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organic compounds
(E,E)-Methyl 2-[(3-nitrobenzylidene)aminomethyl]-3-phenylpropenoate
aDepto. de Química - UFSC, 88040-900 - Florianópolis, SC, Brazil
*Correspondence e-mail: adajb@qmc.ufsc.br
The molecule of the title compound, C18H16N2O4, adopts a T-shaped conformation with E stereochemistry for the imine double bond. The (3-nitrobenzylidene)amino fragment is almost planar, the mean planes of phenyl ring and nitro group forming a dihedral angle of 8.9 (3)°. In the 3-phenylacryloyl unit, the acrylic ester fragment is also almost planar, with the phenyl ring twisted by 41.44 (7)°. In the crystal, the molecules are linked by C—H⋯O hydrogen-bond interactions into chains running parallel to [01].
Related literature
For general background to the chemistry of Morita–Baylis–Hillman adducts, see: Singh & Batra (2008); Masson et al. (2007
); Basavaiah et al. (2003
). For background to this study, see: Bortoluzzi et al. (2006
); Fernandes et al. (2004
); Sá et al. (2006
, 2007
, 2008
). For the synthesis, see: Sá (2003
). For a description of the Cambridge Structural Database, see: Allen (2002
); and of MOGUL, see: Bruno et al. (2004
).
Experimental
Crystal data
|
Data collection
|
Refinement
|
|
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell SET4 in CAD-4 Software; data reduction: HELENA (Spek, 1996
); program(s) used to solve structure: SIR97 (Altomare et al., 1999
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: PLATON (Spek, 2003
); Mercury (Macrae et al., 2006
); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536808043262/rz2278sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808043262/rz2278Isup2.hkl
Allyl imine (I) was prepared as previously described (Sá, 2003). Allyl azide (II) and triphenylphosphine (1.0 mmol each) were stirred in anhydrous CHCl3 (3.0 ml) and after evolution of N2 has ceased, 3-nitrobenzaldehyde (1.0 mmol) was added and the mixture was stirred for further 20 h at room temperature. Concentration of the final mixture and separation of triphenylphosphine oxide by crystallization from ethyl ether furnished a white solid (84% yield). A careful recrystallization from ethyl acetate/hexane (1:3 v/v) provided crystals (mp 114.3–115.3 °C) suitable for X-ray crystallographic analysis.
All H atoms were placed at idealized positions and refined as riding, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl H atoms.
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell
SET4 in CAD-4 Software (Enraf–Nonius, 1989); data reduction: HELENA (Spek, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C18H16N2O4 | Z = 2 |
Mr = 324.33 | F(000) = 340 |
Triclinic, P1 | Dx = 1.323 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 8.6035 (12) Å | Cell parameters from 25 reflections |
b = 8.7829 (14) Å | θ = 5.3–16.7° |
c = 12.4680 (14) Å | µ = 0.10 mm−1 |
α = 79.275 (18)° | T = 293 K |
β = 76.526 (13)° | Irregular block, colorless |
γ = 63.158 (14)° | 0.50 × 0.30 × 0.20 mm |
V = 813.9 (2) Å3 |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.024 |
