Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112020112/eg3082sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112020112/eg3082Isup2.hkl |
CCDC reference: 889375
The title compound was synthesized from (p-FC6H4)3P (0.418 g, 1.32 mmol) dissolved in anhydrous diethyl ether (30 ml). To this was added iodine (two equivalents, 0.671 g, 2.64 mmol), which caused rapid precipitation of a brown solid. The reaction was stirred for 48 h, after which time the solid was isolated by standard Schlenk techniques. Crystals were prepared by dissolving the brown solid in dichloromethane (5 ml) in a Rotaflo tube. Hexane (15 ml) was layered on top of the solution and the layers were allowed to diffuse slowly over 48 h, after which time purple–brown [Yellow given in CIF - please clarify] crystals of (I) had formed.
C-bound H atoms were idealized with C—H bond lengths of 0.95 Å and with the H atom on the external bisector of the C—C—C angle, with Uiso(H) = 1.2Ueq(C). Initial refinement with anisotropic displacement parameters for all non-H atoms converged to R1 = 0.0659, with a maximum Δρmax of 5.79 e Å-3.
A posteriori screening for twinning by looking for Fo2 >> Fc2 was carried out using PLATON (Spek, 2009). A nonmerohedral twin with twin matrix (1 0 0.459, 0 -1 0, 0 0 -1) was identified and used to construct expanded reflection files, in which overlapping reflections were assigned indices for each contributing twin domain. The inclusion of racemic twins gave a total of four domains: (i) the initial domain, (1 0 0, 0 1 0, 0 0 1); (ii) the inverse of (i), (-1 0 0, 0 -1 0, 0 0 -1); (iii) a nonmerohedral twin, (1 0 0.459, 0 -1 0, 0 0 -1); and (iv) the inverse of (iii), (-1 0 -0.459, 0 1 0, 0 0 1).
Three expanded reflection files were generated using three different 2θ resolution tolerance criteria for establishing nonmerohedral reflection overlap, namely 0.05, 0.10 and 0.15°, which gave 465, 863 and 1210 overlapping reflections, respectively. Refinements carried out using these reflection files, in which the fractional contribution volumes of the above domains were allowed to vary, were compared on the basis of R factors, bond-length s.u. values, mean (Fo2)/mean (Fc2) distribution versus Fc/Fc(max) and Δρmax, and, in each case, the 0.05° data were found to be the best, e.g. Δρmax values for the 0.05, 0.10 and 0.15° 2θ tolerance data were 3.24, 4.02 and 5.28 e Å-3, respectively. All further structure refinement was therefore carried out using the 0.05° data. The fractional contribution volumes refined to 0.37 (3), 0.38 (3), 0.124 (6) and 0.123 (6) for domains (i), (ii), (iii) and (iv), respectively. The last two numbers were restrained to be equal because of the high correlation between the two parameters (-0.99).
Ideally, twinning should be dealt with at the data-processing stage, but this was not possible with the version of diffractometer software being used in the current case. Given the rudimentary method used to assign non-merohedral reflection overlap, i.e. a global 2θ tolerance parameter, which assumes average reflection width, shape and twin obliquity, it is reasonable to anticipate that further improvements could be achieved if the software examined each reflection on a more individual basis, allowing for crystal anisotropy and the way the area detector intersects the Ewald sphere. Also, the small changes that are automatically made to the orientation matrix to compensate for slight crystal movement during the data collection could also be taken into account, rather than assuming a fixed orientation matrix.
In fact, the nonmerohedral twin correction was only partially successful and left rows of residual electron-density peaks spanning the cell in the z direction near the triiodide ions, with an inter-peak separation of approximately half an I—I bond, which also approximates to c/12. The two highest remaining peaks in the residual electron-density map were suitably positioned to be modelled as a translational disorder of the triiodide anions along the channels. They were therefore treated as disordered minor I-atom sites, I2B and I3B, whose occupancies refined to 0.021 (4) and 0.030 (4), respectively, reducing Δρmax to 2.03 e Å-3. The minor site displacement parameters were subjected to `rigid body' restraints, in which the anisotropic displacement parameters in the direction of their I—I bonds, I2—I3B and I3—I2B, were restrained to be equal. Also, the Uij values for the minor I-atom sites were restrained to be equal to those of the major I-atom sites they are bonded to, as the I atoms in the minor sites are generated from those in the major sites by translation of the triiodide along the channels parallel to c.
Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: DIRDIF08 (Beurskens et al., 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: WinGX (Farrugia, 1999).
