Halogen bonding to phosphorus atoms remains uncommon, with relatively few examples reported in the literature. Here, the preparation and investigation of the cocrystal bis(dicyclohexylphenylphosphine)(1,6-diiodoperfluorohexane) by X-ray crystallography and solid-state multinuclear magnetic resonance spectroscopy is described. The crystal structure features two crystallographically unique C—I
P halogen bonds [
dIP = 3.090 (5) Å, 3.264 (5) Å] and crystallographic disorder of one of the 1,6-diiodoperfluorohexane molecules. The first of these is the shortest and most linear I
P halogen bond reported to date.
13C,
19F, and
31P magic angle spinning solid-state NMR spectra are reported. A
31P chemical shift change of −7.0 p.p.m. in the cocrystal relative to pure dicyclohexylphenylphosphine, consistent with halogen bond formation, is noted. This work establishes iodoperfluoroalkanes as viable halogen bond donors when paired with phosphorus acceptors, and also shows that dicyclohexylphenylphosphine can act as a practical halogen bond acceptor.
Supporting information
CCDC reference: 2128052
Data collection: Bruker APEX3; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXT 2014/5 (Sheldrick, 2014); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2018).
Crystal data top
2(C18H27P)·(C6F12I2) | Z = 2 |
Mr = 1102.59 | F(000) = 1100 |
Triclinic, P1 | Dx = 1.593 Mg m−3 |
a = 10.321 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 15.231 (4) Å | Cell parameters from 5993 reflections |
c = 15.663 (4) Å | θ = 2.7–23.3° |
α = 82.730 (6)° | µ = 1.52 mm−1 |
β = 80.201 (5)° | T = 293 K |
γ = 71.847 (6)° | Plate, colourless |
V = 2298.5 (11) Å3 | 0.13 × 0.09 × 0.05 mm |
Data collection top
Bruker APEX-II CCD diffractometer | 3224 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
ω and πhi scans | θmax = 23.3°, θmin = 1.3° |
Absorption correction: multi-scan SADABS | h = −11→8 |
Tmin = 0.604, Tmax = 0.745 | k = −16→16 |
19267 measured reflections | l = −17→17 |
6489 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.123 | H-atom parameters constrained |
wR(F2) = 0.192 | w = 1/[σ2(Fo2) + 37.981P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
6489 reflections | Δρmax = 1.13 e Å−3 |
605 parameters | Δρmin = −1.21 e Å−3 |
259 restraints | |
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. none |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
I1 | 0.85453 (12) | 0.07248 (8) | 0.81871 (7) | 0.0571 (4) | |
F1 | 0.937 (2) | −0.0922 (8) | 0.7217 (7) | 0.170 (8) | |
F2 | 1.1011 (14) | −0.0336 (11) | 0.7164 (7) | 0.165 (8) | |
F3 | 0.8073 (10) | 0.0621 (8) | 0.6231 (6) | 0.105 (4) | |
F4 | 0.9876 (13) | 0.1049 (7) | 0.6140 (6) | 0.110 (4) | |
F5 | 0.9439 (10) | −0.0931 (6) | 0.5504 (5) | 0.076 (3) | |
F6 | 1.1400 (10) | −0.0683 (6) | 0.5520 (5) | 0.074 (3) | |
C1 | 0.9616 (19) | −0.0122 (13) | 0.7122 (11) | 0.084 (6) | |
C2 | 0.9428 (15) | 0.0312 (9) | 0.6229 (8) | 0.046 (4) | |
C3 | 1.0090 (16) | −0.0259 (10) | 0.5441 (9) | 0.053 (4) | |
P1 | 0.7051 (4) | 0.1885 (3) | 0.9742 (3) | 0.0499 (11) | |
P2 | 0.2100 (4) | 0.5613 (3) | 0.5934 (3) | 0.0563 (12) | |
C7 | 0.5526 (16) | 0.2876 (10) | 0.9505 (11) | 0.051 (4) | |
C8 | 0.4892 (17) | 0.2810 (11) | 0.8825 (11) | 0.060 (5) | |
H8 | 0.523905 | 0.229878 | 0.849644 | 0.072* | |
C9 | 0.3735 (17) | 0.3511 (13) | 0.8632 (11) | 0.067 (5) | |
H9 | 0.332459 | 0.348606 | 0.815391 | 0.080* | |
C10 | 0.3188 (18) | 0.4241 (12) | 0.9141 (13) | 0.070 (5) | |
