Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040481/at6062sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040481/at6062Isup2.hkl |
CCDC reference: 296513
To a solution of iminophosphorane (1.32 g, 3 mmol) in dry dichloromethane (15 ml) was added phenyl isocyanate (3 mmol) under nitrogen at room temperature. After the reaction mixture was stood for 10 h at room temperature, the solvent was removed under reduced pressure and ether/petroleum ether (1:2, 20 ml) was added to precipitate triphenylphosphine oxide. After filtration the solvent was removed to give carbodiimide (II), which was used directly without further purification. To the solution of (II) prepared above in dichloromethane (15 ml) was added morphiline (3 mmol). After the reaction mixture was allowed to stand for 6 h, the solution was concentrated under reduced pressure and the residue was recrystallized from dichloromethane / petroleum ether (1:4) to give the title compound (I) in yield of 85% (m.p. 491 K). Suitable crystals were obtained by vapor diffusion of ethanol and dichloromethane at room temperature. Spectroscopic analysis: 1H NMR (CDCl3, 200 MHz) 3.33 (t, 4H, NCH2, J = 4.4 Hz), 3.64 (t, 4H, OCH2, J = 4.9 Hz), 6.80 (s, 1H, =CH), 6.51–7.49 (m, 8H, Ar—H). MS (EI 70 eV) m/z (%): 323 (M+, 100), 266 (17), 189 (30), 77 (77). Elemental analysis: calculated for C18H17N3O3: C 66.86, H 5.30, N 13.00%; found: C 66.71, H 5.42, N 13.05%.
H atoms were placed at calculated positions and treated as riding atoms (C—H in the range 0.93–0.98 Å), with Uiso(H) = 1.2 (CH) or 1.5 (CH3) times Ueq(parent atom). In the absence of significant anomalous dispersion effects, Friedel pairs were averaged.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL.
C18H17N3O3 | F(000) = 340 |
Mr = 323.35 | Dx = 1.332 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2460 reflections |
a = 5.5926 (12) Å | θ = 2.5–24.9° |
b = 8.8449 (19) Å | µ = 0.09 mm−1 |
c = 16.442 (4) Å | T = 292 K |
β = 97.536 (3)° | Block, yellow |
V = 806.3 (3) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1705 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.082 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ϕ and ω scans | h = −7→7 |
5883 measured reflections | k = −11→11 |
1970 independent reflections | l = −20→21 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.051P)2] where P = (Fo2 + 2Fc2)/3 |
1970 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 0.16 e Å−3 |
1 restraint | Δρmin = −0.20 e Å−3 |
C18H17N3O3 | V = 806.3 (3) Å3 |
Mr = 323.35 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.5926 (12) Å | µ = 0.09 mm−1 |
