Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109005265/sk3295sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109005265/sk3295Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109005265/sk3295IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109005265/sk3295IIIsup4.hkl |
CCDC references: 730094; 730095; 730096
To a stirred solution of 0.10 mol of the appropriately substituted 2-allyl-N-benzyl-1-naphthylamine 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 room temperature for 45–50 h. Each mixture was filtered and then evaporated to dryness. The crude products were purified by column chromatography on silica gel using heptane/ethyl acetate (30:1 v/v) as eluant. Finally, the resulting 2-exo-aryl-1,4-epoxycycloadducts were recrystallized from heptane, providing crystals of compounds (I)–(III) suitable for single-crystal X-ray diffraction. For (I), colourless crystals, yield 52%, m.p. 412–413 K; MS (70 eV) m/z (%): 365 (M+, 79Br, 10), 336 (5), 286 (2), 257 (9), 243 (22), 220 (100), 180 (4), 139 (28), 128 (14), 115 (6); analysis found: C 65.7, H 4.4, N, 3.8%; C20H16BrNO requires: C 65.6, H 4.4, N 3.8%. For (II), colourless crystals, yield 48%, m.p. 459–460 K; MS (70 eV) m/z (%): 399 (M+, 79Br, 35Cl, 5), 370 (3), 291 (6), 277 (14), 220 (100), 180 (5), 152 (5), 139 (33), 128 (19), 115 (5); analysis found: C 59.9, H 3.8, N 3.6%; C20H15BrClNO requires: C 59.95, H 3.8, N 3.5%. For (III), pale-yellow crystals, yield 49%, m.p. 401–402 K; MS (70 eV) m/z (%): 305 (M+, 10), 276 (5), 262 (14), 142 (100), 115 (17); analysis found: C 78.5, H 5.3, N 4.6%; C20H16FNO requires: C 78.7, H 5.3, N, 4.6%.
For (I) the systematic absences permitted P21 and P21/m as possible space groups; P21 was selected and confirmed by the successful structure analysis. For (II) and (III), the space groups were uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions with C—H distances 0.95 Å (aromatic), 0.99 Å (CH2) or 1.00 Å (aliphatic C—H) and with Uiso(H) = 1.2Ueq(C). A straightforward (`hole-in-one') calculation of the Flack (1983) x parameter for (I) gave a value of 0.089 (14), with a Hooft y parameter (Hooft et al., 2008) of 0.186 (12). In the presence of a Br atom, the deviation from zero of the Flack x parameter was significant and it seemed rather large, possibly suggesting a modest degree of inversion twinning. Calculation of the twin fractions using the TWIN/BASF procedure in SHELXL (Sheldrick, 2008) gave, for the crystal under study, twin fractions of 0.901 (15) for the (2R,4S) enantiomer and 0.099 (15) for the (2S,4R) form. Accordingly, the (2R,4S) configuration was selected for the reference molecules in the racemic compounds (II) and (III).
For all compounds, data collection: COLLECT (Hooft, 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, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
C20H16BrNO | F(000) = 372 |
Mr = 366.24 | Dx = 1.567 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3132 reflections |
a = 7.8444 (3) Å | θ = 3.2–27.5° |
b = 9.8146 (4) Å | µ = 2.65 mm−1 |
c = 10.0871 (4) Å | T = 120 K |
β = 92.103 (3)° | Lath, colourless |
V = 776.08 (5) Å3 | 0.20 × 0.04 × 0.01 mm |
Z = 2 |
Bruker–Nonius KappaCCD diffractometer | 3132 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 2810 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ϕ & ω scans | h = −8→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.619, Tmax = 0.974 | l = −12→13 |
7511 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)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.P)2 + 1.3066P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
3132 reflections | Δρmax = 0.44 e Å−3 |
209 parameters | Δρmin = −0.53 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1237 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.099 (15) |
C20H16BrNO | V = 776.08 (5) Å3 |
Mr = 366.24 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.8444 (3) Å | µ = 2.65 mm−1 |
b = 9.8146 (4) Å | T = 120 K |
c = 10.0871 (4) Å | 0.20 × 0.04 × 0.01 mm |
β = 92.103 (3)° |
Bruker–Nonius KappaCCD diffractometer | 3132 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2810 reflections with I > 2σ(I) |
Tmin = 0.619, Tmax = 0.974 | Rint = 0.055 |
7511 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.102 | Δρmax = 0.44 e Å−3 |
S = 1.09 | Δρmin = −0.53 e Å−3 |
3132 reflections | Absolute structure: Flack (1983), 1237 Friedel pairs |
209 parameters | Absolute structure parameter: 0.099 (15) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
N1 | 0.3120 (4) | 0.4045 (5) | 0.8557 (3) | 0.0199 (10) | |
C2 | 0.3417 (6) | 0.5346 (5) | 0.7883 (5) | 0.0201 (11) | |
H2 | 0.3459 | 0.5180 | 0.6906 | 0.024* | |
C3 | 0.5203 (6) | 0.5823 (6) | 0.8414 (6) | 0.0242 (12) | |
H31 | 0.6046 | 0.5802 | 0.7707 | 0.029* | |
H32 | 0.5155 | 0.6755 | 0.8786 | 0.029* | |
C4 | 0.5639 (5) | 0.4762 (5) | 0.9507 (5) | 0.0209 (9) | |
H4 | 0.6201 | 0.5210 | 1.0299 | 0.025* | |
C5 | 0.6708 (6) | 0.3582 (5) | 0.9037 (5) | 0.0213 (10) | |
H51 | 0.7693 | 0.3935 | 0.8557 | 0.026* | |
H52 | 0.7151 | 0.3054 | 0.9812 | 0.026* | |
C5A | 0.5655 (6) | 0.2670 (6) | 0.8136 (5) | 0.0184 (10) | |
C6 | 0.6385 (6) | 0.1533 (5) | 0.7509 (5) | 0.0214 (10) | |
H6 | 0.7536 | 0.1292 | 0.7721 | 0.026* | |
C7 | 0.5455 (6) | 0.0775 (5) | 0.6600 (5) | 0.0237 (10) | |
Br7 | 0.65110 (6) | −0.07516 (7) | 0.58212 (4) | 0.03017 (14) | |
C7A | 0.3737 (6) | 0.1107 (5) | 0.6227 (4) | 0.0206 (10) | |