H10 | 0.238455 | 0.469642 | 0.902174 | 0.083* | |
C11 | 0.3804 (19) | 0.4308 (12) | 0.9814 (12) | 0.067 (5) | |
H11 | 0.343229 | 0.481279 | 1.015006 | 0.080* | |
C12 | 0.4978 (18) | 0.3631 (12) | 1.0005 (11) | 0.062 (5) | |
H12 | 0.540448 | 0.367856 | 1.046690 | 0.075* | |
C13 | 0.8177 (15) | 0.2419 (10) | 1.0136 (9) | 0.048 (4) | |
H13 | 0.763501 | 0.281890 | 1.059435 | 0.057* | |
C14 | 0.8761 (17) | 0.3020 (12) | 0.9394 (10) | 0.065 (5) | |
H14A | 0.923129 | 0.263995 | 0.891630 | 0.079* | |
H14B | 0.800389 | 0.351229 | 0.918412 | 0.079* | |
C15 | 0.9762 (19) | 0.3446 (12) | 0.9679 (12) | 0.077 (6) | |
H15A | 1.013479 | 0.378854 | 0.918481 | 0.093* | |
H15B | 0.927453 | 0.387644 | 1.011556 | 0.093* | |
C16 | 1.0932 (17) | 0.2694 (13) | 1.0051 (12) | 0.076 (6) | |
H16A | 1.146855 | 0.229486 | 0.959959 | 0.091* | |
H16B | 1.153435 | 0.297656 | 1.025314 | 0.091* | |
C17 | 1.0363 (19) | 0.2121 (13) | 1.0801 (12) | 0.078 (6) | |
H17A | 1.111474 | 0.162834 | 1.101596 | 0.094* | |
H17B | 0.989095 | 0.251015 | 1.127133 | 0.094* | |
C18 | 0.9367 (17) | 0.1704 (11) | 1.0507 (11) | 0.067 (5) | |
H18A | 0.986541 | 0.127622 | 1.007061 | 0.080* | |
H18B | 0.900613 | 0.135198 | 1.099914 | 0.080* | |
C19 | 0.6403 (16) | 0.1243 (10) | 1.0717 (9) | 0.050 (4) | |
H19 | 0.658369 | 0.147509 | 1.122682 | 0.060* | |
C20 | 0.7189 (18) | 0.0201 (11) | 1.0722 (11) | 0.071 (5) | |
H20A | 0.705078 | −0.003986 | 1.021155 | 0.085* | |
H20B | 0.816586 | 0.012044 | 1.068877 | 0.085* | |
C21 | 0.673 (2) | −0.0357 (12) | 1.1533 (12) | 0.086 (6) | |
H21A | 0.721116 | −0.101015 | 1.148415 | 0.103* | |
H21B | 0.697106 | −0.017124 | 1.203942 | 0.103* | |
C22 | 0.522 (2) | −0.0218 (13) | 1.1654 (12) | 0.077 (6) | |
H22A | 0.495683 | −0.053627 | 1.220111 | 0.093* | |
H22B | 0.499646 | −0.048914 | 1.119100 | 0.093* | |
C23 | 0.4414 (18) | 0.0791 (13) | 1.1651 (12) | 0.077 (6) | |
H23A | 0.453487 | 0.104191 | 1.216125 | 0.093* | |
H23B | 0.344247 | 0.085566 | 1.168000 | 0.093* | |
C24 | 0.4881 (16) | 0.1346 (12) | 1.0829 (11) | 0.067 (5) | |
H24A | 0.467114 | 0.113483 | 1.032383 | 0.080* | |
H24B | 0.436648 | 0.199569 | 1.086110 | 0.080* | |
C25 | 0.2951 (16) | 0.6179 (11) | 0.6505 (10) | 0.054 (4) | |
C26 | 0.2725 (16) | 0.7138 (11) | 0.6462 (10) | 0.057 (5) | |
H26 | 0.207946 | 0.753362 | 0.613054 | 0.069* | |
C27 | 0.3464 (19) | 0.7501 (14) | 0.6915 (12) | 0.077 (6) | |
H27 | 0.340907 | 0.812593 | 0.681041 | 0.092* | |
C28 | 0.4267 (18) | 0.6965 (15) | 0.7508 (12) | 0.074 (6) | |
H28 | 0.464350 | 0.723016 | 0.786948 | 0.089* | |
C29 | 0.4508 (19) | 0.6005 (14) | 0.7556 (11) | 0.073 (5) | |
H29 | 0.514865 | 0.561396 | 0.789369 | 0.087* | |
C30 | 0.3782 (16) | 0.5639 (11) | 0.7097 (10) | 0.058 (5) | |
H30 | 0.385821 | 0.501122 | 0.719070 | 0.070* | |
C31 | 0.0325 (15) | 0.5913 (11) | 0.6525 (11) | 0.055 (4) | |
H31 | −0.013862 | 0.558676 | 0.623577 | 0.066* | |
C32 | 0.0270 (17) | 0.5470 (12) | 0.7451 (13) | 0.078 (6) | |
H32A | 0.068148 | 0.480468 | 0.743745 | 0.093* | |
H32B | 0.081384 | 0.569904 | 0.776602 | 0.093* | |
C33 | −0.1170 (18) | 0.5663 (12) | 0.7927 (11) | 0.074 (5) | |
H33A | −0.162317 | 0.528017 | 0.771629 | 0.088* | |
H33B | −0.111676 | 0.547625 | 0.853898 | 0.088* | |
C34 | −0.2030 (18) | 0.6634 (12) | 0.7845 (12) | 0.074 (5) | |
H34A | −0.297235 | 0.667026 | 0.808900 | 0.088* | |
H34B | −0.171048 | 0.700141 | 0.817802 | 0.088* | |
C35 | −0.1995 (18) | 0.7023 (12) | 0.6941 (11) | 0.073 (5) | |
