Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005608/na6057sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005608/na6057Isup2.hkl |
CCDC reference: 165644
The title compound was obtained as a single diastereomer from 4-arylmethyleneisoxazol-5-one, (I), and the in situ prepared N-ylide (II) (Risitano et al., 1997).
Due to the small crystal size, the diffraction data were collected twice at room temperature. A preliminary data collection of a small crystal was collected up to 2θ = 46°. The structure determination was carried out using the data of this reduced 2θ shell. When it was possible to obtain bigger crystals, a complete data collection was performed up to 2θ = 50° and this was used to refine the structure model. Reflection intensities were evaluated by profile fitting of a 96-steps peak scan among 2θ shells procedure (Diamond, 1969) and then corrected for Lorentz–polarization effects. Standard uncertainties σ(I) were estimated from counting statistics. H atoms have been located at idealized positions and were allowed to ride on their parent C atoms with a unique fixed isotropic displacement parameter (0.08 Å2).
Data collection: XSCANS (Siemens, 1999); cell refinement: XSCANS; data reduction: SHELXTL-Plus (Sheldrick, 1990); program(s) used to solve structure: SIR92 (Altomare, 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW (Siemens, 1996); software used to prepare material for publication: PARST97 (Nardelli, 1995) and SHELXL97.
Fig. 1. Perspective view of the title compound showing the atomic numbering scheme. The displacement ellipsoids are drawn at 30% of probability level for non-H atoms. |
C33H26N2O2 | F(000) = 1016 |
Mr = 482.56 | Dx = 1.222 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.909 (3) Å | Cell parameters from 28 reflections |
b = 18.502 (7) Å | θ = 2.2–12.5° |
c = 13.092 (4) Å | µ = 0.08 mm−1 |
β = 97.143 (12)° | T = 298 K |
V = 2621.9 (15) Å3 | Prism, colourless |
Z = 4 | 0.46 × 0.27 × 0.22 mm |
Siemens P4 diffractometer | Rint = 0.032 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.9° |
Graphite monochromator | h = −1→12 |
ω scans | k = −1→21 |
5738 measured reflections | l = −15→15 |
4602 independent reflections | 3 standard reflections every 97 reflections |
1712 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0278P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
4602 reflections | Δρmax = 0.21 e Å−3 |
335 parameters | Δρmin = −0.20 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: 0.0063 (6) |
C33H26N2O2 | V = 2621.9 (15) Å3 |
Mr = 482.56 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.909 (3) Å | µ = 0.08 mm−1 |
