Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101019084/bk1616sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101019084/bk1616Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101019084/bk1616IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101019084/bk1616IIIsup4.hkl |
CCDC references: 182042; 182043; 182044
The three title complexes were prepared as previously described by Hinkle et al. (1999) and were crystallized from CH2Cl2 solutions layered with pentane in 1-dram vials. These vials were kept at 258 K for 24–72 h before the solvent was decanted.
H atoms were treated as riding, with C—H = 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C). Are these the correct constraints? For (I), the CF3 group was found to be rotationally disordered. Thus, two sets of three F atoms each (with occupancy factors of 60% for F1A, F2A and F3A, and 40% for F1B, F2B and F3B) were refined. For this compound, the terminal C atom of the 2-methyl-1-butenyl group was determined to be disordered over two positions (C5A 55% and C5B 45%). The largest residual peaks of electron density (1.40 and -1.16 e Å-3) were found within 0.81 Å of the I atom. For (II), the largest residual peaks of electron density (2.07 and -1.21 e Å-3) were found within 0.94 Å of one of the I atoms (I1). For (III), one of the CF3 groups on the phenyl ring attached to I1 was found to be rotationally disordered. Thus, two sets of three F atoms each (with occupancy factors of 70% for F11A, F12A and F13A, and 30% for F11B, F12B and F13B) were refined. Also for (III), both of the CF3 groups on the phenyl ring attached to I2 displayed a rotational disorder, such that each was refined with two sets of three F atoms (F21A, F22A and F23A, and F21B, F22B and F23B attached to C27, and F24A, F25A and F26A, and F24B, F25B and F26B attached to C28), each set with an occupancy factor of 50%. For (III), the two terminal butenyl C atoms of the 2-methyl-1-butenyl group attached to I2 were refined as two sets of positions (C9A and C10A at 66.67% occupancy, and C9B and C10B at 33.33% occupancy). The largest residual peaks of electron density (0.49 and -0.64 e Å-3) were found within 1.06 Å of one of the Cl atoms (Cl2S) of the solvent dichloromethane molecule.
Data collection: SMART (Bruker, 1997) for (I), (III); SMART (Bruker 1997) for (II). For all compounds, cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1997a). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (I), (III); DIRDIF96 (Beurskens et al., 1996) for (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b) for (I), (II); SHELXL97 (Sheldrick, 1997) for (III). For all compounds, molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C12H13F3I+·CF3O3S− | F(000) = 952 |
Mr = 490.19 | Dx = 1.839 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5676 (7) Å | Cell parameters from 5559 reflections |
b = 17.2459 (18) Å | θ = 2.4–26.4° |
c = 15.7394 (16) Å | µ = 1.99 mm−1 |
β = 96.803 (10)° | T = 193 K |
V = 1770.2 (3) Å3 | Prism, colorless |
Z = 4 | 0.33 × 0.22 × 0.13 mm |
Bruker P4/RA/SMART 1000 CCD area-detector diffractometer | 3622 independent reflections |
Radiation source: fine-focus rotating anode | 2912 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.4°, θmin = 1.8° |
ϕ and ω scans | h = −8→3 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −21→21 |
Tmin = 0.601, Tmax = 0.772 | l = −19→18 |
8591 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0793P)2 + 3.5701P] where P = (Fo2 + 2Fc2)/3 |
3622 reflections | (Δ/σ)max < 0.001 |
256 parameters | Δρmax = 1.40 e Å−3 |
0 restraints | Δρmin = −1.16 e Å−3 |
C12H13F3I+·CF3O3S− | V = 1770.2 (3) Å3 |
Mr = 490.19 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.5676 (7) Å | µ = 1.99 mm−1 |
b = 17.2459 (18) Å | T = 193 K |
c = 15.7394 (16) Å | 0.33 × 0.22 × 0.13 mm |
β = 96.803 (10)° |
Bruker P4/RA/SMART 1000 CCD area-detector diffractometer | 3622 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2912 reflections with I > 2σ(I) |
Tmin = 0.601, Tmax = 0.772 | Rint = 0.028 |
8591 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.40 e Å−3 |
3622 reflections | Δρmin = −1.16 e Å−3 |
256 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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. For compound (I), the CF3 group was found to be rotationally disordered, thus two sets of three fluorine atoms each (with occupancy factors of 60% for F1A, F2A, F3A and 40% for F1B, F2B, F3B) were refined. For this compound the terminal carbon of the 2-methyl-1-butenyl group was determined to be disordered over two positions (C5A:55%; C5B:45%). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
I | 0.25211 (6) | 0.07166 (2) | 0.39397 (2) | 0.05832 (17) | |
F1A | 0.779 (3) | −0.0780 (8) | 0.0715 (15) | 0.114 (6) | 0.60 |
F2A | 1.008 (2) | −0.0094 (12) | 0.1313 (13) | 0.116 (8) | 0.60 |
F3A | 0.778 (3) | 0.0378 (11) | 0.0353 (9) | 0.130 (5) | 0.60 |
F1B | 0.898 (3) | 0.0584 (10) | 0.0788 (13) | 0.110 (5) | 0.40 |
F2B | 0.728 (5) | −0.040 (2) | 0.046 (2) | 0.163 (16) | 0.40 |
F3B | 0.992 (5) | −0.0410 (19) | 0.137 (3) | 0.148 (15) | 0.40 |
C1 | 0.2892 (9) | 0.1912 (3) | 0.3831 (4) | 0.0582 (13) | |
H1 | 0.4107 | 0.2139 | 0.4113 | 0.070* | |
C2 | 0.1548 (9) | 0.2374 (3) | 0.3396 (4) | 0.0611 (14) | |
C3 | 0.2051 (13) | 0.3224 (4) | 0.3387 (6) | 0.087 (2) | |
H3A | 0.3412 | 0.3311 | 0.3700 | 0.104* | |
H3B | 0.1026 | 0.3516 | 0.3660 | 0.104* | |
H3C | 0.2042 | 0.3399 | 0.2794 | 0.104* | |
C4 | −0.0440 (12) | 0.2128 (5) | 0.2897 (6) | 0.087 (2) | |
H4A | −0.0287 | 0.2156 | 0.2279 | 0.104* | 0.55 |
H4B | −0.0698 | 0.1579 | 0.3034 | 0.104* | 0.55 |
H4C | −0.0540 | 0.1558 | 0.2953 | 0.104* | 0.45 |
H4D | −0.1561 | 0.2355 | 0.3185 | 0.104* | 0.45 |
C5A | −0.2194 (19) | 0.2575 (11) | 0.3050 (11) | 0.099 (5) | 0.55 |
H5AA | −0.3411 | 0.2371 | 0.2700 | 0.119* | 0.55 |
H5AB | −0.1984 | 0.3117 | 0.2897 | 0.119* | 0.55 |
H5AC | −0.2389 | 0.2541 | 0.3656 | 0.119* | 0.55 |
C5B | −0.085 (4) | 0.2304 (14) | 0.2029 (17) | 0.127 (9) | 0.45 |
H5BA | −0.2199 | 0.2099 | 0.1806 | 0.152* | 0.45 |
H5BB | 0.0203 | 0.2067 | 0.1719 | 0.152* | 0.45 |
H5BC | −0.0835 | 0.2867 | 0.1952 | 0.152* | 0.45 |
C11 | 0.4408 (8) | 0.0436 (3) | 0.2992 (3) | 0.0505 (11) | |
C12 | 0.3911 (10) | 0.0741 (3) | 0.2178 (4) | 0.0617 (14) | |
H12 | 0.2738 | 0.1061 | 0.2052 | 0.074* | |
C13 | 0.5142 (12) | 0.0571 (4) | 0.1558 (4) | 0.0686 (16) | |
H13 | 0.4814 | 0.0773 | 0.0997 | 0.082* | |
C14 | 0.6853 (9) | 0.0109 (3) | 0.1741 (4) | 0.0597 (13) | |
C15 | 0.7324 (9) | −0.0197 (3) | 0.2560 (4) | 0.0613 (14) | |
H15 | 0.8482 | −0.0525 | 0.2683 | 0.074* | |
C16 | 0.6113 (9) | −0.0024 (3) | 0.3190 (4) | 0.0586 (13) | |
H16 | 0.6447 | −0.0219 | 0.3754 | 0.070* | |
C17 | 0.8163 (14) | −0.0069 (5) | 0.1053 (5) | 0.083 (2) | |
S | 0.1446 (2) | −0.13161 (7) | 0.45215 (9) | 0.0509 (3) | |
F4 | 0.0404 (14) | −0.2746 (3) | 0.4769 (4) | 0.153 (3) | |
F5 | 0.3494 (17) | −0.2596 (5) | 0.4455 (7) | 0.211 (5) | |
F6 | 0.1033 (11) | −0.2512 (3) | 0.3506 (3) | 0.1194 (19) | |
O1 | 0.2266 (14) | −0.0966 (4) | 0.3842 (4) | 0.138 (4) | |
O2 | −0.0661 (10) | −0.1162 (5) | 0.4485 (5) | 0.134 (3) | |
O3 | 0.2366 (11) | −0.1253 (4) | 0.5371 (4) | 0.123 (2) | |
C20 | 0.151 (2) | −0.2333 (5) | 0.4286 (6) | 0.107 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
I | 0.0642 (3) | 0.0482 (2) | 0.0632 (3) | −0.00288 (15) | 0.01052 (17) | 0.01018 (15) |
F1A | 0.131 (13) | 0.085 (7) | 0.137 (13) | −0.017 (7) | 0.057 (10) | −0.050 (7) |
F2A | 0.073 (8) | 0.161 (18) | 0.120 (11) | −0.026 (10) | 0.029 (7) | −0.040 (12) |
F3A | 0.175 (14) | 0.137 (12) | 0.087 (8) | 0.064 (11) | 0.058 (8) | 0.032 (8) |
F1B | 0.143 (15) | 0.096 (10) | 0.104 (12) | 0.016 (11) | 0.072 (11) | 0.010 (10) |
F2B | 0.129 (17) | 0.24 (4) | 0.12 (2) | −0.02 (3) | 0.036 (16) | −0.12 (3) |
F3B | 0.14 (3) | 0.15 (2) | 0.17 (2) | 0.09 (2) | 0.07 (2) | 0.040 (19) |
C1 | 0.055 (3) | 0.046 (3) | 0.074 (4) | −0.006 (2) | 0.008 (3) | 0.003 (3) |
