Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702853X/cs2040sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702853X/cs2040Isup2.hkl |
CCDC reference: 654981
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C)= 0.002 Å
- R factor = 0.034
- wR factor = 0.048
- Data-to-parameter ratio = 11.2
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
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.
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.
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).
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.
C9H3F18O4P | F(000) = 2128 |
Mr = 548.06 | Dx = 2.12 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 4008 reflections |
a = 18.9045 (4) Å | θ = 0.7–27.9° |
b = 9.9101 (3) Å | µ = 0.37 mm−1 |
c = 19.1760 (5) Å | T = 150 K |
β = 107.044 (2)° | Block, colourless |
V = 3434.75 (16) Å3 | 0.49 × 0.47 × 0.43 mm |
Z = 8 |
Nonius KappaCCD diffractometer | Rint = 0.015 |
φ and ω scans | θmax = 27.9°, θmin = 2.2° |
7697 measured reflections | h = −24→24 |
4071 independent reflections | k = −13→12 |
3242 reflections with I > 3.0σ(I) | l = −25→25 |
Refinement on F | H-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) = 0.048 | Δρmax = 0.3 e Å−3 |
S = 1.1 | Δρmin = −0.32 e Å−3 |
3242 reflections | Extinction correction: Larson (1970), equation 22 |
290 parameters | Extinction coefficient: 47 (11) |
0 restraints |
C9H3F18O4P | V = 3434.75 (16) Å3 |
Mr = 548.06 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.9045 (4) Å | µ = 0.37 mm−1 |
b = 9.9101 (3) Å | T = 150 K |
c = 19.1760 (5) Å | 0.49 × 0.47 × 0.43 mm |
β = 107.044 (2)° |
Nonius KappaCCD diffractometer | 3242 reflections with I > 3.0σ(I) |
7697 measured reflections | Rint = 0.015 |
4071 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.048 | H-atom parameters constrained |
S = 1.1 | Δρmax = 0.3 e Å−3 |
3242 reflections | Δρmin = −0.32 e Å−3 |
290 parameters |
x | y | z | Uiso*/Ueq | ||
P1 | 0.285712 (18) | 0.11784 (4) | 0.391786 (19) | 0.0248 | |
O2 | 0.33023 (5) | 0.19877 (11) | 0.34797 (6) | 0.0283 | |
C1 | 0.40324 (8) | 0.24709 (16) | 0.38269 (8) | 0.0313 | |
H1 | 0.4189 | 0.2226 | 0.4339 | 0.0354* | |
C3 | 0.45415 (9) | 0.1793 (2) | 0.34444 (10) | 0.042 | |
F4 | 0.52180 (6) | 0.23100 (16) | 0.36764 (7) | 0.0587 | |
F5 | 0.43015 (6) | 0.19094 (16) | 0.27324 (6) | 0.0586 | |
F6 | 0.45908 (7) | 0.04837 (14) | 0.36086 (9) | 0.0637 | |
C2 | 0.40066 (11) | 0.40022 (19) | 0.37700 (12) | 0.0462 | |
F1 | 0.34688 (8) | 0.44681 (12) | 0.40228 (8) | 0.06 | |
F2 | 0.46441 (8) | 0.45198 (15) | 0.41796 (9) | 0.0719 | |
F3 | 0.38851 (10) | 0.44423 (14) | 0.30982 (8) | 0.0713 | |
