In the title compound, C
24H
9F
18OP, an intramolecular C—H

O short contact generates a five-membered ring, producing an
S(5) ring motif. The dihedral angles between the benzene rings are 57.68 (10), 77.80 (11) and 79.48 (10)°. Each of the six trifluoromethyl substituents shows rotational disorder over two positions with refined site-occupany ratios of 0.64 (3)/0.36 (3), 0.649 (14)/0.351 (14), 0.52 (2)/0.48 (2), 0.545 (16)/0.455 (16), 0.774 (9)/0.226 (9) and 0.63 (5)/0.37 (5). The crystal structure is stabilized by intermolecular C—H

O and C—H

F interactions.
Supporting information
CCDC reference: 731306
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean
(C-C) = 0.003 Å
- Disorder in main residue
- R factor = 0.041
- wR factor = 0.113
- Data-to-parameter ratio = 8.0
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT242_ALERT_2_A Check Low Ueq as Compared to Neighbors for C15
| Author Response: this is due to the disorder component of the
neighbouring atoms.
|
PLAT242_ALERT_2_A Check Low Ueq as Compared to Neighbors for C23
| Author Response: this is due to the disorder component of the
neighbouring atoms.
|
Alert level B
PLAT213_ALERT_2_B Atom F14B has ADP max/min Ratio ............. 4.80 prola
PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C7
| Author Response: this is due to the disorder component of the
neighbouring atoms.
|
PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C8
| Author Response: this is due to the disorder component of the
neighbouring atoms.
|
PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C16
| Author Response: this is due to the disorder component of the
neighbouring atoms.
|
Alert level C
Value of measurement temperature given = 294.000
Value of melting point given = 0.000
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
PLAT088_ALERT_3_C Poor Data / Parameter Ratio .................... 8.03
PLAT213_ALERT_2_C Atom F12A has ADP max/min Ratio ............. 3.40 prola
PLAT213_ALERT_2_C Atom F2B has ADP max/min Ratio ............. 3.20 prola
PLAT213_ALERT_2_C Atom F12B has ADP max/min Ratio ............. 3.80 prola
PLAT213_ALERT_2_C Atom F15B has ADP max/min Ratio ............. 3.90 prola
PLAT220_ALERT_2_C Large Non-Solvent F Ueq(max)/Ueq(min) ... 2.94 Ratio
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C24
| Author Response: this is due to the disorder component of the
neighbouring atoms.
|
Alert level G
PLAT301_ALERT_3_G Note Main Residue Disorder .................... 29.00 Perc.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 168
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal (x 10000) 1000 Deg.
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms .... !
2 ALERT level A = In general: serious problem
4 ALERT level B = Potentially serious problem
8 ALERT level C = Check and explain
5 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
12 ALERT type 2 Indicator that the structure model may be wrong or deficient
4 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
1 ALERT type 5 Informative message, check
The title compound was supplied by Strem Chemicals. Single crystals of (I) were
obtained by slow evaporation of an ethanol solution.
All of the hydrogen atoms were positioned geometrically and refined with a
riding approximation model with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C).
The trifluoromethyl substituents show rotational disorder over two positions
with a refined site-occupany ratios of 0.64 (3)/0.36 (3) for F1, F2, F3,
0.649 (14)/0.351 (14) for F4, F5, F6, 0.52 (2)/0.48 (2) for F7, F8, F9,
0.545 (16)/0.455 (16) for F10, F11, F12, 0.774 (9)/0.226 (9) for F13, F14, F15 and
