The title compound, C33H26N2O4, is derived from an unexpected spiran synthesis. Its crystal structure has been determined at room temperature. The skeleton is composed of a spiro[4.4] system formed by an isoxazolone and a substituted pyrroline ring obtained by a series of tandem reactions. The carbonyl exocyclic bond angles [121.9 (2) and 129.9 (2)°] of the isoxazolone ring show the usual asymmetry.
Supporting information
CCDC reference: 165645
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.041
- wR factor = 0.097
- Data-to-parameter ratio = 17.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
GOODF_01 Alert C The least squares goodness of fit parameter lies
outside the range 0.80 <> 2.00
Goodness of fit given = 0.716
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was obtained as a single diastereomer from
4-arylmethyleneisoxazol-5-one and in situ prepared N-ylide (Risitano
et al., 1997).
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 were located in idealized positions and
allowed to ride on their parent C atoms with isotropic displacement parameters
related to the refined values of their corresponding parent atoms.
Data collection: P3/V (Siemens,1989); cell refinement: P3/V; 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.
9-(2-Methoxy-benzylidene)-6-(2-methoxy-phenyl)-4,8-diphenyl-2-oxa-
3,7-diazaspiro[4.4]nona-3,7-dien-1-one
top
Crystal data top
C33H26N2O4 | Z = 2 |
Mr = 514.56 | F(000) = 540 |
Triclinic, P1 | Dx = 1.300 Mg m−3 |
a = 9.127 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.450 (3) Å | Cell parameters from 33 reflections |
c = 14.632 (3) Å | θ = 6.0–12.9° |
α = 99.172 (19)° | µ = 0.09 mm−1 |
β = 101.131 (17)° | T = 293 K |
γ = 101.239 (18)° | Irregular, colourless |
V = 1314.6 (5) Å3 | 0.17 × 0.13 × 0.10 mm |
Data collection top
Siemens P4 diffractometer | Rint = 0.032 |
Radiation source: fine-focus sealed tube | θmax = 27.6°, θmin = 2.0° |
Graphite monochromator | h = 0→11 |
ω–2θ scans | k = −13→13 |
6449 measured reflections | l = −19→18 |
6067 independent reflections | 3 standard reflections every 197 reflections |
2324 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
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)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0434P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.72 | (Δ/σ)max < 0.001 |
6067 reflections | Δρmax = 0.14 e Å−3 |
353 parameters | Δρmin = −0.12 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: 0.0066 (10) |
