Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104008224/bm1565sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104008224/bm1565Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104008224/bm1565IIsup3.hkl |
CCDC references: 243612; 243613
Diels-Alder adducts were obtained by reaction between of 1H-pirrole-1-[2'-acetoxyphenyl]-2,5-dione or 1H-pirrole-1- [4'-acetoxyphenyl]-2,5-dione (1.0 mmol) and furan (2.2 mmol) dissolved in xylene (3 ml) in a sealed ampoule at 140 °C for 8 h. The products crystallize as white solids in 73% and 56% yield, respectively. In both cases crystals suitable for X-ray analysis were obtained from chloroform solutions by slow hexane diffusion. Melting points were measured on a Gallenkamp MFB-595 apparatus and are uncorrected. IR spectra were recorded as KBr discs using a Perkin-Elmer 16 F PC IR spectrophotometer. 1H and 13C NMR spectra were recorded with a Jeol Eclipse instrument (1H, 270.17; 13C, 67.94 MHz) in CDCl3 solutions, measured with SiMe4 as internal reference following standard techniques. Mass spectra were recorded on a Hewlett Packard 5989 A Series II spectrometer.
Exo-4-(2'-acetoxyphenyl)-10-oxa-4-azatricyclo(5.2.1.02,6)dec-8-en −3,5-dione (I). Colourless crystals, mp 175–179 °C; IR (KBr) ν/cm−1: 1728, 1766 (C═O), 1592 (C ═C), 1384 (OAc), 1310 (C—N); 1H NMR δ/(p.p.m.): 7.44 (m, 1H, H-13), 7.32 (m, 1H, H-14), 7.27 (m, 1H, H-12), 7.26 (m, 1H, H-15), 6.56 (s, 2H, H-8,9), 5.37 (s, 2H, H-1,7), 3.00 (s, 2H, H-2,6), 2.19 (s, 3H, Me); 13C NMR δ/(p.p.m.): 174.6 (C-3,5), 168.4 (C-17), 146.3 (C-11), 136.7 (C-8,9), 130.5 (C-13), 129.1 (C-15), 126.5 (C-14), 124.4 (C-10), 123.8 (C-12), 81.3 (C-1,7), 47.7 (C-2,6), 20.6 (Me); MS m/z (%) 299 (2) (M+), 257 (14), 231 (13), 189 (100), 161 (3), 145 (62).
Exo-4-(4'-acetoxyphenyl)-10-oxa-4-azatricyclo(5.2.1.02,6)dec-8-en −3,5-dione (II). Colourless crystals, mp 165–170 °C; IR (KBr) ν/cm−1: 1710, 1758 (C═O), 1600 (C═C), 1366 (OAc), 1310 (C—N); 1H NMR δ/(p.p.m.): 7.31 (d, 2H, H-11,15), 7.19 (d, 2H, H-12,14), 6.53 (s, 2H, H-8,9), 5.36 (s, 2H, H-1,7), 2.97 (s, 2H, H-2,6), 2.29 (s, 3H, Me); 13C NMR δ/(p.p.m.): 175.2 (C-3,5), 168.8 (C-17), 150.4 (C-13), 136.6 (C-8,9), 129.0 (C-11), 127.5 (C-11,15), 122.2 (C-12,14), 81.3 (C-1,7), 47.4 (C-2,6), 21.0 (Me); MS m/z (%) 299 (4) (M+), 257 (6), 231 (13), 189 (100), 161 (5), 145 (7).
H atoms were treated as riding atoms, with distances in the range 0.93–0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C) for others.
For both compounds, data collection: CAD-4 EXPRESS (Enraf Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: JANA98 (Vaclav, 1998). Program(s) used to solve structure: SHELXS97(Sheldrick, 1997) for (I); SHELXS97 (Sheldrick, 1997) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: SHELXL97 and RESVIEW (Schwenk, 1996).
C16H13NO5 | F(000) = 624 |
Mr = 299.27 | Dx = 1.423 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 24 reflections |
a = 8.859 (1) Å | θ = 10–11° |
b = 12.830 (2) Å | µ = 0.11 mm−1 |
c = 12.615 (1) Å | T = 293 K |
β = 102.971 (2)° | Square prism, colorless |
V = 1397.2 (3) Å3 | 0.5 × 0.3 × 0.1 mm |
Z = 4 |
Enraf-Nonius CAD4 diffractometer | 1767 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.012 |
Graphite monochromator | θmax = 27.0°, θmin = 2.3° |
Detector resolution: 3 pixels mm-1 | h = −11→11 |
ω/2θ scans | k = 0→16 |
3024 measured reflections | l = 0→16 |
3024 independent reflections |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0648P)2] where P = (Fo2 + 2Fc2)/3 |
3024 reflections | (Δ/σ)max < 0.001 |
199 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C16H13NO5 | V = 1397.2 (3) Å3 |
Mr = 299.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.859 (1) Å | µ = 0.11 mm−1 |
b = 12.830 (2) Å | T = 293 K |
c = 12.615 (1) Å | 0.5 × 0.3 × 0.1 mm |
β = 102.971 (2)° |
Enraf-Nonius CAD4 diffractometer | 1767 reflections with I > 2σ(I) |
3024 measured reflections | Rint = 0.012 |
3024 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.22 e Å−3 |
3024 reflections | Δρmin = −0.22 e Å−3 |
199 parameters |
Experimental. Diffractometer operator Susana Rojas scanwidth_degrees 0.7 low_scanspeed_degrees/min 16.1 high_scanspeed_degrees/min 60 Background measurement: Moving crystal and moving counter at the beginning and end of scan, each for 25% of total scan area. Crystal mounted on a glass fiber. |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O1 | 0.49533 (15) | 0.20117 (10) | 0.40385 (10) | 0.0517 (4) | |
O3 | 0.47902 (14) | 0.06648 (10) | 0.13987 (11) | 0.0513 (4) | |
O5 | 0.75555 (18) | 0.35679 (12) | 0.26498 (16) | 0.0825 (7) | |
O16 | 0.77638 (13) | 0.02143 (10) | 0.31047 (9) | 0.0442 (4) | |
O17 | 0.92242 (19) | 0.11933 (12) | 0.44083 (12) | 0.0698 (6) | |
N4 | 0.64920 (15) | 0.20033 (10) | 0.20070 (11) | 0.0377 (4) | |
C1 | 0.3540 (2) | 0.17664 (15) | 0.32589 (15) | 0.0483 (6) | |
C2 | 0.39280 (19) | 0.22151 (13) | 0.22041 (13) | 0.0388 (5) | |