Radiation source: fine-focus sealed tube | θmax = 25.1°, θmin = 1.7° |
Graphite monochromator | h = −10→9 |
ω–2θ scans | k = −10→10 |
3026 measured reflections | l = −14→0 |
2883 independent reflections | 3 standard reflections every 200 reflections |
2165 reflections with > 2σ (I) | intensity decay: 1% |
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) = 0.124 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0588P)2 + 0.1527P] where P = (Fo2 + 2Fc2)/3 |
2883 reflections | (Δ/σ)max < 0.001 |
218 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C18H16N2O4 | γ = 63.158 (14)° |
Mr = 324.33 | V = 813.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.6035 (12) Å | Mo Kα radiation |
b = 8.7829 (14) Å | µ = 0.10 mm−1 |
c = 12.4680 (14) Å | T = 293 K |
α = 79.275 (18)° | 0.50 × 0.30 × 0.20 mm |
β = 76.526 (13)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.024 |
3026 measured reflections | 3 standard reflections every 200 reflections |
2883 independent reflections | intensity decay: 1% |
2165 reflections with > 2σ (I) |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.17 e Å−3 |
2883 reflections | Δρmin = −0.22 e Å−3 |
218 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1755 (2) | 0.5606 (2) | 0.77725 (14) | 0.0470 (4) | |
H1 | 0.1648 | 0.6615 | 0.7983 | 0.056* | |
N2 | 0.1722 (2) | 0.55429 (18) | 0.67793 (12) | 0.0492 (4) | |
C3 | 0.1642 (3) | 0.7065 (2) | 0.60179 (15) | 0.0514 (5) | |
H3A | 0.2700 | 0.6741 | 0.5459 | 0.062* | |
H3B | 0.1627 | 0.7908 | 0.6430 | 0.062* | |
C4 | 0.0043 (2) | 0.7874 (2) | 0.54518 (14) | 0.0465 (4) | |
C5 | 0.0074 (2) | 0.7661 (2) | 0.44100 (14) | 0.0488 (4) | |
H5 | −0.0960 | 0.8330 | 0.4121 | 0.059* | |
C6 | −0.1594 (3) | 0.9030 (2) | 0.61246 (15) | 0.0515 (5) | |
O7 | −0.1704 (2) | 0.91839 (19) | 0.70815 (11) | 0.0734 (4) | |
O8 | −0.29582 (18) | 0.98968 (18) | 0.55747 (11) | 0.0639 (4) | |
C9 | −0.4579 (3) | 1.1040 (3) | 0.6204 (2) | 0.0796 (7) | |
H9A | −0.4923 | 1.0411 | 0.6855 | 0.119* | |
H9B | −0.5493 | 1.1532 | 0.5758 | 0.119* | |
H9C | −0.4398 | 1.1936 | 0.6416 | 0.119* | |
C11 | 0.1958 (2) | 0.4135 (2) | 0.86183 (14) | 0.0446 (4) | |
C12 | 0.1900 (2) | 0.2681 (2) | 0.83818 (13) | 0.0434 (4) | |
H12 | 0.1726 | 0.2610 | 0.7687 | 0.052* | |
C13 | 0.2104 (2) | 0.1340 (2) | 0.91989 (14) | 0.0471 (4) | |
N13 | 0.2048 (2) | −0.01950 (19) | 0.89347 (14) | 0.0573 (4) | |
O14 | 0.2052 (2) | −0.03191 (17) | 0.79774 (13) | 0.0745 (5) | |
O15 | 0.2022 (3) | −0.13071 (19) | 0.96882 (14) | 0.0879 (5) | |
C14 | 0.2357 (3) | 0.1386 (3) | 1.02445 (15) | 0.0579 (5) | |
H14 | 0.2487 | 0.0465 | 1.0780 | 0.069* | |
C15 | 0.2412 (3) | 0.2832 (3) | 1.04694 (16) | 0.0625 (5) | |
H15 | 0.2582 | 0.2896 | 1.1166 | 0.075* | |
C16 | 0.2215 (3) | 0.4193 (3) | 0.96652 (15) | 0.0555 (5) | |
H16 | 0.2255 | 0.5163 | 0.9829 | 0.067* | |
C21 | 0.1565 (2) | 0.6482 (2) | 0.36716 (14) | 0.0465 (4) | |
C22 | 0.1946 (3) | 0.7024 (2) | 0.25635 (15) | 0.0546 (5) | |
H22 | 0.1252 | 0.8133 | 0.2294 | 0.066* | |
C23 | 0.3330 (3) | 0.5951 (3) | 0.18584 (17) | 0.0615 (5) | |
H23 | 0.3578 | 0.6345 | 0.1122 | 0.074* | |
C24 | 0.4353 (3) | 0.4296 (3) | 0.22366 (18) | 0.0631 (5) | |