Crystal data top
C33H26N2O4 | γ = 101.239 (18)° |
Mr = 514.56 | V = 1314.6 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.127 (2) Å | Mo Kα radiation |
b = 10.450 (3) Å | µ = 0.09 mm−1 |
c = 14.632 (3) Å | T = 293 K |
α = 99.172 (19)° | 0.17 × 0.13 × 0.10 mm |
β = 101.131 (17)° | |
Data collection top
Siemens P4 diffractometer | Rint = 0.032 |
6449 measured reflections | 3 standard reflections every 197 reflections |
6067 independent reflections | intensity decay: none |
2324 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.72 | Δρmax = 0.14 e Å−3 |
6067 reflections | Δρmin = −0.12 e Å−3 |
353 parameters | |
Special details top
Experimental. 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.10977 (17) | 0.19704 (15) | 0.05703 (10) | 0.0697 (4) | |
O2 | 0.06428 (19) | 0.08620 (16) | 0.10916 (11) | 0.0778 (5) | |
O3 | −0.44275 (16) | 0.06542 (16) | 0.18440 (11) | 0.0767 (5) | |
O4 | 0.13162 (16) | 0.62202 (13) | 0.38007 (11) | 0.0627 (4) | |
N1 | −0.1893 (2) | 0.28770 (18) | 0.09999 (12) | 0.0623 (5) | |
N2 | −0.01940 (19) | 0.05973 (15) | 0.33299 (11) | 0.0522 (5) | |
C1 | −0.0554 (2) | 0.20630 (18) | 0.22057 (13) | 0.0427 (5) | |
C2 | −0.1566 (2) | 0.29628 (19) | 0.19064 (14) | 0.0472 (5) | |
C3 | −0.0222 (2) | 0.1529 (2) | 0.12636 (15) | 0.0546 (6) | |
C4 | −0.1401 (2) | 0.08823 (18) | 0.26221 (13) | 0.0465 (5) | |
H4A | −0.2103 | 0.1237 | 0.2968 | 0.056* | |
C5 | 0.1027 (2) | 0.15468 (18) | 0.35306 (13) | 0.0438 (5) | |
C6 | 0.0927 (2) | 0.26075 (18) | 0.29690 (13) | 0.0416 (5) | |
C7 | −0.2340 (2) | −0.03312 (19) | 0.18993 (14) | 0.0502 (5) | |
C8 | −0.1717 (3) | −0.1378 (2) | 0.16066 (17) | 0.0764 (7) | |
H8A | −0.0686 | −0.1329 | 0.1857 | 0.092* | |
C9 | −0.2581 (4) | −0.2496 (3) | 0.0953 (2) | 0.1033 (10) | |
H9A | −0.2135 | −0.3189 | 0.0758 | 0.124* | |
C10 | −0.4097 (4) | −0.2574 (3) | 0.0596 (2) | 0.1042 (10) | |
H10A | −0.4689 | −0.3329 | 0.0157 | 0.125* | |
C11 | −0.4760 (3) | −0.1553 (3) | 0.08741 (18) | 0.0842 (8) | |
H11A | −0.5796 | −0.1618 | 0.0626 | 0.101* | |
C12 | −0.3888 (3) | −0.0427 (2) | 0.15233 (16) | 0.0594 (6) | |
C13 | −0.5991 (3) | 0.0641 (3) | 0.1489 (2) | 0.1016 (9) | |
H13A | −0.6206 | 0.1455 | 0.1775 | 0.122* | |
H13B | −0.6633 | −0.0101 | 0.1640 | 0.122* | |
H13C | −0.6192 | 0.0558 | 0.0811 | 0.122* | |
C14 | −0.2262 (2) | 0.38041 (18) | 0.25122 (15) | 0.0484 (5) | |
C15 | −0.3275 (3) | 0.4497 (2) | 0.21214 (18) | 0.0766 (7) | |
H15A | −0.3502 | 0.4449 | 0.1467 | 0.092* | |
