Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005981/cv6177sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005981/cv6177Isup2.hkl |
CCDC reference: 209967
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- R factor = 0.042
- wR factor = 0.097
- Data-to-parameter ratio = 13.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.757 1.000 Tmin' and Tmax expected: 0.966 0.983 RR' = 0.771 Please check that your absorption correction is appropriate.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The azide alcohol PhCH(OH)CH(N3)C═CCO2Et (2.48 g, 9.51 mmol) in DCM (10 ml) was added dropwise to a stirred solution of PPh3 (3.41 mg, 13.1 mmol) at 273 K. Acetic acid (100 µl) in DCM (5 ml) was added under argon. The reaction mixture was warmed to room temperature over 3 h, after 1 h it was cooled to 273 K and triethylamine (4 g, 40 mmol) was added until the pH increased to 8 (measured using universal testing paper). Benzoyl chloride was added (1.4 g, 10 mmol) and the reaction stirred for 18 h while warming to room temperature. The mixture was washed with water (2 × 30 ml) and the aqueous washes back extracted with DCM (30 ml). The combined organic layers were dried (MgSO4), the solvent removed and product purified by flash chromatography (eluting with 10% ethyl acetate in petrol) to yield the title amide, (I), as a colourless crystalline solid (1.32 g, 44%). M.p. 390.7–391.1 K. Analysis calculated for C20H19NO3: C 74.7, H 5.92, N 4.36%; found: C 74.71, H 5.96, N 4.51. IR, ν (cm−1): 1710 and 1654 (C═O), 1623 (C═C), 1447, 1297, 1257. 1H NMR (d, p.p.m., 400 MHz): 7.96 (2H, d, J= 6.8 Hz, o-Ph), 7.3–7.6 (8H, m, Ph), 6.44 (1H, dd, J = 10 Hz, 16 Hz, H3), 6.14 (1H, d, J = 16 Hz, H2), 4.13 (2H, q, J = 7 Hz, CH2), 3.83 (1H, d, J = 2.4 Hz, H3'), 3.43 (1H, dd, J = 10 Hz, 2.4 Hz, H2'), 1.23 (3H, t, J = 7 Hz, Me). 13C NMR (d, p.p.m., 100 MHz): 176 (C6), 165 (C1), 143 (C2), 135, 133, 132, 130, 129, 128, 128, 126 (Ph), 125 (C3), 60 (C3'), 49 (C2'), 47 (C4), 14 (C5). m/z (CI/NH3): 322 (M+ + H, 33%), 276, 248, 216, 105 (100%).
All H atoms were located in a difference Fourier synthesis and were refined in isotropic approximation. Bond lengths: Csp2—H = 0.97 (1) and 0.98 (1) Å, Csp3—H = 0.96 (2)–1.03 (2) Å and O—H = 0.82 (4) and 0.84 (4) Å.
Data collection: SMART (Bruker, 1995); cell refinement: SMART; data reduction: SAINT (Bruker, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I). Atomic displacement ellipsoids are shown at the 50% probability level and double bonds are shown in black. |
C20H19NO3 | Dx = 1.264 Mg m−3 |
Mr = 321.36 | Melting point: 391 K K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.746 (1) Å | Cell parameters from 499 reflections |
b = 14.319 (1) Å | θ = 10.2–20.9° |
