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The configuration of the chiral ring atoms of the title compound, C
26H
26N
2O, obtained in an enantioselective synthesis, has been established relative to the known
R configuration of the α-methylbenzyl moieties. The crystal packing involves a two-dimensional network of C—H
π interactions between the aromatic rings.
Supporting information
CCDC reference: 144648
Details of the synthesis of (I) are given elsewhere (Kleijn et al.,
1992). Light yellow crystals were obtained from a solution in diethyl ether
(m.p. 360 K).
H atoms were introduced at calculated positions, and included in the refinement
riding on their carrier atoms. Methyl moieties were refined as rigid groups,
allowing for rotation around the C—C bonds, while maintaining tetrahedral
geometry at the methyl C atoms. The isotropic displacement parameters of the H
atoms were set to a fixed value, related to the equivalent isotropic
displacement parameter of the carrier atom by a factor of 1.5 for the methyl H
atoms and a factor of 1.2 for all other H atoms. For 2104 Friedel pairs the
intensities of both members were measured, i.e. 76% of the total number
of Friedel pairs with θ < θmax. Due to the lack of anomalous scatterers,
the absolute configuration could not be established reliably, as is
illustrated by the value of -0.3 (19) obtained for the Flack x parameter
(Flack, 1983) derived during a structure factor calculation using all data
(meaning that only the symmetry-related intensities were averaged and not the
Friedel pairs). The absolute structure was therefore set in accordance with
the known configuration of the (R)-α-methylbenzyl moieties. Since
there is no significant dispersion, the final refinement cycles were carried
out using a data set in which the Friedel-related reflections were also
averaged.
Data collection: locally modified CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97-2 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: PLATON.
(3
R,4S)-3-Phenyl-1-[(
R)-1-phenylethyl]-4-[(
R)-1-phenylethyliminomethyl]azet idin-2-one
top
Crystal data top
C26H26N2O | Dx = 1.186 Mg m−3 |
Mr = 382.49 | Melting point: 360 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 9.4958 (10) Å | θ = 11.5–14.0° |
b = 10.1947 (8) Å | µ = 0.07 mm−1 |
c = 22.124 (2) Å | T = 293 K |
V = 2141.7 (3) Å3 | Block, light yellow |
Z = 4 | 0.4 × 0.4 × 0.2 mm |
F(000) = 816 | |
Data collection top
Enraf-Nonius CAD-4T diffractometer | Rint = 0.027 |
Radiation source: rotating anode | θmax = 27.5°, θmin = 1.8° |
Graphite monochromator | h = 0→12 |
ω/2θ scans | k = 0→13 |
5566 measured reflections | l = −28→28 |
2783 independent reflections | 3 standard reflections every 60 min |
2033 reflections with I > 2σ(I) | intensity decay: 1% |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0551P)2 + 0.1317P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.040 | (Δ/σ)max = 0.001 |
