Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101007983/gg1055sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101007983/gg1055Isup2.hkl |
CCDC reference: 170200
The compound was synthesized in two stages. 1,2-Bis(benzenesulfanamido)ethane was obtained by the dropwise addition of diethylamine (6.21 g, 0.085 mol) to benzenesulfonyl chloride (30.0 g, 0.170 mol) at room temperature with vigorous stirring. The reaction mixture was heated to 353 K for 0.5 h and then cooled and washed with water (100 ml). The resulting white solid was filtered and recystallized from boiling ethanol. 1,2-bis(benzenesulfanamido)ethane (0.5 g, 1.5 mmol) was dissolved in chloroform (180 ml) and the solution cooled to 195 K. Elemental fluorine (15 mmol, 5% in N2) was bubbled through the cold, stirred solution for 15 min. After warming to room temperature the solvent was removed under vacuum and the crude solid was washed with diethyl ether. Crystals suitable for X-ray diffraction studies were grown by slow evaporation of the solvent from a CHCl3 solution.
Molecule (I) crystallized in the monoclininc system; space group P2/n from the systematic absences. H atoms were treated as riding atoms (C—H 0.93 and 0.97 Å). The solvent molecules located in the channels within the structure exist as disordered pairs (50:50 occupancy) around the crystallographic twofold axis. This leads to the chlorine atoms nearly coalescing with another from a symmetry-related molecule so distorting the vibrational ellipsoids for these atoms.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
C16H18F2N2O4S2·CHCl3 | F(000) = 1072 |
Mr = 523.81 | Dx = 1.532 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 25 reflections |
a = 10.9948 (10) Å | θ = 12.7–17.2° |
b = 9.6922 (10) Å | µ = 0.63 mm−1 |
c = 21.381 (5) Å | T = 293 K |
β = 94.815 (10)° | Plate, colourless |
V = 2270.4 (6) Å3 | 0.35 × 0.3 × 0.1 mm |
Z = 4 |
Enraf Nonius CAD4 diffractometer | 2572 reflections with I > 2σ(I) |
Radiation source: Enraf Nonius FR590 | Rint = 0.017 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
non–profiled ω scans | h = 0→13 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→11 |
Tmin = 0.810, Tmax = 0.940 | l = −25→25 |
4222 measured reflections | 3 standard reflections every 60 min |
3999 independent reflections | intensity decay: 3% |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0717P)2 + 0.3412P] where P = (Fo2 + 2Fc2)/3 |
3999 reflections | (Δ/σ)max = 0.026 |
309 parameters | Δρmax = 0.36 e Å−3 |
72 restraints | Δρmin = −0.30 e Å−3 |
C16H18F2N2O4S2·CHCl3 | V = 2270.4 (6) Å3 |
