organic compounds
3-(1H,1H,2H,2H-Perfluorooctyl)-1-vinyl-4-imidazoline-2-thione
aUniversity of Innsbruck, Faculty of Chemistry and Pharmacy, Innrain 80, 6020 Innsbruck, Austria
*Correspondence e-mail: herwig.schottenberger@uibk.ac.at
The title compound, C13H9F13N2S, was obtained by reaction of sulfur with the corresponding quaternary salt in the presence of K2CO3. The quaternary salt in turn was obtained by alkylation of 1-vinylimidazole. The contains two independent molecules with disordered fluoroalkyl chains with occupancy ratios of 0.7:0.3 and 0.57:0.43.
Keywords: fluoroalkyl; imidazole; thione; vinyl; crystal structure.
CCDC reference: 1547029
Structure description
Polyfluorinated compounds are utilized as surfactants and dispersants with numerous applications (Kovalchuk et al., 2014; Krafft & Riess, 2009). Imidazoline-2-thiones (Laus et al., 2013) are versatile building blocks whose properties have been reviewed (Trzhtsinskaya & Abramova, 1991). The key advantages of these thiones are simple synthesis and simple derivatization. The vinyl substituent makes the title molecule polymerizable, thus giving access to functionalized imidazolium-containing polymers (Anderson & Long, 2010). It was intended to combine these structural features in order to derive new materials with advantageous properties.
The most striking feature of the title molecule (Fig. 1) is the extensive disorder of the large substituent. The major component of the disordered fluoroalkyl chain adopts the typical helical conformation (Fournier et al., 2010; Jang et al., 2003) with an average CCCC twist angle (deviation from 180°) of 11°.
Specific C—F⋯F—C interactions have been identified in fluorous molecules (Baker et al., 2012; Omorodion et al., 2015). Here, a short F9D⋯F12C contact of 2.797 (6) Å is observed between the two chains (Fig. 2). In addition, C—H⋯S and C—H⋯F hydrogen bonds (Table 1) cross-link the rod-shaped molecules.
Related structures have been reported recently (Hummel et al., 2017), notably a 4-(1H,1H,2H,2H-perfluorooctyl)-1,2,4-triazolium salt (Adamer et al., 2011) and a 1-(1H,1H,2H,2H-perfluorooctyl)-1,2,3-triazole (Omorodion et al., 2015) have been described.
Synthesis and crystallization
3-(1H,1H,2H,2H-Perfluorooctyl)-1-vinylimidazolium iodide: A mixture of 1-vinylimidazole (5.0 g, 53.1 mmol) and 1H,1H,2H,2H-perfluorooctyl iodide (26.0 g, 54.9 mmol) was stirred at 70°C for 72 h. After cooling, the mixture was dissolved in MeOH (25 ml) and the product precipitated by addition of Et2O (250 ml). The product was filtered off, washed with Et2O and dried in high vacuum overnight, affording 23.0 g (76%) of colourless product; m.p. 434 K. 1H NMR (300 MHz, CD3OD): δ 9.54 (t, J = 1.9 Hz, 1H), 8.07 (t, J = 1.9 Hz, 1H), 7.93 (t, J = 1.9 Hz, 1H), 7.30 (dd, J = 15.6, 8.7 Hz, 1H), 5.98 (dd, J = 15.6, 2.8 Hz, 1H), 5.49 (dd, J = 8.7, 2.8 Hz, 1H), 4.72 (t, J = 7.2 Hz, 2H), 3.06 (tt, J = 18.0, 7.2 Hz, 2H) p.p.m. 13C NMR (75 MHz, CD3OD): δ 137.3, 129.8, 124.7, 124.4–109.0 (m, 6C), 121.1, 110.6, 43.5 (t, J = 5.3 Hz), 31.9 (t, J = 21.4 Hz) p.p.m. IR (neat): ν 3117, 2991, 1652, 1568, 1142, 1119, 1071, 1020, 735, 699, 640, 620, 524 cm−1.
3-(1H,1H,2H,2H-Perfluorooctyl)-1-vinylimidazoline-2-thione: A mixture of 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinylimidazolium iodide (80.0 g, 141 mmol), elemental sulfur (4.6 g, 144 mmol) and K2CO3 (19.9 g, 144 mmol) in MeOH (240 ml) was refluxed for 3 h. The solvent was evaporated and the residue extracted thrice with Et2O (total 700 ml). The organic phase was treated with filtered and the solvent was evaporated. The residue was dried in high vacuum overnight, affording 60.5 g (91%) of the product as an off-white powder; m.p. 359 K. Single crystals suitable for were fashioned by slow evaporation of a solution in CHCl3. 1H NMR (300 MHz, CDCl3): δ 7.53 (dd, J = 16.1, 9.0 Hz, 1H), 6.99 (d, J = 2.6 Hz, 1H), 6.75 (d, J = 2.6 Hz, 1H), 5.16 (dd, J = 16.1, 1.8 Hz, 1H), 4.96 (dd, J = 9.0, 1.8 Hz, 1H), 4.36 (t, J = 6.9 Hz, 2H), 2.70 (tt, J = 18.6, 6.9 Hz, 2H) p.p.m. 13C NMR (75 MHz, CDCl3): δ 163.4, 130.3, 124–105 (m, 6C), 118.6, 112.8, 101.4, 40.5 (t, J = 5.1 Hz), 29.6 (t, J = 21.5 Hz) p.p.m. IR (neat): ν 3133, 3104, 2995, 1643, 1234, 1182, 1139, 1118, 1077, 1062, 894, 694, 647, 509 cm−1.
