Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107005690/av3067sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107005690/av3067Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107005690/av3067IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107005690/av3067IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107005690/av3067IVsup5.hkl |
CCDC references: 641817; 641818; 641819; 641820
For related literature, see: Choi et al. (1997); Frisch et al. (2004); Jacquemin et al. (2005); Møller & Plesset (1934); Michels et al. (1994); Ros et al. (2005); Sonoda et al. (2006); Szezesna & Urbańczyk-Lipkowska (2002); Tsuzuki (2003); Yamaguchi et al. (2005); Yang & Kertesz (2006); Yannoni & Clarke (1983); Zeller & Hunter (2004).
Compounds (I)–(IV) were prepared by the Wittig reactions of the triphenylphosphonium salt of (E)-4-nitrocinnamyl bromide and (E)-4-alkoxycinnamaldehydes (Sonoda et al., 2006). The reaction gave a mixture of E,Z,E and E,E,E isomers as a crude product, from which the E,E,E isomer was removed by recrystallization from toluene. Toluene was evaporated from the mother liquor under reduced pressure, and the resulting isomeric mixture (predominantly E,Z,E) was dissolved in an appropriate solvent [acetonitrile for (I) and dichloromethane–toluene for (II)–(IV)]. Crystals suitable for X-ray diffraction were obtained from these solutions by slow evaporation at room temperature in the dark. The melting points of (I)–(IV) could not be determined, probably because of thermal conversion to the E,E,E isomers in the solid state. 1H NMR (CDCl3, 300 MHz): for (I), δ 8.20 (2H, d, J = 8.9 Hz, arom.), 7.58 (2H, d, J = 8.6 Hz, arom.), 7.44 (2H, d, J = 8.6 Hz, arom.), 7.24 (1H, dd, J = 15.8 and 11.6 Hz, triene), 6.90 (2H, d, J = 8.9 Hz, arom.), 6.56–6.68 (3H, m, triene), 6.36 (1H, apparently (app.) t, J = 11.1 Hz, triene), 6.21 (1H, app. t, J = 11.4 Hz, triene), 3.84 (3H, s, OCH3); for (II), δ 8.19 (2H, d, J = 8.8 Hz, arom.), 7.58 (2H, d, J = 8.8 Hz, arom.), 7.43 (2H, d, J = 8.9 Hz, arom.), 7.23 (1H, dd, J = 15.4 and 11.5 Hz, triene), 6.89 (2H, d, J = 8.8 Hz, arom.), 6.56–6.67 (3H, m, triene), 6.36 (1H, app. t, J = 11.3 Hz, triene), 6.20 (1H, app. t, J = 11.4 Hz, triene), 4.07 (2H, q, J = 7.0 Hz, OCH2), 1.43 (3H, t, J = 7.0 Hz, CH3); for (III), δ 8.20 (2H, d, J = 8.7 Hz, arom.), 7.58 (2H, d, J = 8.8 Hz, arom.), 7.43 (2H, d, J = 8.7 Hz, arom.), 7.23 (1H, dd, J = 15.4 and 10.9 Hz, triene), 6.89 (2H, d, J = 8.8 Hz, arom.), 6.56–6.67 (3H, m, triene), 6.36 (1H, app. t, J = 11.1 Hz, triene), 6.20 (1H, app. t, J = 11.0 Hz, triene), 3.94 (2H, t, J = 6.6 Hz, OCH2), 1.76–1.87 (2H, m, CH2Me), 1.04 (3H, t, J = 7.4 Hz, CH3); for (IV), δ 8.20 (2H, d, J = 8.5 Hz, arom.), 7.58 (2H, d, J = 8.9 Hz, arom.), 7.42 (2H, d, J = 8.7 Hz, arom.), 7.23 (1H, dd, J = 15.5 and 11.3 Hz, triene), 6.89 (2H, d, J = 8.6 Hz, arom.), 6.56–6.67 (3H, m, triene), 6.36 (1H, app. t, J = 11.0 Hz, triene), 6.20 (1H, app. t, J = 11.0 Hz, triene), 3.99 (2H, t, J = 6.4 Hz, OCH2), 1.73–1.83 (2H, m, CH2Et), 1.44–1.57 (2H, m, CH2Me), 0.99 (3H, t, J = 7.4 Hz, CH3).
All H atoms were located by geometric considerations and refined as riding on their carrier atoms.
For all compounds, data collection: SMART (Bruker, 2001). Cell refinement: SMART [or SAINT?] for (I), (III), (IV); SMART for (II). For all compounds, data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.
C19H17NO3 | F(000) = 1296 |
Mr = 307.34 | Dx = 1.297 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 5293 reflections |
a = 13.0541 (11) Å | θ = 2.4–27.6° |
b = 6.9672 (6) Å | µ = 0.09 mm−1 |
c = 34.604 (3) Å | T = 183 K |
V = 3147.2 (5) Å3 | Rectangular, orange |
Z = 8 | 0.30 × 0.10 × 0.04 mm |
Bruker SMART CCD area-detector diffractometer | 3715 independent reflections |
Radiation source: rotating anode | 2905 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 8.366 pixels mm-1 | θmax = 28.3°, θmin = 1.2° |
ϕ and ω scans | h = −16→17 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −8→9 |
Tmin = 0.914, Tmax = 0.997 | l = −34→45 |
18236 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0827P)2 + 0.2636P] where P = (Fo2 + 2Fc2)/3 |
3715 reflections | (Δ/σ)max = 0.005 |
209 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C19H17NO3 | V = 3147.2 (5) Å3 |
Mr = 307.34 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 13.0541 (11) Å | µ = 0.09 mm−1 |
b = 6.9672 (6) Å | T = 183 K |
c = 34.604 (3) Å | 0.30 × 0.10 × 0.04 mm |
Bruker SMART CCD area-detector diffractometer | 3715 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2905 reflections with I > 2σ(I) |
Tmin = 0.914, Tmax = 0.997 | Rint = 0.026 |
18236 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.24 e Å−3 |
3715 reflections | Δρmin = −0.19 e Å−3 |
209 parameters |
Experimental. Sheldrick, G. M. (1996). SADABS, program for scaling and correction of area detector data. University of Göttingen, Germany. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.88041 (10) | 0.5098 (2) | 0.95611 (4) | 0.0397 (3) | |
C2 | 0.86381 (11) | 0.7040 (2) | 0.96131 (4) | 0.0456 (4) | |
H2 | 0.8572 | 0.7568 | 0.9865 | 0.055* | |
C3 | 0.85708 (11) | 0.8192 (2) | 0.92906 (4) | 0.0433 (3) | |
H3 | 0.8454 | 0.9529 | 0.9323 | 0.052* | |
C4 | 0.86695 (9) | 0.7449 (2) | 0.89172 (4) | 0.0377 (3) | |
C5 | 0.88609 (11) | 0.54830 (19) | 0.88796 (4) | 0.0400 (3) | |
H5 | 0.8947 | 0.4949 | 0.8629 | 0.048* | |
C6 | 0.89277 (10) | 0.4309 (2) | 0.91968 (4) | 0.0409 (3) | |
H6 | 0.9057 | 0.2976 | 0.9167 | 0.049* | |
C7 | 0.85465 (10) | 0.87210 (19) | 0.85869 (4) | 0.0413 (3) | |
H7 | 0.8410 | 1.0030 | 0.8644 | 0.050* | |
C8 | 0.86025 (10) | 0.8263 (2) | 0.82117 (4) | 0.0397 (3) | |
H8 | 0.8775 | 0.6980 | 0.8145 | 0.048* | |
C9 | 0.84162 (10) | 0.96038 (19) | 0.79042 (4) | 0.0422 (3) | |
H9 | 0.8265 | 1.0886 | 0.7978 | 0.051* | |
C10 | 0.84339 (10) | 0.92345 (19) | 0.75229 (4) | 0.0416 (3) | |
H10 | 0.8270 | 1.0277 | 0.7357 | 0.050* | |
C11 | 0.86719 (9) | 0.74411 (19) | 0.73368 (4) | 0.0376 (3) | |
H11 | 0.8898 | 0.6398 | 0.7492 | 0.045* | |
C12 | 0.85890 (10) | 0.71789 (19) | 0.69554 (4) | 0.0381 (3) | |
H12 | 0.8378 | 0.8264 | 0.6810 | 0.046* | |
C13 | 0.87831 (9) | 0.54296 (18) | 0.67359 (4) | 0.0350 (3) | |
C14 | 0.85294 (10) | 0.53563 (19) | 0.63447 (4) | 0.0390 (3) | |
H14 | 0.8261 | 0.6475 | 0.6225 | 0.047* | |
C15 | 0.86538 (10) | 0.3715 (2) | 0.61254 (4) | 0.0402 (3) | |
H15 | 0.8465 | 0.3709 | 0.5860 | 0.048* | |
C16 | 0.90548 (9) | 0.20826 (18) | 0.62948 (4) | 0.0374 (3) | |
C17 | 0.93447 (10) | 0.21290 (18) | 0.66831 (4) | 0.0383 (3) | |
H17 | 0.9642 | 0.1025 | 0.6799 | 0.046* | |
C18 | 0.92020 (10) | 0.37636 (18) | 0.68995 (4) | 0.0369 (3) | |
H18 | 0.9391 | 0.3764 | 0.7165 | 0.044* | |
C19 | 0.89107 (13) | 0.0236 (3) | 0.57142 (4) | 0.0530 (4) | |
H19A | 0.8182 | 0.0556 | 0.5690 | 0.079* | |
H19B | 0.9026 | −0.1077 | 0.5622 | 0.079* | |
H19C | 0.9317 | 0.1132 | 0.5559 | 0.079* | |
N1 | 0.88338 (10) | 0.3837 (2) | 0.98965 (3) | 0.0478 (3) | |
O1 | 0.87144 (11) | 0.45429 (19) | 1.02176 (3) | 0.0714 (4) | |
O2 | 0.89724 (11) | 0.21154 (17) | 0.98479 (3) | 0.0650 (4) | |
O3 | 0.92112 (8) | 0.03779 (15) | 0.61096 (3) | 0.0490 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0354 (6) | 0.0482 (8) | 0.0355 (7) | −0.0007 (6) | −0.0010 (5) | −0.0042 (5) |
C2 | 0.0469 (8) | 0.0523 (9) | 0.0375 (8) | 0.0003 (6) | −0.0011 (6) | −0.0146 (6) |
C3 | 0.0459 (7) | 0.0402 (7) | 0.0438 (8) | 0.0005 (6) | −0.0005 (6) | −0.0107 (6) |