H35A | −0.249203 | 0.767854 | 0.693037 | 0.088* | |
H35B | −0.247276 | 0.672865 | 0.663696 | 0.088* | |
C36 | −0.0570 (15) | 0.6905 (10) | 0.6461 (10) | 0.052 (4) | |
H36A | −0.014595 | 0.728954 | 0.669708 | 0.063* | |
H36B | −0.062935 | 0.711496 | 0.585403 | 0.063* | |
C37 | 0.1979 (14) | 0.6283 (10) | 0.4867 (9) | 0.045 (4) | |
H37 | 0.150825 | 0.693662 | 0.496240 | 0.055* | |
C38 | 0.1154 (15) | 0.5947 (10) | 0.4330 (9) | 0.050 (4) | |
H38A | 0.023038 | 0.602677 | 0.463652 | 0.060* | |
H38B | 0.158171 | 0.529120 | 0.426002 | 0.060* | |
C39 | 0.1073 (15) | 0.6476 (11) | 0.3436 (10) | 0.054 (4) | |
H39A | 0.059264 | 0.621893 | 0.309784 | 0.064* | |
H39B | 0.055507 | 0.712077 | 0.350136 | 0.064* | |
C40 | 0.2504 (15) | 0.6413 (11) | 0.2960 (10) | 0.057 (5) | |
H40A | 0.296571 | 0.577790 | 0.282060 | 0.068* | |
H40B | 0.242315 | 0.679784 | 0.241713 | 0.068* | |
C41 | 0.3372 (16) | 0.6714 (12) | 0.3480 (10) | 0.061 (5) | |
H41A | 0.430210 | 0.659457 | 0.317389 | 0.074* | |
H41B | 0.299816 | 0.737563 | 0.353774 | 0.074* | |
C42 | 0.3406 (15) | 0.6205 (11) | 0.4369 (10) | 0.052 (4) | |
H42A | 0.390697 | 0.645017 | 0.470220 | 0.062* | |
H42B | 0.390135 | 0.555545 | 0.430864 | 0.062* | |
I2A | 0.29643 (13) | 0.33716 (10) | 0.58439 (9) | 0.0791 (5) | 0.469 (12) |
F7A | 0.2401 (17) | 0.1627 (18) | 0.6452 (18) | 0.123 (8) | 0.469 (12) |
F8A | 0.4465 (19) | 0.1626 (16) | 0.6660 (17) | 0.152 (11) | 0.469 (12) |
F9A | 0.3239 (19) | 0.1617 (17) | 0.4774 (17) | 0.145 (10) | 0.469 (12) |
F10A | 0.5315 (16) | 0.1600 (16) | 0.4972 (17) | 0.109 (7) | 0.469 (12) |
F11A | 0.3470 (18) | 0.004 (2) | 0.5700 (18) | 0.098 (7) | 0.469 (12) |
F12A | 0.5472 (18) | 0.0013 (15) | 0.6042 (14) | 0.095 (7) | 0.469 (12) |
C4A | 0.350 (3) | 0.1874 (14) | 0.6088 (16) | 0.099 (6) | 0.469 (12) |
C5A | 0.419 (2) | 0.1344 (14) | 0.5313 (14) | 0.088 (5) | 0.469 (12) |
C6A | 0.467 (3) | 0.0275 (15) | 0.5433 (16) | 0.082 (5) | 0.469 (12) |
I2B | 0.29643 (13) | 0.33716 (10) | 0.58439 (9) | 0.0791 (5) | 0.531 (12) |
F7B | 0.1972 (16) | 0.1863 (12) | 0.5467 (11) | 0.097 (7) | 0.531 (12) |
F8B | 0.307 (2) | 0.1532 (17) | 0.6615 (11) | 0.123 (8) | 0.531 (12) |
F9B | 0.437 (2) | 0.1717 (14) | 0.4467 (9) | 0.106 (7) | 0.531 (12) |
F10B | 0.5385 (18) | 0.1351 (16) | 0.5651 (13) | 0.131 (9) | 0.531 (12) |
F11B | 0.352 (3) | 0.0342 (19) | 0.4624 (13) | 0.173 (12) | 0.531 (12) |
F12B | 0.399 (3) | −0.008 (2) | 0.5966 (12) | 0.120 (8) | 0.531 (12) |
C4B | 0.305 (2) | 0.1936 (14) | 0.5763 (17) | 0.093 (6) | 0.531 (12) |
C5B | 0.432 (2) | 0.1325 (14) | 0.5281 (13) | 0.083 (4) | 0.531 (12) |
C6B | 0.442 (2) | 0.0302 (15) | 0.5217 (16) | 0.085 (5) | 0.531 (12) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.0591 (8) | 0.0619 (7) | 0.0473 (7) | −0.0132 (6) | −0.0056 (6) | −0.0082 (6) |
F1 | 0.38 (3) | 0.054 (7) | 0.057 (8) | −0.072 (11) | 0.033 (11) | −0.007 (6) |
F2 | 0.123 (12) | 0.230 (18) | 0.067 (9) | 0.082 (12) | −0.040 (8) | −0.052 (9) |
F3 | 0.055 (7) | 0.159 (11) | 0.075 (8) | 0.029 (7) | −0.021 (6) | −0.053 (7) |
F4 | 0.189 (13) | 0.093 (8) | 0.074 (8) | −0.097 (9) | 0.028 (8) | −0.029 (6) |
F5 | 0.126 (9) | 0.074 (7) | 0.043 (6) | −0.056 (7) | −0.002 (6) | −0.004 (5) |
F6 | 0.067 (7) | 0.080 (7) | 0.049 (6) | 0.018 (5) | −0.011 (5) | −0.005 (5) |
C1 | 0.068 (15) | 0.112 (18) | 0.059 (14) | −0.010 (13) | −0.007 (11) | −0.010 (13) |
C2 | 0.057 (12) | 0.049 (10) | 0.030 (10) | −0.010 (9) | −0.006 (8) | −0.010 (8) |
