Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108025638/gg3177sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108025638/gg3177Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108025638/gg3177IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108025638/gg3177IIIsup4.hkl |
CCDC references: 703737; 703738; 703739
For each of compounds (I)–(III), to a stirred solution of the appropriately substituted 2-allylaniline (0.10 mol; see scheme) in methanol (40 ml) was added sodium tungstate dihydrate, Na2WO4.2H2O (5 mol%), followed by 30% aqueous hydrogen peroxide solution (0.30 mol). The resulting mixtures were then stirred at ambient temperature for periods ranging from 8 to 72 h. Each mixture was then filtered and the solvent was removed under reduced pressure. Toluene (50 ml) was added to the solid residue and the resulting solution was heated under reflux for periods ranging from 3 h to 10 h. After cooling the solution to ambient temperature, the solvent was removed under reduced pressure and the crude product was purified by chromatography on silica using heptane–ethyl acetate (compositions ranged from 10:1 to 60:1 v/v) as eluent. Crystallization from heptane gave crystals of compounds (I)–(III) suitable for single-crystal X-ray diffraction.
For (I): colourless crystals, yield 54%, m.p. 415–416 K; MS (70 eV) m/z (%): 297 (M+, 35Cl, 75), 296 (7), 280 (36), 267 (11), 164 (32), 139 (71), 138 (100), 130 (96), 129 (77), 128 (41), 112 (25). Analysis, found: C 72.4, H 5.8, N 4.5%; C18H16ClNO requires: C 72.6, H 5.4, N 4.7%.
For (II): colourless crystals, yield 25%, m.p. 403–404 K; MS (70 eV) m/z (%): 297 (M+, 35Cl, 67), 296 (11), 280 (36), 267 (11), 164 (27), 139 (72), 138 (100), 130 (95), 129 (76), 128 (44), 112 (23). Analysis, found: C 72.9, H 5.1, N 4.5%; C18H16ClNO requires: C 72.6, H 5.4, N 4.7%.
For (III): orange crystals, yield 20%, m.p. 407–408 K; MS (70 eV) m/z (%): 281 (M+, 64), 280 (41), 264 (33), 251 (12), 148 (29), 130 (62), 129 (58), 128 (33), 123 (56), 122 (100), 96 (30). Analysis, found: C 76.6, H 5.9, N 4.8%; C18H16FNO requires: C 76.8, H 5.7, N 5.0%.
The space group P212121 was uniquely assigned from the systematic absences for compound (II). For compounds (I) and (III), the systematic absences permitted P21 or P21/m as possible space groups; in each case, P21 was selected and confirmed by the subsequent structure analyses. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic, heteroaromatic and alkene), 0.99 (CH2) or 1.00 Å (aliphatic CH), and with Uiso(H) = 1.2Ueq(C). In the absence of significant resonant scattering in (III), the Flack parameter (Flack, 1983) was indeterminate (Flack & Bernardinelli, 2000), and hence Friedel-equivalent reflections were merged prior to the final refinements; the reference molecule in (III) was set to have the R configuration at C4. Compounds (I) and (II) crystallized as racemic twins and they were refined using the TWIN and BASF instructions in SHELXL97 (Sheldrick, 2008), giving twin fractions of 0.32 (9)/0.68 (9) in (I) and 0.44 (8)/0.56 (8) in (II), and again the reference molecules were chosen as those having the R configuration at C4.
For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
C18H16ClNO | F(000) = 312 |
Mr = 297.77 | Dx = 1.359 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3305 reflections |
a = 10.5798 (8) Å | θ = 5.1–27.5° |
b = 5.3448 (10) Å | µ = 0.26 mm−1 |
c = 12.873 (3) Å | T = 120 K |
β = 90.204 (12)° | Lath, colourless |
V = 727.9 (2) Å3 | 0.45 × 0.15 × 0.08 mm |
Z = 2 |
Bruker Nonius KappaCCD area-detector diffractometer | 3305 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2033 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.083 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 5.1° |
ϕ and ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −6→6 |
Tmin = 0.924, Tmax = 0.979 | l = −16→16 |
17564 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.048P)2 + 0.173P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3305 reflections | Δρmax = 0.31 e Å−3 |
191 parameters | Δρmin = −0.33 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 1460 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.32 (9) |
C18H16ClNO | V = 727.9 (2) Å3 |
Mr = 297.77 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.5798 (8) Å | µ = 0.26 mm−1 |
b = 5.3448 (10) Å | T = 120 K |
c = 12.873 (3) Å | 0.45 × 0.15 × 0.08 mm |
β = 90.204 (12)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3305 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2033 reflections with I > 2σ(I) |
Tmin = 0.924, Tmax = 0.979 | Rint = 0.083 |
17564 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.120 | Δρmax = 0.31 e Å−3 |
S = 1.05 | Δρmin = −0.33 e Å−3 |
3305 reflections | Absolute structure: Flack (1983), with 1460 Friedel pairs |
191 parameters | Absolute structure parameter: 0.32 (9) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
Cl7 | 1.20480 (7) | 0.6898 (2) | 0.65479 (7) | 0.0577 (3) | |
O14 | 0.62139 (18) | 0.3471 (4) | 0.57943 (17) | 0.0416 (6) | |
N1 | 0.6811 (2) | 0.3167 (5) | 0.67945 (19) | 0.0321 (6) | |