b = 8.8449 (19) Å | T = 292 K |
c = 16.442 (4) Å | 0.20 × 0.20 × 0.10 mm |
β = 97.536 (3)° |
Bruker SMART CCD area-detector diffractometer | 1705 reflections with I > 2σ(I) |
5883 measured reflections | Rint = 0.082 |
1970 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 1 restraint |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.16 e Å−3 |
1970 reflections | Δρmin = −0.20 e Å−3 |
217 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 | 1.2985 (5) | 0.6485 (4) | 0.01926 (16) | 0.0565 (7) | |
H1 | 1.4335 | 0.6799 | −0.0037 | 0.068* | |
C2 | 1.1596 (5) | 0.5311 (4) | −0.00729 (16) | 0.0598 (7) | |
H2 | 1.1780 | 0.4686 | −0.0515 | 0.072* | |
C3 | 0.9796 (5) | 0.5209 (4) | 0.04486 (15) | 0.0525 (6) | |
H3 | 0.8572 | 0.4491 | 0.0419 | 0.063* | |
C4 | 1.0180 (4) | 0.6347 (3) | 0.10002 (13) | 0.0393 (5) | |
C5 | 0.9025 (4) | 0.6865 (3) | 0.16757 (13) | 0.0382 (5) | |
H5 | 0.9514 | 0.7795 | 0.1903 | 0.046* | |
C6 | 0.7295 (4) | 0.6122 (2) | 0.20101 (13) | 0.0347 (5) | |
C7 | 0.6272 (4) | 0.6664 (2) | 0.27454 (13) | 0.0363 (5) | |
C8 | 0.4854 (4) | 0.4384 (2) | 0.23077 (13) | 0.0344 (5) | |
C9 | 0.3839 (4) | 0.5365 (3) | 0.36866 (13) | 0.0371 (5) | |
C10 | 0.2014 (4) | 0.6297 (3) | 0.38680 (15) | 0.0448 (5) | |
H10 | 0.1359 | 0.7016 | 0.3491 | 0.054* | |
C11 | 0.1159 (5) | 0.6155 (4) | 0.46190 (17) | 0.0600 (7) | |
H11 | −0.0086 | 0.6774 | 0.4745 | 0.072* | |
C12 | 0.2154 (6) | 0.5098 (4) | 0.51763 (17) | 0.0654 (8) | |
H12 | 0.1558 | 0.4992 | 0.5675 | 0.079* | |
C13 | 0.3996 (6) | 0.4208 (4) | 0.50041 (17) | 0.0668 (8) | |
H13 | 0.4679 | 0.3512 | 0.5390 | 0.080* | |
C14 | 0.4871 (5) | 0.4330 (3) | 0.42535 (15) | 0.0527 (6) | |
H14 | 0.6136 | 0.3721 | 0.4135 | 0.063* | |
C15 | 0.1306 (5) | 0.2857 (3) | 0.25833 (19) | 0.0541 (7) | |
H15A | 0.0069 | 0.3114 | 0.2135 | 0.065* | |
H15B | 0.1141 | 0.3527 | 0.3040 | 0.065* | |
C16 | 0.1006 (7) | 0.1246 (4) | 0.2837 (2) | 0.0732 (10) | |
H16A | 0.2186 | 0.1020 | 0.3308 | 0.088* | |
H16B | −0.0586 | 0.1117 | 0.3000 | 0.088* | |
C17 | 0.4063 (5) | 0.1962 (3) | 0.16698 (17) | 0.0531 (7) | |
H17A | 0.5698 | 0.2046 | 0.1538 | 0.064* | |
H17B | 0.2959 | 0.2187 | 0.1179 | 0.064* | |
C18 | 0.3623 (6) | 0.0389 (3) | 0.1956 (2) | 0.0724 (9) | |
H18A | 0.3794 | −0.0319 | 0.1517 | 0.087* | |
H18B | 0.4831 | 0.0140 | 0.2415 | 0.087* | |
N1 | 0.6287 (3) | 0.4719 (2) | 0.17728 (11) | 0.0360 (4) | |
N2 | 0.4715 (3) | 0.5496 (2) | 0.29096 (11) | 0.0375 (4) | |
N3 | 0.3696 (4) | 0.3041 (2) | 0.23243 (13) | 0.0412 (5) | |
O1 | 1.2157 (3) | 0.7155 (2) | 0.08430 (11) | 0.0491 (4) | |
O2 | 0.6680 (3) | 0.77927 (18) | 0.31536 (10) | 0.0488 (4) | |