C16 | −0.3958 (3) | 0.5264 (3) | 0.2692 (3) | 0.0960 (10) | |
H16A | −0.4638 | 0.5729 | 0.2418 | 0.115* | |
C17 | −0.3644 (3) | 0.5347 (2) | 0.3659 (2) | 0.0851 (8) | |
H17A | −0.4125 | 0.5847 | 0.4038 | 0.102* | |
C18 | −0.2614 (3) | 0.4686 (2) | 0.40581 (19) | 0.0758 (7) | |
H18A | −0.2376 | 0.4749 | 0.4713 | 0.091* | |
C19 | −0.1932 (3) | 0.3928 (2) | 0.34877 (16) | 0.0621 (6) | |
H19A | −0.1229 | 0.3488 | 0.3767 | 0.075* | |
C20 | 0.2378 (2) | 0.15512 (17) | 0.42693 (13) | 0.0435 (5) | |
C21 | 0.3866 (2) | 0.19547 (19) | 0.41597 (15) | 0.0546 (6) | |
H21A | 0.4024 | 0.2241 | 0.3609 | 0.066* | |
C22 | 0.5108 (2) | 0.1935 (2) | 0.48570 (17) | 0.0656 (7) | |
H22A | 0.6098 | 0.2197 | 0.4771 | 0.079* | |
C23 | 0.4892 (3) | 0.1531 (2) | 0.56798 (17) | 0.0685 (7) | |
H23A | 0.5732 | 0.1537 | 0.6157 | 0.082* | |
C24 | 0.3423 (3) | 0.1118 (2) | 0.57934 (15) | 0.0615 (6) | |
H24A | 0.3271 | 0.0829 | 0.6344 | 0.074* | |
C25 | 0.2183 (2) | 0.11304 (17) | 0.50995 (14) | 0.0509 (5) | |
H25A | 0.1197 | 0.0852 | 0.5186 | 0.061* | |
C26 | 0.1870 (2) | 0.38002 (18) | 0.31301 (13) | 0.0476 (5) | |
H26A | 0.2679 | 0.4026 | 0.3666 | 0.057* | |
C27 | 0.1740 (2) | 0.48004 (19) | 0.25258 (15) | 0.0488 (5) | |
C28 | 0.1902 (2) | 0.4540 (2) | 0.15946 (16) | 0.0660 (6) | |
H28A | 0.2097 | 0.3729 | 0.1348 | 0.079* | |
C29 | 0.1778 (3) | 0.5481 (3) | 0.10244 (18) | 0.0778 (7) | |
H29A | 0.1879 | 0.5301 | 0.0399 | 0.093* | |
C30 | 0.1504 (3) | 0.6678 (3) | 0.1399 (2) | 0.0799 (8) | |
H30A | 0.1410 | 0.7306 | 0.1020 | 0.096* | |
C31 | 0.1365 (2) | 0.6964 (2) | 0.23166 (18) | 0.0678 (7) | |
H31A | 0.1197 | 0.7787 | 0.2562 | 0.081* | |
C32 | 0.1475 (2) | 0.6025 (2) | 0.28819 (16) | 0.0534 (6) | |
C33 | 0.0652 (3) | 0.7288 (2) | 0.41123 (17) | 0.0815 (8) | |
H33A | 0.0604 | 0.7320 | 0.4765 | 0.122* | |
H33C | −0.0366 | 0.7150 | 0.3726 | 0.122* | |
H33D | 0.1270 | 0.8115 | 0.4056 | 0.122* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0692 (11) | 0.0961 (12) | 0.0420 (9) | 0.0187 (10) | 0.0065 (8) | 0.0176 (8) |
O2 | 0.0702 (11) | 0.0891 (12) | 0.0728 (12) | 0.0252 (10) | 0.0191 (9) | 0.0017 (9) |
O3 | 0.0398 (9) | 0.0899 (12) | 0.0910 (12) | 0.0117 (9) | −0.0002 (9) | 0.0142 (10) |
O4 | 0.0714 (11) | 0.0528 (9) | 0.0639 (10) | 0.0198 (8) | 0.0061 (8) | 0.0172 (8) |
N1 | 0.0555 (12) | 0.0834 (13) | 0.0501 (12) | 0.0187 (11) | 0.0043 (10) | 0.0263 (10) |
N2 | 0.0473 (11) | 0.0515 (10) | 0.0534 (11) | 0.0050 (9) | −0.0001 (9) | 0.0209 (8) |
C1 | 0.0385 (11) | 0.0499 (11) | 0.0393 (11) | 0.0091 (9) | 0.0035 (9) | 0.0160 (9) |