0.63 (5)/0.37 (5) for F16, F17, F18 respectively. Rigid-bond restraints were
applied for the fluorine groups in order to improve the high displacement
ellipsoids of the groups but this was not particularly succesful, except that
the refinement convergence was more stable.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
Tris[3,5-bis(trifluoromethyl)phenyl]phosphine oxide
top
Crystal data top
C24H9F18OP | Z = 2 |
Mr = 686.28 | F(000) = 676 |
Triclinic, P1 | Dx = 1.717 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7937 (2) Å | Cell parameters from 5230 reflections |
b = 11.8786 (10) Å | θ = 1.9–28.3° |
c = 12.5066 (10) Å | µ = 0.25 mm−1 |
α = 111.065 (10)° | T = 294 K |
β = 103.645 (10)° | Block, colourless |
γ = 106.562 (10)° | 0.48 × 0.38 × 0.22 mm |
V = 1327.7 (3) Å3 | |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 4535 independent reflections |
Radiation source: fine-focus sealed tube | 3611 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −11→12 |
Tmin = 0.890, Tmax = 0.947 | k = −13→14 |
7134 measured reflections | l = −14→10 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0656P)2 + 0.1383P] where P = (Fo2 + 2Fc2)/3 |
4535 reflections | (Δ/σ)max = 0.001 |
565 parameters | Δρmax = 0.20 e Å−3 |
168 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C24H9F18OP | γ = 106.562 (10)° |
Mr = 686.28 | V = 1327.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.7937 (2) Å | Mo Kα radiation |
b = 11.8786 (10) Å | µ = 0.25 mm−1 |
c = 12.5066 (10) Å | T = 294 K |
α = 111.065 (10)° | 0.48 × 0.38 × 0.22 mm |
β = 103.645 (10)° | |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 4535 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 3611 reflections with I > 2σ(I) |
Tmin = 0.890, Tmax = 0.947 | Rint = 0.021 |
7134 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 168 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.20 e Å−3 |
4535 reflections | Δρmin = −0.27 e Å−3 |
565 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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 | Uiso*/Ueq | Occ. (<1) |
P1 | 0.69584 (5) | 0.56123 (5) | 0.16458 (4) | 0.03853 (15) | |
O1 | 0.66832 (14) | 0.62576 (14) | 0.08623 (14) | 0.0516 (4) | |
C1 | 0.56380 (18) | 0.52657 (18) | 0.22911 (18) | 0.0408 (4) | |
C2 | 0.4957 (2) | 0.6106 (2) | 0.24927 (19) | 0.0473 (5) | |
H2A | 0.5191 | 0.6809 | 0.2305 | 0.057* | |
C3 | 0.3928 (2) | 0.5897 (2) | 0.2974 (2) | 0.0532 (5) | |
C4 | 0.3564 (2) | 0.4856 (2) | 0.3248 (2) | 0.0552 (5) | |
H4A | 0.2866 | 0.4716 | 0.3562 | 0.066* | |
C5 | 0.4241 (2) | 0.4021 (2) | 0.3053 (2) | 0.0506 (5) | |
C6 | 0.5283 (2) | 0.42242 (19) | 0.25787 (19) | 0.0460 (5) | |
H6A | 0.5740 | 0.3661 | 0.2455 | 0.055* | |
C7 | 0.3816 (3) | 0.2847 (3) | 0.3293 (3) | 0.0733 (7) | |
C8 | 0.3197 (4) | 0.6811 (4) | 0.3178 (3) | 0.0804 (8) | |
C9 | 0.70486 (19) | 0.40435 (18) | 0.08552 (17) | 0.0404 (4) | |
C10 | 0.5806 (2) | 0.29374 (19) | 0.00606 (18) | 0.0459 (5) | |
H10A | 0.4954 | 0.3003 | −0.0021 | 0.055* | |
C11 | 0.5843 (2) | 0.1740 (2) | −0.0606 (2) | 0.0531 (5) | |
C12 | 0.7100 (2) | 0.1634 (2) | −0.0525 (2) | 0.0574 (6) | |
H12A | 0.7117 | 0.0828 | −0.0982 | 0.069* | |
C13 | 0.8329 (2) | 0.2734 (2) | 0.02403 (19) | 0.0537 (5) | |
C14 | 0.8311 (2) | 0.3936 (2) | 0.09427 (18) | 0.0474 (5) | |
H14A | 0.9146 | 0.4669 | 0.1472 | 0.057* | |
C15 | 0.4488 (3) | 0.0560 (3) | −0.1458 (3) | 0.0801 (8) | |
C16 | 0.9705 (3) | 0.2659 (3) | 0.0296 (3) | 0.0809 (9) | |
C17 | 0.85895 (18) | 0.66656 (17) | 0.29756 (17) | 0.0378 (4) | |
C18 | 0.94351 (19) | 0.78052 (18) | 0.29999 (18) | 0.0422 (4) | |