C3 | 0.060 (12) | 0.046 (10) | 0.049 (11) | −0.011 (9) | −0.014 (10) | 0.002 (8) |
P1 | 0.049 (3) | 0.056 (3) | 0.041 (3) | −0.009 (2) | −0.005 (2) | −0.013 (2) |
P2 | 0.046 (3) | 0.064 (3) | 0.060 (3) | −0.020 (2) | −0.010 (2) | 0.001 (2) |
C7 | 0.054 (11) | 0.035 (9) | 0.060 (12) | −0.012 (8) | 0.002 (10) | −0.005 (9) |
C8 | 0.063 (13) | 0.061 (12) | 0.056 (12) | −0.013 (10) | −0.018 (10) | −0.009 (9) |
C9 | 0.046 (12) | 0.089 (14) | 0.055 (12) | −0.010 (11) | −0.012 (10) | 0.014 (11) |
C10 | 0.043 (12) | 0.060 (13) | 0.076 (15) | 0.013 (9) | 0.002 (11) | 0.014 (11) |
C11 | 0.064 (13) | 0.060 (12) | 0.073 (14) | −0.015 (11) | −0.015 (11) | 0.004 (10) |
C12 | 0.062 (13) | 0.069 (13) | 0.055 (12) | −0.020 (10) | −0.014 (10) | 0.007 (10) |
C13 | 0.057 (11) | 0.048 (9) | 0.034 (9) | −0.010 (8) | −0.009 (8) | 0.003 (8) |
C14 | 0.064 (12) | 0.076 (12) | 0.048 (11) | −0.011 (10) | −0.019 (10) | 0.016 (9) |
C15 | 0.091 (15) | 0.069 (13) | 0.086 (15) | −0.048 (12) | −0.019 (12) | 0.012 (11) |
C16 | 0.053 (12) | 0.087 (14) | 0.089 (15) | −0.025 (11) | −0.019 (11) | 0.007 (12) |
C17 | 0.081 (14) | 0.091 (14) | 0.081 (14) | −0.047 (12) | −0.041 (12) | 0.022 (12) |
C18 | 0.070 (13) | 0.070 (12) | 0.067 (13) | −0.027 (10) | −0.034 (10) | 0.018 (10) |
C19 | 0.059 (11) | 0.057 (10) | 0.034 (10) | −0.018 (9) | 0.001 (8) | −0.012 (8) |
C20 | 0.072 (13) | 0.059 (12) | 0.069 (13) | −0.004 (10) | −0.005 (11) | −0.001 (10) |
C21 | 0.113 (19) | 0.057 (12) | 0.063 (14) | −0.009 (12) | 0.010 (13) | 0.013 (10) |
C22 | 0.085 (16) | 0.093 (16) | 0.062 (13) | −0.045 (13) | 0.011 (12) | −0.013 (11) |
C23 | 0.061 (13) | 0.086 (15) | 0.078 (15) | −0.017 (11) | 0.003 (11) | −0.007 (12) |
C24 | 0.048 (12) | 0.075 (13) | 0.073 (13) | −0.012 (10) | −0.011 (10) | 0.000 (10) |
C25 | 0.054 (11) | 0.049 (10) | 0.066 (12) | −0.017 (8) | −0.030 (9) | 0.004 (9) |
C26 | 0.050 (11) | 0.066 (12) | 0.052 (11) | −0.011 (9) | −0.019 (9) | 0.008 (9) |
C27 | 0.074 (14) | 0.088 (14) | 0.080 (15) | −0.033 (12) | −0.026 (12) | −0.007 (12) |
C28 | 0.053 (12) | 0.117 (18) | 0.061 (14) | −0.022 (12) | −0.014 (10) | −0.037 (13) |
C29 | 0.074 (14) | 0.079 (15) | 0.055 (13) | −0.002 (11) | −0.019 (11) | −0.011 (11) |
C30 | 0.062 (12) | 0.045 (10) | 0.057 (12) | 0.004 (9) | −0.022 (10) | 0.000 (9) |
C31 | 0.046 (11) | 0.055 (11) | 0.062 (12) | −0.009 (9) | −0.011 (9) | −0.012 (9) |
C32 | 0.046 (12) | 0.072 (13) | 0.105 (17) | 0.021 (10) | −0.039 (12) | −0.029 (12) |
C33 | 0.060 (13) | 0.081 (14) | 0.066 (13) | −0.006 (11) | 0.004 (11) | −0.009 (11) |
C34 | 0.059 (13) | 0.080 (14) | 0.078 (15) | −0.015 (11) | −0.006 (11) | −0.008 (11) |
C35 | 0.064 (13) | 0.081 (13) | 0.057 (13) | 0.005 (10) | 0.006 (11) | −0.027 (11) |
C36 | 0.039 (10) | 0.066 (11) | 0.044 (10) | −0.008 (8) | −0.001 (8) | 0.001 (8) |
C37 | 0.038 (10) | 0.049 (10) | 0.045 (10) | −0.016 (8) | 0.010 (8) | −0.005 (8) |
C38 | 0.042 (10) | 0.058 (10) | 0.050 (11) | −0.013 (8) | −0.002 (8) | −0.012 (9) |
C39 | 0.044 (10) | 0.071 (11) | 0.048 (11) | −0.015 (9) | −0.015 (9) | −0.004 (9) |
C40 | 0.047 (11) | 0.073 (12) | 0.045 (11) | −0.007 (9) | −0.008 (9) | −0.008 (9) |
C41 | 0.043 (11) | 0.083 (13) | 0.053 (12) | −0.019 (9) | −0.003 (9) | 0.008 (10) |
C42 | 0.038 (10) | 0.061 (11) | 0.057 (12) | −0.017 (8) | 0.000 (9) | −0.010 (9) |
I2A | 0.0527 (8) | 0.1017 (11) | 0.0855 (10) | −0.0293 (7) | −0.0171 (7) | 0.0103 (8) |
F7A | 0.087 (13) | 0.107 (15) | 0.159 (16) | −0.036 (12) | 0.037 (11) | −0.007 (14) |
