Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103029111/na1631sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103029111/na1631Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103029111/na1631IIsup3.hkl |
CCDC references: 235328; 235329
The title compounds were synthesized via intermolecular Michael addition, followed by an intramolecular amidification reaction, between diethyl-4-fluoro/3,4-dichloroanilinomalonate (synthesized by the condensation reaction between substituted aniline and bromodiethylmalonate) and 3-(2-furyl)acryloyl chloride in the presence of triethylamine, using dry benzene as solvent. Single crystals were grown by slow evaporation, at room temperature, of a solution of the resulting compound in 2-propanol. Compound (I): colourless solid; m.p. 355–357 K (2-propanol). 1H NMR (200 MHz, CDCl3): δ 0.92–1.24 (m, 6H), 2.80–3.13 (dd, 2H,J = 8.8, 16.7 Hz), 3.74–3.86 (m, 1H), 3.91–4.17 (m, 3H), 4.61–4.71 (dd, 1H, J = 8.7, 11.3 Hz), 6.28–6.35 (m, 2H), 7.01–7.09 (m, 1H), 7.21–7.28 (m, 3H), 7.37–7.38 (d, 1H, J = 1.31 Hz). Compound (II): colourless solid; m.p. 353–355 K (2-propanol). 1H NMR (200 MHz, CDCl3): δ 0.99–1.06 (t, 6H, J = 7.1 Hz), 2.82–3.12 (dd, 2H, J = 8.8, 16.7 Hz), 3.73–3.85 (m, 1H), 3.98–4.20 (m, 3H), 4.57–4.67 (dd, 1H, J = 8.8, 10.8 Hz), 6.28–6.36 (m, 2H), 7.12–7.17 (dd, 1H, J = 2.4, 8.6 Hz), 7.38–7.46 (m, 3H).
All H atoms were placed geometrically and treated as riding on their parent atoms, with aromatic C—H distances of 0.93 Å, methylene C—H distances of 0.97 Å, and methyl C—H distances of 0.96 Å. The Uiso(H) values were set to 1.5Ueq(C) for the methyl H atoms and 1.2Ueq(C) for other C-bound H atoms.
For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); 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, 1997) for (I); SHELXTL (Sheldrick, 1997a) for (II). For both compounds, software used to prepare material for publication: SHELXTL.
C20H20FNO6 | Z = 2 |
Mr = 389.37 | F(000) = 408 |
Triclinic, P1 | Dx = 1.319 Mg m−3 |
Hall symbol: -P 1 | Melting point = 355–357 K |
a = 9.582 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.157 (3) Å | Cell parameters from 2470 reflections |
c = 11.384 (4) Å | θ = 2.0–28.0° |
α = 90.305 (6)° | µ = 0.10 mm−1 |
β = 105.358 (6)° | T = 293 K |
γ = 112.405 (5)° | Block, colourless |
V = 980.6 (5) Å3 | 0.39 × 0.36 × 0.22 mm |
Bruker CCD area-detector diffractometer | 4167 independent reflections |