Mr = 523.81 | Z = 4 |
Monoclinic, P2/n | Mo Kα radiation |
a = 10.9948 (10) Å | µ = 0.63 mm−1 |
b = 9.6922 (10) Å | T = 293 K |
c = 21.381 (5) Å | 0.35 × 0.3 × 0.1 mm |
β = 94.815 (10)° |
Enraf Nonius CAD4 diffractometer | 2572 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.017 |
Tmin = 0.810, Tmax = 0.940 | 3 standard reflections every 60 min |
4222 measured reflections | intensity decay: 3% |
3999 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 72 restraints |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.36 e Å−3 |
3999 reflections | Δρmin = −0.30 e Å−3 |
309 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.44043 (8) | 0.73110 (9) | 0.09126 (4) | 0.0288 (2) | |
S2 | 0.55434 (8) | 0.66118 (9) | 0.39870 (4) | 0.0296 (2) | |
O1 | 0.3355 (2) | 0.7897 (2) | 0.05851 (11) | 0.0371 (6) | |
O2 | 0.5580 (2) | 0.7885 (3) | 0.08700 (11) | 0.0374 (6) | |
O3 | 0.4355 (2) | 0.6062 (3) | 0.40219 (11) | 0.0376 (6) | |
O4 | 0.6586 (2) | 0.5992 (3) | 0.43060 (11) | 0.0394 (7) | |
N1 | 0.4215 (2) | 0.7556 (3) | 0.16913 (13) | 0.0318 (7) | |
N2 | 0.5732 (2) | 0.6425 (3) | 0.32075 (13) | 0.0334 (7) | |
F1 | 0.30386 (18) | 0.7000 (3) | 0.17801 (10) | 0.0469 (6) | |
F2 | 0.69174 (18) | 0.6982 (3) | 0.31291 (10) | 0.0507 (6) | |
C1 | 0.5056 (3) | 0.6782 (4) | 0.21174 (15) | 0.0335 (8) | |
H1A | 0.5888 | 0.6957 | 0.2021 | 0.04* | |
H1B | 0.4897 | 0.5802 | 0.2069 | 0.04* | |
C2 | 0.4895 (3) | 0.7215 (4) | 0.27823 (15) | 0.0339 (8) | |
H2A | 0.5063 | 0.8193 | 0.2833 | 0.041* | |
H2B | 0.4061 | 0.7047 | 0.2878 | 0.041* | |
C3 | 0.4433 (3) | 0.5535 (3) | 0.07972 (14) | 0.0261 (8) | |
C4 | 0.3341 (3) | 0.4847 (4) | 0.06630 (16) | 0.0333 (9) | |
H4 | 0.2611 | 0.5331 | 0.0602 | 0.04* | |
C5 | 0.3358 (3) | 0.3441 (4) | 0.06220 (16) | 0.0374 (9) | |
H5 | 0.2629 | 0.2968 | 0.0529 | 0.045* | |
C6 | 0.4435 (4) | 0.2705 (4) | 0.07166 (16) | 0.0361 (9) | |
C7 | 0.5514 (3) | 0.3431 (4) | 0.08387 (16) | 0.0367 (9) | |
H7 | 0.6246 | 0.2948 | 0.0895 | 0.044* | |
C8 | 0.5532 (3) | 0.4838 (4) | 0.08793 (16) | 0.0325 (8) | |
H8 | 0.6263 | 0.5314 | 0.096 | 0.039* | |
C9 | 0.4425 (4) | 0.1149 (4) | 0.0684 (2) | 0.0541 (12) | |
H9A | 0.4153 | 0.0781 | 0.1065 | 0.081* | |
H9B | 0.5234 | 0.082 | 0.0632 | 0.081* | |
H9C | 0.3882 | 0.0855 | 0.0334 | 0.081* | |
C10 | 0.5556 (3) | 0.8378 (3) | 0.41312 (15) | 0.0275 (8) | |
C11 | 0.4480 (3) | 0.9117 (4) | 0.40652 (16) | 0.0320 (8) | |
H11 | 0.374 | 0.867 | 0.3967 | 0.038* | |
C12 | 0.4519 (3) | 1.0521 (4) | 0.41466 (16) | 0.0367 (9) | |
H12 | 0.3797 | 1.1025 | 0.4101 | 0.044* | |
C13 | 0.5612 (4) | 1.1203 (4) | 0.42947 (16) | 0.0358 (9) | |
