Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108025961/ln3112sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108025961/ln3112Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108025961/ln3112IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108025961/ln3112IIIsup4.hkl |
CCDC references: 703740; 703741; 703742
For each of compounds (I)–(III), to a stirred solution of the appropriately substituted 2-allylaniline (0.10 mol) 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 48 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 to 7 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 46%, m.p. 406–407 K; MS (70 eV) m/z (%): 305 (M+, 35Cl, 31), 288 (12), 276 (3), 262 (5), 164 (7), 138 (100), 125 (13), 111 (5). Analysis, found: C 63.0, H 4.5, N 4.7%; C16H13Cl2NO requires: C 62.8, H 4.3, N 4.6%.
For (II): colourless crystals, yield 50%, m.p. 440–442 K; MS (70 eV) m/z (%): 305 (M+, 35Cl, 21), 288 (7), 276 (1), 262 (1), 164 (6), 138 (100), 125 (13), 111 (4). Analysis, found: C 62.5, H 4.6, N 4.4%; C16H13Cl2NO requires: C 62.8, H 4.3, N, 4.6%.
For (III): colourless crystals, yield 60%, m.p. 469–470 K; MS (70 eV) m/z (%): 321 (M+, 35Cl, 20), 304 (10), 292 (6), 278 (6), 154 (100), 153 (75), 139 (33), 138 (35), 127 (20). Analysis, found: C 74.9, H 4.9, N 4.5%; C20H16ClNO requires: C 74.7, H 5.0, N 4.4%.
Unique assignments of space groups were made from the systematic absences for compounds (II) and (III), both P212121. For compound (I), the systematic absences permitted Pna21 or Pnam (= Pnma, No. 62) as possible space groups; Pna21 was selected, and confirmed by the structure analysis. 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). Compounds (II) and (III) were refined as single enantiomorphs, in each case having the R configuration at atom C4, as suggested by the values of the Flack x parameter (Flack, 1983; Flack & Bernardinelli, 1999). However, particularly for compound (II), the enantiomorph-discrimating power (Flack & Bernardinelli, 2000) is not high. The reference molecule in the racemic compound, (I), was chosen as that having the R configuration at atom C4; here the correct orientation of the structure with respect to the polar axis direction was established by means of the Flack x parameter. Compound (II) diffracted rather weakly, with only ca 49% of the reflections labelled `observed', even at 120 K.
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).
C16H13Cl2NO | F(000) = 632 |
Mr = 306.17 | Dx = 1.487 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 3116 reflections |
a = 11.9348 (11) Å | θ = 3.3–27.5° |
b = 21.617 (2) Å | µ = 0.47 mm−1 |
c = 5.3024 (6) Å | T = 120 K |
V = 1368.0 (2) Å3 | Plate, colourless |
Z = 4 | 0.45 × 0.27 × 0.05 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3116 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2124 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ϕ and ω scans | h = −13→15 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −28→21 |
Tmin = 0.817, Tmax = 0.977 | l = −6→6 |
12986 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)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0411P)2 + 0.5401P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
3116 reflections | Δρmax = 0.30 e Å−3 |
181 parameters | Δρmin = −0.30 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 1380 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.09 (9) |
C16H13Cl2NO | V = 1368.0 (2) Å3 |
Mr = 306.17 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 11.9348 (11) Å | µ = 0.47 mm−1 |
b = 21.617 (2) Å | T = 120 K |
c = 5.3024 (6) Å | 0.45 × 0.27 × 0.05 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3116 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2124 reflections with I > 2σ(I) |
Tmin = 0.817, Tmax = 0.977 | Rint = 0.058 |
12986 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.104 | Δρmax = 0.30 e Å−3 |
S = 1.05 | Δρmin = −0.30 e Å−3 |
3116 reflections | Absolute structure: Flack (1983), with 1380 Friedel pairs |
181 parameters | Absolute structure parameter: 0.09 (9) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
Cl7 | 0.27978 (8) | 0.27881 (4) | 1.1092 (2) | 0.0470 (3) | |
Cl24 | 0.99300 (7) | 0.67574 (4) | 0.8265 (2) | 0.0371 (2) | |
O14 | 0.67229 (19) | 0.42691 (10) | 0.4982 (4) | 0.0282 (6) | |
N1 | 0.6336 (2) | 0.44608 (11) | 0.7431 (5) | 0.0251 (6) | |
C2 | 0.7363 (3) | 0.43863 (14) | 0.8972 (6) | 0.0249 (7) | |
C3 | 0.7892 (3) | 0.37935 (14) | 0.7898 (6) | 0.0272 (8) | |
C4 | 0.7265 (3) | 0.36889 (13) | 0.5454 (6) | 0.0269 (8) | |
C5 | 0.6345 (3) | 0.32047 (14) | 0.5617 (7) | 0.0304 (8) | |
C5a | 0.5464 (3) | 0.34263 (14) | 0.7425 (6) | 0.0266 (8) | |
C6 | 0.4627 (3) | 0.30475 (14) | 0.8304 (7) | 0.0302 (8) | |
C7 | 0.3858 (3) | 0.32706 (15) | 0.9998 (7) | 0.0305 (8) | |
C8 | 0.3887 (3) | 0.38686 (14) | 1.0844 (7) | 0.0321 (8) | |