C2 | 0.0390 (12) | 0.0538 (12) | 0.0451 (12) | 0.0035 (10) | −0.0010 (10) | 0.0220 (10) |
C3 | 0.0454 (14) | 0.0619 (14) | 0.0494 (14) | 0.0053 (12) | 0.0036 (12) | 0.0090 (11) |
C4 | 0.0404 (12) | 0.0490 (12) | 0.0467 (12) | 0.0054 (10) | 0.0005 (10) | 0.0179 (10) |
C5 | 0.0428 (12) | 0.0437 (11) | 0.0437 (12) | 0.0084 (10) | 0.0049 (10) | 0.0140 (9) |
C6 | 0.0389 (12) | 0.0428 (11) | 0.0417 (11) | 0.0084 (9) | 0.0042 (9) | 0.0123 (9) |
C7 | 0.0427 (13) | 0.0465 (12) | 0.0531 (13) | 0.0009 (10) | −0.0025 (11) | 0.0140 (10) |
C8 | 0.0692 (17) | 0.0556 (15) | 0.0890 (18) | 0.0135 (14) | −0.0092 (15) | 0.0045 (13) |
C9 | 0.116 (3) | 0.0648 (18) | 0.107 (2) | 0.0165 (18) | −0.006 (2) | −0.0032 (17) |
C10 | 0.110 (3) | 0.073 (2) | 0.087 (2) | −0.0171 (19) | −0.017 (2) | −0.0099 (16) |
C11 | 0.0605 (17) | 0.089 (2) | 0.0777 (18) | −0.0130 (16) | −0.0094 (15) | 0.0132 (16) |
C12 | 0.0466 (14) | 0.0621 (15) | 0.0586 (14) | −0.0035 (12) | 0.0003 (12) | 0.0152 (12) |
C13 | 0.0485 (16) | 0.144 (3) | 0.110 (2) | 0.0258 (17) | 0.0029 (16) | 0.0354 (19) |
C14 | 0.0402 (12) | 0.0450 (11) | 0.0604 (14) | 0.0078 (10) | 0.0063 (11) | 0.0211 (10) |
C15 | 0.0726 (17) | 0.0775 (16) | 0.0789 (17) | 0.0307 (15) | −0.0030 (15) | 0.0226 (14) |
C16 | 0.0678 (19) | 0.0796 (19) | 0.139 (3) | 0.0383 (16) | 0.004 (2) | 0.016 (2) |
C17 | 0.0696 (19) | 0.0610 (16) | 0.128 (3) | 0.0144 (14) | 0.0401 (19) | 0.0101 (17) |
C18 | 0.093 (2) | 0.0602 (15) | 0.0859 (18) | 0.0224 (15) | 0.0390 (16) | 0.0205 (14) |
C19 | 0.0717 (17) | 0.0591 (14) | 0.0653 (16) | 0.0242 (13) | 0.0220 (13) | 0.0224 (12) |
C20 | 0.0421 (12) | 0.0380 (11) | 0.0462 (12) | 0.0065 (9) | −0.0005 (10) | 0.0126 (9) |
C21 | 0.0505 (14) | 0.0588 (13) | 0.0568 (14) | 0.0135 (11) | 0.0057 (12) | 0.0255 (11) |
C22 | 0.0425 (14) | 0.0680 (15) | 0.0871 (18) | 0.0117 (11) | 0.0045 (13) | 0.0321 (14) |
C23 | 0.0550 (16) | 0.0624 (14) | 0.0770 (17) | 0.0052 (12) | −0.0157 (13) | 0.0300 (13) |
C24 | 0.0647 (16) | 0.0606 (14) | 0.0550 (14) | 0.0064 (12) | −0.0015 (13) | 0.0281 (11) |
C25 | 0.0457 (13) | 0.0465 (12) | 0.0564 (13) | 0.0034 (10) | 0.0022 (11) | 0.0194 (10) |
C26 | 0.0448 (12) | 0.0482 (12) | 0.0461 (12) | 0.0087 (10) | −0.0005 (10) | 0.0152 (10) |
C27 | 0.0408 (12) | 0.0475 (12) | 0.0523 (13) | 0.0016 (10) | −0.0001 (10) | 0.0177 (10) |
C28 | 0.0644 (16) | 0.0661 (15) | 0.0627 (16) | 0.0021 (12) | 0.0095 (13) | 0.0221 (13) |
C29 | 0.0784 (19) | 0.0881 (19) | 0.0638 (16) | −0.0014 (15) | 0.0134 (14) | 0.0354 (15) |