C14 | 0.6681 (3) | 1.0424 (4) | 0.43703 (16) | 0.0379 (9) | |
H14 | 0.7419 | 1.0865 | 0.4482 | 0.045* | |
C15 | 0.6667 (3) | 0.9027 (4) | 0.42838 (16) | 0.0325 (8) | |
H15 | 0.7388 | 0.8521 | 0.4326 | 0.039* | |
C16 | 0.5664 (4) | 1.2734 (4) | 0.4374 (2) | 0.0538 (12) | |
H16A | 0.6176 | 1.2958 | 0.4746 | 0.081* | |
H16B | 0.4857 | 1.3084 | 0.4412 | 0.081* | |
H16C | 0.5993 | 1.3144 | 0.4016 | 0.081* | |
C1A | 0.7322 (13) | 0.1319 (14) | 0.2707 (5) | 0.111 (5) | 0.5 |
H1A1 | 0.7019 | 0.1311 | 0.3125 | 0.133* | 0.5 |
Cl1A | 0.7819 (8) | 0.3068 (5) | 0.2331 (3) | 0.167 (3) | 0.5 |
Cl2A | 0.6507 (5) | 0.0434 (6) | 0.2067 (2) | 0.1073 (15) | 0.5 |
Cl3A | 0.8873 (8) | 0.0958 (11) | 0.2615 (4) | 0.224 (4) | 0.5 |
C1B | 0.2276 (14) | 0.2717 (13) | 0.2700 (5) | 0.104 (5) | 0.5 |
H1B1 | 0.191 | 0.301 | 0.3081 | 0.125* | 0.5 |
Cl1B | 0.2203 (10) | 0.1003 (4) | 0.2645 (5) | 0.157 (4) | 0.5 |
Cl2B | 0.1552 (6) | 0.3600 (7) | 0.2045 (2) | 0.0919 (14) | 0.5 |
Cl3B | 0.3801 (9) | 0.3230 (12) | 0.2748 (5) | 0.222 (5) | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0290 (5) | 0.0237 (5) | 0.0335 (5) | 0.0003 (4) | 0.0008 (4) | −0.0001 (4) |
S2 | 0.0270 (5) | 0.0279 (5) | 0.0336 (5) | 0.0003 (4) | 0.0004 (4) | −0.0029 (4) |
O1 | 0.0368 (15) | 0.0325 (14) | 0.0405 (14) | 0.0067 (12) | −0.0048 (11) | 0.0037 (11) |
O2 | 0.0327 (15) | 0.0322 (14) | 0.0476 (15) | −0.0067 (12) | 0.0061 (12) | −0.0015 (11) |
O3 | 0.0302 (14) | 0.0372 (15) | 0.0457 (15) | −0.0092 (12) | 0.0056 (11) | −0.0018 (12) |
O4 | 0.0370 (16) | 0.0342 (15) | 0.0451 (15) | 0.0055 (12) | −0.0078 (12) | −0.0001 (12) |
N1 | 0.0231 (16) | 0.0346 (17) | 0.0377 (16) | 0.0002 (14) | 0.0024 (12) | −0.0060 (14) |
N2 | 0.0203 (16) | 0.0418 (18) | 0.0378 (17) | 0.0035 (14) | 0.0014 (12) | −0.0050 (14) |
F1 | 0.0231 (11) | 0.0726 (16) | 0.0455 (13) | −0.0024 (11) | 0.0065 (9) | −0.0049 (11) |
F2 | 0.0242 (12) | 0.0849 (18) | 0.0436 (12) | −0.0050 (12) | 0.0063 (9) | −0.0087 (12) |
C1 | 0.028 (2) | 0.037 (2) | 0.0356 (19) | 0.0037 (17) | 0.0018 (15) | −0.0067 (16) |
C2 | 0.031 (2) | 0.037 (2) | 0.0344 (19) | 0.0028 (17) | 0.0016 (15) | −0.0037 (16) |
C3 | 0.0265 (19) | 0.0268 (18) | 0.0252 (17) | 0.0009 (16) | 0.0036 (14) | −0.0016 (14) |
C4 | 0.028 (2) | 0.033 (2) | 0.038 (2) | 0.0020 (17) | −0.0016 (15) | −0.0001 (16) |
C5 | 0.037 (2) | 0.033 (2) | 0.041 (2) | −0.0085 (18) | −0.0028 (17) | −0.0032 (17) |
C6 | 0.050 (3) | 0.028 (2) | 0.0310 (19) | 0.0003 (19) | 0.0055 (17) | −0.0014 (16) |
C7 | 0.035 (2) | 0.038 (2) | 0.037 (2) | 0.0134 (18) | 0.0002 (16) | −0.0041 (17) |