wR(F2) = 0.106 | Δρmax = 0.17 e Å−3 |
S = 1.02 | Δρmin = −0.16 e Å−3 |
2783 reflections | Extinction correction: SHELXL97-2 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
265 parameters | Extinction coefficient: 0.0114 (16) |
0 restraints | Absolute structure: see text |
Crystal data top
C26H26N2O | V = 2141.7 (3) Å3 |
Mr = 382.49 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.4958 (10) Å | µ = 0.07 mm−1 |
b = 10.1947 (8) Å | T = 293 K |
c = 22.124 (2) Å | 0.4 × 0.4 × 0.2 mm |
Data collection top
Enraf-Nonius CAD-4T diffractometer | Rint = 0.027 |
5566 measured reflections | 3 standard reflections every 60 min |
2783 independent reflections | intensity decay: 1% |
2033 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.17 e Å−3 |
2783 reflections | Δρmin = −0.16 e Å−3 |
265 parameters | Absolute structure: see text |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O13 | 0.30671 (19) | 0.31146 (19) | 0.43217 (8) | 0.0640 (6) | |
N1 | 0.22007 (18) | 0.4889 (2) | 0.48973 (8) | 0.0444 (6) | |
N21 | −0.0867 (2) | 0.5727 (2) | 0.57702 (8) | 0.0493 (6) | |
C2 | 0.2170 (3) | 0.3740 (2) | 0.45833 (10) | 0.0467 (7) | |
C3 | 0.0588 (2) | 0.3552 (2) | 0.47042 (9) | 0.0441 (7) | |
C4 | 0.0663 (2) | 0.4948 (2) | 0.49916 (9) | 0.0421 (6) | |
C5 | 0.3212 (2) | 0.5952 (3) | 0.49775 (10) | 0.0489 (7) | |
C6 | 0.4662 (3) | 0.5575 (3) | 0.47531 (12) | 0.0773 (13) | |
C7 | 0.3262 (2) | 0.6395 (2) | 0.56324 (9) | 0.0411 (6) | |
C8 | 0.3503 (3) | 0.5511 (2) | 0.60949 (11) | 0.0509 (8) | |
C9 | 0.3594 (3) | 0.5941 (3) | 0.66879 (11) | 0.0597 (9) | |
C10 | 0.3453 (3) | 0.7240 (3) | 0.68185 (13) | 0.0634 (9) | |
C11 | 0.3222 (3) | 0.8134 (3) | 0.63675 (13) | 0.0604 (9) | |
C12 | 0.3117 (2) | 0.7708 (2) | 0.57735 (11) | 0.0492 (8) | |
C14 | −0.0452 (2) | 0.3352 (2) | 0.42006 (9) | 0.0421 (6) | |
C15 | −0.0041 (3) | 0.3020 (3) | 0.36178 (10) | 0.0535 (8) | |
C16 | −0.1051 (3) | 0.2837 (3) | 0.31704 (12) | 0.0636 (10) | |
C17 | −0.2440 (3) | 0.2964 (3) | 0.32973 (12) | 0.0619 (9) | |
C18 | −0.2873 (3) | 0.3289 (3) | 0.38722 (12) | 0.0581 (9) | |
C19 | −0.1873 (2) | 0.3484 (2) | 0.43204 (11) | 0.0509 (8) | |
C20 | 0.0184 (2) | 0.5052 (2) | 0.56318 (9) | 0.0443 (7) | |
C22 | −0.1294 (3) | 0.5709 (3) | 0.64164 (11) | 0.0557 (8) | |
C23 | −0.2580 (4) | 0.4864 (4) | 0.64857 (18) | 0.0993 (16) | |
C24 | −0.1464 (3) | 0.7120 (3) | 0.66165 (9) | 0.0497 (7) | |
C25 | −0.0329 (3) | 0.7761 (3) | 0.68612 (13) | 0.0695 (10) | |
C26 | −0.0441 (5) | 0.9078 (4) | 0.70292 (14) | 0.0919 (15) | |
C27 | −0.1694 (5) | 0.9723 (4) | 0.69464 (15) | 0.0943 (16) | |
C28 | −0.2815 (4) | 0.9089 (3) | 0.67113 (15) | 0.0804 (11) | |
C29 | −0.2707 (3) | 0.7796 (3) | 0.65455 (12) | 0.0609 (9) | |
H31 | 0.04460 | 0.28900 | 0.50200 | 0.0530* | |