O3 | 0.29796 (6) | −0.03253 (11) | 0.37036 (5) | 0.0286 | |
C4 | 0.29168 (9) | −0.14024 (15) | 0.41696 (8) | 0.0307 | |
H4 | 0.2749 | −0.1082 | 0.457 | 0.0368* | |
C5 | 0.36786 (10) | −0.20370 (17) | 0.44678 (10) | 0.0427 | |
F9 | 0.36608 (8) | −0.30226 (12) | 0.49341 (7) | 0.0593 | |
F7 | 0.41562 (7) | −0.11032 (13) | 0.48275 (8) | 0.0652 | |
F8 | 0.39356 (7) | −0.25376 (13) | 0.39505 (8) | 0.0586 | |
C6 | 0.23308 (10) | −0.23648 (17) | 0.37223 (10) | 0.0384 | |
F12 | 0.24868 (7) | −0.28390 (12) | 0.31417 (6) | 0.0525 | |
F11 | 0.16861 (7) | −0.17261 (14) | 0.35037 (9) | 0.062 | |
F10 | 0.22502 (8) | −0.34205 (12) | 0.41274 (7) | 0.0546 | |
O1 | 0.30422 (6) | 0.14500 (11) | 0.46961 (6) | 0.031 | |
O4 | 0.20340 (5) | 0.14476 (11) | 0.34549 (6) | 0.0297 | |
C7 | 0.15810 (8) | 0.23802 (16) | 0.36972 (8) | 0.0304 | |
H7 | 0.185 | 0.2802 | 0.4143 | 0.0358* | |
C9 | 0.13179 (10) | 0.34502 (19) | 0.31043 (10) | 0.041 | |
F17 | 0.19015 (7) | 0.40591 (13) | 0.29919 (8) | 0.0569 | |
F18 | 0.09199 (8) | 0.29449 (15) | 0.24786 (7) | 0.0637 | |
F16 | 0.09202 (9) | 0.43758 (15) | 0.33152 (9) | 0.0716 | |
C8 | 0.09563 (9) | 0.1560 (2) | 0.38443 (10) | 0.0415 | |
F15 | 0.12421 (7) | 0.06582 (15) | 0.43625 (7) | 0.0582 | |
F14 | 0.05100 (7) | 0.23522 (17) | 0.40846 (8) | 0.0643 | |
F13 | 0.05572 (6) | 0.09030 (15) | 0.32645 (7) | 0.0594 |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.02380 (17) | 0.02631 (18) | 0.02450 (18) | 0.00023 (12) | 0.00763 (12) | −0.00099 (13) |
O2 | 0.0260 (5) | 0.0304 (5) | 0.0274 (5) | −0.0036 (4) | 0.0064 (4) | 0.0011 (4) |
C1 | 0.0260 (6) | 0.0377 (8) | 0.0299 (7) | −0.0064 (5) | 0.0078 (5) | −0.0017 (6) |
C3 | 0.0284 (7) | 0.0595 (11) | 0.0390 (8) | −0.0004 (7) | 0.0112 (6) | −0.0023 (8) |
F4 | 0.0268 (5) | 0.0958 (10) | 0.0547 (7) | −0.0081 (5) | 0.0136 (4) | −0.0013 (7) |
F5 | 0.0435 (6) | 0.0997 (10) | 0.0353 (5) | 0.0052 (6) | 0.0158 (4) | −0.0103 (6) |
F6 | 0.0559 (7) | 0.0534 (7) | 0.0893 (10) | 0.0158 (6) | 0.0326 (7) | −0.0024 (7) |
C2 | 0.0524 (10) | 0.0369 (9) | 0.0520 (10) | −0.0130 (7) | 0.0195 (8) | −0.0044 (8) |
F1 | 0.0693 (8) | 0.0364 (6) | 0.0819 (9) | −0.0020 (5) | 0.0338 (7) | −0.0128 (6) |
F2 | 0.0672 (8) | 0.0608 (8) | 0.0876 (10) | −0.0372 (7) | 0.0223 (7) | −0.0217 (7) |
F3 | 0.1083 (12) | 0.0472 (7) | 0.0623 (8) | −0.0113 (7) | 0.0312 (8) | 0.0150 (6) |
O3 | 0.0342 (5) | 0.0260 (5) | 0.0274 (5) | 0.0013 (4) | 0.0118 (4) | 0.0009 (4) |
C4 | 0.0397 (8) | 0.0271 (7) | 0.0264 (6) | −0.0016 (5) | 0.0114 (6) | 0.0008 (5) |
C5 | 0.0471 (9) | 0.0316 (8) | 0.0425 (9) | 0.0016 (7) | 0.0025 (7) | 0.0059 (7) |