C3 | 0.50446 (18) | 0.15109 (13) | 0.18062 (13) | 0.0365 (5) | |
C5 | 0.6463 (2) | 0.29921 (13) | 0.24562 (16) | 0.0457 (6) | |
C6 | 0.4870 (2) | 0.31903 (13) | 0.26490 (14) | 0.0408 (5) | |
C7 | 0.4861 (2) | 0.31216 (14) | 0.38806 (15) | 0.0468 (6) | |
C8 | 0.3207 (2) | 0.33437 (16) | 0.39648 (15) | 0.0531 (6) | |
C9 | 0.2407 (2) | 0.25130 (17) | 0.35860 (16) | 0.0574 (7) | |
C10 | 0.78422 (18) | 0.15391 (13) | 0.17741 (13) | 0.0373 (5) | |
C11 | 0.84853 (18) | 0.06624 (13) | 0.23344 (13) | 0.0379 (5) | |
C12 | 0.97745 (19) | 0.01889 (15) | 0.21066 (14) | 0.0459 (6) | |
C13 | 1.0443 (2) | 0.06109 (16) | 0.13155 (16) | 0.0517 (6) | |
C14 | 0.9822 (2) | 0.14950 (16) | 0.07573 (15) | 0.0529 (6) | |
C15 | 0.8522 (2) | 0.19553 (15) | 0.09806 (14) | 0.0470 (6) | |
C17 | 0.8240 (2) | 0.05535 (14) | 0.41477 (14) | 0.0461 (6) | |
C18 | 0.7362 (3) | 0.00211 (17) | 0.48723 (16) | 0.0617 (7) | |
H1A | 0.32345 | 0.10309 | 0.32240 | 0.0580* | |
H2A | 0.30023 | 0.23767 | 0.16397 | 0.0466* | |
H6A | 0.44056 | 0.38363 | 0.23093 | 0.0490* | |
H7A | 0.56627 | 0.35291 | 0.43683 | 0.0562* | |
H8A | 0.28388 | 0.39458 | 0.42307 | 0.0636* | |
H9A | 0.13540 | 0.24046 | 0.35298 | 0.0689* | |
H12A | 1.01880 | −0.04072 | 0.24815 | 0.0551* | |
H13A | 1.13146 | 0.02993 | 0.11574 | 0.0621* | |
H14A | 1.02818 | 0.17798 | 0.02295 | 0.0635* | |
H15A | 0.81014 | 0.25459 | 0.05986 | 0.0564* | |
H18A | 0.77172 | 0.02691 | 0.56038 | 0.0926* | |
H18B | 0.75252 | −0.07176 | 0.48525 | 0.0926* | |
H18C | 0.62771 | 0.01694 | 0.46267 | 0.0926* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0510 (8) | 0.0551 (8) | 0.0488 (7) | 0.0098 (6) | 0.0110 (6) | 0.0121 (6) |
O3 | 0.0460 (7) | 0.0456 (7) | 0.0632 (8) | −0.0074 (6) | 0.0139 (6) | −0.0094 (6) |
O5 | 0.0560 (9) | 0.0586 (9) | 0.1474 (16) | −0.0264 (8) | 0.0537 (10) | −0.0365 (10) |
O16 | 0.0424 (7) | 0.0465 (7) | 0.0450 (6) | −0.0055 (6) | 0.0127 (5) | 0.0045 (5) |
O17 | 0.0822 (11) | 0.0713 (10) | 0.0613 (9) | −0.0290 (9) | 0.0278 (8) | −0.0195 (7) |
N4 | 0.0303 (7) | 0.0352 (7) | 0.0505 (8) | −0.0018 (6) | 0.0154 (6) | 0.0004 (6) |
C1 | 0.0453 (10) | 0.0461 (10) | 0.0583 (10) | −0.0040 (8) | 0.0217 (8) | 0.0080 (8) |
C2 | 0.0290 (8) | 0.0433 (9) | 0.0450 (9) | 0.0007 (7) | 0.0099 (7) | 0.0054 (7) |
C3 | 0.0313 (8) | 0.0382 (9) | 0.0409 (8) | −0.0028 (7) | 0.0097 (6) | 0.0034 (7) |
C5 | 0.0405 (9) | 0.0360 (9) | 0.0665 (11) | −0.0057 (8) | 0.0247 (8) | −0.0008 (8) |
C6 | 0.0372 (9) | 0.0338 (8) | 0.0540 (10) | 0.0041 (7) | 0.0155 (7) | 0.0042 (7) |
C7 | 0.0410 (10) | 0.0478 (10) | 0.0514 (10) | 0.0070 (8) | 0.0100 (8) | −0.0017 (8) |
C8 | 0.0521 (11) | 0.0595 (12) | 0.0535 (10) | 0.0112 (10) | 0.0244 (9) | 0.0022 (9) |
C9 | 0.0469 (10) | 0.0712 (14) | 0.0624 (12) | 0.0036 (10) | 0.0298 (10) | 0.0042 (11) |
C10 | 0.0295 (8) | 0.0410 (8) | 0.0430 (8) | −0.0020 (7) | 0.0116 (6) | −0.0029 (7) |
C11 | 0.0348 (8) | 0.0408 (9) | 0.0391 (8) | −0.0034 (7) | 0.0104 (7) | −0.0023 (7) |
C12 | 0.0366 (9) | 0.0458 (10) | 0.0536 (10) | 0.0057 (8) | 0.0066 (8) | −0.0039 (8) |
C13 | 0.0352 (9) | 0.0670 (13) | 0.0560 (10) | 0.0027 (9) | 0.0166 (8) | −0.0132 (9) |
C14 | 0.0417 (10) | 0.0719 (13) | 0.0499 (10) | −0.0045 (10) | 0.0206 (8) | −0.0002 (10) |
C15 | 0.0409 (10) | 0.0538 (11) | 0.0493 (10) | −0.0010 (8) | 0.0164 (8) | 0.0075 (8) |
C17 | 0.0463 (10) | 0.0443 (10) | 0.0494 (10) | 0.0028 (8) | 0.0144 (8) | 0.0007 (8) |
C18 | 0.0677 (13) | 0.0686 (13) | 0.0545 (11) | 0.0023 (11) | 0.0256 (10) | 0.0140 (10) |
O1—C1 | 1.443 (2) | C10—C15 | 1.386 (2) |
O1—C7 | 1.438 (2) | C11—C12 | 1.380 (2) |
O3—C3 | 1.201 (2) | C12—C13 | 1.380 (3) |
O5—C5 | 1.198 (2) | C13—C14 | 1.382 (3) |
O16—C11 | 1.401 (2) | C14—C15 | 1.378 (3) |
O16—C17 | 1.360 (2) | C17—C18 | 1.492 (3) |
O17—C17 | 1.189 (2) | C1—H1A | 0.9800 |
N4—C3 | 1.401 (2) | C2—H2A | 0.9800 |
N4—C5 | 1.392 (2) | C6—H6A | 0.9801 |
N4—C10 | 1.425 (2) | C7—H7A | 0.9799 |
C1—C2 | 1.557 (2) | C8—H8A | 0.9299 |
C1—C9 | 1.510 (3) | C9—H9A | 0.9300 |
C2—C3 | 1.507 (2) | C12—H12A | 0.9301 |
C2—C6 | 1.538 (2) | C13—H13A | 0.9300 |
C5—C6 | 1.506 (3) | C14—H14A | 0.9298 |
C6—C7 | 1.558 (3) | C15—H15A | 0.9299 |
C7—C8 | 1.520 (3) | C18—H18A | 0.9599 |
C8—C9 | 1.309 (3) | C18—H18B | 0.9599 |
C10—C11 | 1.382 (2) | C18—H18C | 0.9603 |
O1···N4 | 3.1613 (19) | C12···C8ii | 3.578 (3) |
O1···C18 | 3.343 (3) | C12···O5x | 3.113 (2) |
O3···C8i | 3.329 (2) | C13···O5x | 3.268 (3) |
O3···O16 | 3.0594 (18) | C13···C13xi | 3.594 (3) |
O3···C11 | 3.221 (2) | C13···C1vi | 3.566 (3) |
O3···C6ii | 3.384 (2) | C14···O17i | 3.401 (3) |
O3···C7ii | 3.304 (2) | C15···O5 | 3.203 (3) |
O5···C15 | 3.203 (3) | C15···O17i | 3.243 (2) |
O5···C12iii | 3.113 (2) | C17···O17iv | 3.399 (2) |
O5···C13iii | 3.268 (3) | C17···N4 | 3.358 (2) |
O16···N4 | 2.7848 (18) | C18···O17iv | 3.341 (3) |
O16···O3 | 3.0594 (18) | C18···C1viii | 3.507 (3) |
O16···C3 | 3.079 (2) | C18···O1 | 3.343 (3) |