C36H25F6O2P2+·I3− | F(000) = 2000 |
Mr = 1046 | Dx = 1.872 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 3916 reflections |
a = 13.2153 (4) Å | θ = 2–27° |
b = 15.9752 (6) Å | µ = 2.68 mm−1 |
c = 18.5695 (6) Å | T = 100 K |
β = 108.818 (2)° | Plate, purple–brown |
V = 3710.8 (2) Å3 | 0.18 × 0.15 × 0.06 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 5376 independent reflections |
Radiation source: Enraf–Nonius FR590 | 4363 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.081 |
Detector resolution: 9 pixels mm-1 | θmax = 25.5°, θmin = 3.3° |
CCD rotation images, thick slices scans | h = −15→15 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −19→19 |
Tmin = 0.645, Tmax = 0.856 | l = −22→22 |
14255 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.0392P)2 + 81.0459P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
5376 reflections | Δρmax = 2.03 e Å−3 |
466 parameters | Δρmin = −1.60 e Å−3 |
17 restraints | Absolute structure: Flack (1983), with 1024 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.50 (3) |
C36H25F6O2P2+·I3− | V = 3710.8 (2) Å3 |
Mr = 1046 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 13.2153 (4) Å | µ = 2.68 mm−1 |
b = 15.9752 (6) Å | T = 100 K |
c = 18.5695 (6) Å | 0.18 × 0.15 × 0.06 mm |
β = 108.818 (2)° |
Nonius KappaCCD area-detector diffractometer | 5376 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 4363 reflections with I > 2σ(I) |
Tmin = 0.645, Tmax = 0.856 | Rint = 0.081 |
14255 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.0392P)2 + 81.0459P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | Δρmax = 2.03 e Å−3 |
5376 reflections | Δρmin = −1.60 e Å−3 |
466 parameters | Absolute structure: Flack (1983), with 1024 Friedel pairs |
17 restraints | Absolute structure parameter: 0.50 (3) |
Experimental. Absorption correction: multi-scan from symmetry-related measurements (SORTAV; Blessing, 1995) |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.3142 (11) | 0.7551 (8) | 0.8804 (7) | 0.030 (3) | |
C2 | 0.3588 (10) | 0.8204 (9) | 0.9302 (7) | 0.025 (3) | |
H2 | 0.4209 | 0.8489 | 0.9282 | 0.031* | |
C3 | 0.3084 (11) | 0.8424 (8) | 0.9836 (7) | 0.032 (3) | |
H3 | 0.3361 | 0.8864 | 1.0189 | 0.039* | |
C4 | 0.2187 (13) | 0.7995 (9) | 0.9838 (8) | 0.027 (3) | |
C5 | 0.1753 (10) | 0.7338 (8) | 0.9348 (7) | 0.027 (3) | |
H5 | 0.1137 | 0.7047 | 0.937 | 0.032* | |
C6 | 0.2252 (11) | 0.7126 (9) | 0.8827 (8) | 0.031 (3) | |
H6 | 0.1978 | 0.668 | 0.848 | 0.038* | |
C7 | 0.4100 (10) | 0.6170 (8) | 0.8284 (8) | 0.028 (3) | |
C8 | 0.4407 (11) | 0.5863 (8) | 0.9016 (7) | 0.032 (3) | |
H8 | 0.4397 | 0.6225 | 0.942 | 0.039* | |
C9 | 0.4732 (11) | 0.5034 (9) | 0.9179 (7) | 0.034 (3) | |
H9 | 0.4959 | 0.4825 | 0.9686 | 0.041* | |
C10 | 0.4707 (11) | 0.4537 (9) | 0.8576 (8) | 0.034 (3) | |
C11 | 0.4369 (11) | 0.4790 (8) | 0.7835 (7) | 0.031 (3) | |
H11 | 0.4333 | 0.4407 | 0.7436 | 0.037* | |
C12 | 0.4079 (10) | 0.5624 (8) | 0.7679 (7) | 0.031 (3) | |
H12 | 0.3869 | 0.5825 | 0.7171 | 0.037* | |
C13 | 0.3018 (10) | 0.7437 (9) | 0.7165 (7) | 0.028 (3) | |
C14 | 0.3257 (11) | 0.8104 (8) | 0.6791 (7) | 0.032 (3) | |
H14 | 0.3836 | 0.8462 | 0.7046 | 0.039* | |
C15 | 0.2660 (12) | 0.8264 (10) | 0.6039 (8) | 0.039 (3) | |
H15 | 0.2829 | 0.8723 | 0.5774 | 0.046* | |
