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The title compound, C9H3F18O4P, was synthesized by condensation of sodium hexa­fluoro­isopropanolate and phosphoryl chloride. The P atom is in a distorted tetra­hedral environment. The mol­ecules are stabilized by weak O...H and F...H hydrogen-bond inter­actions as well as F...F inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702853X/cs2040sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680702853X/cs2040Isup2.hkl
Contains datablock I

CCDC reference: 654981

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C)= 0.002 Å
  • R factor = 0.034
  • wR factor = 0.048
  • Data-to-parameter ratio = 11.2

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Comment top

Due to its specific properties, fluorine atom has been introduced in a large variety of organic derivatives in order to modify their physical and chemical properties (Smart, 2001). The steric and electronic effects of aliphatic fluoroalkyl groups are still the subject of experimental and theoretical work (Timperley & White, 2003). We report here the X-ray structure of the title compound, (I), which represents one of the very few examples of crystallized polyfluorinated phosphotriester (Hanes et al., 2002; Gubaidullin et al., 2004).

The phosphorus atom is single bonded to three oxygen atoms from the three hexafluoroisopropoxy ligands and double bonded to a fourth oxygen atom. The coordination polyhedra of the P atom shows a tetragonal distortion with a 1.858 Å3 tetrahedral volume (Robinson et al., 1971). It displays a nearly regular C3 symmetry as usually observed for P(V) atom. All bond lengths in (I) show expected values (Allen et al., 1987).

The title compound displays three intramolecular C—H···O hydrogen interactions, similar to that found in polyfluorinated dioxaphosphepinone oxide derivatives (Gubaidullin et al., 2004). These hydrogen bonds display an S(6) graph-set motif (Bernstein et al., 1995). The crystal packing is achieved through C—H···O and C—H···F hydrogen interactions as well as F···F repulsion interactions. Indeed, the shortest intermolecular distance between two fluorine atoms is 2.873 (2) Å (Halper & Cohen, 2005).

Related literature top

For related literature, see: Allen et al. (1987); Dakternieks et al. (1978); Gubaidullin et al. (2004); Halper & Cohen (2005); Hanes et al. (2002); Robinson et al. (1971); Smart (2001); Timperley & White (2003); Timperley et al. (2000); Bernstein et al. (1995), Larson (1970); Prince (1982); Watkin (1994).

Experimental top

The title compound (I) was prepared according to a procedure adapted from Dakternieks et al. (1978): to a suspension of NaH (30 mmol) in anhydrous diethylether at 0°C, hexafluoroisopropanol (30 mmol) was added over a 10 minutes period. After 30 minutes at room temperature, the resulting turbid solution was cooled down to 0°C. POCl3 (10 mmol) diluted in anhydrous diethylether was added dropwise and the reaction mixture was refluxed for 2 h. After removal of the volatile materials, the crude solid was purified by sublimation (T = 150 °C, P= 8 m mH g) to afford the title compound (2.6 mmol, 26%). 1H, 13C, 19F and 31P NMR were identical to the data reported by Timperley et al. (2000). Single crystals suitable for X-ray measurements were obtained after recrystallization at 0 °C from a 7:2 cyclohexane/diethylether mixture.

Refinement top

In the absence of significant anomalous scattering effects, the Friedel pairs have been merged. All the hydrogen atoms were discernible in a difference Fourier map. They were initially refined with soft restraints on the bond length (C—H in the range 0.93–0.98 Å) and their isotropic displacement ellipsoid (Uiso(H) in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints.

Structure description top

Due to its specific properties, fluorine atom has been introduced in a large variety of organic derivatives in order to modify their physical and chemical properties (Smart, 2001). The steric and electronic effects of aliphatic fluoroalkyl groups are still the subject of experimental and theoretical work (Timperley & White, 2003). We report here the X-ray structure of the title compound, (I), which represents one of the very few examples of crystallized polyfluorinated phosphotriester (Hanes et al., 2002; Gubaidullin et al., 2004).