O3 | 0.1295 (4) | 0.0226 (3) | 0.21994 (14) | 0.0769 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0602 (15) | 0.0685 (19) | 0.0458 (14) | −0.0007 (14) | 0.0257 (12) | 0.0032 (13) |
C2 | 0.0722 (17) | 0.0673 (19) | 0.0421 (14) | −0.0020 (16) | 0.0158 (12) | −0.0088 (14) |
C3 | 0.0633 (15) | 0.0531 (15) | 0.0427 (13) | −0.0132 (13) | 0.0126 (11) | −0.0122 (12) |
C4 | 0.0467 (12) | 0.0381 (13) | 0.0335 (12) | −0.0063 (9) | 0.0070 (9) | 0.0050 (9) |
C5 | 0.0507 (12) | 0.0300 (11) | 0.0340 (11) | −0.0071 (9) | 0.0063 (9) | −0.0020 (9) |
C6 | 0.0433 (11) | 0.0304 (11) | 0.0307 (10) | −0.0018 (9) | 0.0061 (8) | 0.0003 (9) |
C7 | 0.0449 (12) | 0.0283 (11) | 0.0360 (11) | −0.0001 (8) | 0.0064 (9) | 0.0019 (9) |
C8 | 0.0407 (11) | 0.0290 (10) | 0.0340 (11) | 0.0031 (9) | 0.0067 (8) | 0.0006 (9) |
C9 | 0.0395 (11) | 0.0402 (12) | 0.0331 (11) | −0.0031 (10) | 0.0100 (8) | −0.0001 (10) |
C10 | 0.0474 (12) | 0.0434 (13) | 0.0443 (13) | 0.0029 (10) | 0.0088 (10) | −0.0037 (11) |
C11 | 0.0600 (15) | 0.0634 (19) | 0.0623 (18) | 0.0033 (14) | 0.0289 (13) | −0.0120 (15) |
C12 | 0.089 (2) | 0.073 (2) | 0.0405 (13) | −0.0076 (17) | 0.0288 (14) | 0.0016 (15) |
C13 | 0.084 (2) | 0.073 (2) | 0.0460 (14) | 0.0101 (17) | 0.0188 (14) | 0.0209 (15) |
C14 | 0.0562 (14) | 0.0549 (16) | 0.0495 (14) | 0.0109 (13) | 0.0161 (11) | 0.0120 (13) |
C15 | 0.0492 (14) | 0.0556 (16) | 0.0600 (16) | −0.0150 (12) | 0.0169 (12) | −0.0096 (13) |
C16 | 0.089 (2) | 0.072 (2) | 0.0620 (19) | −0.0421 (18) | 0.0219 (16) | 0.0006 (17) |
C17 | 0.0648 (16) | 0.0406 (14) | 0.0575 (15) | −0.0129 (12) | 0.0213 (13) | −0.0131 (12) |
C18 | 0.086 (2) | 0.0385 (15) | 0.094 (2) | −0.0151 (15) | 0.0140 (18) | −0.0108 (17) |
N1 | 0.0433 (10) | 0.0320 (10) | 0.0339 (9) | −0.0077 (8) | 0.0099 (8) | −0.0033 (8) |
N2 | 0.0488 (10) | 0.0323 (9) | 0.0333 (10) | −0.0031 (8) | 0.0130 (8) | −0.0025 (8) |
N3 | 0.0472 (11) | 0.0343 (11) | 0.0443 (11) | −0.0092 (8) | 0.0141 (8) | −0.0032 (8) |
O1 | 0.0556 (10) | 0.0481 (10) | 0.0473 (10) | −0.0119 (8) | 0.0206 (8) | −0.0013 (8) |
O2 | 0.0689 (11) | 0.0335 (9) | 0.0459 (9) | −0.0060 (8) | 0.0150 (8) | −0.0085 (8) |
O3 | 0.0944 (15) | 0.0521 (13) | 0.0864 (15) | −0.0406 (12) | 0.0202 (12) | −0.0074 (12) |
C1—C2 | 1.335 (5) | C10—H10 | 0.9300 |
C1—O1 | 1.356 (3) | C11—C12 | 1.375 (4) |
C1—H1 | 0.9300 | C11—H11 | 0.9300 |
C2—C3 | 1.408 (4) | C12—C13 | 1.356 (4) |
C2—H2 | 0.9300 | C12—H12 | 0.9300 |
C3—C4 | 1.353 (4) | C13—C14 | 1.390 (4) |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—O1 | 1.369 (3) | C14—H14 | 0.9300 |
C4—C5 | 1.431 (3) | C15—N3 | 1.464 (3) |
C5—C6 | 1.345 (3) | C15—C16 | 1.500 (5) |