H24 | 0.5284 | 0.3567 | 0.1758 | 0.076* | |
C25 | 0.3986 (3) | 0.3727 (3) | 0.33283 (19) | 0.0660 (6) | |
H25 | 0.4671 | 0.2607 | 0.3585 | 0.079* | |
C26 | 0.2610 (3) | 0.4802 (2) | 0.40479 (17) | 0.0575 (5) | |
H26 | 0.2379 | 0.4405 | 0.4785 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0563 (11) | 0.0396 (9) | 0.0488 (10) | −0.0228 (8) | −0.0137 (8) | 0.0000 (7) |
N2 | 0.0628 (9) | 0.0407 (8) | 0.0475 (9) | −0.0251 (7) | −0.0172 (7) | 0.0061 (6) |
C3 | 0.0672 (12) | 0.0433 (10) | 0.0499 (10) | −0.0310 (9) | −0.0165 (9) | 0.0089 (8) |
C4 | 0.0590 (11) | 0.0372 (9) | 0.0456 (10) | −0.0253 (8) | −0.0114 (8) | 0.0066 (7) |
C5 | 0.0529 (10) | 0.0424 (9) | 0.0495 (10) | −0.0203 (8) | −0.0123 (8) | 0.0039 (7) |
C6 | 0.0668 (12) | 0.0407 (9) | 0.0452 (10) | −0.0263 (9) | −0.0070 (9) | 0.0059 (8) |
O7 | 0.0964 (11) | 0.0643 (9) | 0.0464 (8) | −0.0243 (8) | −0.0094 (7) | −0.0052 (7) |
O8 | 0.0579 (8) | 0.0640 (9) | 0.0542 (8) | −0.0156 (7) | −0.0047 (6) | −0.0037 (6) |
C9 | 0.0652 (14) | 0.0729 (15) | 0.0783 (16) | −0.0156 (12) | 0.0041 (11) | −0.0130 (12) |
C11 | 0.0488 (10) | 0.0412 (9) | 0.0426 (9) | −0.0192 (8) | −0.0077 (7) | −0.0012 (7) |
C12 | 0.0486 (10) | 0.0415 (9) | 0.0377 (9) | −0.0174 (8) | −0.0083 (7) | −0.0019 (7) |
C13 | 0.0512 (10) | 0.0381 (9) | 0.0462 (10) | −0.0161 (8) | −0.0066 (8) | −0.0008 (7) |
N13 | 0.0659 (10) | 0.0370 (8) | 0.0624 (10) | −0.0180 (7) | −0.0122 (8) | 0.0017 (7) |
O14 | 0.1120 (13) | 0.0471 (8) | 0.0688 (10) | −0.0313 (8) | −0.0292 (9) | −0.0051 (7) |
O15 | 0.1339 (15) | 0.0511 (9) | 0.0784 (11) | −0.0470 (10) | −0.0178 (10) | 0.0146 (8) |
C14 | 0.0723 (13) | 0.0535 (11) | 0.0439 (10) | −0.0271 (10) | −0.0127 (9) | 0.0088 (8) |
C15 | 0.0845 (15) | 0.0690 (13) | 0.0398 (10) | −0.0371 (11) | −0.0171 (10) | 0.0012 (9) |
C16 | 0.0724 (13) | 0.0543 (11) | 0.0467 (10) | −0.0325 (10) | −0.0109 (9) | −0.0047 (8) |
C21 | 0.0509 (10) | 0.0436 (9) | 0.0493 (10) | −0.0228 (8) | −0.0130 (8) | −0.0018 (8) |
C22 | 0.0623 (12) | 0.0505 (11) | 0.0479 (10) | −0.0202 (9) | −0.0164 (9) | 0.0015 (8) |
C23 | 0.0650 (12) | 0.0672 (13) | 0.0484 (11) | −0.0253 (11) | −0.0078 (9) | −0.0065 (9) |
C24 | 0.0579 (12) | 0.0596 (12) | 0.0693 (14) | −0.0199 (10) | −0.0076 (10) | −0.0179 (10) |
C25 | 0.0702 (13) | 0.0401 (10) | 0.0814 (15) | −0.0167 (10) | −0.0171 (11) | −0.0040 (10) |
C26 | 0.0683 (12) | 0.0432 (10) | 0.0593 (12) | −0.0253 (9) | −0.0111 (9) | 0.0034 (8) |
C1—N2 | 1.257 (2) | C13—C14 | 1.381 (3) |
C1—C11 | 1.478 (2) | C13—N13 | 1.470 (2) |
C1—H1 | 0.9300 | N13—O14 | 1.218 (2) |
N2—C3 | 1.473 (2) | N13—O15 | 1.227 (2) |
C3—C4 | 1.509 (2) | C14—C15 | 1.373 (3) |
C3—H3A | 0.9700 | C14—H14 | 0.9300 |
C3—H3B | 0.9700 | C15—C16 | 1.383 (3) |
C4—C5 | 1.339 (2) | C15—H15 | 0.9300 |
C4—C6 | 1.481 (3) | C16—H16 | 0.9300 |
C5—C21 | 1.473 (2) | C21—C22 | 1.389 (3) |
C5—H5 | 0.9300 | C21—C26 | 1.395 (3) |
C6—O7 | 1.203 (2) | C22—C23 | 1.373 (3) |
C6—O8 | 1.342 (2) | C22—H22 | 0.9300 |
O8—C9 | 1.445 (2) | C23—C24 | 1.376 (3) |
C9—H9A | 0.9600 | C23—H23 | 0.9300 |
C9—H9B | 0.9600 | C24—C25 | 1.375 (3) |
C9—H9C | 0.9600 | C24—H24 | 0.9300 |