C2 | 0.061 (3) | 0.056 (3) | 0.068 (4) | 0.002 (3) | 0.018 (3) | 0.012 (3) |
C3 | 0.096 (5) | 0.053 (4) | 0.114 (6) | 0.004 (3) | 0.025 (4) | 0.014 (4) |
C4 | 0.072 (4) | 0.073 (4) | 0.111 (6) | −0.001 (3) | −0.007 (4) | 0.023 (4) |
C5A | 0.046 (6) | 0.137 (14) | 0.111 (11) | 0.014 (7) | −0.002 (7) | 0.008 (10) |
C5B | 0.107 (16) | 0.111 (17) | 0.15 (2) | 0.019 (13) | −0.043 (15) | 0.027 (15) |
C11 | 0.055 (3) | 0.041 (2) | 0.054 (3) | −0.002 (2) | 0.000 (2) | 0.004 (2) |
C12 | 0.071 (4) | 0.054 (3) | 0.059 (3) | 0.014 (3) | 0.002 (3) | 0.012 (2) |
C13 | 0.092 (5) | 0.055 (3) | 0.058 (3) | 0.013 (3) | 0.006 (3) | 0.007 (3) |
C14 | 0.065 (3) | 0.049 (3) | 0.065 (3) | −0.001 (3) | 0.006 (3) | −0.004 (3) |
C15 | 0.055 (3) | 0.057 (3) | 0.068 (3) | 0.010 (3) | −0.008 (3) | −0.001 (3) |
C16 | 0.063 (3) | 0.053 (3) | 0.056 (3) | 0.005 (2) | −0.010 (2) | 0.006 (2) |
C17 | 0.097 (5) | 0.073 (5) | 0.082 (5) | 0.008 (4) | 0.020 (4) | −0.002 (4) |
S | 0.0582 (7) | 0.0398 (6) | 0.0563 (7) | −0.0007 (5) | 0.0138 (6) | 0.0003 (5) |
F4 | 0.275 (9) | 0.059 (3) | 0.135 (5) | −0.039 (4) | 0.072 (5) | −0.001 (3) |
F5 | 0.219 (9) | 0.164 (7) | 0.231 (10) | 0.118 (7) | −0.044 (7) | −0.054 (7) |
F6 | 0.176 (5) | 0.093 (3) | 0.088 (3) | −0.019 (3) | 0.013 (3) | −0.044 (3) |
O1 | 0.249 (10) | 0.057 (3) | 0.135 (6) | −0.033 (4) | 0.127 (6) | −0.012 (3) |
O2 | 0.097 (4) | 0.146 (6) | 0.163 (7) | 0.050 (4) | 0.039 (4) | 0.043 (5) |
O3 | 0.133 (5) | 0.125 (5) | 0.102 (4) | −0.009 (4) | −0.017 (4) | −0.037 (4) |
C20 | 0.182 (10) | 0.065 (5) | 0.076 (5) | −0.010 (6) | 0.018 (6) | 0.000 (4) |
I—C1 | 2.086 (6) | C5A—H5AB | 0.9800 |
I—O1 | 2.909 (6) | C5A—H5AC | 0.9800 |
I—O2i | 2.991 (8) | C5B—H5BA | 0.9800 |
I—C11 | 2.106 (6) | C5B—H5BB | 0.9800 |
F1A—C17 | 1.347 (18) | C5B—H5BC | 0.9800 |
F2A—C17 | 1.279 (18) | C11—C12 | 1.387 (8) |
F3A—C17 | 1.344 (14) | C11—C16 | 1.378 (8) |
F1B—C17 | 1.336 (19) | C12—C13 | 1.371 (10) |
F2B—C17 | 1.18 (3) | C12—H12 | 0.9500 |
F3B—C17 | 1.34 (3) | C13—C14 | 1.379 (9) |
C1—C2 | 1.319 (8) | C13—H13 | 0.9500 |
C1—H1 | 0.9500 | C14—C15 | 1.393 (8) |
C2—C3 | 1.502 (9) | C14—C17 | 1.493 (10) |
C2—C4 | 1.503 (10) | C15—C16 | 1.375 (9) |
C3—H3A | 0.9800 | C15—H15 | 0.9500 |
C3—H3B | 0.9800 | C16—H16 | 0.9500 |
C3—H3C | 0.9800 | S—O1 | 1.391 (5) |
C4—C5A | 1.429 (16) | S—O2 | 1.403 (6) |
C4—C5B | 1.39 (2) | S—O3 | 1.405 (6) |
C4—H4A | 0.9900 | S—C20 | 1.794 (9) |
C4—H4B | 0.9900 | F4—C20 | 1.321 (11) |
C4—H4C | 0.9900 | F5—C20 | 1.378 (14) |
C4—H4D | 0.9900 | F6—C20 | 1.268 (10) |
C5A—H5AA | 0.9800 | ||
O1—I—O2i | 105.86 (19) | C12—C11—C16 | 121.6 (6) |
O1—I—C1 | 171.2 (2) | I—C11—C12 | 118.3 (4) |
O1—I—C11 | 76.64 (18) | I—C11—C16 | 120.2 (4) |
O2i—I—C1 | 82.9 (2) | C11—C12—C13 | 118.8 (6) |
O2i—I—C11 | 168.2 (2) | C11—C12—H12 | 120.6 |
C1—I—C11 | 94.9 (2) | C13—C12—H12 | 120.6 |
I—C1—C2 | 124.2 (5) | C12—C13—C14 | 120.6 (6) |
I—C1—H1 | 117.9 | C12—C13—H13 | 119.7 |
C2—C1—H1 | 117.9 | C14—C13—H13 | 119.7 |
C1—C2—C3 | 117.4 (6) | C13—C14—C15 | 119.9 (6) |
C1—C2—C4 | 126.0 (6) | C13—C14—C17 | 119.5 (6) |
C3—C2—C4 | 116.6 (6) | C15—C14—C17 | 120.6 (6) |
C2—C3—H3A | 109.5 | C14—C15—C16 | 120.1 (5) |
C2—C3—H3B | 109.5 | C16—C15—H15 | 120.0 |
C2—C3—H3C | 109.5 | C14—C15—H15 | 120.0 |
H3A—C3—H3B | 109.5 | C11—C16—C15 | 119.0 (5) |
H3A—C3—H3C | 109.5 | C11—C16—H16 | 120.5 |
H3B—C3—H3C | 109.5 | C15—C16—H16 | 120.5 |
C2—C4—C5A | 115.3 (9) | F1A—C17—F2A | 102.7 (13) |
C2—C4—C5B | 120.4 (12) | F1A—C17—F3A | 101.0 (13) |
C2—C4—H4A | 108.4 | F1A—C17—C14 | 112.5 (11) |
C2—C4—H4B | 108.4 | F2A—C17—F3A | 111.3 (15) |
C2—C4—H4C | 107.2 | F2A—C17—C14 | 113.9 (11) |
C2—C4—H4D | 107.2 | F3A—C17—C14 | 114.2 (8) |
C5A—C4—H4A | 108.4 | F1B—C17—F2B | 110 (2) |
C5A—C4—H4B | 108.4 | F1B—C17—F3B | 97.1 (18) |
C5A—C4—H4C | 117.1 | F2B—C17—F3B | 113 (2) |
C5B—C4—H4C | 107.2 | F1B—C17—C14 | 109.8 (9) |
C5B—C4—H4D | 107.2 | F2B—C17—C14 | 113.6 (16) |
H4A—C4—H4B | 107.5 | F3B—C17—C14 | 111.8 (19) |
H4C—C4—H4D | 106.9 | O1—S—O2 | 110.9 (5) |
C4—C5A—H5AA | 109.5 | O1—S—O3 | 122.4 (5) |
C4—C5A—H5AB | 109.5 | O2—S—O3 | 109.6 (5) |
C4—C5A—H5AC | 109.5 | O1—S—C20 | 104.2 (4) |
H5AA—C5A—H5AB | 109.5 | O2—S—C20 | 102.9 (6) |
H5AA—C5A—H5AC | 109.5 | O3—S—C20 | 104.7 (4) |
H5AB—C5A—H5AC | 109.5 | I—O1—S | 114.7 (3) |
C4—C5B—H5BA | 109.5 | S—C20—F4 | 112.4 (7) |
C4—C5B—H5BB | 109.5 | S—C20—F5 | 109.0 (8) |
C4—C5B—H5BC | 109.5 | S—C20—F6 | 115.5 (7) |
H5BA—C5B—H5BB | 109.5 | F4—C20—F5 | 106.4 (9) |
H5BA—C5B—H5BC | 109.5 | F4—C20—F6 | 109.7 (9) |
H5BB—C5B—H5BC | 109.5 | F5—C20—F6 | 103.0 (9) |
O2i—I—O1—S | −2.6 (6) | C13—C14—C17—F1A | −100.8 (13) |
C11—I—O1—S | 165.5 (6) | C13—C14—C17—F2A | 142.8 (12) |
O2i—I—C1—C2 | −92.1 (6) | C13—C14—C17—F3A | 13.5 (16) |
C11—I—C1—C2 | 99.6 (6) | C13—C14—C17—F1B | 63.0 (15) |
O1—I—C11—C12 | 120.3 (5) | C13—C14—C17—F2B | −60 (3) |
O1—I—C11—C16 | −61.1 (5) | C13—C14—C17—F3B | 169.5 (17) |
O2i—I—C11—C12 | −136.1 (9) | C15—C14—C17—F1A | 78.0 (13) |
O2i—I—C11—C16 | 42.5 (12) | C15—C14—C17—F2A | −38.3 (14) |
C1—I—C11—C12 | −57.4 (5) | C15—C14—C17—F3A | −167.6 (13) |
C1—I—C11—C16 | 121.2 (5) | C15—C14—C17—F1B | −118.2 (14) |
I—C1—C2—C3 | 179.7 (5) | C15—C14—C17—F2B | 118 (3) |
I—C1—C2—C4 | −1.1 (10) | C15—C14—C17—F3B | −11.6 (19) |
C1—C2—C4—C5A | 132.1 (10) | C14—C15—C16—C11 | 1.8 (9) |
C1—C2—C4—C5B | −123.2 (14) | O2—S—O1—I | 70.4 (6) |
C3—C2—C4—C5A | −48.7 (12) | O3—S—O1—I | −61.4 (7) |
C3—C2—C4—C5B | 56.0 (16) | C20—S—O1—I | −179.6 (5) |
I—C11—C12—C13 | 179.2 (5) | O1—S—C20—F4 | −167.0 (8) |
C16—C11—C12—C13 | 0.6 (9) | O1—S—C20—F5 | 75.3 (8) |
I—C11—C16—C15 | −179.8 (4) | O1—S—C20—F6 | −40.0 (10) |
C12—C11—C16—C15 | −1.3 (9) | O2—S—C20—F4 | −51.2 (9) |
C11—C12—C13—C14 | −0.4 (10) | O2—S—C20—F5 | −168.9 (8) |
C12—C13—C14—C15 | 0.9 (10) | O2—S—C20—F6 | 75.8 (10) |
C12—C13—C14—C17 | 179.8 (7) | O3—S—C20—F5 | −54.4 (8) |
C13—C14—C15—C16 | −1.6 (9) | O3—S—C20—F4 | 63.3 (10) |
C17—C14—C15—C16 | 179.6 (6) | O3—S—C20—F6 | −169.7 (9) |
Symmetry code: (i) −x, −y, −z+1. |
C11H12Cl2I+·CF3O3S− | Z = 4 |
Mr = 491.08 | F(000) = 952 |
Triclinic, P1 | Dx = 1.889 Mg m−3 |
a = 9.1705 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.4357 (15) Å | Cell parameters from 4172 reflections |
c = 15.6030 (17) Å | θ = 2.6–26.4° |
α = 69.245 (10)° | µ = 2.32 mm−1 |
β = 88.342 (10)° | T = 193 K |
γ = 74.358 (10)° | Prism, colorless |
V = 1726.4 (3) Å3 | 0.49 × 0.07 × 0.04 mm |
Bruker PLATFORM/SMART 1000 CCD area-detector diffractometer | 6950 independent reflections |
Radiation source: fine-focus sealed tube | 4412 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.5°, θmin = 1.4° |
ω scans | h = −10→11 |
Absorption correction: integration (SHELXTL; Sheldrick, 1997a) | k = −16→14 |
Tmin = 0.559, Tmax = 0.922 | l = −19→10 |
8587 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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0846P)2] where P = (Fo2 + 2Fc2)/3 |
6950 reflections | (Δ/σ)max < 0.001 |
399 parameters | Δρmax = 2.07 e Å−3 |
0 restraints | Δρmin = −1.21 e Å−3 |
C11H12Cl2I+·CF3O3S− | γ = 74.358 (10)° |
Mr = 491.08 | V = 1726.4 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.1705 (10) Å | Mo Kα radiation |
b = 13.4357 (15) Å | µ = 2.32 mm−1 |
c = 15.6030 (17) Å | T = 193 K |
α = 69.245 (10)° | 0.49 × 0.07 × 0.04 mm |
β = 88.342 (10)° |
Bruker PLATFORM/SMART 1000 CCD area-detector diffractometer | 6950 independent reflections |
Absorption correction: integration (SHELXTL; Sheldrick, 1997a) | 4412 reflections with I > 2σ(I) |
Tmin = 0.559, Tmax = 0.922 | Rint = 0.049 |
8587 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 0.96 | Δρmax = 2.07 e Å−3 |
6950 reflections | Δρmin = −1.21 e Å−3 |
399 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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. The structure of (II) was solved via a combined Patterson location of heavy atoms and structure expansion using the DIRDIF96 program system (Beurskens et al., 1996) |
x | y | z | Uiso*/Ueq | ||
I1 | 0.27857 (6) | −0.04577 (4) | −0.10042 (4) | 0.03387 (16) | |
Cl1 | 0.8331 (3) | 0.0800 (2) | −0.15773 (16) | 0.0558 (7) | |