H18A | 0.9176 | 0.7986 | 0.2337 | 0.051* | |
C19 | 1.0671 (2) | 0.86781 (18) | 0.40158 (19) | 0.0445 (5) | |
C20 | 1.1054 (2) | 0.84267 (19) | 0.50081 (19) | 0.0475 (5) | |
H20A | 1.1879 | 0.9015 | 0.5688 | 0.057* | |
C21 | 1.0203 (2) | 0.72894 (19) | 0.49895 (18) | 0.0436 (4) | |
C22 | 0.89764 (19) | 0.64089 (18) | 0.39795 (18) | 0.0417 (4) | |
H22A | 0.8411 | 0.5647 | 0.3970 | 0.050* | |
C23 | 1.1590 (3) | 0.9907 (2) | 0.4026 (2) | 0.0608 (6) | |
C24 | 1.0639 (3) | 0.7057 (2) | 0.6091 (2) | 0.0627 (6) | |
F1A | 0.3107 (17) | 0.2938 (11) | 0.4026 (13) | 0.127 (3) | 0.64 (3) |
F2A | 0.3053 (13) | 0.1725 (6) | 0.2330 (7) | 0.106 (2) | 0.64 (3) |
F3A | 0.4911 (12) | 0.2685 (12) | 0.3845 (8) | 0.103 (3) | 0.64 (3) |
F1B | 0.347 (2) | 0.3116 (17) | 0.4269 (11) | 0.101 (4) | 0.36 (3) |
F2B | 0.265 (3) | 0.1929 (19) | 0.2265 (17) | 0.167 (8) | 0.36 (3) |
F3B | 0.474 (3) | 0.238 (3) | 0.345 (4) | 0.143 (8) | 0.36 (3) |
F4A | 0.2145 (11) | 0.6369 (9) | 0.3520 (13) | 0.132 (3) | 0.649 (14) |
F5A | 0.4017 (7) | 0.7979 (6) | 0.3979 (11) | 0.149 (4) | 0.649 (14) |
F6A | 0.2564 (13) | 0.6778 (13) | 0.2152 (7) | 0.149 (4) | 0.649 (14) |
F4B | 0.3833 (18) | 0.7925 (14) | 0.307 (2) | 0.129 (5) | 0.351 (14) |
F5B | 0.2026 (13) | 0.6458 (12) | 0.242 (2) | 0.153 (9) | 0.351 (14) |
F6B | 0.319 (2) | 0.733 (2) | 0.4278 (10) | 0.134 (7) | 0.351 (14) |
F7A | 1.0083 (16) | 0.289 (3) | −0.0448 (13) | 0.171 (6) | 0.52 (2) |
F8A | 0.9558 (9) | 0.1390 (8) | 0.010 (2) | 0.166 (6) | 0.52 (2) |
F9A | 1.0656 (11) | 0.3334 (14) | 0.1386 (10) | 0.123 (5) | 0.52 (2) |
F7B | 1.0531 (13) | 0.3664 (12) | 0.009 (2) | 0.142 (5) | 0.48 (2) |
F8B | 0.9664 (8) | 0.1631 (12) | −0.0554 (10) | 0.112 (4) | 0.48 (2) |
F9B | 1.0478 (16) | 0.292 (2) | 0.1352 (11) | 0.141 (6) | 0.48 (2) |
F10A | 0.3748 (10) | 0.0774 (10) | −0.2275 (11) | 0.124 (4) | 0.545 (16) |
F11A | 0.3666 (10) | 0.0405 (10) | −0.0809 (7) | 0.124 (3) | 0.545 (16) |
F12A | 0.4594 (10) | −0.0513 (8) | −0.1913 (19) | 0.174 (6) | 0.545 (16) |
F10B | 0.4473 (14) | −0.0498 (9) | −0.1405 (11) | 0.125 (5) | 0.455 (16) |
F11B | 0.4366 (18) | 0.0163 (16) | −0.2650 (6) | 0.151 (6) | 0.455 (16) |
F12B | 0.3425 (7) | 0.0689 (11) | −0.140 (3) | 0.215 (10) | 0.455 (16) |
F13A | 1.2266 (7) | 1.0906 (3) | 0.5147 (3) | 0.107 (2) | 0.774 (9) |
F14A | 1.0835 (3) | 1.0359 (4) | 0.3402 (5) | 0.0925 (13) | 0.774 (9) |
F15A | 1.2459 (5) | 0.9734 (4) | 0.3515 (6) | 0.102 (2) | 0.774 (9) |
F13B | 1.2974 (10) | 1.030 (2) | 0.481 (2) | 0.119 (7) | 0.226 (9) |
F14B | 1.136 (3) | 1.0800 (13) | 0.438 (4) | 0.163 (11) | 0.226 (9) |
F15B | 1.184 (3) | 0.9613 (17) | 0.3041 (18) | 0.156 (11) | 0.226 (9) |
F16A | 1.1855 (12) | 0.6770 (8) | 0.6200 (8) | 0.082 (2) | 0.63 (5) |
F17A | 1.1071 (13) | 0.8101 (11) | 0.7152 (10) | 0.094 (3) | 0.63 (5) |
F18A | 0.9620 (17) | 0.6078 (13) | 0.6047 (10) | 0.092 (3) | 0.63 (5) |
F16B | 1.162 (2) | 0.689 (2) | 0.625 (2) | 0.132 (7) | 0.37 (5) |
F17B | 1.068 (5) | 0.802 (2) | 0.7088 (18) | 0.117 (6) | 0.37 (5) |
F18B | 0.978 (2) | 0.5964 (15) | 0.6035 (17) | 0.073 (4) | 0.37 (5) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0314 (2) | 0.0401 (3) | 0.0421 (3) | 0.0116 (2) | 0.01248 (19) | 0.0200 (2) |
O1 | 0.0436 (8) | 0.0596 (9) | 0.0578 (9) | 0.0192 (7) | 0.0165 (6) | 0.0363 (7) |
C1 | 0.0311 (9) | 0.0424 (10) | 0.0435 (10) | 0.0110 (8) | 0.0108 (8) | 0.0194 (8) |
C2 | 0.0456 (11) | 0.0496 (11) | 0.0509 (12) | 0.0213 (9) | 0.0184 (9) | 0.0258 (9) |
C3 | 0.0473 (11) | 0.0668 (13) | 0.0562 (13) | 0.0304 (11) | 0.0239 (10) | 0.0309 (11) |
C4 | 0.0409 (11) | 0.0706 (14) | 0.0581 (13) | 0.0201 (10) | 0.0243 (10) | 0.0321 (12) |