C8 | 0.2790 (6) | 0.0455 (5) | 0.5184 (5) | 0.0248 (10) | |
H8 | 0.3299 | −0.0258 | 0.4700 | 0.030* | |
C9 | 0.1138 (6) | 0.0846 (5) | 0.4863 (5) | 0.0251 (10) | |
H9 | 0.0525 | 0.0416 | 0.4149 | 0.030* | |
C10 | 0.0358 (6) | 0.1881 (5) | 0.5591 (5) | 0.0248 (10) | |
H10 | −0.0788 | 0.2131 | 0.5374 | 0.030* | |
C11 | 0.1222 (6) | 0.2534 (5) | 0.6606 (5) | 0.0242 (10) | |
H11 | 0.0670 | 0.3220 | 0.7098 | 0.029* | |
C11A | 0.2961 (6) | 0.2181 (5) | 0.6925 (4) | 0.0183 (9) | |
C11B | 0.3954 (6) | 0.2940 (5) | 0.7873 (5) | 0.0186 (11) | |
O14 | 0.3988 (3) | 0.4218 (6) | 0.9831 (2) | 0.0201 (6) | |
C21 | 0.1990 (5) | 0.6365 (5) | 0.8145 (4) | 0.0185 (9) | |
C22 | 0.2026 (6) | 0.7628 (5) | 0.7539 (5) | 0.0218 (10) | |
H22 | 0.2936 | 0.7854 | 0.6984 | 0.026* | |
C23 | 0.0735 (6) | 0.8565 (5) | 0.7741 (5) | 0.0253 (10) | |
H23 | 0.0748 | 0.9424 | 0.7307 | 0.030* | |
C24 | −0.0574 (6) | 0.8248 (5) | 0.8576 (5) | 0.0244 (10) | |
H24 | −0.1459 | 0.8888 | 0.8716 | 0.029* | |
C25 | −0.0585 (6) | 0.7003 (5) | 0.9200 (5) | 0.0247 (10) | |
H25 | −0.1466 | 0.6789 | 0.9787 | 0.030* | |
C26 | 0.0675 (6) | 0.6065 (5) | 0.8978 (5) | 0.0217 (10) | |
H26 | 0.0644 | 0.5201 | 0.9401 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0195 (16) | 0.022 (3) | 0.0183 (16) | 0.0027 (17) | −0.0010 (13) | −0.0014 (19) |
C2 | 0.025 (3) | 0.015 (3) | 0.020 (2) | 0.001 (2) | 0.0019 (19) | 0.001 (2) |
C3 | 0.022 (3) | 0.016 (3) | 0.034 (3) | −0.0010 (19) | 0.003 (2) | 0.001 (2) |
C4 | 0.014 (2) | 0.020 (2) | 0.028 (2) | −0.0022 (16) | 0.0016 (18) | −0.0001 (18) |
C5 | 0.021 (2) | 0.021 (2) | 0.022 (2) | 0.0003 (18) | −0.0072 (18) | 0.001 (2) |
C5A | 0.020 (2) | 0.018 (3) | 0.017 (2) | −0.0017 (19) | −0.0016 (18) | −0.0003 (19) |
C6 | 0.015 (2) | 0.022 (3) | 0.026 (2) | 0.0017 (18) | −0.0016 (17) | −0.002 (2) |
C7 | 0.027 (2) | 0.023 (3) | 0.022 (2) | 0.006 (2) | 0.0039 (19) | 0.002 (2) |
Br7 | 0.0374 (2) | 0.0256 (2) | 0.0276 (2) | 0.0118 (3) | 0.00207 (16) | −0.0042 (3) |
C7A | 0.031 (2) | 0.015 (2) | 0.016 (2) | 0.0028 (19) | 0.0005 (18) | 0.0024 (18) |
C8 | 0.030 (3) | 0.024 (3) | 0.021 (2) | 0.000 (2) | 0.0014 (19) | −0.001 (2) |
C9 | 0.033 (3) | 0.019 (3) | 0.023 (2) | −0.005 (2) | −0.006 (2) | 0.000 (2) |
C10 | 0.023 (2) | 0.020 (3) | 0.031 (3) | −0.0011 (19) | −0.0038 (19) | 0.007 (2) |
C11 | 0.027 (2) | 0.019 (2) | 0.027 (2) | −0.0015 (19) | 0.0014 (19) | 0.002 (2) |
C11A | 0.020 (2) | 0.019 (2) | 0.016 (2) | 0.0009 (18) | 0.0037 (17) | 0.0058 (18) |
C11B | 0.026 (3) | 0.010 (2) | 0.020 (2) | −0.0031 (19) | 0.003 (2) | 0.0024 (19) |
O14 | 0.0199 (13) | 0.0250 (15) | 0.0153 (12) | −0.005 (2) | 0.0000 (10) | 0.000 (2) |
C21 | 0.014 (2) | 0.021 (2) | 0.020 (2) | −0.0001 (17) | −0.0023 (16) | −0.0044 (19) |
C22 | 0.026 (2) | 0.019 (2) | 0.020 (2) | 0.0017 (19) | 0.0008 (18) | 0.0005 (19) |
C23 | 0.031 (3) | 0.020 (3) | 0.024 (2) | 0.0037 (19) | −0.0018 (19) | 0.002 (2) |
C24 | 0.020 (2) | 0.031 (3) | 0.022 (2) | 0.008 (2) | −0.0046 (18) | −0.002 (2) |
C25 | 0.020 (2) | 0.027 (3) | 0.028 (3) | 0.0001 (19) | 0.0036 (18) | 0.002 (2) |
C26 | 0.023 (2) | 0.018 (2) | 0.024 (2) | 0.0005 (18) | 0.0023 (18) | −0.0018 (19) |
N1—O14 | 1.442 (4) | C7A—C8 | 1.418 (7) |
N1—C11B | 1.454 (6) | C8—C9 | 1.378 (7) |
N1—C2 | 1.469 (7) | C8—H8 | 0.9500 |
C2—C21 | 1.532 (7) | C9—C10 | 1.407 (7) |
C2—C3 | 1.554 (7) | C9—H9 | 0.9500 |
C2—H2 | 1.0000 | C10—C11 | 1.366 (7) |
C3—C4 | 1.545 (7) | C10—H10 | 0.9500 |
C3—H31 | 0.9900 | C11—C11A | 1.433 (6) |
C3—H32 | 0.9900 | C11—H11 | 0.9500 |
C4—O14 | 1.449 (5) | C11A—C11B | 1.421 (7) |
C4—C5 | 1.516 (6) | C21—C22 | 1.382 (7) |
C4—H4 | 1.0000 | C21—C26 | 1.386 (6) |
C5—C5A | 1.501 (7) | C22—C23 | 1.389 (7) |
C5—H51 | 0.9900 | C22—H22 | 0.9500 |
C5—H52 | 0.9900 | C23—C24 | 1.387 (7) |
C5A—C11B | 1.377 (7) | C23—H23 | 0.9500 |
C5A—C6 | 1.414 (7) | C24—C25 | 1.375 (7) |
C6—C7 | 1.370 (7) | C24—H24 | 0.9500 |
C6—H6 | 0.9500 | C25—C26 | 1.375 (7) |
C7—C7A | 1.424 (6) | C25—H25 | 0.9500 |
C7—Br7 | 1.896 (5) | C26—H26 | 0.9500 |
C7A—C11A | 1.418 (6) | ||
O14—N1—C11B | 107.8 (4) | C8—C7A—C7 | 123.9 (4) |
O14—N1—C2 | 103.5 (4) | C9—C8—C7A | 120.7 (5) |
C11B—N1—C2 | 110.3 (3) | C9—C8—H8 | 119.6 |
N1—C2—C21 | 111.0 (4) | C7A—C8—H8 | 119.6 |
N1—C2—C3 | 105.0 (4) | C8—C9—C10 | 120.1 (4) |
C21—C2—C3 | 113.5 (4) | C8—C9—H9 | 120.0 |
N1—C2—H2 | 109.1 | C10—C9—H9 | 120.0 |
C21—C2—H2 | 109.1 | C11—C10—C9 | 121.1 (5) |
C3—C2—H2 | 109.1 | C11—C10—H10 | 119.4 |
C4—C3—C2 | 102.5 (4) | C9—C10—H10 | 119.4 |
C4—C3—H31 | 111.3 | C10—C11—C11A | 119.8 (5) |
C2—C3—H31 | 111.3 | C10—C11—H11 | 120.1 |
C4—C3—H32 | 111.3 | C11A—C11—H11 | 120.1 |
C2—C3—H32 | 111.3 | C7A—C11A—C11B | 119.3 (4) |
H31—C3—H32 | 109.2 | C7A—C11A—C11 | 119.4 (4) |
O14—C4—C5 | 107.3 (4) | C11B—C11A—C11 | 121.3 (4) |
O14—C4—C3 | 103.5 (4) | C5A—C11B—C11A | 122.2 (5) |
C5—C4—C3 | 113.7 (4) | C5A—C11B—N1 | 120.1 (5) |
O14—C4—H4 | 110.7 | C11A—C11B—N1 | 117.7 (4) |
C5—C4—H4 | 110.7 | N1—O14—C4 | 103.8 (3) |
C3—C4—H4 | 110.7 | C22—C21—C26 | 119.1 (4) |
C5A—C5—C4 | 110.3 (4) | C22—C21—C2 | 118.8 (4) |
C5A—C5—H51 | 109.6 | C26—C21—C2 | 122.0 (4) |
C4—C5—H51 | 109.6 | C21—C22—C23 | 120.1 (4) |
C5A—C5—H52 | 109.6 | C21—C22—H22 | 119.9 |
C4—C5—H52 | 109.6 | C23—C22—H22 | 119.9 |
H51—C5—H52 | 108.1 | C24—C23—C22 | 120.0 (5) |
C11B—C5A—C6 | 118.1 (5) | C24—C23—H23 | 120.0 |
C11B—C5A—C5 | 120.7 (5) | C22—C23—H23 | 120.0 |