C4 | 0.0312 (6) | 0.0415 (7) | 0.0403 (7) | −0.0024 (5) | 0.0019 (5) | −0.0050 (6) |
C5 | 0.0439 (7) | 0.0415 (7) | 0.0347 (7) | 0.0018 (6) | 0.0059 (5) | −0.0075 (5) |
C6 | 0.0439 (7) | 0.0407 (7) | 0.0380 (7) | 0.0025 (6) | 0.0036 (5) | −0.0066 (5) |
C7 | 0.0399 (7) | 0.0365 (7) | 0.0474 (8) | 0.0010 (5) | 0.0036 (6) | −0.0047 (6) |
C8 | 0.0379 (7) | 0.0358 (7) | 0.0454 (8) | 0.0019 (5) | 0.0027 (5) | −0.0037 (5) |
C9 | 0.0438 (7) | 0.0340 (7) | 0.0489 (8) | 0.0039 (5) | 0.0032 (6) | −0.0002 (6) |
C10 | 0.0424 (7) | 0.0364 (6) | 0.0461 (8) | 0.0033 (5) | 0.0021 (6) | 0.0057 (6) |
C11 | 0.0379 (6) | 0.0336 (6) | 0.0413 (7) | 0.0012 (5) | 0.0009 (5) | 0.0061 (5) |
C12 | 0.0382 (7) | 0.0352 (7) | 0.0408 (7) | 0.0002 (5) | 0.0006 (5) | 0.0073 (5) |
C13 | 0.0329 (6) | 0.0367 (7) | 0.0356 (7) | −0.0026 (5) | 0.0005 (5) | 0.0073 (5) |
C14 | 0.0382 (7) | 0.0410 (7) | 0.0378 (7) | 0.0018 (5) | −0.0020 (5) | 0.0114 (6) |
C15 | 0.0396 (7) | 0.0511 (8) | 0.0300 (7) | −0.0027 (6) | −0.0024 (5) | 0.0063 (6) |
C16 | 0.0363 (6) | 0.0398 (7) | 0.0360 (7) | −0.0029 (5) | 0.0025 (5) | 0.0002 (5) |
C17 | 0.0421 (7) | 0.0364 (7) | 0.0365 (7) | 0.0020 (5) | −0.0014 (5) | 0.0076 (5) |
C18 | 0.0409 (7) | 0.0387 (7) | 0.0310 (6) | −0.0009 (5) | −0.0031 (5) | 0.0061 (5) |
C19 | 0.0554 (9) | 0.0641 (10) | 0.0395 (8) | −0.0074 (7) | 0.0014 (7) | −0.0100 (7) |
N1 | 0.0505 (7) | 0.0578 (8) | 0.0352 (6) | 0.0031 (6) | −0.0021 (5) | −0.0044 (5) |
O1 | 0.1087 (11) | 0.0737 (9) | 0.0317 (6) | 0.0128 (7) | 0.0002 (6) | −0.0076 (5) |
O2 | 0.0999 (10) | 0.0511 (7) | 0.0442 (7) | 0.0088 (6) | 0.0002 (6) | −0.0003 (5) |
O3 | 0.0607 (6) | 0.0471 (6) | 0.0393 (6) | 0.0035 (5) | −0.0029 (4) | −0.0075 (4) |
C1—C2 | 1.382 (2) | C11—H11 | 0.9500 |
C1—C6 | 1.3845 (18) | C12—C13 | 1.4582 (19) |
C1—N1 | 1.4564 (19) | C12—H12 | 0.9500 |
C2—C3 | 1.377 (2) | C13—C14 | 1.3948 (19) |
C2—H2 | 0.9500 | C13—C18 | 1.4024 (17) |
C3—C4 | 1.3978 (18) | C14—C15 | 1.382 (2) |
C3—H3 | 0.9500 | C14—H14 | 0.9500 |
C4—C5 | 1.3985 (19) | C15—C16 | 1.3825 (18) |
C4—C7 | 1.455 (2) | C15—H15 | 0.9500 |
C5—C6 | 1.372 (2) | C16—O3 | 1.3648 (16) |
C5—H5 | 0.9500 | C16—C17 | 1.3964 (19) |
C6—H6 | 0.9500 | C17—C18 | 1.3757 (19) |
C7—C8 | 1.339 (2) | C17—H17 | 0.9500 |
C7—H7 | 0.9500 | C18—H18 | 0.9500 |
C8—C9 | 1.4369 (19) | C19—O3 | 1.4270 (18) |
C8—H8 | 0.9500 | C19—H19A | 0.9800 |
C9—C10 | 1.345 (2) | C19—H19B | 0.9800 |
C9—H9 | 0.9500 | C19—H19C | 0.9800 |
C10—C11 | 1.4397 (19) | N1—O2 | 1.2246 (18) |
C10—H10 | 0.9500 | N1—O1 | 1.2250 (16) |
C11—C12 | 1.3367 (18) | ||
C2—C1—C6 | 121.69 (14) | C10—C11—H11 | 118.6 |
C2—C1—N1 | 119.41 (13) | C11—C12—C13 | 127.90 (12) |
C6—C1—N1 | 118.88 (14) | C11—C12—H12 | 116.0 |
C3—C2—C1 | 118.36 (13) | C13—C12—H12 | 116.0 |
C3—C2—H2 | 120.8 | C14—C13—C18 | 117.01 (12) |
C1—C2—H2 | 120.8 | C14—C13—C12 | 119.66 (11) |
C2—C3—C4 | 121.81 (13) | C18—C13—C12 | 123.32 (12) |
C2—C3—H3 | 119.1 | C15—C14—C13 | 122.37 (12) |
C4—C3—H3 | 119.1 | C15—C14—H14 | 118.8 |
C3—C4—C5 | 117.74 (13) | C13—C14—H14 | 118.8 |
C3—C4—C7 | 119.35 (13) | C14—C15—C16 | 119.50 (12) |
C5—C4—C7 | 122.89 (12) | C14—C15—H15 | 120.3 |
C6—C5—C4 | 121.38 (13) | C16—C15—H15 | 120.3 |
C6—C5—H5 | 119.3 | O3—C16—C15 | 124.99 (12) |
C4—C5—H5 | 119.3 | O3—C16—C17 | 115.56 (11) |
C5—C6—C1 | 118.98 (13) | C15—C16—C17 | 119.45 (12) |
C5—C6—H6 | 120.5 | C18—C17—C16 | 120.42 (12) |
C1—C6—H6 | 120.5 | C18—C17—H17 | 119.8 |
C8—C7—C4 | 127.61 (13) | C16—C17—H17 | 119.8 |
C8—C7—H7 | 116.2 | C17—C18—C13 | 121.21 (12) |
C4—C7—H7 | 116.2 | C17—C18—H18 | 119.4 |
C7—C8—C9 | 123.62 (13) | C13—C18—H18 | 119.4 |
C7—C8—H8 | 118.2 | O3—C19—H19A | 109.5 |
C9—C8—H8 | 118.2 | O3—C19—H19B | 109.5 |
C10—C9—C8 | 126.83 (13) | H19A—C19—H19B | 109.5 |
C10—C9—H9 | 116.6 | O3—C19—H19C | 109.5 |
C8—C9—H9 | 116.6 | H19A—C19—H19C | 109.5 |
C9—C10—C11 | 127.50 (13) | H19B—C19—H19C | 109.5 |
C9—C10—H10 | 116.2 | O2—N1—O1 | 122.46 (14) |
C11—C10—H10 | 116.2 | O2—N1—C1 | 119.03 (12) |
C12—C11—C10 | 122.88 (12) | O1—N1—C1 | 118.51 (14) |
C12—C11—H11 | 118.6 | C16—O3—C19 | 117.99 (11) |
C6—C1—C2—C3 | 1.6 (2) | C11—C12—C13—C18 | −7.0 (2) |
N1—C1—C2—C3 | −177.35 (12) | C18—C13—C14—C15 | 1.67 (19) |
C1—C2—C3—C4 | −0.2 (2) | C12—C13—C14—C15 | −177.17 (12) |
C2—C3—C4—C5 | −1.2 (2) | C13—C14—C15—C16 | −0.8 (2) |
C2—C3—C4—C7 | 177.31 (13) | C14—C15—C16—O3 | 179.79 (12) |
C3—C4—C5—C6 | 1.4 (2) | C14—C15—C16—C17 | −1.14 (19) |
C7—C4—C5—C6 | −177.06 (13) | O3—C16—C17—C18 | −178.69 (12) |
C4—C5—C6—C1 | −0.1 (2) | C15—C16—C17—C18 | 2.15 (19) |
C2—C1—C6—C5 | −1.4 (2) | C16—C17—C18—C13 | −1.2 (2) |
N1—C1—C6—C5 | 177.53 (12) | C14—C13—C18—C17 | −0.64 (19) |
C3—C4—C7—C8 | −179.20 (13) | C12—C13—C18—C17 | 178.15 (12) |
C5—C4—C7—C8 | −0.7 (2) | C2—C1—N1—O2 | 179.37 (14) |
C4—C7—C8—C9 | 176.58 (12) | C6—C1—N1—O2 | 0.4 (2) |
C7—C8—C9—C10 | −178.23 (14) | C2—C1—N1—O1 | −0.3 (2) |
C8—C9—C10—C11 | −2.0 (2) | C6—C1—N1—O1 | −179.33 (14) |
C9—C10—C11—C12 | 174.50 (14) | C15—C16—O3—C19 | −2.08 (19) |
C10—C11—C12—C13 | −178.43 (12) | C17—C16—O3—C19 | 178.81 (12) |
C11—C12—C13—C14 | 171.77 (13) |
C20H19NO3 | F(000) = 1360 |
Mr = 321.36 | Dx = 1.265 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 946 reflections |
a = 18.914 (9) Å | θ = 2.3–24.4° |
b = 6.880 (3) Å | µ = 0.09 mm−1 |
c = 25.927 (11) Å | T = 183 K |
V = 3374 (3) Å3 | Rectangular, orange |
Z = 8 | 0.30 × 0.10 × 0.03 mm |
Bruker SMART CCD area-detector diffractometer | 2972 independent reflections |
Radiation source: rotating unit | 1583 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.135 |
Detector resolution: 8.366 pixels mm-1 | θmax = 25.0°, θmin = 1.6° |
ϕ and ω scans | h = −22→19 |
Absorption correction: multi-scan (SADABS; Sheldrick 1996) | k = −7→8 |
Tmin = 0.933, Tmax = 0.998 | l = −30→30 |
11787 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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0531P)2] where P = (Fo2 + 2Fc2)/3 |
2972 reflections | (Δ/σ)max = 0.003 |
435 parameters | Δρmax = 0.19 e Å−3 |
1 restraint | Δρmin = −0.20 e Å−3 |
C20H19NO3 | V = 3374 (3) Å3 |
Mr = 321.36 | Z = 8 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 18.914 (9) Å | µ = 0.09 mm−1 |
b = 6.880 (3) Å | T = 183 K |
c = 25.927 (11) Å | 0.30 × 0.10 × 0.03 mm |
Bruker SMART CCD area-detector diffractometer | 2972 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick 1996) | 1583 reflections with I > 2σ(I) |
Tmin = 0.933, Tmax = 0.998 | Rint = 0.135 |
11787 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 1 restraint |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.19 e Å−3 |
2972 reflections | Δρmin = −0.20 e Å−3 |
435 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3896 (4) | 1.1009 (12) | 1.0080 (3) | 0.0429 (19) | |
C2 | 0.3283 (4) | 1.1630 (12) | 0.9856 (3) | 0.046 (2) | |
H2 | 0.3109 | 1.2911 | 0.9906 | 0.055* | |
C3 | 0.2923 (4) | 1.0269 (12) | 0.9548 (3) | 0.046 (2) | |
H3 | 0.2495 | 1.0657 | 0.9386 | 0.055* | |
C4 | 0.3161 (3) | 0.8406 (11) | 0.9469 (3) | 0.0397 (18) | |
C5 | 0.3782 (3) | 0.7860 (12) | 0.9713 (3) | 0.050 (2) | |
H5 | 0.3950 | 0.6566 | 0.9676 | 0.060* | |
C6 | 0.4159 (3) | 0.9148 (12) | 1.0009 (3) | 0.0468 (19) | |
H6 | 0.4594 | 0.8770 | 1.0162 | 0.056* | |
C7 | 0.2765 (3) | 0.7124 (11) | 0.9126 (3) | 0.0407 (19) | |
H7 | 0.2300 | 0.7522 | 0.9037 | 0.049* | |
C8 | 0.2991 (3) | 0.5434 (11) | 0.8921 (3) | 0.0407 (19) | |
H8 | 0.3456 | 0.4990 | 0.8994 | 0.049* | |