c = 10.998 (1) Å | µ = 0.09 mm−1 |
β = 93.52 (1)° | T = 150 K |
V = 1689.1 (2) Å3 | Block, colourless |
Z = 4 | 0.4 × 0.3 × 0.2 mm |
F(000) = 680 |
SMART 1K CCD area-detector diffractometer | 3880 independent reflections |
Radiation source: fine-focus sealed tube | 2850 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 8 pixels mm-1 | θmax = 27.5°, θmin = 1.9° |
ω scans | h = −13→13 |
Absorption correction: multi-scan [SADABS (Sheldrick, 1998), before correction Rint = 0.054] | k = −18→16 |
Tmin = 0.757, Tmax = 1.000 | l = −14→14 |
17984 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | All H-atom parameters refined |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0243P)2 + 0.6441P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
3880 reflections | Δρmax = 0.21 e Å−3 |
294 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0099 (9) |
C20H19NO3 | V = 1689.1 (2) Å3 |
Mr = 321.36 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.746 (1) Å | µ = 0.09 mm−1 |
b = 14.319 (1) Å | T = 150 K |
c = 10.998 (1) Å | 0.4 × 0.3 × 0.2 mm |
β = 93.52 (1)° |
SMART 1K CCD area-detector diffractometer | 3880 independent reflections |
Absorption correction: multi-scan [SADABS (Sheldrick, 1998), before correction Rint = 0.054] | 2850 reflections with I > 2σ(I) |
Tmin = 0.757, Tmax = 1.000 | Rint = 0.046 |
17984 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.097 | All H-atom parameters refined |
S = 1.09 | Δρmax = 0.21 e Å−3 |
3880 reflections | Δρmin = −0.23 e Å−3 |
294 parameters |
Experimental. The data collection nominally covered full sphere of reciprocal space, by a combination of 5 sets of ω scans; each set at different ϕ and/or 2θ angles and each scan (10 sec exposure) covering 0.3° in ω. Crystal to detector distance 4.58 cm. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and comparing 171 duplicate reflections. |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.26714 (9) | 0.52785 (7) | 0.30593 (9) | 0.0305 (3) | |
O2 | 0.30380 (10) | 0.51798 (8) | 0.10672 (10) | 0.0356 (3) | |
O3 | 0.59806 (10) | 0.19502 (8) | 0.00123 (9) | 0.0360 (3) | |
N1' | 0.65835 (11) | 0.26564 (9) | 0.18177 (10) | 0.0243 (3) | |
C1 | 0.33476 (13) | 0.50297 (10) | 0.21242 (14) | 0.0266 (3) | |
C2 | 0.44911 (14) | 0.45394 (11) | 0.25797 (14) | 0.0269 (3) | |
H2 | 0.4709 (15) | 0.4552 (12) | 0.3455 (15) | 0.033 (4)* | |
C2' | 0.63614 (13) | 0.36121 (10) | 0.22540 (13) | 0.0255 (3) | |
H2' | 0.6653 (13) | 0.3705 (10) | 0.3093 (14) | 0.022 (4)* | |
C3 | 0.52116 (14) | 0.40980 (11) | 0.18334 (14) | 0.0272 (3) | |
H3 | 0.4968 (15) | 0.4099 (12) | 0.0980 (16) | 0.036 (5)* | |
C3' | 0.73303 (14) | 0.34125 (11) | 0.13450 (14) | 0.0267 (3) | |
H3' | 0.7072 (14) | 0.3610 (11) | 0.0507 (15) | 0.029 (4)* | |