C8 | 0.026 (2) | 0.036 (2) | 0.035 (2) | 0.0029 (17) | −0.0002 (15) | −0.0052 (16) |
C9 | 0.075 (3) | 0.029 (2) | 0.057 (3) | 0.003 (2) | 0.000 (2) | −0.0056 (19) |
C10 | 0.0275 (19) | 0.0269 (19) | 0.0282 (18) | −0.0002 (17) | 0.0041 (14) | −0.0018 (15) |
C11 | 0.0243 (19) | 0.036 (2) | 0.035 (2) | 0.0014 (16) | 0.0027 (15) | −0.0037 (16) |
C12 | 0.037 (2) | 0.035 (2) | 0.038 (2) | 0.0098 (18) | 0.0018 (16) | −0.0022 (17) |
C13 | 0.050 (2) | 0.027 (2) | 0.0304 (19) | −0.0052 (19) | 0.0046 (17) | −0.0025 (15) |
C14 | 0.032 (2) | 0.041 (2) | 0.040 (2) | −0.0091 (18) | 0.0012 (16) | −0.0045 (17) |
C15 | 0.027 (2) | 0.036 (2) | 0.035 (2) | 0.0006 (17) | 0.0028 (15) | −0.0024 (16) |
C16 | 0.073 (3) | 0.034 (2) | 0.054 (3) | 0.001 (2) | 0.002 (2) | −0.0018 (19) |
C1A | 0.116 (10) | 0.160 (12) | 0.054 (8) | 0.023 (10) | −0.021 (8) | −0.007 (6) |
Cl1A | 0.213 (9) | 0.148 (3) | 0.131 (6) | −0.045 (4) | −0.043 (5) | 0.023 (3) |
Cl2A | 0.111 (4) | 0.128 (3) | 0.078 (3) | −0.030 (3) | −0.018 (2) | 0.005 (2) |
Cl3A | 0.174 (7) | 0.280 (11) | 0.211 (8) | 0.077 (7) | −0.020 (6) | −0.102 (7) |
C1B | 0.124 (12) | 0.127 (10) | 0.058 (8) | 0.017 (10) | −0.015 (8) | 0.021 (6) |
Cl1B | 0.178 (10) | 0.110 (3) | 0.169 (9) | −0.030 (4) | −0.058 (6) | 0.035 (4) |
Cl2B | 0.107 (3) | 0.099 (3) | 0.0668 (19) | 0.029 (2) | −0.0142 (19) | 0.0148 (19) |
Cl3B | 0.178 (8) | 0.225 (10) | 0.246 (11) | −0.076 (7) | −0.073 (7) | 0.115 (8) |
S1—O1 | 1.417 (2) | C8—H8 | 0.93 |
S1—O2 | 1.418 (2) | C9—H9A | 0.96 |
S1—N1 | 1.712 (3) | C9—H9B | 0.96 |
S1—C3 | 1.740 (3) | C9—H9C | 0.96 |
S2—O4 | 1.417 (2) | C10—C11 | 1.380 (5) |
S2—O3 | 1.419 (2) | C10—C15 | 1.389 (5) |
S2—N2 | 1.706 (3) | C11—C12 | 1.373 (5) |
S2—C10 | 1.739 (3) | C11—H11 | 0.93 |
N1—F1 | 1.428 (3) | C12—C13 | 1.385 (5) |
N1—C1 | 1.451 (4) | C12—H12 | 0.93 |
N2—F2 | 1.433 (3) | C13—C14 | 1.395 (5) |
N2—C2 | 1.456 (4) | C13—C16 | 1.494 (5) |
C1—C2 | 1.507 (5) | C14—C15 | 1.366 (5) |
C1—H1A | 0.97 | C14—H14 | 0.93 |
C1—H1B | 0.97 | C15—H15 | 0.93 |
C2—H2A | 0.97 | C16—H16A | 0.96 |
C2—H2B | 0.97 | C16—H16B | 0.96 |
C3—C4 | 1.382 (5) | C16—H16C | 0.96 |
C3—C8 | 1.382 (5) | C1A—Cl3A | 1.767 (15) |
C4—C5 | 1.366 (5) | C1A—Cl2A | 1.790 (13) |
C4—H4 | 0.93 | C1A—Cl1A | 1.973 (13) |
C5—C6 | 1.383 (5) | C1A—H1A1 | 0.98 |
C5—H5 | 0.93 | Cl1A—Cl3A | 2.403 (11) |
C6—C7 | 1.385 (5) | C1B—Cl1B | 1.666 (13) |
C6—C9 | 1.510 (5) | C1B—Cl3B | 1.744 (15) |
C7—C8 | 1.367 (5) | C1B—Cl2B | 1.773 (11) |
C7—H7 | 0.93 | C1B—H1B1 | 0.98 |
O1—S1—O2 | 121.33 (16) | C7—C8—H8 | 120.9 |
O1—S1—N1 | 105.35 (15) | C3—C8—H8 | 120.9 |