C9 | 0.4708 (3) | 0.42498 (15) | 0.9935 (7) | 0.0299 (8) | |
C9a | 0.5490 (3) | 0.40341 (14) | 0.8243 (7) | 0.0255 (7) | |
C21 | 0.8054 (3) | 0.49636 (14) | 0.8811 (6) | 0.0258 (8) | |
C22 | 0.7931 (3) | 0.54124 (14) | 1.0647 (7) | 0.0282 (8) | |
C23 | 0.8500 (3) | 0.59673 (15) | 1.0509 (7) | 0.0313 (8) | |
C24 | 0.9209 (3) | 0.60655 (14) | 0.8503 (7) | 0.0282 (8) | |
C25 | 0.9356 (3) | 0.56266 (14) | 0.6660 (7) | 0.0300 (8) | |
C26 | 0.8784 (3) | 0.50758 (15) | 0.6819 (6) | 0.0280 (8) | |
H2 | 0.7146 | 0.4313 | 1.0770 | 0.030* | |
H3A | 0.8703 | 0.3852 | 0.7583 | 0.033* | |
H3B | 0.7789 | 0.3441 | 0.9065 | 0.033* | |
H4 | 0.7799 | 0.3587 | 0.4060 | 0.032* | |
H5A | 0.6011 | 0.3138 | 0.3930 | 0.036* | |
H5B | 0.6661 | 0.2807 | 0.6211 | 0.036* | |
H6 | 0.4580 | 0.2631 | 0.7739 | 0.036* | |
H8 | 0.3352 | 0.4015 | 1.2028 | 0.038* | |
H9 | 0.4738 | 0.4668 | 1.0478 | 0.036* | |
H22 | 0.7444 | 0.5337 | 1.2032 | 0.034* | |
H23 | 0.8404 | 0.6275 | 1.1771 | 0.038* | |
H25 | 0.9849 | 0.5703 | 0.5289 | 0.036* | |
H26 | 0.8888 | 0.4769 | 0.5556 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl7 | 0.0446 (5) | 0.0307 (4) | 0.0658 (7) | −0.0058 (4) | 0.0225 (6) | −0.0055 (5) |
Cl24 | 0.0320 (4) | 0.0306 (4) | 0.0486 (5) | −0.0033 (4) | −0.0055 (5) | 0.0011 (5) |
O14 | 0.0335 (13) | 0.0321 (12) | 0.0189 (12) | 0.0047 (10) | 0.0024 (11) | 0.0014 (10) |
N1 | 0.0312 (15) | 0.0267 (14) | 0.0174 (15) | 0.0026 (12) | 0.0025 (12) | 0.0021 (12) |
C2 | 0.0305 (18) | 0.0258 (16) | 0.0184 (17) | 0.0041 (14) | −0.0013 (14) | 0.0021 (14) |
C3 | 0.0336 (18) | 0.0227 (16) | 0.025 (2) | 0.0058 (14) | −0.0004 (16) | 0.0024 (14) |
C4 | 0.0296 (17) | 0.0272 (17) | 0.024 (2) | 0.0055 (14) | 0.0040 (16) | −0.0043 (15) |
C5 | 0.0325 (19) | 0.0289 (17) | 0.030 (2) | 0.0037 (15) | 0.0053 (16) | −0.0071 (16) |
C5a | 0.0279 (18) | 0.0244 (16) | 0.0276 (19) | 0.0046 (14) | 0.0035 (15) | −0.0014 (14) |
C6 | 0.0354 (18) | 0.0199 (15) | 0.035 (2) | 0.0016 (13) | 0.0037 (19) | −0.0054 (17) |
C7 | 0.0323 (19) | 0.0255 (17) | 0.034 (2) | 0.0034 (15) | 0.0050 (17) | 0.0011 (16) |
C8 | 0.0343 (19) | 0.0273 (17) | 0.035 (2) | 0.0074 (14) | 0.0090 (18) | 0.0000 (17) |
C9 | 0.035 (2) | 0.0212 (17) | 0.033 (2) | 0.0045 (15) | 0.0028 (17) | −0.0009 (15) |
C9a | 0.0269 (16) | 0.0234 (15) | 0.0261 (18) | 0.0033 (13) | 0.0029 (17) | 0.0009 (15) |
C21 | 0.0327 (19) | 0.0229 (16) | 0.0216 (19) | 0.0053 (14) | −0.0016 (15) | 0.0039 (14) |
C22 | 0.0318 (18) | 0.0320 (17) | 0.0206 (18) | 0.0034 (15) | 0.0025 (16) | 0.0008 (15) |
C23 | 0.0349 (19) | 0.0313 (18) | 0.028 (2) | 0.0039 (15) | −0.0035 (17) | −0.0042 (15) |
C24 | 0.0250 (17) | 0.0247 (16) | 0.035 (2) | 0.0044 (13) | −0.0093 (18) | 0.0020 (17) |
C25 | 0.0337 (19) | 0.0277 (17) | 0.029 (2) | 0.0026 (15) | 0.0007 (16) | 0.0027 (15) |
C26 | 0.0319 (19) | 0.0285 (17) | 0.0236 (19) | 0.0063 (15) | 0.0000 (16) | −0.0017 (15) |
Cl7—C7 | 1.740 (3) | C5a—C9a | 1.384 (4) |
Cl24—C24 | 1.730 (3) | C6—C7 | 1.372 (5) |
O14—C4 | 1.433 (4) | C6—H6 | 0.95 |
O14—N1 | 1.439 (3) | C7—C8 | 1.369 (4) |
N1—C9a | 1.433 (4) | C8—C9 | 1.368 (5) |
N1—C2 | 1.482 (4) | C8—H8 | 0.95 |
C2—C21 | 1.499 (4) | C9—C9a | 1.377 (5) |
C2—C3 | 1.538 (4) | C9—H9 | 0.95 |
C2—H2 | 1.00 | C21—C22 | 1.383 (4) |
C3—C4 | 1.513 (5) | C21—C26 | 1.390 (5) |
C3—H3A | 0.99 | C22—C23 | 1.380 (5) |
C3—H3B | 0.99 | C22—H22 | 0.95 |
C4—C5 | 1.519 (4) | C23—C24 | 1.376 (5) |
C4—H4 | 1.00 | C23—H23 | 0.95 |
C5—C5a | 1.502 (5) | C24—C25 | 1.373 (5) |
C5—H5A | 0.99 | C25—C26 | 1.375 (4) |
C5—H5B | 0.99 | C25—H25 | 0.95 |
C5a—C6 | 1.373 (4) | C26—H26 | 0.95 |
C4—O14—N1 | 103.8 (2) | C7—C6—H6 | 120.0 |
C9a—N1—O14 | 108.2 (2) | C5a—C6—H6 | 120.0 |
C9a—N1—C2 | 110.3 (2) | C8—C7—C6 | 122.0 (3) |
O14—N1—C2 | 101.6 (2) | C8—C7—Cl7 | 118.4 (3) |
N1—C2—C21 | 109.5 (2) | C6—C7—Cl7 | 119.6 (3) |
N1—C2—C3 | 103.1 (2) | C9—C8—C7 | 118.1 (3) |
C21—C2—C3 | 116.5 (3) | C9—C8—H8 | 120.9 |
N1—C2—H2 | 109.2 | C7—C8—H8 | 120.9 |
C21—C2—H2 | 109.2 | C8—C9—C9a | 120.8 (3) |
C3—C2—H2 | 109.2 | C8—C9—H9 | 119.6 |
C4—C3—C2 | 103.8 (3) | C9a—C9—H9 | 119.6 |
C4—C3—H3A | 111.0 | C9—C9a—C5a | 120.7 (3) |
C2—C3—H3A | 111.0 | C9—C9a—N1 | 117.1 (3) |
C4—C3—H3B | 111.0 | C5a—C9a—N1 | 122.2 (3) |
C2—C3—H3B | 111.0 | C22—C21—C26 | 118.7 (3) |
H3A—C3—H3B | 109.0 | C22—C21—C2 | 119.0 (3) |
O14—C4—C3 | 104.0 (2) | C26—C21—C2 | 122.3 (3) |
O14—C4—C5 | 106.6 (3) | C23—C22—C21 | 121.3 (3) |
C3—C4—C5 | 114.3 (3) | C23—C22—H22 | 119.3 |
O14—C4—H4 | 110.5 | C21—C22—H22 | 119.3 |
C3—C4—H4 | 110.5 | C24—C23—C22 | 118.5 (3) |
C5—C4—H4 | 110.5 | C24—C23—H23 | 120.7 |
C5a—C5—C4 | 108.8 (3) | C22—C23—H23 | 120.7 |
C5a—C5—H5A | 109.9 | C25—C24—C23 | 121.5 (3) |
C4—C5—H5A | 109.9 | C25—C24—Cl24 | 118.8 (3) |
C5a—C5—H5B | 109.9 | C23—C24—Cl24 | 119.7 (3) |
C4—C5—H5B | 109.9 | C24—C25—C26 | 119.4 (3) |
H5A—C5—H5B | 108.3 | C24—C25—H25 | 120.3 |