C16 | 0.1829 (12) | 0.7751 (10) | 0.5689 (7) | 0.036 (3) | |
C17 | 0.1550 (11) | 0.7058 (10) | 0.6046 (8) | 0.040 (4) | |
H17 | 0.0975 | 0.67 | 0.5784 | 0.048* | |
C18 | 0.2146 (11) | 0.6920 (9) | 0.6796 (7) | 0.032 (3) | |
H18 | 0.1964 | 0.647 | 0.7065 | 0.038* | |
C19 | 0.7064 (11) | 0.6438 (9) | 0.7811 (7) | 0.033 (3) | |
C20 | 0.6955 (10) | 0.5990 (8) | 0.7131 (8) | 0.029 (3) | |
H20 | 0.6979 | 0.6289 | 0.6695 | 0.035* | |
C21 | 0.6815 (10) | 0.5141 (9) | 0.7085 (7) | 0.029 (3) | |
H21 | 0.6698 | 0.4856 | 0.6616 | 0.035* | |
C22 | 0.6848 (11) | 0.4710 (8) | 0.7731 (8) | 0.034 (3) | |
C23 | 0.6986 (10) | 0.5093 (8) | 0.8425 (7) | 0.026 (3) | |
H23 | 0.7016 | 0.4775 | 0.8863 | 0.032* | |
C24 | 0.7078 (10) | 0.5954 (8) | 0.8456 (7) | 0.030 (3) | |
H24 | 0.7153 | 0.6232 | 0.8923 | 0.036* | |
C25 | 0.7782 (11) | 0.7850 (9) | 0.7181 (8) | 0.027 (3) | |
C26 | 0.7317 (11) | 0.8453 (8) | 0.6630 (6) | 0.029 (3) | |
H26 | 0.664 | 0.8686 | 0.659 | 0.035* | |
C27 | 0.7857 (12) | 0.8707 (9) | 0.6141 (7) | 0.034 (3) | |
H27 | 0.7563 | 0.9121 | 0.5765 | 0.041* | |
C28 | 0.8820 (12) | 0.8348 (10) | 0.6211 (8) | 0.038 (3) | |
C29 | 0.9322 (11) | 0.7784 (8) | 0.6766 (7) | 0.028 (3) | |
H29 | 1.0021 | 0.7586 | 0.6819 | 0.034* | |
C30 | 0.8775 (11) | 0.7511 (9) | 0.7247 (8) | 0.034 (3) | |
H30 | 0.9078 | 0.7095 | 0.7619 | 0.041* | |
C31 | 0.7746 (10) | 0.7894 (8) | 0.8764 (7) | 0.026 (3) | |
C32 | 0.7293 (11) | 0.8604 (9) | 0.9013 (8) | 0.034 (3) | |
H32 | 0.667 | 0.8862 | 0.8679 | 0.041* | |
C33 | 0.7752 (12) | 0.8914 (10) | 0.9732 (8) | 0.038 (3) | |
H33 | 0.7455 | 0.9384 | 0.9905 | 0.046* | |
C34 | 0.8651 (11) | 0.8527 (9) | 1.0196 (8) | 0.038 (3) | |
C35 | 0.9097 (11) | 0.7790 (9) | 0.9989 (8) | 0.037 (3) | |
H35 | 0.969 | 0.7512 | 1.0336 | 0.045* | |
C36 | 0.8633 (10) | 0.7510 (9) | 0.9276 (7) | 0.031 (3) | |
H36 | 0.8924 | 0.703 | 0.9115 | 0.038* | |
F1 | 0.1701 (6) | 0.8209 (5) | 1.0367 (5) | 0.0405 (19) | |
F2 | 0.5024 (7) | 0.3720 (5) | 0.8725 (4) | 0.044 (2) | |
F3 | 0.1250 (7) | 0.7886 (6) | 0.4947 (5) | 0.053 (2) | |
F4 | 0.6695 (7) | 0.3867 (5) | 0.7683 (5) | 0.045 (2) | |
F5 | 0.9367 (7) | 0.8619 (6) | 0.5733 (5) | 0.047 (2) | |
F6 | 0.9122 (8) | 0.8825 (6) | 1.0919 (5) | 0.059 (3) | |
O1 | 0.4837 (7) | 0.7793 (5) | 0.8323 (5) | 0.029 (2) | |
O2 | 0.5949 (7) | 0.7899 (6) | 0.7509 (5) | 0.032 (2) | |
P1 | 0.3826 (3) | 0.7261 (2) | 0.81384 (19) | 0.0272 (7) | |
P2 | 0.7075 (3) | 0.7527 (2) | 0.7815 (2) | 0.0288 (8) | |
I1 | −0.00204 (10) | 0.53170 (5) | 0.84472 (7) | 0.02541 (19) | |
I2 | 0.00364 (5) | 0.53424 (6) | 1.00457 (4) | 0.0319 (3) | 0.979 (4) |
I3 | −0.00631 (6) | 0.52672 (7) | 0.68753 (4) | 0.0317 (3) | 0.970 (4) |
I2B | −0.013 (5) | 0.531 (3) | 0.527 (3) | 0.028 (2) | 0.021 (4) |
I3B | 0.009 (4) | 0.522 (3) | 1.167 (3) | 0.028 (2) | 0.030 (4) |
H12P | 0.5381 | 0.7843 | 0.7915 | 0.10 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.033 (7) | 0.022 (7) | 0.022 (6) | −0.003 (6) | −0.008 (6) | 0.003 (5) |
C2 | 0.025 (7) | 0.035 (8) | 0.017 (6) | −0.003 (6) | 0.009 (5) | −0.004 (6) |
C3 | 0.042 (8) | 0.023 (7) | 0.026 (7) | −0.008 (6) | 0.004 (6) | 0.002 (5) |
C4 | 0.041 (9) | 0.021 (7) | 0.017 (6) | 0.003 (7) | 0.006 (6) | 0.005 (6) |
C5 | 0.018 (6) | 0.024 (7) | 0.037 (7) | −0.004 (5) | 0.009 (6) | 0.002 (6) |