C5 | 0.0439 (11) | 0.0504 (11) | 0.0528 (12) | 0.0113 (9) | 0.0182 (9) | 0.0250 (10) |
C6 | 0.0419 (10) | 0.0449 (11) | 0.0531 (12) | 0.0181 (9) | 0.0180 (9) | 0.0240 (9) |
C7 | 0.0803 (19) | 0.0633 (16) | 0.084 (2) | 0.0198 (15) | 0.0439 (17) | 0.0412 (16) |
C8 | 0.087 (2) | 0.109 (3) | 0.098 (2) | 0.069 (2) | 0.0594 (19) | 0.064 (2) |
C9 | 0.0359 (9) | 0.0433 (10) | 0.0375 (10) | 0.0137 (8) | 0.0111 (8) | 0.0175 (8) |
C10 | 0.0381 (10) | 0.0464 (11) | 0.0447 (11) | 0.0129 (8) | 0.0076 (8) | 0.0207 (9) |
C11 | 0.0488 (12) | 0.0432 (11) | 0.0479 (12) | 0.0105 (9) | 0.0056 (9) | 0.0153 (9) |
C12 | 0.0634 (14) | 0.0495 (12) | 0.0467 (12) | 0.0260 (11) | 0.0127 (10) | 0.0120 (10) |
C13 | 0.0475 (11) | 0.0623 (13) | 0.0435 (11) | 0.0258 (10) | 0.0140 (9) | 0.0157 (10) |
C14 | 0.0365 (10) | 0.0518 (11) | 0.0404 (10) | 0.0141 (9) | 0.0103 (8) | 0.0131 (9) |
C15 | 0.0668 (18) | 0.0488 (15) | 0.079 (2) | 0.0073 (13) | −0.0006 (15) | 0.0127 (14) |
C16 | 0.0639 (16) | 0.093 (2) | 0.0667 (18) | 0.0435 (17) | 0.0220 (15) | 0.0102 (16) |
C17 | 0.0345 (9) | 0.0346 (9) | 0.0435 (10) | 0.0132 (7) | 0.0170 (8) | 0.0164 (8) |
C18 | 0.0431 (10) | 0.0394 (10) | 0.0453 (11) | 0.0158 (8) | 0.0205 (8) | 0.0191 (8) |
C19 | 0.0430 (10) | 0.0332 (9) | 0.0508 (11) | 0.0101 (8) | 0.0226 (9) | 0.0137 (9) |
C20 | 0.0388 (10) | 0.0391 (10) | 0.0475 (11) | 0.0075 (8) | 0.0123 (9) | 0.0115 (9) |
C21 | 0.0408 (10) | 0.0410 (10) | 0.0428 (11) | 0.0144 (8) | 0.0122 (8) | 0.0168 (8) |
C22 | 0.0382 (10) | 0.0351 (9) | 0.0477 (11) | 0.0101 (8) | 0.0158 (8) | 0.0187 (8) |
C23 | 0.0576 (14) | 0.0456 (13) | 0.0674 (15) | 0.0077 (11) | 0.0273 (12) | 0.0216 (12) |
C24 | 0.0612 (16) | 0.0544 (14) | 0.0514 (14) | 0.0100 (12) | 0.0050 (11) | 0.0234 (12) |
F1A | 0.156 (6) | 0.100 (4) | 0.199 (9) | 0.056 (5) | 0.140 (7) | 0.095 (5) |
F2A | 0.147 (6) | 0.0449 (19) | 0.087 (3) | 0.008 (3) | 0.025 (3) | 0.028 (2) |
F3A | 0.122 (5) | 0.106 (4) | 0.112 (4) | 0.048 (4) | 0.041 (4) | 0.082 (3) |
F1B | 0.126 (8) | 0.108 (6) | 0.062 (6) | 0.012 (5) | 0.039 (5) | 0.059 (4) |
F2B | 0.131 (9) | 0.079 (7) | 0.196 (14) | −0.035 (6) | −0.045 (8) | 0.094 (9) |
F3B | 0.172 (17) | 0.151 (14) | 0.28 (2) | 0.125 (13) | 0.168 (16) | 0.178 (16) |
F4A | 0.153 (6) | 0.162 (5) | 0.219 (9) | 0.124 (5) | 0.154 (6) | 0.131 (6) |
F5A | 0.138 (4) | 0.082 (3) | 0.185 (8) | 0.075 (3) | 0.027 (5) | 0.016 (4) |
F6A | 0.191 (8) | 0.279 (10) | 0.141 (4) | 0.204 (8) | 0.107 (6) | 0.152 (6) |
F4B | 0.152 (11) | 0.130 (8) | 0.209 (14) | 0.112 (8) | 0.119 (11) | 0.109 (9) |
F5B | 0.077 (6) | 0.133 (7) | 0.193 (15) | 0.075 (6) | −0.001 (6) | 0.025 (8) |
F6B | 0.189 (15) | 0.206 (15) | 0.096 (6) | 0.162 (14) | 0.088 (8) | 0.075 (8) |
F7A | 0.129 (8) | 0.337 (18) | 0.133 (7) | 0.135 (11) | 0.106 (7) | 0.128 (10) |
F8A | 0.103 (4) | 0.117 (5) | 0.245 (14) | 0.081 (4) | 0.045 (7) | 0.035 (7) |
F9A | 0.044 (3) | 0.141 (5) | 0.100 (7) | 0.043 (3) | 0.000 (3) | −0.015 (5) |
F7B | 0.089 (5) | 0.136 (7) | 0.263 (15) | 0.059 (4) | 0.118 (8) | 0.111 (7) |
F8B | 0.087 (3) | 0.101 (5) | 0.108 (6) | 0.054 (4) | 0.041 (3) | −0.008 (4) |
F9B | 0.094 (8) | 0.283 (17) | 0.092 (8) | 0.119 (10) | 0.042 (6) | 0.098 (10) |
F10A | 0.097 (5) | 0.083 (4) | 0.093 (5) | −0.011 (3) | −0.048 (4) | 0.029 (4) |
F11A | 0.076 (5) | 0.111 (5) | 0.111 (4) | −0.028 (3) | 0.020 (3) | 0.037 (3) |
F12A | 0.093 (4) | 0.052 (4) | 0.230 (12) | 0.018 (3) | 0.008 (7) | −0.044 (5) |
F10B | 0.131 (8) | 0.055 (5) | 0.108 (5) | −0.022 (5) | −0.014 (5) | 0.037 (5) |
F11B | 0.157 (9) | 0.101 (6) | 0.063 (3) | −0.033 (6) | −0.031 (4) | 0.014 (4) |