C6—C5a—C9a | 118.5 (3) | C26—C25—H25 | 120.3 |
C6—C5a—C5 | 122.4 (3) | C25—C26—C21 | 120.6 (3) |
C9a—C5a—C5 | 119.1 (3) | C25—C26—H26 | 119.7 |
C7—C6—C5a | 119.9 (3) | C21—C26—H26 | 119.7 |
C4—O14—N1—C9a | −66.2 (3) | C8—C9—C9a—N1 | −178.6 (3) |
C4—O14—N1—C2 | 49.9 (3) | C6—C5a—C9a—C9 | 1.2 (5) |
C9a—N1—C2—C21 | −158.9 (3) | C5—C5a—C9a—C9 | −178.8 (3) |
O14—N1—C2—C21 | 86.6 (3) | C6—C5a—C9a—N1 | 179.7 (3) |
C9a—N1—C2—C3 | 76.5 (3) | C5—C5a—C9a—N1 | −0.3 (5) |
O14—N1—C2—C3 | −38.1 (3) | O14—N1—C9a—C9 | −154.2 (3) |
N1—C2—C3—C4 | 13.8 (3) | C2—N1—C9a—C9 | 95.6 (3) |
C21—C2—C3—C4 | −106.1 (3) | O14—N1—C9a—C5a | 27.2 (4) |
N1—O14—C4—C3 | −40.7 (3) | C2—N1—C9a—C5a | −83.0 (4) |
N1—O14—C4—C5 | 80.5 (3) | N1—C2—C21—C22 | 94.3 (3) |
C2—C3—C4—O14 | 15.6 (3) | C3—C2—C21—C22 | −149.3 (3) |
C2—C3—C4—C5 | −100.3 (3) | N1—C2—C21—C26 | −83.0 (4) |
O14—C4—C5—C5a | −50.5 (3) | C3—C2—C21—C26 | 33.4 (4) |
C3—C4—C5—C5a | 63.8 (4) | C26—C21—C22—C23 | 1.1 (5) |
C4—C5—C5a—C6 | −168.4 (3) | C2—C21—C22—C23 | −176.3 (3) |
C4—C5—C5a—C9a | 11.6 (4) | C21—C22—C23—C24 | −0.6 (5) |
C9a—C5a—C6—C7 | −1.5 (5) | C22—C23—C24—C25 | 0.1 (5) |
C5—C5a—C6—C7 | 178.5 (3) | C22—C23—C24—Cl24 | 179.7 (2) |
C5a—C6—C7—C8 | 0.7 (6) | C23—C24—C25—C26 | 0.0 (5) |
C5a—C6—C7—Cl7 | 179.8 (3) | Cl24—C24—C25—C26 | −179.7 (3) |
C6—C7—C8—C9 | 0.5 (5) | C24—C25—C26—C21 | 0.5 (5) |
Cl7—C7—C8—C9 | −178.6 (3) | C22—C21—C26—C25 | −1.1 (5) |
C7—C8—C9—C9a | −0.8 (5) | C2—C21—C26—C25 | 176.2 (3) |
C8—C9—C9a—C5a | 0.0 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O14i | 1.00 | 2.29 | 3.287 (4) | 173 |
C9—H9···N1ii | 0.95 | 2.50 | 3.328 (4) | 145 |
C8—H8···Cg1ii | 0.95 | 2.72 | 3.615 (4) | 157 |
Symmetry codes: (i) x, y, z+1; (ii) −x+1, −y+1, z+1/2. |
C16H13Cl2NO | F(000) = 632 |
Mr = 306.17 | Dx = 1.482 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3131 reflections |
a = 7.4328 (11) Å | θ = 2.7–27.5° |
b = 12.3746 (16) Å | µ = 0.47 mm−1 |
c = 14.9187 (19) Å | T = 120 K |
V = 1372.2 (3) Å3 | Lath, colourless |
Z = 4 | 0.27 × 0.10 × 0.07 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3131 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1541 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.147 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
ϕ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −16→14 |
Tmin = 0.926, Tmax = 0.968 | l = −19→17 |
12048 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)] = 0.061 | H-atom parameters constrained |
wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.056P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3131 reflections | Δρmax = 0.38 e Å−3 |
181 parameters | Δρmin = −0.48 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 1316 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (15) |
C16H13Cl2NO | V = 1372.2 (3) Å3 |
Mr = 306.17 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.4328 (11) Å | µ = 0.47 mm−1 |
b = 12.3746 (16) Å | T = 120 K |
c = 14.9187 (19) Å | 0.27 × 0.10 × 0.07 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3131 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1541 reflections with I > 2σ(I) |
Tmin = 0.926, Tmax = 0.968 | Rint = 0.147 |
12048 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | H-atom parameters constrained |
wR(F2) = 0.153 | Δρmax = 0.38 e Å−3 |
S = 1.05 | Δρmin = −0.48 e Å−3 |
3131 reflections | Absolute structure: Flack (1983), with 1316 Friedel pairs |
181 parameters | Absolute structure parameter: 0.01 (15) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
Cl7 | 0.91147 (19) | 0.25680 (13) | 0.04857 (8) | 0.0380 (4) | |
Cl26 | 0.63144 (17) | 0.25582 (13) | 0.60354 (9) | 0.0357 (4) | |
O14 | 0.5843 (5) | 0.5547 (3) | 0.3685 (2) | 0.0350 (10) | |
N1 | 0.5225 (6) | 0.4453 (3) | 0.3547 (3) | 0.0286 (11) | |
C2 | 0.5803 (7) | 0.3925 (4) | 0.4394 (3) | 0.0271 (13) | |
C3 | 0.7614 (7) | 0.4474 (5) | 0.4614 (4) | 0.0351 (15) | |
C4 | 0.7677 (8) | 0.5423 (5) | 0.3987 (4) | 0.0359 (15) | |
C5 | 0.8810 (8) | 0.5241 (5) | 0.3167 (4) | 0.0391 (15) | |
C5a | 0.7934 (8) | 0.4375 (4) | 0.2601 (4) | 0.0292 (14) | |
C6 | 0.8795 (8) | 0.3929 (4) | 0.1873 (4) | 0.0297 (14) | |
C7 | 0.7959 (8) | 0.3148 (4) | 0.1384 (3) | 0.0298 (14) | |
C8 | 0.6297 (7) | 0.2757 (4) | 0.1590 (3) | 0.0278 (14) | |
C9 | 0.5405 (8) | 0.3220 (4) | 0.2312 (3) | 0.0263 (14) | |
C9a | 0.6214 (8) | 0.4020 (4) | 0.2804 (3) | 0.0256 (13) | |
C21 | 0.4438 (7) | 0.4070 (4) | 0.5123 (4) | 0.0254 (13) | |
C22 | 0.3029 (7) | 0.4784 (4) | 0.5061 (4) | 0.0294 (14) | |
C23 | 0.1792 (8) | 0.4895 (4) | 0.5747 (4) | 0.0317 (14) | |
C24 | 0.1922 (7) | 0.4259 (4) | 0.6492 (4) | 0.0310 (14) | |
C25 | 0.3322 (8) | 0.3542 (4) | 0.6575 (4) | 0.0287 (14) | |
C26 | 0.4547 (7) | 0.3460 (4) | 0.5903 (4) | 0.0282 (13) | |
H2 | 0.6003 | 0.3137 | 0.4285 | 0.032* | |
H3A | 0.7649 | 0.4715 | 0.5247 | 0.042* | |