The phosphorus atom is single bonded to three oxygen atoms from the three hexafluoroisopropoxy ligands and double bonded to a fourth oxygen atom. The coordination polyhedra of the P atom shows a tetragonal distortion with a 1.858 Å3 tetrahedral volume (Robinson et al., 1971). It displays a nearly regular C3 symmetry as usually observed for P(V) atom. All bond lengths in (I) show expected values (Allen et al., 1987).

The title compound displays three intramolecular C—H···O hydrogen interactions, similar to that found in polyfluorinated dioxaphosphepinone oxide derivatives (Gubaidullin et al., 2004). These hydrogen bonds display an S(6) graph-set motif (Bernstein et al., 1995). The crystal packing is achieved through C—H···O and C—H···F hydrogen interactions as well as F···F repulsion interactions. Indeed, the shortest intermolecular distance between two fluorine atoms is 2.873 (2) Å (Halper & Cohen, 2005).

For related literature, see: Allen et al. (1987); Dakternieks et al. (1978); Gubaidullin et al. (2004); Halper & Cohen (2005); Hanes et al. (2002); Robinson et al. (1971); Smart (2001); Timperley & White (2003); Timperley et al. (2000); Bernstein et al. (1995), Larson (1970); Prince (1982); Watkin (1994).

Computing details top

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: DIAMOND (Brandenburg et al., 1996); software used to prepare material for publication: CRYSTALS.