C9 | 0.2535 (4) | 0.4287 (11) | 0.8592 (3) | 0.0453 (19) | |
H9 | 0.2069 | 0.4761 | 0.8539 | 0.054* | |
C10 | 0.2707 (4) | 0.2612 (12) | 0.8353 (3) | 0.050 (2) | |
H10 | 0.2354 | 0.2064 | 0.8137 | 0.060* | |
C11 | 0.3366 (4) | 0.1552 (12) | 0.8385 (3) | 0.0442 (19) | |
H11 | 0.3749 | 0.2103 | 0.8572 | 0.053* | |
C12 | 0.3453 (4) | −0.0193 (12) | 0.8159 (3) | 0.0460 (19) | |
H12 | 0.3061 | −0.0648 | 0.7964 | 0.055* | |
C13 | 0.4061 (4) | −0.1473 (11) | 0.8171 (3) | 0.0421 (19) | |
C14 | 0.4035 (4) | −0.3243 (11) | 0.7903 (3) | 0.0438 (19) | |
H14 | 0.3614 | −0.3571 | 0.7723 | 0.053* | |
C15 | 0.4590 (4) | −0.4516 (11) | 0.7890 (3) | 0.0439 (19) | |
H15 | 0.4551 | −0.5701 | 0.7704 | 0.053* | |
C16 | 0.5207 (4) | −0.4067 (11) | 0.8150 (3) | 0.0424 (19) | |
C17 | 0.5253 (4) | −0.2315 (12) | 0.8424 (3) | 0.048 (2) | |
H17 | 0.5673 | −0.1997 | 0.8608 | 0.057* | |
C18 | 0.4692 (4) | −0.1068 (12) | 0.8426 (3) | 0.045 (2) | |
H18 | 0.4733 | 0.0125 | 0.8609 | 0.054* | |
C19 | 0.5769 (4) | −0.6955 (11) | 0.7850 (3) | 0.050 (2) | |
H19A | 0.5675 | −0.6614 | 0.7486 | 0.060* | |
H19B | 0.5380 | −0.7799 | 0.7973 | 0.060* | |
C20 | 0.6463 (5) | −0.8012 (13) | 0.7893 (4) | 0.079 (3) | |
H20A | 0.6840 | −0.7205 | 0.7748 | 0.119* | |
H20B | 0.6435 | −0.9240 | 0.7703 | 0.119* | |
H20C | 0.6564 | −0.8280 | 0.8257 | 0.119* | |
C21 | 0.5910 (3) | −0.5610 (12) | −0.0304 (3) | 0.0410 (19) | |
C22 | 0.6498 (4) | −0.6266 (11) | −0.0036 (3) | 0.0411 (19) | |
H22 | 0.6657 | −0.7569 | −0.0071 | 0.049* | |
C23 | 0.6848 (3) | −0.4960 (12) | 0.0287 (3) | 0.0409 (18) | |
H23 | 0.7262 | −0.5370 | 0.0463 | 0.049* | |
C24 | 0.6610 (3) | −0.3121 (12) | 0.0354 (3) | 0.0397 (19) | |
C25 | 0.6027 (3) | −0.2474 (11) | 0.0067 (3) | 0.0444 (19) | |
H25 | 0.5876 | −0.1161 | 0.0094 | 0.053* | |
C26 | 0.5670 (4) | −0.3746 (12) | −0.0256 (3) | 0.049 (2) | |
H26 | 0.5264 | −0.3328 | −0.0442 | 0.059* | |
C27 | 0.6992 (4) | −0.1802 (12) | 0.0704 (3) | 0.0423 (19) | |
H27 | 0.7460 | −0.2176 | 0.0791 | 0.051* | |
C28 | 0.6761 (3) | −0.0134 (12) | 0.0917 (3) | 0.044 (2) | |
H28 | 0.6309 | 0.0340 | 0.0818 | 0.053* | |
C29 | 0.7158 (4) | 0.0955 (12) | 0.1282 (3) | 0.0467 (19) | |
H29 | 0.7609 | 0.0446 | 0.1368 | 0.056* | |
C30 | 0.6973 (4) | 0.2619 (13) | 0.1520 (3) | 0.053 (2) | |
H30 | 0.7300 | 0.3094 | 0.1768 | 0.063* | |
C31 | 0.6346 (3) | 0.3771 (11) | 0.1449 (3) | 0.0406 (18) | |
H31 | 0.5979 | 0.3303 | 0.1232 | 0.049* | |
C32 | 0.6268 (4) | 0.5532 (12) | 0.1689 (3) | 0.0432 (19) | |
H32 | 0.6645 | 0.5934 | 0.1906 | 0.052* | |
C33 | 0.5674 (3) | 0.6846 (10) | 0.1647 (2) | 0.0346 (17) | |
C34 | 0.5695 (4) | 0.8555 (12) | 0.1930 (3) | 0.0440 (19) | |
H34 | 0.6100 | 0.8803 | 0.2137 | 0.053* | |
C35 | 0.5154 (4) | 0.9927 (12) | 0.1925 (3) | 0.0455 (19) | |
H35 | 0.5193 | 1.1099 | 0.2116 | 0.055* | |
C36 | 0.4558 (4) | 0.9536 (12) | 0.1633 (3) | 0.0450 (19) | |
C37 | 0.4520 (4) | 0.7843 (12) | 0.1341 (3) | 0.046 (2) | |
H37 | 0.4109 | 0.7583 | 0.1142 | 0.055* | |
C38 | 0.5066 (4) | 0.6556 (12) | 0.1336 (3) | 0.0466 (19) | |
H38 | 0.5039 | 0.5441 | 0.1121 | 0.056* | |
C39 | 0.3993 (4) | 1.2473 (11) | 0.1912 (4) | 0.056 (2) | |
H39A | 0.4384 | 1.3328 | 0.1798 | 0.067* | |
H39B | 0.4073 | 1.2131 | 0.2279 | 0.067* | |
C40 | 0.3306 (4) | 1.3494 (14) | 0.1854 (4) | 0.084 (3) | |
H40A | 0.3322 | 1.4332 | 0.1548 | 0.126* | |
H40B | 0.3216 | 1.4289 | 0.2161 | 0.126* | |
H40C | 0.2927 | 1.2536 | 0.1814 | 0.126* | |
N1 | 0.4304 (4) | 1.2402 (11) | 1.0395 (3) | 0.0567 (18) | |
N2 | 0.5519 (4) | −0.7003 (11) | −0.0627 (3) | 0.0541 (19) | |
O1 | 0.4013 (3) | 1.3938 (10) | 1.0511 (2) | 0.0761 (19) | |
O2 | 0.4899 (3) | 1.1938 (9) | 1.0535 (2) | 0.0694 (19) | |
O3 | 0.5800 (2) | −0.5236 (7) | 0.8155 (2) | 0.0479 (13) | |
O4 | 0.5801 (3) | −0.8518 (9) | −0.0741 (2) | 0.0740 (18) | |
O5 | 0.4919 (3) | −0.6508 (8) | −0.0770 (2) | 0.0673 (16) | |
O6 | 0.3976 (2) | 1.0752 (8) | 0.1604 (2) | 0.0538 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.044 (4) | 0.053 (6) | 0.031 (4) | −0.003 (4) | −0.002 (3) | 0.005 (4) |
C2 | 0.053 (5) | 0.044 (5) | 0.041 (5) | 0.007 (4) | 0.008 (3) | 0.009 (4) |
C3 | 0.038 (4) | 0.061 (6) | 0.039 (5) | 0.007 (4) | −0.002 (3) | 0.005 (4) |
C4 | 0.040 (4) | 0.037 (5) | 0.042 (5) | 0.005 (3) | 0.009 (3) | 0.001 (4) |
C5 | 0.038 (4) | 0.047 (6) | 0.065 (6) | 0.009 (3) | −0.008 (4) | 0.002 (4) |
C6 | 0.035 (4) | 0.056 (6) | 0.049 (5) | 0.008 (4) | −0.003 (3) | −0.006 (4) |
C7 | 0.036 (4) | 0.043 (5) | 0.043 (5) | −0.002 (3) | 0.005 (3) | 0.008 (4) |
C8 | 0.036 (4) | 0.045 (5) | 0.041 (5) | −0.004 (3) | 0.002 (3) | 0.005 (4) |
C9 | 0.048 (4) | 0.042 (5) | 0.046 (5) | −0.005 (4) | −0.012 (4) | 0.006 (4) |
C10 | 0.062 (5) | 0.048 (6) | 0.039 (5) | −0.009 (4) | −0.009 (4) | 0.006 (4) |
C11 | 0.056 (5) | 0.048 (6) | 0.028 (4) | −0.008 (4) | 0.000 (3) | 0.003 (4) |
C12 | 0.050 (4) | 0.055 (6) | 0.034 (4) | −0.012 (4) | −0.003 (3) | −0.005 (4) |
C13 | 0.058 (5) | 0.043 (5) | 0.026 (4) | −0.011 (4) | 0.006 (3) | 0.002 (4) |
C14 | 0.043 (4) | 0.053 (6) | 0.036 (4) | −0.011 (4) | −0.001 (3) | −0.004 (4) |
C15 | 0.049 (5) | 0.048 (5) | 0.035 (4) | −0.011 (4) | 0.000 (4) | −0.005 (4) |
C16 | 0.049 (5) | 0.051 (6) | 0.028 (4) | −0.011 (4) | 0.004 (3) | −0.003 (4) |
C17 | 0.049 (4) | 0.056 (6) | 0.037 (5) | −0.018 (4) | −0.002 (3) | −0.014 (4) |
C18 | 0.049 (4) | 0.052 (6) | 0.035 (4) | −0.008 (4) | −0.003 (3) | −0.013 (4) |
C19 | 0.055 (5) | 0.041 (5) | 0.053 (5) | −0.006 (4) | −0.005 (4) | −0.003 (4) |
C20 | 0.088 (7) | 0.057 (7) | 0.092 (8) | 0.011 (5) | −0.019 (5) | −0.029 (6) |
C21 | 0.034 (4) | 0.051 (6) | 0.038 (5) | 0.001 (3) | 0.001 (3) | −0.003 (4) |
C22 | 0.052 (4) | 0.033 (5) | 0.039 (5) | 0.009 (3) | 0.009 (3) | 0.010 (4) |
C23 | 0.033 (4) | 0.057 (6) | 0.032 (4) | 0.005 (4) | 0.001 (3) | 0.007 (4) |
C24 | 0.027 (4) | 0.057 (6) | 0.035 (4) | 0.009 (3) | 0.004 (3) | 0.004 (4) |
C25 | 0.054 (4) | 0.047 (5) | 0.033 (4) | 0.001 (4) | 0.005 (4) | −0.004 (4) |
C26 | 0.046 (4) | 0.058 (6) | 0.043 (5) | 0.009 (4) | −0.001 (3) | 0.006 (4) |
C27 | 0.037 (4) | 0.046 (6) | 0.044 (5) | 0.000 (4) | −0.003 (3) | 0.011 (4) |
C28 | 0.037 (4) | 0.056 (6) | 0.040 (5) | −0.001 (4) | 0.008 (3) | 0.013 (4) |
C29 | 0.044 (4) | 0.045 (6) | 0.050 (5) | 0.002 (4) | −0.002 (4) | 0.005 (4) |
C30 | 0.059 (5) | 0.059 (7) | 0.040 (5) | −0.001 (4) | −0.001 (4) | 0.016 (4) |
C31 | 0.046 (4) | 0.047 (5) | 0.029 (4) | −0.003 (3) | 0.004 (3) | 0.007 (4) |
C32 | 0.058 (5) | 0.049 (6) | 0.023 (4) | −0.004 (4) | 0.000 (3) | 0.002 (4) |
C33 | 0.057 (4) | 0.026 (5) | 0.020 (4) | −0.009 (3) | 0.004 (3) | 0.002 (3) |
C34 | 0.046 (4) | 0.047 (5) | 0.039 (5) | −0.020 (4) | −0.003 (3) | 0.004 (4) |
C35 | 0.043 (4) | 0.043 (5) | 0.051 (5) | −0.008 (4) | 0.002 (4) | 0.001 (4) |
C36 | 0.049 (5) | 0.048 (6) | 0.038 (5) | 0.001 (4) | −0.006 (4) | −0.005 (4) |
C37 | 0.044 (4) | 0.055 (6) | 0.040 (4) | −0.014 (4) | −0.011 (3) | −0.002 (4) |
C38 | 0.062 (5) | 0.045 (5) | 0.033 (5) | −0.005 (4) | −0.005 (4) | −0.004 (4) |
C39 | 0.079 (6) | 0.030 (5) | 0.058 (6) | 0.003 (4) | −0.013 (4) | −0.006 (4) |
C40 | 0.065 (6) | 0.083 (8) | 0.104 (8) | 0.026 (5) | −0.024 (5) | −0.022 (6) |
N1 | 0.065 (5) | 0.060 (6) | 0.046 (4) | −0.002 (4) | 0.006 (4) | −0.003 (4) |
N2 | 0.057 (5) | 0.062 (6) | 0.042 (4) | −0.005 (4) | 0.001 (3) | 0.003 (4) |
O1 | 0.097 (5) | 0.062 (5) | 0.069 (4) | 0.012 (4) | −0.007 (3) | −0.015 (4) |
O2 | 0.059 (4) | 0.083 (5) | 0.067 (5) | −0.006 (3) | −0.019 (3) | 0.001 (3) |