C6—C5A—C5 | 121.2 (4) | C25—C24—C23 | 119.6 (4) |
C7—C6—C5A | 120.9 (4) | C25—C24—H24 | 120.2 |
C7—C6—H6 | 119.6 | C23—C24—H24 | 120.2 |
C5A—C6—H6 | 119.6 | C26—C25—C24 | 120.3 (4) |
C6—C7—C7A | 121.9 (4) | C26—C25—H25 | 119.9 |
C6—C7—Br7 | 118.4 (3) | C24—C25—H25 | 119.9 |
C7A—C7—Br7 | 119.7 (4) | C25—C26—C21 | 120.8 (5) |
C11A—C7A—C8 | 118.8 (4) | C25—C26—H26 | 119.6 |
C11A—C7A—C7 | 117.3 (4) | C21—C26—H26 | 119.6 |
O14—N1—C2—C21 | −90.7 (4) | C10—C11—C11A—C11B | 172.9 (5) |
C11B—N1—C2—C21 | 154.4 (4) | C6—C5A—C11B—C11A | −4.8 (7) |
O14—N1—C2—C3 | 32.4 (4) | C5—C5A—C11B—C11A | 173.6 (4) |
C11B—N1—C2—C3 | −82.6 (5) | C6—C5A—C11B—N1 | 176.1 (4) |
N1—C2—C3—C4 | −6.6 (5) | C5—C5A—C11B—N1 | −5.4 (7) |
C21—C2—C3—C4 | 114.8 (5) | C7A—C11A—C11B—C5A | 0.2 (7) |
C2—C3—C4—O14 | −21.2 (5) | C11—C11A—C11B—C5A | −176.0 (5) |
C2—C3—C4—C5 | 94.9 (5) | C7A—C11A—C11B—N1 | 179.3 (4) |
O14—C4—C5—C5A | 42.3 (5) | C11—C11A—C11B—N1 | 3.0 (7) |
C3—C4—C5—C5A | −71.5 (5) | O14—N1—C11B—C5A | −28.3 (6) |
C4—C5—C5A—C11B | −1.8 (6) | C2—N1—C11B—C5A | 83.9 (5) |
C4—C5—C5A—C6 | 176.6 (4) | O14—N1—C11B—C11A | 152.6 (4) |
C11B—C5A—C6—C7 | 4.2 (7) | C2—N1—C11B—C11A | −95.2 (5) |
C5—C5A—C6—C7 | −174.3 (5) | C11B—N1—O14—C4 | 69.3 (4) |
C5A—C6—C7—C7A | 1.2 (7) | C2—N1—O14—C4 | −47.4 (4) |
C5A—C6—C7—Br7 | −179.0 (4) | C5—C4—O14—N1 | −78.1 (4) |
C6—C7—C7A—C11A | −5.8 (7) | C3—C4—O14—N1 | 42.4 (5) |
Br7—C7—C7A—C11A | 174.4 (3) | N1—C2—C21—C22 | −177.3 (4) |
C6—C7—C7A—C8 | 172.3 (5) | C3—C2—C21—C22 | 64.7 (6) |
Br7—C7—C7A—C8 | −7.5 (6) | N1—C2—C21—C26 | 3.3 (6) |
C11A—C7A—C8—C9 | −0.8 (7) | C3—C2—C21—C26 | −114.7 (5) |
C7—C7A—C8—C9 | −178.9 (4) | C26—C21—C22—C23 | −1.6 (7) |
C7A—C8—C9—C10 | −1.4 (7) | C2—C21—C22—C23 | 179.0 (4) |
C8—C9—C10—C11 | 1.3 (7) | C21—C22—C23—C24 | 1.5 (7) |
C9—C10—C11—C11A | 1.1 (7) | C22—C23—C24—C25 | 0.0 (7) |
C8—C7A—C11A—C11B | −173.2 (4) | C23—C24—C25—C26 | −1.3 (7) |
C7—C7A—C11A—C11B | 5.0 (6) | C24—C25—C26—C21 | 1.2 (7) |
C8—C7A—C11A—C11 | 3.1 (6) | C22—C21—C26—C25 | 0.3 (7) |
C7—C7A—C11A—C11 | −178.7 (4) | C2—C21—C26—C25 | 179.7 (4) |
C10—C11—C11A—C7A | −3.3 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Br7i | 1.00 | 2.90 | 3.891 (5) | 171 |
C5—H52···Cg1ii | 0.99 | 2.55 | 3.484 (5) | 157 |
C23—H23···Cg2iii | 0.95 | 2.70 | 3.596 (5) | 157 |
C24—H24···O14iv | 0.95 | 2.53 | 3.313 (6) | 140 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+2; (iii) x, y+1, z; (iv) −x, y+1/2, −z+2. |
C20H15BrClNO | F(000) = 1616 |
Mr = 400.69 | Dx = 1.671 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3658 reflections |
a = 9.7758 (16) Å | θ = 3.2–27.5° |
b = 9.8211 (14) Å | µ = 2.76 mm−1 |
c = 33.174 (3) Å | T = 120 K |
V = 3185.0 (7) Å3 | Block, colourless |
Z = 8 | 0.32 × 0.12 × 0.04 mm |
Bruker–Nonius KappaCCD diffractometer | 3658 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 2574 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ϕ & ω scans | h = −12→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −11→12 |
Tmin = 0.551, Tmax = 0.896 | l = −42→42 |
28541 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0262P)2 + 5.3752P] where P = (Fo2 + 2Fc2)/3 |
3658 reflections | (Δ/σ)max = 0.001 |
217 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
C20H15BrClNO | V = 3185.0 (7) Å3 |
Mr = 400.69 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.7758 (16) Å | µ = 2.76 mm−1 |
b = 9.8211 (14) Å | T = 120 K |
c = 33.174 (3) Å | 0.32 × 0.12 × 0.04 mm |
Bruker–Nonius KappaCCD diffractometer | 3658 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2574 reflections with I > 2σ(I) |
Tmin = 0.551, Tmax = 0.896 | Rint = 0.073 |
28541 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.39 e Å−3 |
3658 reflections | Δρmin = −0.51 e Å−3 |
217 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.4336 (3) | 0.5489 (3) | 0.37768 (7) | 0.0152 (5) | |
C2 | 0.3734 (3) | 0.4859 (3) | 0.41377 (9) | 0.0161 (7) | |
H2 | 0.4193 | 0.3968 | 0.4192 | 0.019* | |
C3 | 0.2232 (3) | 0.4606 (3) | 0.40147 (9) | 0.0189 (7) | |
H31 | 0.2063 | 0.3627 | 0.3965 | 0.023* | |
H32 | 0.1595 | 0.4931 | 0.4226 | 0.023* | |
C4 | 0.2072 (3) | 0.5427 (3) | 0.36305 (9) | 0.0184 (7) | |
H4 | 0.1196 | 0.5954 | 0.3633 | 0.022* | |
C5 | 0.2181 (3) | 0.4565 (3) | 0.32548 (9) | 0.0175 (7) | |
H51 | 0.1518 | 0.3805 | 0.3268 | 0.021* | |
H52 | 0.1965 | 0.5122 | 0.3015 | 0.021* | |
C5A | 0.3599 (3) | 0.4015 (3) | 0.32217 (9) | 0.0153 (6) | |
C6 | 0.3921 (3) | 0.3014 (3) | 0.29326 (9) | 0.0172 (7) | |
H6 | 0.3234 | 0.2704 | 0.2752 | 0.021* | |
C7 | 0.5195 (3) | 0.2493 (3) | 0.29095 (9) | 0.0174 (7) | |
Br7 | 0.55294 (3) | 0.11186 (3) | 0.251972 (10) | 0.02465 (10) | |
C7A | 0.6265 (3) | 0.2930 (3) | 0.31632 (9) | 0.0155 (7) | |
C8 | 0.7600 (3) | 0.2415 (3) | 0.31442 (9) | 0.0197 (7) | |
H8 | 0.7812 | 0.1709 | 0.2959 | 0.024* | |
C9 | 0.8594 (3) | 0.2916 (3) | 0.33882 (10) | 0.0206 (7) | |
H9 | 0.9493 | 0.2553 | 0.3374 | 0.025* | |
C10 | 0.8305 (3) | 0.3963 (3) | 0.36610 (10) | 0.0208 (7) | |
H10 | 0.9014 | 0.4321 | 0.3825 | 0.025* | |
C11 | 0.7015 (3) | 0.4473 (3) | 0.36930 (9) | 0.0186 (7) | |
H11 | 0.6828 | 0.5176 | 0.3882 | 0.022* | |
C11A | 0.5959 (3) | 0.3970 (3) | 0.34491 (9) | 0.0149 (6) | |
C11B | 0.4605 (3) | 0.4467 (3) | 0.34744 (9) | 0.0146 (6) | |
O14 | 0.3237 (2) | 0.6333 (2) | 0.36334 (6) | 0.0174 (5) | |
C21 | 0.3881 (3) | 0.5770 (3) | 0.44995 (9) | 0.0151 (7) | |
C22 | 0.3230 (3) | 0.5412 (3) | 0.48554 (9) | 0.0200 (7) | |