C2 | 0.6050 (3) | 0.4855 (6) | 0.7457 (3) | 0.0359 (8) | |
C3 | 0.5667 (3) | 0.7010 (7) | 0.6734 (3) | 0.0493 (9) | |
C4 | 0.6093 (3) | 0.6136 (6) | 0.5665 (3) | 0.0469 (9) | |
C5 | 0.7361 (3) | 0.7137 (7) | 0.5354 (2) | 0.0425 (8) | |
C5a | 0.8373 (3) | 0.6060 (5) | 0.6031 (2) | 0.0309 (7) | |
C6 | 0.9611 (3) | 0.6886 (7) | 0.5988 (2) | 0.0355 (7) | |
C7 | 1.0508 (3) | 0.5803 (6) | 0.6613 (2) | 0.0361 (8) | |
C8 | 1.0234 (3) | 0.3899 (7) | 0.7272 (2) | 0.0382 (8) | |
C9 | 0.8999 (3) | 0.3028 (6) | 0.7310 (2) | 0.0354 (8) | |
C9a | 0.8085 (2) | 0.4117 (5) | 0.6701 (2) | 0.0287 (7) | |
C21 | 0.4925 (2) | 0.3474 (6) | 0.7873 (3) | 0.0363 (8) | |
C22 | 0.4526 (3) | 0.3671 (6) | 0.8840 (3) | 0.0368 (8) | |
C221 | 0.3400 (3) | 0.2490 (5) | 0.9274 (2) | 0.0317 (7) | |
C222 | 0.2866 (3) | 0.0386 (6) | 0.8834 (2) | 0.0375 (8) | |
C223 | 0.1788 (3) | −0.0674 (6) | 0.9246 (2) | 0.0379 (8) | |
C224 | 0.1238 (3) | 0.0329 (6) | 1.0107 (2) | 0.0373 (8) | |
C225 | 0.1763 (3) | 0.2392 (6) | 1.0569 (2) | 0.0400 (8) | |
C226 | 0.2837 (3) | 0.3460 (6) | 1.0163 (2) | 0.0367 (8) | |
H2 | 0.6578 | 0.5505 | 0.8043 | 0.043* | |
H3A | 0.4742 | 0.7285 | 0.6748 | 0.059* | |
H3B | 0.6100 | 0.8581 | 0.6934 | 0.059* | |
H4 | 0.5440 | 0.6539 | 0.5127 | 0.056* | |
H5A | 0.7530 | 0.6701 | 0.4620 | 0.051* | |
H5B | 0.7363 | 0.8983 | 0.5415 | 0.051* | |
H6 | 0.9838 | 0.8199 | 0.5528 | 0.043* | |
H8 | 1.0873 | 0.3179 | 0.7698 | 0.046* | |
H9 | 0.8786 | 0.1679 | 0.7757 | 0.043* | |
H21 | 0.4476 | 0.2397 | 0.7415 | 0.044* | |
H22 | 0.5017 | 0.4676 | 0.9297 | 0.044* | |
H222 | 0.3244 | −0.0343 | 0.8238 | 0.045* | |
H223 | 0.1428 | −0.2112 | 0.8928 | 0.046* | |
H224 | 0.0494 | −0.0401 | 1.0385 | 0.045* | |
H225 | 0.1385 | 0.3087 | 1.1172 | 0.048* | |
H226 | 0.3199 | 0.4880 | 1.0493 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl7 | 0.0311 (4) | 0.0791 (7) | 0.0629 (6) | −0.0168 (5) | 0.0110 (4) | −0.0268 (5) |
O14 | 0.0376 (12) | 0.0313 (13) | 0.0558 (14) | −0.0017 (10) | −0.0188 (10) | −0.0034 (11) |
N1 | 0.0254 (13) | 0.0295 (14) | 0.0413 (15) | −0.0004 (10) | −0.0063 (11) | −0.0017 (12) |
C2 | 0.0250 (15) | 0.0312 (18) | 0.051 (2) | −0.0015 (14) | −0.0014 (14) | −0.0104 (15) |
C3 | 0.0222 (15) | 0.0321 (18) | 0.094 (3) | 0.0023 (16) | 0.0015 (16) | −0.002 (2) |
C4 | 0.0400 (19) | 0.037 (2) | 0.064 (2) | 0.0040 (15) | −0.0237 (17) | 0.0095 (17) |
C5 | 0.0489 (19) | 0.0340 (19) | 0.0444 (19) | 0.0012 (18) | −0.0105 (15) | 0.0070 (17) |
C5a | 0.0347 (17) | 0.0266 (17) | 0.0315 (17) | 0.0013 (13) | −0.0045 (13) | −0.0019 (13) |
C6 | 0.0373 (16) | 0.0330 (17) | 0.0362 (17) | −0.0094 (17) | 0.0052 (13) | −0.0010 (17) |
C7 | 0.0305 (17) | 0.043 (2) | 0.0347 (18) | −0.0054 (14) | 0.0051 (14) | −0.0149 (16) |
C8 | 0.0230 (15) | 0.053 (2) | 0.0383 (18) | 0.0081 (15) | −0.0061 (13) | 0.0016 (17) |
C9 | 0.0316 (17) | 0.0364 (19) | 0.0382 (18) | 0.0052 (14) | 0.0003 (14) | 0.0028 (15) |
C9a | 0.0268 (15) | 0.0261 (17) | 0.0331 (17) | 0.0021 (13) | −0.0026 (13) | −0.0043 (13) |
C21 | 0.0207 (14) | 0.0341 (18) | 0.054 (2) | −0.0026 (14) | −0.0040 (14) | −0.0071 (16) |
C22 | 0.0267 (16) | 0.0343 (19) | 0.049 (2) | 0.0000 (14) | −0.0065 (14) | −0.0070 (17) |
C221 | 0.0261 (15) | 0.034 (2) | 0.0350 (17) | 0.0026 (14) | −0.0077 (13) | 0.0018 (14) |
C222 | 0.0340 (17) | 0.037 (2) | 0.0417 (19) | 0.0011 (14) | −0.0006 (15) | −0.0028 (16) |
C223 | 0.0366 (17) | 0.034 (2) | 0.0429 (19) | −0.0046 (15) | −0.0026 (15) | −0.0029 (15) |
C224 | 0.0310 (17) | 0.039 (2) | 0.0417 (19) | −0.0018 (14) | −0.0036 (15) | 0.0022 (17) |
C225 | 0.0366 (17) | 0.047 (2) | 0.0365 (18) | 0.0071 (17) | 0.0004 (14) | −0.0036 (16) |
C226 | 0.0362 (17) | 0.0325 (19) | 0.0414 (19) | 0.0009 (15) | −0.0102 (14) | −0.0025 (16) |
Cl7—C7 | 1.733 (3) | C7—C8 | 1.357 (5) |
O14—C4 | 1.439 (4) | C8—C9 | 1.389 (4) |
O14—N1 | 1.441 (3) | C8—H8 | 0.95 |
N1—C9a | 1.446 (4) | C9—C9a | 1.372 (4) |
N1—C2 | 1.481 (4) | C9—H9 | 0.95 |
C2—C21 | 1.500 (4) | C21—C22 | 1.321 (4) |
C2—C3 | 1.534 (5) | C21—H21 | 0.95 |
C2—H2 | 1.00 | C22—C221 | 1.461 (4) |
C3—C4 | 1.522 (5) | C22—H22 | 0.95 |
C3—H3A | 0.99 | C221—C222 | 1.379 (4) |
C3—H3B | 0.99 | C221—C226 | 1.391 (4) |
C4—C5 | 1.501 (4) | C222—C223 | 1.381 (4) |
C4—H4 | 1.00 | C222—H222 | 0.95 |
C5—C5a | 1.494 (4) | C223—C224 | 1.363 (4) |
C5—H5A | 0.99 | C223—H223 | 0.95 |
C5—H5B | 0.99 | C224—C225 | 1.370 (4) |
C5a—C6 | 1.384 (4) | C224—H224 | 0.95 |
C5a—C9a | 1.384 (4) | C225—C226 | 1.377 (4) |
C6—C7 | 1.370 (4) | C225—H225 | 0.95 |
C6—H6 | 0.95 | C226—H226 | 0.95 |
C4—O14—N1 | 104.7 (2) | C8—C7—Cl7 | 119.1 (3) |
O14—N1—C9a | 107.0 (2) | C6—C7—Cl7 | 118.6 (3) |
O14—N1—C2 | 102.0 (2) | C7—C8—C9 | 118.5 (3) |
C9a—N1—C2 | 110.0 (2) | C7—C8—H8 | 120.8 |
N1—C2—C21 | 109.8 (2) | C9—C8—H8 | 120.8 |
N1—C2—C3 | 104.5 (3) | C9a—C9—C8 | 119.9 (3) |
C21—C2—C3 | 112.3 (2) | C9a—C9—H9 | 120.0 |
N1—C2—H2 | 110.0 | C8—C9—H9 | 120.0 |
C21—C2—H2 | 110.0 | C9—C9a—C5a | 121.2 (3) |
C3—C2—H2 | 110.0 | C9—C9a—N1 | 117.3 (3) |
C4—C3—C2 | 103.9 (3) | C5a—C9a—N1 | 121.5 (2) |
C4—C3—H3A | 111.0 | C22—C21—C2 | 123.7 (3) |
C2—C3—H3A | 111.0 | C22—C21—H21 | 118.2 |
C4—C3—H3B | 111.0 | C2—C21—H21 | 118.2 |
C2—C3—H3B | 111.0 | C21—C22—C221 | 126.2 (3) |