H3B | 0.8633 | 0.3977 | 0.4503 | 0.042* | |
H4 | 0.8082 | 0.6086 | 0.4312 | 0.043* | |
H5A | 1.0035 | 0.5011 | 0.3344 | 0.047* | |
H5B | 0.8909 | 0.5920 | 0.2819 | 0.047* | |
H6 | 0.9967 | 0.4165 | 0.1713 | 0.036* | |
H8 | 0.5768 | 0.2189 | 0.1253 | 0.033* | |
H9 | 0.4229 | 0.2981 | 0.2465 | 0.032* | |
H22 | 0.2901 | 0.5211 | 0.4536 | 0.035* | |
H23 | 0.0854 | 0.5414 | 0.5700 | 0.038* | |
H24 | 0.1044 | 0.4313 | 0.6952 | 0.037* | |
H25 | 0.3433 | 0.3107 | 0.7097 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl7 | 0.0468 (8) | 0.0406 (8) | 0.0264 (7) | 0.0092 (9) | 0.0072 (6) | −0.0012 (7) |
Cl26 | 0.0329 (8) | 0.0372 (8) | 0.0369 (8) | 0.0074 (8) | 0.0008 (6) | 0.0033 (8) |
O14 | 0.038 (2) | 0.027 (2) | 0.039 (2) | −0.0019 (19) | 0.008 (2) | −0.0034 (19) |
N1 | 0.031 (3) | 0.024 (3) | 0.031 (3) | −0.004 (2) | 0.006 (2) | −0.001 (2) |
C2 | 0.026 (3) | 0.030 (3) | 0.025 (3) | 0.001 (3) | 0.002 (3) | 0.000 (3) |
C3 | 0.027 (3) | 0.049 (4) | 0.029 (3) | −0.004 (3) | 0.004 (3) | −0.008 (3) |
C4 | 0.035 (4) | 0.027 (3) | 0.046 (4) | −0.010 (3) | 0.004 (3) | −0.009 (3) |
C5 | 0.043 (4) | 0.037 (4) | 0.037 (3) | −0.002 (3) | 0.013 (3) | −0.008 (3) |
C5a | 0.029 (4) | 0.028 (3) | 0.031 (3) | 0.004 (3) | 0.005 (3) | 0.000 (3) |
C6 | 0.033 (3) | 0.029 (3) | 0.028 (3) | 0.001 (3) | 0.008 (3) | 0.003 (3) |
C7 | 0.044 (4) | 0.028 (3) | 0.017 (3) | 0.006 (3) | 0.003 (3) | 0.002 (3) |
C8 | 0.030 (3) | 0.029 (3) | 0.025 (3) | 0.000 (3) | −0.003 (2) | 0.000 (2) |
C9 | 0.025 (3) | 0.034 (3) | 0.021 (3) | −0.001 (3) | −0.001 (3) | 0.007 (3) |
C9a | 0.024 (3) | 0.029 (3) | 0.023 (3) | 0.008 (3) | 0.000 (3) | −0.001 (3) |
C21 | 0.019 (3) | 0.026 (3) | 0.031 (3) | 0.003 (3) | −0.001 (3) | −0.005 (3) |
C22 | 0.031 (3) | 0.026 (3) | 0.031 (3) | −0.003 (3) | −0.006 (3) | −0.002 (3) |
C23 | 0.024 (3) | 0.032 (3) | 0.039 (3) | 0.004 (3) | 0.001 (3) | −0.005 (3) |
C24 | 0.024 (3) | 0.036 (3) | 0.033 (3) | −0.006 (3) | 0.003 (3) | −0.003 (3) |
C25 | 0.035 (4) | 0.027 (3) | 0.024 (3) | −0.003 (3) | −0.004 (3) | −0.002 (3) |
C26 | 0.026 (3) | 0.026 (3) | 0.032 (3) | 0.003 (3) | 0.002 (3) | −0.002 (3) |
Cl7—C7 | 1.747 (6) | C5a—C6 | 1.376 (7) |
Cl26—C26 | 1.735 (5) | C6—C7 | 1.361 (7) |
O14—N1 | 1.444 (5) | C6—H6 | 0.95 |
O14—C4 | 1.443 (7) | C7—C8 | 1.362 (8) |
N1—C9a | 1.434 (6) | C8—C9 | 1.388 (7) |
N1—C2 | 1.486 (7) | C8—H8 | 0.95 |
C2—C21 | 1.498 (7) | C9—C9a | 1.372 (7) |
C2—C3 | 1.543 (7) | C9—H9 | 0.95 |
C2—H2 | 1.00 | C21—C22 | 1.374 (7) |
C3—C4 | 1.502 (8) | C21—C26 | 1.389 (7) |
C3—H3A | 0.99 | C22—C23 | 1.382 (7) |
C3—H3B | 0.99 | C22—H22 | 0.95 |
C4—C5 | 1.502 (8) | C23—C24 | 1.365 (8) |
C4—H4 | 1.00 | C23—H23 | 0.95 |
C5—C5a | 1.511 (8) | C24—C25 | 1.374 (8) |
C5—H5A | 0.99 | C24—H24 | 0.95 |
C5—H5B | 0.99 | C25—C26 | 1.357 (8) |
C5a—C9a | 1.385 (8) | C25—H25 | 0.95 |
N1—O14—C4 | 104.2 (4) | C7—C6—H6 | 120.1 |
C9a—N1—O14 | 107.3 (4) | C5a—C6—H6 | 120.1 |
C9a—N1—C2 | 110.2 (4) | C6—C7—C8 | 123.1 (5) |
O14—N1—C2 | 101.5 (4) | C6—C7—Cl7 | 118.6 (4) |
N1—C2—C21 | 111.7 (4) | C8—C7—Cl7 | 118.2 (4) |
N1—C2—C3 | 103.8 (4) | C7—C8—C9 | 117.5 (5) |
C21—C2—C3 | 112.6 (4) | C7—C8—H8 | 121.3 |
N1—C2—H2 | 109.5 | C9—C8—H8 | 121.3 |
C21—C2—H2 | 109.5 | C8—C9—C9a | 120.2 (5) |
C3—C2—H2 | 109.5 | C8—C9—H9 | 119.9 |
C4—C3—C2 | 103.8 (5) | C9a—C9—H9 | 119.9 |
C4—C3—H3A | 111.0 | C5a—C9a—C9 | 121.1 (5) |
C2—C3—H3A | 111.0 | C5a—C9a—N1 | 121.6 (5) |
C4—C3—H3B | 111.0 | C9—C9a—N1 | 117.3 (5) |
C2—C3—H3B | 111.0 | C22—C21—C26 | 116.8 (5) |
H3A—C3—H3B | 109.0 | C22—C21—C2 | 123.0 (5) |
O14—C4—C3 | 104.3 (4) | C26—C21—C2 | 120.3 (5) |
O14—C4—C5 | 107.0 (5) | C21—C22—C23 | 121.4 (5) |
C3—C4—C5 | 114.1 (5) | C21—C22—H22 | 119.3 |
O14—C4—H4 | 110.4 | C23—C22—H22 | 119.3 |
C3—C4—H4 | 110.4 | C24—C23—C22 | 119.9 (5) |
C5—C4—H4 | 110.4 | C24—C23—H23 | 120.1 |
C4—C5—C5a | 108.6 (5) | C22—C23—H23 | 120.1 |
C4—C5—H5A | 110.0 | C23—C24—C25 | 120.0 (5) |
C5a—C5—H5A | 110.0 | C23—C24—H24 | 120.0 |
C4—C5—H5B | 110.0 | C25—C24—H24 | 120.0 |
C5a—C5—H5B | 110.0 | C26—C25—C24 | 119.3 (5) |
H5A—C5—H5B | 108.3 | C26—C25—H25 | 120.3 |
C9a—C5a—C6 | 118.3 (5) | C24—C25—H25 | 120.3 |
C9a—C5a—C5 | 120.0 (5) | C25—C26—C21 | 122.6 (5) |
C6—C5a—C5 | 121.7 (5) | C25—C26—Cl26 | 118.1 (4) |
C7—C6—C5a | 119.7 (5) | C21—C26—Cl26 | 119.3 (4) |
C4—O14—N1—C9a | −67.4 (5) | C5—C5a—C9a—C9 | −178.7 (5) |
C4—O14—N1—C2 | 48.2 (4) | C6—C5a—C9a—N1 | −179.4 (5) |
C9a—N1—C2—C21 | −161.2 (5) | C5—C5a—C9a—N1 | −0.2 (8) |
O14—N1—C2—C21 | 85.4 (5) | C8—C9—C9a—C5a | −0.7 (8) |
C9a—N1—C2—C3 | 77.3 (5) | C8—C9—C9a—N1 | −179.3 (4) |
O14—N1—C2—C3 | −36.2 (5) | O14—N1—C9a—C5a | 28.4 (6) |
N1—C2—C3—C4 | 12.2 (5) | C2—N1—C9a—C5a | −81.2 (6) |
C21—C2—C3—C4 | −108.8 (5) | O14—N1—C9a—C9 | −153.0 (4) |
N1—O14—C4—C3 | −40.5 (5) | C2—N1—C9a—C9 | 97.3 (5) |
N1—O14—C4—C5 | 80.7 (5) | N1—C2—C21—C22 | −12.4 (7) |
C2—C3—C4—O14 | 16.4 (5) | C3—C2—C21—C22 | 104.0 (6) |