F9 | 0.0788 (9) | 0.0386 (6) | 0.0499 (7) | 0.0065 (5) | 0.0025 (6) | 0.0160 (5) |
F7 | 0.0519 (7) | 0.0470 (6) | 0.0727 (9) | −0.0050 (5) | −0.0189 (6) | 0.0060 (6) |
F8 | 0.0505 (7) | 0.0559 (7) | 0.0741 (8) | 0.0173 (5) | 0.0256 (6) | 0.0066 (6) |
C6 | 0.0424 (8) | 0.0346 (8) | 0.0396 (8) | −0.0084 (6) | 0.0140 (7) | −0.0032 (7) |
F12 | 0.0712 (8) | 0.0489 (6) | 0.0383 (6) | −0.0180 (5) | 0.0176 (5) | −0.0150 (5) |
F11 | 0.0381 (6) | 0.0591 (7) | 0.0823 (9) | −0.0084 (5) | 0.0077 (6) | −0.0036 (7) |
F10 | 0.0751 (8) | 0.0390 (6) | 0.0571 (7) | −0.0198 (5) | 0.0309 (6) | −0.0012 (5) |
O1 | 0.0303 (5) | 0.0356 (5) | 0.0268 (5) | 0.0005 (4) | 0.0080 (4) | −0.0034 (4) |
O4 | 0.0240 (5) | 0.0346 (5) | 0.0296 (5) | 0.0008 (4) | 0.0067 (4) | −0.0042 (4) |
C7 | 0.0257 (6) | 0.0367 (7) | 0.0303 (7) | 0.0040 (5) | 0.0106 (5) | −0.0011 (6) |
C9 | 0.0380 (8) | 0.0433 (9) | 0.0425 (9) | 0.0090 (7) | 0.0130 (7) | 0.0079 (7) |
F17 | 0.0592 (7) | 0.0478 (6) | 0.0689 (8) | 0.0000 (5) | 0.0271 (6) | 0.0192 (6) |
F18 | 0.0642 (8) | 0.0772 (9) | 0.0378 (6) | 0.0015 (7) | −0.0034 (5) | 0.0148 (6) |
F16 | 0.0772 (9) | 0.0614 (8) | 0.0851 (10) | 0.0398 (7) | 0.0377 (8) | 0.0198 (7) |
C8 | 0.0285 (7) | 0.0586 (11) | 0.0390 (9) | −0.0007 (7) | 0.0124 (6) | 0.0060 (8) |
F15 | 0.0504 (6) | 0.0717 (8) | 0.0547 (7) | −0.0052 (6) | 0.0186 (5) | 0.0254 (6) |
F14 | 0.0395 (6) | 0.0890 (10) | 0.0762 (9) | 0.0075 (6) | 0.0357 (6) | 0.0009 (7) |
F13 | 0.0414 (6) | 0.0755 (8) | 0.0564 (7) | −0.0230 (6) | 0.0065 (5) | −0.0021 (6) |
P1—O2 | 1.5723 (11) | C4—C6 | 1.522 (2) |
P1—O3 | 1.5808 (13) | C5—F9 | 1.331 (2) |
P1—O1 | 1.4545 (12) | C5—F7 | 1.335 (2) |
P1—O4 | 1.5719 (11) | C5—F8 | 1.322 (2) |
O2—C1 | 1.4278 (17) | C6—F12 | 1.319 (2) |
C1—H1 | 0.97 | C6—F11 | 1.328 (2) |
C1—C3 | 1.526 (2) | C6—F10 | 1.338 (2) |
C1—C2 | 1.521 (3) | O4—C7 | 1.4269 (17) |
C3—F4 | 1.327 (2) | C7—H7 | 0.953 |
C3—F5 | 1.312 (2) | C7—C9 | 1.527 (2) |
C3—F6 | 1.332 (3) | C7—C8 | 1.527 (2) |
C2—F1 | 1.331 (2) | C9—F17 | 1.329 (2) |
C2—F2 | 1.333 (2) | C9—F18 | 1.314 (2) |
C2—F3 | 1.315 (3) | C9—F16 | 1.322 (2) |
O3—C4 | 1.4192 (18) | C8—F15 | 1.328 (2) |
C4—H4 | 0.966 | C8—F14 | 1.330 (2) |
C4—C5 | 1.521 (2) | C8—F13 | 1.318 (2) |
O2—P1—O3 | 101.53 (7) | C4—C5—F9 | 110.38 (16) |
O2—P1—O1 | 116.64 (7) | C4—C5—F7 | 109.27 (14) |
O3—P1—O1 | 115.57 (6) | F9—C5—F7 | 107.94 (15) |
O2—P1—O4 | 102.00 (6) | C4—C5—F8 | 112.86 (15) |
O3—P1—O4 | 102.08 (6) | F9—C5—F8 | 108.41 (15) |
O1—P1—O4 | 116.66 (6) | F7—C5—F8 | 107.83 (17) |
P1—O2—C1 | 121.17 (9) | C4—C6—F12 | 113.15 (14) |
O2—C1—H1 | 110.8 | C4—C6—F11 | 109.17 (15) |
O2—C1—C3 | 106.74 (13) | F12—C6—F11 | 108.37 (16) |