C5—H5 | 0.9300 | C15—H15A | 0.9700 |
C6—N1 | 1.397 (3) | C15—H15B | 0.9700 |
C6—C7 | 1.484 (3) | C16—O3 | 1.408 (4) |
C7—O2 | 1.208 (3) | C16—H16A | 0.9700 |
C7—N2 | 1.401 (3) | C16—H16B | 0.9700 |
C8—N1 | 1.299 (3) | C17—N3 | 1.473 (3) |
C8—N3 | 1.355 (3) | C17—C18 | 1.499 (4) |
C8—N2 | 1.404 (3) | C17—H17A | 0.9700 |
C9—C10 | 1.375 (3) | C17—H17B | 0.9700 |
C9—C14 | 1.378 (3) | C18—O3 | 1.419 (4) |
C9—N2 | 1.431 (3) | C18—H18A | 0.9700 |
C10—C11 | 1.387 (3) | C18—H18B | 0.9700 |
C2—C1—O1 | 110.7 (2) | C14—C13—H13 | 119.8 |
C2—C1—H1 | 124.7 | C9—C14—C13 | 119.2 (3) |
O1—C1—H1 | 124.7 | C9—C14—H14 | 120.4 |
C1—C2—C3 | 106.4 (3) | C13—C14—H14 | 120.4 |
C1—C2—H2 | 126.8 | N3—C15—C16 | 109.0 (3) |
C3—C2—H2 | 126.8 | N3—C15—H15A | 109.9 |
C4—C3—C2 | 107.3 (2) | C16—C15—H15A | 109.9 |
C4—C3—H3 | 126.4 | N3—C15—H15B | 109.9 |
C2—C3—H3 | 126.4 | C16—C15—H15B | 109.9 |
C3—C4—O1 | 108.8 (2) | H15A—C15—H15B | 108.3 |
C3—C4—C5 | 135.3 (2) | O3—C16—C15 | 111.9 (2) |
O1—C4—C5 | 115.91 (19) | O3—C16—H16A | 109.2 |
C6—C5—C4 | 125.6 (2) | C15—C16—H16A | 109.2 |
C6—C5—H5 | 117.2 | O3—C16—H16B | 109.2 |
C4—C5—H5 | 117.2 | C15—C16—H16B | 109.2 |
C5—C6—N1 | 127.2 (2) | H16A—C16—H16B | 107.9 |
C5—C6—C7 | 123.4 (2) | N3—C17—C18 | 109.1 (2) |
N1—C6—C7 | 109.29 (18) | N3—C17—H17A | 109.9 |
O2—C7—N2 | 125.4 (2) | C18—C17—H17A | 109.9 |
O2—C7—C6 | 130.9 (2) | N3—C17—H17B | 109.9 |
N2—C7—C6 | 103.55 (19) | C18—C17—H17B | 109.9 |
N1—C8—N3 | 123.5 (2) | H17A—C17—H17B | 108.3 |
N1—C8—N2 | 114.43 (19) | O3—C18—C17 | 112.1 (3) |
N3—C8—N2 | 121.91 (19) | O3—C18—H18A | 109.2 |
C10—C9—C14 | 120.5 (2) | C17—C18—H18A | 109.2 |
C10—C9—N2 | 119.7 (2) | O3—C18—H18B | 109.2 |
C14—C9—N2 | 119.7 (2) | C17—C18—H18B | 109.2 |
C9—C10—C11 | 119.4 (2) | H18A—C18—H18B | 107.9 |
C9—C10—H10 | 120.3 | C8—N1—C6 | 105.99 (18) |
C11—C10—H10 | 120.3 | C7—N2—C8 | 106.70 (17) |
C12—C11—C10 | 119.9 (3) | C7—N2—C9 | 121.71 (18) |
C12—C11—H11 | 120.1 | C8—N2—C9 | 129.03 (19) |
C10—C11—H11 | 120.1 | C8—N3—C15 | 124.1 (2) |
C13—C12—C11 | 120.5 (3) | C8—N3—C17 | 116.15 (19) |
C13—C12—H12 | 119.7 | C15—N3—C17 | 111.1 (2) |
C11—C12—H12 | 119.7 | C1—O1—C4 | 106.8 (2) |
C12—C13—C14 | 120.4 (3) | C16—O3—C18 | 110.1 (2) |
C12—C13—H13 | 119.8 | ||
O1—C1—C2—C3 | −1.1 (3) | O2—C7—N2—C8 | −177.4 (2) |
C1—C2—C3—C4 | 0.7 (3) | C6—C7—N2—C8 | −0.2 (2) |
C2—C3—C4—O1 | −0.1 (3) | O2—C7—N2—C9 | −14.1 (3) |
C2—C3—C4—C5 | 179.7 (3) | C6—C7—N2—C9 | 163.18 (18) |
C3—C4—C5—C6 | 10.4 (4) | N1—C8—N2—C7 | −1.0 (2) |
O1—C4—C5—C6 | −169.7 (2) | N3—C8—N2—C7 | 175.0 (2) |
C4—C5—C6—N1 | 0.1 (4) | N1—C8—N2—C9 | −162.7 (2) |
C4—C5—C6—C7 | 175.9 (2) | N3—C8—N2—C9 | 13.3 (3) |