Refinement
Crystal data, data collection and structure . The terminal C4F9 units of the fluoroalkyl chains of both molecules are disordered over two sets of sites, and their disorder components were found to have relative occupancies of approximately 0.7:0.3 and 0.57:0.43 in the two molecules. Occupancies were fixed at these values in the final cycles. The of the disordered fragments was carried out with distance restraints (SAME/SADI) for all chemically equivalent 1,2- and 1,3-distances. All other non-H atoms were refined anisotropically, except for those in the minor disorder component of the first molecule, which were refined isotropically.
details are summarized in Table 2
|
Structural data
CCDC reference: 1547029
https://doi.org/10.1107/S2414314617006484/sj4108sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617006484/sj4108Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617006484/sj4108Isup3.mol
Supporting information file. DOI: https://doi.org/10.1107/S2414314617006484/sj4108Isup4.cml
Data collection: APEX2 (Bruker 2014); cell
SAINT (Bruker 2014); data reduction: SAINT (Bruker 2014); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008).C13H9F13N2S | Z = 4 |
Mr = 472.28 | F(000) = 936 |
Triclinic, P1 | Dx = 1.761 Mg m−3 |
a = 7.425 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.952 (2) Å | Cell parameters from 9960 reflections |
c = 24.359 (4) Å | θ = 2.3–25.0° |
α = 85.076 (5)° | µ = 0.31 mm−1 |
β = 83.431 (5)° | T = 193 K |
γ = 88.720 (5)° | Plate, colourless |
V = 1781.4 (5) Å3 | 0.22 × 0.18 × 0.04 mm |
Bruker D8 QUEST PHOTON 100 diffractometer | 6372 independent reflections |
Radiation source: Incoatec Microfocus | 4851 reflections with I > 2σ(I) |
Multi layered optics monochromator | Rint = 0.043 |
Detector resolution: 10.4 pixels mm-1 | θmax = 25.2°, θmin = 2.2° |
φ and ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −11→11 |
Tmin = 0.449, Tmax = 0.490 | l = −29→29 |
44091 measured reflections |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.176 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0762P)2 + 3.9492P] where P = (Fo2 + 2Fc2)/3 |
6372 reflections | (Δ/σ)max < 0.001 |
679 parameters | Δρmax = 0.86 e Å−3 |
1685 restraints | Δρmin = −0.64 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.40414 (12) | 0.52354 (9) | 0.88826 (5) | 0.0443 (3) | |
N1 | 0.7681 (4) | 0.5518 (3) | 0.89347 (12) | 0.0340 (7) | |
N2 | 0.6520 (4) | 0.7057 (3) | 0.83893 (13) | 0.0370 (7) | |
C1 | 0.6094 (4) | 0.5939 (3) | 0.87344 (15) | 0.0327 (7) | |
C2 | 0.9074 (5) | 0.6388 (4) | 0.87116 (17) | 0.0441 (9) | |
H2 | 1.0305 | 0.6323 | 0.8783 | 0.053* | |
C3 | 0.8345 (5) | 0.7331 (4) | 0.83786 (18) | 0.0462 (10) | |
H3 | 0.8969 | 0.8063 | 0.8170 | 0.055* | |
C4 | 0.7800 (5) | 0.4409 (4) | 0.93323 (15) | 0.0394 (8) | |
H4 | 0.6720 | 0.3928 | 0.9457 | 0.047* | |
C5 | 0.9282 (5) | 0.3992 (4) | 0.95423 (17) | 0.0476 (10) | |
H5A | 1.0391 | 0.4446 | 0.9428 | 0.057* | |
H5B | 0.9247 | 0.3235 | 0.9809 | 0.057* | |
C6 | 0.5221 (5) | 0.7852 (4) | 0.80941 (15) | 0.0408 (9) | |
H6A | 0.5709 | 0.8765 | 0.7983 | 0.049* | |
H6B | 0.4082 | 0.7948 | 0.8343 | 0.049* | |