O17···C17iv | 3.399 (2) | C1···H18Bviii | 3.0638 |
O17···C15v | 3.243 (2) | C5···H15A | 3.0745 |
O17···C18iv | 3.341 (3) | C9···H18Bviii | 3.0227 |
O17···C12 | 3.311 (2) | C11···H8Aii | 3.0141 |
O17···C14v | 3.401 (3) | C12···H8Aii | 2.9994 |
O17···C10 | 3.303 (2) | C13···H1Avi | 3.0870 |
O1···H18C | 2.6688 | C14···H2Avi | 3.0081 |
O3···H7Aii | 2.9036 | C15···H7Ai | 2.9371 |
O3···H6Aii | 2.8542 | C17···H15Av | 3.0679 |
O5···H13Aiii | 2.7431 | C18···H1Aviii | 2.9048 |
O5···H12Aiii | 2.4293 | H1A···C13vii | 3.0870 |
O16···H6Aii | 2.5771 | H1A···C18viii | 2.9048 |
O17···H9Avi | 2.8534 | H1A···H18Aviii | 2.4978 |
O17···H18Biv | 2.8860 | H2A···C14vii | 3.0081 |
O17···H14Av | 2.8771 | H6A···O3ix | 2.8542 |
O17···H15Av | 2.5556 | H6A···O16ix | 2.5771 |
N4···O1 | 3.1613 (19) | H7A···O3ix | 2.9036 |
N4···O16 | 2.7848 (18) | H7A···C15v | 2.9371 |
N4···C17 | 3.358 (2) | H8A···C11ix | 3.0141 |
C1···C13vii | 3.566 (3) | H8A···C12ix | 2.9994 |
C1···C18viii | 3.507 (3) | H9A···O17vii | 2.8534 |
C3···O16 | 3.079 (2) | H12A···O5x | 2.4293 |
C3···C8i | 3.594 (3) | H13A···O5x | 2.7431 |
C6···O3ix | 3.384 (2) | H14A···O17i | 2.8771 |
C7···O3ix | 3.304 (2) | H15A···C5 | 3.0745 |
C8···C12ix | 3.578 (3) | H15A···O17i | 2.5556 |
C8···C11ix | 3.561 (3) | H15A···C17i | 3.0679 |
C8···C3v | 3.594 (3) | H18A···H1Aviii | 2.4978 |
C8···O3v | 3.329 (2) | H18B···O17iv | 2.8860 |
C10···O17 | 3.303 (2) | H18B···C1viii | 3.0638 |
C11···C8ii | 3.561 (3) | H18B···C9viii | 3.0227 |
C11···O3 | 3.221 (2) | H18C···O1 | 2.6688 |
C12···O17 | 3.311 (2) | ||
C1—O1—C7 | 96.20 (13) | C10—C15—C14 | 120.07 (17) |
C11—O16—C17 | 116.68 (13) | O16—C17—O17 | 122.51 (17) |
C3—N4—C5 | 112.64 (14) | O16—C17—C18 | 110.80 (15) |
C3—N4—C10 | 123.44 (13) | O17—C17—C18 | 126.69 (17) |
C5—N4—C10 | 123.92 (14) | O1—C1—H1A | 115.43 |
O1—C1—C2 | 100.23 (13) | C2—C1—H1A | 115.42 |
O1—C1—C9 | 101.75 (14) | C9—C1—H1A | 115.42 |
C2—C1—C9 | 106.66 (15) | C1—C2—H2A | 112.94 |
C1—C2—C3 | 110.51 (14) | C3—C2—H2A | 112.94 |
C1—C2—C6 | 101.22 (13) | C6—C2—H2A | 112.95 |
C3—C2—C6 | 105.45 (14) | C2—C6—H6A | 112.84 |
O3—C3—N4 | 124.16 (15) | C5—C6—H6A | 112.87 |
O3—C3—C2 | 127.64 (15) | C7—C6—H6A | 112.85 |
N4—C3—C2 | 108.19 (13) | O1—C7—H7A | 115.52 |
O5—C5—N4 | 123.84 (17) | C6—C7—H7A | 115.51 |
O5—C5—C6 | 127.30 (17) | C8—C7—H7A | 115.49 |
N4—C5—C6 | 108.85 (14) | C7—C8—H8A | 127.07 |
C2—C6—C5 | 104.77 (14) | C9—C8—H8A | 127.07 |
C2—C6—C7 | 101.19 (13) | C1—C9—H9A | 126.95 |
C5—C6—C7 | 111.48 (15) | C8—C9—H9A | 126.94 |
O1—C7—C6 | 100.45 (13) | C11—C12—H12A | 120.41 |
O1—C7—C8 | 101.64 (14) | C13—C12—H12A | 120.42 |
C6—C7—C8 | 106.26 (15) | C12—C13—H13A | 119.87 |
C7—C8—C9 | 105.86 (17) | C14—C13—H13A | 119.87 |
C1—C9—C8 | 106.11 (16) | C13—C14—H14A | 119.93 |
N4—C10—C11 | 120.25 (14) | C15—C14—H14A | 119.89 |
N4—C10—C15 | 120.60 (15) | C10—C15—H15A | 119.99 |
C11—C10—C15 | 119.15 (16) | C14—C15—H15A | 119.95 |
O16—C11—C10 | 119.28 (14) | C17—C18—H18A | 109.49 |
O16—C11—C12 | 119.46 (15) | C17—C18—H18B | 109.50 |
C10—C11—C12 | 121.17 (15) | C17—C18—H18C | 109.47 |
C11—C12—C13 | 119.17 (17) | H18A—C18—H18B | 109.48 |
C12—C13—C14 | 120.26 (17) | H18A—C18—H18C | 109.44 |
C13—C14—C15 | 120.17 (17) | H18B—C18—H18C | 109.45 |
C7—O1—C1—C2 | 60.14 (15) | C3—C2—C6—C5 | 1.13 (17) |
C7—O1—C1—C9 | −49.44 (16) | C1—C2—C6—C7 | 0.32 (16) |
C1—O1—C7—C8 | 49.21 (15) | C1—C2—C3—O3 | 71.2 (2) |
C1—O1—C7—C6 | −59.98 (15) | C1—C2—C6—C5 | 116.31 (15) |
C17—O16—C11—C12 | 92.22 (19) | C1—C2—C3—N4 | −107.77 (15) |
C11—O16—C17—O17 | −0.4 (3) | C6—C2—C3—O3 | 179.84 (17) |
C11—O16—C17—C18 | 179.29 (15) | N4—C5—C6—C7 | 105.87 (17) |
C17—O16—C11—C10 | −91.29 (19) | O5—C5—C6—C2 | 177.5 (2) |
C3—N4—C10—C11 | −65.7 (2) | O5—C5—C6—C7 | −73.9 (3) |
C3—N4—C5—O5 | −176.73 (19) | N4—C5—C6—C2 | −2.76 (19) |
C10—N4—C3—O3 | −1.7 (3) | C2—C6—C7—C8 | −69.56 (17) |
C5—N4—C10—C11 | 114.37 (19) | C2—C6—C7—O1 | 35.96 (16) |
C10—N4—C3—C2 | 177.32 (14) | C5—C6—C7—C8 | 179.52 (14) |
C3—N4—C5—C6 | 3.5 (2) | C5—C6—C7—O1 | −74.96 (16) |
C5—N4—C3—O3 | 178.22 (17) | C6—C7—C8—C9 | 72.94 (19) |
C10—N4—C5—O5 | 3.2 (3) | O1—C7—C8—C9 | −31.71 (19) |
C5—N4—C3—C2 | −2.73 (19) | C7—C8—C9—C1 | −0.2 (2) |
C10—N4—C5—C6 | −176.54 (14) | C15—C10—C11—O16 | −177.34 (15) |
C3—N4—C10—C15 | 113.93 (18) | C15—C10—C11—C12 | −0.9 (3) |
C5—N4—C10—C15 | −66.0 (2) | C11—C10—C15—C14 | 0.1 (3) |
C9—C1—C2—C6 | 69.32 (17) | N4—C10—C11—O16 | 2.3 (2) |
C9—C1—C2—C3 | −179.33 (14) | N4—C10—C15—C14 | −179.55 (16) |
O1—C1—C2—C3 | 75.00 (16) | N4—C10—C11—C12 | 178.71 (15) |
C2—C1—C9—C8 | −72.70 (19) | C10—C11—C12—C13 | 1.0 (3) |
O1—C1—C2—C6 | −36.35 (16) | O16—C11—C12—C13 | 177.41 (16) |
O1—C1—C9—C8 | 31.9 (2) | C11—C12—C13—C14 | −0.2 (3) |
C3—C2—C6—C7 | −114.85 (14) | C12—C13—C14—C15 | −0.6 (3) |