Figures top
[Figure 1] Fig. 1. View of (I) (30% probability displacement ellipsoids).
Tris(1,1,1,3,3,3-hexafluoroisopropyl) phosphate top
Crystal data top
C9H3F18O4PF(000) = 2128
Mr = 548.06Dx = 2.12 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2ycCell parameters from 4008 reflections
a = 18.9045 (4) Åθ = 0.7–27.9°
b = 9.9101 (3) ŵ = 0.37 mm1
c = 19.1760 (5) ÅT = 150 K
β = 107.044 (2)°Block, colourless
V = 3434.75 (16) Å30.49 × 0.47 × 0.43 mm
Z = 8
Data collection top
Nonius KappaCCD
diffractometer
Rint = 0.015
φ and ω scansθmax = 27.9°, θmin = 2.2°
7697 measured reflectionsh = 2424
4071 independent reflectionsk = 1312
3242 reflections with I > 3.0σ(I)l = 2525
Refinement top
Refinement on FH-atom parameters constrained
Least-squares matrix: full Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 2.02 1.91 1.40
R[F2 > 2σ(F2)] = 0.034(Δ/σ)max = 0.001
wR(F2) = 0.048Δρmax = 0.3 e Å3
S = 1.1Δρmin = 0.32 e Å3
3242 reflectionsExtinction correction: Larson (1970), equation 22
290 parametersExtinction coefficient: 47 (11)
0 restraints
Crystal data top
C9H3F18O4PV = 3434.75 (16) Å3
Mr = 548.06Z = 8
Monoclinic, C2/cMo Kα radiation
a = 18.9045 (4) ŵ = 0.37 mm1
b = 9.9101 (3) ÅT = 150 K
c = 19.1760 (5) Å0.49 × 0.47 × 0.43 mm
β = 107.044 (2)°
Data collection top
Nonius KappaCCD
diffractometer
3242 reflections with I > 3.0σ(I)
7697 measured reflectionsRint = 0.015
4071 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.048H-atom parameters constrained
S = 1.1Δρmax = 0.3 e Å3
3242 reflectionsΔρmin = 0.32 e Å3
290 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.285712 (18)0.11784 (4)0.391786 (19)0.0248
O20.33023 (5)0.19877 (11)0.34797 (6)0.0283
C10.40324 (8)0.24709 (16)0.38269 (8)0.0313
H10.41890.22260.43390.0354*
C30.45415 (9)0.1793 (2)0.34444 (10)0.042
F40.52180 (6)0.23100 (16)0.36764 (7)0.0587
F50.43015 (6)0.19094 (16)0.27324 (6)0.0586
F60.45908 (7)0.04837 (14)0.36086 (9)0.0637
C20.40066 (11)0.40022 (19)0.37700 (12)0.0462
F10.34688 (8)0.44681 (12)0.40228 (8)0.06
F20.46441 (8)0.45198 (15)0.41796 (9)0.0719
F30.38851 (10)0.44423 (14)0.30982 (8)0.0713
O30.29796 (6)0.03253 (11)0.37036 (5)0.0286
C40.29168 (9)0.14024 (15)0.41696 (8)0.0307
H40.27490.10820.4570.0368*
C50.36786 (10)0.20370 (17)0.44678 (10)0.0427
F90.36608 (8)0.30226 (12)0.49341 (7)0.0593
F70.41562 (7)0.11032 (13)0.48275 (8)0.0652
F80.39356 (7)0.25376 (13)0.39505 (8)0.0586
C60.23308 (10)0.23648 (17)0.37223 (10)0.0384
F120.24868 (7)0.28390 (12)0.31417 (6)0.0525
F110.16861 (7)0.17261 (14)0.35037 (9)0.062
F100.22502 (8)0.34205 (12)0.41274 (7)0.0546
O10.30422 (6)0.14500 (11)0.46961 (6)0.031
O40.20340 (5)0.14476 (11)0.34549 (6)0.0297
C70.15810 (8)0.23802 (16)0.36972 (8)0.0304
H70.1850.28020.41430.0358*
C90.13179 (10)0.34502 (19)0.31043 (10)0.041
F170.19015 (7)0.40591 (13)0.29919 (8)0.0569
F180.09199 (8)0.29449 (15)0.24786 (7)0.0637
F160.09202 (9)0.43758 (15)0.33152 (9)0.0716
C80.09563 (9)0.1560 (2)0.38443 (10)0.0415
F150.12421 (7)0.06582 (15)0.43625 (7)0.0582
F140.05100 (7)0.23522 (17)0.40846 (8)0.0643
F130.05572 (6)0.09030 (15)0.32645 (7)0.0594
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.02380 (17)0.02631 (18)0.02450 (18)0.00023 (12)0.00763 (12)0.00099 (13)
O20.0260 (5)0.0304 (5)0.0274 (5)0.0036 (4)0.0064 (4)0.0011 (4)
C10.0260 (6)0.0377 (8)0.0299 (7)0.0064 (5)0.0078 (5)0.0017 (6)
C30.0284 (7)0.0595 (11)0.0390 (8)0.0004 (7)0.0112 (6)0.0023 (8)
F40.0268 (5)0.0958 (10)0.0547 (7)0.0081 (5)0.0136 (4)0.0013 (7)
F50.0435 (6)0.0997 (10)0.0353 (5)0.0052 (6)0.0158 (4)0.0103 (6)
F60.0559 (7)0.0534 (7)0.0893 (10)0.0158 (6)0.0326 (7)0.0024 (7)