Cl2 | 0.3148 (3) | 0.3833 (2) | −0.32663 (18) | 0.0640 (7) | |
C1 | 0.4329 (9) | −0.1711 (7) | −0.1347 (6) | 0.038 (2) | |
H1 | 0.4356 | −0.1647 | −0.1973 | 0.045* | |
C2 | 0.5243 (9) | −0.2567 (7) | −0.0737 (6) | 0.0340 (18) | |
C3 | 0.6354 (10) | −0.3386 (8) | −0.1084 (7) | 0.047 (2) | |
H3A | 0.6295 | −0.3085 | −0.1758 | 0.056* | |
H3B | 0.6093 | −0.4091 | −0.0874 | 0.056* | |
H3C | 0.7388 | −0.3507 | −0.0844 | 0.056* | |
C4 | 0.5340 (11) | −0.2844 (7) | 0.0285 (6) | 0.043 (2) | |
H4A | 0.4597 | −0.2248 | 0.0429 | 0.052* | |
H4B | 0.6366 | −0.2863 | 0.0483 | 0.052* | |
C5 | 0.5033 (14) | −0.3945 (9) | 0.0829 (8) | 0.073 (4) | |
H5A | 0.5141 | −0.4085 | 0.1487 | 0.088* | |
H5B | 0.5763 | −0.4540 | 0.0689 | 0.088* | |
H5C | 0.4000 | −0.3920 | 0.0660 | 0.088* | |
C11 | 0.4038 (9) | 0.0708 (8) | −0.1578 (5) | 0.038 (2) | |
C12 | 0.5610 (9) | 0.0373 (7) | −0.1394 (5) | 0.0344 (19) | |
H12 | 0.6118 | −0.0362 | −0.1007 | 0.041* | |
C13 | 0.6402 (9) | 0.1138 (8) | −0.1789 (6) | 0.038 (2) | |
C14 | 0.5652 (10) | 0.2219 (8) | −0.2371 (6) | 0.044 (2) | |
H14 | 0.6207 | 0.2740 | −0.2651 | 0.053* | |
C15 | 0.4080 (10) | 0.2515 (7) | −0.2530 (5) | 0.038 (2) | |
C16 | 0.3243 (9) | 0.1767 (7) | −0.2134 (5) | 0.0347 (19) | |
H16 | 0.2169 | 0.1975 | −0.2241 | 0.042* | |
I2 | 0.22863 (6) | 0.04216 (4) | 0.37309 (3) | 0.03471 (16) | |
Cl3 | −0.3283 (3) | −0.0775 (2) | 0.38885 (18) | 0.0533 (6) | |
Cl4 | 0.1947 (3) | −0.3919 (2) | 0.42002 (19) | 0.0580 (6) | |
C6 | 0.0836 (9) | 0.1670 (7) | 0.2635 (5) | 0.0358 (19) | |
H6 | 0.0839 | 0.1583 | 0.2057 | 0.043* | |
C7 | −0.0076 (10) | 0.2566 (7) | 0.2716 (6) | 0.038 (2) | |
C8 | −0.1113 (11) | 0.3400 (8) | 0.1880 (6) | 0.050 (2) | |
H8A | −0.0911 | 0.3150 | 0.1359 | 0.060* | |
H8B | −0.0920 | 0.4124 | 0.1724 | 0.060* | |
H8C | −0.2175 | 0.3462 | 0.2021 | 0.060* | |
C9 | −0.0251 (12) | 0.2860 (8) | 0.3558 (6) | 0.049 (2) | |
H9A | 0.0318 | 0.2215 | 0.4088 | 0.059* | |
H9B | −0.1337 | 0.3022 | 0.3685 | 0.059* | |
C10 | 0.0311 (13) | 0.3847 (9) | 0.3471 (7) | 0.062 (3) | |
H10A | 0.0152 | 0.4011 | 0.4036 | 0.074* | |
H10B | −0.0251 | 0.4490 | 0.2949 | 0.074* | |
H10C | 0.1396 | 0.3681 | 0.3370 | 0.074* | |
C21 | 0.1032 (10) | −0.0740 (7) | 0.3867 (5) | 0.0346 (19) | |
C22 | −0.0558 (9) | −0.0363 (7) | 0.3815 (5) | 0.0352 (19) | |
H22 | −0.1082 | 0.0384 | 0.3726 | 0.042* | |
C23 | −0.1308 (9) | −0.1153 (8) | 0.3900 (5) | 0.038 (2) | |
C24 | −0.0559 (10) | −0.2252 (7) | 0.4020 (5) | 0.041 (2) | |
H24 | −0.1112 | −0.2773 | 0.4070 | 0.049* | |
C25 | 0.1011 (10) | −0.2560 (7) | 0.4063 (5) | 0.0362 (19) | |
C26 | 0.1839 (10) | −0.1820 (7) | 0.4004 (5) | 0.0356 (19) | |
H26 | 0.2918 | −0.2045 | 0.4055 | 0.043* | |
S1 | 0.0312 (2) | 0.20713 (18) | −0.01520 (14) | 0.0345 (5) | |
F1 | −0.0746 (9) | 0.4215 (5) | −0.0614 (6) | 0.101 (3) | |
F2 | 0.0973 (7) | 0.3702 (5) | −0.1458 (4) | 0.0717 (19) | |
F3 | −0.1295 (8) | 0.3610 (7) | −0.1608 (5) | 0.100 (3) | |
O1 | 0.0808 (7) | 0.1406 (5) | −0.0704 (4) | 0.0473 (15) | |
O2 | −0.1085 (7) | 0.1973 (6) | 0.0263 (5) | 0.0572 (19) | |
O3 | 0.1475 (7) | 0.2077 (6) | 0.0431 (4) | 0.0564 (18) | |
C30 | −0.0236 (11) | 0.3468 (9) | −0.1007 (8) | 0.055 (3) | |
S2 | 0.4592 (2) | −0.20668 (17) | 0.61226 (14) | 0.0351 (5) | |
F4 | 0.5763 (8) | −0.4212 (5) | 0.6939 (4) | 0.079 (2) | |
F5 | 0.4061 (7) | −0.3748 (5) | 0.5842 (5) | 0.0755 (19) | |
F6 | 0.6293 (7) | −0.3579 (5) | 0.5539 (5) | 0.0768 (19) | |
O4 | 0.4100 (7) | −0.1416 (5) | 0.5179 (4) | 0.0485 (16) | |
O5 | 0.5966 (7) | −0.1935 (5) | 0.6440 (4) | 0.0503 (16) | |
O6 | 0.3417 (7) | −0.2094 (6) | 0.6747 (5) | 0.0585 (19) | |
C40 | 0.5199 (11) | −0.3475 (8) | 0.6123 (7) | 0.048 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0358 (3) | 0.0326 (3) | 0.0389 (3) | −0.0150 (2) | 0.0091 (2) | −0.0161 (2) |
Cl1 | 0.0453 (13) | 0.0763 (18) | 0.0499 (14) | −0.0342 (13) | 0.0058 (10) | −0.0149 (12) |
Cl2 | 0.0730 (17) | 0.0388 (14) | 0.0664 (17) | −0.0169 (12) | 0.0151 (13) | −0.0025 (11) |
C1 | 0.049 (5) | 0.032 (5) | 0.043 (5) | −0.017 (4) | 0.016 (4) | −0.023 (4) |
C2 | 0.040 (5) | 0.026 (4) | 0.042 (5) | −0.011 (4) | 0.006 (4) | −0.019 (4) |
C3 | 0.046 (5) | 0.040 (5) | 0.058 (6) | −0.006 (4) | 0.004 (4) | −0.025 (4) |
C4 | 0.056 (6) | 0.034 (5) | 0.039 (5) | −0.009 (4) | −0.005 (4) | −0.015 (4) |
C5 | 0.094 (9) | 0.041 (6) | 0.067 (7) | −0.013 (6) | 0.019 (6) | −0.002 (5) |
C11 | 0.031 (4) | 0.056 (6) | 0.031 (4) | −0.018 (4) | 0.014 (3) | −0.016 (4) |
C12 | 0.040 (5) | 0.036 (5) | 0.031 (4) | −0.012 (4) | 0.005 (3) | −0.016 (4) |
C13 | 0.044 (5) | 0.049 (6) | 0.037 (5) | −0.026 (4) | 0.013 (4) | −0.026 (4) |
C14 | 0.056 (6) | 0.051 (6) | 0.036 (5) | −0.028 (5) | 0.017 (4) | −0.021 (4) |
C15 | 0.060 (6) | 0.029 (5) | 0.031 (4) | −0.019 (4) | 0.012 (4) | −0.012 (3) |
C16 | 0.035 (4) | 0.039 (5) | 0.030 (4) | −0.011 (4) | 0.008 (3) | −0.013 (4) |
I2 | 0.0389 (3) | 0.0333 (3) | 0.0355 (3) | −0.0156 (2) | 0.0068 (2) | −0.0128 (2) |
Cl3 | 0.0413 (12) | 0.0644 (17) | 0.0752 (16) | −0.0259 (11) | 0.0170 (11) | −0.0427 (13) |
Cl4 | 0.0703 (16) | 0.0354 (13) | 0.0734 (17) | −0.0109 (12) | 0.0054 (13) | −0.0284 (12) |
C6 | 0.043 (5) | 0.025 (4) | 0.035 (4) | −0.006 (4) | 0.004 (3) | −0.008 (3) |
C7 | 0.051 (5) | 0.028 (5) | 0.035 (5) | −0.021 (4) | 0.004 (4) | −0.003 (3) |
C8 | 0.057 (6) | 0.035 (5) | 0.051 (6) | −0.008 (4) | 0.002 (4) | −0.011 (4) |
C9 | 0.077 (7) | 0.034 (5) | 0.038 (5) | −0.012 (5) | 0.009 (4) | −0.016 (4) |
C10 | 0.077 (7) | 0.060 (7) | 0.063 (7) | −0.024 (6) | 0.006 (5) | −0.036 (6) |
C21 | 0.054 (5) | 0.030 (5) | 0.029 (4) | −0.021 (4) | 0.008 (4) | −0.014 (3) |
C22 | 0.037 (5) | 0.038 (5) | 0.034 (4) | −0.012 (4) | 0.008 (3) | −0.016 (4) |
C23 | 0.038 (5) | 0.054 (6) | 0.031 (4) | −0.020 (4) | 0.009 (3) | −0.022 (4) |
C24 | 0.053 (6) | 0.040 (5) | 0.032 (4) | −0.019 (4) | 0.010 (4) | −0.014 (4) |
C25 | 0.052 (5) | 0.029 (5) | 0.031 (4) | −0.010 (4) | 0.008 (4) | −0.016 (3) |
C26 | 0.044 (5) | 0.040 (5) | 0.028 (4) | −0.013 (4) | 0.007 (3) | −0.018 (4) |
S1 | 0.0370 (11) | 0.0332 (11) | 0.0390 (11) | −0.0175 (9) | 0.0109 (9) | −0.0148 (9) |
F1 | 0.122 (6) | 0.037 (4) | 0.140 (7) | −0.018 (4) | 0.064 (5) | −0.033 (4) |
F2 | 0.066 (4) | 0.055 (4) | 0.075 (4) | −0.020 (3) | 0.029 (3) | −0.001 (3) |
F3 | 0.078 (5) | 0.090 (6) | 0.091 (5) | −0.006 (4) | −0.025 (4) | 0.006 (4) |
O1 | 0.051 (4) | 0.044 (4) | 0.059 (4) | −0.016 (3) | 0.012 (3) | −0.031 (3) |
O2 | 0.043 (4) | 0.053 (4) | 0.080 (5) | −0.024 (3) | 0.030 (3) | −0.024 (4) |
O3 | 0.062 (4) | 0.073 (5) | 0.046 (4) | −0.039 (4) | 0.005 (3) | −0.019 (3) |
C30 | 0.049 (6) | 0.047 (6) | 0.068 (7) | −0.014 (5) | 0.012 (5) | −0.018 (5) |
S2 | 0.0360 (11) | 0.0317 (11) | 0.0414 (12) | −0.0136 (9) | 0.0043 (9) | −0.0146 (9) |
F4 | 0.113 (5) | 0.036 (3) | 0.074 (4) | −0.022 (3) | −0.018 (4) | 0.001 (3) |
F5 | 0.087 (5) | 0.049 (4) | 0.107 (5) | −0.032 (3) | −0.014 (4) | −0.037 (3) |
F6 | 0.081 (4) | 0.063 (4) | 0.095 (5) | −0.007 (3) | 0.021 (4) | −0.049 (4) |
O4 | 0.049 (4) | 0.031 (3) | 0.059 (4) | −0.006 (3) | −0.004 (3) | −0.011 (3) |
O5 | 0.049 (4) | 0.036 (4) | 0.066 (4) | −0.016 (3) | −0.010 (3) | −0.015 (3) |
O6 | 0.063 (4) | 0.075 (5) | 0.065 (4) | −0.047 (4) | 0.036 (3) | −0.039 (4) |
C40 | 0.055 (6) | 0.041 (6) | 0.052 (6) | −0.019 (5) | 0.004 (5) | −0.017 (5) |
I1—O1 | 2.848 (6) | C6—H6 | 0.9500 |
I1—O2i | 2.802 (6) | C7—C8 | 1.524 (12) |
I1—C1 | 2.106 (8) | C7—C9 | 1.492 (12) |
I1—C11 | 2.119 (8) | C8—H8A | 0.9800 |
Cl1—C13 | 1.715 (9) | C8—H8B | 0.9800 |
Cl2—C15 | 1.728 (9) | C8—H8C | 0.9800 |
C1—C2 | 1.297 (11) | C9—C10 | 1.510 (14) |
C1—H1 | 0.9500 | C9—H9A | 0.9900 |
C2—C3 | 1.525 (11) | C9—H9B | 0.9900 |
C2—C4 | 1.503 (11) | C10—H10A | 0.9800 |
C3—H3A | 0.9800 | C10—H10B | 0.9800 |
C3—H3B | 0.9800 | C10—H10C | 0.9800 |
C3—H3C | 0.9800 | C21—C22 | 1.404 (11) |
C4—C5 | 1.520 (13) | C21—C26 | 1.382 (11) |
C4—H4A | 0.9900 | C22—C23 | 1.380 (12) |
C4—H4B | 0.9900 | C22—H22 | 0.9500 |
C5—H5A | 0.9800 | C23—C24 | 1.397 (12) |