b = 18.502 (7) Å | T = 298 K |
c = 13.092 (4) Å | 0.46 × 0.27 × 0.22 mm |
β = 97.143 (12)° |
Siemens P4 diffractometer | Rint = 0.032 |
5738 measured reflections | 3 standard reflections every 97 reflections |
4602 independent reflections | intensity decay: none |
1712 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.21 e Å−3 |
4602 reflections | Δρmin = −0.20 e Å−3 |
335 parameters |
Experimental. due to the small size of crystal samples of compound III, diffraction data have been recolleted on a new bigger sample. All calculations were performed on a µ-VAX 3400 and on a DEC-alpha 3000/400. |
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 | ||
C3 | 0.8696 (4) | 0.23869 (19) | 0.2732 (3) | 0.0657 (10) | |
O2 | 0.9447 (2) | 0.20392 (13) | 0.23488 (18) | 0.0828 (8) | |
C1 | 0.8783 (3) | 0.27669 (17) | 0.3770 (2) | 0.0542 (8) | |
C2 | 0.7621 (3) | 0.31989 (18) | 0.3618 (2) | 0.0568 (9) | |
N1 | 0.6886 (3) | 0.30278 (16) | 0.2801 (2) | 0.0752 (9) | |
O1 | 0.7530 (2) | 0.25016 (13) | 0.22350 (17) | 0.0810 (8) | |
C14 | 0.7272 (3) | 0.38018 (18) | 0.4265 (3) | 0.0585 (9) | |
C15 | 0.6598 (3) | 0.4372 (2) | 0.3791 (3) | 0.0773 (11) | |
H15 | 0.6331 | 0.4353 | 0.3089 | 0.093* | |
C16 | 0.6323 (4) | 0.4968 (2) | 0.4353 (4) | 0.0946 (14) | |
H16 | 0.5887 | 0.5352 | 0.4025 | 0.113* | |
C17 | 0.6688 (4) | 0.4997 (2) | 0.5397 (4) | 0.0980 (14) | |
H17 | 0.6487 | 0.5397 | 0.5774 | 0.118* | |
C18 | 0.7351 (4) | 0.4437 (2) | 0.5881 (3) | 0.0891 (12) | |
H18 | 0.7592 | 0.4455 | 0.6587 | 0.107* | |
C19 | 0.7664 (3) | 0.38412 (19) | 0.5317 (3) | 0.0732 (11) | |
H19 | 0.8135 | 0.3469 | 0.5643 | 0.088* | |
C4 | 0.8801 (3) | 0.21671 (17) | 0.4665 (2) | 0.0591 (9) | |
H4 | 0.8351 | 0.2367 | 0.5203 | 0.071* | |
N2 | 1.0105 (3) | 0.20973 (15) | 0.5103 (2) | 0.0646 (8) | |
C5 | 1.0739 (3) | 0.26304 (19) | 0.4793 (2) | 0.0587 (9) | |
C6 | 1.0018 (3) | 0.31331 (19) | 0.4075 (2) | 0.0563 (9) | |
C7 | 0.8206 (3) | 0.14485 (19) | 0.4336 (2) | 0.0609 (9) | |
C8 | 0.8888 (3) | 0.0855 (2) | 0.4104 (2) | 0.0710 (10) | |
H8 | 0.9743 | 0.0889 | 0.4148 | 0.085* | |
C9 | 0.8309 (4) | 0.0207 (2) | 0.3805 (3) | 0.0811 (12) | |
H9 | 0.8786 | −0.0186 | 0.3653 | 0.097* | |
C10 | 0.7049 (5) | 0.0133 (3) | 0.3730 (3) | 0.0932 (14) | |
C11 | 0.6373 (4) | 0.0725 (3) | 0.3966 (3) | 0.1070 (16) | |
H11 | 0.5518 | 0.0687 | 0.3922 | 0.128* | |
C12 | 0.6935 (4) | 0.1377 (2) | 0.4267 (3) | 0.0927 (13) | |
H12 | 0.6455 | 0.1768 | 0.4424 | 0.111* | |
C13 | 0.6431 (4) | −0.0589 (2) | 0.3402 (3) | 0.143 (2) | |
H13A | 0.5552 | −0.0542 | 0.3379 | 0.171* | |