Radiation source: fine-focus sealed tube | 2936 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 27.0°, θmin = 2.2° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.885, Tmax = 0.978 | k = −12→12 |
6019 measured reflections | l = −14→11 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0644P)2 + 0.1569P] where P = (Fo2 + 2Fc2)/3 |
4167 reflections | (Δ/σ)max < 0.001 |
255 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C20H20FNO6 | γ = 112.405 (5)° |
Mr = 389.37 | V = 980.6 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.582 (3) Å | Mo Kα radiation |
b = 10.157 (3) Å | µ = 0.10 mm−1 |
c = 11.384 (4) Å | T = 293 K |
α = 90.305 (6)° | 0.39 × 0.36 × 0.22 mm |
β = 105.358 (6)° |
Bruker CCD area-detector diffractometer | 4167 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2936 reflections with I > 2σ(I) |
Tmin = 0.885, Tmax = 0.978 | Rint = 0.015 |
6019 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.22 e Å−3 |
4167 reflections | Δρmin = −0.25 e Å−3 |
255 parameters |
Experimental. Data was collected using a Siemens SMART CCD based diffractometer operating at room temperature. Data was measured using omega scans of 0.3 degrees per frame for 60 s. A total of 1271 frames were collected. The first 50 frames were recollected at the end of each set of frames. As usual in organic compounds high theta reflections are too weak to be measured. |
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 | ||
F1 | 0.4839 (2) | 1.69158 (16) | 0.20331 (17) | 0.1212 (7) | |
O1 | −0.12609 (16) | 1.21079 (14) | 0.23505 (15) | 0.0643 (4) | |
O2 | −0.03167 (19) | 0.66550 (14) | 0.19518 (14) | 0.0675 (4) | |
O3 | 0.19164 (17) | 1.07698 (14) | 0.46584 (11) | 0.0557 (4) | |
O4 | 0.25249 (14) | 0.90995 (13) | 0.38829 (10) | 0.0454 (3) | |
O5 | 0.15804 (16) | 0.95687 (17) | 0.05851 (12) | 0.0655 (4) | |
O6 | 0.36412 (14) | 1.08679 (15) | 0.21550 (11) | 0.0539 (3) | |
N1 | 0.07687 (15) | 1.14449 (13) | 0.23426 (12) | 0.0355 (3) | |
C1 | −0.0740 (2) | 1.11918 (18) | 0.23530 (16) | 0.0420 (4) | |
C2 | −0.1583 (2) | 0.96201 (17) | 0.24003 (17) | 0.0436 (4) | |
H2A | −0.2632 | 0.9252 | 0.1825 | 0.052* | |
H2B | −0.1671 | 0.9436 | 0.3219 | 0.052* | |
C3 | −0.05662 (18) | 0.89350 (16) | 0.20475 (15) | 0.0360 (4) | |
H3A | −0.0886 | 0.8751 | 0.1150 | 0.043* | |
C4 | 0.11306 (17) | 1.01679 (16) | 0.24659 (13) | 0.0324 (3) | |
C5 | 0.18628 (19) | 1.28553 (16) | 0.22720 (15) | 0.0382 (4) | |
C6 | 0.3174 (2) | 1.35984 (19) | 0.32375 (18) | 0.0533 (5) | |
H6A | 0.3374 | 1.3182 | 0.3955 | 0.064* | |
C7 | 0.4195 (3) | 1.4963 (2) | 0.3143 (2) | 0.0683 (6) | |