H3A—C3—H3B | 109.0 | C21—C22—H22 | 116.9 |
O14—C4—C5 | 107.7 (3) | C221—C22—H22 | 116.9 |
O14—C4—C3 | 103.1 (3) | C222—C221—C226 | 117.8 (3) |
C5—C4—C3 | 113.6 (3) | C222—C221—C22 | 121.9 (3) |
O14—C4—H4 | 110.7 | C226—C221—C22 | 120.3 (3) |
C5—C4—H4 | 110.7 | C221—C222—C223 | 121.0 (3) |
C3—C4—H4 | 110.7 | C221—C222—H222 | 119.5 |
C5a—C5—C4 | 110.2 (3) | C223—C222—H222 | 119.5 |
C5a—C5—H5A | 109.6 | C224—C223—C222 | 120.4 (3) |
C4—C5—H5A | 109.6 | C224—C223—H223 | 119.8 |
C5a—C5—H5B | 109.6 | C222—C223—H223 | 119.8 |
C4—C5—H5B | 109.6 | C223—C224—C225 | 119.8 (3) |
H5A—C5—H5B | 108.1 | C223—C224—H224 | 120.1 |
C6—C5a—C9a | 118.3 (3) | C225—C224—H224 | 120.1 |
C6—C5a—C5 | 122.0 (3) | C224—C225—C226 | 120.2 (3) |
C9a—C5a—C5 | 119.6 (3) | C224—C225—H225 | 119.9 |
C7—C6—C5a | 119.7 (3) | C226—C225—H225 | 119.9 |
C7—C6—H6 | 120.1 | C225—C226—C221 | 120.9 (3) |
C5a—C6—H6 | 120.1 | C225—C226—H226 | 119.5 |
C8—C7—C6 | 122.3 (3) | C221—C226—H226 | 119.5 |
C4—O14—N1—C9a | −67.9 (3) | C8—C9—C9a—C5a | 1.0 (4) |
C4—O14—N1—C2 | 47.6 (3) | C8—C9—C9a—N1 | −178.5 (3) |
O14—N1—C2—C21 | 87.4 (3) | C6—C5a—C9a—C9 | 0.0 (4) |
C9a—N1—C2—C21 | −159.3 (2) | C5—C5a—C9a—C9 | 177.8 (3) |
O14—N1—C2—C3 | −33.2 (3) | C6—C5a—C9a—N1 | 179.5 (3) |
C9a—N1—C2—C3 | 80.1 (3) | C5—C5a—C9a—N1 | −2.7 (4) |
N1—C2—C3—C4 | 8.2 (3) | O14—N1—C9a—C9 | −149.2 (2) |
C21—C2—C3—C4 | −110.7 (3) | C2—N1—C9a—C9 | 100.8 (3) |
N1—O14—C4—C5 | 78.3 (3) | O14—N1—C9a—C5a | 31.3 (3) |
N1—O14—C4—C3 | −42.0 (3) | C2—N1—C9a—C5a | −78.7 (3) |
C2—C3—C4—O14 | 19.8 (3) | N1—C2—C21—C22 | 137.8 (3) |
C2—C3—C4—C5 | −96.5 (3) | C3—C2—C21—C22 | −106.4 (4) |
O14—C4—C5—C5a | −46.3 (4) | C2—C21—C22—C221 | 176.3 (3) |
C3—C4—C5—C5a | 67.1 (4) | C21—C22—C221—C222 | 22.7 (5) |
C4—C5—C5a—C6 | −172.5 (3) | C21—C22—C221—C226 | −158.0 (3) |
C4—C5—C5a—C9a | 9.8 (4) | C226—C221—C222—C223 | 1.8 (4) |
C9a—C5a—C6—C7 | −1.0 (4) | C22—C221—C222—C223 | −178.8 (3) |
C5—C5a—C6—C7 | −178.8 (3) | C221—C222—C223—C224 | −0.7 (5) |
C5a—C6—C7—C8 | 1.0 (5) | C222—C223—C224—C225 | −0.4 (5) |
C5a—C6—C7—Cl7 | −179.5 (2) | C223—C224—C225—C226 | 0.5 (4) |
C6—C7—C8—C9 | 0.0 (5) | C224—C225—C226—C221 | 0.7 (4) |
Cl7—C7—C8—C9 | −179.5 (2) | C222—C221—C226—C225 | −1.8 (4) |
C7—C8—C9—C9a | −1.0 (5) | C22—C221—C226—C225 | 178.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···N1i | 0.99 | 2.57 | 3.507 (5) | 158 |
C4—H4···O14ii | 1.00 | 2.35 | 3.318 (4) | 163 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y+1/2, −z+1. |
C18H16ClNO | F(000) = 624 |
Mr = 297.77 | Dx = 1.337 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3384 reflections |
a = 5.2855 (10) Å | θ = 3.5–27.5° |
b = 15.649 (2) Å | µ = 0.26 mm−1 |
c = 17.880 (3) Å | T = 120 K |
V = 1478.9 (4) Å3 | Block, colourless |
Z = 4 | 0.36 × 0.27 × 0.14 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3384 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2525 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.5° |
ϕ and ω scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −20→20 |
Tmin = 0.929, Tmax = 0.965 | l = −23→23 |
32581 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.0236P)2 + 0.5604P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.001 |
3384 reflections | Δρmax = 0.24 e Å−3 |
191 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 1401 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.44 (8) |
C18H16ClNO | V = 1478.9 (4) Å3 |
Mr = 297.77 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.2855 (10) Å | µ = 0.26 mm−1 |
b = 15.649 (2) Å | T = 120 K |
c = 17.880 (3) Å | 0.36 × 0.27 × 0.14 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3384 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2525 reflections with I > 2σ(I) |
Tmin = 0.929, Tmax = 0.965 | Rint = 0.063 |
32581 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.084 | Δρmax = 0.24 e Å−3 |
S = 1.12 | Δρmin = −0.22 e Å−3 |
3384 reflections | Absolute structure: Flack (1983), with 1401 Friedel pairs |
191 parameters | Absolute structure parameter: 0.44 (8) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
Cl7 | 0.26769 (16) | 0.37935 (4) | 0.83238 (3) | 0.04339 (19) | |
O14 | 0.5908 (3) | 0.69616 (9) | 0.61265 (10) | 0.0305 (4) | |
N1 | 0.6466 (3) | 0.60833 (11) | 0.59337 (11) | 0.0271 (5) | |
C2 | 0.5013 (5) | 0.59945 (15) | 0.52196 (13) | 0.0269 (6) | |
C3 | 0.2559 (5) | 0.65030 (13) | 0.53609 (12) | 0.0255 (5) | |
C4 | 0.3163 (4) | 0.70133 (14) | 0.60672 (13) | 0.0264 (5) | |
C5 | 0.2071 (5) | 0.66351 (12) | 0.67763 (11) | 0.0240 (5) | |
C5a | 0.3357 (4) | 0.57909 (13) | 0.69370 (12) | 0.0209 (5) | |
C6 | 0.2514 (5) | 0.52469 (13) | 0.75038 (12) | 0.0238 (5) | |
C7 | 0.3772 (5) | 0.44850 (14) | 0.76345 (12) | 0.0261 (6) | |
C8 | 0.5868 (5) | 0.42502 (14) | 0.72237 (13) | 0.0277 (6) | |
C9 | 0.6709 (4) | 0.47882 (13) | 0.66638 (14) | 0.0271 (5) | |
C9a | 0.5462 (4) | 0.55505 (13) | 0.65238 (12) | 0.0211 (5) | |
C21 | 0.4707 (5) | 0.50834 (15) | 0.49879 (13) | 0.0261 (6) | |
C22 | 0.6092 (5) | 0.47215 (15) | 0.44635 (13) | 0.0274 (6) | |
C221 | 0.5971 (4) | 0.38406 (15) | 0.41849 (12) | 0.0232 (5) | |
C222 | 0.4196 (5) | 0.32487 (16) | 0.44247 (13) | 0.0317 (6) | |