O2—S1—N1 | 101.20 (14) | C6—C9—H9A | 109.5 |
O1—S1—C3 | 110.51 (16) | C6—C9—H9B | 109.5 |
O2—S1—C3 | 110.60 (16) | H9A—C9—H9B | 109.5 |
N1—S1—C3 | 106.26 (15) | C6—C9—H9C | 109.5 |
O4—S2—O3 | 121.78 (16) | H9A—C9—H9C | 109.5 |
O4—S2—N2 | 105.39 (15) | H9B—C9—H9C | 109.5 |
O3—S2—N2 | 101.51 (14) | C11—C10—C15 | 121.2 (3) |
O4—S2—C10 | 109.75 (16) | C11—C10—S2 | 119.9 (3) |
O3—S2—C10 | 110.72 (16) | C15—C10—S2 | 118.8 (3) |
N2—S2—C10 | 106.13 (15) | C12—C11—C10 | 119.0 (3) |
F1—N1—C1 | 105.0 (3) | C12—C11—H11 | 120.5 |
F1—N1—S1 | 105.22 (18) | C10—C11—H11 | 120.5 |
C1—N1—S1 | 114.6 (2) | C11—C12—C13 | 121.3 (4) |
F2—N2—C2 | 105.2 (3) | C11—C12—H12 | 119.4 |
F2—N2—S2 | 105.10 (19) | C13—C12—H12 | 119.4 |
C2—N2—S2 | 115.6 (2) | C12—C13—C14 | 118.4 (3) |
N1—C1—C2 | 109.2 (3) | C12—C13—C16 | 121.6 (4) |
N1—C1—H1A | 109.8 | C14—C13—C16 | 120.0 (4) |
C2—C1—H1A | 109.8 | C15—C14—C13 | 121.4 (3) |
N1—C1—H1B | 109.8 | C15—C14—H14 | 119.3 |
C2—C1—H1B | 109.8 | C13—C14—H14 | 119.3 |
H1A—C1—H1B | 108.3 | C14—C15—C10 | 118.7 (3) |
N2—C2—C1 | 109.0 (3) | C14—C15—H15 | 120.6 |
N2—C2—H2A | 109.9 | C10—C15—H15 | 120.6 |
C1—C2—H2A | 109.9 | C13—C16—H16A | 109.5 |
N2—C2—H2B | 109.9 | C13—C16—H16B | 109.5 |
C1—C2—H2B | 109.9 | H16A—C16—H16B | 109.5 |
H2A—C2—H2B | 108.3 | C13—C16—H16C | 109.5 |
C8—C3—C4 | 121.7 (3) | H16A—C16—H16C | 109.5 |
C8—C3—S1 | 119.5 (3) | H16B—C16—H16C | 109.5 |
C4—C3—S1 | 118.8 (3) | Cl3A—C1A—Cl2A | 104.2 (7) |
C5—C4—C3 | 118.6 (3) | Cl3A—C1A—Cl1A | 79.7 (7) |
C5—C4—H4 | 120.7 | Cl2A—C1A—Cl1A | 103.8 (6) |
C3—C4—H4 | 120.7 | Cl3A—C1A—H1A1 | 120.4 |
C4—C5—C6 | 121.4 (4) | Cl2A—C1A—H1A1 | 120.4 |
C4—C5—H5 | 119.3 | Cl1A—C1A—H1A1 | 120.4 |
C6—C5—H5 | 119.3 | C1A—Cl1A—Cl3A | 46.4 (4) |
C5—C6—C7 | 118.4 (3) | C1A—Cl3A—Cl1A | 53.9 (5) |
C5—C6—C9 | 120.4 (4) | Cl1B—C1B—Cl3B | 109.2 (9) |
C7—C6—C9 | 121.3 (4) | Cl1B—C1B—Cl2B | 114.2 (9) |
C8—C7—C6 | 121.8 (3) | Cl3B—C1B—Cl2B | 105.9 (7) |
C8—C7—H7 | 119.1 | Cl1B—C1B—H1B1 | 109.1 |
C6—C7—H7 | 119.1 | Cl3B—C1B—H1B1 | 109.1 |
C7—C8—C3 | 118.1 (3) | Cl2B—C1B—H1B1 | 109.1 |
O1—S1—N1—F1 | 52.9 (2) | C4—C5—C6—C7 | −1.7 (5) |
O2—S1—N1—F1 | −179.94 (19) | C4—C5—C6—C9 | 178.5 (3) |
C3—S1—N1—F1 | −64.4 (2) | C5—C6—C7—C8 | 1.3 (5) |
O1—S1—N1—C1 | 167.6 (2) | C9—C6—C7—C8 | −178.9 (3) |
O2—S1—N1—C1 | −65.2 (3) | C6—C7—C8—C3 | 0.3 (5) |
C3—S1—N1—C1 | 50.4 (3) | C4—C3—C8—C7 | −1.5 (5) |
O4—S2—N2—F2 | −53.0 (2) | S1—C3—C8—C7 | 174.5 (3) |
O3—S2—N2—F2 | 179.1 (2) | O4—S2—C10—C11 | −157.3 (3) |
C10—S2—N2—F2 | 63.4 (2) | O3—S2—C10—C11 | −20.0 (3) |
O4—S2—N2—C2 | −168.5 (2) | N2—S2—C10—C11 | 89.3 (3) |