F8A | 0.16 (2) | 0.13 (2) | 0.173 (18) | −0.017 (18) | −0.076 (18) | −0.008 (16) |
F9A | 0.158 (19) | 0.099 (18) | 0.18 (2) | −0.010 (17) | −0.095 (19) | −0.014 (16) |
F10A | 0.075 (11) | 0.097 (13) | 0.141 (18) | −0.036 (11) | 0.027 (10) | 0.010 (14) |
F11A | 0.069 (12) | 0.090 (14) | 0.131 (17) | −0.036 (11) | 0.012 (10) | 0.003 (13) |
F12A | 0.094 (16) | 0.091 (16) | 0.087 (14) | 0.000 (12) | −0.025 (12) | −0.014 (11) |
C4A | 0.075 (10) | 0.116 (12) | 0.098 (10) | −0.035 (7) | 0.002 (8) | 0.015 (8) |
C5A | 0.068 (9) | 0.103 (8) | 0.090 (10) | −0.038 (7) | −0.003 (7) | 0.023 (7) |
C6A | 0.068 (10) | 0.104 (8) | 0.076 (13) | −0.041 (7) | −0.008 (8) | 0.021 (8) |
I2B | 0.0527 (8) | 0.1017 (11) | 0.0855 (10) | −0.0293 (7) | −0.0171 (7) | 0.0103 (8) |
F7B | 0.052 (9) | 0.076 (14) | 0.159 (18) | −0.013 (9) | −0.004 (11) | −0.026 (13) |
F8B | 0.117 (18) | 0.114 (14) | 0.109 (10) | −0.016 (14) | 0.010 (9) | 0.013 (10) |
F9B | 0.088 (15) | 0.102 (12) | 0.097 (10) | −0.006 (12) | 0.007 (8) | 0.018 (9) |
F10B | 0.069 (11) | 0.13 (2) | 0.20 (2) | −0.002 (11) | −0.055 (14) | −0.060 (19) |
F11B | 0.17 (2) | 0.15 (2) | 0.22 (2) | −0.04 (2) | −0.12 (2) | −0.02 (2) |
F12B | 0.114 (17) | 0.100 (12) | 0.117 (13) | −0.025 (15) | 0.024 (11) | 0.022 (10) |
C4B | 0.063 (8) | 0.110 (12) | 0.107 (10) | −0.044 (6) | 0.003 (7) | 0.010 (8) |
C5B | 0.056 (8) | 0.107 (8) | 0.091 (9) | −0.041 (6) | −0.011 (7) | 0.012 (7) |
C6B | 0.063 (12) | 0.108 (8) | 0.092 (12) | −0.044 (8) | −0.011 (8) | 0.013 (7) |
Geometric parameters (Å, º) top
I1—C1 | 2.167 (16) | C26—C27 | 1.39 (2) |
F1—C1 | 1.303 (19) | C26—H26 | 0.9300 |
F2—C1 | 1.385 (19) | C27—C28 | 1.37 (2) |
F3—C2 | 1.329 (14) | C27—H27 | 0.9300 |
F4—C2 | 1.324 (14) | C28—C29 | 1.40 (2) |
F5—C3 | 1.373 (15) | C28—H28 | 0.9300 |
F6—C3 | 1.324 (15) | C29—C30 | 1.39 (2) |
C1—C2 | 1.487 (19) | C29—H29 | 0.9300 |
C2—C3 | 1.536 (17) | C30—H30 | 0.9300 |
C3—C3i | 1.51 (3) | C31—C36 | 1.506 (19) |
P1—C13 | 1.832 (15) | C31—C32 | 1.52 (2) |
P1—C19 | 1.848 (15) | C31—H31 | 0.9800 |
P1—C7 | 1.863 (16) | C32—C33 | 1.50 (2) |
P2—C25 | 1.802 (15) | C32—H32A | 0.9700 |
P2—C37 | 1.847 (15) | C32—H32B | 0.9700 |
P2—C31 | 1.852 (16) | C33—C34 | 1.47 (2) |
C7—C8 | 1.37 (2) | C33—H33A | 0.9700 |
C7—C12 | 1.39 (2) | C33—H33B | 0.9700 |
C8—C9 | 1.38 (2) | C34—C35 | 1.46 (2) |
C8—H8 | 0.9300 | C34—H34A | 0.9700 |
C9—C10 | 1.37 (2) | C34—H34B | 0.9700 |
C9—H9 | 0.9300 | C35—C36 | 1.50 (2) |
C10—C11 | 1.35 (2) | C35—H35A | 0.9700 |
C10—H10 | 0.9300 | C35—H35B | 0.9700 |
C11—C12 | 1.37 (2) | C36—H36A | 0.9700 |
C11—H11 | 0.9300 | C36—H36B | 0.9700 |
C12—H12 | 0.9300 | C37—C42 | 1.521 (18) |
C13—C18 | 1.510 (19) | C37—C38 | 1.523 (19) |
C13—C14 | 1.545 (19) | C37—H37 | 0.9800 |
C13—H13 | 0.9800 | C38—C39 | 1.526 (19) |
C14—C15 | 1.53 (2) | C38—H38A | 0.9700 |
C14—H14A | 0.9700 | C38—H38B | 0.9700 |
C14—H14B | 0.9700 | C39—C40 | 1.517 (19) |
C15—C16 | 1.52 (2) | C39—H39A | 0.9700 |
C15—H15A | 0.9700 | C39—H39B | 0.9700 |
C15—H15B | 0.9700 | C40—C41 | 1.51 (2) |
C16—C17 | 1.52 (2) | C40—H40A | 0.9700 |
C16—H16A | 0.9700 | C40—H40B | 0.9700 |
C16—H16B | 0.9700 | C41—C42 | 1.507 (19) |
C17—C18 | 1.52 (2) | C41—H41A | 0.9700 |
C17—H17A | 0.9700 | C41—H41B | 0.9700 |
C17—H17B | 0.9700 | C42—H42A | 0.9700 |
C18—H18A | 0.9700 | C42—H42B | 0.9700 |
C18—H18B | 0.9700 | I2A—C4A | 2.17 (2) |
C19—C24 | 1.512 (19) | F7A—C4A | 1.32 (2) |
C19—C20 | 1.54 (2) | F8A—C4A | 1.39 (2) |
C19—H19 | 0.9800 | F9A—C5A | 1.337 (19) |