H22 | 0.2710 | 0.4596 | 0.4866 | 0.024* | |
C23 | 0.3323 (3) | 0.6222 (3) | 0.51960 (10) | 0.0216 (7) | |
H23 | 0.2873 | 0.5970 | 0.5439 | 0.026* | |
C24 | 0.4077 (3) | 0.7393 (3) | 0.51753 (9) | 0.0184 (7) | |
Cl24 | 0.41575 (9) | 0.84425 (9) | 0.55984 (2) | 0.0279 (2) | |
C25 | 0.4763 (3) | 0.7764 (3) | 0.48327 (10) | 0.0206 (7) | |
H25 | 0.5304 | 0.8568 | 0.4827 | 0.025* | |
C26 | 0.4652 (3) | 0.6943 (3) | 0.44955 (9) | 0.0192 (7) | |
H26 | 0.5118 | 0.7194 | 0.4256 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0147 (13) | 0.0147 (13) | 0.0162 (13) | 0.0064 (11) | 0.0008 (10) | 0.0000 (10) |
C2 | 0.0173 (16) | 0.0132 (16) | 0.0178 (16) | 0.0004 (13) | 0.0037 (13) | 0.0008 (13) |
C3 | 0.0202 (18) | 0.0160 (17) | 0.0206 (17) | −0.0013 (14) | 0.0020 (13) | −0.0036 (13) |
C4 | 0.0124 (15) | 0.0188 (17) | 0.0241 (17) | 0.0000 (14) | 0.0029 (13) | 0.0015 (14) |
C5 | 0.0130 (16) | 0.0173 (17) | 0.0223 (17) | −0.0006 (13) | 0.0007 (13) | 0.0001 (13) |
C5A | 0.0157 (15) | 0.0126 (16) | 0.0175 (15) | −0.0012 (13) | 0.0020 (12) | 0.0044 (13) |
C6 | 0.0172 (16) | 0.0177 (17) | 0.0166 (16) | −0.0022 (13) | −0.0017 (13) | −0.0001 (13) |
C7 | 0.0229 (17) | 0.0134 (15) | 0.0158 (16) | 0.0005 (14) | 0.0041 (13) | −0.0034 (13) |
Br7 | 0.02227 (16) | 0.02535 (17) | 0.02632 (18) | 0.00087 (15) | 0.00264 (15) | −0.01117 (15) |
C7A | 0.0187 (17) | 0.0145 (16) | 0.0133 (15) | 0.0009 (13) | 0.0038 (12) | 0.0040 (12) |
C8 | 0.0190 (16) | 0.0183 (17) | 0.0219 (17) | 0.0017 (15) | 0.0036 (14) | 0.0018 (14) |
C9 | 0.0166 (16) | 0.0225 (18) | 0.0228 (18) | 0.0041 (15) | 0.0003 (13) | 0.0015 (15) |
C10 | 0.0197 (17) | 0.0214 (18) | 0.0214 (17) | −0.0021 (15) | −0.0065 (13) | −0.0010 (15) |
C11 | 0.0193 (16) | 0.0163 (16) | 0.0201 (17) | −0.0026 (15) | 0.0001 (13) | 0.0007 (13) |
C11A | 0.0142 (14) | 0.0152 (16) | 0.0154 (15) | −0.0017 (14) | 0.0032 (12) | 0.0056 (13) |
C11B | 0.0165 (16) | 0.0117 (15) | 0.0157 (15) | −0.0001 (14) | 0.0029 (13) | 0.0019 (12) |
O14 | 0.0147 (11) | 0.0133 (12) | 0.0243 (12) | 0.0025 (9) | 0.0011 (9) | 0.0016 (9) |
C21 | 0.0141 (15) | 0.0123 (16) | 0.0188 (16) | 0.0028 (12) | −0.0003 (12) | −0.0007 (12) |
C22 | 0.0190 (17) | 0.0204 (18) | 0.0206 (17) | −0.0035 (14) | 0.0009 (13) | 0.0019 (14) |
C23 | 0.0201 (17) | 0.0257 (19) | 0.0190 (16) | −0.0009 (15) | 0.0010 (13) | 0.0001 (15) |
C24 | 0.0187 (16) | 0.0162 (17) | 0.0203 (16) | 0.0051 (14) | −0.0036 (13) | −0.0044 (13) |
Cl24 | 0.0353 (5) | 0.0248 (4) | 0.0237 (4) | 0.0017 (4) | −0.0041 (4) | −0.0085 (4) |
C25 | 0.0206 (17) | 0.0150 (17) | 0.0263 (18) | −0.0004 (14) | −0.0015 (14) | −0.0018 (13) |
C26 | 0.0186 (17) | 0.0196 (17) | 0.0195 (16) | −0.0012 (14) | 0.0021 (13) | 0.0028 (13) |
N1—O14 | 1.438 (3) | C7A—C11A | 1.425 (4) |
N1—C11B | 1.443 (4) | C8—C9 | 1.357 (4) |
N1—C2 | 1.471 (4) | C8—H8 | 0.9500 |
C2—C21 | 1.504 (4) | C9—C10 | 1.398 (5) |
C2—C3 | 1.544 (4) | C9—H9 | 0.9500 |
C2—H2 | 1.0000 | C10—C11 | 1.361 (4) |
C3—C4 | 1.516 (4) | C10—H10 | 0.9500 |
C3—H31 | 0.9900 | C11—C11A | 1.402 (4) |
C3—H32 | 0.9900 | C11—H11 | 0.9500 |
C4—O14 | 1.445 (4) | C11A—C11B | 1.414 (4) |
C4—C5 | 1.511 (4) | C21—C26 | 1.377 (4) |
C4—H4 | 1.0000 | C21—C22 | 1.386 (4) |
C5—C5A | 1.492 (4) | C22—C23 | 1.385 (5) |
C5—H51 | 0.9900 | C22—H22 | 0.9500 |
C5—H52 | 0.9900 | C23—C24 | 1.368 (5) |
C5A—C11B | 1.366 (4) | C23—H23 | 0.9500 |
C5A—C6 | 1.408 (4) | C24—C25 | 1.369 (4) |
C6—C7 | 1.349 (4) | C24—Cl24 | 1.743 (3) |
C6—H6 | 0.9500 | C25—C26 | 1.383 (4) |
C7—C7A | 1.410 (4) | C25—H25 | 0.9500 |
C7—Br7 | 1.897 (3) | C26—H26 | 0.9500 |
C7A—C8 | 1.401 (4) | ||
O14—N1—C11B | 107.9 (2) | C7—C7A—C11A | 117.4 (3) |
O14—N1—C2 | 102.3 (2) | C9—C8—C7A | 120.6 (3) |
C11B—N1—C2 | 110.3 (2) | C9—C8—H8 | 119.7 |
N1—C2—C21 | 111.2 (3) | C7A—C8—H8 | 119.7 |
N1—C2—C3 | 103.5 (2) | C8—C9—C10 | 120.5 (3) |
C21—C2—C3 | 113.4 (3) | C8—C9—H9 | 119.7 |
N1—C2—H2 | 109.5 | C10—C9—H9 | 119.7 |
C21—C2—H2 | 109.5 | C11—C10—C9 | 120.6 (3) |
C3—C2—H2 | 109.5 | C11—C10—H10 | 119.7 |
C4—C3—C2 | 103.6 (2) | C9—C10—H10 | 119.7 |
C4—C3—H31 | 111.0 | C10—C11—C11A | 120.5 (3) |
C2—C3—H31 | 111.0 | C10—C11—H11 | 119.8 |
C4—C3—H32 | 111.0 | C11A—C11—H11 | 119.8 |
C2—C3—H32 | 111.0 | C11—C11A—C11B | 122.2 (3) |
H31—C3—H32 | 109.0 | C11—C11A—C7A | 118.8 (3) |
O14—C4—C5 | 107.1 (2) | C11B—C11A—C7A | 118.9 (3) |
O14—C4—C3 | 103.9 (2) | C5A—C11B—C11A | 121.7 (3) |
C5—C4—C3 | 112.8 (3) | C5A—C11B—N1 | 121.4 (3) |
O14—C4—H4 | 110.9 | C11A—C11B—N1 | 116.9 (3) |
C5—C4—H4 | 110.9 | N1—O14—C4 | 103.7 (2) |
C3—C4—H4 | 110.9 | C26—C21—C22 | 118.1 (3) |
C5A—C5—C4 | 109.2 (3) | C26—C21—C2 | 122.9 (3) |
C5A—C5—H51 | 109.8 | C22—C21—C2 | 119.0 (3) |
C4—C5—H51 | 109.8 | C23—C22—C21 | 121.3 (3) |
C5A—C5—H52 | 109.8 | C23—C22—H22 | 119.4 |
C4—C5—H52 | 109.8 | C21—C22—H22 | 119.4 |
H51—C5—H52 | 108.3 | C24—C23—C22 | 118.5 (3) |
C11B—C5A—C6 | 119.0 (3) | C24—C23—H23 | 120.7 |
C11B—C5A—C5 | 120.4 (3) | C22—C23—H23 | 120.7 |
C6—C5A—C5 | 120.7 (3) | C23—C24—C25 | 122.0 (3) |
C7—C6—C5A | 120.6 (3) | C23—C24—Cl24 | 118.7 (3) |
C7—C6—H6 | 119.7 | C25—C24—Cl24 | 119.3 (3) |
C5A—C6—H6 | 119.7 | C24—C25—C26 | 118.5 (3) |
C6—C7—C7A | 122.4 (3) | C24—C25—H25 | 120.7 |
C6—C7—Br7 | 117.9 (2) | C26—C25—H25 | 120.7 |
C7A—C7—Br7 | 119.7 (2) | C21—C26—C25 | 121.6 (3) |
C8—C7A—C7 | 123.7 (3) | C21—C26—H26 | 119.2 |
C8—C7A—C11A | 119.0 (3) | C25—C26—H26 | 119.2 |
O14—N1—C2—C21 | −84.7 (3) | C6—C5A—C11B—C11A | 0.8 (4) |