C30 | 0.0794 (19) | 0.0803 (19) | 0.0777 (19) | 0.0048 (15) | −0.0002 (15) | 0.0489 (16) |
C31 | 0.0657 (16) | 0.0562 (14) | 0.0778 (18) | 0.0078 (12) | −0.0008 (14) | 0.0320 (13) |
C32 | 0.0451 (13) | 0.0532 (13) | 0.0559 (14) | 0.0033 (11) | −0.0022 (11) | 0.0210 (11) |
C33 | 0.0901 (19) | 0.0718 (16) | 0.0862 (19) | 0.0351 (15) | 0.0136 (15) | 0.0147 (14) |
Geometric parameters (Å, º) top
O1—C3 | 1.364 (2) | C9—C10 | 1.364 (4) |
O1—N1 | 1.440 (2) | C10—C11 | 1.371 (4) |
O2—C3 | 1.187 (2) | C11—C12 | 1.381 (3) |
O3—C12 | 1.369 (3) | C14—C15 | 1.377 (3) |
O3—C13 | 1.417 (2) | C14—C19 | 1.380 (3) |
O4—C32 | 1.367 (2) | C15—C16 | 1.382 (3) |
O4—C33 | 1.425 (2) | C16—C17 | 1.373 (4) |
N1—C2 | 1.287 (2) | C17—C18 | 1.368 (3) |
N2—C5 | 1.289 (2) | C18—C19 | 1.376 (3) |
N2—C4 | 1.470 (2) | C20—C25 | 1.387 (2) |
C1—C2 | 1.498 (2) | C20—C21 | 1.389 (3) |
C1—C3 | 1.512 (3) | C21—C22 | 1.377 (3) |
C1—C6 | 1.520 (2) | C22—C23 | 1.374 (3) |
C1—C4 | 1.594 (2) | C23—C24 | 1.376 (3) |
C2—C14 | 1.466 (3) | C24—C25 | 1.370 (3) |
C4—C7 | 1.503 (3) | C26—C27 | 1.480 (2) |
C5—C20 | 1.473 (2) | C27—C32 | 1.388 (3) |
C5—C6 | 1.488 (2) | C27—C28 | 1.389 (3) |
C6—C26 | 1.327 (2) | C28—C29 | 1.395 (3) |
C7—C8 | 1.374 (3) | C29—C30 | 1.372 (3) |
C7—C12 | 1.392 (3) | C30—C31 | 1.363 (3) |
C8—C9 | 1.376 (3) | C31—C32 | 1.386 (3) |
| | | |
C3—O1—N1 | 109.45 (16) | C10—C11—C12 | 119.9 (3) |
C12—O3—C13 | 118.61 (19) | O3—C12—C11 | 124.8 (2) |
C32—O4—C33 | 117.50 (16) | O3—C12—C7 | 115.1 (2) |
C2—N1—O1 | 108.89 (16) | C11—C12—C7 | 120.1 (2) |
C5—N2—C4 | 110.15 (14) | C15—C14—C19 | 117.7 (2) |
C2—C1—C3 | 100.42 (15) | C15—C14—C2 | 120.7 (2) |
C2—C1—C6 | 120.68 (16) | C19—C14—C2 | 121.53 (17) |
C3—C1—C6 | 110.80 (16) | C14—C15—C16 | 120.6 (2) |
C2—C1—C4 | 112.84 (15) | C17—C16—C15 | 120.7 (2) |
C3—C1—C4 | 110.79 (16) | C18—C17—C16 | 119.3 (3) |
C6—C1—C4 | 101.51 (13) | C17—C18—C19 | 119.8 (2) |
N1—C2—C14 | 119.84 (17) | C18—C19—C14 | 121.8 (2) |
N1—C2—C1 | 112.62 (19) | C25—C20—C21 | 118.10 (18) |
C14—C2—C1 | 127.38 (17) | C25—C20—C5 | 119.96 (18) |
O2—C3—O1 | 121.9 (2) | C21—C20—C5 | 121.94 (18) |
O2—C3—C1 | 129.93 (19) | C22—C21—C20 | 120.8 (2) |
O1—C3—C1 | 108.16 (18) | C23—C22—C21 | 120.2 (2) |
N2—C4—C7 | 113.56 (15) | C22—C23—C24 | 119.5 (2) |
N2—C4—C1 | 105.44 (14) | C25—C24—C23 | 120.4 (2) |
C7—C4—C1 | 115.81 (16) | C24—C25—C20 | 120.9 (2) |
N2—C5—C20 | 121.16 (16) | C6—C26—C27 | 125.27 (18) |
N2—C5—C6 | 114.44 (16) | C32—C27—C28 | 118.59 (18) |