C7 | 0.4820 (5) | 0.7189 (4) | 0.75785 (15) | 0.0453 (9) | |
H7A | 0.5961 | 0.7096 | 0.7331 | 0.054* | |
H7B | 0.4341 | 0.6274 | 0.7691 | 0.054* | |
C8 | 0.3448 (4) | 0.8008 (3) | 0.72632 (13) | 0.0406 (8) | |
F8A | 0.1985 (3) | 0.8280 (3) | 0.76251 (10) | 0.0623 (7) | |
F8B | 0.4136 (4) | 0.9224 (2) | 0.70743 (11) | 0.0669 (7) | |
C9 | 0.2799 (5) | 0.7328 (3) | 0.67842 (13) | 0.0449 (9) | |
F9A | 0.2100 (5) | 0.6147 (3) | 0.69848 (12) | 0.0874 (10) | |
F9B | 0.4259 (4) | 0.7087 (3) | 0.64324 (12) | 0.0849 (10) | |
C10 | 0.1424 (5) | 0.8101 (4) | 0.64541 (14) | 0.0553 (11) | |
F10A | 0.0164 (6) | 0.8699 (5) | 0.67659 (17) | 0.0861 (16) | 0.7 |
F10B | 0.2389 (7) | 0.9168 (4) | 0.6158 (2) | 0.0916 (17) | 0.7 |
C11 | 0.0614 (8) | 0.7358 (6) | 0.6021 (2) | 0.053 (3) | 0.7 |
F11A | 0.1752 (8) | 0.6416 (6) | 0.5817 (2) | 0.0975 (19) | 0.7 |
F11B | −0.0764 (8) | 0.6655 (5) | 0.6313 (2) | 0.111 (2) | 0.7 |
C12 | −0.0167 (8) | 0.8189 (5) | 0.5552 (2) | 0.070 (2) | 0.7 |
F12A | −0.0968 (7) | 0.9311 (4) | 0.57322 (19) | 0.0761 (14) | 0.7 |
F12B | 0.1245 (7) | 0.8610 (6) | 0.51811 (19) | 0.1042 (17) | 0.7 |
C13 | −0.1448 (7) | 0.7494 (6) | 0.5229 (2) | 0.056 (3) | 0.7 |
F13A | −0.0747 (10) | 0.6335 (5) | 0.5060 (3) | 0.092 (2) | 0.7 |
F13B | −0.3064 (7) | 0.7206 (7) | 0.5497 (2) | 0.121 (2) | 0.7 |
F13C | −0.1745 (9) | 0.8273 (5) | 0.47815 (19) | 0.1055 (17) | 0.7 |
F10E | 0.1515 (15) | 0.9404 (7) | 0.6429 (5) | 0.075 (3)* | 0.3 |
F10F | −0.0086 (12) | 0.7804 (11) | 0.6841 (4) | 0.077 (3)* | 0.3 |
C11A | 0.0840 (11) | 0.7482 (11) | 0.5963 (3) | 0.061 (9)* | 0.3 |
F11E | 0.2058 (11) | 0.7957 (8) | 0.5557 (3) | 0.061 (2)* | 0.3 |
F11F | 0.1012 (18) | 0.6148 (10) | 0.6003 (6) | 0.071 (4)* | 0.3 |
C12A | −0.1085 (10) | 0.7732 (12) | 0.5828 (4) | 0.059 (4)* | 0.3 |
F12E | −0.170 (2) | 0.8957 (10) | 0.5935 (6) | 0.102 (6)* | 0.3 |
F12F | −0.2213 (18) | 0.6889 (10) | 0.6146 (5) | 0.104 (4)* | 0.3 |
C13A | −0.1427 (17) | 0.7621 (17) | 0.5233 (4) | 0.19 (3)* | 0.3 |
F13G | −0.0388 (17) | 0.8340 (14) | 0.4839 (6) | 0.107 (4)* | 0.3 |
F13H | −0.3131 (15) | 0.7907 (16) | 0.5150 (7) | 0.124 (5)* | 0.3 |
F13I | −0.114 (3) | 0.6331 (14) | 0.5142 (13) | 0.148 (12)* | 0.3 |
S1' | 1.14881 (11) | −0.08928 (10) | 0.93033 (4) | 0.0420 (3) | |
N1' | 1.5143 (3) | −0.0605 (3) | 0.93303 (11) | 0.0304 (6) | |
N2' | 1.3884 (4) | 0.1043 (3) | 0.88608 (12) | 0.0320 (6) | |
C1' | 1.3513 (4) | −0.0151 (3) | 0.91672 (14) | 0.0302 (7) | |
C2' | 1.6495 (4) | 0.0316 (4) | 0.91273 (15) | 0.0380 (8) | |
H2' | 1.7741 | 0.0238 | 0.9182 | 0.046* | |
C3' | 1.5710 (5) | 0.1328 (4) | 0.88420 (16) | 0.0396 (8) | |
H3' | 1.6299 | 0.2106 | 0.8658 | 0.048* | |
C4' | 1.5358 (4) | −0.1827 (3) | 0.96593 (14) | 0.0338 (8) | |
H4' | 1.4367 | −0.2430 | 0.9717 | 0.041* | |
C5' | 1.6825 (5) | −0.2188 (4) | 0.98903 (16) | 0.0414 (9) | |
H5'1 | 1.7843 | −0.1611 | 0.9842 | 0.050* | |
H5'2 | 1.6869 | −0.3027 | 1.0106 | 0.050* | |
C6' | 1.2529 (5) | 0.1929 (3) | 0.86435 (14) | 0.0365 (8) | |
H6'1 | 1.3028 | 0.2848 | 0.8562 | 0.044* | |
H6'2 | 1.1469 | 0.1976 | 0.8928 | 0.044* | |
C7' | 1.1912 (5) | 0.1455 (3) | 0.81163 (14) | 0.0385 (8) | |