C11B—N1—C2—C21 | 160.8 (2) | C5—C5A—C11B—C11A | −179.7 (3) |
O14—N1—C2—C3 | 37.4 (3) | C6—C5A—C11B—N1 | −179.9 (3) |
C11B—N1—C2—C3 | −77.1 (3) | C5—C5A—C11B—N1 | −0.4 (4) |
N1—C2—C3—C4 | −12.9 (3) | C11—C11A—C11B—C5A | 176.8 (3) |
C21—C2—C3—C4 | 107.7 (3) | C7A—C11A—C11B—C5A | −2.6 (4) |
C2—C3—C4—O14 | −16.1 (3) | C11—C11A—C11B—N1 | −2.5 (4) |
C2—C3—C4—C5 | 99.6 (3) | C7A—C11A—C11B—N1 | 178.1 (3) |
O14—C4—C5—C5A | 47.8 (3) | O14—N1—C11B—C5A | −28.6 (4) |
C3—C4—C5—C5A | −66.0 (3) | C2—N1—C11B—C5A | 82.4 (3) |
C4—C5—C5A—C11B | −9.1 (4) | O14—N1—C11B—C11A | 150.7 (2) |
C4—C5—C5A—C6 | 170.3 (3) | C2—N1—C11B—C11A | −98.3 (3) |
C11B—C5A—C6—C7 | 1.1 (5) | C11B—N1—O14—C4 | 67.0 (3) |
C5—C5A—C6—C7 | −178.4 (3) | C2—N1—O14—C4 | −49.3 (3) |
C5A—C6—C7—C7A | −1.3 (5) | C5—C4—O14—N1 | −79.3 (3) |
C5A—C6—C7—Br7 | 178.5 (2) | C3—C4—O14—N1 | 40.4 (3) |
C6—C7—C7A—C8 | −179.5 (3) | N1—C2—C21—C26 | −8.4 (4) |
Br7—C7—C7A—C8 | 0.7 (4) | C3—C2—C21—C26 | −124.5 (3) |
C6—C7—C7A—C11A | −0.5 (5) | N1—C2—C21—C22 | 172.4 (3) |
Br7—C7—C7A—C11A | 179.7 (2) | C3—C2—C21—C22 | 56.3 (4) |
C7—C7A—C8—C9 | 177.7 (3) | C26—C21—C22—C23 | 1.4 (5) |
C11A—C7A—C8—C9 | −1.3 (5) | C2—C21—C22—C23 | −179.4 (3) |
C7A—C8—C9—C10 | −0.5 (5) | C21—C22—C23—C24 | −0.1 (5) |
C8—C9—C10—C11 | 1.6 (5) | C22—C23—C24—C25 | −1.6 (5) |
C9—C10—C11—C11A | −0.9 (5) | C22—C23—C24—Cl24 | 178.1 (2) |
C10—C11—C11A—C11B | 179.7 (3) | C23—C24—C25—C26 | 1.8 (5) |
C10—C11—C11A—C7A | −1.0 (5) | Cl24—C24—C25—C26 | −177.9 (2) |
C8—C7A—C11A—C11 | 2.0 (4) | C22—C21—C26—C25 | −1.1 (5) |
C7—C7A—C11A—C11 | −177.0 (3) | C2—C21—C26—C25 | 179.7 (3) |
C8—C7A—C11A—C11B | −178.6 (3) | C24—C25—C26—C21 | −0.4 (5) |
C7—C7A—C11A—C11B | 2.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H31···O14i | 0.99 | 2.52 | 3.485 (4) | 164 |
Symmetry code: (i) −x+1/2, y−1/2, z. |
C20H16FNO | F(000) = 640 |
Mr = 305.34 | Dx = 1.332 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3467 reflections |
a = 11.3036 (4) Å | θ = 3.2–27.5° |
b = 12.7585 (5) Å | µ = 0.09 mm−1 |
c = 11.1730 (3) Å | T = 120 K |
β = 109.137 (2)° | Plate, pale yellow |
V = 1522.29 (9) Å3 | 0.09 × 0.08 × 0.03 mm |
Z = 4 |
Bruker–Nonius KappaCCD diffractometer | 3467 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 2667 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ϕ & ω scans | h = −14→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −15→16 |
Tmin = 0.986, Tmax = 0.997 | l = −14→14 |
15443 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.018P)2 + 1.6124P] where P = (Fo2 + 2Fc2)/3 |
3467 reflections | (Δ/σ)max = 0.001 |
208 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C20H16FNO | V = 1522.29 (9) Å3 |
Mr = 305.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.3036 (4) Å | µ = 0.09 mm−1 |
b = 12.7585 (5) Å | T = 120 K |
c = 11.1730 (3) Å | 0.09 × 0.08 × 0.03 mm |
β = 109.137 (2)° |
Bruker–Nonius KappaCCD diffractometer | 3467 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2667 reflections with I > 2σ(I) |
Tmin = 0.986, Tmax = 0.997 | Rint = 0.044 |
15443 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.26 e Å−3 |
3467 reflections | Δρmin = −0.24 e Å−3 |
208 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.66621 (14) | 0.62564 (13) | 0.43066 (15) | 0.0209 (4) | |
C2 | 0.73297 (19) | 0.55233 (15) | 0.37140 (18) | 0.0221 (4) | |
H2 | 0.8188 | 0.5802 | 0.3837 | 0.027* | |
C3 | 0.6548 (2) | 0.55638 (17) | 0.22753 (19) | 0.0275 (5) | |
H31 | 0.7020 | 0.5918 | 0.1785 | 0.033* | |
H32 | 0.6316 | 0.4850 | 0.1930 | 0.033* | |
C4 | 0.53856 (19) | 0.61970 (17) | 0.22436 (19) | 0.0260 (4) | |
H4 | 0.4615 | 0.5879 | 0.1632 | 0.031* | |
C5 | 0.5454 (2) | 0.73585 (17) | 0.19739 (19) | 0.0268 (5) | |
H51 | 0.5671 | 0.7452 | 0.1191 | 0.032* | |
H52 | 0.4628 | 0.7688 | 0.1842 | 0.032* | |
C5A | 0.64302 (19) | 0.78813 (16) | 0.30709 (18) | 0.0236 (4) | |
C6 | 0.67807 (19) | 0.89389 (16) | 0.29931 (19) | 0.0256 (4) | |
H6 | 0.6362 | 0.9336 | 0.2257 | 0.031* | |
C7 | 0.7710 (2) | 0.93982 (16) | 0.3958 (2) | 0.0271 (5) | |
H7 | 0.7940 | 1.0104 | 0.3875 | 0.033* | |
C7A | 0.83385 (18) | 0.88344 (16) | 0.50856 (19) | 0.0230 (4) | |
C8 | 0.92798 (19) | 0.92934 (17) | 0.6122 (2) | 0.0271 (5) | |
H8 | 0.9543 | 0.9992 | 0.6055 | 0.033* | |
C9 | 0.98160 (19) | 0.87396 (18) | 0.7221 (2) | 0.0293 (5) | |
H9 | 1.0442 | 0.9058 | 0.7911 | 0.035* | |
C10 | 0.94407 (19) | 0.77008 (17) | 0.73300 (19) | 0.0275 (5) | |
H10 | 0.9806 | 0.7327 | 0.8098 | 0.033* | |
C11 | 0.85535 (18) | 0.72270 (16) | 0.63372 (18) | 0.0241 (4) | |
H11 | 0.8326 | 0.6520 | 0.6415 | 0.029* | |
C11A | 0.79700 (18) | 0.77790 (15) | 0.51930 (18) | 0.0206 (4) | |
C11B | 0.70082 (18) | 0.73298 (15) | 0.41552 (18) | 0.0205 (4) | |
O14 | 0.53635 (12) | 0.61056 (11) | 0.35326 (13) | 0.0249 (3) | |
C21 | 0.74384 (18) | 0.44406 (15) | 0.42875 (18) | 0.0207 (4) | |
C22 | 0.81765 (19) | 0.36951 (17) | 0.39509 (19) | 0.0263 (4) | |
H22 | 0.8598 | 0.3879 | 0.3372 | 0.032* | |
C23 | 0.8303 (2) | 0.26892 (17) | 0.44504 (19) | 0.0278 (5) | |
H23 | 0.8803 | 0.2181 | 0.4220 | 0.033* | |
C24 | 0.76834 (19) | 0.24505 (16) | 0.52867 (19) | 0.0245 (4) | |
F24 | 0.77986 (13) | 0.14603 (9) | 0.57801 (12) | 0.0346 (3) | |
C25 | 0.69542 (18) | 0.31562 (16) | 0.56540 (18) | 0.0228 (4) | |
H25 | 0.6547 | 0.2965 | 0.6243 | 0.027* | |
C26 | 0.68271 (18) | 0.41599 (15) | 0.51395 (18) | 0.0214 (4) | |
H26 | 0.6318 | 0.4659 | 0.5372 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0179 (8) | 0.0214 (8) | 0.0231 (8) | −0.0002 (7) | 0.0065 (7) | −0.0006 (7) |