C20.0524 (10)0.0369 (9)0.0520 (10)0.0130 (7)0.0195 (8)0.0044 (8)
F10.0693 (8)0.0364 (6)0.0819 (9)0.0020 (5)0.0338 (7)0.0128 (6)
F20.0672 (8)0.0608 (8)0.0876 (10)0.0372 (7)0.0223 (7)0.0217 (7)
F30.1083 (12)0.0472 (7)0.0623 (8)0.0113 (7)0.0312 (8)0.0150 (6)
O30.0342 (5)0.0260 (5)0.0274 (5)0.0013 (4)0.0118 (4)0.0009 (4)
C40.0397 (8)0.0271 (7)0.0264 (6)0.0016 (5)0.0114 (6)0.0008 (5)
C50.0471 (9)0.0316 (8)0.0425 (9)0.0016 (7)0.0025 (7)0.0059 (7)
F90.0788 (9)0.0386 (6)0.0499 (7)0.0065 (5)0.0025 (6)0.0160 (5)
F70.0519 (7)0.0470 (6)0.0727 (9)0.0050 (5)0.0189 (6)0.0060 (6)
F80.0505 (7)0.0559 (7)0.0741 (8)0.0173 (5)0.0256 (6)0.0066 (6)
C60.0424 (8)0.0346 (8)0.0396 (8)0.0084 (6)0.0140 (7)0.0032 (7)
F120.0712 (8)0.0489 (6)0.0383 (6)0.0180 (5)0.0176 (5)0.0150 (5)
F110.0381 (6)0.0591 (7)0.0823 (9)0.0084 (5)0.0077 (6)0.0036 (7)
F100.0751 (8)0.0390 (6)0.0571 (7)0.0198 (5)0.0309 (6)0.0012 (5)
O10.0303 (5)0.0356 (5)0.0268 (5)0.0005 (4)0.0080 (4)0.0034 (4)
O40.0240 (5)0.0346 (5)0.0296 (5)0.0008 (4)0.0067 (4)0.0042 (4)
C70.0257 (6)0.0367 (7)0.0303 (7)0.0040 (5)0.0106 (5)0.0011 (6)
C90.0380 (8)0.0433 (9)0.0425 (9)0.0090 (7)0.0130 (7)0.0079 (7)
F170.0592 (7)0.0478 (6)0.0689 (8)0.0000 (5)0.0271 (6)0.0192 (6)
F180.0642 (8)0.0772 (9)0.0378 (6)0.0015 (7)0.0034 (5)0.0148 (6)
F160.0772 (9)0.0614 (8)0.0851 (10)0.0398 (7)0.0377 (8)0.0198 (7)
C80.0285 (7)0.0586 (11)0.0390 (9)0.0007 (7)0.0124 (6)0.0060 (8)
F150.0504 (6)0.0717 (8)0.0547 (7)0.0052 (6)0.0186 (5)0.0254 (6)
F140.0395 (6)0.0890 (10)0.0762 (9)0.0075 (6)0.0357 (6)0.0009 (7)
F130.0414 (6)0.0755 (8)0.0564 (7)0.0230 (6)0.0065 (5)0.0021 (6)
Geometric parameters (Å, º) top
P1—O21.5723 (11)C4—C61.522 (2)
P1—O31.5808 (13)C5—F91.331 (2)
P1—O11.4545 (12)C5—F71.335 (2)
P1—O41.5719 (11)C5—F81.322 (2)
O2—C11.4278 (17)C6—F121.319 (2)
C1—H10.97C6—F111.328 (2)
C1—C31.526 (2)C6—F101.338 (2)
C1—C21.521 (3)O4—C71.4269 (17)
C3—F41.327 (2)C7—H70.953
C3—F51.312 (2)C7—C91.527 (2)
C3—F61.332 (3)C7—C81.527 (2)
C2—F11.331 (2)C9—F171.329 (2)
C2—F21.333 (2)C9—F181.314 (2)
C2—F31.315 (3)C9—F161.322 (2)
O3—C41.4192 (18)C8—F151.328 (2)
C4—H40.966C8—F141.330 (2)
C4—C51.521 (2)C8—F131.318 (2)
O2—P1—O3101.53 (7)C4—C5—F9110.38 (16)
O2—P1—O1116.64 (7)C4—C5—F7109.27 (14)
O3—P1—O1115.57 (6)F9—C5—F7107.94 (15)
O2—P1—O4102.00 (6)C4—C5—F8112.86 (15)
O3—P1—O4102.08 (6)F9—C5—F8108.41 (15)
O1—P1—O4116.66 (6)F7—C5—F8107.83 (17)
P1—O2—C1121.17 (9)C4—C6—F12113.15 (14)
O2—C1—H1110.8C4—C6—F11109.17 (15)
O2—C1—C3106.74 (13)F12—C6—F11108.37 (16)
H1—C1—C3109.1C4—C6—F10110.53 (14)
O2—C1—C2107.15 (14)F12—C6—F10107.65 (14)
H1—C1—C2108.4F11—C6—F10107.81 (15)
C3—C1—C2114.57 (15)P1—O4—C7121.01 (9)
C1—C3—F4110.53 (15)O4—C7—H7111.3
C1—C3—F5112.79 (15)O4—C7—C9107.64 (12)
F4—C3—F5108.69 (15)H7—C7—C9109.5
C1—C3—F6108.99 (15)O4—C7—C8106.62 (14)
F4—C3—F6107.62 (16)H7—C7—C8107.8
F5—C3—F6108.07 (17)C9—C7—C8113.98 (13)
C1—C2—F1109.38 (15)C7—C9—F17109.34 (14)
C1—C2—F2109.70 (17)C7—C9—F18112.92 (16)
F1—C2—F2107.88 (17)F17—C9—F18107.76 (16)
C1—C2—F3113.19 (16)C7—C9—F16110.14 (15)
F1—C2—F3108.01 (18)F17—C9—F16107.94 (17)
F2—C2—F3108.53 (16)F18—C9—F16108.60 (16)
P1—O3—C4119.98 (9)C7—C8—F15109.24 (14)
O3—C4—H4111.1C7—C8—F14110.71 (16)
O3—C4—C5107.64 (13)F15—C8—F14107.36 (15)
H4—C4—C5109.4C7—C8—F13112.92 (14)
O3—C4—C6107.33 (13)F15—C8—F13107.78 (17)
H4—C4—C6107.5F14—C8—F13108.64 (15)
C5—C4—C6113.92 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O10.972.573.022 (2)108
C4—H4···O10.972.572.988 (2)107
C7—H7···O10.952.573.008 (2)108
C7—H7···O1i0.952.303.171 (2)152
C4—H4···F10ii0.972.553.376 (3)144
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1/2, y1/2, z+1.