H7A | 0.5099 | 1.5463 | 0.3783 | 0.082* | |
C8 | 0.3852 (3) | 1.5555 (2) | 0.2103 (2) | 0.0751 (7) | |
C9 | 0.2567 (3) | 1.4849 (2) | 0.1131 (2) | 0.0812 (7) | |
H9A | 0.2367 | 1.5284 | 0.0425 | 0.097* | |
C10 | 0.1561 (2) | 1.3470 (2) | 0.12134 (18) | 0.0572 (5) | |
H10A | 0.0686 | 1.2962 | 0.0555 | 0.069* | |
C11 | −0.0740 (2) | 0.75493 (17) | 0.25436 (17) | 0.0436 (4) | |
C12 | −0.1202 (3) | 0.6984 (2) | 0.3499 (2) | 0.0684 (6) | |
H12A | −0.1533 | 0.7387 | 0.4052 | 0.082* | |
C13 | −0.1077 (3) | 0.5610 (3) | 0.3490 (3) | 0.0880 (9) | |
H13A | −0.1325 | 0.4943 | 0.4039 | 0.106* | |
C14 | −0.0549 (3) | 0.5479 (2) | 0.2565 (3) | 0.0841 (8) | |
H14A | −0.0359 | 0.4690 | 0.2356 | 0.101* | |
C15 | 0.19318 (18) | 1.00859 (17) | 0.38058 (14) | 0.0367 (4) | |
C16 | 0.3037 (2) | 0.8702 (2) | 0.51026 (17) | 0.0565 (5) | |
H16A | 0.2171 | 0.8367 | 0.5464 | 0.068* | |
H16B | 0.3891 | 0.9520 | 0.5635 | 0.068* | |
C17 | 0.3578 (3) | 0.7535 (2) | 0.4944 (2) | 0.0700 (6) | |
H17A | 0.3897 | 0.7219 | 0.5725 | 0.105* | |
H17B | 0.4455 | 0.7889 | 0.4608 | 0.105* | |
H17C | 0.2732 | 0.6745 | 0.4395 | 0.105* | |
C18 | 0.21248 (19) | 1.01333 (18) | 0.16132 (15) | 0.0382 (4) | |
C19 | 0.4739 (3) | 1.1002 (3) | 0.1436 (2) | 0.0738 (7) | |
H19A | 0.5700 | 1.0964 | 0.1959 | 0.089* | |
H19B | 0.4271 | 1.0208 | 0.0786 | 0.089* | |
C20 | 0.5115 (3) | 1.2358 (3) | 0.0902 (3) | 0.0996 (9) | |
H20A | 0.5834 | 1.2431 | 0.0433 | 0.149* | |
H20B | 0.5592 | 1.3143 | 0.1547 | 0.149* | |
H20C | 0.4165 | 1.2390 | 0.0377 | 0.149* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.1137 (13) | 0.0608 (9) | 0.1225 (13) | −0.0275 (9) | 0.0205 (10) | 0.0290 (8) |
O1 | 0.0553 (8) | 0.0426 (7) | 0.1133 (12) | 0.0296 (7) | 0.0382 (8) | 0.0200 (7) |
O2 | 0.0892 (11) | 0.0470 (8) | 0.0707 (9) | 0.0375 (8) | 0.0142 (8) | 0.0005 (7) |
O3 | 0.0799 (9) | 0.0605 (8) | 0.0369 (7) | 0.0364 (7) | 0.0205 (6) | 0.0065 (6) |
O4 | 0.0527 (7) | 0.0531 (7) | 0.0397 (6) | 0.0320 (6) | 0.0116 (5) | 0.0128 (5) |
O5 | 0.0571 (8) | 0.0914 (11) | 0.0423 (8) | 0.0225 (8) | 0.0162 (6) | −0.0084 (7) |
O6 | 0.0384 (7) | 0.0739 (9) | 0.0492 (7) | 0.0172 (6) | 0.0200 (5) | 0.0032 (6) |
N1 | 0.0339 (7) | 0.0296 (7) | 0.0453 (8) | 0.0136 (6) | 0.0133 (6) | 0.0078 (5) |
C1 | 0.0396 (9) | 0.0384 (9) | 0.0542 (10) | 0.0185 (8) | 0.0187 (7) | 0.0103 (7) |
C2 | 0.0368 (9) | 0.0368 (9) | 0.0611 (11) | 0.0148 (7) | 0.0199 (8) | 0.0113 (8) |
C3 | 0.0364 (8) | 0.0327 (8) | 0.0385 (8) | 0.0134 (7) | 0.0103 (7) | 0.0058 (6) |