H1—C1—C3 | 109.1 | C4—C6—F10 | 110.53 (14) |
O2—C1—C2 | 107.15 (14) | F12—C6—F10 | 107.65 (14) |
H1—C1—C2 | 108.4 | F11—C6—F10 | 107.81 (15) |
C3—C1—C2 | 114.57 (15) | P1—O4—C7 | 121.01 (9) |
C1—C3—F4 | 110.53 (15) | O4—C7—H7 | 111.3 |
C1—C3—F5 | 112.79 (15) | O4—C7—C9 | 107.64 (12) |
F4—C3—F5 | 108.69 (15) | H7—C7—C9 | 109.5 |
C1—C3—F6 | 108.99 (15) | O4—C7—C8 | 106.62 (14) |
F4—C3—F6 | 107.62 (16) | H7—C7—C8 | 107.8 |
F5—C3—F6 | 108.07 (17) | C9—C7—C8 | 113.98 (13) |
C1—C2—F1 | 109.38 (15) | C7—C9—F17 | 109.34 (14) |
C1—C2—F2 | 109.70 (17) | C7—C9—F18 | 112.92 (16) |
F1—C2—F2 | 107.88 (17) | F17—C9—F18 | 107.76 (16) |
C1—C2—F3 | 113.19 (16) | C7—C9—F16 | 110.14 (15) |
F1—C2—F3 | 108.01 (18) | F17—C9—F16 | 107.94 (17) |
F2—C2—F3 | 108.53 (16) | F18—C9—F16 | 108.60 (16) |
P1—O3—C4 | 119.98 (9) | C7—C8—F15 | 109.24 (14) |
O3—C4—H4 | 111.1 | C7—C8—F14 | 110.71 (16) |
O3—C4—C5 | 107.64 (13) | F15—C8—F14 | 107.36 (15) |
H4—C4—C5 | 109.4 | C7—C8—F13 | 112.92 (14) |
O3—C4—C6 | 107.33 (13) | F15—C8—F13 | 107.78 (17) |
H4—C4—C6 | 107.5 | F14—C8—F13 | 108.64 (15) |
C5—C4—C6 | 113.92 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1 | 0.97 | 2.57 | 3.022 (2) | 108 |
C4—H4···O1 | 0.97 | 2.57 | 2.988 (2) | 107 |
C7—H7···O1 | 0.95 | 2.57 | 3.008 (2) | 108 |
C7—H7···O1i | 0.95 | 2.30 | 3.171 (2) | 152 |
C4—H4···F10ii | 0.97 | 2.55 | 3.376 (3) | 144 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1/2, −y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C9H3F18O4P |
Mr | 548.06 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 18.9045 (4), 9.9101 (3), 19.1760 (5) |
β (°) | 107.044 (2) |
V (Å3) | 3434.75 (16) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.49 × 0.47 × 0.43 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 3.0σ(I)] reflections | 7697, 4071, 3242 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.657 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.048, 1.1 |
No. of reflections | 3242 |
No. of parameters | 290 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
P1—O2 | 1.5723 (11) | P1—O1 | 1.4545 (12) |
P1—O3 | 1.5808 (13) | P1—O4 | 1.5719 (11) |
O2—P1—O3 | 101.53 (7) | O2—P1—O4 | 102.00 (6) |
O2—P1—O1 | 116.64 (7) | O3—P1—O4 | 102.08 (6) |
O3—P1—O1 | 115.57 (6) | O1—P1—O4 | 116.66 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1 | 0.97 | 2.57 | 3.022 (2) | 108 |
C4—H4···O1 | 0.97 | 2.57 | 2.988 (2) | 107 |
C7—H7···O1 | 0.95 | 2.57 | 3.008 (2) | 108 |
C7—H7···O1i | 0.95 | 2.30 | 3.171 (2) | 152 |
C4—H4···F10ii | 0.97 | 2.55 | 3.376 (3) | 144 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1/2, −y−1/2, −z+1. |
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).