Experimental details

Crystal data
Chemical formulaC9H3F18O4P
Mr548.06
Crystal system, space groupMonoclinic, C2/c
Temperature (K)150
a, b, c (Å)18.9045 (4), 9.9101 (3), 19.1760 (5)
β (°) 107.044 (2)
V3)3434.75 (16)
Z8
Radiation typeMo Kα
µ (mm1)0.37
Crystal size (mm)0.49 × 0.47 × 0.43
Data collection
DiffractometerNonius KappaCCD
Absorption correction
No. of measured, independent and
observed [I > 3.0σ(I)] reflections
7697, 4071, 3242
Rint0.015
(sin θ/λ)max1)0.657
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.048, 1.1
No. of reflections3242
No. of parameters290
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.3, 0.32

Computer programs: COLLECT (Nonius, 2001), DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SIR97 (Altomare et al., 1999), CRYSTALS (Betteridge et al., 2003), DIAMOND (Brandenburg et al., 1996), CRYSTALS.

Selected geometric parameters (Å, º) top
P1—O21.5723 (11)P1—O11.4545 (12)
P1—O31.5808 (13)P1—O41.5719 (11)
O2—P1—O3101.53 (7)O2—P1—O4102.00 (6)
O2—P1—O1116.64 (7)O3—P1—O4102.08 (6)
O3—P1—O1115.57 (6)O1—P1—O4116.66 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O10.972.573.022 (2)108
C4—H4···O10.972.572.988 (2)107
C7—H7···O10.952.573.008 (2)108
C7—H7···O1i0.952.303.171 (2)152
C4—H4···F10ii0.972.553.376 (3)144
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1/2, y1/2, z+1.
 

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