C4 | 0.0345 (8) | 0.0315 (8) | 0.0341 (8) | 0.0154 (6) | 0.0112 (6) | 0.0058 (6) |
C5 | 0.0387 (9) | 0.0303 (8) | 0.0457 (9) | 0.0121 (7) | 0.0150 (7) | 0.0050 (7) |
C6 | 0.0512 (11) | 0.0429 (10) | 0.0529 (11) | 0.0109 (9) | 0.0058 (9) | 0.0057 (8) |
C7 | 0.0570 (12) | 0.0464 (12) | 0.0711 (14) | −0.0014 (10) | 0.0030 (10) | 0.0000 (10) |
C8 | 0.0718 (15) | 0.0437 (12) | 0.0807 (16) | −0.0078 (11) | 0.0211 (12) | 0.0152 (11) |
C9 | 0.0887 (17) | 0.0573 (13) | 0.0648 (14) | −0.0008 (12) | 0.0140 (12) | 0.0280 (11) |
C10 | 0.0578 (12) | 0.0465 (11) | 0.0487 (11) | 0.0049 (9) | 0.0093 (9) | 0.0117 (8) |
C11 | 0.0420 (9) | 0.0316 (8) | 0.0552 (10) | 0.0143 (7) | 0.0112 (8) | 0.0047 (7) |
C12 | 0.0696 (14) | 0.0619 (13) | 0.0930 (16) | 0.0321 (11) | 0.0449 (12) | 0.0403 (12) |
C13 | 0.0740 (16) | 0.0572 (14) | 0.132 (2) | 0.0217 (13) | 0.0348 (16) | 0.0571 (16) |
C14 | 0.0899 (19) | 0.0357 (11) | 0.116 (2) | 0.0276 (12) | 0.0084 (16) | 0.0114 (13) |
C15 | 0.0372 (8) | 0.0375 (8) | 0.0370 (8) | 0.0146 (7) | 0.0133 (7) | 0.0072 (7) |
C16 | 0.0600 (12) | 0.0640 (12) | 0.0456 (10) | 0.0289 (10) | 0.0087 (9) | 0.0230 (9) |
C17 | 0.0666 (14) | 0.0617 (13) | 0.0828 (15) | 0.0338 (11) | 0.0103 (11) | 0.0288 (11) |
C18 | 0.0416 (9) | 0.0430 (9) | 0.0366 (9) | 0.0221 (8) | 0.0138 (7) | 0.0090 (7) |
C19 | 0.0488 (12) | 0.113 (2) | 0.0690 (14) | 0.0309 (13) | 0.0345 (11) | 0.0125 (13) |
C20 | 0.0822 (18) | 0.120 (2) | 0.093 (2) | 0.0182 (17) | 0.0523 (16) | 0.0333 (17) |
F1—C8 | 1.362 (2) | C6—H6A | 0.9300 |
O1—C1 | 1.2120 (19) | C7—C8 | 1.351 (3) |
O2—C14 | 1.361 (3) | C7—H7A | 0.9300 |
O2—C11 | 1.365 (2) | C8—C9 | 1.361 (3) |
O3—C15 | 1.1970 (19) | C9—C10 | 1.386 (3) |
O4—C15 | 1.3203 (19) | C9—H9A | 0.9300 |
O4—C16 | 1.459 (2) | C10—H10A | 0.9300 |
O5—C18 | 1.188 (2) | C11—C12 | 1.333 (3) |
O6—C18 | 1.320 (2) | C12—C13 | 1.446 (3) |
O6—C19 | 1.464 (2) | C12—H12A | 0.9300 |
N1—C1 | 1.371 (2) | C13—C14 | 1.309 (4) |
N1—C5 | 1.435 (2) | C13—H13A | 0.9300 |
N1—C4 | 1.4635 (19) | C14—H14A | 0.9300 |
C1—C2 | 1.498 (2) | C16—C17 | 1.491 (3) |
C2—C3 | 1.522 (2) | C16—H16A | 0.9700 |
C2—H2A | 0.9700 | C16—H16B | 0.9700 |
C2—H2B | 0.9700 | C17—H17A | 0.9600 |
C3—C11 | 1.486 (2) | C17—H17B | 0.9600 |
C3—C4 | 1.572 (2) | C17—H17C | 0.9600 |
C3—H3A | 0.9800 | C19—C20 | 1.463 (4) |
C4—C15 | 1.534 (2) | C19—H19A | 0.9700 |
C4—C18 | 1.538 (2) | C19—H19B | 0.9700 |
C5—C10 | 1.373 (2) | C20—H20A | 0.9600 |
C5—C6 | 1.376 (2) | C20—H20B | 0.9600 |
C6—C7 | 1.383 (3) | C20—H20C | 0.9600 |