F12B | 0.042 (3) | 0.084 (7) | 0.32 (2) | 0.004 (3) | 0.003 (9) | −0.052 (10) |
F13A | 0.117 (4) | 0.0482 (17) | 0.0828 (18) | −0.024 (2) | 0.0195 (18) | 0.0112 (12) |
F14A | 0.0812 (16) | 0.061 (2) | 0.141 (3) | 0.0181 (15) | 0.033 (2) | 0.065 (2) |
F15A | 0.096 (3) | 0.075 (2) | 0.185 (6) | 0.042 (2) | 0.105 (4) | 0.071 (3) |
F13B | 0.050 (5) | 0.114 (11) | 0.152 (12) | −0.021 (6) | 0.003 (6) | 0.084 (10) |
F14B | 0.181 (19) | 0.039 (7) | 0.34 (3) | 0.065 (11) | 0.207 (19) | 0.072 (13) |
F15B | 0.189 (18) | 0.103 (10) | 0.097 (9) | −0.053 (12) | 0.077 (12) | 0.036 (6) |
F16A | 0.054 (3) | 0.098 (5) | 0.101 (4) | 0.036 (3) | 0.010 (2) | 0.063 (4) |
F17A | 0.111 (5) | 0.066 (4) | 0.045 (3) | 0.003 (5) | −0.007 (3) | 0.013 (2) |
F18A | 0.078 (4) | 0.111 (6) | 0.065 (4) | −0.003 (4) | 0.012 (2) | 0.059 (4) |
F16B | 0.093 (7) | 0.223 (18) | 0.171 (12) | 0.108 (10) | 0.048 (7) | 0.149 (13) |
F17B | 0.205 (18) | 0.109 (11) | 0.039 (6) | 0.080 (10) | 0.038 (8) | 0.028 (6) |
F18B | 0.082 (7) | 0.052 (5) | 0.070 (6) | 0.018 (5) | 0.005 (4) | 0.035 (4) |
Geometric parameters (Å, º) top
P1—O1 | 1.4726 (15) | C14—H14A | 0.9300 |
P1—C9 | 1.8122 (19) | C15—F12B | 1.215 (9) |
P1—C17 | 1.8160 (19) | C15—F12A | 1.246 (7) |
P1—C1 | 1.8163 (19) | C15—F10B | 1.277 (9) |
C1—C6 | 1.386 (3) | C15—F10A | 1.290 (7) |
C1—C2 | 1.387 (3) | C15—F11B | 1.352 (10) |
C2—C3 | 1.386 (3) | C15—F11A | 1.354 (8) |
C2—H2A | 0.9300 | C16—F7A | 1.187 (11) |
C3—C4 | 1.376 (3) | C16—F9B | 1.256 (11) |
C3—C8 | 1.500 (3) | C16—F8B | 1.279 (7) |
C4—C5 | 1.379 (3) | C16—F9A | 1.280 (10) |
C4—H4A | 0.9300 | C16—F8A | 1.392 (11) |
C5—C6 | 1.392 (3) | C16—F7B | 1.417 (9) |
C5—C7 | 1.498 (3) | C17—C18 | 1.385 (3) |
C6—H6A | 0.9300 | C17—C22 | 1.394 (3) |
C7—F3B | 1.286 (19) | C18—C19 | 1.391 (3) |
C7—F2A | 1.287 (7) | C18—H18A | 0.9300 |
C7—F1B | 1.320 (13) | C19—C20 | 1.377 (3) |
C7—F1A | 1.321 (8) | C19—C23 | 1.506 (3) |
C7—F3A | 1.323 (11) | C20—C21 | 1.389 (3) |
C7—F2B | 1.368 (15) | C20—H20A | 0.9300 |
C8—F5B | 1.232 (10) | C21—C22 | 1.383 (3) |
C8—F5A | 1.263 (6) | C21—C24 | 1.496 (3) |
C8—F6A | 1.285 (7) | C22—H22A | 0.9300 |
C8—F6B | 1.293 (8) | C23—F14B | 1.117 (9) |
C8—F4A | 1.341 (5) | C23—F15B | 1.268 (16) |
C8—F4B | 1.374 (10) | C23—F15A | 1.277 (4) |
C9—C14 | 1.387 (3) | C23—F13A | 1.317 (4) |
C9—C10 | 1.393 (3) | C23—F14A | 1.346 (4) |
C10—C11 | 1.384 (3) | C23—F13B | 1.412 (10) |
C10—H10A | 0.9300 | C24—F16B | 1.11 (3) |
C11—C12 | 1.382 (3) | C24—F17A | 1.308 (11) |
C11—C15 | 1.504 (3) | C24—F18A | 1.327 (11) |
C12—C13 | 1.377 (3) | C24—F18B | 1.330 (17) |
C12—H12A | 0.9300 | C24—F17B | 1.33 (2) |
C13—C14 | 1.390 (3) | C24—F16A | 1.436 (15) |
C13—C16 | 1.500 (3) | | |
| | | |
O1—P1—C9 | 114.30 (9) | F10B—C15—F11B | 97.3 (8) |
O1—P1—C17 | 111.18 (8) | F10A—C15—F11B | 52.6 (6) |
C9—P1—C17 | 107.20 (8) | F12A—C15—F11A | 105.5 (8) |
O1—P1—C1 | 113.04 (8) | F10B—C15—F11A | 77.7 (7) |
C9—P1—C1 | 105.36 (9) | F10A—C15—F11A | 101.5 (6) |
C17—P1—C1 | 105.12 (8) | F11B—C15—F11A | 139.0 (6) |
C6—C1—C2 | 119.39 (18) | F12B—C15—C11 | 116.7 (4) |
C6—C1—P1 | 123.91 (14) | F12A—C15—C11 | 115.2 (5) |
C2—C1—P1 | 116.70 (15) | F10B—C15—C11 | 113.1 (6) |
C3—C2—C1 | 120.0 (2) | F10A—C15—C11 | 111.6 (4) |
C3—C2—H2A | 120.0 | F11B—C15—C11 | 110.5 (4) |
C1—C2—H2A | 120.0 | F11A—C15—C11 | 108.7 (4) |
C4—C3—C2 | 120.7 (2) | F7A—C16—F9B | 126.0 (9) |
C4—C3—C8 | 120.1 (2) | F7A—C16—F8B | 67.9 (8) |
C2—C3—C8 | 119.2 (2) | F9B—C16—F8B | 112.0 (8) |
C3—C4—C5 | 119.53 (19) | F7A—C16—F9A | 112.2 (10) |
C3—C4—H4A | 120.2 | F8B—C16—F9A | 124.6 (7) |
C5—C4—H4A | 120.2 | F7A—C16—F8A | 109.7 (7) |