C4 | 0.15064 (15) | 0.57653 (12) | 0.27355 (16) | 0.0333 (4) | |
H41 | 0.1715 (15) | 0.6334 (13) | 0.2273 (15) | 0.036 (5)* | |
H42 | 0.0962 (16) | 0.5345 (13) | 0.2231 (16) | 0.042 (5)* | |
C5 | 0.09334 (18) | 0.59959 (15) | 0.39096 (19) | 0.0431 (4) | |
H51 | 0.155 (2) | 0.6342 (16) | 0.4438 (19) | 0.065 (7)* | |
H52 | 0.0702 (17) | 0.5406 (15) | 0.4310 (18) | 0.051 (6)* | |
H53 | 0.0155 (18) | 0.6379 (13) | 0.3730 (16) | 0.046 (5)* | |
C6 | 0.57468 (14) | 0.21469 (10) | 0.10577 (13) | 0.0263 (3) | |
C11 | 0.46185 (13) | 0.17807 (10) | 0.16270 (13) | 0.0262 (3) | |
C12 | 0.44962 (14) | 0.18199 (11) | 0.28769 (14) | 0.0278 (3) | |
H12 | 0.5141 (14) | 0.2123 (11) | 0.3371 (14) | 0.026 (4)* | |
C13 | 0.34666 (15) | 0.14153 (12) | 0.33770 (16) | 0.0355 (4) | |
H13 | 0.3394 (16) | 0.1443 (13) | 0.4253 (17) | 0.044 (5)* | |
C14 | 0.25607 (16) | 0.09719 (13) | 0.26331 (19) | 0.0420 (4) | |
H14 | 0.1852 (18) | 0.0648 (13) | 0.3002 (17) | 0.049 (5)* | |
C15 | 0.26706 (16) | 0.09426 (13) | 0.13910 (19) | 0.0443 (5) | |
H15 | 0.2043 (19) | 0.0635 (14) | 0.0841 (18) | 0.058 (6)* | |
C16 | 0.36941 (15) | 0.13438 (12) | 0.08820 (16) | 0.0370 (4) | |
H16 | 0.3785 (16) | 0.1329 (13) | 0.0009 (17) | 0.046 (5)* | |
C21 | 0.86940 (14) | 0.34048 (10) | 0.16850 (13) | 0.0266 (3) | |
C22 | 0.91746 (15) | 0.31498 (11) | 0.28430 (15) | 0.0313 (4) | |
H22 | 0.8612 (16) | 0.2982 (12) | 0.3477 (16) | 0.040 (5)* | |
C23 | 1.04537 (16) | 0.30884 (12) | 0.30946 (17) | 0.0371 (4) | |
H23 | 1.0780 (16) | 0.2913 (13) | 0.3906 (17) | 0.041 (5)* | |
C24 | 1.12637 (16) | 0.32799 (12) | 0.21903 (18) | 0.0396 (4) | |
H24 | 1.2144 (18) | 0.3227 (13) | 0.2361 (17) | 0.051 (5)* | |
C25 | 1.07945 (16) | 0.35550 (13) | 0.10544 (17) | 0.0406 (4) | |
H25 | 1.1355 (17) | 0.3725 (13) | 0.0426 (17) | 0.049 (5)* | |
C26 | 0.95181 (16) | 0.36204 (12) | 0.07984 (15) | 0.0345 (4) | |
H26 | 0.9160 (16) | 0.3805 (12) | 0.0004 (17) | 0.041 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0266 (5) | 0.0323 (6) | 0.0327 (6) | 0.0057 (4) | 0.0029 (4) | −0.0025 (5) |
O2 | 0.0364 (6) | 0.0384 (7) | 0.0320 (6) | 0.0036 (5) | 0.0022 (5) | 0.0064 (5) |
O3 | 0.0422 (7) | 0.0432 (7) | 0.0226 (6) | 0.0052 (5) | 0.0025 (5) | −0.0040 (5) |
N1' | 0.0259 (6) | 0.0256 (7) | 0.0218 (6) | 0.0017 (5) | 0.0038 (5) | 0.0003 (5) |
C1 | 0.0268 (8) | 0.0214 (8) | 0.0318 (8) | −0.0030 (6) | 0.0036 (6) | 0.0009 (6) |
C2 | 0.0269 (8) | 0.0252 (8) | 0.0286 (8) | −0.0028 (6) | 0.0031 (6) | 0.0017 (6) |
C2' | 0.0286 (8) | 0.0251 (8) | 0.0232 (8) | 0.0010 (6) | 0.0046 (6) | 0.0002 (6) |
C3 | 0.0291 (8) | 0.0254 (8) | 0.0271 (8) | 0.0002 (6) | 0.0020 (6) | 0.0029 (6) |
C3' | 0.0290 (8) | 0.0288 (8) | 0.0227 (7) | 0.0009 (6) | 0.0054 (6) | 0.0034 (6) |