C11—C16 | 1.387 (2) | C25—C26 | 1.382 (3) |
C11—C12 | 1.388 (2) | C25—H25 | 0.9300 |
C12—C13 | 1.380 (2) | C26—H26 | 0.9300 |
C12—H12 | 0.9300 | ||
N2—C1—C11 | 122.48 (16) | C12—C13—N13 | 118.04 (16) |
N2—C1—H1 | 118.8 | C14—C13—N13 | 119.12 (16) |
C11—C1—H1 | 118.8 | O14—N13—O15 | 122.86 (17) |
C1—N2—C3 | 116.16 (15) | O14—N13—C13 | 118.70 (15) |
N2—C3—C4 | 113.24 (14) | O15—N13—C13 | 118.44 (17) |
N2—C3—H3A | 108.9 | C15—C14—C13 | 118.01 (17) |
C4—C3—H3A | 108.9 | C15—C14—H14 | 121.0 |
N2—C3—H3B | 108.9 | C13—C14—H14 | 121.0 |
C4—C3—H3B | 108.9 | C14—C15—C16 | 120.37 (18) |
H3A—C3—H3B | 107.7 | C14—C15—H15 | 119.8 |
C5—C4—C6 | 121.26 (17) | C16—C15—H15 | 119.8 |
C5—C4—C3 | 124.23 (17) | C15—C16—C11 | 121.17 (18) |
C6—C4—C3 | 114.43 (16) | C15—C16—H16 | 119.4 |
C4—C5—C21 | 127.15 (17) | C11—C16—H16 | 119.4 |
C4—C5—H5 | 116.4 | C22—C21—C26 | 118.14 (17) |
C21—C5—H5 | 116.4 | C22—C21—C5 | 120.03 (16) |
O7—C6—O8 | 122.52 (18) | C26—C21—C5 | 121.82 (16) |
O7—C6—C4 | 123.31 (18) | C23—C22—C21 | 121.17 (18) |
O8—C6—C4 | 114.17 (16) | C23—C22—H22 | 119.4 |
C6—O8—C9 | 115.78 (16) | C21—C22—H22 | 119.4 |
O8—C9—H9A | 109.5 | C22—C23—C24 | 120.28 (19) |
O8—C9—H9B | 109.5 | C22—C23—H23 | 119.9 |
H9A—C9—H9B | 109.5 | C24—C23—H23 | 119.9 |
O8—C9—H9C | 109.5 | C25—C24—C23 | 119.5 (2) |
H9A—C9—H9C | 109.5 | C25—C24—H24 | 120.3 |
H9B—C9—H9C | 109.5 | C23—C24—H24 | 120.3 |
C16—C11—C12 | 118.96 (16) | C24—C25—C26 | 120.70 (19) |
C16—C11—C1 | 120.11 (16) | C24—C25—H25 | 119.7 |
C12—C11—C1 | 120.93 (15) | C26—C25—H25 | 119.7 |
C13—C12—C11 | 118.65 (16) | C25—C26—C21 | 120.21 (19) |
C13—C12—H12 | 120.7 | C25—C26—H26 | 119.9 |
C11—C12—H12 | 120.7 | C21—C26—H26 | 119.9 |
C12—C13—C14 | 122.84 (17) | ||
C11—C1—N2—C3 | −175.74 (16) | C14—C13—N13—O14 | −170.73 (18) |
C1—N2—C3—C4 | −121.34 (18) | C12—C13—N13—O15 | −171.67 (17) |
N2—C3—C4—C5 | −101.1 (2) | C14—C13—N13—O15 | 8.4 (3) |
N2—C3—C4—C6 | 82.07 (19) | C12—C13—C14—C15 | −0.2 (3) |
C6—C4—C5—C21 | −175.96 (15) | N13—C13—C14—C15 | 179.74 (18) |
C3—C4—C5—C21 | 7.5 (3) | C13—C14—C15—C16 | 0.1 (3) |
C5—C4—C6—O7 | 175.67 (18) | C14—C15—C16—C11 | 0.0 (3) |
C3—C4—C6—O7 | −7.4 (2) | C12—C11—C16—C15 | 0.0 (3) |
C5—C4—C6—O8 | −4.2 (2) | C1—C11—C16—C15 | −179.85 (18) |
C3—C4—C6—O8 | 172.71 (14) | C4—C5—C21—C22 | −138.14 (19) |
O7—C6—O8—C9 | 0.2 (3) | C4—C5—C21—C26 | 42.9 (3) |
C4—C6—O8—C9 | −179.94 (16) | C26—C21—C22—C23 | −1.1 (3) |
N2—C1—C11—C16 | 171.68 (18) | C5—C21—C22—C23 | 179.90 (17) |
N2—C1—C11—C12 | −8.2 (3) | C21—C22—C23—C24 | 1.2 (3) |
C16—C11—C12—C13 | −0.1 (3) | C22—C23—C24—C25 | −0.5 (3) |
C1—C11—C12—C13 | 179.71 (16) | C23—C24—C25—C26 | −0.3 (3) |
C11—C12—C13—C14 | 0.3 (3) | C24—C25—C26—C21 | 0.4 (3) |
C11—C12—C13—N13 | −179.70 (15) | C22—C21—C26—C25 | 0.3 (3) |
C12—C13—N13—O14 | 9.2 (3) | C5—C21—C26—C25 | 179.29 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···O15i | 0.93 | 2.55 | 3.307 (3) | 139 |
Symmetry code: (i) x, y+1, z−1. |
Experimental details
Crystal data | |
Chemical formula | C18H16N2O4 |
Mr | 324.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.6035 (12), 8.7829 (14), 12.4680 (14) |
α, β, γ (°) | 79.275 (18), 76.526 (13), 63.158 (14) |