H13B | 0.6724 | −0.0957 | 0.3890 | 0.171* | |
H13C | 0.6631 | −0.0719 | 0.2733 | 0.171* | |
C20 | 1.2067 (3) | 0.27094 (17) | 0.5154 (3) | 0.0611 (9) | |
C21 | 1.2897 (3) | 0.29086 (18) | 0.4488 (3) | 0.0756 (11) | |
H21 | 1.2612 | 0.3009 | 0.3804 | 0.091* | |
C22 | 1.4142 (4) | 0.2960 (2) | 0.4825 (4) | 0.0928 (13) | |
H22 | 1.4693 | 0.3082 | 0.4365 | 0.111* | |
C23 | 1.4565 (4) | 0.2833 (2) | 0.5838 (4) | 0.1046 (16) | |
H23 | 1.5404 | 0.2877 | 0.6067 | 0.125* | |
C24 | 1.3756 (4) | 0.2639 (2) | 0.6521 (4) | 0.1035 (15) | |
H24 | 1.4048 | 0.2551 | 0.7208 | 0.124* | |
C25 | 1.2506 (4) | 0.25749 (19) | 0.6180 (3) | 0.0821 (12) | |
H25 | 1.1959 | 0.2442 | 0.6638 | 0.099* | |
C26 | 1.0358 (3) | 0.38088 (18) | 0.3855 (2) | 0.0609 (9) | |
H26 | 1.1133 | 0.3954 | 0.4164 | 0.073* | |
C27 | 0.9665 (3) | 0.43470 (19) | 0.3192 (3) | 0.0589 (9) | |
C28 | 0.9031 (3) | 0.41793 (18) | 0.2233 (3) | 0.0675 (10) | |
H28 | 0.9081 | 0.3714 | 0.1974 | 0.081* | |
C29 | 0.8324 (3) | 0.4695 (2) | 0.1655 (3) | 0.0721 (11) | |
H29 | 0.7890 | 0.4567 | 0.1024 | 0.087* | |
C30 | 0.8260 (3) | 0.5397 (2) | 0.2010 (3) | 0.0688 (10) | |
C31 | 0.8929 (3) | 0.55711 (19) | 0.2943 (3) | 0.0741 (11) | |
H31 | 0.8911 | 0.6043 | 0.3186 | 0.089* | |
C32 | 0.9623 (3) | 0.50596 (19) | 0.3519 (3) | 0.0676 (10) | |
H32 | 1.0073 | 0.5194 | 0.4140 | 0.081* | |
C33 | 0.7501 (4) | 0.5968 (2) | 0.1383 (3) | 0.1054 (14) | |
H33A | 0.7104 | 0.5755 | 0.0759 | 0.127* | |
H33B | 0.8033 | 0.6352 | 0.1217 | 0.127* | |
H33C | 0.6887 | 0.6156 | 0.1776 | 0.127* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C3 | 0.072 (3) | 0.063 (3) | 0.060 (2) | −0.005 (2) | 0.001 (2) | 0.005 (2) |
O2 | 0.097 (2) | 0.0794 (18) | 0.0742 (17) | −0.0003 (16) | 0.0208 (16) | −0.0103 (14) |
C1 | 0.050 (2) | 0.063 (2) | 0.0482 (19) | −0.0031 (19) | −0.0004 (16) | −0.0003 (17) |
C2 | 0.050 (2) | 0.063 (2) | 0.056 (2) | −0.0063 (19) | −0.0007 (18) | 0.0039 (19) |
N1 | 0.064 (2) | 0.085 (2) | 0.072 (2) | −0.0039 (18) | −0.0083 (17) | −0.0061 (18) |
O1 | 0.0822 (19) | 0.0867 (18) | 0.0686 (16) | −0.0029 (16) | −0.0127 (14) | −0.0155 (14) |
C14 | 0.045 (2) | 0.066 (2) | 0.064 (2) | −0.0017 (19) | 0.0048 (18) | 0.004 (2) |
C15 | 0.067 (3) | 0.083 (3) | 0.084 (3) | 0.013 (2) | 0.019 (2) | 0.008 (2) |
C16 | 0.072 (3) | 0.090 (4) | 0.125 (4) | 0.020 (3) | 0.028 (3) | 0.015 (3) |
C17 | 0.077 (3) | 0.078 (3) | 0.144 (5) | 0.007 (3) | 0.034 (3) | −0.018 (3) |
C18 | 0.083 (3) | 0.094 (3) | 0.093 (3) | −0.008 (3) | 0.020 (3) | −0.027 (3) |
C19 | 0.072 (3) | 0.072 (3) | 0.074 (3) | −0.001 (2) | 0.002 (2) | −0.007 (2) |