C4 | 0.0271 (8) | 0.0293 (9) | 0.0433 (10) | 0.0061 (7) | −0.0002 (7) | −0.0027 (8) |
C5 | 0.0333 (10) | 0.0450 (12) | 0.0523 (12) | 0.0087 (9) | 0.0128 (8) | 0.0057 (9) |
C6 | 0.0299 (8) | 0.0262 (8) | 0.0223 (7) | 0.0068 (6) | −0.0016 (6) | 0.0001 (6) |
C11 | 0.0261 (7) | 0.0237 (8) | 0.0283 (8) | 0.0042 (6) | −0.0017 (6) | −0.0027 (6) |
C12 | 0.0262 (8) | 0.0278 (8) | 0.0292 (8) | −0.0006 (6) | 0.0000 (6) | −0.0010 (6) |
C13 | 0.0318 (8) | 0.0368 (10) | 0.0384 (10) | 0.0025 (7) | 0.0069 (7) | 0.0041 (8) |
C14 | 0.0275 (9) | 0.0353 (10) | 0.0637 (13) | −0.0015 (7) | 0.0067 (8) | −0.0017 (9) |
C15 | 0.0290 (9) | 0.0413 (11) | 0.0613 (12) | −0.0015 (8) | −0.0066 (8) | −0.0152 (9) |
C16 | 0.0335 (9) | 0.0398 (10) | 0.0369 (9) | 0.0060 (7) | −0.0045 (7) | −0.0127 (8) |
C21 | 0.0280 (8) | 0.0229 (8) | 0.0295 (8) | −0.0003 (6) | 0.0063 (6) | −0.0010 (6) |
C22 | 0.0337 (8) | 0.0293 (8) | 0.0311 (8) | −0.0006 (7) | 0.0044 (6) | 0.0013 (7) |
C23 | 0.0371 (9) | 0.0296 (9) | 0.0437 (10) | −0.0007 (7) | −0.0049 (8) | 0.0013 (8) |
C24 | 0.0276 (9) | 0.0276 (9) | 0.0637 (12) | −0.0030 (7) | 0.0025 (8) | −0.0056 (8) |
C25 | 0.0351 (9) | 0.0397 (10) | 0.0485 (11) | −0.0090 (8) | 0.0149 (8) | −0.0054 (8) |
C26 | 0.0374 (9) | 0.0356 (9) | 0.0312 (9) | −0.0063 (7) | 0.0092 (7) | −0.0014 (7) |
O1—C1 | 1.3432 (18) | C11—C12 | 1.390 (2) |
O1—C4 | 1.4577 (18) | C11—C16 | 1.396 (2) |
O2—C1 | 1.2087 (18) | C12—C13 | 1.392 (2) |
O3—C6 | 1.2246 (17) | C12—H12 | 0.958 (16) |
N1'—C6 | 1.3953 (19) | C13—C14 | 1.386 (2) |
N1'—C3' | 1.4620 (19) | C13—H13 | 0.972 (18) |
N1'—C2' | 1.4745 (19) | C14—C15 | 1.379 (3) |
C1—C2 | 1.476 (2) | C14—H14 | 0.999 (19) |
C2—C3 | 1.323 (2) | C15—C16 | 1.389 (3) |
C2—H2 | 0.976 (16) | C15—H15 | 0.98 (2) |
C2'—C3 | 1.468 (2) | C16—H16 | 0.971 (19) |
C2'—C3' | 1.514 (2) | C21—C26 | 1.392 (2) |
C2'—H2' | 0.965 (15) | C21—C22 | 1.393 (2) |
C3—H3 | 0.958 (17) | C22—C23 | 1.388 (2) |
C3'—C21 | 1.490 (2) | C22—H22 | 0.980 (17) |
C3'—H3' | 0.988 (16) | C23—C24 | 1.389 (3) |
C4—C5 | 1.501 (2) | C23—H23 | 0.972 (18) |
C4—H41 | 0.994 (18) | C24—C25 | 1.376 (3) |
C4—H42 | 0.986 (18) | C24—H24 | 0.956 (19) |
C5—H51 | 0.99 (2) | C25—C26 | 1.386 (2) |
C5—H52 | 0.99 (2) | C25—H25 | 0.974 (19) |
C5—H53 | 1.009 (19) | C26—H26 | 0.970 (18) |
C6—C11 | 1.493 (2) | ||
C1—O1—C4 | 115.89 (12) | O3—C6—C11 | 122.10 (14) |
C6—N1'—C3' | 121.45 (12) | N1'—C6—C11 | 116.25 (12) |
C6—N1'—C2' | 124.68 (12) | C12—C11—C16 | 119.43 (15) |
C3'—N1'—C2' | 62.08 (9) | C12—C11—C6 | 121.93 (13) |
O2—C1—O1 | 124.01 (14) | C16—C11—C6 | 118.55 (14) |
O2—C1—C2 | 125.83 (14) | C11—C12—C13 | 119.98 (15) |
O1—C1—C2 | 110.16 (12) | C11—C12—H12 | 118.1 (9) |
C3—C2—C1 | 121.56 (14) | C13—C12—H12 | 122.0 (9) |
C3—C2—H2 | 120.4 (10) | C14—C13—C12 | 120.25 (17) |