C223 | 0.4147 (5) | 0.24267 (17) | 0.41448 (14) | 0.0343 (6) | |
C224 | 0.5891 (5) | 0.21790 (16) | 0.36117 (14) | 0.0326 (6) | |
C225 | 0.7634 (6) | 0.27566 (15) | 0.33536 (15) | 0.0405 (6) | |
C226 | 0.7685 (5) | 0.35768 (14) | 0.36393 (14) | 0.0359 (6) | |
H2 | 0.5982 | 0.6295 | 0.4818 | 0.032* | |
H3A | 0.2174 | 0.6887 | 0.4936 | 0.031* | |
H3B | 0.1106 | 0.6115 | 0.5443 | 0.031* | |
H4 | 0.2614 | 0.7621 | 0.6008 | 0.032* | |
H5A | 0.2341 | 0.7033 | 0.7199 | 0.029* | |
H5B | 0.0228 | 0.6546 | 0.6716 | 0.029* | |
H6 | 0.1085 | 0.5398 | 0.7798 | 0.029* | |
H8 | 0.6718 | 0.3728 | 0.7324 | 0.033* | |
H9 | 0.8146 | 0.4635 | 0.6374 | 0.033* | |
H21 | 0.3453 | 0.4748 | 0.5231 | 0.031* | |
H22 | 0.7329 | 0.5077 | 0.4236 | 0.033* | |
H222 | 0.2985 | 0.3413 | 0.4790 | 0.038* | |
H223 | 0.2915 | 0.2032 | 0.4319 | 0.041* | |
H224 | 0.5883 | 0.1611 | 0.3425 | 0.039* | |
H225 | 0.8808 | 0.2593 | 0.2978 | 0.049* | |
H226 | 0.8915 | 0.3969 | 0.3460 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl7 | 0.0695 (5) | 0.0337 (3) | 0.0270 (3) | 0.0059 (4) | 0.0102 (4) | 0.0102 (3) |
O14 | 0.0242 (9) | 0.0181 (8) | 0.0493 (10) | −0.0046 (7) | −0.0068 (8) | 0.0023 (8) |
N1 | 0.0228 (11) | 0.0182 (10) | 0.0403 (12) | −0.0024 (8) | −0.0018 (9) | 0.0027 (9) |
C2 | 0.0239 (13) | 0.0279 (13) | 0.0290 (13) | −0.0012 (11) | 0.0056 (11) | 0.0070 (10) |
C3 | 0.0254 (13) | 0.0267 (11) | 0.0244 (11) | 0.0031 (12) | −0.0014 (12) | 0.0050 (9) |
C4 | 0.0248 (14) | 0.0191 (11) | 0.0353 (13) | 0.0052 (10) | −0.0060 (11) | 0.0037 (10) |
C5 | 0.0255 (13) | 0.0208 (11) | 0.0257 (12) | 0.0056 (10) | −0.0060 (11) | −0.0045 (9) |
C5a | 0.0242 (13) | 0.0191 (11) | 0.0194 (10) | −0.0025 (10) | −0.0084 (9) | −0.0063 (9) |
C6 | 0.0264 (13) | 0.0259 (11) | 0.0191 (10) | 0.0019 (12) | −0.0025 (11) | −0.0041 (9) |
C7 | 0.0394 (16) | 0.0209 (12) | 0.0179 (12) | −0.0036 (11) | −0.0047 (11) | −0.0002 (9) |
C8 | 0.0319 (14) | 0.0182 (11) | 0.0330 (13) | 0.0036 (11) | −0.0069 (12) | −0.0001 (10) |
C9 | 0.0213 (13) | 0.0241 (12) | 0.0360 (13) | −0.0009 (9) | −0.0006 (11) | −0.0004 (11) |
C9a | 0.0191 (12) | 0.0164 (11) | 0.0279 (13) | −0.0043 (10) | −0.0048 (10) | 0.0012 (9) |
C21 | 0.0276 (14) | 0.0263 (13) | 0.0245 (12) | −0.0038 (12) | 0.0063 (12) | 0.0065 (10) |
C22 | 0.0265 (14) | 0.0284 (13) | 0.0274 (13) | −0.0011 (11) | 0.0041 (11) | 0.0091 (11) |
C221 | 0.0202 (12) | 0.0290 (12) | 0.0205 (11) | 0.0002 (11) | −0.0014 (10) | 0.0062 (10) |
C222 | 0.0282 (14) | 0.0408 (15) | 0.0260 (12) | −0.0057 (13) | 0.0068 (12) | −0.0040 (11) |
C223 | 0.0313 (15) | 0.0389 (15) | 0.0327 (14) | −0.0102 (13) | 0.0024 (13) | −0.0026 (12) |
C224 | 0.0301 (15) | 0.0350 (14) | 0.0329 (14) | −0.0021 (12) | −0.0013 (13) | −0.0058 (11) |
C225 | 0.0344 (15) | 0.0406 (14) | 0.0467 (15) | 0.0007 (14) | 0.0189 (16) | −0.0082 (13) |
C226 | 0.0274 (14) | 0.0327 (13) | 0.0477 (15) | −0.0060 (13) | 0.0144 (14) | 0.0019 (11) |
Cl7—C7 | 1.739 (2) | C7—C8 | 1.379 (3) |
O14—N1 | 1.447 (2) | C8—C9 | 1.382 (3) |
O14—C4 | 1.457 (3) | C8—H8 | 0.95 |
N1—C9a | 1.446 (3) | C9—C9a | 1.386 (3) |
N1—C2 | 1.497 (3) | C9—H9 | 0.95 |
C2—C21 | 1.494 (3) | C21—C22 | 1.317 (3) |
C2—C3 | 1.542 (3) | C21—H21 | 0.95 |
C2—H2 | 1.00 | C22—C221 | 1.467 (3) |
C3—C4 | 1.528 (3) | C22—H22 | 0.95 |
C3—H3A | 0.99 | C221—C222 | 1.386 (3) |
C3—H3B | 0.99 | C221—C226 | 1.394 (3) |
C4—C5 | 1.513 (3) | C222—C223 | 1.381 (4) |
C4—H4 | 1.00 | C222—H222 | 0.95 |
C5—C5a | 1.513 (3) | C223—C224 | 1.381 (4) |
C5—H5A | 0.99 | C223—H223 | 0.95 |
C5—H5B | 0.99 | C224—C225 | 1.371 (4) |
C5a—C9a | 1.387 (3) | C224—H224 | 0.95 |
C5a—C6 | 1.397 (3) | C225—C226 | 1.382 (3) |
C6—C7 | 1.385 (3) | C225—H225 | 0.95 |
C6—H6 | 0.95 | C226—H226 | 0.95 |
N1—O14—C4 | 103.78 (15) | C8—C7—Cl7 | 118.61 (18) |
C9a—N1—O14 | 107.40 (17) | C6—C7—Cl7 | 119.70 (19) |
C9a—N1—C2 | 112.37 (17) | C7—C8—C9 | 118.8 (2) |
O14—N1—C2 | 100.76 (16) | C7—C8—H8 | 120.6 |
C21—C2—N1 | 112.38 (19) | C9—C8—H8 | 120.6 |
C21—C2—C3 | 116.6 (2) | C8—C9—C9a | 120.2 (2) |
N1—C2—C3 | 104.12 (18) | C8—C9—H9 | 119.9 |
C21—C2—H2 | 107.8 | C9a—C9—H9 | 119.9 |
N1—C2—H2 | 107.8 | C9—C9a—C5a | 121.2 (2) |
C3—C2—H2 | 107.8 | C9—C9a—N1 | 117.0 (2) |
C4—C3—C2 | 103.26 (19) | C5a—C9a—N1 | 121.78 (19) |
C4—C3—H3A | 111.1 | C22—C21—C2 | 123.2 (2) |
C2—C3—H3A | 111.1 | C22—C21—H21 | 118.4 |
C4—C3—H3B | 111.1 | C2—C21—H21 | 118.4 |
C2—C3—H3B | 111.1 | C21—C22—C221 | 128.4 (2) |
H3A—C3—H3B | 109.1 | C21—C22—H22 | 115.8 |
O14—C4—C5 | 107.28 (18) | C221—C22—H22 | 115.8 |
O14—C4—C3 | 103.85 (19) | C222—C221—C226 | 117.3 (2) |
C5—C4—C3 | 114.10 (18) | C222—C221—C22 | 123.5 (2) |
O14—C4—H4 | 110.5 | C226—C221—C22 | 119.2 (2) |
C5—C4—H4 | 110.5 | C223—C222—C221 | 121.5 (2) |
C3—C4—H4 | 110.5 | C223—C222—H222 | 119.2 |
C5a—C5—C4 | 109.22 (18) | C221—C222—H222 | 119.2 |
C5a—C5—H5A | 109.8 | C222—C223—C224 | 119.9 (2) |
C4—C5—H5A | 109.8 | C222—C223—H223 | 120.0 |
C5a—C5—H5B | 109.8 | C224—C223—H223 | 120.0 |
C4—C5—H5B | 109.8 | C225—C224—C223 | 119.7 (2) |
H5A—C5—H5B | 108.3 | C225—C224—H224 | 120.1 |
C9a—C5a—C6 | 118.5 (2) | C223—C224—H224 | 120.1 |
C9a—C5a—C5 | 119.7 (2) | C224—C225—C226 | 120.1 (2) |