C20—C21 | 1.53 (2) | F10A—C5A | 1.343 (18) |
C20—H20A | 0.9700 | F11A—C6A | 1.38 (2) |
C20—H20B | 0.9700 | F12A—C6A | 1.31 (2) |
C21—C22 | 1.49 (2) | C4A—C5A | 1.49 (2) |
C21—H21A | 0.9700 | C5A—C6A | 1.54 (2) |
C21—H21B | 0.9700 | C6A—C6Aii | 1.62 (5) |
C22—C23 | 1.50 (2) | I2B—C4B | 2.180 (19) |
C22—H22A | 0.9700 | F7B—C4B | 1.31 (2) |
C22—H22B | 0.9700 | F8B—C4B | 1.40 (2) |
C23—C24 | 1.54 (2) | F9B—C5B | 1.338 (19) |
C23—H23A | 0.9700 | F10B—C5B | 1.342 (18) |
C23—H23B | 0.9700 | F11B—C6B | 1.40 (2) |
C24—H24A | 0.9700 | F12B—C6B | 1.31 (2) |
C24—H24B | 0.9700 | C4B—C5B | 1.49 (2) |
C25—C30 | 1.38 (2) | C5B—C6B | 1.54 (2) |
C25—C26 | 1.40 (2) | C6B—C6Bii | 1.39 (5) |
| | | |
F1—C1—F2 | 104.7 (15) | C28—C27—C26 | 121.7 (18) |
F1—C1—C2 | 110.0 (15) | C28—C27—H27 | 119.1 |
F2—C1—C2 | 105.5 (14) | C26—C27—H27 | 119.1 |
F1—C1—I1 | 112.0 (12) | C27—C28—C29 | 118.1 (17) |
F2—C1—I1 | 106.9 (11) | C27—C28—H28 | 121.0 |
C2—C1—I1 | 116.8 (11) | C29—C28—H28 | 121.0 |
F4—C2—F3 | 107.0 (12) | C30—C29—C28 | 119.5 (17) |
F4—C2—C1 | 106.5 (13) | C30—C29—H29 | 120.2 |
F3—C2—C1 | 104.9 (13) | C28—C29—H29 | 120.2 |
F4—C2—C3 | 108.6 (11) | C25—C30—C29 | 122.2 (16) |
F3—C2—C3 | 109.1 (11) | C25—C30—H30 | 118.9 |
C1—C2—C3 | 119.9 (12) | C29—C30—H30 | 118.9 |
F6—C3—F5 | 107.5 (11) | C36—C31—C32 | 112.8 (13) |
F6—C3—C3i | 112.2 (16) | C36—C31—P2 | 119.0 (11) |
F5—C3—C3i | 106.2 (15) | C32—C31—P2 | 112.1 (11) |
F6—C3—C2 | 108.5 (12) | C36—C31—H31 | 103.6 |
F5—C3—C2 | 105.9 (11) | C32—C31—H31 | 103.6 |
C3i—C3—C2 | 115.9 (15) | P2—C31—H31 | 103.6 |
C13—P1—C19 | 104.4 (7) | C33—C32—C31 | 113.0 (14) |
C13—P1—C7 | 104.3 (7) | C33—C32—H32A | 109.0 |
C19—P1—C7 | 104.4 (7) | C31—C32—H32A | 109.0 |
C25—P2—C37 | 104.2 (7) | C33—C32—H32B | 109.0 |
C25—P2—C31 | 102.9 (8) | C31—C32—H32B | 109.0 |
C37—P2—C31 | 105.7 (7) | H32A—C32—H32B | 107.8 |
C8—C7—C12 | 119.8 (15) | C34—C33—C32 | 115.4 (16) |
C8—C7—P1 | 116.6 (13) | C34—C33—H33A | 108.4 |
C12—C7—P1 | 123.5 (14) | C32—C33—H33A | 108.4 |
C7—C8—C9 | 119.4 (16) | C34—C33—H33B | 108.4 |
C7—C8—H8 | 120.3 | C32—C33—H33B | 108.4 |
C9—C8—H8 | 120.3 | H33A—C33—H33B | 107.5 |
C10—C9—C8 | 120.2 (17) | C35—C34—C33 | 112.3 (16) |
C10—C9—H9 | 119.9 | C35—C34—H34A | 109.1 |
C8—C9—H9 | 119.9 | C33—C34—H34A | 109.1 |
C11—C10—C9 | 120.7 (17) | C35—C34—H34B | 109.1 |
C11—C10—H10 | 119.7 | C33—C34—H34B | 109.1 |
C9—C10—H10 | 119.7 | H34A—C34—H34B | 107.9 |
C10—C11—C12 | 120.1 (18) | C34—C35—C36 | 114.1 (15) |
C10—C11—H11 | 119.9 | C34—C35—H35A | 108.7 |
C12—C11—H11 | 119.9 | C36—C35—H35A | 108.7 |
C11—C12—C7 | 119.8 (17) | C34—C35—H35B | 108.7 |
C11—C12—H12 | 120.1 | C36—C35—H35B | 108.7 |
C7—C12—H12 | 120.1 | H35A—C35—H35B | 107.6 |
C18—C13—C14 | 108.6 (13) | C35—C36—C31 | 112.3 (13) |
C18—C13—P1 | 112.0 (10) | C35—C36—H36A | 109.1 |
C14—C13—P1 | 110.6 (10) | C31—C36—H36A | 109.1 |
C18—C13—H13 | 108.5 | C35—C36—H36B | 109.1 |
C14—C13—H13 | 108.5 | C31—C36—H36B | 109.1 |
P1—C13—H13 | 108.5 | H36A—C36—H36B | 107.9 |
C15—C14—C13 | 112.7 (13) | C42—C37—C38 | 109.5 (12) |
C15—C14—H14A | 109.1 | C42—C37—P2 | 110.7 (10) |
C13—C14—H14A | 109.1 | C38—C37—P2 | 110.8 (10) |
C15—C14—H14B | 109.1 | C42—C37—H37 | 108.6 |
C13—C14—H14B | 109.1 | C38—C37—H37 | 108.6 |
H14A—C14—H14B | 107.8 | P2—C37—H37 | 108.6 |
C16—C15—C14 | 110.5 (14) | C37—C38—C39 | 111.6 (12) |
C16—C15—H15A | 109.5 | C37—C38—H38A | 109.3 |
C14—C15—H15A | 109.5 | C39—C38—H38A | 109.3 |
C16—C15—H15B | 109.5 | C37—C38—H38B | 109.3 |