C5—H5B | 0.9800 | C24—C25 | 1.384 (12) |
C5—H5C | 0.9800 | C24—H24 | 0.9500 |
C11—C12 | 1.394 (11) | C25—C26 | 1.382 (12) |
C11—C16 | 1.383 (12) | C26—H26 | 0.9500 |
C12—C13 | 1.375 (11) | S1—O1 | 1.432 (6) |
C12—H12 | 0.9500 | S1—O2 | 1.436 (6) |
C13—C14 | 1.404 (13) | S1—O3 | 1.426 (7) |
C14—C15 | 1.392 (12) | S1—C30 | 1.819 (11) |
C14—H14 | 0.9500 | F1—C30 | 1.330 (13) |
C15—C16 | 1.389 (11) | F2—C30 | 1.345 (11) |
C16—H16 | 0.9500 | F3—C30 | 1.299 (13) |
I2—O4 | 2.832 (6) | S2—O4 | 1.431 (6) |
I2—O5ii | 2.850 (6) | S2—O5 | 1.443 (6) |
I2—C6 | 2.098 (8) | S2—O6 | 1.430 (6) |
I2—C21 | 2.127 (8) | S2—C40 | 1.822 (10) |
Cl3—C23 | 1.743 (8) | F4—C40 | 1.319 (11) |
Cl4—C25 | 1.733 (8) | F5—C40 | 1.327 (11) |
C6—C7 | 1.313 (12) | F6—C40 | 1.349 (11) |
O1—I1—O2i | 98.49 (18) | C7—C8—H8B | 109.5 |
O1—I1—C1 | 173.8 (3) | C7—C8—H8C | 109.5 |
O1—I1—C11 | 80.9 (3) | H8A—C8—H8B | 109.5 |
O2i—I1—C1 | 87.1 (3) | H8A—C8—H8C | 109.5 |
O2i—I1—C11 | 179.0 (3) | H8B—C8—H8C | 109.5 |
C1—I1—C11 | 93.5 (3) | C7—C9—C10 | 112.9 (8) |
I1—C1—C2 | 122.6 (6) | C7—C9—H9A | 109.0 |
I1—C1—H1 | 118.7 | C7—C9—H9B | 109.0 |
C2—C1—H1 | 118.7 | C10—C9—H9A | 109.0 |
C1—C2—C3 | 117.2 (8) | C10—C9—H9B | 109.0 |
C1—C2—C4 | 127.0 (8) | H9A—C9—H9B | 107.8 |
C3—C2—C4 | 115.8 (7) | C9—C10—H10A | 109.5 |
C2—C3—H3A | 109.5 | C9—C10—H10B | 109.5 |
C2—C3—H3B | 109.5 | C9—C10—H10C | 109.5 |
C2—C3—H3C | 109.5 | H10A—C10—H10B | 109.5 |
H3A—C3—H3B | 109.5 | H10A—C10—H10C | 109.5 |
H3A—C3—H3C | 109.5 | H10B—C10—H10C | 109.5 |
H3B—C3—H3C | 109.5 | I2—C21—C22 | 118.0 (6) |
C2—C4—C5 | 113.5 (8) | I2—C21—C26 | 117.7 (6) |
C2—C4—H4A | 108.9 | C22—C21—C26 | 124.3 (8) |
C2—C4—H4B | 108.9 | C21—C22—C23 | 115.3 (8) |
C5—C4—H4A | 108.9 | C21—C22—H22 | 122.4 |
C5—C4—H4B | 108.9 | C23—C22—H22 | 122.4 |
H4A—C4—H4B | 107.7 | Cl3—C23—C22 | 118.6 (7) |
C4—C5—H5A | 109.5 | Cl3—C23—C24 | 118.1 (7) |
C4—C5—H5B | 109.5 | C22—C23—C24 | 123.2 (8) |
C4—C5—H5C | 109.5 | C23—C24—C25 | 118.0 (8) |
H5A—C5—H5B | 109.5 | C23—C24—H24 | 121.0 |
H5A—C5—H5C | 109.5 | C25—C24—H24 | 121.0 |
H5B—C5—H5C | 109.5 | Cl4—C25—C24 | 118.3 (7) |
I1—C11—C12 | 119.1 (6) | Cl4—C25—C26 | 119.7 (7) |
I1—C11—C16 | 117.6 (6) | C24—C25—C26 | 122.0 (8) |
C12—C11—C16 | 123.3 (8) | C21—C26—C25 | 117.2 (8) |
C11—C12—C13 | 118.1 (8) | C21—C26—H26 | 121.4 |
C11—C12—H12 | 121.0 | C25—C26—H26 | 121.4 |
C13—C12—H12 | 121.0 | O1—S1—O2 | 114.5 (4) |
Cl1—C13—C12 | 120.9 (7) | O1—S1—O3 | 115.2 (4) |
Cl1—C13—C14 | 118.2 (7) | O2—S1—O3 | 115.3 (4) |
C12—C13—C14 | 120.9 (8) | O1—S1—C30 | 102.4 (5) |
C13—C14—C15 | 118.8 (8) | O2—S1—C30 | 102.5 (4) |
C13—C14—H14 | 120.6 | O3—S1—C30 | 104.5 (5) |
C15—C14—H14 | 120.6 | I1—O1—S1 | 151.5 (4) |
Cl2—C15—C14 | 119.3 (7) | S1—C30—F1 | 111.1 (8) |
Cl2—C15—C16 | 118.9 (7) | S1—C30—F2 | 110.1 (7) |
C14—C15—C16 | 121.8 (8) | S1—C30—F3 | 112.8 (8) |
C11—C16—C15 | 117.1 (8) | F1—C30—F2 | 107.1 (9) |
C11—C16—H16 | 121.4 | F1—C30—F3 | 107.3 (9) |
C15—C16—H16 | 121.4 | F2—C30—F3 | 108.1 (9) |
O4—I2—O5ii | 98.26 (18) | O4—S2—O5 | 114.8 (4) |
O4—I2—C6 | 174.1 (3) | O4—S2—O6 | 115.3 (4) |
O4—I2—C21 | 80.6 (3) | O4—S2—C40 | 102.9 (4) |
O5ii—I2—C6 | 87.4 (3) | O5—S2—O6 | 115.0 (4) |
O5ii—I2—C21 | 178.6 (3) | O5—S2—C40 | 102.6 (4) |
C6—I2—C21 | 93.7 (3) | O6—S2—C40 | 103.8 (4) |
I2—C6—C7 | 122.7 (7) | I2—O4—S2 | 154.4 (4) |
I2—C6—H6 | 118.7 | S2—C40—F4 | 112.4 (7) |
C7—C6—H6 | 118.7 | S2—C40—F5 | 111.3 (7) |
C6—C7—C8 | 118.0 (8) | S2—C40—F6 | 111.1 (7) |
C6—C7—C9 | 127.0 (8) | F4—C40—F5 | 108.8 (8) |
C8—C7—C9 | 114.9 (8) | F4—C40—F6 | 106.7 (8) |
C7—C8—H8A | 109.5 | F5—C40—F6 | 106.3 (8) |
O2i—I1—O1—S1 | 90.8 (8) | I2—C21—C22—C23 | 179.5 (5) |
C11—I1—O1—S1 | −89.9 (8) | C26—C21—C22—C23 | −0.7 (11) |
O2i—I1—C1—C2 | −73.2 (7) | I2—C21—C26—C25 | −178.1 (5) |
C11—I1—C1—C2 | 107.6 (8) | C22—C21—C26—C25 | 2.1 (12) |
O1—I1—C11—C12 | 137.7 (7) | C21—C22—C23—Cl3 | 177.6 (6) |
O1—I1—C11—C16 | −43.4 (6) | C21—C22—C23—C24 | −0.7 (12) |
C1—I1—C11—C12 | −45.1 (7) | Cl3—C23—C24—C25 | −177.7 (6) |
C1—I1—C11—C16 | 133.8 (7) | C22—C23—C24—C25 | 0.7 (12) |
I1—C1—C2—C3 | −177.2 (6) | C23—C24—C25—Cl4 | −179.4 (6) |
I1—C1—C2—C4 | 2.4 (13) | C23—C24—C25—C26 | 0.9 (12) |
C1—C2—C4—C5 | 120.0 (10) | Cl4—C25—C26—C21 | 178.1 (6) |
C3—C2—C4—C5 | −60.4 (11) | C24—C25—C26—C21 | −2.2 (11) |
I1—C11—C12—C13 | 178.7 (6) | O2—S1—O1—I1 | −106.5 (8) |
C16—C11—C12—C13 | −0.2 (12) | O3—S1—O1—I1 | 30.6 (9) |
I1—C11—C16—C15 | −178.0 (6) | C30—S1—O1—I1 | 143.4 (8) |
C12—C11—C16—C15 | 0.8 (12) | O1—S1—C30—F1 | 179.6 (7) |
C11—C12—C13—Cl1 | 178.6 (6) | O1—S1—C30—F2 | −61.8 (9) |
C11—C12—C13—C14 | −0.9 (12) | O1—S1—C30—F3 | 59.1 (8) |
Cl1—C13—C14—C15 | −178.3 (6) | O2—S1—C30—F1 | 60.7 (9) |
C12—C13—C14—C15 | 1.1 (12) | O2—S1—C30—F2 | 179.2 (8) |
C13—C14—C15—Cl2 | −178.5 (7) | O2—S1—C30—F3 | −59.9 (9) |
C13—C14—C15—C16 | −0.4 (13) | O3—S1—C30—F1 | −59.9 (8) |
Cl2—C15—C16—C11 | 177.5 (6) | O3—S1—C30—F2 | 58.6 (9) |
C14—C15—C16—C11 | −0.5 (12) | O3—S1—C30—F3 | 179.5 (7) |
O5ii—I2—O4—S2 | 84.7 (9) | O5—S2—O4—I2 | −100.3 (9) |
C21—I2—O4—S2 | −96.1 (9) | O6—S2—O4—I2 | 36.8 (10) |
C21—I2—C6—C7 | 110.0 (8) | C40—S2—O4—I2 | 149.1 (9) |
O5ii—I2—C6—C7 | −70.8 (7) | O4—S2—C40—F4 | 177.3 (7) |
O4—I2—C21—C22 | 138.5 (6) | O4—S2—C40—F5 | −60.4 (7) |
O4—I2—C21—C26 | −41.3 (6) | O4—S2—C40—F6 | 57.9 (8) |
C6—I2—C21—C22 | −43.0 (6) | O5—S2—C40—F4 | 57.9 (8) |
C6—I2—C21—C26 | 137.2 (6) | O5—S2—C40—F5 | −179.8 (7) |
I2—C6—C7—C8 | −178.2 (6) | O5—S2—C40—F6 | −61.6 (8) |
I2—C6—C7—C9 | 0.1 (13) | O6—S2—C40—F4 | −62.2 (8) |
C6—C7—C9—C10 | 112.5 (10) | O6—S2—C40—F5 | 60.1 (8) |
C8—C7—C9—C10 | −69.2 (11) | O6—S2—C40—F6 | 178.3 (7) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z+1. |
2C13H12F6I+·2CF3O3S−·CH2Cl2 | Z = 2 |
Mr = 1201.32 | F(000) = 1164 |
Triclinic, P1 | Dx = 1.878 Mg m−3 |
a = 12.5807 (13) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.2381 (14) Å | Cell parameters from 8192 reflections |
c = 13.6567 (14) Å | θ = 2.3–26.3° |
α = 81.854 (10)° | µ = 1.82 mm−1 |
β = 72.429 (10)° | T = 193 K |
γ = 79.851 (10)° | Prism, colorless |
V = 2124.9 (4) Å3 | 0.39 × 0.17 × 0.12 mm |
Bruker P4/RA/SMART 1000 CCD area-detector diffractometer | 8628 independent reflections |
Radiation source: fine-focus rotating anode | 6911 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.4°, θmin = 1.6° |
ϕ and ω scans | h = −13→15 |
Absorption correction: integration (SHELXTL; Sheldrick, 1997a) | k = −13→16 |
Tmin = 0.629, Tmax = 0.857 | l = −17→17 |
12749 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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0417P)2] where P = (Fo2 + 2Fc2)/3 |
8628 reflections | (Δ/σ)max = 0.002 |
618 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
2C13H12F6I+·2CF3O3S−·CH2Cl2 | γ = 79.851 (10)° |
Mr = 1201.32 | V = 2124.9 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.5807 (13) Å | Mo Kα radiation |
b = 13.2381 (14) Å | µ = 1.82 mm−1 |
c = 13.6567 (14) Å | T = 193 K |
α = 81.854 (10)° | 0.39 × 0.17 × 0.12 mm |
β = 72.429 (10)° |
Bruker P4/RA/SMART 1000 CCD area-detector diffractometer | 8628 independent reflections |
Absorption correction: integration (SHELXTL; Sheldrick, 1997a) | 6911 reflections with I > 2σ(I) |
Tmin = 0.629, Tmax = 0.857 | Rint = 0.027 |
12749 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.49 e Å−3 |
8628 reflections | Δρmin = −0.64 e Å−3 |
618 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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. For compound (III), one of the CF3 groups on the phenyl ring attached to I1 was found to be rotationally disordered, thus two sets of three fluorine atoms each were refined (F11A, F12A, F13A with occupancy factor 70%, and F11B, F12B, F13B with occupancy factor 30%). Also for (III), both of the CF3 groups on the phenyl ring attached to I2 displayed a rotational disorder such that each was refined with two sets of three fluorine atoms (F21A, F22A, F23A and F21B, F22B, F23B attached to C27; F24A, F25A, F26A and F24B, F25B F26B attached to C28), each set with an occupancy factor of 50%. For (III) the two terminal butenyl carbons of the 2-methyl-1-butenyl group attached to I2 were refined as two sets of positions (C9A, C10A: 66.67%; C9B, C10B: 33.33%). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