H41 | 0.02180 | 0.56110 | 0.47340 | 0.0510* | |
H51 | 0.28880 | 0.66970 | 0.47350 | 0.0590* | |
H61 | 0.52900 | 0.63060 | 0.48000 | 0.1160* | |
H62 | 0.46090 | 0.53380 | 0.43340 | 0.1160* | |
H63 | 0.50060 | 0.48430 | 0.49830 | 0.1160* | |
H81 | 0.36050 | 0.46240 | 0.60080 | 0.0610* | |
H91 | 0.37510 | 0.53410 | 0.69970 | 0.0720* | |
H101 | 0.35140 | 0.75230 | 0.72170 | 0.0760* | |
H111 | 0.31360 | 0.90200 | 0.64590 | 0.0730* | |
H121 | 0.29470 | 0.83130 | 0.54670 | 0.0590* | |
H151 | 0.09090 | 0.29210 | 0.35270 | 0.0640* | |
H161 | −0.07700 | 0.26260 | 0.27800 | 0.0760* | |
H171 | −0.31050 | 0.28300 | 0.29950 | 0.0740* | |
H181 | −0.38270 | 0.33780 | 0.39590 | 0.0700* | |
H191 | −0.21640 | 0.37080 | 0.47080 | 0.0610* | |
H201 | 0.06760 | 0.46090 | 0.59330 | 0.0530* | |
H221 | −0.05290 | 0.53150 | 0.66520 | 0.0670* | |
H231 | −0.28830 | 0.48770 | 0.69000 | 0.1490* | |
H232 | −0.23590 | 0.39810 | 0.63700 | 0.1490* | |
H233 | −0.33200 | 0.51950 | 0.62320 | 0.1490* | |
H251 | 0.05180 | 0.73180 | 0.69150 | 0.0830* | |
H261 | 0.03270 | 0.95130 | 0.71960 | 0.1100* | |
H271 | −0.17720 | 1.06020 | 0.70530 | 0.1130* | |
H281 | −0.36640 | 0.95300 | 0.66620 | 0.0970* | |
H291 | −0.34850 | 0.73710 | 0.63830 | 0.0730* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O13 | 0.0583 (10) | 0.0700 (12) | 0.0638 (11) | 0.0150 (9) | 0.0054 (9) | −0.0146 (10) |
N1 | 0.0422 (10) | 0.0505 (11) | 0.0406 (9) | −0.0002 (9) | 0.0022 (8) | −0.0063 (9) |
N21 | 0.0472 (11) | 0.0601 (12) | 0.0407 (10) | 0.0047 (9) | 0.0032 (9) | −0.0052 (9) |
C2 | 0.0496 (12) | 0.0510 (13) | 0.0395 (11) | 0.0061 (12) | −0.0016 (10) | −0.0003 (11) |
C3 | 0.0512 (12) | 0.0436 (12) | 0.0374 (10) | 0.0012 (11) | −0.0010 (9) | −0.0017 (10) |
C4 | 0.0429 (11) | 0.0472 (12) | 0.0363 (10) | 0.0023 (10) | −0.0026 (9) | −0.0040 (10) |
C5 | 0.0488 (12) | 0.0579 (13) | 0.0400 (11) | −0.0087 (11) | −0.0026 (10) | 0.0031 (11) |
C6 | 0.0551 (16) | 0.112 (3) | 0.0647 (16) | −0.0182 (17) | 0.0174 (14) | −0.0226 (17) |
C7 | 0.0344 (10) | 0.0477 (12) | 0.0413 (11) | −0.0052 (10) | −0.0010 (9) | 0.0016 (10) |
C8 | 0.0554 (14) | 0.0500 (13) | 0.0474 (12) | 0.0050 (12) | −0.0047 (12) | 0.0003 (11) |
C9 | 0.0565 (15) | 0.0789 (18) | 0.0438 (13) | 0.0052 (15) | −0.0064 (12) | 0.0078 (13) |
C10 | 0.0469 (14) | 0.093 (2) | 0.0502 (13) | −0.0008 (15) | −0.0018 (12) | −0.0188 (15) |
C11 | 0.0525 (15) | 0.0588 (16) | 0.0700 (16) | −0.0005 (13) | −0.0015 (13) | −0.0171 (14) |
C12 | 0.0411 (12) | 0.0495 (14) | 0.0569 (13) | −0.0031 (11) | −0.0028 (11) | 0.0024 (11) |
C14 | 0.0501 (12) | 0.0376 (11) | 0.0386 (10) | −0.0037 (10) | −0.0019 (10) | −0.0016 (9) |
C15 | 0.0531 (14) | 0.0610 (15) | 0.0463 (12) | −0.0030 (13) | 0.0045 (11) | −0.0090 (12) |
C16 | 0.0740 (19) | 0.0783 (18) | 0.0386 (12) | −0.0099 (16) | −0.0011 (12) | −0.0130 (13) |