C14—C15—H15B | 109.5 | C39—C38—H38B | 109.3 |
H15A—C15—H15B | 108.1 | H38A—C38—H38B | 108.0 |
C17—C16—C15 | 110.3 (14) | C40—C39—C38 | 110.6 (12) |
C17—C16—H16A | 109.6 | C40—C39—H39A | 109.5 |
C15—C16—H16A | 109.6 | C38—C39—H39A | 109.5 |
C17—C16—H16B | 109.6 | C40—C39—H39B | 109.5 |
C15—C16—H16B | 109.6 | C38—C39—H39B | 109.5 |
H16A—C16—H16B | 108.1 | H39A—C39—H39B | 108.1 |
C18—C17—C16 | 110.5 (14) | C41—C40—C39 | 113.0 (13) |
C18—C17—H17A | 109.5 | C41—C40—H40A | 109.0 |
C16—C17—H17A | 109.5 | C39—C40—H40A | 109.0 |
C18—C17—H17B | 109.5 | C41—C40—H40B | 109.0 |
C16—C17—H17B | 109.5 | C39—C40—H40B | 109.0 |
H17A—C17—H17B | 108.1 | H40A—C40—H40B | 107.8 |
C13—C18—C17 | 113.4 (14) | C42—C41—C40 | 111.0 (13) |
C13—C18—H18A | 108.9 | C42—C41—H41A | 109.4 |
C17—C18—H18A | 108.9 | C40—C41—H41A | 109.4 |
C13—C18—H18B | 108.9 | C42—C41—H41B | 109.4 |
C17—C18—H18B | 108.9 | C40—C41—H41B | 109.4 |
H18A—C18—H18B | 107.7 | H41A—C41—H41B | 108.0 |
C24—C19—C20 | 107.9 (13) | C41—C42—C37 | 113.1 (13) |
C24—C19—P1 | 115.3 (11) | C41—C42—H42A | 109.0 |
C20—C19—P1 | 110.7 (10) | C37—C42—H42A | 109.0 |
C24—C19—H19 | 107.5 | C41—C42—H42B | 109.0 |
C20—C19—H19 | 107.5 | C37—C42—H42B | 109.0 |
P1—C19—H19 | 107.5 | H42A—C42—H42B | 107.8 |
C21—C20—C19 | 112.8 (14) | F7A—C4A—F8A | 109.3 (16) |
C21—C20—H20A | 109.0 | F7A—C4A—C5A | 110 (2) |
C19—C20—H20A | 109.0 | F8A—C4A—C5A | 105 (2) |
C21—C20—H20B | 109.0 | F7A—C4A—I2A | 110.1 (18) |
C19—C20—H20B | 109.0 | F8A—C4A—I2A | 106.5 (17) |
H20A—C20—H20B | 107.8 | C5A—C4A—I2A | 115.0 (14) |
C22—C21—C20 | 111.8 (16) | F9A—C5A—F10A | 111.0 (15) |
C22—C21—H21A | 109.3 | F9A—C5A—C4A | 103.1 (18) |
C20—C21—H21A | 109.3 | F10A—C5A—C4A | 108.8 (19) |
C22—C21—H21B | 109.3 | F9A—C5A—C6A | 109.3 (18) |
C20—C21—H21B | 109.3 | F10A—C5A—C6A | 106.0 (17) |
H21A—C21—H21B | 107.9 | C4A—C5A—C6A | 118.7 (17) |
C21—C22—C23 | 111.8 (15) | F12A—C6A—F11A | 110.2 (16) |
C21—C22—H22A | 109.2 | F12A—C6A—C5A | 109.2 (19) |
C23—C22—H22A | 109.2 | F11A—C6A—C5A | 104.0 (19) |
C21—C22—H22B | 109.2 | F12A—C6A—C6Aii | 113 (3) |
C23—C22—H22B | 109.2 | F11A—C6A—C6Aii | 103 (2) |
H22A—C22—H22B | 107.9 | C5A—C6A—C6Aii | 117 (2) |
C22—C23—C24 | 111.4 (15) | F7B—C4B—F8B | 109.0 (15) |
C22—C23—H23A | 109.3 | F7B—C4B—C5B | 108.4 (18) |
C24—C23—H23A | 109.3 | F8B—C4B—C5B | 102.9 (18) |
C22—C23—H23B | 109.3 | F7B—C4B—I2B | 112.7 (15) |
C24—C23—H23B | 109.3 | F8B—C4B—I2B | 105.4 (17) |
H23A—C23—H23B | 108.0 | C5B—C4B—I2B | 117.7 (14) |
C19—C24—C23 | 112.4 (14) | F9B—C5B—F10B | 111.0 (15) |
C19—C24—H24A | 109.1 | F9B—C5B—C4B | 104.7 (18) |
C23—C24—H24A | 109.1 | F10B—C5B—C4B | 106.9 (17) |
C19—C24—H24B | 109.1 | F9B—C5B—C6B | 106.4 (17) |
C23—C24—H24B | 109.1 | F10B—C5B—C6B | 108.7 (17) |
H24A—C24—H24B | 107.8 | C4B—C5B—C6B | 119.1 (16) |
C30—C25—C26 | 117.1 (14) | F12B—C6B—C6Bii | 112 (3) |
C30—C25—P2 | 117.7 (12) | F12B—C6B—F11B | 108.9 (15) |
C26—C25—P2 | 124.9 (12) | C6Bii—C6B—F11B | 97 (3) |
C27—C26—C25 | 120.2 (16) | F12B—C6B—C5B | 112 (2) |
C27—C26—H26 | 119.9 | C6Bii—C6B—C5B | 122 (2) |
C25—C26—H26 | 119.9 | F11B—C6B—C5B | 104.3 (18) |
| | | |
F1—C1—C2—F4 | −171.4 (15) | C26—C25—C30—C29 | −8 (3) |
F2—C1—C2—F4 | −59.0 (17) | P2—C25—C30—C29 | 178.5 (13) |
I1—C1—C2—F4 | 59.5 (16) | C28—C29—C30—C25 | 8 (3) |
F1—C1—C2—F3 | 75.4 (17) | C25—P2—C31—C36 | 68.1 (14) |
F2—C1—C2—F3 | −172.2 (13) | C37—P2—C31—C36 | −40.9 (14) |
I1—C1—C2—F3 | −53.7 (16) | C25—P2—C31—C32 | −66.6 (13) |
F1—C1—C2—C3 | −48 (2) | C37—P2—C31—C32 | −175.6 (11) |