C4 | 0.058 (2) | 0.062 (2) | 0.057 (2) | −0.001 (2) | 0.0095 (18) | 0.0007 (18) |
N2 | 0.060 (2) | 0.0633 (19) | 0.0672 (18) | −0.0036 (17) | −0.0049 (15) | 0.0037 (15) |
C5 | 0.059 (2) | 0.060 (2) | 0.056 (2) | 0.005 (2) | 0.0009 (18) | −0.0042 (18) |
C6 | 0.054 (2) | 0.062 (2) | 0.052 (2) | 0.000 (2) | 0.0038 (17) | 0.0001 (18) |
C7 | 0.057 (2) | 0.058 (2) | 0.066 (2) | −0.005 (2) | 0.0022 (19) | 0.0050 (19) |
C8 | 0.075 (3) | 0.069 (3) | 0.071 (2) | −0.006 (2) | 0.019 (2) | −0.005 (2) |
C9 | 0.107 (4) | 0.066 (3) | 0.072 (3) | −0.008 (3) | 0.018 (3) | −0.011 (2) |
C10 | 0.106 (4) | 0.084 (3) | 0.082 (3) | −0.027 (3) | −0.015 (3) | 0.004 (3) |
C11 | 0.066 (3) | 0.100 (4) | 0.148 (4) | −0.025 (3) | −0.016 (3) | 0.020 (3) |
C12 | 0.071 (3) | 0.073 (3) | 0.131 (4) | −0.002 (3) | 0.000 (3) | 0.015 (3) |
C13 | 0.189 (5) | 0.108 (4) | 0.119 (4) | −0.068 (4) | −0.035 (3) | 0.000 (3) |
C20 | 0.056 (2) | 0.056 (2) | 0.067 (2) | 0.0028 (19) | −0.008 (2) | −0.0018 (19) |
C21 | 0.059 (3) | 0.078 (3) | 0.086 (3) | 0.002 (2) | −0.003 (2) | −0.001 (2) |
C22 | 0.062 (3) | 0.095 (3) | 0.119 (4) | 0.003 (3) | 0.002 (3) | 0.007 (3) |
C23 | 0.058 (3) | 0.097 (3) | 0.149 (5) | 0.003 (3) | −0.025 (3) | −0.002 (3) |
C24 | 0.082 (3) | 0.111 (4) | 0.107 (4) | 0.000 (3) | −0.029 (3) | 0.010 (3) |
C25 | 0.071 (3) | 0.092 (3) | 0.078 (3) | 0.000 (2) | −0.013 (2) | 0.008 (2) |
C26 | 0.054 (2) | 0.068 (2) | 0.060 (2) | −0.004 (2) | 0.0043 (18) | 0.0003 (19) |
C27 | 0.056 (2) | 0.064 (2) | 0.057 (2) | −0.005 (2) | 0.0061 (18) | 0.0035 (19) |
C28 | 0.080 (3) | 0.059 (2) | 0.064 (2) | −0.004 (2) | 0.012 (2) | 0.003 (2) |
C29 | 0.079 (3) | 0.079 (3) | 0.058 (2) | −0.003 (2) | 0.006 (2) | 0.004 (2) |
C30 | 0.069 (3) | 0.067 (3) | 0.071 (3) | 0.003 (2) | 0.011 (2) | 0.016 (2) |
C31 | 0.085 (3) | 0.059 (2) | 0.080 (3) | −0.002 (2) | 0.015 (2) | 0.005 (2) |
C32 | 0.076 (3) | 0.063 (2) | 0.065 (2) | −0.012 (2) | 0.012 (2) | 0.002 (2) |
C33 | 0.107 (3) | 0.099 (3) | 0.110 (3) | 0.023 (3) | 0.011 (3) | 0.030 (3) |
C3—O2 | 1.199 (4) | C7—C8 | 1.382 (4) |
C3—O1 | 1.372 (4) | C7—C12 | 1.384 (4) |
C3—C1 | 1.522 (4) | C8—C9 | 1.388 (4) |
C1—C2 | 1.490 (4) | C9—C10 | 1.373 (5) |
C1—C6 | 1.517 (4) | C10—C11 | 1.377 (5) |
C1—C4 | 1.612 (4) | C10—C13 | 1.532 (5) |
C2—N1 | 1.293 (3) | C11—C12 | 1.389 (5) |
C2—C14 | 1.479 (4) | C20—C21 | 1.382 (4) |
N1—O1 | 1.456 (3) | C20—C25 | 1.392 (4) |
C14—C15 | 1.388 (4) | C21—C22 | 1.378 (5) |
C14—C19 | 1.392 (4) | C22—C23 | 1.369 (5) |
C15—C16 | 1.378 (5) | C23—C24 | 1.381 (5) |
C16—C17 | 1.376 (5) | C24—C25 | 1.386 (5) |
C17—C18 | 1.373 (5) | C26—C27 | 1.468 (4) |