C20—C5—C6 | 124.40 (18) | C32—C27—C26 | 120.73 (19) |
C26—C6—C5 | 127.72 (17) | C28—C27—C26 | 120.67 (19) |
C26—C6—C1 | 127.28 (16) | C27—C28—C29 | 120.7 (2) |
C5—C6—C1 | 104.89 (16) | C30—C29—C28 | 119.0 (2) |
C8—C7—C12 | 118.3 (2) | C31—C30—C29 | 121.3 (2) |
C8—C7—C4 | 121.70 (19) | C30—C31—C32 | 119.8 (2) |
C12—C7—C4 | 119.97 (19) | O4—C32—C31 | 123.5 (2) |
C7—C8—C9 | 121.7 (2) | O4—C32—C27 | 115.87 (17) |
C10—C9—C8 | 119.1 (3) | C31—C32—C27 | 120.6 (2) |
C9—C10—C11 | 120.8 (3) | | |
| | | |
C3—O1—N1—C2 | −1.8 (2) | C10—C11—C12—O3 | 179.4 (2) |
O1—N1—C2—C14 | −178.58 (16) | C10—C11—C12—C7 | −0.4 (4) |
O1—N1—C2—C1 | −2.8 (2) | C8—C7—C12—O3 | −179.8 (2) |
C3—C1—C2—N1 | 5.7 (2) | C4—C7—C12—O3 | 1.5 (3) |
C6—C1—C2—N1 | 127.63 (19) | C8—C7—C12—C11 | 0.1 (3) |
C4—C1—C2—N1 | −112.26 (19) | C4—C7—C12—C11 | −178.6 (2) |
C3—C1—C2—C14 | −178.88 (18) | N1—C2—C14—C15 | 0.6 (3) |
C6—C1—C2—C14 | −57.0 (3) | C1—C2—C14—C15 | −174.53 (19) |
C4—C1—C2—C14 | 63.1 (2) | N1—C2—C14—C19 | −179.57 (19) |
N1—O1—C3—O2 | −173.32 (19) | C1—C2—C14—C19 | 5.3 (3) |
N1—O1—C3—C1 | 5.5 (2) | C19—C14—C15—C16 | −1.4 (3) |
C2—C1—C3—O2 | 172.1 (2) | C2—C14—C15—C16 | 178.4 (2) |
C6—C1—C3—O2 | 43.5 (3) | C14—C15—C16—C17 | −0.2 (4) |
C4—C1—C3—O2 | −68.4 (3) | C15—C16—C17—C18 | 1.6 (4) |
C2—C1—C3—O1 | −6.5 (2) | C16—C17—C18—C19 | −1.3 (4) |
C6—C1—C3—O1 | −135.18 (16) | C17—C18—C19—C14 | −0.4 (3) |
C4—C1—C3—O1 | 112.95 (17) | C15—C14—C19—C18 | 1.7 (3) |
C5—N2—C4—C7 | 141.90 (18) | C2—C14—C19—C18 | −178.12 (19) |
C5—N2—C4—C1 | 14.1 (2) | N2—C5—C20—C25 | −38.8 (3) |
C2—C1—C4—N2 | −149.07 (16) | C6—C5—C20—C25 | 140.34 (19) |
C3—C1—C4—N2 | 99.23 (17) | N2—C5—C20—C21 | 140.5 (2) |
C6—C1—C4—N2 | −18.48 (18) | C6—C5—C20—C21 | −40.4 (3) |
C2—C1—C4—C7 | 84.5 (2) | C25—C20—C21—C22 | 0.0 (3) |
C3—C1—C4—C7 | −27.2 (2) | C5—C20—C21—C22 | −179.28 (18) |
C6—C1—C4—C7 | −144.93 (16) | C20—C21—C22—C23 | −0.9 (3) |
C4—N2—C5—C20 | 175.92 (17) | C21—C22—C23—C24 | 1.4 (3) |
C4—N2—C5—C6 | −3.3 (2) | C22—C23—C24—C25 | −1.1 (3) |
N2—C5—C6—C26 | 167.00 (19) | C23—C24—C25—C20 | 0.3 (3) |
C20—C5—C6—C26 | −12.2 (3) | C21—C20—C25—C24 | 0.3 (3) |
N2—C5—C6—C1 | −9.4 (2) | C5—C20—C25—C24 | 179.59 (18) |
C20—C5—C6—C1 | 171.37 (17) | C5—C6—C26—C27 | 177.86 (19) |
C2—C1—C6—C26 | −34.5 (3) | C1—C6—C26—C27 | −6.5 (3) |
C3—C1—C6—C26 | 82.2 (2) | C6—C26—C27—C32 | 116.8 (2) |
C4—C1—C6—C26 | −160.08 (19) | C6—C26—C27—C28 | −64.1 (3) |
C2—C1—C6—C5 | 141.88 (17) | C32—C27—C28—C29 | −1.0 (3) |