C6 | 0.029 (7) | 0.027 (7) | 0.040 (7) | 0.001 (6) | 0.015 (6) | −0.011 (6) |
C7 | 0.025 (7) | 0.026 (7) | 0.036 (7) | 0.000 (6) | 0.014 (6) | 0.001 (6) |
C8 | 0.046 (8) | 0.022 (7) | 0.033 (7) | 0.000 (6) | 0.019 (6) | −0.001 (6) |
C9 | 0.035 (8) | 0.042 (8) | 0.028 (6) | 0.000 (6) | 0.013 (6) | 0.007 (7) |
C10 | 0.029 (8) | 0.036 (8) | 0.038 (8) | 0.000 (6) | 0.013 (6) | 0.012 (6) |
C11 | 0.041 (8) | 0.028 (7) | 0.028 (6) | 0.006 (6) | 0.017 (6) | −0.009 (6) |
C12 | 0.032 (7) | 0.030 (7) | 0.027 (6) | 0.005 (6) | 0.006 (5) | −0.002 (6) |
C13 | 0.025 (7) | 0.039 (8) | 0.015 (5) | −0.011 (6) | 0.000 (5) | 0.000 (6) |
C14 | 0.038 (8) | 0.026 (7) | 0.031 (7) | 0.002 (6) | 0.009 (6) | −0.003 (6) |
C15 | 0.040 (8) | 0.040 (8) | 0.049 (9) | 0.008 (7) | 0.031 (7) | 0.011 (7) |
C16 | 0.042 (9) | 0.045 (9) | 0.020 (6) | 0.009 (7) | 0.008 (6) | 0.002 (6) |
C17 | 0.031 (8) | 0.051 (10) | 0.032 (7) | −0.002 (7) | 0.002 (6) | −0.014 (7) |
C18 | 0.042 (8) | 0.029 (8) | 0.028 (6) | −0.007 (6) | 0.016 (6) | −0.007 (6) |
C19 | 0.034 (7) | 0.043 (8) | 0.026 (6) | 0.005 (7) | 0.016 (6) | 0.000 (6) |
C20 | 0.030 (7) | 0.019 (7) | 0.044 (8) | 0.001 (6) | 0.017 (6) | 0.010 (6) |
C21 | 0.030 (7) | 0.037 (8) | 0.030 (6) | −0.002 (6) | 0.021 (6) | 0.001 (6) |
C22 | 0.030 (7) | 0.034 (8) | 0.042 (8) | −0.009 (6) | 0.018 (6) | 0.001 (7) |
C23 | 0.027 (7) | 0.033 (7) | 0.021 (6) | −0.004 (6) | 0.010 (5) | 0.007 (6) |
C24 | 0.031 (7) | 0.029 (8) | 0.028 (6) | −0.005 (6) | 0.006 (5) | 0.004 (6) |
C25 | 0.016 (6) | 0.041 (8) | 0.027 (7) | −0.003 (6) | 0.011 (6) | −0.005 (6) |
C26 | 0.032 (7) | 0.030 (7) | 0.019 (6) | 0.001 (6) | −0.001 (5) | 0.002 (5) |
C27 | 0.045 (9) | 0.029 (8) | 0.024 (6) | 0.001 (7) | 0.004 (6) | 0.010 (6) |
C28 | 0.040 (8) | 0.045 (9) | 0.029 (7) | −0.008 (7) | 0.011 (6) | −0.007 (7) |
C29 | 0.030 (7) | 0.033 (7) | 0.024 (6) | −0.002 (6) | 0.012 (5) | −0.004 (6) |
C30 | 0.038 (8) | 0.025 (7) | 0.047 (8) | 0.000 (6) | 0.024 (7) | 0.008 (6) |
C31 | 0.022 (7) | 0.024 (7) | 0.036 (7) | 0.006 (5) | 0.015 (6) | 0.005 (6) |
C32 | 0.027 (7) | 0.029 (8) | 0.049 (8) | 0.000 (6) | 0.017 (7) | 0.002 (7) |
C33 | 0.046 (9) | 0.039 (9) | 0.033 (7) | 0.000 (7) | 0.018 (7) | 0.003 (7) |
C34 | 0.036 (8) | 0.044 (9) | 0.042 (8) | −0.015 (7) | 0.026 (7) | −0.017 (7) |
C35 | 0.030 (8) | 0.037 (8) | 0.043 (8) | 0.004 (6) | 0.009 (6) | 0.004 (7) |
C36 | 0.029 (7) | 0.037 (8) | 0.028 (6) | 0.005 (6) | 0.009 (6) | −0.005 (6) |
F1 | 0.038 (5) | 0.048 (5) | 0.042 (4) | 0.005 (4) | 0.021 (4) | −0.003 (4) |
F2 | 0.052 (5) | 0.022 (4) | 0.055 (5) | 0.001 (4) | 0.015 (5) | 0.012 (3) |
F3 | 0.048 (5) | 0.068 (6) | 0.038 (4) | 0.015 (5) | 0.007 (4) | 0.010 (5) |
F4 | 0.054 (5) | 0.027 (5) | 0.059 (5) | −0.001 (4) | 0.026 (4) | 0.000 (4) |
F5 | 0.054 (5) | 0.055 (6) | 0.039 (5) | −0.006 (4) | 0.025 (4) | 0.002 (4) |
F6 | 0.070 (6) | 0.068 (6) | 0.042 (5) | −0.027 (5) | 0.019 (5) | −0.027 (5) |
O1 | 0.027 (5) | 0.029 (5) | 0.035 (6) | −0.003 (4) | 0.014 (5) | 0.001 (4) |
O2 | 0.035 (5) | 0.034 (5) | 0.029 (5) | 0.004 (4) | 0.014 (4) | −0.002 (4) |
P1 | 0.0282 (17) | 0.0293 (18) | 0.0248 (15) | −0.0032 (15) | 0.0093 (13) | −0.0032 (14) |
P2 | 0.0305 (19) | 0.0276 (18) | 0.0290 (17) | 0.0033 (16) | 0.0108 (15) | 0.0030 (16) |