C4—C5—C6 | 120.4 (2) | F9B—C16—F8A | 80.4 (9) |
C4—C5—C7 | 120.3 (2) | F9A—C16—F8A | 100.0 (9) |
C6—C5—C7 | 119.3 (2) | F9B—C16—F7B | 101.4 (8) |
C1—C6—C5 | 120.01 (18) | F8B—C16—F7B | 100.6 (6) |
C1—C6—H6A | 120.0 | F9A—C16—F7B | 82.5 (9) |
C5—C6—H6A | 120.0 | F8A—C16—F7B | 136.6 (8) |
F3B—C7—F2A | 86.2 (14) | F7A—C16—C13 | 112.9 (6) |
F3B—C7—F1B | 108.0 (14) | F9B—C16—C13 | 113.6 (7) |
F2A—C7—F1B | 118.1 (8) | F8B—C16—C13 | 116.5 (4) |
F3B—C7—F1A | 118.5 (11) | F9A—C16—C13 | 113.4 (6) |
F2A—C7—F1A | 104.9 (7) | F8A—C16—C13 | 107.7 (6) |
F2A—C7—F3A | 104.5 (7) | F7B—C16—C13 | 110.8 (5) |
F1B—C7—F3A | 92.2 (9) | C18—C17—C22 | 119.66 (17) |
F1A—C7—F3A | 105.4 (8) | C18—C17—P1 | 117.27 (15) |
F3B—C7—F2B | 110.3 (12) | C22—C17—P1 | 122.98 (14) |
F1B—C7—F2B | 108.4 (11) | C17—C18—C19 | 119.98 (19) |
F1A—C7—F2B | 92.6 (10) | C17—C18—H18A | 120.0 |
F3A—C7—F2B | 128.3 (13) | C19—C18—H18A | 120.0 |
F3B—C7—C5 | 114.7 (9) | C20—C19—C18 | 120.43 (18) |
F2A—C7—C5 | 115.9 (5) | C20—C19—C23 | 120.03 (18) |
F1B—C7—C5 | 111.4 (7) | C18—C19—C23 | 119.5 (2) |
F1A—C7—C5 | 113.4 (4) | C19—C20—C21 | 119.68 (18) |
F3A—C7—C5 | 111.8 (6) | C19—C20—H20A | 120.2 |
F2B—C7—C5 | 103.9 (8) | C21—C20—H20A | 120.2 |
F5B—C8—F5A | 126.4 (6) | C22—C21—C20 | 120.38 (19) |
F5A—C8—F6A | 110.9 (6) | C22—C21—C24 | 121.32 (18) |
F5B—C8—F6B | 108.5 (8) | C20—C21—C24 | 118.29 (18) |
F5A—C8—F6B | 57.5 (8) | C21—C22—C17 | 119.86 (17) |
F6A—C8—F6B | 133.5 (5) | C21—C22—H22A | 120.1 |
F5B—C8—F4A | 65.5 (10) | C17—C22—H22A | 120.1 |
F5A—C8—F4A | 109.6 (5) | F14B—C23—F15B | 117.7 (15) |
F6A—C8—F4A | 102.7 (5) | F14B—C23—F15A | 128.5 (7) |
F6B—C8—F4A | 54.4 (8) | F14B—C23—F13A | 55 (2) |
F5B—C8—F4B | 96.6 (8) | F15B—C23—F13A | 133.0 (8) |
F5A—C8—F4B | 48.0 (6) | F15A—C23—F13A | 109.2 (3) |
F6A—C8—F4B | 66.4 (7) | F14B—C23—F14A | 50 (2) |
F6B—C8—F4B | 101.1 (9) | F15B—C23—F14A | 76.9 (14) |
F4A—C8—F4B | 136.2 (4) | F15A—C23—F14A | 105.2 (3) |
F5B—C8—C3 | 119.3 (6) | F13A—C23—F14A | 103.7 (3) |
F5A—C8—C3 | 112.2 (3) | F14B—C23—F13B | 104.7 (14) |
F6A—C8—C3 | 110.6 (4) | F15B—C23—F13B | 95.3 (11) |
F6B—C8—C3 | 115.2 (4) | F15A—C23—F13B | 62.9 (10) |
F4A—C8—C3 | 110.3 (3) | F13A—C23—F13B | 53.5 (10) |
F4B—C8—C3 | 113.1 (4) | F14A—C23—F13B | 139.5 (5) |
C14—C9—C10 | 119.36 (18) | F14B—C23—C19 | 117.4 (6) |
C14—C9—P1 | 122.02 (14) | F15B—C23—C19 | 110.3 (7) |
C10—C9—P1 | 118.42 (14) | F15A—C23—C19 | 113.7 (3) |
C11—C10—C9 | 119.79 (18) | F13A—C23—C19 | 112.7 (2) |
C11—C10—H10A | 120.1 | F14A—C23—C19 | 111.5 (2) |
C9—C10—H10A | 120.1 | F13B—C23—C19 | 108.5 (5) |
C12—C11—C10 | 120.84 (18) | F16B—C24—F17A | 97.2 (13) |
C12—C11—C15 | 120.3 (2) | F16B—C24—F18A | 110.4 (12) |
C10—C11—C15 | 118.9 (2) | F17A—C24—F18A | 108.7 (7) |
C13—C12—C11 | 119.3 (2) | F16B—C24—F18B | 99.9 (13) |
C13—C12—H12A | 120.3 | F17A—C24—F18B | 113.2 (9) |
C11—C12—H12A | 120.3 | F16B—C24—F17B | 112.9 (19) |
C12—C13—C14 | 120.58 (19) | F18A—C24—F17B | 96.7 (14) |
C12—C13—C16 | 120.3 (2) | F18B—C24—F17B | 103.4 (16) |
C14—C13—C16 | 119.1 (2) | F17A—C24—F16A | 101.4 (7) |
C9—C14—C13 | 120.04 (18) | F18A—C24—F16A | 109.1 (9) |
C9—C14—H14A | 120.0 | F18B—C24—F16A | 98.5 (9) |
C13—C14—H14A | 120.0 | F17B—C24—F16A | 117 (2) |
F12B—C15—F12A | 125.6 (6) | F16B—C24—C21 | 114.0 (12) |
F12B—C15—F10B | 110.1 (12) | F17A—C24—C21 | 114.0 (7) |
F12B—C15—F10A | 59.9 (12) | F18A—C24—C21 | 111.6 (6) |
F12A—C15—F10A | 113.0 (7) | F18B—C24—C21 | 116.0 (8) |
F10B—C15—F10A | 132.8 (6) | F17B—C24—C21 | 109.9 (12) |
F12B—C15—F11B | 107.1 (10) | F16A—C24—C21 | 111.6 (4) |
F12A—C15—F11B | 67.5 (6) | | |
| | | |
O1—P1—C1—C6 | 150.78 (16) | C10—C11—C15—F12A | −171.8 (13) |