C6—C2—C3—N4 | 0.83 (17) | C13—C14—C15—C10 | 0.7 (3) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+2, y+1/2, −z+1/2; (iv) −x+2, −y, −z+1; (v) x, −y+1/2, z+1/2; (vi) x+1, y, z; (vii) x−1, y, z; (viii) −x+1, −y, −z+1; (ix) −x+1, y+1/2, −z+1/2; (x) −x+2, y−1/2, −z+1/2; (xi) −x+2, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···O16ix | 0.9800 | 2.5800 | 3.478 (2) | 153.00 |
C12—H12A···O5x | 0.9300 | 2.4300 | 3.113 (2) | 130.00 |
C15—H15A···O17i | 0.9300 | 2.5600 | 3.243 (2) | 131.00 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ix) −x+1, y+1/2, −z+1/2; (x) −x+2, y−1/2, −z+1/2. |
C16H13NO5 | F(000) = 1248 |
Mr = 299.27 | Dx = 1.402 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 24 reflections |
a = 9.703 (1) Å | θ = 11–12° |
b = 15.856 (1) Å | µ = 0.11 mm−1 |
c = 18.8450 (19) Å | T = 293 K |
β = 101.962 (5)° | Square prism, yellow |
V = 2836.4 (4) Å3 | 0.3 × 0.25 × 0.2 mm |
Z = 8 |
Enraf-Nonius CAD4 diffractometer | 2253 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 26.0°, θmin = 2.2° |
Detector resolution: 3 pixels mm-1 | h = −11→11 |
ω/2θ scans | k = 0→19 |
5538 measured reflections | l = 0→23 |
5538 independent reflections |
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) = 0.147 | H-atom parameters constrained |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0646P)2] where P = (Fo2 + 2Fc2)/3 |
5538 reflections | (Δ/σ)max = 0.020 |
400 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
C16H13NO5 | V = 2836.4 (4) Å3 |
Mr = 299.27 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.703 (1) Å | µ = 0.11 mm−1 |
b = 15.856 (1) Å | T = 293 K |
c = 18.8450 (19) Å | 0.3 × 0.25 × 0.2 mm |
β = 101.962 (5)° |
Enraf-Nonius CAD4 diffractometer | 2253 reflections with I > 2σ(I) |
5538 measured reflections | Rint = 0.034 |
5538 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 0.93 | Δρmax = 0.35 e Å−3 |
5538 reflections | Δρmin = −0.35 e Å−3 |
400 parameters |
Experimental. Diffractometer operator H. Höpfl scanwidth_degrees 0.7 low_scanspeed_degrees/min 16.1 high_scanspeed_degrees/min 60 Background measurement: Moving crystal and moving counter at the beginning and end of scan, each for 25% of total scan area. Crystal mounted on a glass fiber. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.0191 (2) | −0.16913 (14) | 0.11849 (12) | 0.0746 (9) | |
O3 | 0.1657 (2) | −0.00908 (14) | 0.01384 (11) | 0.0744 (9) | |
O5 | 0.1441 (3) | −0.01752 (15) | 0.25202 (11) | 0.0858 (10) | |
O16 | 0.0880 (2) | 0.35516 (12) | 0.15138 (10) | 0.0630 (8) | |
O17 | 0.0795 (3) | 0.37797 (15) | 0.03384 (13) | 0.0946 (10) | |
N4 | 0.1473 (2) | 0.00695 (14) | 0.13263 (12) | 0.0512 (8) | |
C1 | 0.0690 (3) | −0.1885 (2) | 0.06816 (18) | 0.0707 (12) | |
C2 | 0.1958 (3) | −0.12936 (17) | 0.09564 (15) | 0.0544 (10) | |
C3 | 0.1693 (3) | −0.03871 (18) | 0.07322 (16) | 0.0544 (11) | |
C5 | 0.1623 (3) | −0.04275 (18) | 0.19440 (16) | 0.0575 (11) | |
C6 | 0.2010 (3) | −0.13028 (17) | 0.17702 (15) | 0.0546 (10) | |
C7 | 0.0815 (3) | −0.1938 (2) | 0.18225 (17) | 0.0693 (12) | |
C8 | 0.1279 (4) | −0.2790 (2) | 0.1611 (2) | 0.0843 (16) | |
C9 | 0.1210 (4) | −0.2759 (2) | 0.0918 (2) | 0.0837 (16) | |
C10 | 0.1276 (3) | 0.09630 (17) | 0.13336 (13) | 0.0489 (9) | |
C11 | 0.2287 (3) | 0.1484 (2) | 0.11614 (18) | 0.0711 (13) | |
C12 | 0.2143 (3) | 0.23500 (19) | 0.12056 (19) | 0.0739 (14) | |
C13 | 0.0997 (3) | 0.26800 (17) | 0.14145 (14) | 0.0526 (10) | |
C14 | −0.0035 (3) | 0.21669 (18) | 0.15609 (15) | 0.0583 (11) | |
C15 | 0.0105 (3) | 0.13043 (18) | 0.15254 (15) | 0.0564 (11) | |
C17 | 0.0838 (3) | 0.4056 (2) | 0.09228 (18) | 0.0616 (11) | |
C18 | 0.0844 (4) | 0.49638 (19) | 0.11220 (19) | 0.0785 (14) | |
O21 | 1.00593 (19) | 0.46221 (12) | 0.32806 (10) | 0.0573 (7) | |
O23 | 0.9221 (2) | 0.34904 (12) | 0.48155 (10) | 0.0720 (8) | |
O25 | 0.7380 (2) | 0.29353 (12) | 0.24434 (10) | 0.0636 (7) | |
O36 | 0.9386 (2) | −0.04083 (12) | 0.41482 (11) | 0.0705 (8) | |
O37 | 0.7207 (3) | −0.08364 (16) | 0.4113 (2) | 0.1404 (16) | |
N24 | 0.8376 (2) | 0.30206 (13) | 0.36563 (10) | 0.0437 (7) | |
C21 | 0.9522 (3) | 0.50362 (17) | 0.38433 (15) | 0.0561 (10) | |
C22 | 0.8220 (3) | 0.44778 (16) | 0.38632 (13) | 0.0473 (9) | |
C23 | 0.8664 (3) | 0.36358 (17) | 0.41917 (15) | 0.0495 (9) | |
C25 | 0.7769 (3) | 0.33530 (17) | 0.29842 (14) | 0.0454 (9) | |
C26 | 0.7681 (3) | 0.42965 (15) | 0.30516 (13) | 0.0436 (8) | |
C27 | 0.8817 (3) | 0.47567 (18) | 0.27199 (15) | 0.0568 (10) | |
C28 | 0.8562 (3) | 0.56844 (19) | 0.28022 (19) | 0.0681 (11) | |
C29 | 0.8980 (3) | 0.58555 (19) | 0.34885 (18) | 0.0658 (11) | |
C30 | 0.8623 (3) | 0.21400 (16) | 0.37867 (13) | 0.0440 (9) | |
C31 | 0.9615 (3) | 0.17200 (18) | 0.34938 (15) | 0.0551 (10) | |
C32 | 0.9820 (3) | 0.08666 (18) | 0.36162 (15) | 0.0579 (11) | |
C33 | 0.9040 (3) | 0.04472 (16) | 0.40281 (15) | 0.0520 (10) | |
C34 | 0.8054 (3) | 0.08589 (18) | 0.43337 (15) | 0.0555 (10) | |
C35 | 0.7835 (3) | 0.17141 (16) | 0.41975 (14) | 0.0516 (10) | |
C37 | 0.8424 (4) | −0.0994 (2) | 0.41970 (18) | 0.0723 (12) | |
C38 | 0.9026 (4) | −0.18475 (18) | 0.43178 (19) | 0.0855 (14) | |