O3 | 0.055 (3) | 0.037 (3) | 0.052 (4) | −0.004 (2) | −0.008 (2) | −0.006 (3) |
O4 | 0.082 (4) | 0.067 (5) | 0.073 (5) | 0.013 (3) | −0.013 (3) | −0.020 (4) |
O5 | 0.058 (4) | 0.077 (4) | 0.067 (4) | −0.009 (3) | −0.008 (3) | −0.010 (4) |
O6 | 0.051 (3) | 0.049 (4) | 0.061 (4) | −0.003 (2) | −0.012 (2) | −0.013 (3) |
C1—C2 | 1.366 (10) | C21—N2 | 1.470 (10) |
C1—C6 | 1.386 (10) | C22—C23 | 1.395 (10) |
C1—N1 | 1.476 (10) | C22—H22 | 0.9500 |
C2—C3 | 1.407 (11) | C23—C24 | 1.354 (10) |
C2—H2 | 0.9500 | C23—H23 | 0.9500 |
C3—C4 | 1.374 (10) | C24—C25 | 1.405 (10) |
C3—H3 | 0.9500 | C24—C27 | 1.472 (10) |
C4—C5 | 1.387 (9) | C25—C26 | 1.387 (10) |
C4—C7 | 1.459 (10) | C25—H25 | 0.9500 |
C5—C6 | 1.371 (11) | C26—H26 | 0.9500 |
C5—H5 | 0.9500 | C27—C28 | 1.345 (10) |
C6—H6 | 0.9500 | C27—H27 | 0.9500 |
C7—C8 | 1.347 (10) | C28—C29 | 1.421 (11) |
C7—H7 | 0.9500 | C28—H28 | 0.9500 |
C8—C9 | 1.447 (10) | C29—C30 | 1.347 (11) |
C8—H8 | 0.9500 | C29—H29 | 0.9500 |
C9—C10 | 1.348 (10) | C30—C31 | 1.439 (10) |
C9—H9 | 0.9500 | C30—H30 | 0.9500 |
C10—C11 | 1.446 (10) | C31—C32 | 1.370 (10) |
C10—H10 | 0.9500 | C31—H31 | 0.9500 |
C11—C12 | 1.347 (10) | C32—C33 | 1.446 (10) |
C11—H11 | 0.9500 | C32—H32 | 0.9500 |
C12—C13 | 1.449 (10) | C33—C34 | 1.386 (10) |
C12—H12 | 0.9500 | C33—C38 | 1.418 (9) |
C13—C18 | 1.392 (9) | C34—C35 | 1.392 (10) |
C13—C14 | 1.403 (10) | C34—H34 | 0.9500 |
C14—C15 | 1.367 (10) | C35—C36 | 1.384 (10) |
C14—H14 | 0.9500 | C35—H35 | 0.9500 |
C15—C16 | 1.383 (9) | C36—O6 | 1.385 (9) |
C15—H15 | 0.9500 | C36—C37 | 1.390 (10) |
C16—O3 | 1.380 (8) | C37—C38 | 1.359 (10) |
C16—C17 | 1.402 (10) | C37—H37 | 0.9500 |
C17—C18 | 1.366 (10) | C38—H38 | 0.9500 |
C17—H17 | 0.9500 | C39—O6 | 1.428 (9) |
C18—H18 | 0.9500 | C39—C40 | 1.486 (10) |
C19—O3 | 1.423 (9) | C39—H39A | 0.9900 |
C19—C20 | 1.505 (10) | C39—H39B | 0.9900 |
C19—H19A | 0.9900 | C40—H40A | 0.9800 |
C19—H19B | 0.9900 | C40—H40B | 0.9800 |
C20—H20A | 0.9800 | C40—H40C | 0.9800 |
C20—H20B | 0.9800 | N1—O2 | 1.224 (8) |
C20—H20C | 0.9800 | N1—O1 | 1.230 (8) |
C21—C26 | 1.366 (10) | N2—O4 | 1.209 (8) |
C21—C22 | 1.387 (10) | N2—O5 | 1.241 (8) |
C2—C1—C6 | 122.4 (7) | C21—C22—H22 | 120.9 |
C2—C1—N1 | 118.4 (7) | C23—C22—H22 | 120.9 |
C6—C1—N1 | 119.1 (7) | C24—C23—C22 | 121.5 (7) |
C1—C2—C3 | 116.4 (7) | C24—C23—H23 | 119.3 |
C1—C2—H2 | 121.8 | C22—C23—H23 | 119.3 |
C3—C2—H2 | 121.8 | C23—C24—C25 | 119.2 (7) |
C4—C3—C2 | 123.2 (7) | C23—C24—C27 | 119.6 (6) |
C4—C3—H3 | 118.4 | C25—C24—C27 | 121.1 (7) |
C2—C3—H3 | 118.4 | C26—C25—C24 | 120.2 (7) |
C3—C4—C5 | 117.5 (7) | C26—C25—H25 | 119.9 |
C3—C4—C7 | 119.1 (7) | C24—C25—H25 | 119.9 |
C5—C4—C7 | 123.3 (7) | C21—C26—C25 | 119.1 (7) |
C6—C5—C4 | 121.4 (7) | C21—C26—H26 | 120.5 |
C6—C5—H5 | 119.3 | C25—C26—H26 | 120.5 |
C4—C5—H5 | 119.3 | C28—C27—C24 | 128.3 (7) |
C5—C6—C1 | 119.1 (7) | C28—C27—H27 | 115.9 |
C5—C6—H6 | 120.5 | C24—C27—H27 | 115.9 |
C1—C6—H6 | 120.5 | C27—C28—C29 | 123.5 (7) |
C8—C7—C4 | 126.8 (7) | C27—C28—H28 | 118.3 |
C8—C7—H7 | 116.6 | C29—C28—H28 | 118.3 |
C4—C7—H7 | 116.6 | C30—C29—C28 | 128.1 (7) |
C7—C8—C9 | 120.9 (7) | C30—C29—H29 | 116.0 |
C7—C8—H8 | 119.6 | C28—C29—H29 | 116.0 |
C9—C8—H8 | 119.6 | C29—C30—C31 | 128.6 (8) |
C10—C9—C8 | 126.4 (7) | C29—C30—H30 | 115.7 |
C10—C9—H9 | 116.8 | C31—C30—H30 | 115.7 |
C8—C9—H9 | 116.8 | C32—C31—C30 | 121.2 (7) |
C9—C10—C11 | 127.7 (7) | C32—C31—H31 | 119.4 |
C9—C10—H10 | 116.1 | C30—C31—H31 | 119.4 |
C11—C10—H10 | 116.1 | C31—C32—C33 | 127.0 (7) |
C12—C11—C10 | 122.0 (7) | C31—C32—H32 | 116.5 |
C12—C11—H11 | 119.0 | C33—C32—H32 | 116.5 |
C10—C11—H11 | 119.0 | C34—C33—C38 | 116.4 (7) |
C11—C12—C13 | 129.0 (7) | C34—C33—C32 | 117.8 (6) |
C11—C12—H12 | 115.5 | C38—C33—C32 | 125.8 (7) |
C13—C12—H12 | 115.5 | C33—C34—C35 | 123.2 (7) |
C18—C13—C14 | 116.0 (7) | C33—C34—H34 | 118.4 |
C18—C13—C12 | 124.7 (7) | C35—C34—H34 | 118.4 |
C14—C13—C12 | 119.3 (6) | C36—C35—C34 | 118.2 (7) |
C15—C14—C13 | 122.8 (7) | C36—C35—H35 | 120.9 |
C15—C14—H14 | 118.6 | C34—C35—H35 | 120.9 |
C13—C14—H14 | 118.6 | C35—C36—O6 | 124.0 (7) |
C14—C15—C16 | 119.5 (7) | C35—C36—C37 | 120.2 (7) |
C14—C15—H15 | 120.2 | O6—C36—C37 | 115.9 (6) |
C16—C15—H15 | 120.2 | C38—C37—C36 | 120.7 (6) |
O3—C16—C15 | 124.1 (7) | C38—C37—H37 | 119.6 |
O3—C16—C17 | 116.5 (6) | C36—C37—H37 | 119.6 |
C15—C16—C17 | 119.4 (7) | C37—C38—C33 | 121.3 (7) |
C18—C17—C16 | 119.6 (7) | C37—C38—H38 | 119.4 |
C18—C17—H17 | 120.2 | C33—C38—H38 | 119.4 |
C16—C17—H17 | 120.2 | O6—C39—C40 | 108.4 (7) |
C17—C18—C13 | 122.6 (8) | O6—C39—H39A | 110.0 |
C17—C18—H18 | 118.7 | C40—C39—H39A | 110.0 |
C13—C18—H18 | 118.7 | O6—C39—H39B | 110.0 |
O3—C19—C20 | 108.9 (6) | C40—C39—H39B | 110.0 |
O3—C19—H19A | 109.9 | H39A—C39—H39B | 108.4 |
C20—C19—H19A | 109.9 | C39—C40—H40A | 109.5 |
O3—C19—H19B | 109.9 | C39—C40—H40B | 109.5 |
C20—C19—H19B | 109.9 | H40A—C40—H40B | 109.5 |
H19A—C19—H19B | 108.3 | C39—C40—H40C | 109.5 |
C19—C20—H20A | 109.5 | H40A—C40—H40C | 109.5 |
C19—C20—H20B | 109.5 | H40B—C40—H40C | 109.5 |
H20A—C20—H20B | 109.5 | O2—N1—O1 | 124.3 (7) |
C19—C20—H20C | 109.5 | O2—N1—C1 | 118.4 (7) |
H20A—C20—H20C | 109.5 | O1—N1—C1 | 117.3 (7) |
H20B—C20—H20C | 109.5 | O4—N2—O5 | 124.5 (7) |
C26—C21—C22 | 121.7 (7) | O4—N2—C21 | 118.7 (7) |
C26—C21—N2 | 119.8 (7) | O5—N2—C21 | 116.8 (7) |
C22—C21—N2 | 118.4 (7) | C16—O3—C19 | 116.5 (5) |
C21—C22—C23 | 118.1 (7) | C36—O6—C39 | 116.9 (6) |
C6—C1—C2—C3 | 0.4 (10) | C22—C21—C26—C25 | 0.5 (11) |
N1—C1—C2—C3 | 178.2 (6) | N2—C21—C26—C25 | 177.2 (7) |
C1—C2—C3—C4 | 0.1 (11) | C24—C25—C26—C21 | −2.4 (11) |
C2—C3—C4—C5 | 0.8 (11) | C23—C24—C27—C28 | −162.7 (7) |
C2—C3—C4—C7 | −177.6 (6) | C25—C24—C27—C28 | 20.9 (11) |
C3—C4—C5—C6 | −2.2 (11) | C24—C27—C28—C29 | 175.1 (7) |
C7—C4—C5—C6 | 176.1 (7) | C27—C28—C29—C30 | −179.2 (7) |
C4—C5—C6—C1 | 2.7 (12) | C28—C29—C30—C31 | −3.4 (14) |
C2—C1—C6—C5 | −1.8 (11) | C29—C30—C31—C32 | −173.8 (7) |
N1—C1—C6—C5 | −179.5 (7) | C30—C31—C32—C33 | 179.1 (7) |
C3—C4—C7—C8 | 165.1 (7) | C31—C32—C33—C34 | 179.1 (6) |
C5—C4—C7—C8 | −13.2 (12) | C31—C32—C33—C38 | −1.6 (11) |
C4—C7—C8—C9 | 178.9 (7) | C38—C33—C34—C35 | 1.1 (10) |
C7—C8—C9—C10 | 177.8 (7) | C32—C33—C34—C35 | −179.5 (7) |
C8—C9—C10—C11 | 2.7 (13) | C33—C34—C35—C36 | 1.7 (11) |
C9—C10—C11—C12 | 174.6 (7) | C34—C35—C36—O6 | 178.3 (7) |
C10—C11—C12—C13 | −177.1 (7) | C34—C35—C36—C37 | −2.1 (11) |
C11—C12—C13—C18 | −1.3 (12) | C35—C36—C37—C38 | −0.2 (11) |
C11—C12—C13—C14 | −179.9 (7) | O6—C36—C37—C38 | 179.3 (7) |
C18—C13—C14—C15 | 0.3 (10) | C36—C37—C38—C33 | 3.1 (11) |
C12—C13—C14—C15 | 179.0 (7) | C34—C33—C38—C37 | −3.5 (10) |
C13—C14—C15—C16 | 0.0 (11) | C32—C33—C38—C37 | 177.1 (7) |
C14—C15—C16—O3 | −179.0 (6) | C2—C1—N1—O2 | −169.9 (7) |
C14—C15—C16—C17 | 0.3 (10) | C6—C1—N1—O2 | 8.0 (10) |
O3—C16—C17—C18 | 178.5 (7) | C2—C1—N1—O1 | 12.1 (10) |
C15—C16—C17—C18 | −0.8 (11) | C6—C1—N1—O1 | −170.1 (7) |
C16—C17—C18—C13 | 1.1 (11) | C26—C21—N2—O4 | 166.6 (7) |
C14—C13—C18—C17 | −0.8 (10) | C22—C21—N2—O4 | −16.5 (10) |
C12—C13—C18—C17 | −179.5 (7) | C26—C21—N2—O5 | −12.0 (10) |
C26—C21—C22—C23 | −0.5 (10) | C22—C21—N2—O5 | 164.8 (6) |
N2—C21—C22—C23 | −177.2 (6) | C15—C16—O3—C19 | 3.0 (10) |
C21—C22—C23—C24 | 2.5 (10) | C17—C16—O3—C19 | −176.2 (6) |
C22—C23—C24—C25 | −4.4 (10) | C20—C19—O3—C16 | 178.7 (7) |
C22—C23—C24—C27 | 179.1 (6) | C35—C36—O6—C39 | −2.2 (10) |
C23—C24—C25—C26 | 4.3 (10) | C37—C36—O6—C39 | 178.3 (7) |