I1 | 0.492283 (17) | 0.418968 (15) | −0.157974 (15) | 0.03097 (7) | |
F11A | 0.7693 (4) | −0.0326 (3) | −0.2218 (4) | 0.0887 (14) | 0.70 |
F12A | 0.8522 (3) | 0.0517 (5) | −0.3554 (3) | 0.0859 (14) | 0.70 |
F13A | 0.8351 (5) | 0.0981 (5) | −0.2062 (7) | 0.136 (3) | 0.70 |
F11B | 0.8649 (11) | 0.1135 (11) | −0.3212 (12) | 0.103 (4)* | 0.30 |
F12B | 0.7984 (11) | 0.0463 (11) | −0.1839 (11) | 0.091 (4)* | 0.30 |
F13B | 0.7966 (14) | −0.0220 (14) | −0.3027 (15) | 0.130 (5)* | 0.30 |
F14 | 0.3373 (2) | 0.1837 (2) | −0.3724 (2) | 0.0742 (8) | |
F15 | 0.4881 (3) | 0.1282 (2) | −0.48212 (19) | 0.0836 (9) | |
F16 | 0.4158 (3) | 0.02876 (19) | −0.3514 (2) | 0.0797 (9) | |
C1 | 0.4879 (3) | 0.5078 (3) | −0.2966 (3) | 0.0360 (8) | |
H1 | 0.4169 | 0.5393 | −0.3050 | 0.043* | |
C2 | 0.5798 (3) | 0.5222 (3) | −0.3733 (3) | 0.0412 (8) | |
C3 | 0.5654 (4) | 0.5929 (3) | −0.4666 (3) | 0.0590 (11) | |
H3A | 0.4850 | 0.6153 | −0.4588 | 0.071* | |
H3B | 0.5988 | 0.5562 | −0.5286 | 0.071* | |
H3C | 0.6031 | 0.6533 | −0.4729 | 0.071* | |
C4 | 0.6981 (3) | 0.4740 (3) | −0.3762 (3) | 0.0555 (10) | |
H4A | 0.6999 | 0.4453 | −0.3056 | 0.067* | |
H4B | 0.7479 | 0.5281 | −0.3987 | 0.067* | |
C5 | 0.7436 (5) | 0.3886 (4) | −0.4483 (4) | 0.0843 (17) | |
H5A | 0.8202 | 0.3594 | −0.4463 | 0.101* | |
H5B | 0.7448 | 0.4170 | −0.5188 | 0.101* | |
H5C | 0.6950 | 0.3344 | −0.4261 | 0.101* | |
C11 | 0.5378 (3) | 0.2759 (2) | −0.2217 (2) | 0.0320 (7) | |
C12 | 0.6373 (3) | 0.2174 (3) | −0.2161 (3) | 0.0381 (8) | |
H12 | 0.6816 | 0.2375 | −0.1789 | 0.046* | |
C13 | 0.6717 (3) | 0.1281 (3) | −0.2660 (3) | 0.0418 (8) | |
C14 | 0.6069 (3) | 0.0983 (3) | −0.3194 (3) | 0.0411 (8) | |
H14 | 0.6315 | 0.0371 | −0.3536 | 0.049* | |
C15 | 0.5061 (3) | 0.1578 (3) | −0.3229 (2) | 0.0373 (8) | |
C16 | 0.4688 (3) | 0.2478 (2) | −0.2735 (2) | 0.0333 (7) | |
H16 | 0.3991 | 0.2886 | −0.2749 | 0.040* | |
C17 | 0.7819 (4) | 0.0636 (4) | −0.2641 (4) | 0.0587 (11) | |
C18 | 0.4364 (4) | 0.1248 (3) | −0.3820 (3) | 0.0482 (9) | |
I2 | 0.127775 (18) | 0.327951 (17) | 0.047728 (15) | 0.03397 (7) | |
F21A | −0.2371 (15) | 0.154 (2) | 0.2939 (11) | 0.127 (7) | 0.50 |
F22A | −0.2508 (14) | 0.171 (2) | 0.4464 (14) | 0.146 (7) | 0.50 |
F23A | −0.1616 (15) | 0.0402 (12) | 0.379 (3) | 0.184 (8) | 0.50 |
F24A | 0.2325 (12) | 0.242 (2) | 0.4191 (12) | 0.155 (9) | 0.50 |
F25A | 0.1062 (19) | 0.1705 (19) | 0.5296 (12) | 0.161 (10) | 0.50 |
F26A | 0.0958 (16) | 0.3291 (12) | 0.4889 (13) | 0.174 (6) | 0.50 |
F21B | −0.2100 (16) | 0.090 (2) | 0.4471 (12) | 0.129 (8) | 0.50 |
F22B | −0.1968 (17) | 0.086 (2) | 0.2984 (14) | 0.131 (8) | 0.50 |
F23B | −0.2771 (7) | 0.2201 (8) | 0.366 (3) | 0.131 (4) | 0.50 |
F24B | 0.0844 (15) | 0.2210 (18) | 0.5437 (8) | 0.125 (8) | 0.50 |
F25B | 0.2074 (18) | 0.2915 (12) | 0.4342 (13) | 0.112 (7) | 0.50 |
F26B | 0.2265 (11) | 0.1323 (8) | 0.4419 (10) | 0.108 (3) | 0.50 |
C6 | 0.2628 (3) | 0.2088 (3) | 0.0117 (3) | 0.0392 (8) | |
H6 | 0.3313 | 0.2169 | 0.0235 | 0.047* | |
C7 | 0.2599 (3) | 0.1251 (3) | −0.0254 (3) | 0.0540 (10) | |
C8 | 0.3648 (4) | 0.0479 (3) | −0.0483 (3) | 0.0614 (11) | |
H8A | 0.4242 | 0.0729 | −0.0295 | 0.074* | |
H8B | 0.3896 | 0.0383 | −0.1220 | 0.074* | |
H8C | 0.3491 | −0.0181 | −0.0081 | 0.074* | |
C9A | 0.1506 (7) | 0.0848 (6) | −0.0254 (6) | 0.0577 (18) | 0.67 |
H9AA | 0.1467 | 0.0161 | 0.0141 | 0.069* | 0.67 |
H9AB | 0.0839 | 0.1323 | 0.0090 | 0.069* | 0.67 |
C10A | 0.1489 (8) | 0.0770 (10) | −0.1320 (8) | 0.093 (3) | 0.67 |
H10A | 0.0800 | 0.0509 | −0.1300 | 0.112* | 0.67 |
H10B | 0.2147 | 0.0297 | −0.1659 | 0.112* | 0.67 |
H10C | 0.1508 | 0.1453 | −0.1706 | 0.112* | 0.67 |
C9B | 0.1884 (12) | 0.1277 (10) | −0.0973 (12) | 0.056 (3) | 0.33 |
H9BA | 0.2357 | 0.1181 | −0.1687 | 0.067* | 0.33 |
H9BB | 0.1367 | 0.1934 | −0.0972 | 0.067* | 0.33 |
C10B | 0.1229 (16) | 0.0362 (16) | −0.051 (2) | 0.094 (6) | 0.33 |
H10D | 0.0733 | 0.0304 | −0.0923 | 0.113* | 0.33 |
H10E | 0.0776 | 0.0475 | 0.0201 | 0.113* | 0.33 |
H10F | 0.1761 | −0.0274 | −0.0503 | 0.113* | 0.33 |
C21 | 0.0635 (3) | 0.2679 (3) | 0.2016 (2) | 0.0349 (7) | |
C22 | −0.0369 (3) | 0.2273 (3) | 0.2290 (3) | 0.0406 (8) | |
H22 | −0.0760 | 0.2272 | 0.1794 | 0.049* | |
C23 | −0.0787 (3) | 0.1874 (3) | 0.3289 (3) | 0.0447 (9) | |
C24 | −0.0220 (3) | 0.1874 (3) | 0.4017 (3) | 0.0446 (9) | |
H24 | −0.0519 | 0.1599 | 0.4709 | 0.053* | |
C25 | 0.0782 (3) | 0.2276 (3) | 0.3727 (3) | 0.0449 (9) | |
C26 | 0.1222 (3) | 0.2694 (3) | 0.2717 (3) | 0.0393 (8) | |
H26 | 0.1905 | 0.2982 | 0.2519 | 0.047* | |
C27 | −0.1889 (5) | 0.1446 (5) | 0.3610 (4) | 0.0741 (15) | |
C28 | 0.1427 (6) | 0.2244 (5) | 0.4500 (4) | 0.0777 (17) | |
S1 | 0.51521 (7) | 0.69039 (6) | −0.11146 (6) | 0.03420 (19) | |
F31 | 0.5500 (2) | 0.86894 (18) | −0.2122 (2) | 0.0711 (7) | |
F32 | 0.5046 (3) | 0.7652 (2) | −0.29580 (18) | 0.0803 (9) | |
F33 | 0.3802 (2) | 0.8406 (2) | −0.1739 (2) | 0.0731 (7) | |
O31 | 0.4379 (2) | 0.62068 (19) | −0.10796 (19) | 0.0438 (6) | |
O32 | 0.4907 (2) | 0.7392 (2) | −0.01761 (18) | 0.0508 (7) | |
O33 | 0.6310 (2) | 0.6524 (2) | −0.1555 (2) | 0.0571 (7) | |
C30 | 0.4857 (4) | 0.7964 (3) | −0.2038 (3) | 0.0459 (9) | |
S2 | −0.15543 (7) | 0.52162 (7) | 0.20304 (6) | 0.03601 (19) | |
F41 | −0.1875 (3) | 0.6101 (2) | 0.3691 (2) | 0.0861 (9) | |
F42 | −0.0333 (3) | 0.5057 (2) | 0.3294 (2) | 0.0881 (9) | |
F43 | −0.0480 (2) | 0.6536 (2) | 0.2440 (2) | 0.0838 (9) | |
O41 | −0.0549 (2) | 0.4877 (2) | 0.12393 (18) | 0.0468 (6) | |
O42 | −0.2257 (2) | 0.6087 (2) | 0.16797 (19) | 0.0486 (6) | |
O43 | −0.2143 (2) | 0.4412 (2) | 0.2664 (2) | 0.0611 (8) | |
C40 | −0.1022 (4) | 0.5755 (3) | 0.2907 (3) | 0.0535 (10) | |
Cl1S | −0.14130 (12) | 0.23095 (10) | −0.02448 (12) | 0.0841 (4) | |
Cl2S | −0.22381 (13) | 0.42906 (13) | −0.11506 (14) | 0.1038 (6) | |
C1S | −0.1755 (4) | 0.3630 (3) | −0.0157 (4) | 0.0601 (11) | |
H1SA | −0.2339 | 0.3754 | 0.0504 | 0.072* | |
H1SB | −0.1079 | 0.3909 | −0.0144 | 0.072* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.03652 (13) | 0.02817 (12) | 0.02806 (11) | −0.00534 (9) | −0.00741 (9) | −0.00511 (8) |
F11A | 0.079 (3) | 0.053 (3) | 0.103 (4) | 0.019 (2) | −0.015 (3) | 0.035 (2) |
F12A | 0.049 (2) | 0.119 (4) | 0.053 (2) | 0.034 (2) | 0.0082 (18) | 0.007 (2) |
F13A | 0.109 (4) | 0.113 (5) | 0.240 (8) | 0.068 (4) | −0.129 (5) | −0.117 (5) |
F14 | 0.0753 (18) | 0.0678 (18) | 0.097 (2) | 0.0028 (15) | −0.0450 (16) | −0.0364 (15) |
F15 | 0.105 (2) | 0.111 (2) | 0.0428 (14) | −0.0354 (19) | −0.0155 (14) | −0.0201 (14) |
F16 | 0.122 (2) | 0.0434 (15) | 0.097 (2) | −0.0346 (16) | −0.0588 (19) | 0.0061 (13) |
C1 | 0.047 (2) | 0.0285 (18) | 0.0354 (18) | −0.0044 (15) | −0.0166 (16) | −0.0029 (14) |
C2 | 0.057 (2) | 0.0321 (19) | 0.0351 (19) | −0.0125 (17) | −0.0099 (17) | −0.0050 (15) |
C3 | 0.084 (3) | 0.051 (3) | 0.043 (2) | −0.022 (2) | −0.017 (2) | 0.0053 (19) |
C4 | 0.048 (2) | 0.059 (3) | 0.047 (2) | −0.014 (2) | 0.0025 (19) | 0.0064 (19) |
C5 | 0.083 (4) | 0.073 (4) | 0.059 (3) | 0.014 (3) | 0.018 (3) | 0.003 (2) |
C11 | 0.0422 (19) | 0.0232 (17) | 0.0249 (15) | −0.0044 (14) | −0.0009 (14) | −0.0028 (12) |
C12 | 0.041 (2) | 0.037 (2) | 0.0324 (18) | −0.0046 (16) | −0.0076 (15) | 0.0007 (14) |
C13 | 0.046 (2) | 0.032 (2) | 0.0379 (19) | 0.0018 (16) | −0.0043 (16) | 0.0012 (15) |
C14 | 0.058 (2) | 0.0250 (18) | 0.0312 (18) | −0.0035 (17) | −0.0002 (16) | −0.0034 (14) |
C15 | 0.049 (2) | 0.0286 (18) | 0.0300 (17) | −0.0066 (16) | −0.0045 (15) | −0.0018 (14) |
C16 | 0.0391 (19) | 0.0282 (18) | 0.0285 (16) | −0.0039 (14) | −0.0046 (14) | −0.0015 (13) |
C17 | 0.064 (3) | 0.054 (3) | 0.056 (3) | 0.008 (2) | −0.020 (2) | −0.013 (2) |
C18 | 0.066 (3) | 0.034 (2) | 0.046 (2) | −0.0077 (19) | −0.015 (2) | −0.0114 (17) |
I2 | 0.03403 (13) | 0.03573 (13) | 0.02830 (12) | 0.00270 (9) | −0.00715 (9) | −0.00373 (9) |