H7'1 | 1.2986 | 0.1317 | 0.7845 | 0.046* | |
H7'2 | 1.1295 | 0.0579 | 0.8205 | 0.046* | |
C8' | 1.0628 (4) | 0.2470 (3) | 0.78577 (12) | 0.0365 (8) | |
F8C | 0.9324 (3) | 0.2841 (2) | 0.82534 (9) | 0.0545 (6) | |
F8D | 1.1538 (3) | 0.3607 (2) | 0.76671 (10) | 0.0587 (7) | |
C9' | 0.9688 (4) | 0.1972 (3) | 0.73893 (12) | 0.0379 (8) | |
F9C | 0.8781 (4) | 0.0847 (2) | 0.75896 (11) | 0.0676 (8) | |
F9D | 1.0966 (3) | 0.1600 (3) | 0.69965 (10) | 0.0686 (8) | |
C10' | 0.8368 (5) | 0.2946 (4) | 0.71214 (14) | 0.0537 (11) | |
F10C | 0.6801 (6) | 0.2835 (7) | 0.75193 (19) | 0.0753 (17) | 0.57 |
F10D | 0.8782 (11) | 0.4206 (5) | 0.7110 (4) | 0.096 (3) | 0.57 |
C11' | 0.7630 (9) | 0.2554 (8) | 0.6605 (2) | 0.044 (3) | 0.57 |
F11C | 0.7459 (16) | 0.1231 (8) | 0.6598 (7) | 0.091 (3) | 0.57 |
F11D | 0.8918 (6) | 0.2935 (8) | 0.6201 (2) | 0.102 (2) | 0.57 |
C12' | 0.5851 (8) | 0.3183 (7) | 0.6460 (2) | 0.053 (2) | 0.57 |
F12C | 0.4525 (7) | 0.2527 (9) | 0.6777 (3) | 0.128 (3) | 0.57 |
F12D | 0.5822 (18) | 0.4423 (8) | 0.6606 (6) | 0.154 (7) | 0.57 |
C13' | 0.5365 (10) | 0.3114 (10) | 0.5882 (3) | 0.120 (6) | 0.57 |
F13D | 0.5385 (15) | 0.1849 (7) | 0.5766 (5) | 0.163 (9) | 0.57 |
F13E | 0.6497 (11) | 0.3793 (11) | 0.5506 (3) | 0.159 (4) | 0.57 |
F13F | 0.3713 (9) | 0.3592 (9) | 0.5831 (4) | 0.105 (2) | 0.57 |
F10G | 0.9634 (10) | 0.3818 (7) | 0.6787 (3) | 0.082 (3) | 0.43 |
F10H | 0.7523 (13) | 0.3770 (10) | 0.7450 (4) | 0.103 (4) | 0.43 |
C11B | 0.7302 (11) | 0.2438 (9) | 0.6693 (3) | 0.056 (5) | 0.43 |
F11G | 0.5858 (10) | 0.1941 (10) | 0.7016 (3) | 0.106 (3) | 0.43 |
F11H | 0.8144 (19) | 0.1406 (15) | 0.6462 (8) | 0.089 (5) | 0.43 |
C12B | 0.6696 (11) | 0.3427 (9) | 0.6244 (3) | 0.068 (4) | 0.43 |
F12G | 0.8066 (11) | 0.3687 (11) | 0.5844 (3) | 0.117 (3) | 0.43 |
F12H | 0.6144 (17) | 0.4608 (11) | 0.6416 (6) | 0.091 (4) | 0.43 |
C13B | 0.5192 (11) | 0.3016 (10) | 0.5930 (3) | 0.074 (6) | 0.43 |
F13J | 0.567 (2) | 0.1878 (12) | 0.5705 (6) | 0.159 (11) | 0.43 |
F13K | 0.4823 (18) | 0.3900 (11) | 0.5520 (4) | 0.126 (4) | 0.43 |
F13L | 0.3649 (11) | 0.2818 (18) | 0.6255 (4) | 0.215 (10) | 0.43 |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0262 (5) | 0.0372 (5) | 0.0702 (7) | −0.0085 (4) | −0.0110 (4) | 0.0010 (4) |
N1 | 0.0251 (14) | 0.0314 (15) | 0.0463 (17) | −0.0011 (11) | −0.0066 (12) | −0.0047 (13) |
N2 | 0.0303 (15) | 0.0325 (16) | 0.0481 (18) | −0.0015 (12) | −0.0055 (13) | −0.0010 (13) |
C1 | 0.0276 (17) | 0.0286 (17) | 0.043 (2) | −0.0019 (13) | −0.0062 (14) | −0.0072 (15) |
C2 | 0.0226 (17) | 0.046 (2) | 0.063 (3) | −0.0060 (15) | −0.0010 (17) | −0.0026 (19) |
C3 | 0.0284 (18) | 0.044 (2) | 0.063 (3) | −0.0086 (16) | 0.0035 (17) | 0.0045 (19) |
C4 | 0.0344 (19) | 0.038 (2) | 0.046 (2) | −0.0018 (15) | −0.0068 (16) | −0.0021 (16) |
C5 | 0.040 (2) | 0.050 (2) | 0.053 (2) | 0.0072 (18) | −0.0094 (18) | −0.0008 (19) |
C6 | 0.041 (2) | 0.0322 (19) | 0.050 (2) | 0.0037 (15) | −0.0080 (17) | −0.0012 (16) |
C7 | 0.047 (2) | 0.040 (2) | 0.048 (2) | 0.0122 (17) | −0.0056 (18) | −0.0048 (17) |
C8 | 0.042 (2) | 0.0345 (19) | 0.044 (2) | 0.0041 (16) | −0.0007 (17) | −0.0015 (16) |