C2 | 0.0226 (10) | 0.0225 (10) | 0.0234 (10) | 0.0006 (8) | 0.0105 (8) | −0.0007 (8) |
C3 | 0.0351 (12) | 0.0260 (11) | 0.0228 (10) | 0.0019 (9) | 0.0114 (9) | 0.0016 (8) |
C4 | 0.0248 (10) | 0.0293 (11) | 0.0221 (10) | −0.0030 (9) | 0.0053 (8) | 0.0000 (9) |
C5 | 0.0257 (11) | 0.0294 (11) | 0.0231 (10) | 0.0030 (9) | 0.0050 (8) | 0.0038 (8) |
C5A | 0.0239 (10) | 0.0243 (10) | 0.0244 (10) | 0.0036 (8) | 0.0104 (8) | 0.0015 (8) |
C6 | 0.0295 (11) | 0.0225 (10) | 0.0269 (10) | 0.0060 (9) | 0.0120 (9) | 0.0051 (8) |
C7 | 0.0341 (12) | 0.0187 (10) | 0.0333 (11) | 0.0027 (9) | 0.0176 (10) | 0.0019 (9) |
C7A | 0.0230 (10) | 0.0218 (10) | 0.0283 (10) | 0.0019 (8) | 0.0139 (8) | −0.0010 (8) |
C8 | 0.0235 (10) | 0.0234 (11) | 0.0374 (12) | 0.0004 (8) | 0.0140 (9) | −0.0057 (9) |
C9 | 0.0214 (10) | 0.0339 (12) | 0.0315 (11) | −0.0004 (9) | 0.0075 (9) | −0.0095 (9) |
C10 | 0.0246 (10) | 0.0330 (12) | 0.0230 (10) | 0.0034 (9) | 0.0051 (8) | 0.0007 (9) |
C11 | 0.0247 (10) | 0.0236 (11) | 0.0259 (10) | 0.0020 (8) | 0.0109 (8) | 0.0007 (8) |
C11A | 0.0204 (9) | 0.0201 (10) | 0.0233 (10) | 0.0027 (8) | 0.0099 (8) | −0.0007 (8) |
C11B | 0.0214 (9) | 0.0193 (10) | 0.0234 (10) | 0.0023 (8) | 0.0108 (8) | 0.0009 (8) |
O14 | 0.0186 (7) | 0.0300 (8) | 0.0266 (7) | −0.0015 (6) | 0.0080 (6) | 0.0016 (6) |
C21 | 0.0192 (9) | 0.0217 (10) | 0.0196 (9) | −0.0002 (8) | 0.0040 (8) | −0.0019 (8) |
C22 | 0.0281 (11) | 0.0288 (11) | 0.0247 (10) | 0.0036 (9) | 0.0123 (9) | 0.0009 (9) |
C23 | 0.0315 (11) | 0.0256 (11) | 0.0273 (11) | 0.0086 (9) | 0.0111 (9) | −0.0012 (9) |
C24 | 0.0282 (11) | 0.0189 (10) | 0.0225 (10) | 0.0006 (8) | 0.0029 (8) | 0.0015 (8) |
F24 | 0.0452 (8) | 0.0226 (7) | 0.0365 (7) | 0.0072 (6) | 0.0141 (6) | 0.0053 (5) |
C25 | 0.0228 (10) | 0.0239 (10) | 0.0211 (10) | −0.0008 (8) | 0.0063 (8) | 0.0000 (8) |
C26 | 0.0214 (10) | 0.0204 (10) | 0.0228 (10) | 0.0007 (8) | 0.0077 (8) | −0.0028 (8) |
N1—C11B | 1.449 (2) | C7A—C11A | 1.426 (3) |
N1—O14 | 1.452 (2) | C8—C9 | 1.374 (3) |
N1—C2 | 1.487 (2) | C8—H8 | 0.9500 |
C2—C21 | 1.511 (3) | C9—C10 | 1.409 (3) |
C2—C3 | 1.561 (3) | C9—H9 | 0.9500 |
C2—H2 | 1.0000 | C10—C11 | 1.368 (3) |
C3—C4 | 1.533 (3) | C10—H10 | 0.9500 |
C3—H31 | 0.9900 | C11—C11A | 1.419 (3) |
C3—H32 | 0.9900 | C11—H11 | 0.9500 |
C4—O14 | 1.453 (2) | C11A—C11B | 1.424 (3) |
C4—C5 | 1.519 (3) | C21—C26 | 1.394 (3) |
C4—H4 | 1.0000 | C21—C22 | 1.396 (3) |
C5—C5A | 1.509 (3) | C22—C23 | 1.388 (3) |
C5—H51 | 0.9900 | C22—H22 | 0.9500 |
C5—H52 | 0.9900 | C23—C24 | 1.373 (3) |
C5A—C11B | 1.368 (3) | C23—H23 | 0.9500 |
C5A—C6 | 1.417 (3) | C24—F24 | 1.367 (2) |
C6—C7 | 1.366 (3) | C24—C25 | 1.371 (3) |
C6—H6 | 0.9500 | C25—C26 | 1.392 (3) |
C7—C7A | 1.422 (3) | C25—H25 | 0.9500 |
C7—H7 | 0.9500 | C26—H26 | 0.9500 |
C7A—C8 | 1.417 (3) | ||
C11B—N1—O14 | 108.34 (14) | C7—C7A—C11A | 118.51 (19) |
C11B—N1—C2 | 110.28 (15) | C9—C8—C7A | 120.7 (2) |
O14—N1—C2 | 102.30 (14) | C9—C8—H8 | 119.6 |
N1—C2—C21 | 111.65 (15) | C7A—C8—H8 | 119.6 |
N1—C2—C3 | 103.85 (15) | C8—C9—C10 | 120.3 (2) |
C21—C2—C3 | 114.02 (16) | C8—C9—H9 | 119.9 |
N1—C2—H2 | 109.0 | C10—C9—H9 | 119.9 |
C21—C2—H2 | 109.0 | C11—C10—C9 | 120.5 (2) |
C3—C2—H2 | 109.0 | C11—C10—H10 | 119.8 |
C4—C3—C2 | 103.45 (16) | C9—C10—H10 | 119.8 |
C4—C3—H31 | 111.1 | C10—C11—C11A | 120.79 (19) |
C2—C3—H31 | 111.1 | C10—C11—H11 | 119.6 |
C4—C3—H32 | 111.1 | C11A—C11—H11 | 119.6 |
C2—C3—H32 | 111.1 | C11—C11A—C11B | 122.63 (18) |
H31—C3—H32 | 109.0 | C11—C11A—C7A | 118.83 (18) |
O14—C4—C5 | 107.05 (16) | C11B—C11A—C7A | 118.52 (18) |
O14—C4—C3 | 103.18 (15) | C5A—C11B—C11A | 121.98 (18) |
C5—C4—C3 | 114.81 (17) | C5A—C11B—N1 | 121.38 (18) |
O14—C4—H4 | 110.5 | C11A—C11B—N1 | 116.64 (17) |
C5—C4—H4 | 110.5 | N1—O14—C4 | 103.72 (13) |
C3—C4—H4 | 110.5 | C26—C21—C22 | 118.87 (18) |
C5A—C5—C4 | 109.95 (17) | C26—C21—C2 | 122.34 (17) |
C5A—C5—H51 | 109.7 | C22—C21—C2 | 118.79 (17) |
C4—C5—H51 | 109.7 | C23—C22—C21 | 120.90 (19) |
C5A—C5—H52 | 109.7 | C23—C22—H22 | 119.6 |
C4—C5—H52 | 109.7 | C21—C22—H22 | 119.6 |
H51—C5—H52 | 108.2 | C24—C23—C22 | 118.08 (19) |
C11B—C5A—C6 | 118.84 (19) | C24—C23—H23 | 121.0 |
C11B—C5A—C5 | 120.11 (18) | C22—C23—H23 | 121.0 |
C6—C5A—C5 | 121.05 (18) | F24—C24—C25 | 118.24 (18) |
C7—C6—C5A | 121.20 (19) | F24—C24—C23 | 118.49 (18) |
C7—C6—H6 | 119.4 | C25—C24—C23 | 123.27 (19) |
C5A—C6—H6 | 119.4 | C24—C25—C26 | 118.12 (18) |
C6—C7—C7A | 120.91 (19) | C24—C25—H25 | 120.9 |
C6—C7—H7 | 119.5 | C26—C25—H25 | 120.9 |
C7A—C7—H7 | 119.5 | C25—C26—C21 | 120.75 (18) |
C8—C7A—C7 | 122.54 (19) | C25—C26—H26 | 119.6 |
C8—C7A—C11A | 118.90 (19) | C21—C26—H26 | 119.6 |
C11B—N1—C2—C21 | 156.26 (16) | C5—C5A—C11B—C11A | 177.41 (18) |
O14—N1—C2—C21 | −88.66 (17) | C6—C5A—C11B—N1 | 178.02 (17) |
C11B—N1—C2—C3 | −80.44 (18) | C5—C5A—C11B—N1 | −3.0 (3) |
O14—N1—C2—C3 | 34.64 (17) | C11—C11A—C11B—C5A | 178.18 (18) |
N1—C2—C3—C4 | −8.7 (2) | C7A—C11A—C11B—C5A | −0.3 (3) |
C21—C2—C3—C4 | 112.98 (18) | C11—C11A—C11B—N1 | −1.4 (3) |
C2—C3—C4—O14 | −20.2 (2) | C7A—C11A—C11B—N1 | −179.89 (16) |
C2—C3—C4—C5 | 95.89 (19) | O14—N1—C11B—C5A | −27.4 (2) |
O14—C4—C5—C5A | 46.0 (2) | C2—N1—C11B—C5A | 83.8 (2) |
C3—C4—C5—C5A | −67.8 (2) | O14—N1—C11B—C11A | 152.15 (15) |
C4—C5—C5A—C11B | −6.4 (3) | C2—N1—C11B—C11A | −96.64 (19) |
C4—C5—C5A—C6 | 172.52 (18) | C11B—N1—O14—C4 | 67.08 (17) |