C1—C2—H2 | 118.0 (10) | C14—C13—H13 | 120.5 (11) |
C3—C2'—N1' | 119.17 (13) | C12—C13—H13 | 119.2 (11) |
C3—C2'—C3' | 118.76 (13) | C15—C14—C13 | 119.91 (17) |
N1'—C2'—C3' | 58.56 (9) | C15—C14—H14 | 120.1 (11) |
C3—C2'—H2' | 117.0 (9) | C13—C14—H14 | 119.9 (11) |
N1'—C2'—H2' | 112.9 (9) | C14—C15—C16 | 120.32 (17) |
C3'—C2'—H2' | 117.4 (9) | C14—C15—H15 | 121.7 (12) |
C2—C3—C2' | 122.97 (14) | C16—C15—H15 | 117.9 (12) |
C2—C3—H3 | 118.1 (10) | C15—C16—C11 | 120.09 (16) |
C2'—C3—H3 | 118.9 (10) | C15—C16—H16 | 121.3 (11) |
N1'—C3'—C21 | 117.27 (13) | C11—C16—H16 | 118.6 (11) |
N1'—C3'—C2' | 59.36 (9) | C26—C21—C22 | 118.85 (15) |
C21—C3'—C2' | 122.77 (13) | C26—C21—C3' | 118.75 (14) |
N1'—C3'—H3' | 114.5 (9) | C22—C21—C3' | 122.34 (13) |
C21—C3'—H3' | 116.9 (9) | C23—C22—C21 | 120.38 (15) |
C2'—C3'—H3' | 113.4 (9) | C23—C22—H22 | 119.2 (10) |
O1—C4—C5 | 106.65 (14) | C21—C22—H22 | 120.3 (10) |
O1—C4—H41 | 107.5 (10) | C22—C23—C24 | 120.09 (17) |
C5—C4—H41 | 112.2 (10) | C22—C23—H23 | 119.7 (10) |
O1—C4—H42 | 108.5 (10) | C24—C23—H23 | 120.2 (10) |
C5—C4—H42 | 111.0 (10) | C25—C24—C23 | 119.73 (16) |
H41—C4—H42 | 110.9 (14) | C25—C24—H24 | 120.3 (12) |
C4—C5—H51 | 108.7 (12) | C23—C24—H24 | 120.0 (12) |
C4—C5—H52 | 108.8 (11) | C24—C25—C26 | 120.44 (16) |
H51—C5—H52 | 110.1 (17) | C24—C25—H25 | 120.5 (11) |
C4—C5—H53 | 109.3 (10) | C26—C25—H25 | 119.1 (11) |
H51—C5—H53 | 111.2 (16) | C25—C26—C21 | 120.47 (16) |
H52—C5—H53 | 108.8 (15) | C25—C26—H26 | 122.3 (10) |
O3—C6—N1' | 121.39 (14) | C21—C26—H26 | 117.2 (10) |
C5—C4—O1—C1 | −178.44 (14) | C12—C11—C6—N1' | −9.4 (2) |
C4—O1—C1—C2 | −179.57 (12) | C11—C6—N1'—C3' | −149.00 (13) |
O1—C1—C2—C3 | 169.28 (14) | C6—N1'—C3'—C21 | −130.75 (14) |
C1—C2—C3—C2' | 179.34 (14) | N1'—C3'—C21—C22 | −39.0 (2) |
C2—C3—C2'—C3' | −159.78 (15) |
Experimental details
Crystal data | |
Chemical formula | C20H19NO3 |
Mr | 321.36 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 10.746 (1), 14.319 (1), 10.998 (1) |
β (°) | 93.52 (1) |
V (Å3) | 1689.1 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan [SADABS (Sheldrick, 1998), before correction Rint = 0.054] |
Tmin, Tmax | 0.757, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17984, 3880, 2850 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.097, 1.09 |
No. of reflections | 3880 |
No. of parameters | 294 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.21, −0.23 |
Computer programs: SMART (Bruker, 1995), SMART, SAINT (Bruker, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
O1—C1 | 1.3432 (18) | C1—C2 | 1.476 (2) |
O1—C4 | 1.4577 (18) | C2—C3 | 1.323 (2) |
O2—C1 | 1.2087 (18) | C2'—C3 | 1.468 (2) |
O3—C6 | 1.2246 (17) | C2'—C3' | 1.514 (2) |
N1'—C6 | 1.3953 (19) | C3'—C21 | 1.490 (2) |