C6—C5a—C5 | 121.8 (2) | C224—C225—H225 | 120.0 |
C7—C6—C5a | 119.6 (2) | C226—C225—H225 | 120.0 |
C7—C6—H6 | 120.2 | C225—C226—C221 | 121.4 (2) |
C5a—C6—H6 | 120.2 | C225—C226—H226 | 119.3 |
C8—C7—C6 | 121.7 (2) | C221—C226—H226 | 119.3 |
C4—O14—N1—C9a | −67.7 (2) | C8—C9—C9a—C5a | −0.1 (3) |
C4—O14—N1—C2 | 50.05 (19) | C8—C9—C9a—N1 | 179.5 (2) |
C9a—N1—C2—C21 | −51.5 (3) | C6—C5a—C9a—C9 | 0.2 (3) |
O14—N1—C2—C21 | −165.50 (18) | C5—C5a—C9a—C9 | 179.0 (2) |
C9a—N1—C2—C3 | 75.6 (2) | C6—C5a—C9a—N1 | −179.3 (2) |
O14—N1—C2—C3 | −38.5 (2) | C5—C5a—C9a—N1 | −0.5 (3) |
C21—C2—C3—C4 | 138.1 (2) | O14—N1—C9a—C9 | −149.90 (19) |
N1—C2—C3—C4 | 13.7 (2) | C2—N1—C9a—C9 | 100.2 (2) |
N1—O14—C4—C5 | 79.8 (2) | O14—N1—C9a—C5a | 29.6 (3) |
N1—O14—C4—C3 | −41.4 (2) | C2—N1—C9a—C5a | −80.3 (2) |
C2—C3—C4—O14 | 15.9 (2) | N1—C2—C21—C22 | −101.4 (3) |
C2—C3—C4—C5 | −100.5 (2) | C3—C2—C21—C22 | 138.5 (2) |
O14—C4—C5—C5a | −47.7 (2) | C2—C21—C22—C221 | −179.7 (2) |
C3—C4—C5—C5a | 66.8 (2) | C21—C22—C221—C222 | 3.5 (4) |
C4—C5—C5a—C9a | 9.4 (3) | C21—C22—C221—C226 | −177.8 (3) |
C4—C5—C5a—C6 | −171.8 (2) | C226—C221—C222—C223 | 1.0 (4) |
C9a—C5a—C6—C7 | −0.5 (3) | C22—C221—C222—C223 | 179.8 (2) |
C5—C5a—C6—C7 | −179.3 (2) | C221—C222—C223—C224 | −0.2 (4) |
C5a—C6—C7—C8 | 0.7 (3) | C222—C223—C224—C225 | −1.2 (4) |
C5a—C6—C7—Cl7 | −178.36 (17) | C223—C224—C225—C226 | 1.6 (4) |
C6—C7—C8—C9 | −0.6 (3) | C224—C225—C226—C221 | −0.7 (4) |
Cl7—C7—C8—C9 | 178.51 (18) | C222—C221—C226—C225 | −0.6 (4) |
C7—C8—C9—C9a | 0.3 (3) | C22—C221—C226—C225 | −179.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···N1i | 0.99 | 2.61 | 3.443 (3) | 142 |
C5—H5B···N1i | 0.99 | 2.54 | 3.434 (3) | 151 |
C5—H5B···O14i | 0.99 | 2.60 | 3.496 (3) | 151 |
Symmetry code: (i) x−1, y, z. |
C18H16FNO | F(000) = 296 |
Mr = 281.32 | Dx = 1.335 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1715 reflections |
a = 5.4172 (2) Å | θ = 3.6–27.5° |
b = 8.0164 (6) Å | µ = 0.09 mm−1 |
c = 16.2310 (11) Å | T = 120 K |
β = 96.745 (4)° | Block, orange |
V = 699.98 (8) Å3 | 0.23 × 0.21 × 0.15 mm |
Z = 2 |
Bruker Nonius KappaCCD area-detector diffractometer | 1715 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1510 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
ϕ and ω scans | h = −6→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −10→10 |
Tmin = 0.970, Tmax = 0.986 | l = −21→20 |
16046 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0366P)2 + 0.1566P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max < 0.001 |
1715 reflections | Δρmax = 0.17 e Å−3 |
190 parameters | Δρmin = −0.22 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with Friedel pairs merged |
Primary atom site location: structure-invariant direct methods |
C18H16FNO | V = 699.98 (8) Å3 |
Mr = 281.32 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.4172 (2) Å | µ = 0.09 mm−1 |
b = 8.0164 (6) Å | T = 120 K |
c = 16.2310 (11) Å | 0.23 × 0.21 × 0.15 mm |
β = 96.745 (4)° |
Bruker Nonius KappaCCD area-detector diffractometer | 1715 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1510 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.986 | Rint = 0.034 |
16046 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 1 restraint |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.17 | Δρmax = 0.17 e Å−3 |
1715 reflections | Δρmin = −0.22 e Å−3 |
190 parameters | Absolute structure: Flack (1983), with Friedel pairs merged |
x | y | z | Uiso*/Ueq | ||
F7 | 1.0264 (3) | −0.14342 (19) | 0.23347 (10) | 0.0409 (4) | |
O14 | 0.3957 (3) | 0.4145 (2) | 0.04915 (8) | 0.0253 (3) | |
N1 | 0.4135 (3) | 0.3925 (3) | 0.13836 (10) | 0.0220 (4) | |
C2 | 0.5376 (4) | 0.5523 (3) | 0.16776 (13) | 0.0239 (4) | |
C3 | 0.7282 (4) | 0.5844 (3) | 0.10512 (13) | 0.0269 (5) | |
C4 | 0.6459 (4) | 0.4639 (3) | 0.03407 (13) | 0.0262 (5) | |
C5 | 0.8014 (4) | 0.3069 (3) | 0.03615 (13) | 0.0261 (5) | |
C5a | 0.7630 (4) | 0.2072 (3) | 0.11269 (13) | 0.0225 (5) | |
C6 | 0.9128 (4) | 0.0705 (3) | 0.13801 (14) | 0.0271 (5) | |
C7 | 0.8722 (4) | −0.0146 (3) | 0.20819 (15) | 0.0287 (5) | |
C8 | 0.6846 (4) | 0.0262 (3) | 0.25577 (14) | 0.0285 (5) | |
C9 | 0.5330 (4) | 0.1600 (3) | 0.22982 (13) | 0.0242 (5) | |
C9a | 0.5735 (4) | 0.2502 (3) | 0.15977 (13) | 0.0201 (4) | |
C21 | 0.6481 (4) | 0.5455 (3) | 0.25676 (13) | 0.0235 (4) | |
C22 | 0.5467 (4) | 0.6184 (3) | 0.31775 (13) | 0.0225 (4) | |
C221 | 0.6475 (4) | 0.6221 (3) | 0.40601 (13) | 0.0201 (4) | |
C222 | 0.8684 (4) | 0.5415 (3) | 0.43665 (13) | 0.0247 (5) | |
C223 | 0.9548 (4) | 0.5455 (3) | 0.52044 (13) | 0.0271 (5) | |
C224 | 0.8224 (4) | 0.6303 (3) | 0.57557 (14) | 0.0265 (5) | |
C225 | 0.6038 (4) | 0.7116 (3) | 0.54635 (14) | 0.0286 (5) | |
C226 | 0.5178 (4) | 0.7069 (3) | 0.46232 (13) | 0.0246 (5) | |
H2 | 0.4107 | 0.6435 | 0.1616 | 0.029* | |
H3A | 0.7203 | 0.7015 | 0.0856 | 0.032* | |
H3B | 0.8996 | 0.5595 | 0.1303 | 0.032* | |
H4 | 0.6426 | 0.5213 | −0.0208 | 0.031* | |
H5A | 0.7518 | 0.2395 | −0.0142 | 0.031* | |
H5B | 0.9791 | 0.3365 | 0.0372 | 0.031* | |
H6 | 1.0419 | 0.0369 | 0.1067 | 0.033* | |
H8 | 0.6609 | −0.0351 | 0.3043 | 0.034* | |