C11B—C5A—C6—C7 | 2.4 (3) | C2—N1—O14—C4 | −49.41 (17) |
C5—C5A—C6—C7 | −176.54 (18) | C5—C4—O14—N1 | −78.33 (18) |
C5A—C6—C7—C7A | −1.3 (3) | C3—C4—O14—N1 | 43.18 (18) |
C6—C7—C7A—C8 | −178.03 (19) | N1—C2—C21—C26 | 8.1 (3) |
C6—C7—C7A—C11A | −0.6 (3) | C3—C2—C21—C26 | −109.2 (2) |
C7—C7A—C8—C9 | 176.39 (19) | N1—C2—C21—C22 | −171.98 (17) |
C11A—C7A—C8—C9 | −1.1 (3) | C3—C2—C21—C22 | 70.7 (2) |
C7A—C8—C9—C10 | 0.4 (3) | C26—C21—C22—C23 | 0.1 (3) |
C8—C9—C10—C11 | 1.0 (3) | C2—C21—C22—C23 | −179.84 (19) |
C9—C10—C11—C11A | −1.7 (3) | C21—C22—C23—C24 | −0.2 (3) |
C10—C11—C11A—C11B | −177.49 (18) | C22—C23—C24—F24 | 179.76 (18) |
C10—C11—C11A—C7A | 1.0 (3) | C22—C23—C24—C25 | −0.3 (3) |
C8—C7A—C11A—C11 | 0.4 (3) | F24—C24—C25—C26 | −179.29 (17) |
C7—C7A—C11A—C11 | −177.20 (18) | C23—C24—C25—C26 | 0.8 (3) |
C8—C7A—C11A—C11B | 178.95 (17) | C24—C25—C26—C21 | −0.8 (3) |
C7—C7A—C11A—C11B | 1.4 (3) | C22—C21—C26—C25 | 0.4 (3) |
C6—C5A—C11B—C11A | −1.5 (3) | C2—C21—C26—C25 | −179.67 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H31···Cg2i | 0.99 | 2.63 | 3.575 (2) | 160 |
C5—H52···Cg1ii | 0.99 | 2.72 | 3.605 (2) | 149 |
C9—H9···Cg1iii | 0.95 | 2.92 | 3.684 (2) | 139 |
C23—H23···Cg2iv | 0.95 | 2.85 | 3.683 (3) | 147 |
C25—H25···O14v | 0.95 | 2.55 | 3.184 (3) | 125 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+2, y+1/2, −z+3/2; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y+1, −z+1. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C20H16BrNO | C20H15BrClNO | C20H16FNO |
Mr | 366.24 | 400.69 | 305.34 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, Pbca | Monoclinic, P21/c |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 7.8444 (3), 9.8146 (4), 10.0871 (4) | 9.7758 (16), 9.8211 (14), 33.174 (3) | 11.3036 (4), 12.7585 (5), 11.1730 (3) |
α, β, γ (°) | 90, 92.103 (3), 90 | 90, 90, 90 | 90, 109.137 (2), 90 |
V (Å3) | 776.08 (5) | 3185.0 (7) | 1522.29 (9) |
Z | 2 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 2.65 | 2.76 | 0.09 |
Crystal size (mm) | 0.20 × 0.04 × 0.01 | 0.32 × 0.12 × 0.04 | 0.09 × 0.08 × 0.03 |
Data collection | |||
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.619, 0.974 | 0.551, 0.896 | 0.986, 0.997 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7511, 3132, 2810 | 28541, 3658, 2574 | 15443, 3467, 2667 |
Rint | 0.055 | 0.073 | 0.044 |
(sin θ/λ)max (Å−1) | 0.651 | 0.650 | 0.650 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.102, 1.09 | 0.042, 0.088, 1.06 | 0.061, 0.123, 1.11 |
No. of reflections | 3132 | 3658 | 3467 |
No. of parameters | 209 | 217 | 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) | 0.44, −0.53 | 0.39, −0.51 | 0.26, −0.24 |
Absolute structure | Flack (1983), 1237 Friedel pairs | ? | ? |
Absolute structure parameter | 0.099 (15) | ? | ? |
Computer programs: COLLECT (Hooft, 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, 2009), SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
Parameter | (I) | (II) | (III) |
(a) Five-membered rings | |||
Q2 | 0.430 (5) | 0.442 (3) | 0.449 (2) |
ϕ2 | 7.9 (7) | 16.2 (4) | 10.7 (3) |
(b) Six-membered rings | |||
Q | 0.628 (5) | 0.617 (3) | 0.6223 (19) |
θ | 124.4 (5) | 128.3 (3) | 126.51 (18) |
ϕ | 170.1 (5) | 165.1 (4) | 166.1 (2) |
(c) Seven-membered rings | |||
Q | 1.077 (5) | 1.101 (3) | 1.085 (2) |
ϕ2 | 18.7 (3) | 15.80 (17) | 17.09 (12) |
ϕ3 | 302.2 (8)) | 298.8 (6) | 302.6 (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—C11B—C5A—C5—C4 and puckering parameters for seven-membered rings are defined for the atom sequence N1—C2—C3—C4—C5—C5A—C11B. |
Compound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C2—H2···Br7i | 1.00 | 2.90 | 3.891 (5) | 171 |
C5—H52···Cg1ii | 0.99 | 2.55 | 3.484 (5) | 157 | |
C23—H23···Cg2iii | 0.95 | 2.70 | 3.596 (5) | 157 | |
C24—H24···O14iv | 0.95 | 2.53 | 3.313 (6) | 140 | |
(II) | C3-H31···O14v | 0.99 | 2.52 | 3.485 (4) | 164 |
(III) | C3—H31···Cg2vi | 0.99 | 2.63 | 3.575 (2) | 160 |
C5—H52···Cg1vii | 0.99 | 2.72 | 3.605 (2) | 149 | |
C9—H9···Cg1viii | 0.95 | 2.92 | 3.684 (2) | 139 | |
C23—H23···Cg2ix | 0.95 | 2.85 | 3.683 (3) | 147 | |
C25—H25···O14x | 0.95 | 2.55 | 3.184 (3) | 125 |
Notes: Cg1 represents the centroid of the C21–C26 ring and Cg2 represents the centroid of the C7A/C8–C11/C11A ring. Symmetry codes: (i) 1-x, 1/2+y, 1-z; (ii) 1-x, -1/2+y, 2-z; (iii) MISSING COMPONENT, 1+y, z; (iv) -x, 1/2+y, 2-z; (v) 1/2-x, -1/2+y, z; (vi) x, 3/2-y, -1/2+z; (vii) 1-x, 1/2+y, 1/2-z; (viii) 2-x, 1/2+y, 3/2-z; (ix) 2-x, 1-y, 1-z; (x) 1-x, 1-y, 1-z. |
As part of a wider programme aimed at the synthesis and characterization of novel fused azepines, as potential antiprotozoal agents (Gómez et al., 2006; Yépez et al., 2006), we have recently reported on the molecular structures and supramolecular aggregation in several different types of substituted tetrahydro-1,4-epoxy-1-benzazepines (Acosta et al., 2008; Blanco et al., 2008; Gómez et al., 2008;). We have now extended this study to encompass analogues containing the tetrahydro-1,4-epoxy-naphth[2,1-b]azepine framework, and here we report the structure of three such compounds, (2R,4S)-7-bromo-2-exo-4-phenyl-2,3,4,5-tetrahydro-1H-1,4-epoxy naphtho[2,1-b]azepine, (I), (2RS,4SR)-7-bromo-2-exo-4- (4-chlorophenyl-2,3,4,5-tetrahydro-1H-1,4-epoxynaphtho[2,1-b]azepine, (II), and (2RS,4SR)-2-exo-4-(4-fluorophenyl)- 2,3,4,5-tetrahydro-1H-1,4-epoxynaphtho[2,1-b]azepine, (III) (Figs. 1–3).