N1'—C3' | 1.4620 (19) | C4—C5 | 1.501 (2) |
N1'—C2' | 1.4745 (19) | C6—C11 | 1.493 (2) |
C1—O1—C4 | 115.89 (12) | N1'—C2'—C3' | 58.56 (9) |
C6—N1'—C3' | 121.45 (12) | C2—C3—C2' | 122.97 (14) |
C6—N1'—C2' | 124.68 (12) | N1'—C3'—C21 | 117.27 (13) |
C3'—N1'—C2' | 62.08 (9) | N1'—C3'—C2' | 59.36 (9) |
O2—C1—O1 | 124.01 (14) | C21—C3'—C2' | 122.77 (13) |
O2—C1—C2 | 125.83 (14) | O1—C4—C5 | 106.65 (14) |
O1—C1—C2 | 110.16 (12) | O3—C6—N1' | 121.39 (14) |
C3—C2—C1 | 121.56 (14) | O3—C6—C11 | 122.10 (14) |
C3—C2'—N1' | 119.17 (13) | N1'—C6—C11 | 116.25 (12) |
C3—C2'—C3' | 118.76 (13) |
The title compound, (I), was prepared in the course of our studies of thermal earrangements of vinyl epoxydes and vinyl aziridines (Aldous et al., 1999), by a one-pot modification of literature methods for the aziridine formation and subsequent protection, e.g. described for the parent NH aziridine by Wipf & Fritch (1994) and Coldham et al. (1995).
The ethylpropenoate chain, C2'/C3/C2/C1/O1/O2/C4/C5, is planar with a mean atomic deviation of 0.04 Å. It forms a dihedral angle of 74.4 (1)° with the aziridine ring plane. With respect to the latter, the phenyl substituent at C3' is trans and the benzoate substituent at N1' is cis to the ethylpropenoate group.
The N1' atom is strongly pyramidal, with the sum of valent angles of 308.2 (3)° (cf. 360° for the ideally planar and 328.5° for tetrahedral geometry). The out-of-(aziridine)plane tilt of the N1'—C6 bond (Ohwada et al., 1998) is 50.3 (1)°. In this respect, (I) is similar to other acylaziridine derivatives (Zacharis & Trefonas, 1968; Gopalakrishna, 1972; Brzozowski et al., 1988; Ferraris et al., 1998), but different from acyclic tertiary amides, where the nitrogen atom is always planar-trigonal and its lone electron pair is conjugated with the carbonyl group. In (I), the `torsion angle' (around the N1'—C6 bond) between the directions of the N1' lone pair and the C6 pπ orbital does not exceed 16°, i.e. is compatible with conjugation. Nevertheless, the N1'—C6 bond distance of 1.395 (2) Å in (I), while comparable with the range of 1.383–1.388 Å in previously reported acylaziridines (see above), is considerably longer than in acyclic amides with two sp3 C atoms bonded to the N atom [average 1.346 (10) Å (Chakrabarti & Dunitz, 1982) or 1.352 (10) Å (Allen et al., 1987)]. The amides, in which the N atom is incorporated into a larger cycle, e.g. a proline ring, show even shorter C(O)—N bonds, averaging 1.335 (9) Å (Chakrabarti & Dunitz, 1982).
The geometry of the aziridine ring is similar to that previously observed (e.g. Ohwada et al., 1998). It agrees also with the results of a microwave study of the free aziridine, C2H5N, in the gas phase by Turner et al. (1955).