F8A | 0.0455 (13) | 0.0904 (19) | 0.0524 (14) | 0.0194 (13) | −0.0045 (11) | −0.0209 (13) |
F8B | 0.0813 (18) | 0.0425 (14) | 0.0796 (18) | −0.0141 (12) | −0.0314 (15) | 0.0126 (12) |
C9 | 0.055 (2) | 0.035 (2) | 0.043 (2) | 0.0083 (17) | −0.0015 (18) | −0.0031 (16) |
F9A | 0.148 (3) | 0.0412 (14) | 0.0799 (19) | −0.0284 (16) | −0.053 (2) | 0.0146 (13) |
F9B | 0.0703 (19) | 0.120 (3) | 0.0662 (18) | 0.0339 (18) | −0.0012 (15) | −0.0359 (17) |
C10 | 0.064 (3) | 0.047 (2) | 0.058 (3) | 0.006 (2) | −0.016 (2) | −0.007 (2) |
F10A | 0.099 (3) | 0.091 (3) | 0.082 (3) | 0.064 (3) | −0.049 (3) | −0.051 (3) |
F10B | 0.122 (4) | 0.061 (3) | 0.096 (4) | −0.036 (3) | −0.058 (3) | 0.037 (2) |
C11 | 0.079 (6) | 0.033 (4) | 0.048 (4) | 0.007 (3) | −0.012 (3) | −0.005 (3) |
F11A | 0.126 (5) | 0.089 (4) | 0.091 (4) | 0.053 (4) | −0.047 (4) | −0.054 (3) |
F11B | 0.149 (5) | 0.107 (4) | 0.081 (3) | −0.065 (4) | −0.041 (3) | 0.030 (3) |
C12 | 0.095 (6) | 0.060 (4) | 0.059 (4) | 0.000 (4) | −0.022 (4) | −0.001 (3) |
F12A | 0.102 (4) | 0.059 (2) | 0.075 (3) | 0.033 (3) | −0.041 (3) | −0.015 (2) |
F12B | 0.102 (4) | 0.127 (4) | 0.080 (3) | −0.033 (3) | −0.013 (3) | 0.022 (3) |
C13 | 0.064 (5) | 0.063 (5) | 0.046 (4) | 0.008 (3) | −0.025 (3) | −0.010 (3) |
F13A | 0.116 (5) | 0.085 (4) | 0.089 (4) | 0.007 (3) | −0.042 (3) | −0.044 (3) |
F13B | 0.086 (4) | 0.164 (6) | 0.112 (5) | −0.026 (4) | −0.003 (3) | −0.006 (4) |
F13C | 0.133 (5) | 0.100 (4) | 0.087 (4) | −0.020 (3) | −0.039 (3) | 0.013 (3) |
S1' | 0.0220 (4) | 0.0404 (5) | 0.0627 (6) | −0.0056 (4) | −0.0066 (4) | 0.0047 (4) |
N1' | 0.0218 (13) | 0.0340 (15) | 0.0357 (16) | −0.0020 (11) | −0.0032 (11) | −0.0049 (12) |
N2' | 0.0275 (14) | 0.0293 (15) | 0.0398 (16) | −0.0032 (11) | −0.0055 (12) | −0.0034 (12) |
C1' | 0.0248 (16) | 0.0299 (17) | 0.0370 (19) | −0.0010 (13) | −0.0055 (14) | −0.0071 (14) |
C2' | 0.0228 (17) | 0.042 (2) | 0.050 (2) | −0.0082 (15) | −0.0018 (15) | −0.0045 (17) |
C3' | 0.0302 (18) | 0.036 (2) | 0.052 (2) | −0.0099 (15) | −0.0017 (16) | −0.0023 (17) |
C4' | 0.0279 (17) | 0.0335 (18) | 0.040 (2) | −0.0002 (14) | −0.0042 (15) | −0.0028 (15) |
C5' | 0.0353 (19) | 0.043 (2) | 0.047 (2) | 0.0026 (16) | −0.0072 (16) | −0.0031 (17) |
C6' | 0.0377 (19) | 0.0275 (17) | 0.045 (2) | 0.0031 (14) | −0.0091 (16) | −0.0043 (15) |
C7' | 0.041 (2) | 0.0318 (19) | 0.043 (2) | 0.0041 (15) | −0.0080 (16) | −0.0044 (15) |
C8' | 0.0368 (19) | 0.0301 (18) | 0.041 (2) | −0.0023 (15) | −0.0009 (16) | −0.0010 (15) |
F8C | 0.0446 (13) | 0.0722 (16) | 0.0489 (13) | 0.0176 (11) | −0.0077 (10) | −0.0196 (12) |
F8D | 0.0648 (15) | 0.0399 (13) | 0.0732 (17) | −0.0168 (11) | −0.0268 (13) | 0.0135 (11) |
C9' | 0.0382 (19) | 0.0344 (19) | 0.040 (2) | −0.0004 (15) | −0.0008 (16) | −0.0021 (15) |
F9C | 0.0842 (19) | 0.0488 (14) | 0.0737 (17) | −0.0302 (13) | −0.0348 (15) | 0.0141 (12) |
F9D | 0.0536 (15) | 0.100 (2) | 0.0551 (15) | 0.0205 (14) | −0.0059 (12) | −0.0324 (14) |
C10' | 0.061 (3) | 0.043 (2) | 0.060 (3) | 0.009 (2) | −0.021 (2) | −0.009 (2) |
F10C | 0.054 (3) | 0.131 (5) | 0.041 (3) | 0.040 (3) | −0.006 (2) | −0.023 (3) |