O3—S2—N2—C2 | 63.6 (3) | O4—S2—C10—C15 | 25.7 (3) |
C10—S2—N2—C2 | −52.2 (3) | O3—S2—C10—C15 | 162.9 (3) |
F1—N1—C1—C2 | −71.8 (3) | N2—S2—C10—C15 | −87.8 (3) |
S1—N1—C1—C2 | 173.3 (2) | C15—C10—C11—C12 | 0.7 (5) |
F2—N2—C2—C1 | 72.7 (3) | S2—C10—C11—C12 | −176.3 (3) |
S2—N2—C2—C1 | −171.8 (2) | C10—C11—C12—C13 | −0.2 (5) |
N1—C1—C2—N2 | 179.4 (3) | C11—C12—C13—C14 | −1.0 (5) |
O1—S1—C3—C8 | 157.4 (3) | C11—C12—C13—C16 | 179.0 (4) |
O2—S1—C3—C8 | 20.2 (3) | C12—C13—C14—C15 | 1.9 (5) |
N1—S1—C3—C8 | −88.8 (3) | C16—C13—C14—C15 | −178.2 (3) |
O1—S1—C3—C4 | −26.6 (3) | C13—C14—C15—C10 | −1.4 (5) |
O2—S1—C3—C4 | −163.7 (3) | C11—C10—C15—C14 | 0.2 (5) |
N1—S1—C3—C4 | 87.2 (3) | S2—C10—C15—C14 | 177.2 (3) |
C8—C3—C4—C5 | 1.1 (5) | Cl2A—C1A—Cl1A—Cl3A | −102.3 (7) |
S1—C3—C4—C5 | −174.9 (3) | Cl2A—C1A—Cl3A—Cl1A | 101.7 (6) |
C3—C4—C5—C6 | 0.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···F2i | 0.97 | 2.46 | 3.418 (4) | 169 |
C2—H2B···F1ii | 0.97 | 2.48 | 3.439 (4) | 170 |
C4—H4···O3ii | 0.93 | 2.47 | 3.311 (4) | 150 |
C8—H8···O4i | 0.93 | 2.56 | 3.415 (4) | 152 |
C15—H15···O2i | 0.93 | 2.39 | 3.265 (4) | 157 |
Symmetry codes: (i) −x+3/2, y, −z+1/2; (ii) −x+1/2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C16H18F2N2O4S2·CHCl3 |
Mr | 523.81 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.9948 (10), 9.6922 (10), 21.381 (5) |
β (°) | 94.815 (10) |
V (Å3) | 2270.4 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.63 |
Crystal size (mm) | 0.35 × 0.3 × 0.1 |
Data collection | |
Diffractometer | Enraf Nonius CAD4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.810, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4222, 3999, 2572 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.142, 1.04 |
No. of reflections | 3999 |
No. of parameters | 309 |
No. of restraints | 72 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.30 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).
S1—O1 | 1.417 (2) | S2—C10 | 1.739 (3) |
S1—O2 | 1.418 (2) | N1—F1 | 1.428 (3) |
S1—N1 | 1.712 (3) | N1—C1 | 1.451 (4) |
S1—C3 | 1.740 (3) | N2—F2 | 1.433 (3) |
S2—O4 | 1.417 (2) | N2—C2 | 1.456 (4) |
S2—O3 | 1.419 (2) | C1—C2 | 1.507 (5) |
S2—N2 | 1.706 (3) | C3—C4 | 1.382 (5) |
O1—S1—O2 | 121.33 (16) | O4—S2—C10 | 109.75 (16) |
O1—S1—N1 | 105.35 (15) | O3—S2—C10 | 110.72 (16) |
O2—S1—N1 | 101.20 (14) | N2—S2—C10 | 106.13 (15) |
O1—S1—C3 | 110.51 (16) | F1—N1—C1 | 105.0 (3) |
O2—S1—C3 | 110.60 (16) | F1—N1—S1 | 105.22 (18) |
N1—S1—C3 | 106.26 (15) | C1—N1—S1 | 114.6 (2) |
O4—S2—O3 | 121.78 (16) | F2—N2—C2 | 105.2 (3) |
O4—S2—N2 | 105.39 (15) | F2—N2—S2 | 105.10 (19) |