C27—C24—C25—C26 | −179.3 (6) | C40—C39—O6—C36 | −176.2 (8) |
C21H21NO3 | F(000) = 712 |
Mr = 335.39 | Dx = 1.251 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5309 reflections |
a = 15.3615 (11) Å | θ = 2.4–28.3° |
b = 6.8341 (5) Å | µ = 0.08 mm−1 |
c = 17.6625 (12) Å | T = 223 K |
β = 106.215 (1)° | Rectangular, red |
V = 1780.5 (2) Å3 | 0.45 × 0.20 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 4007 independent reflections |
Radiation source: rotating unit | 3307 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 8.366 pixels mm-1 | θmax = 28.3°, θmin = 1.4° |
ϕ and ω scans | h = −19→20 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −9→8 |
Tmin = 0.873, Tmax = 0.984 | l = −19→23 |
10440 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0623P)2 + 0.288P] where P = (Fo2 + 2Fc2)/3 |
4007 reflections | (Δ/σ)max < 0.001 |
227 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C21H21NO3 | V = 1780.5 (2) Å3 |
Mr = 335.39 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.3615 (11) Å | µ = 0.08 mm−1 |
b = 6.8341 (5) Å | T = 223 K |
c = 17.6625 (12) Å | 0.45 × 0.20 × 0.20 mm |
β = 106.215 (1)° |
Bruker SMART CCD area-detector diffractometer | 4007 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3307 reflections with I > 2σ(I) |
Tmin = 0.873, Tmax = 0.984 | Rint = 0.023 |
10440 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.21 e Å−3 |
4007 reflections | Δρmin = −0.23 e Å−3 |
227 parameters |
Experimental. Sheldrick, G. M. (1996). SADABS, program for scaling and correction of area detector data. University of Göttingen, Germany. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.17887 (8) | 0.68308 (18) | 0.40969 (7) | 0.0405 (3) | |
C2 | −0.20386 (8) | 0.87765 (19) | 0.40620 (7) | 0.0429 (3) | |
H2 | −0.2493 | 0.9265 | 0.3630 | 0.052* | |
C3 | −0.16058 (7) | 0.99830 (18) | 0.46754 (7) | 0.0402 (3) | |
H3 | −0.1768 | 1.1312 | 0.4655 | 0.048* | |
C4 | −0.09321 (7) | 0.92933 (16) | 0.53273 (6) | 0.0345 (2) | |
C5 | −0.07023 (8) | 0.73096 (17) | 0.53382 (7) | 0.0409 (3) | |
H5 | −0.0254 | 0.6804 | 0.5771 | 0.049* | |
C6 | −0.11210 (9) | 0.60887 (18) | 0.47269 (7) | 0.0438 (3) | |
H6 | −0.0955 | 0.4763 | 0.4737 | 0.053* | |
C7 | −0.05072 (7) | 1.06399 (17) | 0.59595 (6) | 0.0364 (2) | |
H7 | −0.0745 | 1.1916 | 0.5919 | 0.044* | |
C8 | 0.01881 (7) | 1.02554 (17) | 0.65954 (6) | 0.0361 (2) | |
H8 | 0.0441 | 0.8993 | 0.6650 | 0.043* | |
C9 | 0.05648 (7) | 1.16771 (17) | 0.71968 (6) | 0.0378 (2) | |
H9 | 0.0322 | 1.2948 | 0.7115 | 0.045* | |
C10 | 0.12334 (7) | 1.13672 (17) | 0.78683 (7) | 0.0386 (3) | |
H10 | 0.1406 | 1.2448 | 0.8206 | 0.046* | |
C11 | 0.17121 (7) | 0.95658 (17) | 0.81245 (7) | 0.0385 (3) | |
H11 | 0.1610 | 0.8493 | 0.7778 | 0.046* | |
C12 | 0.23005 (7) | 0.93722 (17) | 0.88440 (7) | 0.0385 (3) | |
H12 | 0.2393 | 1.0496 | 0.9163 | 0.046* | |
C13 | 0.28125 (7) | 0.76450 (16) | 0.91922 (7) | 0.0366 (2) | |
C14 | 0.33490 (8) | 0.77312 (18) | 0.99706 (7) | 0.0430 (3) | |
H14 | 0.3386 | 0.8918 | 1.0247 | 0.052* | |
C15 | 0.38306 (8) | 0.61317 (18) | 1.03520 (7) | 0.0431 (3) | |
H15 | 0.4186 | 0.6237 | 1.0878 | 0.052* | |
C16 | 0.37845 (7) | 0.43777 (17) | 0.99523 (7) | 0.0381 (3) | |
C17 | 0.32796 (8) | 0.42800 (17) | 0.91590 (7) | 0.0393 (3) | |
H17 | 0.3269 | 0.3112 | 0.8875 | 0.047* | |
C18 | 0.28010 (8) | 0.58754 (17) | 0.87928 (7) | 0.0389 (3) | |
H18 | 0.2458 | 0.5777 | 0.8263 | 0.047* | |
C19 | 0.47326 (8) | 0.27455 (18) | 1.10809 (7) | 0.0431 (3) | |
H19A | 0.4354 | 0.3147 | 1.1417 | 0.052* | |
H19B | 0.5223 | 0.3702 | 1.1143 | 0.052* | |
C20 | 0.51229 (9) | 0.0758 (2) | 1.13229 (8) | 0.0511 (3) | |
H20A | 0.5467 | 0.0327 | 1.0962 | 0.061* | |
H20B | 0.4630 | −0.0178 | 1.1287 | 0.061* | |
C21 | 0.57402 (10) | 0.0784 (2) | 1.21601 (9) | 0.0634 (4) | |
H21A | 0.6227 | 0.1716 | 1.2197 | 0.095* | |
H21B | 0.5994 | −0.0510 | 1.2299 | 0.095* | |
H21C | 0.5394 | 0.1163 | 1.2519 | 0.095* | |
N1 | −0.22321 (8) | 0.55365 (18) | 0.34488 (6) | 0.0530 (3) | |
O1 | −0.29183 (7) | 0.61106 (19) | 0.29632 (7) | 0.0761 (4) | |
O2 | −0.18905 (9) | 0.39308 (17) | 0.34138 (6) | 0.0775 (4) | |
O3 | 0.41971 (6) | 0.26844 (12) | 1.02721 (5) | 0.0447 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0431 (6) | 0.0442 (6) | 0.0348 (6) | −0.0008 (5) | 0.0120 (5) | −0.0042 (5) |
C2 | 0.0394 (6) | 0.0495 (7) | 0.0370 (6) | 0.0090 (5) | 0.0059 (5) | −0.0002 (5) |
C3 | 0.0402 (6) | 0.0390 (6) | 0.0399 (6) | 0.0098 (5) | 0.0088 (5) | 0.0005 (5) |
C4 | 0.0347 (5) | 0.0379 (6) | 0.0325 (5) | 0.0032 (4) | 0.0121 (4) | 0.0010 (4) |
C5 | 0.0483 (6) | 0.0385 (6) | 0.0340 (6) | 0.0070 (5) | 0.0081 (5) | 0.0034 (5) |
C6 | 0.0562 (7) | 0.0354 (6) | 0.0392 (6) | 0.0053 (5) | 0.0121 (5) | 0.0008 (5) |
C7 | 0.0390 (5) | 0.0355 (6) | 0.0360 (6) | 0.0043 (4) | 0.0127 (4) | 0.0007 (4) |
C8 | 0.0399 (5) | 0.0347 (6) | 0.0347 (5) | 0.0029 (4) | 0.0122 (4) | 0.0018 (4) |
C9 | 0.0424 (6) | 0.0338 (6) | 0.0377 (6) | 0.0021 (4) | 0.0122 (5) | 0.0007 (4) |
C10 | 0.0433 (6) | 0.0362 (6) | 0.0362 (6) | −0.0031 (5) | 0.0107 (5) | −0.0033 (4) |
C11 | 0.0410 (6) | 0.0366 (6) | 0.0363 (6) | −0.0029 (5) | 0.0082 (5) | −0.0011 (4) |
C12 | 0.0399 (6) | 0.0363 (6) | 0.0376 (6) | −0.0070 (4) | 0.0082 (5) | −0.0013 (4) |
C13 | 0.0348 (5) | 0.0371 (6) | 0.0356 (6) | −0.0073 (4) | 0.0058 (4) | 0.0023 (4) |
C14 | 0.0470 (6) | 0.0370 (6) | 0.0386 (6) | −0.0076 (5) | 0.0017 (5) | −0.0034 (5) |
C15 | 0.0449 (6) | 0.0418 (6) | 0.0343 (6) | −0.0071 (5) | −0.0027 (5) | 0.0002 (5) |
C16 | 0.0358 (5) | 0.0394 (6) | 0.0366 (6) | −0.0051 (4) | 0.0061 (4) | 0.0033 (5) |
C17 | 0.0426 (6) | 0.0389 (6) | 0.0343 (6) | −0.0052 (5) | 0.0071 (5) | −0.0019 (4) |
C18 | 0.0404 (6) | 0.0427 (6) | 0.0303 (5) | −0.0063 (5) | 0.0044 (4) | −0.0001 (4) |
C19 | 0.0421 (6) | 0.0460 (7) | 0.0356 (6) | −0.0059 (5) | 0.0015 (5) | 0.0038 (5) |
C20 | 0.0507 (7) | 0.0500 (8) | 0.0459 (7) | 0.0010 (6) | 0.0024 (6) | 0.0076 (6) |
C21 | 0.0630 (8) | 0.0682 (10) | 0.0487 (8) | 0.0002 (7) | −0.0014 (7) | 0.0179 (7) |
N1 | 0.0642 (7) | 0.0516 (7) | 0.0402 (6) | −0.0015 (5) | 0.0099 (5) | −0.0085 (5) |
O1 | 0.0662 (7) | 0.0855 (8) | 0.0591 (7) | 0.0083 (6) | −0.0112 (5) | −0.0247 (6) |
O2 | 0.1151 (9) | 0.0488 (6) | 0.0550 (6) | 0.0114 (6) | 0.0010 (6) | −0.0145 (5) |
O3 | 0.0494 (5) | 0.0407 (5) | 0.0370 (4) | 0.0009 (4) | 0.0005 (4) | 0.0028 (3) |
C1—C2 | 1.3806 (18) | C13—C14 | 1.3928 (16) |
C1—C6 | 1.3821 (17) | C13—C18 | 1.3977 (16) |
C1—N1 | 1.4565 (16) | C14—C15 | 1.3848 (17) |
C2—C3 | 1.3760 (17) | C14—H14 | 0.9400 |
C2—H2 | 0.9400 | C15—C16 | 1.3829 (17) |
C3—C4 | 1.3977 (15) | C15—H15 | 0.9400 |
C3—H3 | 0.9400 | C16—O3 | 1.3638 (14) |
C4—C5 | 1.3996 (16) | C16—C17 | 1.4009 (16) |
C4—C7 | 1.4535 (15) | C17—C18 | 1.3719 (16) |
C5—C6 | 1.3739 (17) | C17—H17 | 0.9400 |
C5—H5 | 0.9400 | C18—H18 | 0.9400 |
C6—H6 | 0.9400 | C19—O3 | 1.4362 (14) |
C7—C8 | 1.3422 (15) | C19—C20 | 1.4980 (18) |
C7—H7 | 0.9400 | C19—H19A | 0.9800 |
C8—C9 | 1.4366 (16) | C19—H19B | 0.9800 |
C8—H8 | 0.9400 | C20—C21 | 1.5176 (19) |
C9—C10 | 1.3514 (16) | C20—H20A | 0.9800 |
C9—H9 | 0.9400 | C20—H20B | 0.9800 |
C10—C11 | 1.4405 (16) | C21—H21A | 0.9700 |
C10—H10 | 0.9400 | C21—H21B | 0.9700 |
C11—C12 | 1.3446 (15) | C21—H21C | 0.9700 |
C11—H11 | 0.9400 | N1—O1 | 1.2230 (15) |
C12—C13 | 1.4560 (16) | N1—O2 | 1.2253 (16) |
C12—H12 | 0.9400 | ||
C2—C1—C6 | 121.60 (11) | C18—C13—C12 | 123.99 (10) |
C2—C1—N1 | 119.13 (11) | C15—C14—C13 | 122.36 (11) |