C2—C3—C4—C5 | −99.9 (5) | N1—C2—C21—C26 | 166.9 (5) |
O14—C4—C5—C5a | −48.7 (6) | C3—C2—C21—C26 | −76.7 (7) |
C3—C4—C5—C5a | 66.1 (6) | C26—C21—C22—C23 | 0.6 (8) |
C4—C5—C5a—C9a | 10.1 (7) | C2—C21—C22—C23 | 179.9 (5) |
C4—C5—C5a—C6 | −170.6 (5) | C21—C22—C23—C24 | −2.4 (8) |
C9a—C5a—C6—C7 | −1.0 (8) | C22—C23—C24—C25 | 2.7 (8) |
C5—C5a—C6—C7 | 179.8 (5) | C23—C24—C25—C26 | −1.3 (8) |
C5a—C6—C7—C8 | −1.5 (8) | C24—C25—C26—C21 | −0.5 (8) |
C5a—C6—C7—Cl7 | −178.0 (4) | C24—C25—C26—Cl26 | 179.2 (4) |
C6—C7—C8—C9 | 2.9 (8) | C22—C21—C26—C25 | 0.9 (8) |
Cl7—C7—C8—C9 | 179.4 (4) | C2—C21—C26—C25 | −178.5 (5) |
C7—C8—C9—C9a | −1.7 (7) | C22—C21—C26—Cl26 | −178.9 (4) |
C6—C5a—C9a—C9 | 2.0 (8) | C2—C21—C26—Cl26 | 1.8 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O14i | 0.95 | 2.36 | 3.190 (6) | 146 |
C6—H6···Cg1ii | 0.95 | 2.82 | 3.619 (6) | 143 |
C25—H25···Cg2iii | 0.95 | 2.60 | 3.410 (6) | 143 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+3/2, −y+1, z−1/2; (iii) x−1/2, −y+1/2, −z+1. |
C20H16ClNO | F(000) = 672 |
Mr = 321.79 | Dx = 1.428 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab1 | Cell parameters from 3418 reflections |
a = 9.6174 (18) Å | θ = 2.8–27.5° |
b = 11.558 (3) Å | µ = 0.26 mm−1 |
c = 13.465 (4) Å | T = 120 K |
V = 1496.7 (7) Å3 | Needle, colourless |
Z = 4 | 0.32 × 0.08 × 0.06 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3418 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2460 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.085 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.956, Tmax = 0.985 | l = −16→17 |
16825 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)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0435P)2 + 0.5441P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
3418 reflections | Δρmax = 0.30 e Å−3 |
208 parameters | Δρmin = −0.33 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 1446 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (9) |
C20H16ClNO | V = 1496.7 (7) Å3 |
Mr = 321.79 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.6174 (18) Å | µ = 0.26 mm−1 |
b = 11.558 (3) Å | T = 120 K |
c = 13.465 (4) Å | 0.32 × 0.08 × 0.06 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3418 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2460 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 0.985 | Rint = 0.085 |
16825 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.114 | Δρmax = 0.30 e Å−3 |
S = 1.10 | Δρmin = −0.33 e Å−3 |
3418 reflections | Absolute structure: Flack (1983), with 1446 Friedel pairs |
208 parameters | Absolute structure parameter: 0.01 (9) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
Cl7 | 0.77897 (9) | 0.56688 (7) | 0.16877 (6) | 0.0288 (2) | |
O14 | 0.3010 (2) | 0.69865 (19) | 0.49069 (17) | 0.0244 (5) | |
N1 | 0.4112 (3) | 0.6186 (2) | 0.51586 (19) | 0.0192 (6) | |
C2 | 0.4811 (3) | 0.6777 (3) | 0.5990 (2) | 0.0166 (7) | |
C3 | 0.4663 (3) | 0.8084 (3) | 0.5746 (2) | 0.0189 (7) | |
C4 | 0.3715 (3) | 0.8096 (3) | 0.4849 (2) | 0.0203 (7) | |
C5 | 0.4438 (3) | 0.8145 (3) | 0.3855 (3) | 0.0233 (8) | |
C5a | 0.5172 (3) | 0.7021 (3) | 0.3653 (2) | 0.0190 (7) | |
C6 | 0.6011 (3) | 0.6863 (3) | 0.2831 (2) | 0.0193 (7) | |
C7 | 0.6704 (3) | 0.5841 (3) | 0.2712 (2) | 0.0203 (7) | |
C8 | 0.6616 (3) | 0.4950 (3) | 0.3378 (2) | 0.0195 (7) | |
C9 | 0.5733 (3) | 0.5086 (3) | 0.4179 (2) | 0.0191 (7) | |
C9a | 0.5030 (3) | 0.6111 (3) | 0.4312 (2) | 0.0170 (7) | |
C21 | 0.4203 (3) | 0.6408 (3) | 0.6970 (2) | 0.0182 (7) | |
C22 | 0.3068 (3) | 0.5707 (3) | 0.7003 (2) | 0.0213 (7) | |
C23 | 0.2545 (4) | 0.5310 (3) | 0.7913 (3) | 0.0277 (8) | |
C24 | 0.3160 (3) | 0.5607 (3) | 0.8776 (3) | 0.0281 (8) | |
C25 | 0.4338 (3) | 0.6327 (3) | 0.8783 (2) | 0.0227 (8) | |
C26 | 0.5013 (4) | 0.6636 (3) | 0.9654 (3) | 0.0313 (9) | |
C27 | 0.6128 (4) | 0.7343 (3) | 0.9656 (3) | 0.0352 (10) | |
C28 | 0.6630 (4) | 0.7791 (3) | 0.8762 (3) | 0.0276 (8) | |
C29 | 0.6016 (3) | 0.7507 (3) | 0.7888 (3) | 0.0218 (7) | |
C30 | 0.4858 (3) | 0.6751 (3) | 0.7867 (2) | 0.0212 (7) | |
H2 | 0.5820 | 0.6568 | 0.5980 | 0.020* | |
H3A | 0.4242 | 0.8509 | 0.6309 | 0.023* | |
H3B | 0.5577 | 0.8431 | 0.5588 | 0.023* | |
H4 | 0.3027 | 0.8741 | 0.4906 | 0.024* | |
H5A | 0.3747 | 0.8295 | 0.3325 | 0.028* | |
H5B | 0.5120 | 0.8787 | 0.3853 | 0.028* | |
H6 | 0.6104 | 0.7462 | 0.2352 | 0.023* | |
H8 | 0.7144 | 0.4262 | 0.3293 | 0.023* | |
H9 | 0.5611 | 0.4470 | 0.4638 | 0.023* | |
H22 | 0.2625 | 0.5483 | 0.6403 | 0.026* | |
H23 | 0.1746 | 0.4826 | 0.7922 | 0.033* | |
H24 | 0.2794 | 0.5326 | 0.9385 | 0.034* | |
H26 | 0.4680 | 0.6340 | 1.0268 | 0.038* | |
H27 | 0.6571 | 0.7537 | 1.0264 | 0.042* | |
H28 | 0.7407 | 0.8299 | 0.8766 | 0.033* | |
H29 | 0.6366 | 0.7819 | 0.7285 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl7 | 0.0327 (4) | 0.0275 (4) | 0.0262 (4) | −0.0024 (4) | 0.0093 (4) | −0.0047 (4) |