C14—O2—C11 | 106.14 (19) | C9—C10—H10A | 120.1 |
C15—O4—C16 | 116.77 (13) | C12—C11—O2 | 110.88 (17) |
C18—O6—C19 | 117.65 (15) | C12—C11—C3 | 132.82 (17) |
C1—N1—C5 | 121.46 (13) | O2—C11—C3 | 116.28 (15) |
C1—N1—C4 | 113.29 (12) | C11—C12—C13 | 105.0 (2) |
C5—N1—C4 | 125.19 (12) | C11—C12—H12A | 127.5 |
O1—C1—N1 | 124.72 (15) | C13—C12—H12A | 127.5 |
O1—C1—C2 | 127.00 (15) | C14—C13—C12 | 107.2 (2) |
N1—C1—C2 | 108.26 (13) | C14—C13—H13A | 126.4 |
C1—C2—C3 | 104.66 (13) | C12—C13—H13A | 126.4 |
C1—C2—H2A | 110.8 | C13—C14—O2 | 110.8 (2) |
C3—C2—H2A | 110.8 | C13—C14—H14A | 124.6 |
C1—C2—H2B | 110.8 | O2—C14—H14A | 124.6 |
C3—C2—H2B | 110.8 | O3—C15—O4 | 125.43 (15) |
H2A—C2—H2B | 108.9 | O3—C15—C4 | 123.41 (15) |
C11—C3—C2 | 113.57 (13) | O4—C15—C4 | 110.99 (13) |
C11—C3—C4 | 116.31 (13) | O4—C16—C17 | 106.70 (16) |
C2—C3—C4 | 103.10 (12) | O4—C16—H16A | 110.4 |
C11—C3—H3A | 107.8 | C17—C16—H16A | 110.4 |
C2—C3—H3A | 107.8 | O4—C16—H16B | 110.4 |
C4—C3—H3A | 107.8 | C17—C16—H16B | 110.4 |
N1—C4—C15 | 111.45 (12) | H16A—C16—H16B | 108.6 |
N1—C4—C18 | 109.80 (12) | C16—C17—H17A | 109.5 |
C15—C4—C18 | 112.26 (13) | C16—C17—H17B | 109.5 |
N1—C4—C3 | 101.46 (12) | H17A—C17—H17B | 109.5 |
C15—C4—C3 | 109.18 (12) | C16—C17—H17C | 109.5 |
C18—C4—C3 | 112.22 (13) | H17A—C17—H17C | 109.5 |
C10—C5—C6 | 120.04 (16) | H17B—C17—H17C | 109.5 |
C10—C5—N1 | 118.30 (15) | O5—C18—O6 | 125.00 (15) |
C6—C5—N1 | 121.65 (15) | O5—C18—C4 | 123.86 (15) |
C5—C6—C7 | 120.14 (18) | O6—C18—C4 | 111.06 (14) |
C5—C6—H6A | 119.9 | C20—C19—O6 | 110.4 (2) |
C7—C6—H6A | 119.9 | C20—C19—H19A | 109.6 |
C8—C7—C6 | 118.61 (19) | O6—C19—H19A | 109.6 |
C8—C7—H7A | 120.7 | C20—C19—H19B | 109.6 |
C6—C7—H7A | 120.7 | O6—C19—H19B | 109.6 |
C7—C8—C9 | 122.71 (19) | H19A—C19—H19B | 108.1 |
C7—C8—F1 | 118.2 (2) | C19—C20—H20A | 109.5 |
C9—C8—F1 | 119.1 (2) | C19—C20—H20B | 109.5 |
C8—C9—C10 | 118.7 (2) | H20A—C20—H20B | 109.5 |
C8—C9—H9A | 120.6 | C19—C20—H20C | 109.5 |
C10—C9—H9A | 120.6 | H20A—C20—H20C | 109.5 |
C5—C10—C9 | 119.75 (18) | H20B—C20—H20C | 109.5 |
C5—C10—H10A | 120.1 | ||
C5—N1—C1—O1 | −2.8 (3) | N1—C5—C10—C9 | 177.9 (2) |
C4—N1—C1—O1 | 174.55 (17) | C8—C9—C10—C5 | 1.1 (4) |
C5—N1—C1—C2 | 178.61 (14) | C14—O2—C11—C12 | 0.8 (2) |
C4—N1—C1—C2 | −4.03 (19) | C14—O2—C11—C3 | 179.16 (17) |
O1—C1—C2—C3 | 165.64 (18) | C2—C3—C11—C12 | −23.6 (3) |
N1—C1—C2—C3 | −15.83 (19) | C4—C3—C11—C12 | 95.8 (2) |
C1—C2—C3—C11 | 154.40 (15) | C2—C3—C11—O2 | 158.45 (15) |
C1—C2—C3—C4 | 27.67 (16) | C4—C3—C11—O2 | −82.10 (19) |