While compounds (II) and (III) crystallize as racemic mixtures in space groups Pbca and P21/c, respectively, compound (I) crystallizes in space group P21, and it was handled as an inversion twin, giving twin fractions for the crystal selected for data collection of 0.901 (15) for the (2R,4S) enantiomer and 0.099 (15) for the (2S,4R) enantiomer. Accordingly, the reference molecule in the racemic compounds (II) and (III) were each selected as having the (2R,4S) configuration. This behaviour in (I)–(III) may be contrasted with the behaviour (Gómez et al., 2008) of the aryl-substituted tetrahydro-1,4-epoxy-1-benzazepines (IV)–(VI). Compound (IV) crystallizes as a racemic mixture in space group Pna21, while each of (V) and (VI) crystallize as a single enantiomorph, both in space group P212121, having the opposite configuration (2S,4R), as shown by the values of the Flack (1983) x parameter. Since the majority of the other substituted tetrahydro-1,4-epoxy-1-benzazepines that we have studied recently have been found to crystallize either as true racemic mixtures (Blanco et al., 2008) or as inversion twins containing unequal numbers of the two enantiomers (Acosta et al., 2008), it seems likely that all such species are, in fact, synthesized as racemic mixtures, particularly since their syntheses offer no obvious scope for enantiospecific discrimination. It is surprising, however, that of the 12 fused epoxyazepines of this type studied to date by us, including the three reported here, only six crystallize in space groups containing reflection or inversion operators; the other six all crystallize either in P21 or in P212121, three as inversion twins and only three as single enantiomers.
The conformations of the fused heterocyclic systems in (I)–(III) are extremely similar, as shown by the values (Table 1) of the ring-puckering parameters (Cremer & Pople, 1975). The five-membered ring components adopt envelope conformations, folded across the line N1···C4 (Figs. 1–3), while the six-membered rings have conformations intermediate between envelope and half-chair forms, where the idealized values of the ring-puckering angles are θ = 54.7° and ϕ = 60n°, and θ = 50.8° and ϕ = (60n + 30)°, respectively, where n represents an integer. The N1—C2—C21—C22 torsion angles describing the orientation of the pendent aryl ring relative to the azepine ring are also fairly similar: -177.3 (4)° in (I), 172.4 (3)° in (II) and -171.98 (17)° in (III).
Despite the rather similar conformations, and the overall similarity in the molecular shapes in (I)–(III), the patterns of their supramolecular aggregation are significantly different. The hydrogen-bonded structure of (I) is dominated by one C—H···O hydrogen bond and two C—H···π(arene) hydrogen bonds (Table 2). There is a short C—H···Br contact in this structure, but this involves an aliphatic C—H bond of fairly low acidity and, more importantly, it has been shown that Br bonded to C is an extremely poor acceptor of hydrogen bonds (Aakeröy et al., 1999; Brammer et al., 2001; Thallapally & Nangia, 2001); accordingly, this contact must be regarded as being not structurally significant. The C—H···O hydrogen bonds links molecules related by the 21 screw axis along (0, y, 1) into a C(7) (Bernstein et al., 1995) chain running parallel to the [010] direction. At the same time, the C—H···π(arene) hydrogen bond having the aryl atom C23 as the donor links molecules related by translation along [010]. The combination of these two interactions then generates a chain of rings running parallel to the [010] direction (Fig. 3). The other C—H···π(arene) hydrogen bond has an aliphatic C atom as the donor and the pendent phenyl ring as the acceptor, and its effect is to link molecules related by the 21 screw axis along (1/2, y, 1) into a second chain running parallel to the [010] direction (Fig. 4). The combined action of the two independent [010] chains is to link the molecules into a sheet parallel to (001). There are no direction-specific interactions between adjacent sheets, so that the hydrogen-bonded structure in (I) is two-dimensional.
Molecules of compound (II) related by the b-glide plane at x = 1/4 are linked by a single, rather weak C—H···O hydrogen bond (Table 2) into a C(4) chain running parallel to the [010] direction. Chains of this type are linked into sheets by a single aromatic π–π stacking interaction. The chlorinated aryl rings of the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) are strictly parallel with an interplanar spacing of 3.500 (2) Å. The ring-centroid separation is 3.833 (2) Å, corresponding to a ring-centroid offset of 1.563 (2) Å. The effect of this interaction is to link the C(4) chain involving the glide plane at x = 0.25 to the two chains involving glide planes at x = 0.75 and x = -0.25, respectively, so generating a sheet of π-stacked hydrogen-bonded chains lying parallel to (001) (Fig. 6).
The hydrogen-bonded structure of (III) is three-dimensional and it is determined by a combination of one C—H···O hydrogen bond and four independent C—H···π(arene) hydrogen bonds; in the event, just three of these interactions suffice to demonstrate the three-dimensional nature of the hydrogen-bonded structure. The C—H···π(arene) interaction having atom C3 as the donor links molecules related by the c-glide plane at y = 3/4 into a chain running parallel to the [001] direction (Fig. 7), while that having atom C5 as the donor links molecules related by the 21 screw axis along (1/2, y, 1/4) into a chain running parallel to the [010] direction (Fig. 8). The combination of these two chains generates a sheet parallel to (100), and a third hydrogen bond links adjacent sheets to form a continuous three-dimensional framework via a cyclic centrosymmetric motif (Fig. 9). The C—H···O hydrogen bond lies within the (100) sheet, while the final C—H···π(arene) interaction reinforces, albeit weakly, the linking of adjacent (100) sheets.
It is of interest briefly to compare the hydrogen-bonded structures of compounds (I)–(III) with those of the benzazepine analogues (IV)–(VI) (Gómez et al., 2008). In the monohalogented compound (VI), a combination of one C—H···O hydrogen bond and two C—H···π(arene) hydrogen bonds generates a three-dimensional structure in space group P212121. Two substructures can readily be identified, one of them one-dimensional and the other two-dimensional. Not only do the two isomeric dichloro compounds (IV) and (V) exhibit different space groups (Pna21 and P212121, respectively) with very different unit-cell dimensions, but their hydrogen-bonded structures also differ considerably. In (IV), a combination of C—H···O and C—H···N hydrogen bonds generates a chain of edge-fused R33(12) rings; this is the only example so far studied whose structure both contains a C—H···N hydrogen bond and does not contain a C—H···π(arene) hydrogen bond. In the structure of (IV), one C—H···O and two C—H···π(arene) hydrogen bonds acting individually generate three orthogonal chains of molecules related by different 21 screw axes which, in combination, give rise to a three-dimensional framework structure. Thus, although the hydrogen-bonded structures in (III), (V) and (VI) are all three-dimensional, there are few if any similarities in the detailed construction of the frameworks involved. The differences in crystal structures observed for (I)–(VI) are all consequent upon rather modest changes in the substituents.