H1A | 0.02431 | −0.18261 | 0.01677 | 0.0851* | |
H2A | 0.28300 | −0.15098 | 0.08381 | 0.0653* | |
H6A | 0.29285 | −0.14788 | 0.20535 | 0.0655* | |
H7A | 0.04743 | −0.19215 | 0.22767 | 0.0836* | |
H8A | 0.15580 | −0.32469 | 0.19169 | 0.1015* | |
H9A | 0.14353 | −0.31876 | 0.06246 | 0.1003* | |
H11A | 0.30662 | 0.12565 | 0.10153 | 0.0854* | |
H12A | 0.28296 | 0.27051 | 0.10926 | 0.0886* | |
H14A | −0.08330 | 0.23988 | 0.16848 | 0.0701* | |
H15A | −0.05938 | 0.09535 | 0.16312 | 0.0678* | |
H18A | 0.10675 | 0.52984 | 0.07364 | 0.1176* | |
H18B | 0.15371 | 0.50588 | 0.15582 | 0.1176* | |
H18C | −0.00689 | 0.51202 | 0.11999 | 0.1176* | |
H21A | 1.01939 | 0.50921 | 0.43071 | 0.0674* | |
H22A | 0.75201 | 0.47590 | 0.40885 | 0.0567* | |
H26A | 0.67293 | 0.45148 | 0.28680 | 0.0523* | |
H27A | 0.88888 | 0.45735 | 0.22322 | 0.0682* | |
H28A | 0.81808 | 0.60609 | 0.24353 | 0.0815* | |
H29A | 0.89498 | 0.63755 | 0.37130 | 0.0790* | |
H31A | 1.01452 | 0.20101 | 0.32146 | 0.0660* | |
H32A | 1.04869 | 0.05788 | 0.34188 | 0.0696* | |
H34A | 0.75473 | 0.05699 | 0.46248 | 0.0666* | |
H35A | 0.71525 | 0.19993 | 0.43851 | 0.0620* | |
H38A | 0.83326 | −0.22245 | 0.44360 | 0.1282* | |
H38B | 0.98330 | −0.18344 | 0.47108 | 0.1282* | |
H38C | 0.93049 | −0.20399 | 0.38855 | 0.1282* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0470 (12) | 0.0832 (16) | 0.0920 (17) | −0.0087 (11) | 0.0105 (11) | 0.0127 (12) |
O3 | 0.0955 (17) | 0.0773 (15) | 0.0575 (13) | −0.0079 (12) | 0.0321 (12) | 0.0013 (11) |
O5 | 0.120 (2) | 0.0873 (17) | 0.0539 (13) | 0.0389 (14) | 0.0269 (13) | −0.0014 (11) |
O16 | 0.0833 (15) | 0.0476 (12) | 0.0566 (12) | −0.0021 (10) | 0.0109 (10) | 0.0026 (10) |
O17 | 0.142 (2) | 0.0829 (17) | 0.0685 (16) | 0.0170 (16) | 0.0441 (15) | 0.0148 (13) |
N4 | 0.0519 (14) | 0.0514 (14) | 0.0529 (14) | 0.0065 (11) | 0.0169 (11) | 0.0006 (11) |
C1 | 0.073 (2) | 0.067 (2) | 0.069 (2) | −0.0185 (18) | 0.0074 (16) | −0.0082 (17) |
C2 | 0.0501 (16) | 0.0526 (18) | 0.0622 (17) | −0.0022 (13) | 0.0153 (13) | −0.0066 (14) |
C3 | 0.0520 (18) | 0.0596 (19) | 0.0552 (18) | −0.0062 (14) | 0.0196 (14) | −0.0020 (15) |
C5 | 0.0576 (19) | 0.0580 (19) | 0.0563 (18) | 0.0105 (15) | 0.0103 (14) | 0.0002 (15) |
C6 | 0.0446 (16) | 0.0561 (18) | 0.0614 (18) | 0.0030 (13) | 0.0069 (13) | 0.0027 (14) |
C7 | 0.061 (2) | 0.075 (2) | 0.073 (2) | 0.0015 (17) | 0.0162 (16) | 0.0189 (18) |
C8 | 0.079 (3) | 0.056 (2) | 0.117 (3) | −0.0077 (18) | 0.018 (2) | 0.008 (2) |
C9 | 0.091 (3) | 0.055 (2) | 0.102 (3) | −0.0179 (19) | 0.013 (2) | −0.012 (2) |
C10 | 0.0482 (16) | 0.0488 (17) | 0.0493 (15) | 0.0016 (14) | 0.0093 (12) | 0.0012 (13) |
C11 | 0.0476 (18) | 0.062 (2) | 0.109 (3) | 0.0093 (16) | 0.0287 (17) | 0.0091 (18) |
C12 | 0.058 (2) | 0.054 (2) | 0.114 (3) | −0.0072 (16) | 0.0279 (19) | 0.0094 (18) |
C13 | 0.0590 (19) | 0.0473 (18) | 0.0516 (16) | 0.0071 (14) | 0.0119 (14) | 0.0018 (13) |
C14 | 0.0546 (18) | 0.057 (2) | 0.0681 (19) | 0.0074 (15) | 0.0236 (15) | −0.0011 (15) |
C15 | 0.0450 (16) | 0.0531 (19) | 0.075 (2) | −0.0020 (14) | 0.0211 (14) | 0.0009 (15) |
C17 | 0.0600 (19) | 0.061 (2) | 0.064 (2) | 0.0012 (15) | 0.0131 (15) | 0.0101 (17) |
C18 | 0.077 (2) | 0.057 (2) | 0.098 (3) | −0.0080 (18) | 0.0098 (19) | 0.0123 (19) |
O21 | 0.0437 (11) | 0.0618 (12) | 0.0677 (12) | 0.0013 (9) | 0.0143 (9) | 0.0004 (10) |
O23 | 0.1047 (17) | 0.0612 (13) | 0.0417 (11) | 0.0055 (12) | −0.0041 (11) | −0.0017 (10) |
O25 | 0.0769 (14) | 0.0589 (12) | 0.0485 (11) | −0.0022 (11) | −0.0018 (9) | −0.0094 (10) |
O36 | 0.0711 (15) | 0.0489 (13) | 0.0904 (16) | 0.0135 (11) | 0.0143 (12) | 0.0057 (11) |
O37 | 0.075 (2) | 0.0623 (17) | 0.281 (4) | −0.0009 (16) | 0.030 (2) | −0.016 (2) |
N24 | 0.0494 (13) | 0.0378 (12) | 0.0432 (12) | 0.0024 (10) | 0.0082 (10) | −0.0027 (10) |
C21 | 0.0553 (18) | 0.0496 (17) | 0.0567 (17) | −0.0025 (14) | −0.0041 (13) | −0.0063 (14) |
C22 | 0.0490 (16) | 0.0461 (16) | 0.0479 (15) | 0.0050 (13) | 0.0129 (12) | −0.0067 (12) |
C23 | 0.0517 (16) | 0.0514 (17) | 0.0456 (16) | −0.0035 (13) | 0.0104 (12) | −0.0036 (13) |
C25 | 0.0406 (15) | 0.0500 (16) | 0.0456 (16) | 0.0023 (12) | 0.0088 (12) | −0.0012 (13) |
C26 | 0.0367 (14) | 0.0442 (15) | 0.0474 (14) | 0.0017 (11) | 0.0031 (11) | 0.0023 (12) |
C27 | 0.0667 (19) | 0.0550 (18) | 0.0496 (16) | −0.0027 (15) | 0.0142 (14) | 0.0045 (14) |
C28 | 0.064 (2) | 0.0529 (19) | 0.082 (2) | −0.0058 (15) | 0.0027 (17) | 0.0175 (17) |
C29 | 0.062 (2) | 0.0446 (18) | 0.088 (2) | −0.0008 (15) | 0.0092 (17) | −0.0043 (16) |
C30 | 0.0441 (15) | 0.0450 (16) | 0.0417 (14) | 0.0014 (12) | 0.0060 (12) | −0.0030 (12) |
C31 | 0.0520 (17) | 0.057 (2) | 0.0591 (17) | 0.0019 (14) | 0.0182 (14) | −0.0001 (14) |
C32 | 0.0536 (18) | 0.058 (2) | 0.0666 (18) | 0.0133 (15) | 0.0227 (14) | −0.0038 (15) |
C33 | 0.0560 (18) | 0.0395 (16) | 0.0597 (17) | 0.0099 (13) | 0.0101 (14) | 0.0004 (13) |