C6—C1—N1 | 119.27 (11) | C15—C14—H14 | 118.8 |
C3—C2—C1 | 118.35 (11) | C13—C14—H14 | 118.8 |
C3—C2—H2 | 120.8 | C16—C15—C14 | 119.45 (11) |
C1—C2—H2 | 120.8 | C16—C15—H15 | 120.3 |
C2—C3—C4 | 122.03 (11) | C14—C15—H15 | 120.3 |
C2—C3—H3 | 119.0 | O3—C16—C15 | 124.92 (10) |
C4—C3—H3 | 119.0 | O3—C16—C17 | 115.93 (10) |
C3—C4—C5 | 117.63 (10) | C15—C16—C17 | 119.15 (11) |
C3—C4—C7 | 119.32 (10) | C18—C17—C16 | 120.51 (11) |
C5—C4—C7 | 123.05 (10) | C18—C17—H17 | 119.7 |
C6—C5—C4 | 121.10 (11) | C16—C17—H17 | 119.7 |
C6—C5—H5 | 119.4 | C17—C18—C13 | 121.34 (10) |
C4—C5—H5 | 119.4 | C17—C18—H18 | 119.3 |
C5—C6—C1 | 119.28 (11) | C13—C18—H18 | 119.3 |
C5—C6—H6 | 120.4 | O3—C19—C20 | 109.26 (10) |
C1—C6—H6 | 120.4 | O3—C19—H19A | 109.8 |
C8—C7—C4 | 126.91 (11) | C20—C19—H19A | 109.8 |
C8—C7—H7 | 116.5 | O3—C19—H19B | 109.8 |
C4—C7—H7 | 116.5 | C20—C19—H19B | 109.8 |
C7—C8—C9 | 123.26 (11) | H19A—C19—H19B | 108.3 |
C7—C8—H8 | 118.4 | C19—C20—C21 | 111.03 (12) |
C9—C8—H8 | 118.4 | C19—C20—H20A | 109.4 |
C10—C9—C8 | 126.40 (11) | C21—C20—H20A | 109.4 |
C10—C9—H9 | 116.8 | C19—C20—H20B | 109.4 |
C8—C9—H9 | 116.8 | C21—C20—H20B | 109.4 |
C9—C10—C11 | 127.29 (11) | H20A—C20—H20B | 108.0 |
C9—C10—H10 | 116.4 | C20—C21—H21A | 109.5 |
C11—C10—H10 | 116.4 | C20—C21—H21B | 109.5 |
C12—C11—C10 | 122.04 (11) | H21A—C21—H21B | 109.5 |
C12—C11—H11 | 119.0 | C20—C21—H21C | 109.5 |
C10—C11—H11 | 119.0 | H21A—C21—H21C | 109.5 |
C11—C12—C13 | 128.34 (11) | H21B—C21—H21C | 109.5 |
C11—C12—H12 | 115.8 | O1—N1—O2 | 123.32 (12) |
C13—C12—H12 | 115.8 | O1—N1—C1 | 118.60 (12) |
C14—C13—C18 | 117.09 (10) | O2—N1—C1 | 118.08 (11) |
C14—C13—C12 | 118.92 (10) | C16—O3—C19 | 117.27 (9) |
C6—C1—C2—C3 | −0.11 (18) | C18—C13—C14—C15 | −2.19 (18) |
N1—C1—C2—C3 | −179.30 (11) | C12—C13—C14—C15 | 177.69 (11) |
C1—C2—C3—C4 | −0.43 (18) | C13—C14—C15—C16 | 0.12 (19) |
C2—C3—C4—C5 | 0.29 (17) | C14—C15—C16—O3 | −177.26 (11) |
C2—C3—C4—C7 | −179.40 (10) | C14—C15—C16—C17 | 2.54 (18) |
C3—C4—C5—C6 | 0.39 (17) | O3—C16—C17—C18 | 176.71 (10) |
C7—C4—C5—C6 | −179.92 (11) | C15—C16—C17—C18 | −3.11 (17) |
C4—C5—C6—C1 | −0.91 (18) | C16—C17—C18—C13 | 0.99 (17) |
C2—C1—C6—C5 | 0.78 (18) | C14—C13—C18—C17 | 1.61 (17) |
N1—C1—C6—C5 | 179.96 (11) | C12—C13—C18—C17 | −178.26 (10) |
C3—C4—C7—C8 | −175.01 (11) | O3—C19—C20—C21 | 176.62 (11) |
C5—C4—C7—C8 | 5.31 (18) | C2—C1—N1—O1 | −12.90 (18) |
C4—C7—C8—C9 | −179.65 (10) | C6—C1—N1—O1 | 167.89 (12) |
C7—C8—C9—C10 | 176.68 (11) | C2—C1—N1—O2 | 166.30 (13) |
C8—C9—C10—C11 | 0.23 (19) | C6—C1—N1—O2 | −12.90 (18) |
C9—C10—C11—C12 | −172.82 (11) | C15—C16—O3—C19 | −1.22 (17) |
C10—C11—C12—C13 | 178.20 (10) | C17—C16—O3—C19 | 178.98 (9) |
C11—C12—C13—C14 | −176.22 (11) | C20—C19—O3—C16 | 179.74 (10) |
C11—C12—C13—C18 | 3.65 (19) |
C22H23NO3 | F(000) = 744 |
Mr = 349.41 | Dx = 1.222 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5402 reflections |
a = 17.0571 (10) Å | θ = 2.4–28.1° |
b = 6.7244 (4) Å | µ = 0.08 mm−1 |
c = 17.2095 (10) Å | T = 183 K |
β = 105.884 (1)° | Rectangular, orange |
V = 1898.54 (19) Å3 | 0.40 × 0.15 × 0.04 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 4309 independent reflections |
Radiation source: rotating unit | 3596 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 8.366 pixels mm-1 | θmax = 28.2°, θmin = 2.4° |
ϕ and ω scans | h = −21→20 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −8→4 |
Tmin = 0.888, Tmax = 0.997 | l = −20→21 |
11363 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0687P)2 + 0.3548P] where P = (Fo2 + 2Fc2)/3 |
4309 reflections | (Δ/σ)max = 0.001 |
236 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C22H23NO3 | V = 1898.54 (19) Å3 |
Mr = 349.41 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.0571 (10) Å | µ = 0.08 mm−1 |
b = 6.7244 (4) Å | T = 183 K |
c = 17.2095 (10) Å | 0.40 × 0.15 × 0.04 mm |
β = 105.884 (1)° |
Bruker SMART CCD area-detector diffractometer | 4309 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3596 reflections with I > 2σ(I) |
Tmin = 0.888, Tmax = 0.997 | Rint = 0.019 |
11363 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.21 e Å−3 |
4309 reflections | Δρmin = −0.26 e Å−3 |
236 parameters |
Experimental. Sheldrick, G. M. (1996). SADABS, program for scaling and correction of area detector data. University of Göttingen, Germany. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.66312 (7) | 0.82779 (19) | 0.58353 (7) | 0.0379 (3) | |
C2 | 0.69457 (8) | 0.6376 (2) | 0.58700 (8) | 0.0447 (3) | |
H2 | 0.7407 | 0.5999 | 0.6294 | 0.054* | |
C3 | 0.65767 (8) | 0.50399 (19) | 0.52772 (7) | 0.0416 (3) | |
H3 | 0.6790 | 0.3730 | 0.5296 | 0.050* | |
C4 | 0.58955 (7) | 0.55577 (17) | 0.46470 (7) | 0.0335 (2) | |
C5 | 0.56058 (7) | 0.75163 (18) | 0.46264 (7) | 0.0360 (3) | |
H5 | 0.5152 | 0.7916 | 0.4198 | 0.043* | |
C6 | 0.59677 (7) | 0.88668 (18) | 0.52161 (7) | 0.0373 (3) | |
H6 | 0.5765 | 1.0186 | 0.5198 | 0.045* | |
C7 | 0.55240 (7) | 0.40636 (17) | 0.40463 (7) | 0.0360 (3) | |
H7 | 0.5786 | 0.2805 | 0.4095 | 0.043* | |
C8 | 0.48492 (7) | 0.42851 (17) | 0.34316 (7) | 0.0355 (3) | |
H8 | 0.4576 | 0.5530 | 0.3371 | 0.043* | |
C9 | 0.45174 (7) | 0.27339 (18) | 0.28592 (7) | 0.0376 (3) | |
H9 | 0.4769 | 0.1464 | 0.2961 | 0.045* | |
C10 | 0.38838 (7) | 0.29124 (18) | 0.21929 (7) | 0.0379 (3) | |
H10 | 0.3730 | 0.1748 | 0.1875 | 0.045* | |
C11 | 0.34151 (7) | 0.46822 (18) | 0.19116 (7) | 0.0378 (3) | |
H11 | 0.3496 | 0.5815 | 0.2254 | 0.045* | |
C12 | 0.28687 (7) | 0.47921 (18) | 0.11832 (7) | 0.0370 (3) | |
H12 | 0.2796 | 0.3626 | 0.0859 | 0.044* | |
C13 | 0.23756 (7) | 0.65117 (18) | 0.08378 (7) | 0.0356 (3) | |
C14 | 0.19030 (7) | 0.64741 (19) | 0.00360 (7) | 0.0406 (3) | |
H14 | 0.1911 | 0.5319 | −0.0280 | 0.049* | |
C15 | 0.14211 (8) | 0.8074 (2) | −0.03142 (8) | 0.0435 (3) | |
H15 | 0.1110 | 0.8014 | −0.0864 | 0.052* | |
C16 | 0.13960 (8) | 0.97538 (19) | 0.01405 (8) | 0.0426 (3) | |
C17 | 0.18606 (8) | 0.9823 (2) | 0.09453 (8) | 0.0453 (3) | |
H17 | 0.1845 | 1.0973 | 0.1261 | 0.054* | |
C18 | 0.23406 (8) | 0.82371 (19) | 0.12820 (7) | 0.0417 (3) | |
H18 | 0.2656 | 0.8312 | 0.1829 | 0.050* | |
C19 | 0.04326 (9) | 1.1428 (2) | −0.09347 (8) | 0.0521 (3) | |
H19A | 0.0044 | 1.0302 | −0.1026 | 0.063* | |
H19B | 0.0772 | 1.1305 | −0.1316 | 0.063* | |
C20 | −0.00246 (9) | 1.3378 (2) | −0.10661 (9) | 0.0545 (4) | |
H20A | −0.0383 | 1.3442 | −0.0701 | 0.065* | |
H20B | 0.0372 | 1.4485 | −0.0922 | 0.065* | |
C21 | −0.05353 (11) | 1.3651 (3) | −0.19259 (10) | 0.0738 (5) | |
H21A | −0.0918 | 1.2519 | −0.2080 | 0.089* | |
H21B | −0.0176 | 1.3652 | −0.2291 | 0.089* | |
C22 | −0.10171 (11) | 1.5589 (3) | −0.20315 (12) | 0.0838 (6) | |
H22A | −0.1367 | 1.5601 | −0.1665 | 0.126* | |
H22B | −0.1355 | 1.5697 | −0.2591 | 0.126* | |
H22C | −0.0639 | 1.6715 | −0.1907 | 0.126* | |
N1 | 0.70014 (7) | 0.97044 (18) | 0.64688 (7) | 0.0492 (3) | |
O1 | 0.76613 (8) | 0.9295 (2) | 0.69331 (7) | 0.0785 (4) | |
O2 | 0.66309 (7) | 1.12423 (15) | 0.65132 (6) | 0.0616 (3) | |
O3 | 0.09348 (6) | 1.14076 (15) | −0.01225 (6) | 0.0558 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0412 (6) | 0.0404 (6) | 0.0327 (6) | 0.0011 (5) | 0.0112 (5) | 0.0004 (5) |
C2 | 0.0418 (6) | 0.0485 (7) | 0.0392 (6) | 0.0107 (5) | 0.0035 (5) | 0.0037 (5) |
C3 | 0.0433 (6) | 0.0389 (6) | 0.0415 (6) | 0.0118 (5) | 0.0096 (5) | 0.0042 (5) |
C4 | 0.0361 (5) | 0.0360 (6) | 0.0315 (5) | 0.0056 (5) | 0.0145 (4) | 0.0050 (4) |