F21A | 0.089 (11) | 0.24 (2) | 0.080 (9) | −0.101 (13) | −0.045 (9) | 0.050 (12) |
F22A | 0.089 (10) | 0.26 (2) | 0.089 (9) | −0.100 (13) | 0.043 (8) | −0.069 (11) |
F23A | 0.143 (13) | 0.119 (11) | 0.31 (3) | −0.089 (10) | −0.083 (18) | 0.053 (15) |
F24A | 0.073 (6) | 0.34 (3) | 0.077 (6) | −0.071 (14) | −0.047 (5) | 0.002 (15) |
F25A | 0.200 (19) | 0.230 (19) | 0.110 (13) | −0.143 (15) | −0.126 (14) | 0.114 (12) |
F26A | 0.194 (12) | 0.251 (18) | 0.132 (10) | −0.041 (12) | −0.094 (9) | −0.081 (12) |
F21B | 0.114 (13) | 0.199 (19) | 0.089 (8) | −0.115 (14) | −0.041 (8) | 0.079 (11) |
F22B | 0.106 (12) | 0.179 (16) | 0.129 (14) | −0.097 (11) | 0.007 (8) | −0.072 (13) |
F23B | 0.036 (4) | 0.115 (7) | 0.227 (15) | −0.019 (4) | −0.018 (7) | 0.006 (10) |
F24B | 0.124 (8) | 0.25 (2) | 0.024 (4) | −0.099 (11) | −0.009 (4) | −0.015 (8) |
F25B | 0.192 (19) | 0.104 (7) | 0.091 (10) | −0.101 (10) | −0.091 (12) | 0.031 (6) |
F26B | 0.133 (8) | 0.089 (5) | 0.143 (8) | 0.022 (5) | −0.114 (7) | −0.024 (5) |
C6 | 0.0296 (18) | 0.042 (2) | 0.0413 (19) | 0.0068 (15) | −0.0087 (15) | −0.0061 (16) |
C7 | 0.053 (2) | 0.050 (3) | 0.058 (3) | 0.012 (2) | −0.019 (2) | −0.020 (2) |
C8 | 0.066 (3) | 0.048 (3) | 0.057 (3) | 0.013 (2) | −0.008 (2) | −0.009 (2) |
C9A | 0.061 (5) | 0.042 (4) | 0.069 (5) | −0.009 (3) | −0.011 (4) | −0.015 (4) |
C10A | 0.068 (6) | 0.126 (9) | 0.098 (7) | 0.006 (6) | −0.031 (6) | −0.057 (7) |
C9B | 0.069 (9) | 0.046 (8) | 0.049 (8) | −0.012 (7) | −0.004 (7) | −0.018 (7) |
C10B | 0.069 (12) | 0.076 (14) | 0.14 (2) | −0.018 (10) | −0.035 (13) | 0.017 (14) |
C21 | 0.0360 (19) | 0.0358 (19) | 0.0268 (16) | 0.0005 (15) | −0.0037 (14) | −0.0020 (14) |
C22 | 0.038 (2) | 0.047 (2) | 0.0379 (19) | −0.0028 (17) | −0.0150 (16) | −0.0038 (16) |
C23 | 0.047 (2) | 0.045 (2) | 0.043 (2) | −0.0151 (18) | −0.0106 (17) | 0.0000 (17) |
C24 | 0.053 (2) | 0.046 (2) | 0.0317 (18) | −0.0099 (18) | −0.0067 (17) | −0.0003 (16) |
C25 | 0.051 (2) | 0.052 (2) | 0.0339 (19) | −0.0113 (19) | −0.0131 (17) | −0.0041 (16) |
C26 | 0.044 (2) | 0.042 (2) | 0.0329 (18) | −0.0111 (17) | −0.0108 (16) | −0.0041 (15) |
C27 | 0.074 (4) | 0.102 (5) | 0.054 (3) | −0.048 (4) | −0.019 (3) | 0.010 (3) |
C28 | 0.095 (5) | 0.115 (5) | 0.040 (3) | −0.053 (4) | −0.027 (3) | 0.004 (3) |
S1 | 0.0406 (5) | 0.0296 (4) | 0.0330 (4) | −0.0050 (4) | −0.0119 (4) | −0.0017 (3) |
F31 | 0.095 (2) | 0.0414 (14) | 0.0751 (17) | −0.0265 (14) | −0.0212 (15) | 0.0130 (12) |
F32 | 0.136 (3) | 0.0642 (17) | 0.0403 (13) | 0.0008 (17) | −0.0345 (15) | −0.0039 (12) |
F33 | 0.0736 (18) | 0.0556 (16) | 0.092 (2) | 0.0172 (13) | −0.0411 (16) | −0.0077 (14) |
O31 | 0.0462 (15) | 0.0350 (14) | 0.0496 (15) | −0.0109 (11) | −0.0062 (12) | −0.0114 (11) |
O32 | 0.079 (2) | 0.0467 (16) | 0.0338 (13) | −0.0185 (14) | −0.0207 (13) | −0.0033 (11) |
O33 | 0.0386 (15) | 0.0486 (17) | 0.078 (2) | 0.0005 (13) | −0.0126 (14) | −0.0046 (14) |
C30 | 0.063 (3) | 0.036 (2) | 0.039 (2) | −0.0017 (19) | −0.0166 (18) | −0.0039 (16) |
S2 | 0.0352 (5) | 0.0390 (5) | 0.0297 (4) | 0.0005 (4) | −0.0058 (4) | −0.0043 (3) |
F41 | 0.104 (2) | 0.102 (2) | 0.0482 (15) | −0.0071 (18) | −0.0059 (15) | −0.0360 (15) |
F42 | 0.099 (2) | 0.108 (2) | 0.0738 (19) | 0.0056 (19) | −0.0604 (17) | −0.0068 (16) |
F43 | 0.084 (2) | 0.081 (2) | 0.097 (2) | −0.0387 (17) | −0.0219 (17) | −0.0181 (16) |
O41 | 0.0459 (15) | 0.0512 (16) | 0.0337 (13) | 0.0117 (12) | −0.0051 (11) | −0.0097 (11) |
O42 | 0.0406 (15) | 0.0560 (17) | 0.0400 (14) | 0.0120 (12) | −0.0084 (12) | −0.0049 (12) |
O43 | 0.0576 (18) | 0.0531 (18) | 0.0653 (19) | −0.0182 (15) | −0.0065 (15) | 0.0074 (14) |
C40 | 0.058 (3) | 0.061 (3) | 0.042 (2) | −0.008 (2) | −0.014 (2) | −0.0095 (19) |
Cl1S | 0.0840 (9) | 0.0584 (8) | 0.1087 (11) | −0.0079 (7) | −0.0279 (8) | −0.0051 (7) |
Cl2S | 0.0778 (9) | 0.1024 (11) | 0.1505 (15) | −0.0380 (8) | −0.0754 (10) | 0.0511 (10) |
C1S | 0.043 (2) | 0.063 (3) | 0.076 (3) | 0.007 (2) | −0.026 (2) | −0.013 (2) |
I1—O31 | 2.767 (2) | F25B—C28 | 1.263 (12) |
I1—O32i | 2.985 (3) | F26B—C28 | 1.458 (10) |
I1—C1 | 2.093 (3) | C6—C7 | 1.293 (5) |
I1—C11 | 2.111 (3) | C6—H6 | 0.9500 |
F11A—C17 | 1.337 (6) | C7—C8 | 1.500 (5) |
F12A—C17 | 1.305 (6) | C7—C9A | 1.559 (9) |
F13A—C17 | 1.346 (6) | C7—C9B | 1.512 (15) |
F11B—C17 | 1.319 (13) | C8—H8A | 0.9800 |
F12B—C17 | 1.159 (14) | C8—H8B | 0.9800 |
F13B—C17 | 1.278 (16) | C8—H8C | 0.9800 |
F14—C18 | 1.330 (5) | C9A—C10A | 1.481 (11) |
F15—C18 | 1.323 (4) | C9A—H9AA | 0.9900 |
F16—C18 | 1.326 (4) | C9A—H9AB | 0.9900 |
C1—C2 | 1.326 (5) | C10A—H10A | 0.9800 |
C1—H1 | 0.9500 | C10A—H10B | 0.9800 |
C2—C3 | 1.508 (5) | C10A—H10C | 0.9800 |
C2—C4 | 1.504 (6) | C9B—C10B | 1.54 (2) |
C3—H3A | 0.9800 | C9B—H9BA | 0.9900 |
C3—H3B | 0.9800 | C9B—H9BB | 0.9900 |
C3—H3C | 0.9800 | C10B—H10D | 0.9800 |
C4—C5 | 1.524 (6) | C10B—H10E | 0.9800 |
C4—H4A | 0.9900 | C10B—H10F | 0.9800 |
C4—H4B | 0.9900 | C21—C22 | 1.385 (5) |
C5—H5A | 0.9800 | C21—C26 | 1.379 (4) |
C5—H5B | 0.9800 | C22—C23 | 1.371 (5) |
C5—H5C | 0.9800 | C22—H22 | 0.9500 |
C11—C12 | 1.367 (5) | C23—C24 | 1.388 (5) |
C11—C16 | 1.397 (4) | C23—C27 | 1.508 (6) |
C12—C13 | 1.385 (5) | C24—C25 | 1.381 (5) |
C12—H12 | 0.9500 | C24—H24 | 0.9500 |
C13—C14 | 1.381 (5) | C25—C26 | 1.395 (5) |
C13—C17 | 1.500 (6) | C25—C28 | 1.504 (6) |
C14—C15 | 1.379 (5) | C26—H26 | 0.9500 |
C14—H14 | 0.9500 | S1—O31 | 1.441 (2) |
C15—C16 | 1.391 (4) | S1—O32 | 1.443 (2) |
C15—C18 | 1.510 (5) | S1—O33 | 1.426 (3) |
C16—H16 | 0.9500 | S1—C30 | 1.815 (4) |
I2—O41 | 2.881 (2) | F31—C30 | 1.333 (4) |
I2—O42ii | 2.893 (3) | F32—C30 | 1.319 (4) |
I2—C6 | 2.094 (3) | F33—C30 | 1.318 (5) |
I2—C21 | 2.104 (3) | S2—O41 | 1.443 (2) |
F21A—C27 | 1.224 (11) | S2—O42 | 1.442 (3) |
F22A—C27 | 1.247 (11) | S2—O43 | 1.435 (3) |
F23A—C27 | 1.370 (16) | S2—C40 | 1.812 (4) |
F24A—C28 | 1.136 (13) | F41—C40 | 1.334 (5) |
F25A—C28 | 1.223 (15) | F42—C40 | 1.319 (5) |
F26A—C28 | 1.511 (14) | F43—C40 | 1.319 (5) |
F21B—C27 | 1.273 (12) | Cl1S—C1S | 1.738 (5) |
F22B—C27 | 1.266 (12) | Cl2S—C1S | 1.718 (5) |
F23B—C27 | 1.348 (11) | C1S—H1SA | 0.9900 |
F24B—C28 | 1.268 (13) | C1S—H1SB | 0.9900 |
O31—I1—O32i | 115.02 (7) | C9A—C10A—H10A | 109.5 |
O31—I1—C1 | 75.04 (10) | C9A—C10A—H10B | 109.5 |
O31—I1—C11 | 170.49 (10) | C9A—C10A—H10C | 109.5 |
O32i—I1—C1 | 169.94 (10) | H10A—C10A—H10B | 109.5 |
O32i—I1—C11 | 74.41 (10) | H10A—C10A—H10C | 109.5 |
C1—I1—C11 | 95.52 (12) | H10B—C10A—H10C | 109.5 |
I1—C1—C2 | 123.0 (3) | C7—C9B—C10B | 102.5 (15) |
I1—C1—H1 | 118.5 | C7—C9B—H9BA | 111.3 |
C2—C1—H1 | 118.5 | C7—C9B—H9BB | 111.3 |
C1—C2—C3 | 117.7 (4) | C10B—C9B—H9BA | 111.3 |
C1—C2—C4 | 125.9 (3) | C10B—C9B—H9BB | 111.3 |
C3—C2—C4 | 116.4 (3) | H9BA—C9B—H9BB | 109.2 |
C2—C3—H3A | 109.5 | C9B—C10B—H10D | 109.5 |
C2—C3—H3B | 109.5 | C9B—C10B—H10E | 109.5 |
C2—C3—H3C | 109.5 | C9B—C10B—H10F | 109.5 |
H3A—C3—H3B | 109.5 | H10D—C10B—H10E | 109.5 |
H3A—C3—H3C | 109.5 | H10D—C10B—H10F | 109.5 |
H3B—C3—H3C | 109.5 | H10E—C10B—H10F | 109.5 |
C2—C4—C5 | 113.0 (4) | I2—C21—C22 | 118.6 (2) |
C2—C4—H4A | 109.0 | I2—C21—C26 | 119.4 (2) |
C2—C4—H4B | 109.0 | C22—C21—C26 | 122.0 (3) |
C5—C4—H4A | 109.0 | C21—C22—C23 | 118.8 (3) |
C5—C4—H4B | 109.0 | C21—C22—H22 | 120.6 |
H4A—C4—H4B | 107.8 | C23—C22—H22 | 120.6 |
C4—C5—H5A | 109.5 | C22—C23—C24 | 120.9 (3) |
C4—C5—H5B | 109.5 | C22—C23—C27 | 119.8 (3) |
C4—C5—H5C | 109.5 | C24—C23—C27 | 119.3 (4) |
H5A—C5—H5B | 109.5 | C23—C24—C25 | 119.4 (3) |
H5A—C5—H5C | 109.5 | C23—C24—H24 | 120.3 |
H5B—C5—H5C | 109.5 | C25—C24—H24 | 120.3 |
I1—C11—C12 | 118.6 (2) | C24—C25—C26 | 120.8 (3) |
I1—C11—C16 | 118.7 (2) | C24—C25—C28 | 119.9 (4) |
C12—C11—C16 | 122.6 (3) | C26—C25—C28 | 119.3 (4) |
C11—C12—C13 | 118.4 (3) | C21—C26—C25 | 118.0 (3) |
C11—C12—H12 | 120.8 | C21—C26—H26 | 121.0 |
C13—C12—H12 | 120.8 | C25—C26—H26 | 121.0 |
C12—C13—C14 | 120.9 (3) | F21A—C27—F22A | 114.3 (12) |
C12—C13—C17 | 119.9 (3) | F21A—C27—F23A | 104.3 (11) |
C14—C13—C17 | 119.2 (3) | F21A—C27—C23 | 115.0 (7) |