H9 | 0.4002 | 0.1900 | 0.2602 | 0.029* | |
H21 | 0.7989 | 0.4857 | 0.2701 | 0.028* | |
H22 | 0.3930 | 0.6740 | 0.3031 | 0.027* | |
H222 | 0.9605 | 0.4831 | 0.3995 | 0.030* | |
H223 | 1.1052 | 0.4901 | 0.5402 | 0.032* | |
H224 | 0.8814 | 0.6326 | 0.6330 | 0.032* | |
H225 | 0.5129 | 0.7704 | 0.5837 | 0.034* | |
H226 | 0.3675 | 0.7627 | 0.4428 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F7 | 0.0382 (8) | 0.0273 (8) | 0.0544 (10) | 0.0067 (6) | −0.0062 (7) | 0.0031 (7) |
O14 | 0.0168 (7) | 0.0414 (9) | 0.0168 (7) | −0.0031 (7) | −0.0014 (5) | 0.0034 (7) |
N1 | 0.0205 (8) | 0.0307 (10) | 0.0145 (8) | −0.0012 (8) | 0.0000 (6) | 0.0005 (8) |
C2 | 0.0231 (10) | 0.0259 (11) | 0.0218 (10) | 0.0006 (9) | −0.0012 (8) | 0.0017 (9) |
C3 | 0.0256 (11) | 0.0305 (13) | 0.0236 (11) | −0.0061 (9) | −0.0010 (9) | 0.0057 (9) |
C4 | 0.0205 (10) | 0.0390 (13) | 0.0184 (10) | −0.0066 (9) | 0.0001 (8) | 0.0051 (9) |
C5 | 0.0200 (10) | 0.0398 (13) | 0.0184 (10) | −0.0061 (10) | 0.0021 (8) | −0.0019 (10) |
C5a | 0.0194 (10) | 0.0280 (11) | 0.0194 (10) | −0.0054 (9) | −0.0011 (8) | −0.0048 (9) |
C6 | 0.0211 (10) | 0.0300 (12) | 0.0299 (12) | −0.0007 (9) | 0.0009 (8) | −0.0080 (10) |
C7 | 0.0264 (11) | 0.0230 (11) | 0.0342 (12) | −0.0004 (10) | −0.0070 (9) | −0.0036 (10) |
C8 | 0.0342 (12) | 0.0257 (13) | 0.0242 (11) | −0.0072 (10) | −0.0031 (9) | 0.0014 (9) |
C9 | 0.0235 (10) | 0.0280 (12) | 0.0207 (10) | −0.0048 (9) | 0.0014 (8) | −0.0022 (9) |
C9a | 0.0158 (9) | 0.0249 (11) | 0.0187 (10) | −0.0049 (8) | −0.0019 (8) | −0.0027 (9) |
C21 | 0.0245 (10) | 0.0210 (11) | 0.0238 (11) | 0.0006 (9) | −0.0015 (8) | 0.0007 (9) |
C22 | 0.0215 (10) | 0.0208 (10) | 0.0245 (10) | 0.0003 (9) | 0.0000 (8) | 0.0037 (9) |
C221 | 0.0200 (10) | 0.0183 (10) | 0.0223 (10) | −0.0019 (8) | 0.0034 (7) | 0.0006 (9) |
C222 | 0.0235 (10) | 0.0278 (11) | 0.0231 (10) | 0.0030 (10) | 0.0040 (8) | −0.0014 (10) |
C223 | 0.0231 (10) | 0.0322 (13) | 0.0254 (11) | 0.0029 (10) | 0.0005 (8) | 0.0029 (10) |
C224 | 0.0284 (11) | 0.0303 (12) | 0.0209 (10) | −0.0016 (10) | 0.0028 (8) | 0.0014 (10) |
C225 | 0.0328 (12) | 0.0274 (12) | 0.0271 (11) | 0.0037 (10) | 0.0100 (9) | −0.0026 (10) |
C226 | 0.0237 (10) | 0.0224 (11) | 0.0279 (11) | 0.0034 (9) | 0.0042 (8) | 0.0032 (9) |
F7—C7 | 1.361 (3) | C7—C8 | 1.386 (3) |
O14—N1 | 1.451 (2) | C8—C9 | 1.386 (3) |
O14—C4 | 1.460 (2) | C8—H8 | 0.95 |
N1—C9a | 1.450 (3) | C9—C9a | 1.387 (3) |
N1—C2 | 1.498 (3) | C9—H9 | 0.95 |
C2—C21 | 1.498 (3) | C21—C22 | 1.323 (3) |
C2—C3 | 1.553 (3) | C21—H21 | 0.95 |
C2—H2 | 1.00 | C22—C221 | 1.472 (3) |
C3—C4 | 1.530 (3) | C22—H22 | 0.95 |
C3—H3A | 0.99 | C221—C226 | 1.394 (3) |
C3—H3B | 0.99 | C221—C222 | 1.399 (3) |
C4—C5 | 1.513 (3) | C222—C223 | 1.386 (3) |
C4—H4 | 1.00 | C222—H222 | 0.95 |
C5—C5a | 1.512 (3) | C223—C224 | 1.388 (3) |
C5—H5A | 0.99 | C223—H223 | 0.95 |
C5—H5B | 0.99 | C224—C225 | 1.386 (3) |
C5a—C9a | 1.393 (3) | C224—H224 | 0.95 |
C5a—C6 | 1.396 (3) | C225—C226 | 1.389 (3) |
C6—C7 | 1.367 (3) | C225—H225 | 0.95 |
C6—H6 | 0.95 | C226—H226 | 0.95 |
N1—O14—C4 | 104.26 (13) | F7—C7—C8 | 118.4 (2) |
C9a—N1—O14 | 107.61 (16) | C6—C7—C8 | 123.2 (2) |
C9a—N1—C2 | 111.29 (14) | C9—C8—C7 | 117.4 (2) |
O14—N1—C2 | 100.88 (16) | C9—C8—H8 | 121.3 |
C21—C2—N1 | 112.91 (18) | C7—C8—H8 | 121.3 |
C21—C2—C3 | 114.60 (18) | C8—C9—C9a | 120.5 (2) |
N1—C2—C3 | 103.94 (17) | C8—C9—H9 | 119.8 |
C21—C2—H2 | 108.4 | C9a—C9—H9 | 119.8 |
N1—C2—H2 | 108.4 | C9—C9a—C5a | 121.2 (2) |
C3—C2—H2 | 108.4 | C9—C9a—N1 | 117.32 (18) |
C4—C3—C2 | 103.40 (17) | C5a—C9a—N1 | 121.44 (19) |
C4—C3—H3A | 111.1 | C22—C21—C2 | 123.4 (2) |
C2—C3—H3A | 111.1 | C22—C21—H21 | 118.3 |
C4—C3—H3B | 111.1 | C2—C21—H21 | 118.3 |
C2—C3—H3B | 111.1 | C21—C22—C221 | 126.7 (2) |
H3A—C3—H3B | 109.0 | C21—C22—H22 | 116.7 |
O14—C4—C5 | 107.21 (18) | C221—C22—H22 | 116.7 |
O14—C4—C3 | 103.82 (17) | C226—C221—C222 | 117.93 (19) |
C5—C4—C3 | 113.35 (18) | C226—C221—C22 | 119.34 (18) |
O14—C4—H4 | 110.7 | C222—C221—C22 | 122.72 (19) |
C5—C4—H4 | 110.7 | C223—C222—C221 | 120.9 (2) |
C3—C4—H4 | 110.7 | C223—C222—H222 | 119.5 |
C5a—C5—C4 | 109.17 (18) | C221—C222—H222 | 119.5 |
C5a—C5—H5A | 109.8 | C222—C223—C224 | 120.2 (2) |
C4—C5—H5A | 109.8 | C222—C223—H223 | 119.9 |
C5a—C5—H5B | 109.8 | C224—C223—H223 | 119.9 |
C4—C5—H5B | 109.8 | C225—C224—C223 | 119.7 (2) |
H5A—C5—H5B | 108.3 | C225—C224—H224 | 120.2 |
C9a—C5a—C6 | 118.2 (2) | C223—C224—H224 | 120.2 |
C9a—C5a—C5 | 120.1 (2) | C224—C225—C226 | 119.9 (2) |
C6—C5a—C5 | 121.70 (19) | C224—C225—H225 | 120.1 |
C7—C6—C5a | 119.4 (2) | C226—C225—H225 | 120.1 |
C7—C6—H6 | 120.3 | C225—C226—C221 | 121.4 (2) |
C5a—C6—H6 | 120.3 | C225—C226—H226 | 119.3 |
F7—C7—C6 | 118.5 (2) | C221—C226—H226 | 119.3 |
C4—O14—N1—C9a | −67.0 (2) | C8—C9—C9a—C5a | 1.5 (3) |
C4—O14—N1—C2 | 49.69 (19) | C8—C9—C9a—N1 | −177.58 (19) |
C9a—N1—C2—C21 | −49.2 (2) | C6—C5a—C9a—C9 | −0.3 (3) |
O14—N1—C2—C21 | −163.11 (17) | C5—C5a—C9a—C9 | 179.44 (19) |
C9a—N1—C2—C3 | 75.61 (19) | C6—C5a—C9a—N1 | 178.75 (18) |
O14—N1—C2—C3 | −38.31 (19) | C5—C5a—C9a—N1 | −1.6 (3) |
C21—C2—C3—C4 | 137.8 (2) | O14—N1—C9a—C9 | −151.55 (17) |
N1—C2—C3—C4 | 14.1 (2) | C2—N1—C9a—C9 | 98.8 (2) |