C17 | 0.0679 (17) | 0.0693 (17) | 0.0486 (14) | −0.0122 (15) | −0.0162 (12) | −0.0042 (13) |
C18 | 0.0492 (14) | 0.0657 (17) | 0.0593 (14) | −0.0074 (13) | −0.0033 (12) | −0.0012 (13) |
C19 | 0.0552 (14) | 0.0547 (14) | 0.0427 (12) | −0.0052 (12) | 0.0023 (11) | −0.0029 (11) |
C20 | 0.0421 (12) | 0.0534 (13) | 0.0373 (10) | −0.0005 (11) | −0.0007 (9) | −0.0040 (10) |
C22 | 0.0582 (15) | 0.0627 (16) | 0.0462 (12) | 0.0067 (13) | 0.0146 (12) | −0.0020 (12) |
C23 | 0.104 (3) | 0.078 (2) | 0.116 (3) | −0.024 (2) | 0.053 (2) | −0.021 (2) |
C24 | 0.0488 (13) | 0.0658 (15) | 0.0345 (10) | −0.0027 (13) | 0.0117 (10) | −0.0028 (11) |
C25 | 0.0542 (16) | 0.095 (2) | 0.0592 (15) | −0.0116 (16) | 0.0068 (13) | −0.0018 (16) |
C26 | 0.110 (3) | 0.100 (3) | 0.0658 (18) | −0.042 (3) | 0.012 (2) | −0.0222 (19) |
C27 | 0.147 (4) | 0.064 (2) | 0.072 (2) | −0.009 (2) | 0.042 (2) | −0.0152 (17) |
C28 | 0.097 (2) | 0.0652 (19) | 0.079 (2) | 0.015 (2) | 0.029 (2) | 0.0031 (17) |
C29 | 0.0610 (16) | 0.0691 (18) | 0.0525 (14) | 0.0044 (15) | 0.0096 (12) | 0.0016 (13) |
Geometric parameters (Å, º) top
O13—C2 | 1.211 (3) | C26—C27 | 1.372 (6) |
N1—C2 | 1.362 (3) | C27—C28 | 1.350 (6) |
N1—C4 | 1.476 (3) | C28—C29 | 1.372 (4) |
N1—C5 | 1.459 (3) | C3—H31 | 0.9807 |
N21—C20 | 1.250 (3) | C4—H41 | 0.9799 |
N21—C22 | 1.486 (3) | C5—H51 | 0.9795 |
C2—C3 | 1.538 (3) | C6—H61 | 0.9601 |
C3—C4 | 1.560 (3) | C6—H62 | 0.9595 |
C3—C14 | 1.503 (3) | C6—H63 | 0.9604 |
C4—C20 | 1.491 (3) | C8—H81 | 0.9295 |
C5—C6 | 1.513 (3) | C9—H91 | 0.9295 |
C5—C7 | 1.518 (3) | C10—H101 | 0.9294 |
C7—C8 | 1.383 (3) | C11—H111 | 0.9293 |
C7—C12 | 1.381 (3) | C12—H121 | 0.9307 |
C8—C9 | 1.386 (3) | C15—H151 | 0.9297 |
C9—C10 | 1.362 (4) | C16—H161 | 0.9292 |
C10—C11 | 1.369 (4) | C17—H171 | 0.9299 |
C11—C12 | 1.388 (4) | C18—H181 | 0.9305 |
C14—C15 | 1.389 (3) | C19—H191 | 0.9294 |
C14—C19 | 1.382 (3) | C20—H201 | 0.9307 |
C15—C16 | 1.391 (4) | C22—H221 | 0.9802 |
C16—C17 | 1.355 (4) | C23—H231 | 0.9608 |
C17—C18 | 1.377 (4) | C23—H232 | 0.9591 |
C18—C19 | 1.387 (4) | C23—H233 | 0.9606 |
C22—C23 | 1.502 (5) | C25—H251 | 0.9301 |
C22—C24 | 1.514 (4) | C26—H261 | 0.9299 |
C24—C25 | 1.372 (4) | C27—H271 | 0.9296 |
C24—C29 | 1.376 (4) | C28—H281 | 0.9295 |
C25—C26 | 1.397 (5) | C29—H291 | 0.9288 |
| | | |
O13···C6 | 3.082 (4) | H31···O13ii | 2.8763 |
O13···C15 | 3.338 (3) | H41···C19 | 3.0793 |
O13···C19i | 3.418 (3) | H41···C12vi | 2.8597 |
O13···H62 | 2.6986 | H41···H121vi | 2.4600 |
O13···H151 | 2.7073 | H51···H121 | 2.3108 |
O13···H31i | 2.8763 | H51···C29v | 2.9346 |
O13···H191i | 2.8476 | H62···O13 | 2.6986 |
O13···H232i | 2.6589 | H62···C2 | 2.8848 |
N1···H81 | 2.8088 | H62···C26v | 3.0745 |
C2···C19i | 3.442 (3) | H62···C27v | 3.0918 |
C6···O13 | 3.082 (4) | H63···C2 | 3.0494 |
C7···C20 | 3.228 (3) | H63···C8 | 2.9244 |
C8···C20 | 3.347 (3) | H81···N1 | 2.8088 |