C34 | 0.0562 (18) | 0.0526 (18) | 0.0606 (16) | 0.0020 (14) | 0.0188 (14) | 0.0018 (14) |
C35 | 0.0549 (17) | 0.0450 (17) | 0.0580 (17) | 0.0071 (14) | 0.0188 (13) | −0.0019 (13) |
C37 | 0.066 (2) | 0.057 (2) | 0.088 (2) | 0.0057 (19) | 0.0024 (18) | −0.0031 (18) |
C38 | 0.101 (3) | 0.0442 (19) | 0.093 (2) | 0.0092 (18) | −0.022 (2) | −0.0003 (17) |
O1—C1 | 1.436 (4) | C7—H7A | 0.9797 |
O1—C7 | 1.436 (4) | C8—H8A | 0.9305 |
O3—C3 | 1.207 (4) | C9—H9A | 0.9303 |
O5—C5 | 1.204 (4) | C11—H11A | 0.9294 |
O16—C13 | 1.402 (3) | C12—H12A | 0.9301 |
O16—C17 | 1.365 (4) | C14—H14A | 0.9296 |
O17—C17 | 1.178 (4) | C15—H15A | 0.9300 |
O21—C21 | 1.434 (3) | C18—H18A | 0.9601 |
O21—C27 | 1.445 (3) | C18—H18B | 0.9600 |
O23—C23 | 1.210 (3) | C18—H18C | 0.9600 |
O25—C25 | 1.208 (3) | C21—C22 | 1.550 (4) |
O36—C33 | 1.404 (3) | C21—C29 | 1.505 (4) |
O36—C37 | 1.333 (4) | C22—C23 | 1.497 (4) |
O37—C37 | 1.185 (5) | C22—C26 | 1.537 (3) |
N4—C5 | 1.388 (4) | C25—C26 | 1.505 (4) |
N4—C10 | 1.430 (3) | C26—C27 | 1.557 (4) |
N4—C3 | 1.386 (4) | C27—C28 | 1.505 (4) |
N24—C23 | 1.390 (3) | C28—C29 | 1.301 (5) |
N24—C25 | 1.386 (3) | C30—C31 | 1.377 (4) |
N24—C30 | 1.429 (3) | C30—C35 | 1.373 (4) |
C1—C2 | 1.548 (4) | C31—C32 | 1.380 (4) |
C1—C9 | 1.510 (5) | C32—C33 | 1.364 (4) |
C2—C3 | 1.505 (4) | C33—C34 | 1.379 (4) |
C2—C6 | 1.524 (4) | C34—C35 | 1.388 (4) |
C5—C6 | 1.492 (4) | C37—C38 | 1.473 (4) |
C6—C7 | 1.554 (4) | C21—H21A | 0.9801 |
C7—C8 | 1.504 (5) | C22—H22A | 0.9797 |
C8—C9 | 1.295 (5) | C26—H26A | 0.9797 |
C10—C15 | 1.373 (4) | C27—H27A | 0.9800 |
C10—C11 | 1.372 (4) | C28—H28A | 0.9302 |
C11—C12 | 1.384 (4) | C29—H29A | 0.9299 |
C12—C13 | 1.359 (4) | C31—H31A | 0.9302 |
C13—C14 | 1.362 (4) | C32—H32A | 0.9301 |
C14—C15 | 1.377 (4) | C34—H34A | 0.9298 |
C17—C18 | 1.487 (4) | C35—H35A | 0.9301 |
C1—H1A | 0.9801 | C38—H38A | 0.9601 |
C2—H2A | 0.9805 | C38—H38B | 0.9600 |
C6—H6A | 0.9798 | C38—H38C | 0.9599 |
C1—O1—C7 | 95.7 (2) | H18B—C18—H18C | 109.47 |
C13—O16—C17 | 117.3 (2) | C17—C18—H18A | 109.48 |
C21—O21—C27 | 95.6 (2) | C17—C18—H18B | 109.48 |
C33—O36—C37 | 122.4 (2) | C17—C18—H18C | 109.46 |
C5—N4—C10 | 123.0 (2) | H18A—C18—H18B | 109.47 |
C3—N4—C5 | 111.9 (2) | O21—C21—C22 | 100.3 (2) |
C3—N4—C10 | 124.6 (2) | O21—C21—C29 | 102.3 (2) |
C23—N24—C25 | 112.3 (2) | C22—C21—C29 | 107.0 (2) |
C23—N24—C30 | 124.0 (2) | C21—C22—C23 | 110.7 (2) |
C25—N24—C30 | 123.6 (2) | C21—C22—C26 | 101.2 (2) |
C2—C1—C9 | 105.3 (3) | C23—C22—C26 | 104.7 (2) |
O1—C1—C2 | 101.0 (2) | O23—C23—N24 | 123.6 (2) |
O1—C1—C9 | 102.1 (3) | O23—C23—C22 | 127.2 (2) |
C1—C2—C6 | 100.9 (2) | N24—C23—C22 | 109.2 (2) |
C3—C2—C6 | 105.1 (2) | O25—C25—N24 | 124.2 (2) |
C1—C2—C3 | 114.0 (2) | O25—C25—C26 | 127.1 (2) |
N4—C3—C2 | 108.5 (2) | N24—C25—C26 | 108.8 (2) |
O3—C3—C2 | 127.0 (3) | C22—C26—C25 | 104.8 (2) |
O3—C3—N4 | 124.4 (3) | C22—C26—C27 | 100.9 (2) |
O5—C5—N4 | 123.9 (3) | C25—C26—C27 | 112.0 (2) |
N4—C5—C6 | 109.4 (2) | O21—C27—C26 | 100.9 (2) |
O5—C5—C6 | 126.7 (3) | O21—C27—C28 | 101.5 (2) |
C2—C6—C5 | 104.8 (2) | C26—C27—C28 | 105.8 (2) |
C5—C6—C7 | 111.3 (2) | C27—C28—C29 | 106.4 (3) |
C2—C6—C7 | 101.6 (2) | C21—C29—C28 | 105.7 (3) |
O1—C7—C8 | 102.2 (3) | N24—C30—C31 | 120.7 (2) |
O1—C7—C6 | 99.0 (2) | N24—C30—C35 | 119.0 (2) |
C6—C7—C8 | 107.3 (3) | C31—C30—C35 | 120.4 (2) |
C7—C8—C9 | 106.1 (3) | C30—C31—C32 | 119.7 (3) |
C1—C9—C8 | 106.1 (3) | C31—C32—C33 | 119.7 (3) |
C11—C10—C15 | 119.8 (3) | O36—C33—C32 | 114.8 (2) |
N4—C10—C15 | 120.8 (2) | O36—C33—C34 | 123.6 (2) |
N4—C10—C11 | 119.4 (3) | C32—C33—C34 | 121.4 (3) |
C10—C11—C12 | 119.8 (3) | C33—C34—C35 | 118.6 (3) |
C11—C12—C13 | 119.9 (3) | C30—C35—C34 | 120.2 (3) |
O16—C13—C14 | 118.6 (3) | O36—C37—O37 | 122.4 (3) |
C12—C13—C14 | 120.6 (3) | O36—C37—C38 | 112.9 (3) |
O16—C13—C12 | 120.8 (3) | O37—C37—C38 | 124.5 (3) |
C13—C14—C15 | 119.9 (3) | O21—C21—H21A | 115.10 |
C10—C15—C14 | 120.0 (3) | C22—C21—H21A | 115.15 |
O16—C17—C18 | 111.3 (3) | C29—C21—H21A | 115.13 |
O16—C17—O17 | 122.3 (3) | C21—C22—H22A | 113.10 |
O17—C17—C18 | 126.4 (3) | C23—C22—H22A | 113.12 |
C9—C1—H1A | 115.55 | C26—C22—H22A | 113.13 |
O1—C1—H1A | 115.49 | C22—C26—H26A | 112.75 |
C2—C1—H1A | 115.53 | C25—C26—H26A | 112.78 |
C6—C2—H2A | 112.04 | C27—C26—H26A | 112.74 |
C1—C2—H2A | 112.06 | O21—C27—H27A | 115.56 |
C3—C2—H2A | 112.04 | C26—C27—H27A | 115.56 |
C5—C6—H6A | 112.79 | C28—C27—H27A | 115.56 |
C2—C6—H6A | 112.81 | C27—C28—H28A | 126.81 |
C7—C6—H6A | 112.78 | C29—C28—H28A | 126.80 |
O1—C7—H7A | 115.45 | C21—C29—H29A | 127.17 |
C6—C7—H7A | 115.42 | C28—C29—H29A | 127.18 |
C8—C7—H7A | 115.43 | C30—C31—H31A | 120.15 |
C9—C8—H8A | 127.02 | C32—C31—H31A | 120.13 |
C7—C8—H8A | 126.87 | C31—C32—H32A | 120.15 |
C1—C9—H9A | 126.90 | C33—C32—H32A | 120.16 |
C8—C9—H9A | 127.04 | C33—C34—H34A | 120.70 |
C10—C11—H11A | 120.12 | C35—C34—H34A | 120.74 |
C12—C11—H11A | 120.08 | C30—C35—H35A | 119.92 |