C9—P1—C1—C6 | 25.28 (19) | C12—C11—C15—F10B | 44.2 (9) |
C17—P1—C1—C6 | −87.79 (17) | C10—C11—C15—F10B | −137.9 (8) |
O1—P1—C1—C2 | −28.91 (18) | C12—C11—C15—F10A | −120.4 (10) |
C9—P1—C1—C2 | −154.40 (15) | C10—C11—C15—F10A | 57.5 (10) |
C17—P1—C1—C2 | 92.53 (16) | C12—C11—C15—F11B | −63.8 (13) |
C6—C1—C2—C3 | −0.2 (3) | C10—C11—C15—F11B | 114.2 (13) |
P1—C1—C2—C3 | 179.48 (16) | C12—C11—C15—F11A | 128.4 (6) |
C1—C2—C3—C4 | −0.5 (3) | C10—C11—C15—F11A | −53.6 (7) |
C1—C2—C3—C8 | −179.6 (2) | C12—C13—C16—F7A | 88.9 (15) |
C2—C3—C4—C5 | 0.7 (3) | C14—C13—C16—F7A | −89.2 (15) |
C8—C3—C4—C5 | 179.8 (2) | C12—C13—C16—F9B | −119.3 (12) |
C3—C4—C5—C6 | −0.3 (3) | C14—C13—C16—F9B | 62.5 (12) |
C3—C4—C5—C7 | −177.3 (2) | C12—C13—C16—F8B | 13.2 (11) |
C2—C1—C6—C5 | 0.7 (3) | C14—C13—C16—F8B | −165.0 (10) |
P1—C1—C6—C5 | −179.01 (15) | C12—C13—C16—F9A | −142.0 (9) |
C4—C5—C6—C1 | −0.4 (3) | C14—C13—C16—F9A | 39.9 (9) |
C7—C5—C6—C1 | 176.6 (2) | C12—C13—C16—F8A | −32.3 (13) |
C4—C5—C7—F3B | −160 (2) | C14—C13—C16—F8A | 149.6 (13) |
C6—C5—C7—F3B | 23 (2) | C12—C13—C16—F7B | 127.3 (10) |
C4—C5—C7—F2A | 101.8 (7) | C14—C13—C16—F7B | −50.9 (10) |
C6—C5—C7—F2A | −75.3 (7) | O1—P1—C17—C18 | −8.74 (17) |
C4—C5—C7—F1B | −37.0 (9) | C9—P1—C17—C18 | 116.84 (15) |
C6—C5—C7—F1B | 145.9 (9) | C1—P1—C17—C18 | −131.39 (14) |
C4—C5—C7—F1A | −19.6 (9) | O1—P1—C17—C22 | 167.85 (15) |
C6—C5—C7—F1A | 163.3 (9) | C9—P1—C17—C22 | −66.56 (17) |
C4—C5—C7—F3A | −138.6 (5) | C1—P1—C17—C22 | 45.21 (17) |
C6—C5—C7—F3A | 44.3 (6) | C22—C17—C18—C19 | 0.8 (3) |
C4—C5—C7—F2B | 79.5 (15) | P1—C17—C18—C19 | 177.48 (14) |
C6—C5—C7—F2B | −97.6 (15) | C17—C18—C19—C20 | −0.8 (3) |
C4—C3—C8—F5B | −78.3 (16) | C17—C18—C19—C23 | 179.34 (18) |
C2—C3—C8—F5B | 100.9 (16) | C18—C19—C20—C21 | 0.3 (3) |
C4—C3—C8—F5A | 116.9 (9) | C23—C19—C20—C21 | −179.81 (19) |
C2—C3—C8—F5A | −64.0 (9) | C19—C20—C21—C22 | 0.2 (3) |
C4—C3—C8—F6A | −118.7 (8) | C19—C20—C21—C24 | −179.0 (2) |
C2—C3—C8—F6A | 60.5 (8) | C20—C21—C22—C17 | −0.2 (3) |
C4—C3—C8—F6B | 53.5 (15) | C24—C21—C22—C17 | 178.99 (19) |
C2—C3—C8—F6B | −127.4 (15) | C18—C17—C22—C21 | −0.3 (3) |
C4—C3—C8—F4A | −5.7 (8) | P1—C17—C22—C21 | −176.79 (14) |
C2—C3—C8—F4A | 173.4 (7) | C20—C19—C23—F14B | −93 (3) |
C4—C3—C8—F4B | 169.1 (12) | C18—C19—C23—F14B | 87 (3) |
C2—C3—C8—F4B | −11.7 (13) | C20—C19—C23—F15B | 128.5 (17) |
O1—P1—C9—C14 | 98.19 (17) | C18—C19—C23—F15B | −51.6 (17) |
C17—P1—C9—C14 | −25.50 (19) | C20—C19—C23—F15A | 93.1 (4) |
C1—P1—C9—C14 | −137.10 (17) | C18—C19—C23—F15A | −87.0 (4) |
O1—P1—C9—C10 | −76.64 (17) | C20—C19—C23—F13A | −31.9 (5) |
C17—P1—C9—C10 | 159.67 (16) | C18—C19—C23—F13A | 148.0 (4) |
C1—P1—C9—C10 | 48.06 (18) | C20—C19—C23—F14A | −148.1 (3) |
C14—C9—C10—C11 | 1.7 (3) | C18—C19—C23—F14A | 31.8 (4) |
P1—C9—C10—C11 | 176.64 (16) | C20—C19—C23—F13B | 25.4 (14) |
C9—C10—C11—C12 | −2.1 (3) | C18—C19—C23—F13B | −154.8 (14) |
C9—C10—C11—C15 | −180.0 (2) | C22—C21—C24—F16B | 115.3 (11) |
C10—C11—C12—C13 | 0.7 (4) | C20—C21—C24—F16B | −65.5 (12) |
C15—C11—C12—C13 | 178.5 (2) | C22—C21—C24—F17A | −134.3 (7) |
C11—C12—C13—C14 | 1.1 (4) | C20—C21—C24—F17A | 44.9 (7) |
C11—C12—C13—C16 | −177.0 (3) | C22—C21—C24—F18A | −10.7 (9) |
C10—C9—C14—C13 | 0.1 (3) | C20—C21—C24—F18A | 168.5 (8) |
P1—C9—C14—C13 | −174.68 (17) | C22—C21—C24—F18B | 0.0 (9) |
C12—C13—C14—C9 | −1.5 (3) | C20—C21—C24—F18B | 179.2 (9) |
C16—C13—C14—C9 | 176.6 (2) | C22—C21—C24—F17B | −117 (2) |
C12—C11—C15—F12B | 173 (2) | C20—C21—C24—F17B | 62 (2) |
C10—C11—C15—F12B | −9 (2) | C22—C21—C24—F16A | 111.6 (3) |