O14 | 0.0132 (11) | 0.0294 (12) | 0.0308 (13) | 0.0018 (10) | −0.0031 (10) | −0.0015 (10) |
N1 | 0.0146 (13) | 0.0217 (14) | 0.0213 (14) | 0.0005 (11) | −0.0016 (12) | −0.0011 (11) |
C2 | 0.0130 (15) | 0.0185 (17) | 0.0182 (16) | 0.0009 (13) | 0.0013 (13) | −0.0006 (13) |
C3 | 0.0139 (15) | 0.0147 (15) | 0.0279 (18) | 0.0005 (13) | 0.0030 (13) | 0.0011 (14) |
C4 | 0.0131 (15) | 0.0201 (16) | 0.0276 (19) | 0.0053 (13) | −0.0013 (13) | −0.0007 (14) |
C5 | 0.0220 (17) | 0.0227 (18) | 0.0252 (18) | 0.0046 (15) | −0.0049 (15) | 0.0017 (14) |
C5a | 0.0149 (15) | 0.0190 (16) | 0.0231 (18) | −0.0018 (13) | −0.0069 (13) | −0.0006 (13) |
C6 | 0.0229 (16) | 0.0186 (15) | 0.0163 (16) | −0.0041 (14) | −0.0045 (14) | 0.0019 (13) |
C7 | 0.0200 (16) | 0.0244 (18) | 0.0164 (15) | −0.0050 (14) | 0.0013 (13) | −0.0035 (14) |
C8 | 0.0192 (15) | 0.0185 (15) | 0.0207 (16) | 0.0018 (13) | −0.0023 (15) | −0.0034 (14) |
C9 | 0.0213 (17) | 0.0168 (16) | 0.0193 (17) | −0.0053 (13) | −0.0065 (14) | 0.0006 (13) |
C9a | 0.0128 (15) | 0.0217 (17) | 0.0166 (16) | −0.0018 (13) | −0.0056 (13) | −0.0020 (12) |
C21 | 0.0175 (16) | 0.0163 (15) | 0.0206 (17) | 0.0040 (13) | 0.0013 (14) | 0.0002 (13) |
C22 | 0.0157 (16) | 0.0189 (14) | 0.0293 (17) | 0.0025 (14) | 0.0060 (13) | −0.0025 (14) |
C23 | 0.0244 (19) | 0.0233 (17) | 0.035 (2) | 0.0020 (14) | 0.0132 (16) | 0.0044 (14) |
C24 | 0.035 (2) | 0.0215 (17) | 0.0275 (18) | 0.0068 (17) | 0.0141 (16) | 0.0025 (16) |
C25 | 0.0318 (19) | 0.0142 (16) | 0.0222 (17) | 0.0071 (15) | 0.0055 (16) | 0.0006 (14) |
C26 | 0.046 (2) | 0.025 (2) | 0.0221 (19) | 0.0102 (18) | 0.0056 (18) | 0.0037 (15) |
C27 | 0.051 (3) | 0.025 (2) | 0.029 (2) | 0.0088 (18) | −0.007 (2) | −0.0045 (16) |
C28 | 0.0324 (19) | 0.0228 (18) | 0.0276 (19) | 0.0015 (15) | −0.0055 (17) | −0.0019 (15) |
C29 | 0.0237 (18) | 0.0209 (16) | 0.0208 (18) | 0.0041 (14) | 0.0013 (16) | 0.0006 (14) |
C30 | 0.0232 (16) | 0.0159 (16) | 0.0246 (18) | 0.0065 (14) | 0.0002 (15) | −0.0009 (14) |
Cl7—C7 | 1.742 (3) | C8—H8 | 0.95 |
O14—N1 | 1.447 (3) | C9—C9a | 1.376 (4) |
O14—C4 | 1.453 (4) | C9—H9 | 0.95 |
N1—C9a | 1.444 (4) | C21—C22 | 1.360 (4) |
N1—C2 | 1.473 (4) | C21—C30 | 1.419 (5) |
C2—C21 | 1.505 (4) | C22—C23 | 1.401 (4) |
C2—C3 | 1.552 (4) | C22—H22 | 0.95 |
C2—H2 | 1.00 | C23—C24 | 1.348 (5) |
C3—C4 | 1.513 (4) | C23—H23 | 0.95 |
C3—H3A | 0.99 | C24—C25 | 1.405 (5) |
C3—H3B | 0.99 | C24—H24 | 0.95 |
C4—C5 | 1.510 (5) | C25—C26 | 1.388 (5) |
C4—H4 | 1.00 | C25—C30 | 1.419 (4) |
C5—C5a | 1.504 (5) | C26—C27 | 1.348 (6) |
C5—H5A | 0.99 | C26—H26 | 0.95 |
C5—H5B | 0.99 | C27—C28 | 1.396 (5) |
C5a—C6 | 1.382 (5) | C27—H27 | 0.95 |
C5a—C9a | 1.383 (4) | C28—C29 | 1.357 (5) |
C6—C7 | 1.366 (4) | C28—H28 | 0.95 |
C6—H6 | 0.95 | C29—C30 | 1.416 (5) |
C7—C8 | 1.368 (4) | C29—H29 | 0.95 |
C8—C9 | 1.382 (4) | ||
N1—O14—C4 | 103.6 (2) | C7—C8—H8 | 121.2 |
C9a—N1—O14 | 107.6 (2) | C9—C8—H8 | 121.2 |
C9a—N1—C2 | 110.4 (2) | C9a—C9—C8 | 120.1 (3) |
O14—N1—C2 | 102.5 (2) | C9a—C9—H9 | 119.9 |
N1—C2—C21 | 111.0 (2) | C8—C9—H9 | 119.9 |
N1—C2—C3 | 104.4 (2) | C9—C9a—C5a | 121.5 (3) |
C21—C2—C3 | 115.2 (3) | C9—C9a—N1 | 117.1 (3) |
N1—C2—H2 | 108.7 | C5a—C9a—N1 | 121.4 (3) |
C21—C2—H2 | 108.7 | C22—C21—C30 | 119.6 (3) |
C3—C2—H2 | 108.7 | C22—C21—C2 | 120.7 (3) |
C4—C3—C2 | 103.5 (3) | C30—C21—C2 | 119.6 (3) |
C4—C3—H3A | 111.1 | C21—C22—C23 | 120.8 (3) |
C2—C3—H3A | 111.1 | C21—C22—H22 | 119.6 |
C4—C3—H3B | 111.1 | C23—C22—H22 | 119.6 |
C2—C3—H3B | 111.1 | C24—C23—C22 | 120.8 (3) |
H3A—C3—H3B | 109.0 | C24—C23—H23 | 119.6 |
O14—C4—C5 | 107.2 (3) | C22—C23—H23 | 119.6 |
O14—C4—C3 | 103.3 (2) | C23—C24—C25 | 120.7 (3) |
C5—C4—C3 | 115.5 (2) | C23—C24—H24 | 119.6 |
O14—C4—H4 | 110.2 | C25—C24—H24 | 119.6 |
C5—C4—H4 | 110.2 | C26—C25—C24 | 122.4 (3) |
C3—C4—H4 | 110.2 | C26—C25—C30 | 118.8 (3) |
C5a—C5—C4 | 110.1 (3) | C24—C25—C30 | 118.9 (3) |
C5a—C5—H5A | 109.6 | C27—C26—C25 | 122.0 (4) |
C4—C5—H5A | 109.6 | C27—C26—H26 | 119.0 |
C5a—C5—H5B | 109.6 | C25—C26—H26 | 119.0 |
C4—C5—H5B | 109.6 | C26—C27—C28 | 119.9 (4) |
H5A—C5—H5B | 108.2 | C26—C27—H27 | 120.1 |
C6—C5a—C9a | 118.1 (3) | C28—C27—H27 | 120.1 |
C6—C5a—C5 | 122.2 (3) | C29—C28—C27 | 120.5 (3) |
C9a—C5a—C5 | 119.7 (3) | C29—C28—H28 | 119.8 |
C7—C6—C5a | 119.5 (3) | C27—C28—H28 | 119.8 |
C7—C6—H6 | 120.3 | C28—C29—C30 | 120.6 (3) |
C5a—C6—H6 | 120.3 | C28—C29—H29 | 119.7 |
C6—C7—C8 | 123.0 (3) | C30—C29—H29 | 119.7 |
C6—C7—Cl7 | 119.0 (2) | C29—C30—C25 | 118.2 (3) |
C8—C7—Cl7 | 118.0 (2) | C29—C30—C21 | 122.6 (3) |
C7—C8—C9 | 117.6 (3) | C25—C30—C21 | 119.1 (3) |
C4—O14—N1—C9a | −68.2 (3) | O14—N1—C9a—C9 | −151.0 (3) |
C4—O14—N1—C2 | 48.3 (3) | C2—N1—C9a—C9 | 97.9 (3) |
C9a—N1—C2—C21 | −154.1 (3) | O14—N1—C9a—C5a | 27.7 (4) |
O14—N1—C2—C21 | 91.5 (3) | C2—N1—C9a—C5a | −83.4 (3) |