C13—C14—C15 | 119.7 (3) | F22A—C27—F23A | 103.4 (11) |
C13—C14—H14 | 120.2 | F22A—C27—C23 | 112.8 (7) |
C15—C14—H14 | 120.2 | F23A—C27—C23 | 105.6 (8) |
C14—C15—C16 | 121.0 (3) | F21B—C27—F22B | 103.4 (11) |
C14—C15—C18 | 119.2 (3) | F21B—C27—F23B | 106.8 (10) |
C16—C15—C18 | 119.9 (3) | F21B—C27—C23 | 115.8 (7) |
C11—C16—C15 | 117.4 (3) | F22B—C27—F23B | 104.7 (10) |
C11—C16—H16 | 121.3 | F22B—C27—C23 | 113.6 (8) |
C15—C16—H16 | 121.3 | F23B—C27—C23 | 111.6 (6) |
F11A—C17—F12A | 104.1 (4) | F24A—C28—F25A | 125.1 (13) |
F11A—C17—F13A | 103.5 (6) | F24A—C28—F26A | 94.0 (12) |
F11A—C17—C13 | 112.3 (4) | F24A—C28—C25 | 117.2 (8) |
F12A—C17—F13A | 108.3 (5) | F25A—C28—F26A | 98.9 (12) |
F12A—C17—C13 | 113.9 (4) | F25A—C28—C25 | 112.8 (8) |
F13A—C17—C13 | 113.7 (4) | F26A—C28—C25 | 99.4 (6) |
F11B—C17—F12B | 104.5 (9) | F24B—C28—F25B | 108.5 (11) |
F11B—C17—F13B | 106.0 (11) | F24B—C28—F26B | 105.7 (11) |
F11B—C17—C13 | 109.1 (7) | F24B—C28—C25 | 115.6 (9) |
F12B—C17—F13B | 108.0 (11) | F25B—C28—F26B | 98.8 (10) |
F12B—C17—C13 | 115.6 (8) | F25B—C28—C25 | 116.8 (8) |
F13B—C17—C13 | 112.9 (8) | F26B—C28—C25 | 109.6 (5) |
F14—C18—F15 | 106.0 (3) | O31—S1—O32 | 113.82 (15) |
F14—C18—F16 | 107.0 (3) | O31—S1—O33 | 114.71 (16) |
F14—C18—C15 | 113.3 (3) | O31—S1—C30 | 104.05 (17) |
F15—C18—F16 | 106.9 (3) | O32—S1—O33 | 115.31 (17) |
F15—C18—C15 | 111.8 (3) | O32—S1—C30 | 103.24 (16) |
F16—C18—C15 | 111.5 (3) | O33—S1—C30 | 103.67 (19) |
O41—I2—O42ii | 106.24 (7) | I1—O31—S1 | 126.92 (14) |
O41—I2—C6 | 172.58 (10) | S1—C30—F31 | 110.3 (3) |
O41—I2—C21 | 78.73 (10) | S1—C30—F32 | 111.5 (3) |
O42ii—I2—C6 | 80.17 (11) | S1—C30—F33 | 111.3 (3) |
O42ii—I2—C21 | 174.69 (10) | F31—C30—F32 | 108.5 (3) |
C6—I2—C21 | 94.99 (13) | F31—C30—F33 | 106.8 (3) |
I2—C6—C7 | 124.9 (3) | F32—C30—F33 | 108.3 (3) |
I2—C6—H6 | 117.5 | O41—S2—O42 | 113.58 (15) |
C7—C6—H6 | 117.5 | O41—S2—O43 | 115.53 (17) |
C6—C7—C8 | 118.2 (4) | O41—S2—C40 | 103.44 (18) |
C6—C7—C9A | 125.2 (4) | O42—S2—O43 | 115.20 (17) |
C6—C7—C9B | 119.7 (6) | O42—S2—C40 | 103.00 (18) |
C8—C7—C9A | 115.1 (4) | O43—S2—C40 | 103.86 (19) |
C8—C7—C9B | 113.7 (6) | I2—O41—S2 | 149.20 (16) |
C7—C8—H8A | 109.5 | S2—C40—F41 | 110.0 (3) |
C7—C8—H8B | 109.5 | S2—C40—F42 | 111.4 (3) |
C7—C8—H8C | 109.5 | S2—C40—F43 | 111.3 (3) |
H8A—C8—H8B | 109.5 | F41—C40—F42 | 107.8 (4) |
H8A—C8—H8C | 109.5 | F41—C40—F43 | 107.8 (4) |
H8B—C8—H8C | 109.5 | F42—C40—F43 | 108.4 (4) |
C7—C9A—C10A | 110.9 (8) | Cl1S—C1S—Cl2S | 113.8 (3) |
C7—C9A—H9AA | 109.5 | Cl1S—C1S—H1SA | 108.8 |
C7—C9A—H9AB | 109.5 | Cl1S—C1S—H1SB | 108.8 |
C10A—C9A—H9AA | 109.5 | Cl2S—C1S—H1SA | 108.8 |
C10A—C9A—H9AB | 109.5 | Cl2S—C1S—H1SB | 108.8 |
H9AA—C9A—H9AB | 108.0 | H1SA—C1S—H1SB | 107.7 |
O32i—I1—O31—S1 | 90.75 (18) | C26—C21—C22—C23 | −0.2 (5) |
C1—I1—O31—S1 | −89.1 (2) | I2—C21—C26—C25 | −179.1 (3) |
O31—I1—C1—C2 | 108.0 (3) | C22—C21—C26—C25 | 0.6 (5) |
O32i—I1—C1—C2 | −71.2 (7) | C21—C22—C23—C24 | 0.1 (6) |
C11—I1—C1—C2 | −70.8 (3) | C21—C22—C23—C27 | 178.9 (4) |
O32i—I1—C11—C12 | −60.8 (3) | C22—C23—C24—C25 | −0.4 (6) |
O32i—I1—C11—C16 | 123.1 (3) | C27—C23—C24—C25 | −179.2 (4) |
C1—I1—C11—C12 | 119.2 (3) | C23—C24—C25—C26 | 0.9 (6) |
C1—I1—C11—C16 | −56.8 (3) | C23—C24—C25—C28 | −177.7 (4) |
I1—C1—C2—C3 | −176.5 (2) | C24—C25—C26—C21 | −1.0 (6) |
I1—C1—C2—C4 | 3.5 (5) | C28—C25—C26—C21 | 177.6 (4) |
C1—C2—C4—C5 | 106.2 (4) | C22—C23—C27—F21A | −3.8 (19) |
C3—C2—C4—C5 | −73.8 (4) | C22—C23—C27—F22A | −137.2 (19) |
I1—C11—C12—C13 | −174.3 (2) | C22—C23—C27—F23A | 110.5 (18) |
C16—C11—C12—C13 | 1.6 (5) | C22—C23—C27—F21B | 165.4 (17) |
I1—C11—C16—C15 | 174.2 (2) | C22—C23—C27—F22B | 45.9 (18) |
C12—C11—C16—C15 | −1.7 (5) | C22—C23—C27—F23B | −72.1 (16) |
C11—C12—C13—C14 | −0.6 (5) | C24—C23—C27—F21A | 175.0 (18) |
C11—C12—C13—C17 | 178.3 (3) | C24—C23—C27—F22A | 42 (2) |
C12—C13—C14—C15 | −0.3 (5) | C24—C23—C27—F23A | −70.6 (19) |
C17—C13—C14—C15 | −179.1 (4) | C24—C23—C27—F21B | −15.8 (19) |
C13—C14—C15—C16 | 0.1 (5) | C24—C23—C27—F22B | −135.2 (17) |
C13—C14—C15—C18 | 179.6 (3) | C24—C23—C27—F23B | 106.7 (16) |
C14—C15—C16—C11 | 0.8 (5) | C24—C25—C28—F24A | 167.3 (17) |
C18—C15—C16—C11 | −178.7 (3) | C24—C25—C28—F25A | 10.6 (17) |
C12—C13—C17—F11A | 120.9 (5) | C24—C25—C28—F26A | −93.3 (11) |
C12—C13—C17—F12A | −121.0 (5) | C24—C25—C28—F24B | −25.5 (14) |
C12—C13—C17—F13A | 3.7 (8) | C24—C25—C28—F25B | −155.0 (13) |
C12—C13—C17—F11B | −70.1 (9) | C24—C25—C28—F26B | 93.7 (9) |
C12—C13—C17—F12B | 47.2 (10) | C26—C25—C28—F24A | −11.3 (19) |
C12—C13—C17—F13B | 172.3 (10) | C26—C25—C28—F25A | −168.0 (15) |
C14—C13—C17—F11A | −60.2 (6) | C26—C25—C28—F26A | 88.1 (11) |
C14—C13—C17—F12A | 57.8 (6) | C26—C25—C28—F24B | 155.9 (13) |
C14—C13—C17—F13A | −177.4 (6) | C26—C25—C28—F25B | 26.4 (14) |
C14—C13—C17—F11B | 108.8 (8) | C26—C25—C28—F26B | −84.8 (8) |
C14—C13—C17—F12B | −133.9 (9) | O32—S1—O31—I1 | −129.07 (17) |
C14—C13—C17—F13B | −8.8 (12) | O33—S1—O31—I1 | 6.8 (2) |
C14—C15—C18—F14 | 174.8 (3) | C30—S1—O31—I1 | 119.31 (19) |
C14—C15—C18—F15 | −65.5 (5) | O31—S1—C30—F31 | 178.1 (3) |
C14—C15—C18—F16 | 54.0 (5) | O31—S1—C30—F32 | −61.3 (3) |
C16—C15—C18—F14 | −5.8 (5) | O31—S1—C30—F33 | 59.8 (3) |
C16—C15—C18—F15 | 113.9 (4) | O32—S1—C30—F31 | 59.0 (3) |
C16—C15—C18—F16 | −126.5 (4) | O32—S1—C30—F32 | 179.6 (3) |
O42ii—I2—O41—S2 | 165.1 (3) | O32—S1—C30—F33 | −59.3 (3) |
C21—I2—O41—S2 | −13.0 (3) | O33—S1—C30—F31 | −61.6 (3) |
O42ii—I2—C6—C7 | −87.1 (4) | O33—S1—C30—F32 | 59.0 (3) |
C21—I2—C6—C7 | 90.7 (4) | O33—S1—C30—F33 | −179.9 (3) |
O41—I2—C21—C22 | 74.7 (3) | O42—S2—O41—I2 | −159.6 (3) |
O41—I2—C21—C26 | −105.6 (3) | O43—S2—O41—I2 | −23.3 (4) |
C6—I2—C21—C22 | −109.3 (3) | C40—S2—O41—I2 | 89.5 (3) |
C6—I2—C21—C26 | 70.4 (3) | O41—S2—C40—F41 | −179.8 (3) |
I2—C6—C7—C8 | 179.2 (3) | O41—S2—C40—F42 | −60.3 (3) |
I2—C6—C7—C9A | −15.7 (7) | O41—S2—C40—F43 | 60.8 (3) |
I2—C6—C7—C9B | 33.1 (8) | O42—S2—C40—F41 | 61.7 (3) |
C6—C7—C9A—C10A | 119.5 (7) | O42—S2—C40—F42 | −178.8 (3) |
C6—C7—C9B—C10B | −131.2 (11) | O42—S2—C40—F43 | −57.7 (3) |
C8—C7—C9A—C10A | −75.1 (8) | O43—S2—C40—F41 | −58.8 (4) |
C8—C7—C9B—C10B | 81.3 (13) | O43—S2—C40—F42 | 60.7 (3) |
I2—C21—C22—C23 | 179.5 (3) | O43—S2—C40—F43 | −178.2 (3) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C12H13F3I+·CF3O3S− | C11H12Cl2I+·CF3O3S− | 2C13H12F6I+·2CF3O3S−·CH2Cl2 |
Mr | 490.19 | 491.08 | 1201.32 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 193 | 193 | 193 |
a, b, c (Å) | 6.5676 (7), 17.2459 (18), 15.7394 (16) | 9.1705 (10), 13.4357 (15), 15.6030 (17) | 12.5807 (13), 13.2381 (14), 13.6567 (14) |
α, β, γ (°) | 90, 96.803 (10), 90 | 69.245 (10), 88.342 (10), 74.358 (10) | 81.854 (10), 72.429 (10), 79.851 (10) |
V (Å3) | 1770.2 (3) | 1726.4 (3) | 2124.9 (4) |
Z | 4 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.99 | 2.32 | 1.82 |
Crystal size (mm) | 0.33 × 0.22 × 0.13 | 0.49 × 0.07 × 0.04 | 0.39 × 0.17 × 0.12 |
Data collection | |||
Diffractometer | Bruker P4/RA/SMART 1000 CCD area-detector diffractometer | Bruker PLATFORM/SMART 1000 CCD area-detector diffractometer | Bruker P4/RA/SMART 1000 CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Integration (SHELXTL; Sheldrick, 1997a) | Integration (SHELXTL; Sheldrick, 1997a) |
Tmin, Tmax | 0.601, 0.772 | 0.559, 0.922 | 0.629, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8591, 3622, 2912 | 8587, 6950, 4412 | 12749, 8628, 6911 |
Rint | 0.028 | 0.049 | 0.027 |
(sin θ/λ)max (Å−1) | 0.625 | 0.628 | 0.626 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.144, 1.04 | 0.059, 0.152, 0.96 | 0.032, 0.078, 0.97 |
No. of reflections | 3622 | 6950 | 8628 |
No. of parameters | 256 | 399 | 618 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.40, −1.16 | 2.07, −1.21 | 0.49, −0.64 |
Computer programs: SMART (Bruker, 1997), SMART (Bruker 1997), SMART, SHELXTL (Sheldrick, 1997a), SHELXS97 (Sheldrick, 1990), DIRDIF96 (Beurskens et al., 1996), SHELXL97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997), SHELXTL.