C12—C11—C15—F12A | 10.3 (14) | C20—C21—C24—F16A | −69.2 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18A···O1 | 0.93 | 2.58 | 2.992 (3) | 108 |
C10—H10A···O1i | 0.93 | 2.38 | 3.203 (3) | 147 |
C20—H20A···F10Aii | 0.93 | 2.50 | 3.418 (12) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y+1, z+1. |
Experimental details
Crystal data |
Chemical formula | C24H9F18OP |
Mr | 686.28 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 10.7937 (2), 11.8786 (10), 12.5066 (10) |
α, β, γ (°) | 111.065 (10), 103.645 (10), 106.562 (10) |
V (Å3) | 1327.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.48 × 0.38 × 0.22 |
|
Data collection |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.890, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7134, 4535, 3611 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.113, 1.02 |
No. of reflections | 4535 |
No. of parameters | 565 |
No. of restraints | 168 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.27 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18A···O1 | 0.93 | 2.58 | 2.992 (3) | 108 |
C10—H10A···O1i | 0.93 | 2.38 | 3.203 (3) | 147 |
C20—H20A···F10Aii | 0.93 | 2.50 | 3.418 (12) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y+1, z+1. |
There has been considerable research on the stereochemistry of triphenyl phosphine oxide complexes (Bandoli et al., 1970; Ruban & Zabel, 1976; Spek, 1987; Baures & Silverton, 1990; Shawkataly et al., 1997) involving different space groups. A search of the Cambridge Structural Database (Version 5.29; Allen, 2007) revealed only 9 reported structures of the parent triphenylphosphine complexes as opposed to complexes of triphenylphosphine oxides. Our interest in complexes of triphenylphosphine led us to determine the X-ray crystal structure of the title compound, Fig. 1, in order to elucidate its conformation.
The bond lengths and angles of the title compound, Fig. 1, are within normal ranges (Allen et al., 1987). An intramolecular C—H···O hydrogen bond generates a five-membered ring, producing a S(5) ring motif (Bernstein et al., 1995). The P atom binds to three C atoms and one O atom in a nearly ideal tetrahedral geometry with the average O—P—C bond angle 112.84°. In the title compound, the P═O distance of 1.475 (3)Å, is less than the value reported for triphenylphospine oxide [1.487 (2)Å (Baures & Silverton, 1990)]. The average P—C bond distance is 1.813Å which is slightly longer than the distance observed in triphenylphosphine oxides previously studied; 1.799 (3)Å in OPPh3 (Baures & Silverton, 1990) and 1.76 (1)Å in its adduct with tricarboxylic acid (Lynch et al., 1992). This slight lengthening is probably due to the presence of electron withdrawing -CF3 groups bonded to the phenyl rings. The trifluoromethyl substituents show rotational disorder over two positions with a refined site-occupany ratio of 0.64 (3)/0.36 (3), 0.649 (14)/0.351 (14), 0.52 (2)/0.48 (2), 0.545 (16)/0.455 (16), 0.774 (9)/0.226 (9), and 0.63 (5)/0.37 (5) and average C—F distance of 1.300Å. This value is slightly shorter than that of the normal -CF3 bond distance (Allen et al., 1987).
The mean C—P—C bond angle is 105.90°, while the O—P—C bond angles show a slight variation: 113.01 (10), 114.31 (9) and 111.18 (10)° for O—P—C9, O—P—C1, and O—P—C17 respectively. The dihedral angles between the phenyl rings and the planes containing O, P and the corresponding ipso-C atoms are 79.52 (13), 29.14 (13), 10.70 (13)°, respectively. These are close to the values for the unsubstituted analogue [77.2 (1), 36.3 (1) and 11.9 (1)°]. The crystal structure is stabilized by intermolecular C—H···O and C—H···F interactions (Table 1).