I1 | 0.0263 (3) | 0.0264 (4) | 0.0240 (3) | −0.0005 (4) | 0.0087 (3) | 0.0009 (4) |
I2 | 0.0395 (6) | 0.0333 (6) | 0.0216 (5) | −0.0057 (4) | 0.0079 (5) | −0.0004 (4) |
I3 | 0.0426 (7) | 0.0296 (7) | 0.0273 (5) | −0.0021 (5) | 0.0174 (5) | −0.0020 (5) |
I2B | 0.038 (4) | 0.023 (4) | 0.028 (2) | 0.000 (4) | 0.019 (4) | −0.003 (4) |
I3B | 0.034 (4) | 0.028 (4) | 0.021 (2) | 0.000 (4) | 0.008 (3) | −0.010 (4) |
C1—C6 | 1.370 (19) | C21—C22 | 1.371 (18) |
C1—C2 | 1.392 (18) | C21—H21 | 0.95 |
C1—P1 | 1.811 (15) | C22—F4 | 1.360 (15) |
C2—C3 | 1.405 (18) | C22—C23 | 1.384 (18) |
C2—H2 | 0.95 | C23—C24 | 1.380 (18) |
C3—C4 | 1.37 (2) | C23—H23 | 0.95 |
C3—H3 | 0.95 | C24—H24 | 0.95 |
C4—F1 | 1.379 (16) | C25—C30 | 1.388 (19) |
C4—C5 | 1.387 (19) | C25—C26 | 1.396 (19) |
C5—C6 | 1.378 (18) | C25—P2 | 1.799 (14) |
C5—H5 | 0.95 | C26—C27 | 1.383 (19) |
C6—H6 | 0.95 | C26—H26 | 0.95 |
C7—C8 | 1.378 (18) | C27—C28 | 1.36 (2) |
C7—C12 | 1.416 (18) | C27—H27 | 0.95 |
C7—P1 | 1.783 (13) | C28—C29 | 1.368 (19) |
C8—C9 | 1.395 (19) | C28—F5 | 1.382 (16) |
C8—H8 | 0.95 | C29—C30 | 1.389 (18) |
C9—C10 | 1.37 (2) | C29—H29 | 0.95 |
C9—H9 | 0.95 | C30—H30 | 0.95 |
C10—C11 | 1.364 (18) | C31—C36 | 1.391 (18) |
C10—F2 | 1.370 (15) | C31—C32 | 1.427 (18) |
C11—C12 | 1.390 (19) | C31—P2 | 1.797 (14) |
C11—H11 | 0.95 | C32—C33 | 1.37 (2) |
C12—H12 | 0.95 | C32—H32 | 0.95 |
C13—C14 | 1.366 (18) | C33—C34 | 1.37 (2) |
C13—C18 | 1.403 (18) | C33—H33 | 0.95 |
C13—P1 | 1.799 (12) | C34—F6 | 1.371 (16) |
C14—C15 | 1.388 (19) | C34—C35 | 1.42 (2) |
C14—H14 | 0.95 | C35—C36 | 1.343 (19) |
C15—C16 | 1.36 (2) | C35—H35 | 0.95 |
C15—H15 | 0.95 | C36—H36 | 0.95 |
C16—F3 | 1.361 (15) | O1—P1 | 1.526 (10) |
C16—C17 | 1.40 (2) | O1—H12P | 1.203 |
C17—C18 | 1.378 (18) | O2—P2 | 1.530 (10) |
C17—H17 | 0.95 | O2—H12P | 1.228 |
C18—H18 | 0.95 | I1—I3 | 2.9023 (15) |
C19—C20 | 1.416 (18) | I1—I2 | 2.9452 (14) |
C19—C24 | 1.420 (18) | I2—I3B | 2.99 (5) |
C19—P2 | 1.740 (15) | I2—I3i | 3.5774 (11) |
C20—C21 | 1.368 (18) | I3—I2B | 2.95 (6) |
C20—H20 | 0.95 | I3—I2ii | 3.5774 (11) |
C6—C1—C2 | 122.3 (14) | F4—C22—C21 | 118.5 (13) |
C6—C1—P1 | 121.1 (10) | F4—C22—C23 | 118.1 (12) |
C2—C1—P1 | 116.6 (11) | C21—C22—C23 | 123.3 (13) |
C1—C2—C3 | 117.5 (13) | C24—C23—C22 | 117.6 (11) |
C1—C2—H2 | 121.3 | C24—C23—H23 | 121.2 |
C3—C2—H2 | 121.3 | C22—C23—H23 | 121.2 |
C4—C3—C2 | 118.9 (13) | C23—C24—C19 | 122.0 (12) |
C4—C3—H3 | 120.5 | C23—C24—H24 | 119 |
C2—C3—H3 | 120.5 | C19—C24—H24 | 119 |
C3—C4—F1 | 118.7 (12) | C30—C25—C26 | 120.9 (13) |
C3—C4—C5 | 123.4 (13) | C30—C25—P2 | 120.4 (11) |
F1—C4—C5 | 117.8 (13) | C26—C25—P2 | 118.7 (10) |
C6—C5—C4 | 117.2 (12) | C27—C26—C25 | 119.0 (13) |
C6—C5—H5 | 121.4 | C27—C26—H26 | 120.5 |
C4—C5—H5 | 121.4 | C25—C26—H26 | 120.5 |
C1—C6—C5 | 120.6 (13) | C28—C27—C26 | 118.5 (13) |
C1—C6—H6 | 119.7 | C28—C27—H27 | 120.7 |
C5—C6—H6 | 119.7 | C26—C27—H27 | 120.7 |
C8—C7—C12 | 119.2 (12) | C27—C28—C29 | 124.1 (13) |
C8—C7—P1 | 118.6 (10) | C27—C28—F5 | 118.2 (13) |
C12—C7—P1 | 122.1 (10) | C29—C28—F5 | 117.5 (12) |
C7—C8—C9 | 121.6 (12) | C28—C29—C30 | 117.6 (13) |
C7—C8—H8 | 119.2 | C28—C29—H29 | 121.2 |
C9—C8—H8 | 119.2 | C30—C29—H29 | 121.2 |
C10—C9—C8 | 116.7 (12) | C25—C30—C29 | 119.6 (13) |
C10—C9—H9 | 121.6 | C25—C30—H30 | 120.2 |
C8—C9—H9 | 121.6 | C29—C30—H30 | 120.2 |