C3—C1—C6—C5 | −101.35 (17) | C26—C27—C28—C29 | 179.9 (2) |
C4—C1—C6—C5 | 16.34 (18) | C27—C28—C29—C30 | 0.5 (3) |
N2—C4—C7—C8 | −31.9 (3) | C28—C29—C30—C31 | 0.6 (4) |
C1—C4—C7—C8 | 90.4 (2) | C29—C30—C31—C32 | −1.1 (4) |
N2—C4—C7—C12 | 146.80 (18) | C33—O4—C32—C31 | 15.4 (3) |
C1—C4—C7—C12 | −91.0 (2) | C33—O4—C32—C27 | −163.81 (18) |
C12—C7—C8—C9 | 0.5 (4) | C30—C31—C32—O4 | −178.5 (2) |
C4—C7—C8—C9 | 179.2 (2) | C30—C31—C32—C27 | 0.6 (3) |
C7—C8—C9—C10 | −0.8 (4) | C28—C27—C32—O4 | 179.66 (18) |
C8—C9—C10—C11 | 0.4 (5) | C26—C27—C32—O4 | −1.3 (3) |
C9—C10—C11—C12 | 0.1 (4) | C28—C27—C32—C31 | 0.4 (3) |
C13—O3—C12—C11 | −0.4 (3) | C26—C27—C32—C31 | 179.5 (2) |
C13—O3—C12—C7 | 179.44 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O3 | 0.98 | 2.32 | 2.725 (2) | 103 |
C8—H8A···O2 | 0.93 | 2.87 | 3.148 (3) | 98 |
C8—H8A···N2 | 0.93 | 2.61 | 2.902 (3) | 99 |
C15—H15A···N1 | 0.93 | 2.51 | 2.810 (3) | 99 |
C25—H25A···N2 | 0.93 | 2.71 | 2.936 (3) | 94 |
C13—H13A···O2i | 0.96 | 2.77 | 3.076 (3) | 100 |
C30—H30A···O1ii | 0.93 | 2.54 | 3.396 (3) | 153 |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z. |
Experimental details
Crystal data |
Chemical formula | C33H26N2O4 |
Mr | 514.56 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.127 (2), 10.450 (3), 14.632 (3) |
α, β, γ (°) | 99.172 (19), 101.131 (17), 101.239 (18) |
V (Å3) | 1314.6 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.17 × 0.13 × 0.10 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6449, 6067, 2324 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.651 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.097, 0.72 |
No. of reflections | 6067 |
No. of parameters | 353 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.14, −0.12 |
Selected geometric parameters (Å, º) topO1—C3 | 1.364 (2) | C1—C2 | 1.498 (2) |
O1—N1 | 1.440 (2) | C1—C3 | 1.512 (3) |
O2—C3 | 1.187 (2) | C1—C6 | 1.520 (2) |
O3—C12 | 1.369 (3) | C1—C4 | 1.594 (2) |
O3—C13 | 1.417 (2) | C4—C7 | 1.503 (3) |
O4—C32 | 1.367 (2) | C5—C20 | 1.473 (2) |
O4—C33 | 1.425 (2) | C5—C6 | 1.488 (2) |
N1—C2 | 1.287 (2) | C6—C26 | 1.327 (2) |
N2—C5 | 1.289 (2) | C26—C27 | 1.480 (2) |
N2—C4 | 1.470 (2) | | |
| | | |
C12—O3—C13 | 118.61 (19) | O2—C3—O1 | 121.9 (2) |
C32—O4—C33 | 117.50 (16) | O2—C3—C1 | 129.93 (19) |
C2—C1—C3 | 100.42 (15) | O3—C12—C11 | 124.8 (2) |
C2—C1—C6 | 120.68 (16) | O3—C12—C7 | 115.1 (2) |
C3—C1—C6 | 110.80 (16) | C6—C26—C27 | 125.27 (18) |
C2—C1—C4 | 112.84 (15) | O4—C32—C31 | 123.5 (2) |