O3—S2—N2 | 101.51 (14) | C2—N2—S2 | 115.6 (2) |
O2—S1—N1—F1 | −179.94 (19) | C10—S2—N2—F2 | 63.4 (2) |
C3—S1—N1—C1 | 50.4 (3) | N1—C1—C2—N2 | 179.4 (3) |
O3—S2—N2—F2 | 179.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···F2i | 0.97 | 2.46 | 3.418 (4) | 169 |
C2—H2B···F1ii | 0.97 | 2.48 | 3.439 (4) | 170 |
C4—H4···O3ii | 0.93 | 2.47 | 3.311 (4) | 150 |
C8—H8···O4i | 0.93 | 2.56 | 3.415 (4) | 152 |
C15—H15···O2i | 0.93 | 2.39 | 3.265 (4) | 157 |
Symmetry codes: (i) −x+3/2, y, −z+1/2; (ii) −x+1/2, y, −z+1/2. |
Fluorine and fluorine-containing substituents can exert a profound influence on the activity and selectivity of bio-organic molecules. This realisation has lead to much work in identifying reagents which can be used as site-selective fluorinating agents, and many of the more recent advances in this area have involved compounds in which fluorine is bound to a nitrogen atom. Included in this class of compounds are reagents featuring neutral N atoms of the type R2NF, for example N-fluoro-N-alkylsulfonamides (Barnett et al., 1984) and the electrophilic fluorine-delivery agents [R3N+F] such as 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]-octane [BF4]2 (Banks et al., 1996, 1998). However, the amount of structural data for such N—F containing systems is quite limited. There are just twelve crystal structures in the Cambridge Structural Database (Allen & Kennard, 1993) for organic compounds containing N–F bonds, of these six are NF2-containing materials, i.e. formally organic derivatives of NF3. Of the remaining six structures three compounds contain neutral N—F moieties and the other three contain the +N—F group. There are no structures of compounds which contain two separate, single N—F moieties (neutral or charged) within the same organic molecule. Recent work (Ardeshir et al., 1999) has shown that bis(N-halogeno) compounds such as 1,2-bis(N-bromo-2,5-dimethyl benzenesulfamido)ethane are good selective brominating agents and relatively accessible. Here we report an extension of that work to give the fluorinated analogue which has resulted in the first structural characterization of an organic bis(N—F)-containing compound. \sch
The title compound, (I), may be synthesized by passing dilute elemental fluorine through a CHCl3 solution of 1,2-bis(benzenesulfonamido)ethane at low temperature. Crystallization of (I) from a CHCl3 solution resulted in crystals of (I) as the CHCl3 solvate which crystallizes in the space group P2/n. A view of molecule (I) with our numbering scheme is shown in Fig. 1 and selected geometric parameters