C11—C10—C9 | 124.7 (13) | C36—C31—C32 | 118.6 (12) |
C11—C10—F2 | 117.8 (12) | C36—C31—P2 | 124.5 (10) |
C9—C10—F2 | 117.6 (12) | C32—C31—P2 | 116.8 (9) |
C10—C11—C12 | 118.2 (12) | C33—C32—C31 | 120.2 (13) |
C10—C11—H11 | 120.9 | C33—C32—H32 | 119.9 |
C12—C11—H11 | 120.9 | C31—C32—H32 | 119.9 |
C11—C12—C7 | 119.5 (12) | C32—C33—C34 | 118.1 (14) |
C11—C12—H12 | 120.3 | C32—C33—H33 | 120.9 |
C7—C12—H12 | 120.3 | C34—C33—H33 | 120.9 |
C14—C13—C18 | 119.9 (12) | C33—C34—F6 | 119.1 (13) |
C14—C13—P1 | 118.3 (10) | C33—C34—C35 | 123.7 (13) |
C18—C13—P1 | 121.8 (10) | F6—C34—C35 | 117.1 (13) |
C13—C14—C15 | 120.4 (13) | C36—C35—C34 | 116.4 (13) |
C13—C14—H14 | 119.8 | C36—C35—H35 | 121.8 |
C15—C14—H14 | 119.8 | C34—C35—H35 | 121.8 |
C16—C15—C14 | 118.7 (14) | C35—C36—C31 | 122.9 (13) |
C16—C15—H15 | 120.6 | C35—C36—H36 | 118.6 |
C14—C15—H15 | 120.6 | C31—C36—H36 | 118.6 |
C15—C16—F3 | 119.5 (14) | P1—O1—H12P | 123.6 |
C15—C16—C17 | 123.2 (13) | P2—O2—H12P | 117.2 |
F3—C16—C17 | 117.2 (13) | O1—P1—C7 | 112.9 (6) |
C18—C17—C16 | 116.9 (13) | O1—P1—C13 | 109.4 (6) |
C18—C17—H17 | 121.5 | C7—P1—C13 | 109.3 (6) |
C16—C17—H17 | 121.5 | O1—P1—C1 | 107.4 (6) |
C17—C18—C13 | 120.8 (13) | C7—P1—C1 | 105.5 (6) |
C17—C18—H18 | 119.6 | C13—P1—C1 | 112.4 (6) |
C13—C18—H18 | 119.6 | O2—P2—C19 | 112.4 (6) |
C20—C19—C24 | 116.5 (12) | O2—P2—C31 | 110.5 (5) |
C20—C19—P2 | 120.5 (10) | C19—P2—C31 | 109.4 (6) |
C24—C19—P2 | 122.8 (10) | O2—P2—C25 | 107.0 (6) |
C21—C20—C19 | 122.0 (12) | C19—P2—C25 | 106.8 (7) |
C21—C20—H20 | 119 | C31—P2—C25 | 110.6 (6) |
C19—C20—H20 | 119 | I3—I1—I2 | 179.15 (5) |
C20—C21—C22 | 118.5 (13) | I1—I3—I2B | 177.0 (8) |
C20—C21—H21 | 120.7 | I1—I2—I3B | 175.5 (8) |
C22—C21—H21 | 120.7 | ||
C6—C1—C2—C3 | −1 (2) | P2—C25—C30—C29 | −178.3 (10) |
P1—C1—C2—C3 | −178.4 (10) | C28—C29—C30—C25 | −4 (2) |
C1—C2—C3—C4 | −0.3 (19) | C36—C31—C32—C33 | 2 (2) |
C2—C3—C4—F1 | 179.4 (12) | P2—C31—C32—C33 | 179.3 (11) |
C2—C3—C4—C5 | 1 (2) | C31—C32—C33—C34 | 0 (2) |
C3—C4—C5—C6 | −1 (2) | C32—C33—C34—F6 | −179.8 (13) |
F1—C4—C5—C6 | −179.4 (12) | C32—C33—C34—C35 | −4 (2) |
C2—C1—C6—C5 | 1 (2) | C33—C34—C35—C36 | 5 (2) |
P1—C1—C6—C5 | 178.4 (10) | F6—C34—C35—C36 | −179.4 (12) |
C4—C5—C6—C1 | 0 (2) | C34—C35—C36—C31 | −2 (2) |
C12—C7—C8—C9 | 2 (2) | C32—C31—C36—C35 | −2 (2) |
P1—C7—C8—C9 | −173.8 (11) | P2—C31—C36—C35 | −178.2 (11) |
C7—C8—C9—C10 | −1 (2) | C8—C7—P1—O1 | 78.0 (12) |
C8—C9—C10—C11 | −1 (2) | C12—C7—P1—O1 | −97.7 (12) |
C8—C9—C10—F2 | 180.0 (12) | C8—C7—P1—C13 | −160.0 (11) |
C9—C10—C11—C12 | 4 (2) | C12—C7—P1—C13 | 24.2 (13) |
F2—C10—C11—C12 | −177.9 (12) | C8—C7—P1—C1 | −39.0 (12) |
C10—C11—C12—C7 | −3 (2) | C12—C7—P1—C1 | 145.3 (11) |
C8—C7—C12—C11 | 0 (2) | C14—C13—P1—O1 | −13.7 (13) |
P1—C7—C12—C11 | 175.7 (10) | C18—C13—P1—O1 | 167.8 (11) |
C18—C13—C14—C15 | −2 (2) | C14—C13—P1—C7 | −137.8 (11) |
P1—C13—C14—C15 | 179.8 (11) | C18—C13—P1—C7 | 43.7 (14) |
C13—C14—C15—C16 | 1 (2) | C14—C13—P1—C1 | 105.4 (12) |
C14—C15—C16—F3 | −178.5 (12) | C18—C13—P1—C1 | −73.1 (13) |
C14—C15—C16—C17 | −1 (2) | C6—C1—P1—O1 | −173.9 (10) |
C15—C16—C17—C18 | 2 (2) | C2—C1—P1—O1 | 3.9 (11) |
F3—C16—C17—C18 | 179.4 (12) | C6—C1—P1—C7 | −53.2 (12) |
C16—C17—C18—C13 | −3 (2) | C2—C1—P1—C7 | 124.6 (10) |