N1—O14—C4—C5 | 79.56 (19) | O14—N1—C9a—C5a | 29.4 (2) |
N1—O14—C4—C3 | −40.7 (2) | C2—N1—C9a—C5a | −80.2 (2) |
C2—C3—C4—O14 | 15.2 (2) | N1—C2—C21—C22 | −104.4 (3) |
C2—C3—C4—C5 | −100.8 (2) | C3—C2—C21—C22 | 136.8 (2) |
O14—C4—C5—C5a | −48.5 (2) | C2—C21—C22—C221 | −177.8 (2) |
C3—C4—C5—C5a | 65.5 (2) | C21—C22—C221—C226 | 179.1 (2) |
C4—C5—C5a—C9a | 11.0 (3) | C21—C22—C221—C222 | −1.8 (4) |
C4—C5—C5a—C6 | −169.35 (19) | C226—C221—C222—C223 | 0.2 (3) |
C9a—C5a—C6—C7 | −1.0 (3) | C22—C221—C222—C223 | −178.8 (2) |
C5—C5a—C6—C7 | 179.3 (2) | C221—C222—C223—C224 | 0.0 (4) |
C5a—C6—C7—F7 | −177.54 (19) | C222—C223—C224—C225 | −0.3 (4) |
C5a—C6—C7—C8 | 1.1 (3) | C223—C224—C225—C226 | 0.4 (4) |
F7—C7—C8—C9 | 178.72 (19) | C224—C225—C226—C221 | −0.2 (4) |
C6—C7—C8—C9 | 0.1 (3) | C222—C221—C226—C225 | −0.1 (3) |
C7—C8—C9—C9a | −1.3 (3) | C22—C221—C226—C225 | 179.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···O14i | 0.99 | 2.33 | 3.316 (3) | 176 |
Symmetry code: (i) x+1, y, z. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C18H16ClNO | C18H16ClNO | C18H16FNO |
Mr | 297.77 | 297.77 | 281.32 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 | Monoclinic, P21 |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 10.5798 (8), 5.3448 (10), 12.873 (3) | 5.2855 (10), 15.649 (2), 17.880 (3) | 5.4172 (2), 8.0164 (6), 16.2310 (11) |
α, β, γ (°) | 90, 90.204 (12), 90 | 90, 90, 90 | 90, 96.745 (4), 90 |
V (Å3) | 727.9 (2) | 1478.9 (4) | 699.98 (8) |
Z | 2 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.26 | 0.26 | 0.09 |
Crystal size (mm) | 0.45 × 0.15 × 0.08 | 0.36 × 0.27 × 0.14 | 0.23 × 0.21 × 0.15 |
Data collection | |||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.924, 0.979 | 0.929, 0.965 | 0.970, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17564, 3305, 2033 | 32581, 3384, 2525 | 16046, 1715, 1510 |
Rint | 0.083 | 0.063 | 0.034 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.650 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.120, 1.05 | 0.047, 0.084, 1.12 | 0.035, 0.083, 1.17 |
No. of reflections | 3305 | 3384 | 1715 |
No. of parameters | 191 | 191 | 190 |
No. of restraints | 1 | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.33 | 0.24, −0.22 | 0.17, −0.22 |
Absolute structure | Flack (1983), with 1460 Friedel pairs | Flack (1983), with 1401 Friedel pairs | Flack (1983), with Friedel pairs merged |
Absolute structure parameter | 0.32 (9) | 0.44 (8) | ? |
Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
Compound | Five-membered ring | Six-membered ring | |||
Q2 | ϕ2 | Q | θ | ϕ | |
(I) | 0.430 (3) | 190.2 (5) | 0.604 (3) | 50.3 (3) | 348.1 (4) |
(II) | 0.457 (2) | 197.0 (3) | 0.622 (2) | 51.4 (2) | 345.9 (3) |
(III) | 0.453 (2) | 197.9 (2) | 0.616 (2) | 50.6 (2) | 344.7 (2) |
Puckering parameters for five-membered rings are defined for the atom sequence O14/N1/C2/C3/C4. Puckering parameters for six-membered rings are defined for the atom sequence O14/N1/C9a/C5a/C5/C4). |
Compound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C3—H3B···N1i | 0.99 | 2.57 | 3.507 (5) | 158 |
C4—H4···O14ii | 1.00 | 2.35 | 3.318 (4) | 163 | |
(II) | C3—H3B···N1iii | 0.99 | 2.61 | 3.443 (3) | 142 |
C5—H5B···N1iii | 0.99 | 2.54 | 3.434 (3) | 151 | |
C5—H5B···O14iii | 0.99 | 2.60 | 3.496 (3) | 151 | |
(III) | C5—H5B···O14iv | 0.99 | 2.33 | 3.316 (3) | 176 |
Symmetry codes: (i) x, 1 + y, z; (ii) 1 - x, 1/2 + y, 1 - z; (iii) -1 + x, y, z; (iv) 1 + x, y, z. |
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The tetrahydro-1-benzazepine ring is an important pharmacophore in drug discovery and many of its derivatives exhibit a broad spectrum of biological activity (Zuccotto et al., 2001; Fabio et al., 2003; Zhao et al., 2003; Seto et al., 2005; Shimada et al., 2005; Kunick et al., 2006). Accordingly, a number of synthetic methods have recently been developed for the synthesis of new derivatives of this heterocyclic system (Fujita et al., 2004; Ikemoto et al., 2005; Qadir et al., 2005). In this context, we have recently developed a simple and efficient synthetic pathway to obtain new 1,4-epoxy-2-aryltetrahydro-1-benzazepines and 1,4-epoxy-2-aryltetrahydronaphtho[1,2-b]azepines and their reduced amino alcohols from readily available 2-allyl-N-benzyl-substituted anilines or naphthylamines, respectively (Gómez et al., 2006; Yépez et al., 2006). Compounds of this type show promising action against Trypanosoma cruzi and Leishmania chagasi parasites (Palma et al., 2008).
Based on these results, and as part of a programme to identify structurally novel anti-parasitic compounds with new modes of action to combat both T. cruzi and L. chagasi, we have focused our attention on the synthesis of a range of 2-substituted 1,4-epoxy-tetrahydro-1-benzazepines. We report here the structures of three styryl-substituted examples, compounds (I)–(III) (Figs. 1–3); further reports are planned, to deal with aryl-substituted examples and with examples carrying heterocyclic substituents at C2. A search of the Cambridge Structural Database (CSD, Version 5.29, November 2007; Allen, 2002) found 72 examples of the bicyclic perhydro-1-benzazepine skeleton, which is a sub-structural fragment of (I)–(III), but found no examples at all of the 1,4-epoxy-tetrahydro-1-benzazepine skeleton itself.