F10D | 0.142 (8) | 0.035 (3) | 0.129 (8) | 0.021 (4) | −0.090 (6) | −0.018 (4) |
C11' | 0.042 (5) | 0.056 (7) | 0.035 (5) | 0.005 (5) | −0.006 (4) | −0.005 (5) |
F11C | 0.111 (9) | 0.048 (4) | 0.131 (9) | 0.019 (4) | −0.072 (7) | −0.029 (4) |
F11D | 0.048 (3) | 0.211 (8) | 0.040 (3) | −0.001 (4) | 0.001 (2) | 0.013 (4) |
C12' | 0.041 (5) | 0.067 (6) | 0.053 (5) | 0.016 (4) | −0.009 (4) | −0.010 (4) |
F12C | 0.036 (3) | 0.262 (10) | 0.082 (4) | −0.001 (4) | −0.007 (3) | 0.013 (5) |
F12D | 0.239 (13) | 0.113 (9) | 0.140 (11) | 0.128 (9) | −0.136 (9) | −0.063 (8) |
C13' | 0.109 (11) | 0.181 (13) | 0.078 (10) | 0.030 (10) | −0.070 (8) | 0.023 (10) |
F13D | 0.202 (15) | 0.092 (7) | 0.238 (17) | 0.035 (7) | −0.185 (14) | −0.050 (8) |
F13E | 0.143 (7) | 0.262 (11) | 0.070 (4) | 0.013 (7) | −0.046 (5) | 0.043 (5) |
F13F | 0.086 (5) | 0.141 (6) | 0.101 (6) | 0.042 (5) | −0.057 (4) | −0.028 (5) |
F10G | 0.100 (6) | 0.035 (4) | 0.121 (7) | −0.027 (4) | −0.074 (5) | 0.030 (4) |
F10H | 0.124 (9) | 0.089 (8) | 0.116 (9) | 0.070 (7) | −0.075 (7) | −0.064 (7) |
C11B | 0.055 (8) | 0.055 (11) | 0.060 (9) | −0.004 (7) | −0.012 (7) | −0.002 (7) |
F11G | 0.075 (5) | 0.158 (8) | 0.085 (5) | −0.063 (5) | −0.026 (4) | 0.041 (5) |
F11H | 0.087 (9) | 0.098 (9) | 0.102 (9) | 0.048 (7) | −0.058 (7) | −0.070 (8) |
C12B | 0.064 (9) | 0.082 (10) | 0.055 (8) | 0.005 (7) | −0.004 (7) | 0.000 (7) |
F12G | 0.090 (6) | 0.179 (9) | 0.076 (5) | −0.022 (6) | −0.016 (5) | 0.034 (6) |
F12H | 0.132 (8) | 0.054 (5) | 0.102 (9) | 0.018 (6) | −0.085 (6) | −0.007 (5) |
C13B | 0.065 (11) | 0.070 (10) | 0.090 (15) | −0.007 (9) | −0.012 (10) | −0.027 (9) |
F13J | 0.137 (14) | 0.26 (3) | 0.102 (11) | 0.050 (14) | −0.040 (9) | −0.115 (14) |
F13K | 0.130 (10) | 0.136 (9) | 0.117 (9) | −0.001 (8) | −0.071 (8) | 0.036 (7) |
F13L | 0.062 (6) | 0.44 (3) | 0.131 (10) | −0.063 (10) | −0.036 (6) | 0.087 (14) |
S1—C1 | 1.679 (3) | S1'—C1' | 1.676 (3) |
N1—C1 | 1.370 (4) | N1'—C1' | 1.372 (4) |
N1—C2 | 1.395 (4) | N1'—C2' | 1.393 (4) |
N1—C4 | 1.412 (5) | N1'—C4' | 1.415 (4) |
N2—C1 | 1.357 (4) | N2'—C1' | 1.363 (4) |
N2—C3 | 1.385 (5) | N2'—C3' | 1.386 (4) |
N2—C6 | 1.449 (4) | N2'—C6' | 1.440 (4) |
C2—C3 | 1.333 (6) | C2'—C3' | 1.335 (5) |
C2—H2 | 0.9500 | C2'—H2' | 0.9500 |
C3—H3 | 0.9500 | C3'—H3' | 0.9500 |
C4—C5 | 1.310 (5) | C4'—C5' | 1.311 (5) |
C4—H4 | 0.9500 | C4'—H4' | 0.9500 |
C5—H5A | 0.9500 | C5'—H5'1 | 0.9500 |
C5—H5B | 0.9500 | C5'—H5'2 | 0.9500 |
C6—C7 | 1.529 (4) | C6'—C7' | 1.526 (4) |
C6—H6A | 0.9900 | C6'—H6'1 | 0.9900 |
C6—H6B | 0.9900 | C6'—H6'2 | 0.9900 |
C7—C8 | 1.525 (4) | C7'—C8' | 1.521 (4) |
C7—H7A | 0.9900 | C7'—H7'1 | 0.9900 |
C7—H7B | 0.9900 | C7'—H7'2 | 0.9900 |
C8—F8B | 1.348 (4) | C8'—F8D | 1.350 (3) |
C8—F8A | 1.356 (4) | C8'—F8C | 1.354 (4) |
C8—C9 | 1.527 (4) | C8'—C9' | 1.526 (4) |
C9—F9A | 1.327 (4) | C9'—F9D | 1.338 (4) |
C9—F9B | 1.333 (4) | C9'—F9C | 1.346 (4) |
C9—C10 | 1.525 (4) | C9'—C10' | 1.523 (4) |
C10—F10E | 1.296 (6) | C10'—F10D | 1.295 (5) |
C10—F10A | 1.302 (4) | C10'—F10H | 1.297 (6) |
C10—F10B | 1.394 (5) | C10'—F10C | 1.426 (5) |
C10—F10F | 1.400 (6) | C10'—F10G | 1.429 (6) |