C9a—N1—C2—C3 | 81.2 (3) | N1—C2—C21—C22 | −5.9 (4) |
O14—N1—C2—C3 | −33.1 (3) | C3—C2—C21—C22 | 112.4 (3) |
N1—C2—C3—C4 | 7.1 (3) | N1—C2—C21—C30 | 171.1 (3) |
C21—C2—C3—C4 | −114.8 (3) | C3—C2—C21—C30 | −70.6 (4) |
N1—O14—C4—C5 | 79.1 (3) | C30—C21—C22—C23 | −0.5 (4) |
N1—O14—C4—C3 | −43.3 (3) | C2—C21—C22—C23 | 176.5 (3) |
C2—C3—C4—O14 | 21.4 (3) | C21—C22—C23—C24 | −0.5 (5) |
C2—C3—C4—C5 | −95.4 (3) | C22—C23—C24—C25 | 0.4 (5) |
O14—C4—C5—C5a | −44.9 (3) | C23—C24—C25—C26 | −178.9 (3) |
C3—C4—C5—C5a | 69.6 (4) | C23—C24—C25—C30 | 0.8 (5) |
C4—C5—C5a—C6 | −174.7 (3) | C24—C25—C26—C27 | −178.8 (3) |
C4—C5—C5a—C9a | 4.4 (4) | C30—C25—C26—C27 | 1.4 (5) |
C9a—C5a—C6—C7 | −2.2 (4) | C25—C26—C27—C28 | 0.3 (5) |
C5—C5a—C6—C7 | 176.9 (3) | C26—C27—C28—C29 | −0.9 (5) |
C5a—C6—C7—C8 | −0.3 (5) | C27—C28—C29—C30 | −0.1 (5) |
C5a—C6—C7—Cl7 | −178.4 (2) | C28—C29—C30—C25 | 1.7 (5) |
C6—C7—C8—C9 | 3.0 (5) | C28—C29—C30—C21 | −178.5 (3) |
Cl7—C7—C8—C9 | −178.9 (2) | C26—C25—C30—C29 | −2.4 (5) |
C7—C8—C9—C9a | −3.1 (4) | C24—C25—C30—C29 | 177.9 (3) |
C8—C9—C9a—C5a | 0.6 (5) | C26—C25—C30—C21 | 177.9 (3) |
C8—C9—C9a—N1 | 179.3 (3) | C24—C25—C30—C21 | −1.9 (4) |
C6—C5a—C9a—C9 | 2.1 (4) | C22—C21—C30—C29 | −178.0 (3) |
C5—C5a—C9a—C9 | −177.0 (3) | C2—C21—C30—C29 | 5.0 (4) |
C6—C5a—C9a—N1 | −176.5 (3) | C22—C21—C30—C25 | 1.7 (4) |
C5—C5a—C9a—N1 | 4.4 (4) | C2—C21—C30—C25 | −175.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O14i | 0.99 | 2.48 | 3.338 (4) | 145 |
C8—H8···Cg3ii | 0.95 | 2.81 | 3.658 (4) | 149 |
C23—H23···Cg2iii | 0.95 | 2.80 | 3.702 (4) | 158 |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x+3/2, −y+1, z−1/2; (iii) −x+1/2, −y+1, z+1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C16H13Cl2NO | C16H13Cl2NO | C20H16ClNO |
Mr | 306.17 | 306.17 | 321.79 |
Crystal system, space group | Orthorhombic, Pna21 | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 11.9348 (11), 21.617 (2), 5.3024 (6) | 7.4328 (11), 12.3746 (16), 14.9187 (19) | 9.6174 (18), 11.558 (3), 13.465 (4) |
V (Å3) | 1368.0 (2) | 1372.2 (3) | 1496.7 (7) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.47 | 0.47 | 0.26 |
Crystal size (mm) | 0.45 × 0.27 × 0.05 | 0.27 × 0.10 × 0.07 | 0.32 × 0.08 × 0.06 |
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 | 0.817, 0.977 | 0.926, 0.968 | 0.956, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12986, 3116, 2124 | 12048, 3131, 1541 | 16825, 3418, 2460 |
Rint | 0.058 | 0.147 | 0.085 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.650 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.104, 1.05 | 0.061, 0.153, 1.05 | 0.054, 0.114, 1.10 |
No. of reflections | 3116 | 3131 | 3418 |
No. of parameters | 181 | 181 | 208 |
No. of restraints | 1 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.30 | 0.38, −0.48 | 0.30, −0.33 |
Absolute structure | Flack (1983), with 1380 Friedel pairs | Flack (1983), with 1316 Friedel pairs | Flack (1983), with 1446 Friedel pairs |
Absolute structure parameter | 0.09 (9) | 0.01 (15) | 0.01 (9) |
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) | 0.447 (3) | 197.4 (4) | 0.618 (3) | 51.0 (3) | 341.9 (4) |
(II) | 0.436 (6) | 195.7 (8) | 0.620 (5) | 51.3 (5) | 344.5 (7) |
(III) | 0.440 (3) | 188.7 (4) | 0.630 (3) | 54.7 (3) | 347.5 (4) |
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) | C2—H2···O14i | 1.00 | 2.29 | 3.287 (4) | 173 |
C9—H9···N1ii | 0.95 | 2.50 | 3.328 (4) | 145 | |
C8—H8···Cg1ii | 0.95 | 2.72 | 3.615 (4) | 157 | |
(II) | C8—H8···O14iii | 0.95 | 2.36 | 3.190 (6) | 146 |
C6—H6···Cg1iv | 0.95 | 2.82 | 3.619 (6) | 143 | |
C25—H25···Cg2v | 0.95 | 2.60 | 3.410 (6) | 143 | |
C4—H4···Cl7vi | 1.00 | 2.79 | 3.654 (6) | 145 | |
(III) | C3—H3B···O14vii | 0.99 | 2.48 | 3.338 (4) | 145 |
C8—H8···Cg3iv | 0.95 | 2.81 | 3.658 (4) | 149 | |
C23—H23···Cg2viii | 0.95 | 2.80 | 3.702 (4) | 158 |
Cg1, Cg2 and Cg3 represent the centroids of the rings C21–C26,
C5a/C6–C9/C9a and C25–C30. Symmetry codes: (i) x, y, 1 + z; (ii) 1 - x, 1 - y, 1/2 + z; (iii) 1 - x, -1/2 + y, 1/2 - z; (iv) 3/2 - x, 1 - y, -1/2 + z; (v) -1/2 + x, 1/2 - y, 1 - z; (vi) 2 - x, 1/2 + y, 1/2 - z; (vii) 1/2 + x, 3/2 - y, 1 - z; (viii) 1/2 - x, 1 - y, 1/2 + z. |
In a continuation of our structural study of 2-substituted 1,4-epoxy-tetrahydro-1-benzazepines (Acosta et al., 2008), itself part of a programme to identify structurally novel anti-parasitic compounds with new modes of action to combat both Trypanosoma cruzi and Leishmania chagasi parasites (Gómez et al., 2006; Yépez et al., 2006), we now report the structures of three aryl-substituted examples, compounds (I)–(III) (Figs. 1–3).
Compounds (I)–(III) were prepared by reaction of an appropriately substituted 2-allyl-N-benzylaniline or 2-allyl-N-(1-naphthylmethyl) aniline with an excess of hydrogen peroxide solution in the presence of catalytic amounts of sodium tungstate, with subsequent internal 1,3-dipolar cycloaddition of the resulting nitrones across the terminal C═C bond of the pendant allylic fragment.