V (Å3) | 813.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.50 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [ > 2σ (I)] reflections | 3026, 2883, 2165 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.124, 1.09 |
No. of reflections | 2883 |
No. of parameters | 218 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.22 |
Computer programs: , SET4 in CAD-4 Software (Enraf–Nonius, 1989), HELENA (Spek, 1996), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003); Mercury (Macrae et al., 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···O15i | 0.93 | 2.55 | 3.307 (3) | 139.0 |
Symmetry code: (i) x, y+1, z−1. |
Acknowledgements
The authors are grateful to the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and the Fundação de Apoio à Pesquisa Científica e Tecnológica do Estado de Santa Catarina (FAPESC) for financial assistance.
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Nitrogen-containing building blocks derived from α-methylene-β-hydroxy esters (Morita-Baylis-Hillman adducts) have been widely employed in modern organic chemistry for the synthesis of natural products and heterocycles of biological relevance (Singh & Batra, 2008; Masson et al., 2007; Basavaiah et al., 2003). During our studies on the Morita-Baylis-Hillman reaction (Bortoluzzi et al., 2006; Fernandes et al., 2004; Sá et al., 2006; Sá et al., 2007; Sá et al., 2008), we reported the high-yield preparation of N-allylic imine (I) (Scheme 1) and analogs by a tandem Staudinger/Aza-Wittig process involving allyl azide (II) and a combination of triphenylphosphine and 3-nitrobenzaldehyde (Sá, 2003). In spite of the full chemical characterization described for the multifunctional compound (I), the stereochemistry of the imine double bond could not be unambiguously elucidated and was tentatively assigned as being E on the basis of the available data (Sá, 2003).
The molecular structure of the title compound adopts a T-shaped conformation (Fig. 1). The E stereochemistry for the imine double bond was unambiguously elucidated by X-ray analysis. The torsion angles N2—C1—C11—C12 of -8.2 (3)° and C12—C13—N13—O14 of 9.2 (3)° demonstrate that the (3-nitrobenzylidene)amino moiety is almost planar. The plane of the nitro group deviates of 8.9 (3)° with respect to the mean plane of the parent phenyl ring. In the 3-phenylacryloyl moiety, the acrylic ester fragment is also almost planar with as indicated by the C5–C4–C6–O7 torsion angle of 175.67 (18)°, whereas the phenyl ring is twisted by 41.44 (7)°, probably due to steric effect. This observation indicates that the vinyl C═C double bond is strongly conjugated with the carboxyl group instead that with the aromatic phenyl ring. A search using Mogul (Bruno et al., 2004) based on the CCDC system (version 5.29; Allen, 2002) revealed that the bond lengths found in the structure of (I) are within the expected range for organic compounds. In the crystal packing, molecules are linked by intermolecular C—H···O hydrogen bonding interactions (Table 1) to form chains running parallel to the [0 1 1] direction (Fig. 2).