C10—C11A | 1.502 (6) | C10'—C11B | 1.506 (6) |
C10—C11 | 1.524 (5) | C10'—C11' | 1.512 (6) |
C11—F11A | 1.337 (5) | C11'—F11D | 1.327 (7) |
C11—F11B | 1.350 (6) | C11'—F11C | 1.328 (6) |
C11—C12 | 1.514 (5) | C11'—C12' | 1.514 (6) |
C12—F12A | 1.337 (5) | C12'—F12D | 1.313 (6) |
C12—F12B | 1.352 (6) | C12'—F12C | 1.328 (6) |
C12—C13 | 1.515 (6) | C12'—C13' | 1.500 (6) |
C13—F13C | 1.320 (5) | C13'—F13D | 1.313 (7) |
C13—F13B | 1.324 (5) | C13'—F13F | 1.321 (6) |
C13—F13A | 1.333 (5) | C13'—F13E | 1.321 (7) |
C11A—F11E | 1.325 (7) | C11B—F11H | 1.324 (7) |
C11A—F11F | 1.327 (7) | C11B—F11G | 1.333 (7) |
C11A—C12A | 1.514 (7) | C11B—C12B | 1.508 (6) |
C12A—F12E | 1.328 (7) | C12B—F12H | 1.322 (7) |
C12A—F12F | 1.333 (7) | C12B—F12G | 1.339 (7) |
C12A—C13A | 1.514 (7) | C12B—C13B | 1.507 (6) |
C13A—F13H | 1.324 (7) | C13B—F13K | 1.322 (6) |
C13A—F13G | 1.329 (7) | C13B—F13J | 1.323 (7) |
C13A—F13I | 1.330 (7) | C13B—F13L | 1.324 (7) |
C1—N1—C2 | 109.7 (3) | C1'—N1'—C2' | 109.8 (3) |
C1—N1—C4 | 123.3 (3) | C1'—N1'—C4' | 123.5 (3) |
C2—N1—C4 | 126.9 (3) | C2'—N1'—C4' | 126.7 (3) |
C1—N2—C3 | 109.8 (3) | C1'—N2'—C3' | 109.9 (3) |
C1—N2—C6 | 124.1 (3) | C1'—N2'—C6' | 124.2 (3) |
C3—N2—C6 | 126.1 (3) | C3'—N2'—C6' | 125.6 (3) |
N2—C1—N1 | 105.5 (3) | N2'—C1'—N1' | 105.2 (3) |
N2—C1—S1 | 126.7 (3) | N2'—C1'—S1' | 126.7 (2) |
N1—C1—S1 | 127.8 (3) | N1'—C1'—S1' | 128.1 (3) |
C3—C2—N1 | 106.8 (3) | C3'—C2'—N1' | 107.1 (3) |
C3—C2—H2 | 126.6 | C3'—C2'—H2' | 126.4 |
N1—C2—H2 | 126.6 | N1'—C2'—H2' | 126.4 |
C2—C3—N2 | 108.2 (3) | C2'—C3'—N2' | 108.0 (3) |
C2—C3—H3 | 125.9 | C2'—C3'—H3' | 126.0 |
N2—C3—H3 | 125.9 | N2'—C3'—H3' | 126.0 |
C5—C4—N1 | 125.2 (4) | C5'—C4'—N1' | 124.8 (3) |
C5—C4—H4 | 117.4 | C5'—C4'—H4' | 117.6 |
N1—C4—H4 | 117.4 | N1'—C4'—H4' | 117.6 |
C4—C5—H5A | 120.0 | C4'—C5'—H5'1 | 120.0 |
C4—C5—H5B | 120.0 | C4'—C5'—H5'2 | 120.0 |
H5A—C5—H5B | 120.0 | H5'1—C5'—H5'2 | 120.0 |
N2—C6—C7 | 111.1 (3) | N2'—C6'—C7' | 112.1 (3) |
N2—C6—H6A | 109.4 | N2'—C6'—H6'1 | 109.2 |
C7—C6—H6A | 109.4 | C7'—C6'—H6'1 | 109.2 |
N2—C6—H6B | 109.4 | N2'—C6'—H6'2 | 109.2 |
C7—C6—H6B | 109.4 | C7'—C6'—H6'2 | 109.2 |
H6A—C6—H6B | 108.0 | H6'1—C6'—H6'2 | 107.9 |
C8—C7—C6 | 111.9 (3) | C8'—C7'—C6' | 111.6 (3) |
C8—C7—H7A | 109.2 | C8'—C7'—H7'1 | 109.3 |
C6—C7—H7A | 109.2 | C6'—C7'—H7'1 | 109.3 |
C8—C7—H7B | 109.2 | C8'—C7'—H7'2 | 109.3 |
C6—C7—H7B | 109.2 | C6'—C7'—H7'2 | 109.3 |
H7A—C7—H7B | 107.9 | H7'1—C7'—H7'2 | 108.0 |
F8B—C8—F8A | 104.9 (3) | F8D—C8'—F8C | 105.8 (3) |
F8B—C8—C7 | 109.9 (3) | F8D—C8'—C7' | 109.4 (3) |
F8A—C8—C7 | 108.6 (3) | F8C—C8'—C7' | 109.5 (3) |
F8B—C8—C9 | 109.5 (3) | F8D—C8'—C9' | 109.0 (2) |
F8A—C8—C9 | 108.5 (3) | F8C—C8'—C9' | 107.7 (2) |
C7—C8—C9 | 115.0 (3) | C7'—C8'—C9' | 115.0 (3) |
F9A—C9—F9B | 107.7 (3) | F9D—C9'—F9C | 106.3 (3) |
F9A—C9—C10 | 108.6 (3) | F9D—C9'—C10' | 108.9 (3) |
F9B—C9—C10 | 107.7 (3) | F9C—C9'—C10' | 108.0 (3) |
F9A—C9—C8 | 108.1 (3) | F9D—C9'—C8' | 108.2 (2) |
F9B—C9—C8 | 107.2 (3) | F9C—C9'—C8' | 107.9 (2) |
C10—C9—C8 | 117.3 (3) | C10'—C9'—C8' | 117.0 (3) |
F10A—C10—F10B | 103.6 (4) | F10D—C10'—F10C | 102.9 (5) |