F2—C1—C2—C3 | 64.7 (19) | C36—C31—C32—C33 | 45 (2) |
I1—C1—C2—C3 | −176.7 (11) | P2—C31—C32—C33 | −177.0 (12) |
F4—C2—C3—F6 | 73.5 (14) | C31—C32—C33—C34 | −46 (2) |
F3—C2—C3—F6 | −170.2 (12) | C32—C33—C34—C35 | 49 (2) |
C1—C2—C3—F6 | −49.3 (19) | C33—C34—C35—C36 | −52 (2) |
F4—C2—C3—F5 | −171.3 (12) | C34—C35—C36—C31 | 52 (2) |
F3—C2—C3—F5 | −55.0 (14) | C32—C31—C36—C35 | −48.4 (19) |
C1—C2—C3—F5 | 66.0 (18) | P2—C31—C36—C35 | 177.2 (12) |
F4—C2—C3—C3i | −54 (2) | C25—P2—C37—C42 | 63.7 (12) |
F3—C2—C3—C3i | 62 (2) | C31—P2—C37—C42 | 171.7 (10) |
C1—C2—C3—C3i | −176.6 (17) | C25—P2—C37—C38 | −174.6 (11) |
C13—P1—C7—C8 | 146.8 (12) | C31—P2—C37—C38 | −66.5 (12) |
C19—P1—C7—C8 | −103.9 (13) | C42—C37—C38—C39 | −56.2 (16) |
C13—P1—C7—C12 | −36.7 (15) | P2—C37—C38—C39 | −178.6 (10) |
C19—P1—C7—C12 | 72.5 (14) | C37—C38—C39—C40 | 55.6 (17) |
C12—C7—C8—C9 | 2 (2) | C38—C39—C40—C41 | −53.7 (18) |
P1—C7—C8—C9 | 178.3 (12) | C39—C40—C41—C42 | 52.7 (18) |
C7—C8—C9—C10 | −3 (3) | C40—C41—C42—C37 | −54.0 (18) |
C8—C9—C10—C11 | 3 (3) | C38—C37—C42—C41 | 55.7 (17) |
C9—C10—C11—C12 | −1 (3) | P2—C37—C42—C41 | 178.2 (11) |
C10—C11—C12—C7 | 0 (3) | F7A—C4A—C5A—F9A | 63 (2) |
C8—C7—C12—C11 | 0 (2) | F8A—C4A—C5A—F9A | −178.8 (19) |
P1—C7—C12—C11 | −176.3 (12) | I2A—C4A—C5A—F9A | −62 (2) |
C19—P1—C13—C18 | 61.0 (13) | F7A—C4A—C5A—F10A | −179 (2) |
C7—P1—C13—C18 | 170.3 (11) | F8A—C4A—C5A—F10A | −61 (2) |
C19—P1—C13—C14 | −177.7 (11) | I2A—C4A—C5A—F10A | 56 (2) |
C7—P1—C13—C14 | −68.5 (12) | F7A—C4A—C5A—C6A | −58 (3) |
C18—C13—C14—C15 | −54.1 (19) | F8A—C4A—C5A—C6A | 60 (3) |
P1—C13—C14—C15 | −177.3 (12) | I2A—C4A—C5A—C6A | 177.0 (16) |
C13—C14—C15—C16 | 56 (2) | F9A—C5A—C6A—F12A | −172 (2) |
C14—C15—C16—C17 | −57 (2) | F10A—C5A—C6A—F12A | 68 (2) |
C15—C16—C17—C18 | 57 (2) | C4A—C5A—C6A—F12A | −54 (3) |
C14—C13—C18—C17 | 54.8 (19) | F9A—C5A—C6A—F11A | −54 (2) |
P1—C13—C18—C17 | 177.2 (12) | F10A—C5A—C6A—F11A | −174 (2) |
C16—C17—C18—C13 | −58 (2) | C4A—C5A—C6A—F11A | 63 (3) |
C13—P1—C19—C24 | 135.8 (12) | F9A—C5A—C6A—C6Aii | 58 (3) |
C7—P1—C19—C24 | 26.7 (14) | F10A—C5A—C6A—C6Aii | −61 (3) |
C13—P1—C19—C20 | −101.3 (12) | C4A—C5A—C6A—C6Aii | 176 (2) |
C7—P1—C19—C20 | 149.5 (12) | F7B—C4B—C5B—F9B | 68 (2) |
C24—C19—C20—C21 | −55.1 (19) | F8B—C4B—C5B—F9B | −177.0 (17) |
P1—C19—C20—C21 | 177.9 (13) | I2B—C4B—C5B—F9B | −62 (2) |
C19—C20—C21—C22 | 55 (2) | F7B—C4B—C5B—F10B | −174.6 (18) |
C20—C21—C22—C23 | −54 (2) | F8B—C4B—C5B—F10B | −59 (2) |
C21—C22—C23—C24 | 54 (2) | I2B—C4B—C5B—F10B | 56 (2) |
C20—C19—C24—C23 | 55.5 (18) | F7B—C4B—C5B—C6B | −51 (3) |
P1—C19—C24—C23 | 179.8 (12) | F8B—C4B—C5B—C6B | 64 (2) |
C22—C23—C24—C19 | −56 (2) | I2B—C4B—C5B—C6B | 179.5 (15) |
C37—P2—C25—C30 | −148.6 (13) | F9B—C5B—C6B—F12B | −162 (2) |
C31—P2—C25—C30 | 101.2 (14) | F10B—C5B—C6B—F12B | 78 (2) |
C37—P2—C25—C26 | 38.4 (16) | C4B—C5B—C6B—F12B | −44 (3) |
C31—P2—C25—C26 | −71.8 (16) | F9B—C5B—C6B—C6Bii | 63 (3) |
C30—C25—C26—C27 | 8 (2) | F10B—C5B—C6B—C6Bii | −57 (3) |
P2—C25—C26—C27 | −178.5 (13) | C4B—C5B—C6B—C6Bii | −179 (3) |
C25—C26—C27—C28 | −10 (3) | F9B—C5B—C6B—F11B | −44 (2) |
C26—C27—C28—C29 | 10 (3) | F10B—C5B—C6B—F11B | −164 (2) |
C27—C28—C29—C30 | −9 (3) | C4B—C5B—C6B—F11B | 73 (3) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C38—H38A···I2Aiii | 0.97 | 3.33 | 4.098 (15) | 138 |
C42—H42A···I2Aiv | 0.97 | 3.28 | 3.948 (14) | 127 |
Symmetry codes: (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1. |