C11···C25 | 3.565 (4) | H81···C15i | 3.0990 |
C15···O13 | 3.338 (3) | H101···H161iv | 2.4827 |
C19···C2ii | 3.442 (3) | H111···C18v | 2.9969 |
C19···O13ii | 3.418 (3) | H111···C19v | 3.0738 |
C20···C8 | 3.347 (3) | H121···H51 | 2.3108 |
C20···C7 | 3.228 (3) | H121···H41v | 2.4600 |
C25···C11 | 3.565 (4) | H151···O13 | 2.7073 |
C2···H151 | 2.7554 | H151···C2 | 2.7554 |
C2···H63 | 3.0494 | H151···H232i | 2.5528 |
C2···H62 | 2.8848 | H161···C10viii | 3.0634 |
C2···H191i | 3.0144 | H161···H101viii | 2.4827 |
C4···H191 | 3.0328 | H171···C24ix | 3.0775 |
C8···H201 | 2.8601 | H171···C25ix | 2.9776 |
C8···H233iii | 3.0491 | H191···C4 | 3.0328 |
C8···H63 | 2.9244 | H191···O13ii | 2.8476 |
C10···H291iii | 3.0660 | H191···C2ii | 3.0144 |
C10···H161iv | 3.0634 | H201···C8 | 2.8601 |
C10···H251 | 2.7963 | H201···H221 | 2.0875 |
C11···H251 | 2.9584 | H221···H201 | 2.0875 |
C12···H41v | 2.8597 | H221···H251 | 2.3445 |
C15···H81ii | 3.0990 | H231···C29 | 3.0820 |
C15···H281v | 2.8864 | H232···O13ii | 2.6589 |
C18···H111vi | 2.9969 | H232···H151ii | 2.5528 |
C19···H41 | 3.0793 | H233···C8x | 3.0491 |
C19···H111vi | 3.0738 | H233···C29 | 2.8020 |
C23···H291 | 2.7060 | H233···H291 | 2.2488 |
C24···H171vii | 3.0775 | H251···C10 | 2.7963 |
C25···H171vii | 2.9776 | H251···C11 | 2.9584 |
C26···H62vi | 3.0745 | H251···H221 | 2.3445 |
C27···H62vi | 3.0918 | H281···C15vi | 2.8864 |
C29···H231 | 3.0820 | H291···C10x | 3.0660 |
C29···H233 | 2.8020 | H291···C23 | 2.7060 |
C29···H51vi | 2.9346 | H291···H233 | 2.2488 |
| | | |
C2—N1—C4 | 94.93 (18) | N1—C5—H51 | 107.62 |
C2—N1—C5 | 135.6 (2) | C6—C5—H51 | 107.64 |
C4—N1—C5 | 127.13 (19) | C7—C5—H51 | 107.57 |
C20—N21—C22 | 116.5 (2) | C5—C6—H61 | 109.42 |
O13—C2—N1 | 132.9 (2) | C5—C6—H62 | 109.47 |
O13—C2—C3 | 134.8 (2) | C5—C6—H63 | 109.46 |
N1—C2—C3 | 92.26 (18) | H61—C6—H62 | 109.42 |
C2—C3—C4 | 84.99 (14) | H61—C6—H63 | 109.55 |
C2—C3—C14 | 122.00 (17) | H62—C6—H63 | 109.51 |
C4—C3—C14 | 117.12 (16) | C7—C8—H81 | 119.89 |
N1—C4—C3 | 87.16 (15) | C9—C8—H81 | 119.80 |
N1—C4—C20 | 116.03 (16) | C8—C9—H91 | 119.89 |
C3—C4—C20 | 115.97 (17) | C10—C9—H91 | 119.97 |
N1—C5—C6 | 111.7 (2) | C9—C10—H101 | 119.80 |
N1—C5—C7 | 110.95 (18) | C11—C10—H101 | 119.65 |
C6—C5—C7 | 111.11 (18) | C10—C11—H111 | 120.16 |
C5—C7—C8 | 121.2 (2) | C12—C11—H111 | 120.28 |
C5—C7—C12 | 120.0 (2) | C7—C12—H121 | 119.66 |
C8—C7—C12 | 118.7 (2) | C11—C12—H121 | 119.67 |
C7—C8—C9 | 120.3 (2) | C14—C15—H151 | 119.98 |
C8—C9—C10 | 120.1 (2) | C16—C15—H151 | 120.05 |
C9—C10—C11 | 120.6 (3) | C15—C16—H161 | 119.64 |
C10—C11—C12 | 119.6 (3) | C17—C16—H161 | 119.63 |
C7—C12—C11 | 120.7 (2) | C16—C17—H171 | 119.87 |
C3—C14—C15 | 122.46 (19) | C18—C17—H171 | 119.79 |
C3—C14—C19 | 119.10 (18) | C17—C18—H181 | 120.31 |
C15—C14—C19 | 118.4 (2) | C19—C18—H181 | 120.33 |
C14—C15—C16 | 120.0 (2) | C14—C19—H191 | 119.42 |