C5 | 0.0382 (6) | 0.0371 (6) | 0.0324 (6) | 0.0079 (5) | 0.0093 (4) | 0.0039 (4) |
C6 | 0.0431 (6) | 0.0347 (6) | 0.0354 (6) | 0.0069 (5) | 0.0127 (5) | 0.0037 (5) |
C7 | 0.0429 (6) | 0.0318 (6) | 0.0365 (6) | 0.0064 (5) | 0.0166 (5) | 0.0045 (4) |
C8 | 0.0416 (6) | 0.0329 (6) | 0.0353 (6) | 0.0038 (5) | 0.0162 (5) | 0.0028 (4) |
C9 | 0.0457 (6) | 0.0321 (6) | 0.0387 (6) | 0.0042 (5) | 0.0175 (5) | 0.0014 (5) |
C10 | 0.0450 (6) | 0.0341 (6) | 0.0378 (6) | −0.0004 (5) | 0.0171 (5) | −0.0030 (5) |
C11 | 0.0410 (6) | 0.0349 (6) | 0.0392 (6) | −0.0009 (5) | 0.0141 (5) | −0.0033 (5) |
C12 | 0.0378 (6) | 0.0358 (6) | 0.0395 (6) | −0.0033 (5) | 0.0138 (5) | −0.0040 (5) |
C13 | 0.0336 (6) | 0.0363 (6) | 0.0374 (6) | −0.0050 (5) | 0.0108 (4) | −0.0012 (5) |
C14 | 0.0371 (6) | 0.0429 (7) | 0.0409 (6) | −0.0038 (5) | 0.0090 (5) | −0.0070 (5) |
C15 | 0.0389 (6) | 0.0500 (7) | 0.0383 (6) | −0.0033 (5) | 0.0052 (5) | −0.0016 (5) |
C16 | 0.0414 (6) | 0.0385 (6) | 0.0453 (7) | −0.0019 (5) | 0.0076 (5) | 0.0040 (5) |
C17 | 0.0522 (7) | 0.0370 (6) | 0.0431 (7) | −0.0016 (5) | 0.0070 (6) | −0.0043 (5) |
C18 | 0.0465 (7) | 0.0392 (6) | 0.0360 (6) | −0.0019 (5) | 0.0059 (5) | −0.0023 (5) |
C19 | 0.0496 (8) | 0.0602 (9) | 0.0433 (7) | 0.0073 (6) | 0.0072 (6) | 0.0050 (6) |
C20 | 0.0507 (8) | 0.0525 (8) | 0.0576 (8) | 0.0036 (6) | 0.0100 (6) | 0.0116 (7) |
C21 | 0.0629 (10) | 0.1044 (15) | 0.0563 (9) | 0.0327 (10) | 0.0202 (8) | 0.0215 (9) |
C22 | 0.0665 (11) | 0.1091 (16) | 0.0836 (12) | 0.0365 (11) | 0.0341 (9) | 0.0475 (12) |
N1 | 0.0572 (7) | 0.0494 (7) | 0.0377 (6) | −0.0008 (5) | 0.0076 (5) | −0.0020 (5) |
O1 | 0.0676 (7) | 0.0828 (9) | 0.0645 (7) | 0.0102 (6) | −0.0167 (6) | −0.0209 (6) |
O2 | 0.0853 (8) | 0.0427 (6) | 0.0500 (6) | 0.0064 (5) | 0.0068 (5) | −0.0070 (4) |
O3 | 0.0639 (6) | 0.0435 (5) | 0.0494 (6) | 0.0067 (4) | −0.0024 (5) | 0.0027 (4) |
C1—C2 | 1.3815 (18) | C13—C18 | 1.3997 (17) |
C1—C6 | 1.3831 (16) | C14—C15 | 1.3875 (18) |
C1—N1 | 1.4597 (16) | C14—H14 | 0.9500 |
C2—C3 | 1.3759 (18) | C15—C16 | 1.3815 (19) |
C2—H2 | 0.9500 | C15—H15 | 0.9500 |
C3—C4 | 1.3991 (16) | C16—O3 | 1.3658 (16) |
C3—H3 | 0.9500 | C16—C17 | 1.3957 (17) |
C4—C5 | 1.4038 (16) | C17—C18 | 1.3727 (18) |
C4—C7 | 1.4564 (17) | C17—H17 | 0.9500 |
C5—C6 | 1.3759 (17) | C18—H18 | 0.9500 |
C5—H5 | 0.9500 | C19—O3 | 1.4257 (16) |
C6—H6 | 0.9500 | C19—C20 | 1.511 (2) |
C7—C8 | 1.3415 (16) | C19—H19A | 0.9900 |
C7—H7 | 0.9500 | C19—H19B | 0.9900 |
C8—C9 | 1.4400 (17) | C20—C21 | 1.509 (2) |
C8—H8 | 0.9500 | C20—H20A | 0.9900 |
C9—C10 | 1.3486 (17) | C20—H20B | 0.9900 |
C9—H9 | 0.9500 | C21—C22 | 1.525 (3) |
C10—C11 | 1.4415 (17) | C21—H21A | 0.9900 |
C10—H10 | 0.9500 | C21—H21B | 0.9900 |
C11—C12 | 1.3438 (17) | C22—H22A | 0.9800 |
C11—H11 | 0.9500 | C22—H22B | 0.9800 |
C12—C13 | 1.4575 (17) | C22—H22C | 0.9800 |
C12—H12 | 0.9500 | N1—O1 | 1.2203 (15) |
C13—C14 | 1.3948 (16) | N1—O2 | 1.2252 (16) |
C2—C1—C6 | 121.63 (12) | C13—C14—H14 | 119.0 |
C2—C1—N1 | 119.50 (11) | C16—C15—C14 | 119.64 (11) |
C6—C1—N1 | 118.86 (11) | C16—C15—H15 | 120.2 |
C3—C2—C1 | 118.63 (11) | C14—C15—H15 | 120.2 |
C3—C2—H2 | 120.7 | O3—C16—C15 | 125.63 (12) |
C1—C2—H2 | 120.7 | O3—C16—C17 | 114.87 (12) |
C2—C3—C4 | 121.77 (11) | C15—C16—C17 | 119.49 (12) |
C2—C3—H3 | 119.1 | C18—C17—C16 | 120.26 (12) |
C4—C3—H3 | 119.1 | C18—C17—H17 | 119.9 |
C3—C4—C5 | 117.71 (11) | C16—C17—H17 | 119.9 |
C3—C4—C7 | 119.09 (11) | C17—C18—C13 | 121.55 (11) |
C5—C4—C7 | 123.19 (10) | C17—C18—H18 | 119.2 |
C6—C5—C4 | 121.12 (11) | C13—C18—H18 | 119.2 |
C6—C5—H5 | 119.4 | O3—C19—C20 | 107.60 (12) |
C4—C5—H5 | 119.4 | O3—C19—H19A | 110.2 |
C5—C6—C1 | 119.13 (11) | C20—C19—H19A | 110.2 |
C5—C6—H6 | 120.4 | O3—C19—H19B | 110.2 |
C1—C6—H6 | 120.4 | C20—C19—H19B | 110.2 |
C8—C7—C4 | 126.58 (11) | H19A—C19—H19B | 108.5 |
C8—C7—H7 | 116.7 | C21—C20—C19 | 112.84 (14) |
C4—C7—H7 | 116.7 | C21—C20—H20A | 109.0 |
C7—C8—C9 | 123.43 (11) | C19—C20—H20A | 109.0 |
C7—C8—H8 | 118.3 | C21—C20—H20B | 109.0 |
C9—C8—H8 | 118.3 | C19—C20—H20B | 109.0 |
C10—C9—C8 | 126.20 (11) | H20A—C20—H20B | 107.8 |
C10—C9—H9 | 116.9 | C20—C21—C22 | 111.61 (16) |
C8—C9—H9 | 116.9 | C20—C21—H21A | 109.3 |
C9—C10—C11 | 126.92 (11) | C22—C21—H21A | 109.3 |
C9—C10—H10 | 116.5 | C20—C21—H21B | 109.3 |
C11—C10—H10 | 116.5 | C22—C21—H21B | 109.3 |
C12—C11—C10 | 122.55 (11) | H21A—C21—H21B | 108.0 |
C12—C11—H11 | 118.7 | C21—C22—H22A | 109.5 |
C10—C11—H11 | 118.7 | C21—C22—H22B | 109.5 |
C11—C12—C13 | 126.84 (11) | H22A—C22—H22B | 109.5 |
C11—C12—H12 | 116.6 | C21—C22—H22C | 109.5 |
C13—C12—H12 | 116.6 | H22A—C22—H22C | 109.5 |
C14—C13—C18 | 117.12 (11) | H22B—C22—H22C | 109.5 |
C14—C13—C12 | 120.12 (11) | O1—N1—O2 | 123.29 (12) |
C18—C13—C12 | 122.75 (11) | O1—N1—C1 | 118.27 (12) |
C15—C14—C13 | 121.93 (12) | O2—N1—C1 | 118.44 (11) |
C15—C14—H14 | 119.0 | C16—O3—C19 | 118.02 (11) |
C6—C1—C2—C3 | −1.0 (2) | C18—C13—C14—C15 | 0.43 (18) |
N1—C1—C2—C3 | 178.52 (11) | C12—C13—C14—C15 | 179.56 (11) |
C1—C2—C3—C4 | −0.1 (2) | C13—C14—C15—C16 | −0.74 (19) |
C2—C3—C4—C5 | 1.34 (18) | C14—C15—C16—O3 | −178.39 (12) |
C2—C3—C4—C7 | −178.90 (11) | C14—C15—C16—C17 | 0.43 (19) |
C3—C4—C5—C6 | −1.47 (17) | O3—C16—C17—C18 | 179.11 (12) |
C7—C4—C5—C6 | 178.77 (10) | C15—C16—C17—C18 | 0.2 (2) |
C4—C5—C6—C1 | 0.41 (18) | C16—C17—C18—C13 | −0.5 (2) |
C2—C1—C6—C5 | 0.87 (18) | C14—C13—C18—C17 | 0.18 (18) |
N1—C1—C6—C5 | −178.66 (10) | C12—C13—C18—C17 | −178.93 (12) |
C3—C4—C7—C8 | 176.45 (11) | O3—C19—C20—C21 | 175.82 (13) |
C5—C4—C7—C8 | −3.80 (18) | C19—C20—C21—C22 | 177.56 (14) |
C4—C7—C8—C9 | 179.96 (10) | C2—C1—N1—O1 | 12.57 (19) |
C7—C8—C9—C10 | −174.14 (11) | C6—C1—N1—O1 | −167.89 (13) |
C8—C9—C10—C11 | 0.7 (2) | C2—C1—N1—O2 | −166.69 (13) |
C9—C10—C11—C12 | 170.46 (12) | C6—C1—N1—O2 | 12.85 (18) |
C10—C11—C12—C13 | −178.94 (11) | C15—C16—O3—C19 | 0.0 (2) |
C11—C12—C13—C14 | 172.53 (11) | C17—C16—O3—C19 | −178.88 (12) |
C11—C12—C13—C18 | −8.39 (19) | C20—C19—O3—C16 | 178.64 (11) |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C19H17NO3 | C20H19NO3 | C21H21NO3 | C22H23NO3 |
Mr | 307.34 | 321.36 | 335.39 | 349.41 |
Crystal system, space group | Orthorhombic, Pbcn | Orthorhombic, Pca21 | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 183 | 183 | 223 | 183 |
a, b, c (Å) | 13.0541 (11), 6.9672 (6), 34.604 (3) | 18.914 (9), 6.880 (3), 25.927 (11) | 15.3615 (11), 6.8341 (5), 17.6625 (12) | 17.0571 (10), 6.7244 (4), 17.2095 (10) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 106.215 (1), 90 | 90, 105.884 (1), 90 |
V (Å3) | 3147.2 (5) | 3374 (3) | 1780.5 (2) | 1898.54 (19) |
Z | 8 | 8 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 | 0.08 | 0.08 |
Crystal size (mm) | 0.30 × 0.10 × 0.04 | 0.30 × 0.10 × 0.03 | 0.45 × 0.20 × 0.20 | 0.40 × 0.15 × 0.04 |
Data collection | ||||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.914, 0.997 | 0.933, 0.998 | 0.873, 0.984 | 0.888, 0.997 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18236, 3715, 2905 | 11787, 2972, 1583 | 10440, 4007, 3307 | 11363, 4309, 3596 |
Rint | 0.026 | 0.135 | 0.023 | 0.019 |
(sin θ/λ)max (Å−1) | 0.666 | 0.595 | 0.666 | 0.666 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.136, 1.07 | 0.064, 0.155, 0.92 | 0.041, 0.116, 1.03 | 0.046, 0.130, 1.05 |
No. of reflections | 3715 | 2972 | 4007 | 4309 |
No. of parameters | 209 | 435 | 227 | 236 |
No. of restraints | 0 | 1 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.19 | 0.19, −0.20 | 0.21, −0.23 | 0.21, −0.26 |