C1—N1—C4—C15 | −94.87 (16) | O2—C11—C12—C13 | −0.9 (2) |
C5—N1—C4—C15 | 82.38 (17) | C3—C11—C12—C13 | −178.9 (2) |
C1—N1—C4—C18 | 140.10 (14) | C11—C12—C13—C14 | 0.7 (3) |
C5—N1—C4—C18 | −42.65 (19) | C12—C13—C14—O2 | −0.2 (3) |
C1—N1—C4—C3 | 21.22 (16) | C11—O2—C14—C13 | −0.3 (3) |
C5—N1—C4—C3 | −161.53 (14) | C16—O4—C15—O3 | 7.4 (2) |
C11—C3—C4—N1 | −154.13 (13) | C16—O4—C15—C4 | −167.98 (14) |
C2—C3—C4—N1 | −29.15 (14) | N1—C4—C15—O3 | 16.6 (2) |
C11—C3—C4—C15 | −36.38 (17) | C18—C4—C15—O3 | 140.26 (16) |
C2—C3—C4—C15 | 88.60 (14) | C3—C4—C15—O3 | −94.65 (18) |
C11—C3—C4—C18 | 88.74 (16) | N1—C4—C15—O4 | −167.88 (12) |
C2—C3—C4—C18 | −146.29 (13) | C18—C4—C15—O4 | −44.24 (17) |
C1—N1—C5—C10 | −66.6 (2) | C3—C4—C15—O4 | 80.85 (15) |
C4—N1—C5—C10 | 116.36 (18) | C15—O4—C16—C17 | 177.24 (15) |
C1—N1—C5—C6 | 112.42 (19) | C19—O6—C18—O5 | 0.2 (3) |
C4—N1—C5—C6 | −64.6 (2) | C19—O6—C18—C4 | −176.75 (16) |
C10—C5—C6—C7 | −0.3 (3) | N1—C4—C18—O5 | −90.32 (19) |
N1—C5—C6—C7 | −179.27 (18) | C15—C4—C18—O5 | 145.12 (17) |
C5—C6—C7—C8 | 1.7 (3) | C3—C4—C18—O5 | 21.7 (2) |
C6—C7—C8—C9 | −1.8 (4) | N1—C4—C18—O6 | 86.63 (16) |
C6—C7—C8—F1 | 178.0 (2) | C15—C4—C18—O6 | −37.93 (18) |
C7—C8—C9—C10 | 0.4 (4) | C3—C4—C18—O6 | −161.33 (13) |
F1—C8—C9—C10 | −179.4 (2) | C18—O6—C19—C20 | 96.1 (2) |
C6—C5—C10—C9 | −1.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···O3i | 0.97 | 2.49 | 3.457 (2) | 174 |
C14—H14A···O1ii | 0.93 | 2.43 | 3.220 (3) | 143 |
C19—H19A···O1iii | 0.97 | 2.60 | 3.410 (3) | 141 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z; (iii) x+1, y, z. |
C20H19Cl2NO6 | Z = 2 |
Mr = 440.26 | F(000) = 456 |
Triclinic, P1 | Dx = 1.394 Mg m−3 |
Hall symbol: -P 1 | Melting point = 353–355 K |
a = 9.5478 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.2319 (9) Å | Cell parameters from 2877 reflections |
c = 12.5088 (11) Å | θ = 2.0–28.0° |
α = 72.749 (2)° | µ = 0.35 mm−1 |
β = 86.206 (2)° | T = 298 K |
γ = 64.310 (2)° | Block, colourless |
V = 1048.91 (16) Å3 | 0.23 × 0.19 × 0.15 mm |
Bruker CCD area detector diffractometer | 4450 independent reflections |
Radiation source: fine-focus sealed tube | 3184 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
phi and ω scans | θmax = 27.0°, θmin = 1.7° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.875, Tmax = 0.950 | k = −13→7 |
6438 measured reflections | l = −15→15 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0601P)2 + 0.4142P] where P = (Fo2 + 2Fc2)/3 |