C15—C16—C17 | 120.7 (3) | C18—C19—H191 | 119.42 |
C16—C17—C18 | 120.3 (3) | N21—C20—H201 | 119.50 |
C17—C18—C19 | 119.4 (3) | C4—C20—H201 | 119.50 |
C14—C19—C18 | 121.2 (2) | N21—C22—H221 | 108.33 |
N21—C20—C4 | 121.01 (18) | C23—C22—H221 | 108.25 |
N21—C22—C23 | 109.1 (2) | C24—C22—H221 | 108.24 |
N21—C22—C24 | 107.4 (2) | C22—C23—H231 | 109.44 |
C23—C22—C24 | 115.4 (3) | C22—C23—H232 | 109.46 |
C22—C24—C25 | 119.0 (3) | C22—C23—H233 | 109.49 |
C22—C24—C29 | 122.3 (3) | H231—C23—H232 | 109.46 |
C25—C24—C29 | 118.7 (3) | H231—C23—H233 | 109.48 |
C24—C25—C26 | 120.2 (3) | H232—C23—H233 | 109.50 |
C25—C26—C27 | 119.4 (4) | C24—C25—H251 | 119.91 |
C26—C27—C28 | 120.4 (4) | C26—C25—H251 | 119.89 |
C27—C28—C29 | 120.3 (3) | C25—C26—H261 | 120.28 |
C24—C29—C28 | 121.0 (3) | C27—C26—H261 | 120.31 |
C2—C3—H31 | 110.12 | C26—C27—H271 | 119.82 |
C4—C3—H31 | 110.10 | C28—C27—H271 | 119.78 |
C14—C3—H31 | 110.15 | C27—C28—H281 | 119.85 |
N1—C4—H41 | 111.87 | C29—C28—H281 | 119.88 |
C3—C4—H41 | 111.87 | C24—C29—H291 | 119.53 |
C20—C4—H41 | 111.83 | C28—C29—H291 | 119.48 |
| | | |
C4—N1—C2—O13 | 174.6 (3) | C6—C5—C7—C8 | −71.0 (3) |
C4—N1—C2—C3 | −6.51 (16) | C6—C5—C7—C12 | 106.6 (3) |
C5—N1—C2—O13 | 11.9 (4) | C8—C7—C12—C11 | 0.5 (3) |
C5—N1—C2—C3 | −169.2 (2) | C5—C7—C12—C11 | −177.2 (2) |
C2—N1—C4—C3 | 6.42 (16) | C5—C7—C8—C9 | 177.7 (2) |
C2—N1—C4—C20 | 124.05 (19) | C12—C7—C8—C9 | 0.1 (4) |
C5—N1—C4—C3 | 171.3 (2) | C7—C8—C9—C10 | −0.3 (4) |
C5—N1—C4—C20 | −71.1 (3) | C8—C9—C10—C11 | −0.1 (4) |
C2—N1—C5—C6 | −13.7 (4) | C9—C10—C11—C12 | 0.7 (4) |
C2—N1—C5—C7 | −138.3 (2) | C10—C11—C12—C7 | −0.9 (4) |
C4—N1—C5—C6 | −171.9 (2) | C3—C14—C15—C16 | 179.5 (2) |
C4—N1—C5—C7 | 63.5 (3) | C15—C14—C19—C18 | 0.1 (4) |
C22—N21—C20—C4 | 177.1 (2) | C19—C14—C15—C16 | 0.4 (4) |
C20—N21—C22—C23 | −104.5 (3) | C3—C14—C19—C18 | −179.0 (2) |
C20—N21—C22—C24 | 129.8 (2) | C14—C15—C16—C17 | −0.8 (5) |
O13—C2—C3—C14 | −56.0 (4) | C15—C16—C17—C18 | 0.6 (5) |
N1—C2—C3—C4 | 6.16 (16) | C16—C17—C18—C19 | −0.1 (4) |
O13—C2—C3—C4 | −175.0 (3) | C17—C18—C19—C14 | −0.3 (4) |
N1—C2—C3—C14 | 125.2 (2) | C23—C22—C24—C29 | −34.8 (4) |
C14—C3—C4—N1 | −129.24 (17) | C23—C22—C24—C25 | 147.1 (3) |
C14—C3—C4—C20 | 113.1 (2) | N21—C22—C24—C25 | −91.0 (3) |
C2—C3—C4—N1 | −5.69 (14) | N21—C22—C24—C29 | 87.1 (3) |
C2—C3—C4—C20 | −123.36 (18) | C22—C24—C25—C26 | 177.6 (3) |
C4—C3—C14—C15 | 117.2 (2) | C25—C24—C29—C28 | 0.4 (4) |
C2—C3—C14—C15 | 15.4 (3) | C29—C24—C25—C26 | −0.5 (4) |
C2—C3—C14—C19 | −165.52 (19) | C22—C24—C29—C28 | −177.6 (3) |
C4—C3—C14—C19 | −63.7 (2) | C24—C25—C26—C27 | −0.1 (5) |
C3—C4—C20—N21 | −116.2 (2) | C25—C26—C27—C28 | 0.8 (5) |
N1—C4—C20—N21 | 143.7 (2) | C26—C27—C28—C29 | −0.8 (5) |
N1—C5—C7—C8 | 53.9 (3) | C27—C28—C29—C24 | 0.2 (5) |