F10E—C10—F10F | 103.6 (5) | F10H—C10'—F10G | 101.8 (5) |
F10E—C10—C11A | 117.7 (7) | F10H—C10'—C11B | 116.3 (6) |
F10F—C10—C11A | 99.7 (6) | F10G—C10'—C11B | 101.8 (5) |
F10A—C10—C11 | 111.0 (4) | F10D—C10'—C11' | 114.7 (5) |
F10B—C10—C11 | 105.5 (4) | F10C—C10'—C11' | 101.8 (4) |
F10E—C10—C9 | 115.7 (6) | F10D—C10'—C9' | 114.5 (4) |
F10A—C10—C9 | 113.1 (3) | F10H—C10'—C9' | 114.9 (4) |
F10B—C10—C9 | 105.0 (3) | F10C—C10'—C9' | 101.8 (3) |
F10F—C10—C9 | 96.0 (5) | F10G—C10'—C9' | 99.4 (4) |
C11A—C10—C9 | 118.1 (4) | C11B—C10'—C9' | 118.0 (4) |
C11—C10—C9 | 117.1 (3) | C11'—C10'—C9' | 117.9 (4) |
F11A—C11—F11B | 104.6 (5) | F11D—C11'—F11C | 106.8 (6) |
F11A—C11—C12 | 110.0 (5) | F11D—C11'—C10' | 103.5 (5) |
F11B—C11—C12 | 107.1 (5) | F11C—C11'—C10' | 112.9 (9) |
F11A—C11—C10 | 111.7 (4) | F11D—C11'—C12' | 108.3 (5) |
F11B—C11—C10 | 104.1 (4) | F11C—C11'—C12' | 106.4 (8) |
C12—C11—C10 | 118.1 (4) | C10'—C11'—C12' | 118.3 (5) |
F12A—C12—F12B | 105.7 (5) | F12D—C12'—F12C | 107.2 (6) |
F12A—C12—C11 | 110.6 (4) | F12D—C12'—C13' | 112.4 (9) |
F12B—C12—C11 | 107.1 (5) | F12C—C12'—C13' | 104.0 (6) |
F12A—C12—C13 | 109.1 (5) | F12D—C12'—C11' | 106.6 (7) |
F12B—C12—C13 | 106.2 (4) | F12C—C12'—C11' | 107.6 (6) |
C11—C12—C13 | 117.4 (4) | C13'—C12'—C11' | 118.4 (5) |
F13C—C13—F13B | 106.1 (4) | F13D—C13'—F13F | 107.0 (6) |
F13C—C13—F13A | 107.2 (5) | F13D—C13'—F13E | 108.4 (7) |
F13B—C13—F13A | 106.3 (5) | F13F—C13'—F13E | 107.8 (6) |
F13C—C13—C12 | 109.5 (5) | F13D—C13'—C12' | 109.4 (8) |
F13B—C13—C12 | 115.6 (5) | F13F—C13'—C12' | 111.6 (7) |
F13A—C13—C12 | 111.6 (5) | F13E—C13'—C12' | 112.5 (7) |
F11E—C11A—F11F | 107.3 (7) | F11H—C11B—F11G | 106.7 (7) |
F11E—C11A—C10 | 102.0 (7) | F11H—C11B—C10' | 111.1 (10) |
F11F—C11A—C10 | 112.6 (9) | F11G—C11B—C10' | 100.5 (6) |
F11E—C11A—C12A | 112.4 (7) | F11H—C11B—C12B | 109.1 (11) |
F11F—C11A—C12A | 103.9 (10) | F11G—C11B—C12B | 109.6 (7) |
C10—C11A—C12A | 118.4 (7) | C10'—C11B—C12B | 118.9 (7) |
F12E—C12A—F12F | 105.0 (7) | F12H—C12B—F12G | 106.1 (7) |
F12E—C12A—C11A | 112.6 (10) | F12H—C12B—C13B | 103.9 (9) |
F12F—C12A—C11A | 110.3 (10) | F12G—C12B—C13B | 103.1 (7) |
F12E—C12A—C13A | 104.1 (12) | F12H—C12B—C11B | 114.2 (10) |
F12F—C12A—C13A | 107.2 (10) | F12G—C12B—C11B | 110.2 (7) |
C11A—C12A—C13A | 116.8 (7) | C13B—C12B—C11B | 118.1 (6) |
F13H—C13A—F13G | 106.8 (7) | F13K—C13B—F13J | 106.7 (6) |
F13H—C13A—F13I | 106.8 (7) | F13K—C13B—F13L | 106.2 (6) |
F13G—C13A—F13I | 106.8 (8) | F13J—C13B—F13L | 108.4 (7) |
F13H—C13A—C12A | 112.5 (12) | F13K—C13B—C12B | 114.3 (8) |
F13G—C13A—C12A | 117.5 (12) | F13J—C13B—C12B | 108.8 (10) |
F13I—C13A—C12A | 105.7 (18) | F13L—C13B—C12B | 112.2 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···F8Ai | 0.95 | 2.47 | 3.201 (5) | 133 |
C3′—H3′···F8Ci | 0.95 | 2.45 | 3.233 (4) | 140 |
C6′—H6′1···S1i | 0.99 | 2.71 | 3.616 (3) | 152 |
C4—H4···S1 | 0.95 | 2.80 | 3.179 (4) | 105 |
C4′—H4′···S1′ | 0.95 | 2.83 | 3.191 (3) | 104 |
C7′—H7′2···F9C | 0.99 | 2.52 | 2.880 (5) | 101 |
C7—H7B···F9A | 0.99 | 2.54 | 2.875 (5) | 100 |
Symmetry code: (i) x+1, y, z. |
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