C3—C1—C4 | 110.79 (16) | O4—C32—C27 | 115.87 (17) |
| | | |
N2—C4—C7—C8 | −31.9 (3) | C6—C5—C20—C21 | −40.4 (3) |
C13—O3—C12—C7 | 179.44 (19) | C6—C26—C27—C28 | −64.1 (3) |
N1—C2—C14—C15 | 0.6 (3) | C33—O4—C32—C27 | −163.81 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O3 | 0.98 | 2.32 | 2.725 (2) | 103 |
C15—H15A···N1 | 0.93 | 2.51 | 2.810 (3) | 99 |
C30—H30A···O1i | 0.93 | 2.54 | 3.396 (3) | 153 |
Symmetry code: (i) −x, −y+1, −z. |
The formation of the title compound, (I), has been interpreted, like the p-MeC6H4– derivative (Bruno et al., 2001a), as the unexpected product 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 of the C═C double bond and of the tetrahedral C atoms of the product could not easily be established by any spectral technique. The structure at the solid state has been unambiguously determined by X-ray diffraction diffraction.
The title compound is very similar to the already reported p-Me derivative (Bruno et al., 2001a), obtained by the similar reaction with the same N-ylide. The molecular skeleton is a spiro[4.4] system constituted by an isoxazolone and a three-substituted pyrroline ring. The two chiral C atoms, the spiro center C1 and the pyrroline C4 atom, have the same configuration (R,R in Fig. 1). Due to the crystallographic centre of symmetry, the crystal is the racemic mixture of both enhantiomers.
The geometric values of the two similar compounds are comparable within the experimental error and are in good agreement with the known data (Bertolasi et al., 1994; Brehm et al., 1992). The carbonyl group shows almost the same asymmetry, in agreement with the other known carbonyl groups (Allen et al., 1991) and cumarine derivatives (Bruno et al., 2001b). Both compounds have the isoxazolone linked through the C2 atom to a phenyl group.
Although the torsion angles defining the orientation of phenyl with respect to the eterocyclic ring are very different [N1—C2—C14—C15 = 0.6 (3) versus -32.1 (5)° of the p-tolyl derivative] the C2—C14 bond distances are almost equal. The largest discrepancy between the two similar structures is observed for the C6—C26—C27—C28 torsion angle. Due to steric interactions, the methoxy groups are differently oriented with respect to the phenyl to which are bonded [C13—O3—C12—C7 = 179.4 (2)°, while C33—O4—C32—C27 = -163.8 (2)°]. Weak intra- and intermolecular hydrogen-bond interactions determine the crystal packing and the relative orientations of substituents with respect to the single spiranic fragment.