N1—C5—C7—C12 | −128.4 (2) | | |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+1/2, −z+1; (iii) x+1, y, z; (iv) −x+1/2, −y+1, z+1/2; (v) x+1/2, −y+3/2, −z+1; (vi) x−1/2, −y+3/2, −z+1; (vii) −x−1/2, −y+1, z+1/2; (viii) −x+1/2, −y+1, z−1/2; (ix) −x−1/2, −y+1, z−1/2; (x) x−1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H62···Cg3v | 0.96 | 3.00 | 3.741 (3) | 135 |
C8—H81···Cg2i | 0.93 | 2.89 | 3.757 (3) | 156 |
C11—H111···Cg2v | 0.93 | 2.94 | 3.801 (3) | 155 |
C17—H171···Cg3ix | 0.93 | 2.98 | 3.753 (3) | 141 |
C25—H251···Cg1 | 0.93 | 3.14 | 3.890 (3) | 139 |
C29—H291···Cg1x | 0.93 | 3.07 | 3.929 (3) | 155 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (v) x+1/2, −y+3/2, −z+1; (ix) −x−1/2, −y+1, z−1/2; (x) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | C26H26N2O |
Mr | 382.49 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 9.4958 (10), 10.1947 (8), 22.124 (2) |
V (Å3) | 2141.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.4 × 0.4 × 0.2 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4T diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5566, 2783, 2033 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.106, 1.02 |
No. of reflections | 2783 |
No. of parameters | 265 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.16 |
Absolute structure | See text |
Selected geometric parameters (Å, º) topO13—C2 | 1.211 (3) | N21—C22 | 1.486 (3) |
N1—C2 | 1.362 (3) | C2—C3 | 1.538 (3) |
N1—C4 | 1.476 (3) | C3—C4 | 1.560 (3) |
N21—C20 | 1.250 (3) | | |
| | | |
C2—N1—C4 | 94.93 (18) | C2—C3—C4 | 84.99 (14) |
C20—N21—C22 | 116.5 (2) | N1—C4—C3 | 87.16 (15) |
N1—C2—C3 | 92.26 (18) | N21—C20—C4 | 121.01 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H62···Cg3i | 0.96 | 3.00 | 3.741 (3) | 135 |
C8—H81···Cg2ii | 0.93 | 2.89 | 3.757 (3) | 156 |
C11—H111···Cg2i | 0.93 | 2.94 | 3.801 (3) | 155 |
C17—H171···Cg3iii | 0.93 | 2.98 | 3.753 (3) | 141 |
C25—H251···Cg1 | 0.93 | 3.14 | 3.890 (3) | 139 |
C29—H291···Cg1iv | 0.93 | 3.07 | 3.929 (3) | 155 |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x+1/2, −y+1/2, −z+1; (iii) −x−1/2, −y+1, z−1/2; (iv) x−1, y, z. |
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Azetidin-2-ones are of interest as potential building blocks for the synthesis of antibiotic agents (Morin & Gorman, 1982). They can be prepared via zinc-mediated condensations of ester enolates with imines. During a study on 3-amino-substituted azetidin-2-ones it was established that the zinc-mediated condensation resulted in an exclusive trans arrangement of substituents on the newly formed four-membered ring. The enantioselective synthesis favoured the formation of the (3R,4S) configuration on the new chiral centres (van der Steen et al., 1992). During a study on the enantioselective synthesis of 3-hydrocarbon-substituted azetidin-2-ones, the title compound, (I), was one of the compounds prepared (Kleijn et al., 1992). \scheme