C18—C19 | 1.393 (4) | C27—C32 | 1.389 (4) |
C4—N2 | 1.471 (4) | C27—C28 | 1.390 (4) |
C4—C7 | 1.518 (4) | C28—C29 | 1.390 (4) |
N2—C5 | 1.298 (4) | C29—C30 | 1.384 (4) |
C5—C20 | 1.475 (4) | C30—C31 | 1.381 (4) |
C5—C6 | 1.477 (4) | C30—C33 | 1.517 (4) |
C6—C26 | 1.345 (4) | C31—C32 | 1.377 (4) |
O2—C3—O1 | 121.7 (3) | C5—C6—C1 | 105.7 (3) |
O2—C3—C1 | 130.7 (4) | C8—C7—C12 | 118.2 (4) |
O1—C3—C1 | 107.6 (3) | C8—C7—C4 | 122.4 (3) |
C2—C1—C6 | 120.6 (3) | C12—C7—C4 | 119.4 (4) |
C2—C1—C3 | 99.9 (3) | C7—C8—C9 | 120.6 (4) |
C6—C1—C3 | 113.3 (3) | C10—C9—C8 | 121.5 (4) |
C2—C1—C4 | 113.6 (3) | C9—C10—C11 | 117.6 (4) |
C6—C1—C4 | 100.7 (2) | C9—C10—C13 | 120.6 (5) |
C3—C1—C4 | 108.9 (3) | C11—C10—C13 | 121.8 (5) |
N1—C2—C14 | 118.7 (3) | C10—C11—C12 | 121.7 (4) |
N1—C2—C1 | 114.1 (3) | C7—C12—C11 | 120.3 (4) |
C14—C2—C1 | 127.1 (3) | C21—C20—C25 | 118.9 (3) |
C2—N1—O1 | 107.2 (3) | C21—C20—C5 | 121.3 (3) |
C3—O1—N1 | 109.9 (3) | C25—C20—C5 | 119.8 (3) |
C15—C14—C19 | 118.9 (3) | C22—C21—C20 | 120.9 (4) |
C15—C14—C2 | 118.5 (3) | C23—C22—C21 | 119.9 (4) |
C19—C14—C2 | 122.5 (3) | C22—C23—C24 | 120.4 (4) |
C16—C15—C14 | 120.5 (4) | C23—C24—C25 | 119.7 (4) |
C17—C16—C15 | 120.4 (4) | C24—C25—C20 | 120.2 (4) |
C18—C17—C16 | 119.9 (4) | C6—C26—C27 | 128.4 (3) |
C17—C18—C19 | 120.2 (4) | C32—C27—C28 | 117.3 (3) |
C14—C19—C18 | 120.0 (4) | C32—C27—C26 | 119.7 (3) |
N2—C4—C7 | 113.1 (3) | C28—C27—C26 | 123.0 (3) |
N2—C4—C1 | 105.5 (2) | C27—C28—C29 | 121.2 (3) |
C7—C4—C1 | 115.5 (3) | C30—C29—C28 | 120.6 (3) |
C5—N2—C4 | 109.8 (3) | C31—C30—C29 | 118.2 (3) |
N2—C5—C20 | 121.0 (3) | C31—C30—C33 | 120.6 (4) |
N2—C5—C6 | 114.5 (3) | C29—C30—C33 | 121.2 (3) |
C20—C5—C6 | 124.4 (3) | C32—C31—C30 | 121.3 (3) |
C26—C6—C5 | 125.6 (3) | C31—C32—C27 | 121.3 (3) |
C26—C6—C1 | 128.2 (3) | ||
O2—C3—C1—C2 | 169.0 (4) | C4—C1—C6—C26 | −155.3 (3) |
O1—C3—C1—C2 | −11.2 (3) | C2—C1—C6—C5 | 142.9 (3) |
O2—C3—C1—C6 | 39.4 (5) | C3—C1—C6—C5 | −99.0 (3) |
O1—C3—C1—C6 | −140.7 (3) | C4—C1—C6—C5 | 17.2 (3) |
O2—C3—C1—C4 | −71.8 (5) | N2—C4—C7—C8 | −23.0 (4) |
O1—C3—C1—C4 | 108.1 (3) | C1—C4—C7—C8 | 98.7 (4) |
C6—C1—C2—N1 | 135.3 (3) | N2—C4—C7—C12 | 156.7 (3) |
C3—C1—C2—N1 | 10.6 (4) | C1—C4—C7—C12 | −81.6 (4) |
C4—C1—C2—N1 | −105.2 (3) | C12—C7—C8—C9 | 0.3 (5) |
C6—C1—C2—C14 | −41.9 (5) | C4—C7—C8—C9 | −180.0 (3) |
C3—C1—C2—C14 | −166.6 (3) | C7—C8—C9—C10 | 0.0 (6) |
C4—C1—C2—C14 | 77.6 (4) | C8—C9—C10—C11 | −0.2 (6) |
C14—C2—N1—O1 | 171.6 (3) | C8—C9—C10—C13 | −179.8 (3) |
C1—C2—N1—O1 | −5.9 (4) | C9—C10—C11—C12 | 0.1 (7) |
O2—C3—O1—N1 | −171.3 (3) | C13—C10—C11—C12 | 179.7 (4) |