The synthesis of compounds (I)–(III) involved treating the corresponding 2-allyl-N-cinnamylanilines (A) with an excess of hydrogen peroxide solution in the presence of catalytic amounts of sodium tungstate, and subsequent internal 1,3-dipolar cycloaddition of the resulting nitrones (B) across the terminal C═C bond of the pendant allylic fragment connected to the ortho position, giving the tricyclic product (C) (see scheme). The 1,3-dipolar cycloaddition of these nitrones resulted in the formation of diastereomeric mixtures of both 2-exo- and 2-endo-1,4-epoxy-cycloadducts, which were successfully separated by column chromatography.
Compounds (I) and (II) were both found to crystallize as racemic twins; the reference molecules were selected as those having the R configuration at C4. The absolute configuration of (III) was indeterminate, so again the reference molecule was selected as having the R configuration at C4. On this basis, (I) has the S configuration at C2, while (II) and (III) have the R configuration at C2. Compounds (I) and (II) are thus diastereoisomers. However, despite the close similarity between the constitutions of (II) and (III), they are not isomorphous, crystallizing in space groups P212121 and P21, respectively.
The shapes of the heterobicyclic ring systems in (I)–(III), as defined by the ring-puckering parameters (Cremer & Pople, 1975), are very similar (Table 1). For the five-membered rings, those in (II) and (III) adopt half-chair conformations, for which the ideal puckering angle ϕ is (36k + 18)°, where k represents zero or an integer. For the corresponding ring in (I), the conformation is intermediate between an envelope form, where the ideal value of ϕ is 36k°, and the half-chair form observed in the other examples. In each compound studied here, the conformation of the six-membered heterocyclic ring is intermediate between a half-chair form, where the idealized values of the ring-puckering angles are θ = 50.8° and ϕ = (60k + 30)°, and an envelope form, where the idealized values are θ = 54.7° and ϕ = 60k°.
In the title compounds, the torsion angle N1—C2—C21—C22 (Fig. 1) is 137.8 (3)° in (I), as opposed to -101.4 (3) and -104.56 (10)° in (II) and (III), respectively, possibly associated with the difference in configuration at C2 in (I) on the one hand and in (II) and (III) on the other. In addition, the torsion angle C21—C22—C221—C222 defining the orientation of the terminal aryl group is 22.7 (5)° in (I), as opposed to 3.5 (4)° in (II) and -1.45 (14)° in (III), again highlighting the conformational similarity between (II) and (III).
The hydrogen-bonded supramolecular structures of (I)–(III) are all one-dimensional. In compound (I), molecules related by the 21 screw axis along (1/2, y, 1/2) are linked by two hydrogen bonds (Table 2). The C—H···O and C—H···N hydrogen bonds acting individually give rise to C(3) and C(4) (Bernstein et al., 1995) chains, respectively, while the combination of these two hydrogen bonds generates a chain of edge-fused R33(9) rings (Fig. 2). Although compounds (II) and (III) are not isomorphous, their supramolecular hydrogen-bonded structures show considerable similarity. In compound (II), molecules related by translation along [100] are linked by a combination of one two-centre C—H···N hydrogen bond and one three-centre C—H···(N,O) hydrogen bond (Table 2). Although several of the individual components are quite long, the cooperative effect of the three individual components is probably significant. Acting individually, these interactions generate C(5), C(4) and C(4) chains, respectively, while in combination they generate an R22(7) motif divided into R21(3) and R12(6) sectors (Fig. 3). In compound (III), in contrast, molecules related by translation along [100] are linked into simple C(4) chains (Fig. 4) by a single C—H···O hydrogen bond, the donor and acceptor of which correspond exactly to the C—H···O interaction in (III), although this interaction in (III) is characterized by significantly shorter H···O and C···O distances than its counterpart in (II) (Table 2). However, the slightly different mutual orientation of the molecules in (II) and (III) (Figs. 3 and 4) results in H3B···N1i and H5B···N1i [symmetry code: (i) 1 + x, y, z] distances in (III) of 3.08 and 2.74 Å, respectively, which are very much longer than the corresponding distances in (II) and well outside the range for effective hydrogen bonding. However, the overall arrangement of the molecules within the chains along [100] is remarkably similar in these two compounds (Figs. 3 and 4).
In summary, we have characterized three compounds containing a heterocyclic ring system whose structural characteristics have not previously been reported, we have analysed the supramolecular aggregation, and we have found that, for compounds (II) and (III), while the crystals are not isomorphous the molecular arrangements within the crystals are nonetheless very similar.