C5—C6—C7—O2 | 1.8 (4) | C10—C9—N2—C7 | 77.2 (3) |
N1—C6—C7—O2 | 178.2 (2) | C14—C9—N2—C7 | −101.3 (3) |
C5—C6—C7—N2 | −175.2 (2) | C10—C9—N2—C8 | −123.4 (3) |
N1—C6—C7—N2 | 1.2 (2) | C14—C9—N2—C8 | 58.0 (3) |
C14—C9—C10—C11 | −2.1 (4) | N1—C8—N3—C15 | −147.2 (2) |
N2—C9—C10—C11 | 179.4 (2) | N2—C8—N3—C15 | 37.1 (3) |
C9—C10—C11—C12 | 0.6 (4) | N1—C8—N3—C17 | −2.4 (3) |
C10—C11—C12—C13 | 1.1 (5) | N2—C8—N3—C17 | −178.1 (2) |
C11—C12—C13—C14 | −1.4 (5) | C16—C15—N3—C8 | −158.1 (2) |
C10—C9—C14—C13 | 1.9 (4) | C16—C15—N3—C17 | 55.6 (3) |
N2—C9—C14—C13 | −179.6 (3) | C18—C17—N3—C8 | 155.8 (2) |
C12—C13—C14—C9 | −0.1 (5) | C18—C17—N3—C15 | −54.9 (3) |
N3—C15—C16—O3 | −58.0 (3) | C2—C1—O1—C4 | 1.0 (3) |
N3—C17—C18—O3 | 56.3 (3) | C3—C4—O1—C1 | −0.5 (3) |
N3—C8—N1—C6 | −174.2 (2) | C5—C4—O1—C1 | 179.6 (2) |
N2—C8—N1—C6 | 1.8 (2) | C15—C16—O3—C18 | 59.4 (4) |
C5—C6—N1—C8 | 174.5 (2) | C17—C18—O3—C16 | −58.8 (4) |
C7—C6—N1—C8 | −1.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18B···O2i | 0.97 | 2.55 | 3.345 (4) | 139 |
C15—H15A···N1ii | 0.97 | 2.55 | 3.374 (4) | 143 |
C5—H5···O3iii | 0.93 | 2.39 | 3.303 (3) | 166 |
Symmetry codes: (i) x, y−1, z; (ii) x−1, y, z; (iii) x+1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C18H17N3O3 |
Mr | 323.35 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 292 |
a, b, c (Å) | 5.5926 (12), 8.8449 (19), 16.442 (4) |
β (°) | 97.536 (3) |
V (Å3) | 806.3 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5883, 1970, 1705 |
Rint | 0.082 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.099, 1.00 |
No. of reflections | 1970 |
No. of parameters | 217 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.20 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18B···O2i | 0.97 | 2.55 | 3.345 (4) | 139 |
C15—H15A···N1ii | 0.97 | 2.55 | 3.374 (4) | 143 |
C5—H5···O3iii | 0.93 | 2.39 | 3.303 (3) | 166 |
Symmetry codes: (i) x, y−1, z; (ii) x−1, y, z; (iii) x+1, y+1, z. |
Imidazolinones derivatives are of great importance because of their remarkable biological properties (Kiec-Kononowicz et al., 1998). In recent years, we have been engaged in the preparation of heterocyclic derivatives via the aza-Wittig reaction (Hu et al., 2004). The title compound, (I), may be used as a new precursor for obtaining bioactive molecules. The crystal structure of (I) is presented here.
Fig. 1 shows the molecular structure of (I), with the atomic numbering scheme. Selected bond lengths and angles are listed in Table 1. In the crystal structure, there are some weak intermolecular C—H···O hydrogen-bonding interactions and intermolecular π–π interactions (Fig. 2).