C1—C3—O1—N1 | 8.8 (3) | C8—C7—C12—C11 | −0.4 (6) |
C2—N1—O1—C3 | −2.1 (3) | C4—C7—C12—C11 | 179.9 (3) |
N1—C2—C14—C15 | −32.1 (5) | C10—C11—C12—C7 | 0.2 (7) |
C1—C2—C14—C15 | 145.0 (3) | N2—C5—C20—C21 | 138.5 (3) |
N1—C2—C14—C19 | 152.3 (3) | C6—C5—C20—C21 | −42.0 (5) |
C1—C2—C14—C19 | −30.6 (5) | N2—C5—C20—C25 | −40.9 (5) |
C19—C14—C15—C16 | 0.0 (5) | C6—C5—C20—C25 | 138.7 (3) |
C2—C14—C15—C16 | −175.7 (3) | C25—C20—C21—C22 | 1.3 (5) |
C14—C15—C16—C17 | −1.5 (6) | C5—C20—C21—C22 | −178.1 (3) |
C15—C16—C17—C18 | 1.2 (6) | C20—C21—C22—C23 | −1.8 (6) |
C16—C17—C18—C19 | 0.6 (6) | C21—C22—C23—C24 | 1.2 (7) |
C15—C14—C19—C18 | 1.7 (5) | C22—C23—C24—C25 | −0.1 (7) |
C2—C14—C19—C18 | 177.3 (3) | C23—C24—C25—C20 | −0.3 (6) |
C17—C18—C19—C14 | −2.0 (6) | C21—C20—C25—C24 | −0.2 (5) |
C2—C1—C4—N2 | −148.9 (3) | C5—C20—C25—C24 | 179.1 (3) |
C6—C1—C4—N2 | −18.7 (3) | C5—C6—C26—C27 | −176.8 (3) |
C3—C1—C4—N2 | 100.7 (3) | C1—C6—C26—C27 | −5.7 (6) |
C2—C1—C4—C7 | 85.4 (3) | C6—C26—C27—C32 | 135.8 (4) |
C6—C1—C4—C7 | −144.3 (3) | C6—C26—C27—C28 | −44.1 (5) |
C3—C1—C4—C7 | −25.0 (4) | C32—C27—C28—C29 | −3.8 (5) |
C7—C4—N2—C5 | 140.7 (3) | C26—C27—C28—C29 | 176.1 (3) |
C1—C4—N2—C5 | 13.5 (3) | C27—C28—C29—C30 | 1.7 (5) |
C4—N2—C5—C20 | 177.4 (3) | C28—C29—C30—C31 | 0.9 (5) |
C4—N2—C5—C6 | −2.2 (4) | C28—C29—C30—C33 | 179.5 (3) |
N2—C5—C6—C26 | 161.9 (3) | C29—C30—C31—C32 | −1.3 (5) |
C20—C5—C6—C26 | −17.7 (5) | C33—C30—C31—C32 | −179.9 (3) |
N2—C5—C6—C1 | −10.9 (4) | C30—C31—C32—C27 | −0.9 (5) |
C20—C5—C6—C1 | 169.6 (3) | C28—C27—C32—C31 | 3.4 (5) |
C2—C1—C6—C26 | −29.6 (5) | C26—C27—C32—C31 | −176.5 (3) |
C3—C1—C6—C26 | 88.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···N2 | 0.93 | 2.57 | 2.886 (5) | 100 |
C15—H15···N1 | 0.93 | 2.56 | 2.840 (5) | 97 |
C25—H25···N2 | 0.93 | 2.74 | 2.951 (5) | 94 |
C31—H31···O2i | 0.93 | 2.72 | 3.290 (4) | 120 |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C33H26N2O2 |
Mr | 482.56 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 10.909 (3), 18.502 (7), 13.092 (4) |
β (°) | 97.143 (12) |
V (Å3) | 2621.9 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.46 × 0.27 × 0.22 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5738, 4602, 1712 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.126, 1.14 |
No. of reflections | 4602 |
No. of parameters | 335 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.20 |
Computer programs: XSCANS (Siemens, 1999), XSCANS, SHELXTL-Plus (Sheldrick, 1990), SIR92 (Altomare, 1994), SHELXL97 (Sheldrick, 1997), XPW (Siemens, 1996), PARST97 (Nardelli, 1995) and SHELXL97.