Compound (I) was obtained in a trans configuration with an enantiomeric excess of 64%. A crystal structure determination of the predominant diastereoisomer was undertaken to establish the absolute configurations of the atoms in the ring fragment with respect to the known configuration of the (R)-α-methylbenzyl moieties. The absolute configurations of the newly formed chiral centres in the four-membered ring are R on C3 and S on C4. This shows that the enantioselective syntheses of the 3-amino- and the 3-hydrocarbon-substituted azetidin-2-ones favour the same absolute configurations in the newly formed four-membered ring.
The bond lengths and angles in (I) are well within the range reported in similar structures (Cambridge Structural Database, October 1999 version; Allen et al., 1993). The central four-membered ring is slightly bent, as is illustrated by the puckering parameter q(2) which amounts to 0.080 (2) Å (Cremer & Pople, 1975). The improper torsion angle N1—C2—C4—C3, another measure for the puckering of the four-membered ring, takes the value 171.2 (2)°, which is well within the range found in the CSD (160–180°).
Due to the lack of classic hydrogen bond donors, the packing is determined by weaker interactions. No C—H···O or C—H···N interactions are present, not even for those C—H groups neighbouring electronegative moieties. The only directional interactions in the structure appear to be C—H···π hydrogen bonds. In ring A (atoms C7–C12), the atoms C8 and C11, positioned para with respect to each other, donate a C—H···π bond to the B-rings (atoms C14–C19) of the molecules at (1/2 + x, 1/2 - y, 1 - z) and (1/2 + x, 3/2 - y, 1 - z) (geometric details are given in in Table 2), thus creating an infinite string of edge-face π-systems (Hunter, 1994) running in the [010] direction. This string of aromatic rings intersects with a similar string of C—H···π bonded ring systems, consisting of ring C (atoms C24–C29) and ring A, where the latter now acts as the acceptor. This string, which runs in the [100] direction, contains alternating intra- and intermolecular C—H···π interactions. The two intersecting strings create a two-dimensional network with base vectors [100] and [010]. The two symmetry-related two-dimensional C—H···π networks that are located at approximately z = 0.85 and z = 0.65 are joined by a C—H···π interaction between C17 of ring B and ring C, creating a `bilayer' of C—H···π bonded aromatic rings (Fig. 2). Rings A and B accept C—H···π donations from other phenyl rings on both sides of their π-systems. In contrast, ring C receives a C—H···π interaction from another phenyl ring on only one side of its π-system. The other side of ring C receives a C—H···π bond from the methyl group, C6 (geometric details are included in Table 2; this interaction is not drawn in Fig. 2).