C13—C12—H12A | 120.08 | C34—C35—H35A | 119.89 |
C11—C12—H12A | 120.04 | C37—C38—H38A | 109.48 |
C15—C14—H14A | 120.04 | C37—C38—H38B | 109.47 |
C13—C14—H14A | 120.01 | C37—C38—H38C | 109.47 |
C10—C15—H15A | 120.04 | H38A—C38—H38B | 109.47 |
C14—C15—H15A | 119.99 | H38A—C38—H38C | 109.48 |
H18A—C18—H18C | 109.47 | H38B—C38—H38C | 109.47 |
C7—O1—C1—C2 | −60.0 (2) | N4—C5—C6—C2 | −4.5 (3) |
C7—O1—C1—C9 | 48.5 (3) | O5—C5—C6—C7 | 65.5 (4) |
C1—O1—C7—C8 | −48.8 (3) | O5—C5—C6—C2 | 174.4 (3) |
C1—O1—C7—C6 | 61.2 (2) | C2—C6—C7—O1 | −39.1 (3) |
C17—O16—C13—C12 | 62.1 (4) | C2—C6—C7—C8 | 66.8 (3) |
C13—O16—C17—C18 | −174.9 (3) | C5—C6—C7—C8 | 177.8 (3) |
C13—O16—C17—O17 | 5.5 (4) | C5—C6—C7—O1 | 71.9 (3) |
C17—O16—C13—C14 | −120.6 (3) | O1—C7—C8—C9 | 31.9 (4) |
C21—O21—C27—C26 | −59.4 (2) | C6—C7—C8—C9 | −71.7 (4) |
C21—O21—C27—C28 | 49.3 (2) | C7—C8—C9—C1 | −0.4 (4) |
C27—O21—C21—C29 | −49.2 (2) | C15—C10—C11—C12 | 2.2 (4) |
C27—O21—C21—C22 | 60.9 (2) | N4—C10—C15—C14 | 177.1 (2) |
C33—O36—C37—O37 | 3.1 (5) | N4—C10—C11—C12 | −176.5 (3) |
C33—O36—C37—C38 | 179.5 (3) | C11—C10—C15—C14 | −1.5 (4) |
C37—O36—C33—C34 | 38.2 (4) | C10—C11—C12—C13 | −0.4 (5) |
C37—O36—C33—C32 | −145.6 (3) | C11—C12—C13—C14 | −1.9 (5) |
C3—N4—C10—C11 | −56.8 (4) | C11—C12—C13—O16 | 175.3 (3) |
C10—N4—C3—C2 | 175.9 (2) | O16—C13—C14—C15 | −174.8 (2) |
C5—N4—C10—C11 | 115.7 (3) | C12—C13—C14—C15 | 2.6 (4) |
C3—N4—C5—O5 | −177.7 (3) | C13—C14—C15—C10 | −0.8 (4) |
C5—N4—C10—C15 | −62.9 (4) | O21—C21—C22—C26 | −38.5 (2) |
C10—N4—C5—C6 | −172.1 (2) | C29—C21—C22—C26 | 67.9 (3) |
C10—N4—C3—O3 | −4.8 (4) | C29—C21—C22—C23 | 178.5 (2) |
C5—N4—C3—C2 | 2.7 (3) | C22—C21—C29—C28 | −73.5 (3) |
C10—N4—C5—O5 | 8.9 (4) | O21—C21—C22—C23 | 72.1 (2) |
C5—N4—C3—O3 | −178.0 (3) | O21—C21—C29—C28 | 31.5 (3) |
C3—N4—C10—C15 | 124.6 (3) | C23—C22—C26—C27 | −112.9 (2) |
C3—N4—C5—C6 | 1.3 (3) | C23—C22—C26—C25 | 3.6 (3) |
C30—N24—C23—O23 | 4.0 (4) | C21—C22—C26—C25 | 118.7 (2) |
C25—N24—C30—C35 | −110.4 (3) | C26—C22—C23—O23 | 175.9 (3) |
C23—N24—C25—C26 | 2.6 (3) | C21—C22—C23—O23 | 67.7 (4) |
C25—N24—C23—C22 | −0.1 (3) | C21—C22—C26—C27 | 2.2 (2) |
C25—N24—C30—C31 | 68.3 (4) | C26—C22—C23—N24 | −2.3 (3) |
C25—N24—C23—O23 | −178.4 (3) | C21—C22—C23—N24 | −110.5 (2) |
C23—N24—C30—C35 | 67.0 (3) | N24—C25—C26—C27 | 104.7 (2) |
C23—N24—C30—C31 | −114.3 (3) | O25—C25—C26—C27 | −75.6 (4) |
C30—N24—C25—O25 | 0.5 (4) | O25—C25—C26—C22 | 175.9 (3) |
C30—N24—C25—C26 | −179.8 (2) | N24—C25—C26—C22 | −3.8 (3) |
C23—N24—C25—O25 | −177.1 (3) | C22—C26—C27—C28 | −71.0 (3) |
C30—N24—C23—C22 | −177.8 (2) | C22—C26—C27—O21 | 34.4 (2) |
C2—C1—C9—C8 | 73.8 (4) | C25—C26—C27—O21 | −76.7 (2) |
O1—C1—C2—C3 | −78.0 (3) | C25—C26—C27—C28 | 177.9 (2) |
C9—C1—C2—C3 | 176.1 (3) | O21—C27—C28—C29 | −32.5 (3) |
C9—C1—C2—C6 | −71.9 (3) | C26—C27—C28—C29 | 72.5 (3) |
O1—C1—C9—C8 | −31.3 (4) | C27—C28—C29—C21 | 0.8 (3) |
O1—C1—C2—C6 | 34.1 (3) | C31—C30—C35—C34 | 1.4 (4) |
C1—C2—C3—O3 | −75.1 (4) | C35—C30—C31—C32 | −0.2 (4) |
C1—C2—C6—C7 | 3.0 (3) | N24—C30—C35—C34 | −179.9 (2) |
C1—C2—C6—C5 | −112.9 (2) | N24—C30—C31—C32 | −178.9 (2) |
C1—C2—C3—N4 | 104.2 (3) | C30—C31—C32—C33 | −0.2 (4) |
C3—C2—C6—C7 | 121.8 (2) | C31—C32—C33—C34 | −0.7 (4) |
C6—C2—C3—N4 | −5.3 (3) | C31—C32—C33—O36 | −176.9 (2) |
C6—C2—C3—O3 | 175.4 (3) | C32—C33—C34—C35 | 1.8 (4) |
C3—C2—C6—C5 | 5.8 (3) | O36—C33—C34—C35 | 177.7 (3) |
N4—C5—C6—C7 | −113.5 (3) | C33—C34—C35—C30 | −2.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18B···O5i | 0.9600 | 2.3600 | 3.277 (4) | 159 |
C27—H27A···O37ii | 0.9800 | 2.6195 | 3.518 (4) | 153 |
C14—H14A···O25iii | 0.9300 | 2.6079 | 3.503 (4) | 162 |
C32—H32A···O5iv | 0.9300 | 2.4100 | 3.289 (4) | 158 |
C22—H22A···O3v | 0.9800 | 2.3600 | 3.245 (3) | 150 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1, y, z; (iv) x+1, y, z; (v) x+1/2, −y+1/2, z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C16H13NO5 | C16H13NO5 |
Mr | 299.27 | 299.27 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 8.859 (1), 12.830 (2), 12.615 (1) | 9.703 (1), 15.856 (1), 18.8450 (19) |
β (°) | 102.971 (2) | 101.962 (5) |
V (Å3) | 1397.2 (3) | 2836.4 (4) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.11 |
Crystal size (mm) | 0.5 × 0.3 × 0.1 | 0.3 × 0.25 × 0.2 |
Data collection | ||
Diffractometer | Enraf-Nonius CAD4 diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3024, 3024, 1767 | 5538, 5538, 2253 |
Rint | 0.012 | 0.034 |
(sin θ/λ)max (Å−1) | 0.638 | 0.616 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.127, 1.02 | 0.043, 0.147, 0.93 |
No. of reflections | 3024 | 5538 |
No. of parameters | 199 | 400 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.22 | 0.35, −0.35 |
Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1992), CAD-4 EXPRESS, JANA98 (Vaclav, 1998), SHELXS97(Sheldrick, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), WinGX (Farrugia, 1999), SHELXL97 and RESVIEW (Schwenk, 1996).