C3—O2 | 1.199 (4) | C2—C14 | 1.479 (4) |
C3—O1 | 1.372 (4) | N1—O1 | 1.456 (3) |
C3—C1 | 1.522 (4) | C4—N2 | 1.471 (4) |
C1—C2 | 1.490 (4) | N2—C5 | 1.298 (4) |
C1—C6 | 1.517 (4) | C5—C6 | 1.477 (4) |
C1—C4 | 1.612 (4) | C6—C26 | 1.345 (4) |
C2—N1 | 1.293 (3) | C26—C27 | 1.468 (4) |
O2—C3—O1 | 121.7 (3) | C6—C1—C3 | 113.3 (3) |
O2—C3—C1 | 130.7 (4) | C2—C1—C4 | 113.6 (3) |
C2—C1—C6 | 120.6 (3) | C3—C1—C4 | 108.9 (3) |
C2—C1—C3 | 99.9 (3) | C6—C26—C27 | 128.4 (3) |
N1—C2—C14—C15 | −32.1 (5) | C6—C5—C20—C21 | −42.0 (5) |
N2—C4—C7—C8 | −23.0 (4) | C6—C26—C27—C28 | −44.1 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···N2 | 0.93 | 2.57 | 2.886 (5) | 100 |
C15—H15···N1 | 0.93 | 2.56 | 2.840 (5) | 97 |
The formation of the title compound, (I), like the o-MeOC6H4– derivative (Bruno et al., 2001a), was rationalized in terms of a series of tandem reactions involving Michael- and retro-Michael reactions, C-alkylation, aldol addition and diastereospecific cyclization (Risitano et al., 2001).
The stereochemistry around the C═C double bond and the newly created tetrahedral C atoms in the spiro compounds could not easily be established by any spectral technique. Therefore, the present study was undertaken in order to obtain unambiguous structural characterization of this new molecule.
The compound consists of a spiro[4.4] system formed by an isoxazolone and a three-substituted pyrroline rings. The pivot atom C1 of the spiro-center and the C4 pyrroline atom are two chiral centers having the same configuration (R,R for the molecule depicted in Fig. 1). Since the compound crystallizes in a centrosymmetric space group, in the solid state we have a racemic mixture.
Bond distances and angles are in good agreement with the literature values (Bertolasi et al., 1994; Brehm et al., 1992). Here we observe the usual asymmetry in bond angles around the carbonyl group. This significant asymmetry is systematically present in all 2800 five-membered rings reported in the last release (5.19) of the Cambridge Structural Database (Allen et al., 1991) that contain a carbonyl group as well as in cumarine derivatives (Bruno et al., 2001b). The main discrepancy between the title compound and the o-MeO derivative rises from the rotation of the phenyl rings as evidenced by the significant difference of the corresponding torsion angles N1—C2—C14—C15 and C6—C26—C27—C28 of 32.7 (5) and 20.0 (5)°, respectively. All the heteroatoms of the spiranic fragments are engaged in some weak intra- and intermolecular hydrogen bonds which determine the relative orientations of substituents with respect to the spiranic moiety and the whole crystal packing.