are given in Table 1. The bond lengths obtained for compound (I) are mostly in accord with anticipated values (Orpen et al., 1994). Of particular interest are the two N—F distances in this molecule which are the same within experimental limits, 1.428 (3) and 1.433 (3) Å. These distances are comparable with those found in the related neutral N—F containing organic systems, 1.435 (3) Å (Kakuda et al., 1997), 1.420 (4) Å (Davis et al., 1998) and 1.437 (6) Å (Batail et al., 1974), average 1.431 (7) Å. However, as expected, the N—F distances are longer than the distances found in molecules which formally contain +N—F bonds 1.106 (2) Å (Klapötke et al., 1993), 1.37 (2) (Banks, Pritchard & Sharif et al., 1993) and 1.406 (3) Å (Banks, Sharif & Pritchard et al., 1993) [average = 1.294 (20) Å]. However, this average figure is distorted by the very short N—F distance observed by Klapötke for the hexafluoroarsenate salt of N-fluoro-2,4,6-trichlorotriazine, which the authors describe as being unreliable due to severe disorder problems.
The molecule is symmetric about the central C—C bond; this results in an overall Z-like shape and the two N—F moieties are located on opposite sides of the molecule. The two aromatic rings are anti-periplanar with torsion angles of C3—S1—N1—C1 = 50.4 (3), N1—C1—C2—N2 = 179.4 (3) and C2—N2—S2—C10 = -52.2 (2)°. In the solid state there are weak hydrogen bonds between the electronegative fluorine atoms F1 and F2 and the protons attached to the carbon centres C2 and C1, respectively, of the central aliphatic chain, Fig. 2. The average C—H···F distance is 3.429 (6) Å and the angle is 170°. Hydrogen bonding also occurs between the O atoms of the SO2 groups and the ortho protons of the aromatic rings with (C—H···O)av 3.330 (7) Å, 153°. These two features result in a two-dimensional stack of molecules in an alternate head-to-tail fashion in the a axis direction. The aromatic rings of one stack interweave with those of a second stack resulting in the generation of an approximately square arrangement when viewed down the a axis. The next pair of stacks is separated in the c direction by a distance of ca 3.8 Å between the aromatic rings and is offset (Fig. 3); the offset and short distance being indicative of pi-interactions between the aromatic rings.
This combination of intermolecular interactions results in the generation of channels running parallel to the a axis in which solvent molecules may be located. In this case molecules of CHCl3 solvent are located in the channels but are disordered over two equally populated sites.