O16—C11 | 1.401 (2) | N4—C5 | 1.392 (2) |
O16—C17 | 1.360 (2) | N4—C10 | 1.425 (2) |
O17—C17 | 1.189 (2) | C2—C6 | 1.538 (2) |
N4—C3 | 1.401 (2) | C8—C9 | 1.309 (3) |
C1—O1—C7 | 96.20 (13) | N4—C10—C11 | 120.25 (14) |
C11—O16—C17 | 116.68 (13) | N4—C10—C15 | 120.60 (15) |
C3—N4—C5 | 112.64 (14) | O16—C11—C10 | 119.28 (14) |
C3—N4—C10 | 123.44 (13) | O16—C11—C12 | 119.46 (15) |
C5—N4—C10 | 123.92 (14) | O16—C17—O17 | 122.51 (17) |
O1—C7—C6 | 100.45 (13) | O16—C17—C18 | 110.80 (15) |
O1—C7—C8 | 101.64 (14) | O17—C17—C18 | 126.69 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···O16i | 0.9800 | 2.5800 | 3.478 (2) | 153.00 |
C12—H12A···O5ii | 0.9300 | 2.4300 | 3.113 (2) | 130.00 |
C15—H15A···O17iii | 0.9300 | 2.5600 | 3.243 (2) | 131.00 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2. |
O1—C1 | 1.436 (4) | O25—C25 | 1.208 (3) |
O1—C7 | 1.436 (4) | O36—C33 | 1.404 (3) |
O3—C3 | 1.207 (4) | O36—C37 | 1.333 (4) |
O5—C5 | 1.204 (4) | O37—C37 | 1.185 (5) |
O16—C13 | 1.402 (3) | N4—C5 | 1.388 (4) |
O16—C17 | 1.365 (4) | N4—C10 | 1.430 (3) |
O17—C17 | 1.178 (4) | N4—C3 | 1.386 (4) |
O21—C21 | 1.434 (3) | N24—C23 | 1.390 (3) |
O21—C27 | 1.445 (3) | N24—C25 | 1.386 (3) |
O23—C23 | 1.210 (3) | N24—C30 | 1.429 (3) |
C1—O1—C7 | 95.7 (2) | O16—C13—C14 | 118.6 (3) |
C13—O16—C17 | 117.3 (2) | O16—C13—C12 | 120.8 (3) |
C21—O21—C27 | 95.6 (2) | O16—C17—C18 | 111.3 (3) |
C33—O36—C37 | 122.4 (2) | O16—C17—O17 | 122.3 (3) |
C5—N4—C10 | 123.0 (2) | O17—C17—C18 | 126.4 (3) |
C3—N4—C5 | 111.9 (2) | O21—C21—C22 | 100.3 (2) |
C3—N4—C10 | 124.6 (2) | O21—C21—C29 | 102.3 (2) |
C23—N24—C25 | 112.3 (2) | O23—C23—N24 | 123.6 (2) |
C23—N24—C30 | 124.0 (2) | O23—C23—C22 | 127.2 (2) |
C25—N24—C30 | 123.6 (2) | N24—C23—C22 | 109.2 (2) |
O1—C1—C2 | 101.0 (2) | O25—C25—N24 | 124.2 (2) |
O1—C1—C9 | 102.1 (3) | O25—C25—C26 | 127.1 (2) |
N4—C3—C2 | 108.5 (2) | N24—C25—C26 | 108.8 (2) |
O3—C3—C2 | 127.0 (3) | O21—C27—C26 | 100.9 (2) |
O3—C3—N4 | 124.4 (3) | O21—C27—C28 | 101.5 (2) |
O5—C5—N4 | 123.9 (3) | N24—C30—C31 | 120.7 (2) |
N4—C5—C6 | 109.4 (2) | N24—C30—C35 | 119.0 (2) |
O5—C5—C6 | 126.7 (3) | O36—C33—C32 | 114.8 (2) |
O1—C7—C8 | 102.2 (3) | O36—C33—C34 | 123.6 (2) |
O1—C7—C6 | 99.0 (2) | O36—C37—O37 | 122.4 (3) |
N4—C10—C15 | 120.8 (2) | O36—C37—C38 | 112.9 (3) |
N4—C10—C11 | 119.4 (3) | O37—C37—C38 | 124.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18B···O5i | 0.9600 | 2.3600 | 3.277 (4) | 159 |
C27—H27A···O37ii | 0.9800 | 2.6195 | 3.518 (4) | 153 |
C14—H14A···O25iii | 0.9300 | 2.6079 | 3.503 (4) | 162 |
C32—H32A···O5iv | 0.9300 | 2.4100 | 3.289 (4) | 158 |
C22—H22A···O3v | 0.9800 | 2.3600 | 3.245 (3) | 150 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1, y, z; (iv) x+1, y, z; (v) x+1/2, −y+1/2, z+1/2. |
Diels-Alder reactions between furan and maleimide are well studied (Kwart & King, 1968). However, there are few examples of their crystal structures, particularly of those derived from N-arylmaleimides (Allen, 2002). Diels-Alder reactions produce the endo and exo isomers, depending on the relative orientation of the approach of the diene and dienophile. Usually, the exo adduct is the thermodynamic product and the endo the kinetic one (Kwart & Burchuk, 1951). Control of the adduct stereochemistry has been achieved using chiral N-arylmaleimides (Kitagawa et al., 1998). Recently, several efforts have been made to accelerate the rate (Howell et al., 2002) or control the stereochemistry (Philip & Robertson, 1998) of Diels-Alder cycloadditions, on the basis of molecular recognition or supramolecular chemistry. Herein, the molecular and supramolecular structure of the Diels-Alder adducts exo-4-(2'-acetoxyphenyl)-10-oxa-4-azatricyclo(5.2.1.02,6)dec-8- en-3,5-dione I and its para isomer II, are reported.
Compounds (I) and (II) crystallize in the monoclinic crystal system with space groups P21/c and P21/n, respectively, and their molecular structures are depicted in Figures 1 and 2, respectively. The two independent molecules found in the asymmetric unit of II are labelled as IIA and IIB. The common geometric features of both molecules (Tables 1 and 3) show that N—Caryl and N—C(═O) bond lengths are in the mean range reported for free N-aryl maleimides (Miller et al., 2000). The phenyl ring is twisted relative to the succinimide ring in both adducts, with mean interplanar angles of 65.8 (1)°, 61.8 1)° and 66.8 (1)° for I, IIA and IIB, respectively. The torsion angle between these two rings is very similar to the value reported for both a furan-N-phenyl maleimide Diels-Alder adduct (Jarosz et al., 2001) and several free N-aryl maleimides (Miller et al., 2000). The acetoxy group points toward the oxo bridge and is almost perpendicular to the phenyl ring both in the ortho-isomer I and the para-isomer IIA, whereas in the para-isomer IIB it is closer to planarity: the angle between the phenyl and the acetoxy planes are 89.8 (1)°, 63.6 (1)° and 37.0 (1)° for I, IIA and IIB, respectively.
The conformational differences determine the supramolecular structure exhibited by each compound. In the absence of strong hydrogen bonding donors the intermolecular geometry features weak C—H···X (X = O, Ph) interactions (Steiner, 2002; Umezawa et al., 1998) whose geometry is summarized in Tables 2 and 4 for I and II, respectively. Graph set notation is used to describe the hydrogen-bonding patterns throughout this paper (Bernstein et al., 1995). In compound (I) the interlinked C22(14)[DaDb] antiparallel chains zigzagging along the b axis are formed through C6—H6···O16 (Da) and C12—H12···O5 (Db) interactions. Thus, tetrameric units exhibiting a R44(28)[DaDc] ring pattern (Fig. 3) appear by interlinking C15—H15···O17 (Dc) interactions.
The para- isomer presents a different supramolecular structure in which sheets of molecules IIA and sheets of molecules IIB lie in an alternating family of parallel (101) and (202) planes, respectively. Centrosymmetric dimers of IIA are formed by C1—H1···PhA (Dd; C1···PhA = 3.899 (4) Å; C1—H1···PhA 174.5°; symmetry code: −x,-y,-z) hydrogen bonding interactions. IIB sheets are composed by interlinked tetrameric units formed by C28—H28A···PhB (De; C28···PhB = 3.690 (4) Å; C28—H28···PhB = 145.8°; symmetry code: 3/2 − x,1/2 + y,1/2 − z), C38—H38B···PhB (Df; C38···PhB = 3.658 (4) Å; C38—H38B···PhB = 150.8°; symmetry code: 2 − x,-y,1 − z) and C27—H27···O37 (Dg) interactions that define a R46(18) ring pattern (Figure 4). Finally, the three dimensional network is achieved by the association between IIA and IIB, the former molecule providing most of the acceptors and the last one providing most of the donors. Thus zigzag tapes, are formed through C14—H14···O25 (Dh), C18—H18···O37 (Di), C32—H32···O5 (Dj), and C22—H22···O3 (Dk) interactions to conform the tapes described by the C44(23)[R22(14)R22(22)] hydrogen bonding pattern (Figure 5).
In summary, exo Diels-Alder adducts between furan and ortho- and para-N-acetoxyphenyl maleimides I and II, respectively, are characterized by hydrogen bonded tetrameric structures which forms sheets in the bc plane through soft C—H···X (X═O, Ph) interactions. Notably, the interlinked tetrameric units persist when the position of the acetoxy group is altered.