 (15)	C1—C2	1.5438 (17)
F2—C1	1.3399 (16)	C2—C3	1.5352 (15)
F3—C1	1.3402 (15)	C3—C2ⁱ	1.5352 (15)
O1—C2	1.4107 (15)	C3—H3	0.945 (13)
O1—C4	1.4405 (17)	C4—H4A	0.954 (17)
O2—C2	1.3968 (15)	C4—H4B	0.950 (17)
O2—H2	0.835 (17)	C4—H4C	0.98 (2)

C2—O1—C4	118.10 (10)	O1—C2—C1	109.72 (9)
C2—O2—H2	104.9 (11)	C3—C2—C1	109.55 (11)
F1—C1—F2	107.32 (11)	C2—C3—C2ⁱ	112.00 (14)
F1—C1—F3	107.38 (10)	C2—C3—H3	108.1 (8)
F2—C1—F3	107.00 (10)	C2ⁱ—C3—H3	109.8 (8)
F1—C1—C2	111.41 (10)	O1—C4—H4A	105.3 (10)
F2—C1—C2	111.35 (10)	O1—C4—H4B	111.8 (11)
F3—C1—C2	112.12 (11)	H4A—C4—H4B	112.1 (14)
O2—C2—O1	113.56 (11)	O1—C4—H4C	111.7 (12)
O2—C2—C3	113.38 (9)	H4A—C4—H4C	107.4 (15)
O1—C2—C3	106.02 (9)	H4B—C4—H4C	108.4 (15)
O2—C2—C1	104.60 (9)

C4—O1—C2—O2	−48.50 (14)	F3—C1—C2—O1	−71.61 (13)
C4—O1—C2—C3	−173.64 (11)	F1—C1—C2—C3	−67.23 (11)
C4—O1—C2—C1	68.14 (14)	F2—C1—C2—C3	52.54 (12)
F1—C1—C2—O2	170.92 (9)	F3—C1—C2—C3	172.38 (8)
F2—C1—C2—O2	−69.30 (12)	O2—C2—C3—C2ⁱ	−71.42 (8)
F3—C1—C2—O2	50.54 (12)	O1—C2—C3—C2ⁱ	53.84 (6)
F1—C1—C2—O1	48.77 (13)	C1—C2—C3—C2ⁱ	172.17 (10)
F2—C1—C2—O1	168.55 (9)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.835 (17)	1.935 (17)	2.6648 (14)	145.4 (16)
O2—H2···O2ⁱⁱ	0.835 (17)	2.640 (17)	3.073 (2)	113.7 (14)
C4—H4A···F3ⁱⁱⁱ	0.954 (17)	2.741 (17)	3.644 (2)	158.4 (13)
C3—H3···F2^iv	0.945 (13)	2.663 (13)	3.4022 (17)	135.5 (10)
C4—H4A···F1^v	0.954 (17)	2.853 (17)	3.383 (3)	116.1 (11)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z; (iii) x, −y+1, z+1/2; (iv) −x+1, −y, −z; (v) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₇H₁₀F₆O₄
M_r	272.15
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	17.829 (5), 6.713 (5), 9.347 (5)
β (°)	109.509 (5)
V (Å³)	1054.5 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.75 × 0.28 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.936, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	5850, 1277, 1049
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 1.05
No. of reflections	1277
No. of parameters	98
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.24

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.835 (17)	1.935 (17)	2.6648 (14)	145.4 (16)
O2—H2···O2ⁱⁱ	0.835 (17)	2.640 (17)	3.073 (2)	113.7 (14)
C4—H4A···F3ⁱⁱⁱ	0.954 (17)	2.741 (17)	3.644 (2)	158.4 (13)
C3—H3···F2^iv	0.945 (13)	2.663 (13)	3.4022 (17)	135.5 (10)
C4—H4A···F1^v	0.954 (17)	2.853 (17)	3.383 (3)	116.1 (11)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z; (iii) x, −y+1, z+1/2; (iv) −x+1, −y, −z; (v) x, y+1, z.

Acknowledgements

Financial assistance from the Advanced Metals Initiative (AMI) and the Department of Science and Technology (DST) of South Africa, the New Metals Development Network (NMDN), the South African Nuclear Energy Corporation Limited (Necsa) and the University of the Free State is gratefully acknowledged.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). APEX2, SAINT-Plus and SADABS. BrukerAXS Inc, Madison, Wisconsin, USA. Google Scholar
Cole, M. L., Hibbs, D. E., Jones, C., Junk, P. C. & Smithies, N. A. (2005). Inorg. Chim. Acta, 102, 102–108. Web of Science CSD CrossRef Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steyn, M., Roodt, A. & Steyl, G. (2008). Acta Cryst. E64, m827. Web of Science CSD CrossRef IUCr Journals Google Scholar
Viljoen, J. A., Visser, H. G. & Roodt, A. (2010). Acta Cryst. E66, m603–m604. Web of Science CSD CrossRef IUCr Journals Google Scholar