Compound (I) crystallizes as a racemic mixture in space group Pna21, while the positional isomers, (II) and (III), were both refined as single enantiomorphs with the R configuration at atom C4, as indicated by the Flack x parameters (Flack, 1983). Accordingly, the reference molecule for the racemic compound, (I), was selected to have the R configuration at C4. On this basis, the reference molecules in compounds (I)–(III) all have the S configuration at atom C2.
The shapes of the heterobicyclic ring systems in (I)–(III), as defined by the ring-puckering parameters (Cremer & Pople, 1975), are all very similar (Table 1). For the five-membered rings, those in (I) and (II) adopt half-chair conformations, for which the ideal puckering angle ϕ is (36k + 18)°, where k represents an integer. For the corresponding ring in (III), 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. The conformations of the six-membered heterocyclic rings are 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°. The values of the torsion angle N1—C2—C21—C22 in (I)–(III), which defines the orientation of the pendent aryl group [94.3 (3), -12.4 (7) and 5.9 (4)°, respectively], are almost certainly dominated by steric factors.
In compound (I), molecules related by the 21 screw axis along (1/2, 1/2, z) are linked by one each of C—H···O and C—H···N hydrogen bonds (Table 2). Acting individually, these hydrogen bonds both generate C(4) (Bernstein et al., 1995) chains and in combination they generate a chain of edge-fused R33(12) rings (Fig. 4). A C—H···π(arene) hydrogen bond is also present, but this lies within the chain and hence the dimensionality of the hydrogen-bonded structure is unaffected.
In compound (II), on the other hand, where there are again three hydrogen bonds present in the structure, now one of the C—H···O type and two of the C—H···π(arene) type, the hydrogen bonds give rise to a three-dimensional hydrogen-bonded framework. The formation of this framework is readily analysed in terms of three one-dimensional substructures, each constructed using just one hydrogen bond. The C—H···O hydrogen bond, acting alone, generates a C(6) chain running parallel to the [010] direction, linking molecules related by the 21 screw axis along (1/2, y, 1/4). The shorter of the two C—H···π(arene) hydrogen bonds, involving the fused aryl ring as acceptor, forms a chain running parallel to the [100] direction, which consists of molecules related by the 21 screw axis along (x, 1/4, 1/2). The longer of the C—H···π(arene) hydrogen bonds utilizes the pendent aryl ring as the acceptor, and it generates a chain running parallel to the [001] direction and consisting of molecules related by the 21 screw axis along (3/4, 1/2, z). The combination of the chains along [100], [010] and [001] suffices to generate a continuous three-dimensional framework structure. The crystal structure of compound (II) also contains a short intermolecular C—H···Cl contact (Table 2). However, this contact is not likely to be structurally significant, firstly because the C—H bond concerned is of low acidity, and secondly because Cl bonded to C is known to be an extremely poor acceptor of hydrogen bonds, even from O or N (Aakeröy et al., 1999; Brammer et al., 2001; Thallapally & Nangia, 2001).
As in compound (II), the structure of (III) contains one C—H···O hydrogen bond and two C—H···π(arene) hydrogen bonds and, again, these link the molecules into a three-dimensional framework. However, the detailed construction of this framework differs from that in (II), and there are two readily identified substructures in the structure of (III), one of which is one-dimensional and the other two-dimensional. The two-dimensional substructure is built from the two C—H···π(arene) interactions. The hydrogen bond in which the pendent naphthyl substituent is the acceptor generates a chain along (3/4, 1/2, z), while that having the fused aryl ring as acceptor forms a chain along (1/4, 1/2, z), and the combination of these two hydrogen bonds thus generates a sheet parallel to (010) (Fig. 5). Two sheets of this type, containing the 21 axes at y = 0 and y = 1/2, respectively, pass through each unit cell and they are linked by the one-dimensional substructure. This substructure is built using the C—H···O hydrogen bond, which links into a C(4) chain (Fig. 6) the molecules related by the 21 screw axis along (x, 3/4, 1/2). Atom C3 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O14 in the molecule at (1/2 + x, 3/2 - y, 1 - z). Since these two molecules are components of different (010) sheets, the effect of this C(4) chain is to link the sheets into a continuous three-dimensional framework structure.