C14—C13—C18—C17 | 3 (2) | C6—C1—P1—C13 | 65.8 (13) |
P1—C13—C18—C17 | −178.9 (11) | C2—C1—P1—C13 | −116.4 (10) |
C24—C19—C20—C21 | 3.2 (19) | C20—C19—P2—O2 | 80.2 (12) |
P2—C19—C20—C21 | −172.0 (11) | C24—C19—P2—O2 | −94.8 (12) |
C19—C20—C21—C22 | −4 (2) | C20—C19—P2—C31 | −156.7 (10) |
C20—C21—C22—F4 | 179.1 (12) | C24—C19—P2—C31 | 28.4 (13) |
C20—C21—C22—C23 | 2 (2) | C20—C19—P2—C25 | −37.0 (13) |
F4—C22—C23—C24 | −176.3 (11) | C24—C19—P2—C25 | 148.1 (11) |
C21—C22—C23—C24 | 1 (2) | C36—C31—P2—O2 | 161.1 (11) |
C22—C23—C24—C19 | −1.7 (19) | C32—C31—P2—O2 | −15.5 (12) |
C20—C19—C24—C23 | −0.2 (19) | C36—C31—P2—C19 | 36.9 (13) |
P2—C19—C24—C23 | 174.9 (10) | C32—C31—P2—C19 | −139.8 (10) |
C30—C25—C26—C27 | 1 (2) | C36—C31—P2—C25 | −80.5 (13) |
P2—C25—C26—C27 | 179.8 (10) | C32—C31—P2—C25 | 102.9 (11) |
C25—C26—C27—C28 | 1 (2) | C30—C25—P2—O2 | −170.6 (11) |
C26—C27—C28—C29 | −4 (2) | C26—C25—P2—O2 | 10.1 (13) |
C26—C27—C28—F5 | −178.5 (11) | C30—C25—P2—C19 | −50.0 (13) |
C27—C28—C29—C30 | 5 (2) | C26—C25—P2—C19 | 130.7 (11) |
F5—C28—C29—C30 | 180.0 (12) | C30—C25—P2—C31 | 68.9 (13) |
C26—C25—C30—C29 | 1 (2) | C26—C25—P2—C31 | −110.4 (11) |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C36H25F6O2P2+·I3− |
Mr | 1046 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 100 |
a, b, c (Å) | 13.2153 (4), 15.9752 (6), 18.5695 (6) |
β (°) | 108.818 (2) |
V (Å3) | 3710.8 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.68 |
Crystal size (mm) | 0.18 × 0.15 × 0.06 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.645, 0.856 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14255, 5376, 4363 |
Rint | 0.081 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.131, 1.05 |
No. of reflections | 5376 |
No. of parameters | 466 |
No. of restraints | 17 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0392P)2 + 81.0459P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.03, −1.60 |
Absolute structure | Flack (1983), with 1024 Friedel pairs |
Absolute structure parameter | 0.50 (3) |
Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor 1997), DIRDIF08 (Beurskens et al., 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
C1—P1 | 1.811 (15) | O1—P1 | 1.526 (10) |
C7—P1 | 1.783 (13) | O2—P2 | 1.530 (10) |
C13—P1 | 1.799 (12) | I1—I3 | 2.9023 (15) |
C19—P2 | 1.740 (15) | I1—I2 | 2.9452 (14) |
C25—P2 | 1.799 (14) | I2—I3i | 3.5774 (11) |
C31—P2 | 1.797 (14) | ||
O1—P1—C7 | 112.9 (6) | O2—P2—C19 | 112.4 (6) |
O1—P1—C13 | 109.4 (6) | O2—P2—C31 | 110.5 (5) |
O1—P1—C1 | 107.4 (6) | O2—P2—C25 | 107.0 (6) |
C8—C7—P1—O1 | 78.0 (12) | C20—C19—P2—O2 | 80.2 (12) |
C14—C13—P1—O1 | −13.7 (13) | C32—C31—P2—O2 | −15.5 (12) |
C2—C1—P1—O1 | 3.9 (11) | C26—C25—P2—O2 | 10.1 (13) |
Symmetry code: (i) x, −y+1, z+1/2. |
The title structure, (I), consists of triiodide anions and proton counterions that link pairs of tris(4-fluorophenyl)phosphane oxide molecules into hydrogen-bonded dimers (Fig. 1). The two crystallographically unique (p-FC6H4)3PO molecules have similar conformations, as indicated by their O—P—C—C torsions angles of 3.9 (11), 78.0 (12) and -13.7 (13)° around O1—P1, and 80.2 (12), 10.1 (13) and -15.5 (12)° around O2—P2. This type of parallel, parallel, orthogonal conformation has been named `orthogonal flipper' by Dance & Scudder (2000) and is also the conformation adopted in an analogous unfluorinated structure with FeBr4- as the counterion (corresponding torsion angles 19.5, 27.3 and 83.2, and 19.5, 27.3 and 83.2°; Lane et al., 1994). However, when the counterion is ClO4-, a rotor-type conformation is adopted (corresponding torsion angles 29.9, 37.3 and 64.1, and 16.2, 30.0 and 42.7°; Antipin et al. 1980). In the structure of (I) the orthogonal rings are opposite each other in the hydrogen-bonded dimers and participate in face-to-face π interactions. In contrast, each orthogonal ring is opposite a parallel one in the unfluorinated dimer reported by Lane et al., (1994), facilitating edge-to-face π interactions.
In the structure of (I), the P—O bonds of 1.526 (10) and 1.530 (10) Å are significantly longer than typical double P═O bonds of e.g. 1.487 (3) Å in (C6H5)3P═O (Thomas & Hamor, 1993) and 1.467 (2) Å in (C6F5)3P═O (Nicholson & Thwaite, 2003). However, they are shorter than the single P—O bonds of 1.581 (4), 1.579 (4) and 1.553 (3) Å in triphenylphosphane oxyl derivatives (Kunnari et al., 2001; Carcedo et al. 2004; Chow et al. 1996), which average 1.571 Å. As the P—O bond lengths fall midway between single- and double-bond values, it is clear that the correct depiction of these bonds should be as intermediate single/double bonds. Because of this, and as the H atom was not found in the difference electron-density map, it has been fixed at the initial halfway position between the O atoms in this strong hydrogen bond, with its displacement parameter refined freely. Although this is reasonable it may not be strictly correct, as asymmetric positioning of the H atom is common in even the strongest hydrogen bonds. See, for example, Konu & Chivers (2006) and Antipin et al. (1980), who found that the O···H···O bond in [{(C6H5)3P═O}2H]+.ClO4- changes from symmetric at room temperature to asymmetric on cooling.
Packing of the hydrogen-bonded dimers of (I) forms tunnels parallel to the crystallographic c axis (Fig. 2). The tunnels house triiodide anions, which are also aligned along the crystallographic c axis. Within each tunnel, adjacent iodide anions are related by crystallographic c-glide operations. In stacked structures or structures with channels, triiodides often form infinite linear chains with weak I3-···I3- interactions, with typical I···I separations ≥ 3.6 Å (Svensson & Kloo, 2003). The I···I distance of 3.5774 (11) Å seen in (I) is a rare example of an interionic I3-···I3- separation of less than 3.6 Å. In contrast, the most significant contact between the triiodide anion and the surrounding tunnel atoms is 3.156 Å between phenyl atom H32 and central iodine I1, which is only marginally shorter than the van der Waals contact (3.35 Å; Harrison, 1978).
The two I—I bonds [2.9023 (15) and 2.9452 (14) Å] show significant asymmetry. This is not unusual and is caused by nonbonded interaction within the crystal structure. In the case of (I), the most significant sub-van der Waals contacts involving the terminal triiodide I atoms are I···I contacts, which are of equal length for symmetry reasons. However, atom I2 has five I···H contacts shorter than the sum of the van der Waals radii (3.283–3.347 Å), compared with only two for I3 (3.222 and 3.291 Å).