I—C1 | 2.086 (6) | C4—C5B | 1.39 (2) |
I—O1 | 2.909 (6) | S—O1 | 1.391 (5) |
I—O2i | 2.991 (8) | S—O2 | 1.403 (6) |
I—C11 | 2.106 (6) | S—O3 | 1.405 (6) |
C1—C2 | 1.319 (8) | S—C20 | 1.794 (9) |
C2—C3 | 1.502 (9) | F4—C20 | 1.321 (11) |
C2—C4 | 1.503 (10) | F5—C20 | 1.378 (14) |
C4—C5A | 1.429 (16) | F6—C20 | 1.268 (10) |
O1—I—O2i | 105.86 (19) | O1—S—O2 | 110.9 (5) |
O1—I—C1 | 171.2 (2) | O1—S—O3 | 122.4 (5) |
O1—I—C11 | 76.64 (18) | O2—S—O3 | 109.6 (5) |
O2i—I—C1 | 82.9 (2) | O1—S—C20 | 104.2 (4) |
O2i—I—C11 | 168.2 (2) | O2—S—C20 | 102.9 (6) |
C1—I—C11 | 94.9 (2) | O3—S—C20 | 104.7 (4) |
I—C1—C2 | 124.2 (5) | I—O1—S | 114.7 (3) |
C1—C2—C3 | 117.4 (6) | S—C20—F4 | 112.4 (7) |
C1—C2—C4 | 126.0 (6) | S—C20—F5 | 109.0 (8) |
C3—C2—C4 | 116.6 (6) | S—C20—F6 | 115.5 (7) |
C2—C4—C5A | 115.3 (9) | F4—C20—F5 | 106.4 (9) |
C2—C4—C5B | 120.4 (12) | F4—C20—F6 | 109.7 (9) |
I—C11—C12 | 118.3 (4) | F5—C20—F6 | 103.0 (9) |
I—C11—C16 | 120.2 (4) |
Symmetry code: (i) −x, −y, −z+1. |
I1—O1 | 2.848 (6) | C9—C10 | 1.510 (14) |
I1—O2i | 2.802 (6) | S1—O1 | 1.432 (6) |
I1—C1 | 2.106 (8) | S1—O2 | 1.436 (6) |
I1—C11 | 2.119 (8) | S1—O3 | 1.426 (7) |
C1—C2 | 1.297 (11) | S1—C30 | 1.819 (11) |
C2—C3 | 1.525 (11) | F1—C30 | 1.330 (13) |
C2—C4 | 1.503 (11) | F2—C30 | 1.345 (11) |
C4—C5 | 1.520 (13) | F3—C30 | 1.299 (13) |
I2—O4 | 2.832 (6) | S2—O4 | 1.431 (6) |
I2—O5ii | 2.850 (6) | S2—O5 | 1.443 (6) |
I2—C6 | 2.098 (8) | S2—O6 | 1.430 (6) |
I2—C21 | 2.127 (8) | S2—C40 | 1.822 (10) |
C6—C7 | 1.313 (12) | F4—C40 | 1.319 (11) |
C7—C8 | 1.524 (12) | F5—C40 | 1.327 (11) |
C7—C9 | 1.492 (12) | F6—C40 | 1.349 (11) |
O1—I1—O2i | 98.49 (18) | O1—S1—O2 | 114.5 (4) |
O1—I1—C1 | 173.8 (3) | O1—S1—O3 | 115.2 (4) |
O1—I1—C11 | 80.9 (3) | O2—S1—O3 | 115.3 (4) |
O2i—I1—C1 | 87.1 (3) | O1—S1—C30 | 102.4 (5) |
O2i—I1—C11 | 179.0 (3) | O2—S1—C30 | 102.5 (4) |
C1—I1—C11 | 93.5 (3) | O3—S1—C30 | 104.5 (5) |
I1—C1—C2 | 122.6 (6) | I1—O1—S1 | 151.5 (4) |
C1—C2—C3 | 117.2 (8) | S1—C30—F1 | 111.1 (8) |
C1—C2—C4 | 127.0 (8) | S1—C30—F2 | 110.1 (7) |
C3—C2—C4 | 115.8 (7) | S1—C30—F3 | 112.8 (8) |
C2—C4—C5 | 113.5 (8) | F1—C30—F2 | 107.1 (9) |
I1—C11—C12 | 119.1 (6) | F1—C30—F3 | 107.3 (9) |
I1—C11—C16 | 117.6 (6) | F2—C30—F3 | 108.1 (9) |
O4—I2—O5ii | 98.26 (18) | O4—S2—O5 | 114.8 (4) |
O4—I2—C6 | 174.1 (3) | O4—S2—O6 | 115.3 (4) |
O4—I2—C21 | 80.6 (3) | O4—S2—C40 | 102.9 (4) |
O5ii—I2—C6 | 87.4 (3) | O5—S2—O6 | 115.0 (4) |
O5ii—I2—C21 | 178.6 (3) | O5—S2—C40 | 102.6 (4) |
C6—I2—C21 | 93.7 (3) | O6—S2—C40 | 103.8 (4) |
I2—C6—C7 | 122.7 (7) | I2—O4—S2 | 154.4 (4) |
C6—C7—C8 | 118.0 (8) | S2—C40—F4 | 112.4 (7) |
C6—C7—C9 | 127.0 (8) | S2—C40—F5 | 111.3 (7) |
C8—C7—C9 | 114.9 (8) | S2—C40—F6 | 111.1 (7) |
C7—C9—C10 | 112.9 (8) | F4—C40—F5 | 108.8 (8) |
I2—C21—C22 | 118.0 (6) | F4—C40—F6 | 106.7 (8) |
I2—C21—C26 | 117.7 (6) | F5—C40—F6 | 106.3 (8) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z+1. |
I1—O31 | 2.767 (2) | C9A—C10A | 1.481 (11) |
I1—O32i | 2.985 (3) | C9B—C10B | 1.54 (2) |
I1—C1 | 2.093 (3) | S1—O31 | 1.441 (2) |
I1—C11 | 2.111 (3) | S1—O32 | 1.443 (2) |
C1—C2 | 1.326 (5) | S1—O33 | 1.426 (3) |
C2—C3 | 1.508 (5) | S1—C30 | 1.815 (4) |
C2—C4 | 1.504 (6) | F31—C30 | 1.333 (4) |
C4—C5 | 1.524 (6) | F32—C30 | 1.319 (4) |
I2—O41 | 2.881 (2) | F33—C30 | 1.318 (5) |
I2—O42ii | 2.893 (3) | S2—O41 | 1.443 (2) |
I2—C6 | 2.094 (3) | S2—O42 | 1.442 (3) |
I2—C21 | 2.104 (3) | S2—O43 | 1.435 (3) |
C6—C7 | 1.293 (5) | S2—C40 | 1.812 (4) |
C7—C8 | 1.500 (5) | F41—C40 | 1.334 (5) |
C7—C9A | 1.559 (9) | F42—C40 | 1.319 (5) |
C7—C9B | 1.512 (15) | F43—C40 | 1.319 (5) |
O31—I1—O32i | 115.02 (7) | I2—C21—C26 | 119.4 (2) |
O31—I1—C1 | 75.04 (10) | O31—S1—O32 | 113.82 (15) |
O31—I1—C11 | 170.49 (10) | O31—S1—O33 | 114.71 (16) |
O32i—I1—C1 | 169.94 (10) | O31—S1—C30 | 104.05 (17) |
O32i—I1—C11 | 74.41 (10) | O32—S1—O33 | 115.31 (17) |
C1—I1—C11 | 95.52 (12) | O32—S1—C30 | 103.24 (16) |
I1—C1—C2 | 123.0 (3) | O33—S1—C30 | 103.67 (19) |
C1—C2—C3 | 117.7 (4) | I1—O31—S1 | 126.92 (14) |
C1—C2—C4 | 125.9 (3) | S1—C30—F31 | 110.3 (3) |
C3—C2—C4 | 116.4 (3) | S1—C30—F32 | 111.5 (3) |
C2—C4—C5 | 113.0 (4) | S1—C30—F33 | 111.3 (3) |
I1—C11—C12 | 118.6 (2) | F31—C30—F32 | 108.5 (3) |
I1—C11—C16 | 118.7 (2) | F31—C30—F33 | 106.8 (3) |
O41—I2—O42ii | 106.24 (7) | F32—C30—F33 | 108.3 (3) |
O41—I2—C6 | 172.58 (10) | O41—S2—O42 | 113.58 (15) |
O41—I2—C21 | 78.73 (10) | O41—S2—O43 | 115.53 (17) |
O42ii—I2—C6 | 80.17 (11) | O41—S2—C40 | 103.44 (18) |
O42ii—I2—C21 | 174.69 (10) | O42—S2—O43 | 115.20 (17) |
C6—I2—C21 | 94.99 (13) | O42—S2—C40 | 103.00 (18) |
I2—C6—C7 | 124.9 (3) | O43—S2—C40 | 103.86 (19) |
C6—C7—C8 | 118.2 (4) | I2—O41—S2 | 149.20 (16) |
C6—C7—C9A | 125.2 (4) | S2—C40—F41 | 110.0 (3) |
C6—C7—C9B | 119.7 (6) | S2—C40—F42 | 111.4 (3) |
C8—C7—C9A | 115.1 (4) | S2—C40—F43 | 111.3 (3) |
C8—C7—C9B | 113.7 (6) | F41—C40—F42 | 107.8 (4) |
C7—C9A—C10A | 110.9 (8) | F41—C40—F43 | 107.8 (4) |
C7—C9B—C10B | 102.5 (15) | F42—C40—F43 | 108.4 (4) |
I2—C21—C22 | 118.6 (2) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z. |
We have recently shown that alkenyl(aryl)iodonium trifluoromethanesulfonate salts are highly reactive in fragmentation reactions and that an increase in the effective electron-withdrawing nature of the aryl ring increases reactivity (Hinkle & Thomas, 1997; Hinkle et al., 1999; McNeil et al., 2001). In this regard, alkenyl(aryl)iodonium salts are known to be highly reactive alkenylhalide equivalents. The phenyliodonio compounds react 106 times faster in solvolysis experiments than the corresponding trifluoromethanesulfonates (Okuyama et al., 1995). This enhanced reactivity could potentially lead to a variety of new reactions. In fact, alkenyl(phenyl)iodonium tetrafluoroborates are known to be electrophiles in vinylic SN2 substitution reactions (Okuyama et al., 1998, 2001). It was hoped that the increased reactivity of salts containing electron-withdrawing groups on the aromatic ring would lead to vinylic C—I bond elongation proportional to the reactivity. Herein, we report the structures of three different alkenyl(aryl)iodonium trifluoromethanesulfonates, (I), (II) and (III), which show that the structures do not display this relationship. \sch
The alkenyl(aryl)iodonium salts (I)-(III) were obtained by the reaction of `iodonium transfer' reagents (Zhdankin et al., 1993) with stereoisomerically pure (Z)-2-methylbut-1-en-1-yltributylstannane and crystallized from CH2Cl2 by diffusion of pentane. Compound (I) provided monoclinic crystals, whereas both (II) and (III) were triclinic. The crystal of (I) (Fig. 1) contains a single dimeric unit, whereas crystals of (II) (Figs. 2 and 3) and (III) (Figs. 4 and 5) each contain two crystallographically independent dimeric units.
Previously, many iodonium salt structures have been described, including only the closest contact trifluoromethanesulfonate interaction, and have been designated as `T-shaped' trigonal bipyramidal geometries in which the vinylic moiety occupies an equatorial position relative to I, whereas the phenyl moiety and trifluoromethanesulfonate counter-ion are axial. If one considers only the interaction between the closest trifluoromethanesulfonate anion and the I atom, salts (I)-(III) reveal trigonal bipyramidal geometries about the cationic I atom. In this sense, these salts are considered hypervalent 8-I-2 derivatives of iodine in the Martin-Arduengo formalism (Perkins et al., 1980). This geometry is typical of 8-I-2 iodonium compounds, whether they are diaryl-, alkynyl- or alkenyl(aryl)iodonium salts (Varvoglis, 1992; Stang & Zhdankin, 1993).
Each unit cell for (I)-(III) contains two alkenyl(aryl)iodonium trifluoromethanesulfonates which are held in a dimeric arrangement about the I centers, giving the iodonium salts distorted square-planar geometries rather than trigonal pyramidal as described above. The positively charged I atom simultaneously interacts with both trifluoromethanesulfonates, although contact is slightly closer to one of the two. For instance, in one dimer of compound (III), the distance between the I atom and the closest O atom of a trifluoromethanesulfonate anion is 2.767 (2) Å, whereas the distance to the other trifluoromethanesulfonate anion is 2.985 (3) Å. It should be noted that the other crystallographically independent iodonium dimer found for (III) contains more uniform iodine-trifluoromethanesulfonate distances. These bond lengths were found to be 2.893 (3) and 2.881 (2) Å. This variation in non-bonded distances is likely to be due to crystal packing forces rather than any electronic effects. Square-planar geometry has been described by several investigators (e.g. Gately et al., 1992; Kasumov et al., 1996, 1997) and was most recently observed in the case of a (2,2'-bithiophen-5-yl)(phenyl)iodonium trifluoromethanesulfonate (Tykwinski et al., 2000).
Despite the different electron-withdrawing substituents on the aryliodonio moiety, there is little structural difference within the covalently bonded moieties of the three compounds. The vinylic C—C bond lengths range from 1.293 (5) to 1.326 (5) Å for (III), with the corresponding values for (I) and (II) in between. However, given the experimental uncertainties, the bond length differences are inconsequential. The C—I bond lengths between the aryl rings and vinylic C atoms, at approximately 2.1 Å, are typical of those for iodonium salts (Varvoglis, 1992; Stang & Zhdankin, 1993).
The incorporation of increasingly electron-withdrawing aryliodonio moieties (Lowry & Richardson, 1987) results in another slight structural variation. The non-bonded distance between the I atom and the closest trifluoromethanesulfonate counter-ion is longest [2.909 (6) Å] in (I), the compound with the least electron-deficient aromatic ring. In one of the two dimeric units of (II) and (III), the I—O distance decreases to 2.802 (6) and 2.767 (2) Å for (II) and (III), respectively. However, this shortening is not observed in the second dimer of each. Consequently, this variation is also likely to be simply a manifestation of crystal packing forces. The sum of the covalent radii of I and O is 2.08 Å and the sum of the van der Waals radii is 3.45 Å (Huheey et al., 1993).