Computer programs: SMART (Bruker, 2001), SMART [or SAINT?], SMART, SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2000), SHELXTL.
(I) | (II) | (III) | (IV) | |
C4—C7 | 1.455 (2) | 1.459 (10) | 1.4535 (15) | 1.4564 (17) |
C7—C8 | 1.339 (2) | 1.347 (10) | 1.3422 (15) | 1.3415 (16) |
C8—C9 | 1.4369 (19) | 1.447 (10) | 1.4366 (16) | 1.4400 (17) |
C9—C10 | 1.345 (2) | 1.348 (10) | 1.3514 (16) | 1.3486 (17) |
C10—C11 | 1.4397 (19) | 1.446 (10) | 1.4405 (16) | 1.4415 (17) |
C11—C12 | 1.3367 (18) | 1.347 (10) | 1.3446 (15) | 1.3438 (17) |
C12—C13 | 1.4582 (19) | 1.449 (10) | 1.4560 (16) | 1.4575 (17) |
C24—C27 | 1.472 (10) | |||
C27—C28 | 1.345 (10) | |||
C28—C29 | 1.421 (11) | |||
C29—C30 | 1.347 (11) | |||
C30—C31 | 1.439 (10) | |||
C31—C32 | 1.370 (10) | |||
C32—C33 | 1.446 (10) | |||
C5—C4—C7—C8 | -0.7 (2) | -13.2 (12) | 5.31 (18) | -3.80 (18) |
C11—C12—C13—C18 | -7.0 (2) | -1.3 (12) | 3.65 (19) | -8.39 (19) |
C25—C24—C27—C28 | 20.9 (11) | |||
C31—C32—C33—C38 | -1.6 (11) |
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π-Conjugated bent molecules are attracting increased attention at the current time (Yamaguchi et al., 2005; Ros et al., 2005). We have recently reported the crystal structure and photophysical properties of a series of (E,E,E)-1-(4-alkoxyphenyl)-6-(4-nitrophenyl)hexa-1,3,5-trienes, namely the methoxy, ethoxy, n-propoxy and n-butoxy compounds (Sonoda et al., 2006). In the course of our study, we obtained single crystals of their E,Z,E isomers [(I)–(IV)], whose crystal structures we describe here. To the best of our knowledge, the crystal structure of 1,6-diphenylhexa-1,3,5-triene (DPH) having the E,Z,E configuration at the triene double bonds has not been reported so far. Our data can be compared with those for dibenzo[18]annulene incorporating two (E,Z,E)-DPH units (Michels et al., 1994).
For compounds (I), (III) and (IV), only one independent molecule is present in the asymmetric unit, while for compound (II), two crystallographically independent molecules, A and B, are contained in the unit cell (Figs. 1–4). Selected geometric parameters for (I)–(IV) are given in Table 1.
Bond-length alternation is one of the most important structural parameters that correlate tightly with the electronic and optical properties of one-dimensional conjugated compounds, such as polyene and polyyne, since it strongly affects the band gaps of these molecules (Yang & Kertesz, 2006). In the present compounds, the averaged values of bond-length alternation (δr, the difference between C—C single- and C═C double-bond lengths) in the hexatriene chain are 0.107 Å for (I), 0.103 and 0.091 Å for molecules A and B of (II), respectively, 0.101 Å for (III), and 0.104 Å for (IV). The value of δr for (E)-polyacetylene, the polyene with an infinite chain length, has been determined spectroscopically to be 0.08 Å (Yannoni & Clarke, 1983). The bond alternation is thus more distinctly observed in trienes (I)–(IV) than in polyacetylene, as expected. Interestingly, the single- and double-bond lengths and the resulting δr values of (I)–(IV) are not greatly different from those of their E,E,E counterparts. In the crystal of the E,E,E isomer of (I), for example, the single-bond lengths are 1.434 (5)–1.460 (5) Å, the double-bond lengths are 1.333 (5)–1.345 (5) Å, and the values of δr are 0.101 and 0.114 Å for the two crystallographically independent molecules (Sonoda et al., 2006).
The geometries of the isolated molecule of (I) were optimized by ab initio calculations. The GAUSSIAN03 program was used for ab initio calculations (Frisch et al., 2004). The lengths of single bonds in the MP2/6–31G* (Møller & Plesset, 1934) level geometries (C4—C7 = 1.460 Å, C8—C9 = C10—C11 = 1.441 Å and C12—C13 = 1.459 Å) agree well with the values determined from the crystal structure, although the calculated lengths of the double bonds (C7—C8 = C11—C12 = 1.358 Å and C9—C10 = 1.364 Å) are slightly longer than those found in the crystal. The value of δr = 0.090 Å obtained from the calculation is in reasonable agreement with that from the crystal structure determination. It should be noted that the calculation at the HF/6–31G* level yields a considerably large value of δr (0.133 Å). A similar trend has been reported for polyacetylene oligomers (Choi et al., 1997; Jacquemin et al., 2005).
The C—C—C internal bond angles in the hexatriene chain are all somewhat wider than 120° for all structures, which minimizes the steric hindrance between the C5—H and C8—H atoms, between the C8—H and C11—H atoms, and between the C11—H and C18—H atoms.
The torsion angle of the single bond between the aromatic ring and the triene chain is different for each molecule. The angles C5—C4—C7—C8 [-0.7 (2)°] in (I) and C25—C24—C27—C28 [20.9 (11)°] in (II) display the minimum and the maximum deviations from values of 0 or 180° in these molecules, respectively. The optimized geometry of an isolated molecule of (I) is such that the C5—C4—C7—C8 and C11—C12—C13—C18 torsion angles are -22.65 and -18.93°. Ab initio calculations of 4,4'-disubstituted DPHs show that the torsional potential is very shallow when the torsion angle is -30–30° (Tsuzuki, 2003). It is therefore very probable that the torsion angle will have a different value depending on the packing force in each crystal. Other torsion angles in the triene chains are almost 0 or 180° for all four compounds, indicating that the triene planes are nearly planar for conjugation.
Figs. 5–8 show the crystal structures of (I)–(IV). For all compounds, the neighboring molecules have head-to-tail orientation. This results from donor–acceptor substitution on the rings, as the calculated dipole moment of (I) is 6.38 D (MP2/6–311G**//MP2/6–31G* level).
In the crystal structure of (I), attractive N···O interactions between the nitro groups are observed. The nearest two nitro groups are in a parallel arrangement, which allows the overlap of the N—O dipoles (Szezesna & Urbańczyk-Lipkowska, 2002; Zeller & Hunter, 2004). The parallel arrangement is also observed in the E,E,E isomer of (I); however, the shortest intermolecular distance between the N and O atoms in (I) [O1···N1iii = 3.417 (2) Å; symmetry code: (iii) -x + 2, -y + 1, -z + 2] is considerably larger than the N···O distance of 2.938 (4) Å in its E,E,E isomer (Sonoda et al., 2006).
In the crystal structure of (II), two adjacent molecules are linked at both ends through N···O dipole interactions between the N atom of the nitro group and the O atom of the ethoxy group to form a supramolecular ring-like structure. The intermolecular distances between the N and O atoms are 3.392 (9) Å [O6···N1iii: symmetry code: (iii) x, y, z + 1] and 3.427 (9) Å [O3···N2iii; symmetry code: (iii) x, y, z + 1]. These supramolecular rings are piled up along the c axis. The least-squares plane defined by the molecule (x, y, z) makes an angle of 56.47 (3)° with the least-squares plane defined by the molecule with symmetry code (x + 1/2, -y, z).
In the crystal structures of (III) and (IV), the shortest intermolecular distances are those between the two O atoms of the alkoxy groups: O3···O3ii = 4.284 (2) Å [symmetry code: (ii) -x + 1, -y + 1, -z + 2] for (III), and O3···O3ii = 3.832 (2) Å [symmetry code: (ii) -x, -y + 2, -z] for (IV). Thus, the nearest two molecules form an S-shaped supramolecular dimer in these crystal structures.