4450 reflections | (Δ/σ)max < 0.001 |
264 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
C20H19Cl2NO6 | γ = 64.310 (2)° |
Mr = 440.26 | V = 1048.91 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.5478 (9) Å | Mo Kα radiation |
b = 10.2319 (9) Å | µ = 0.35 mm−1 |
c = 12.5088 (11) Å | T = 298 K |
α = 72.749 (2)° | 0.23 × 0.19 × 0.15 mm |
β = 86.206 (2)° |
Bruker CCD area detector diffractometer | 4450 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3184 reflections with I > 2σ(I) |
Tmin = 0.875, Tmax = 0.950 | Rint = 0.018 |
6438 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.37 e Å−3 |
4450 reflections | Δρmin = −0.41 e Å−3 |
264 parameters |
Experimental. Data was collected using a Siemens SMART CCD based diffractometer operating at room temperature. Data was measured using omega scans of 0.3 degrees per frame for 60 s. A total of 1271 frames were collected. The first 50 frames were recollected at the end of each set of frames. |
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 | ||
Cl1 | 0.48018 (8) | 0.71104 (8) | 0.48180 (6) | 0.0648 (2) | |
Cl2 | 0.19057 (11) | 1.02484 (10) | 0.46814 (8) | 0.0985 (4) | |
O1 | 0.1938 (2) | 0.87834 (19) | 0.00114 (14) | 0.0600 (5) | |
O2 | 0.1639 (2) | 0.2812 (2) | 0.10045 (16) | 0.0604 (5) | |
O3 | 0.50154 (19) | 0.4559 (2) | 0.17934 (16) | 0.0586 (5) | |
O4 | 0.41958 (18) | 0.27495 (18) | 0.24500 (14) | 0.0527 (4) | |
O5 | 0.1940 (2) | 0.4423 (3) | 0.37959 (15) | 0.0745 (6) | |
O6 | −0.0102 (2) | 0.5385 (3) | 0.25919 (17) | 0.0870 (7) | |
N1 | 0.2024 (2) | 0.6852 (2) | 0.15596 (14) | 0.0417 (4) | |
C1 | 0.1971 (3) | 0.7538 (3) | 0.04250 (18) | 0.0452 (5) | |
C2 | 0.1988 (3) | 0.6467 (3) | −0.01788 (18) | 0.0473 (5) | |
H2A | 0.3002 | 0.5995 | −0.0456 | 0.057* | |
H2B | 0.1207 | 0.6996 | −0.0807 | 0.057* | |
C3 | 0.1620 (3) | 0.5280 (3) | 0.06979 (18) | 0.0424 (5) | |
H3A | 0.0484 | 0.5675 | 0.0703 | 0.051* | |
C4 | 0.2253 (2) | 0.5273 (2) | 0.18339 (17) | 0.0391 (5) | |
C5 | 0.2003 (3) | 0.7609 (2) | 0.23584 (18) | 0.0420 (5) | |
C6 | 0.3258 (3) | 0.7050 (3) | 0.31264 (19) | 0.0455 (5) | |
H6A | 0.4123 | 0.6146 | 0.3147 | 0.055* | |
C7 | 0.3223 (3) | 0.7839 (3) | 0.38608 (19) | 0.0477 (5) | |
C8 | 0.1948 (3) | 0.9202 (3) | 0.3808 (2) | 0.0581 (6) | |
C9 | 0.0694 (3) | 0.9747 (3) | 0.3046 (2) | 0.0654 (7) | |
H9A | −0.0165 | 1.0659 | 0.3017 | 0.078* | |
C10 | 0.0710 (3) | 0.8947 (3) | 0.2329 (2) | 0.0546 (6) | |
H10A | −0.0145 | 0.9306 | 0.1828 | 0.066* | |
C11 | 0.2222 (3) | 0.3815 (3) | 0.04416 (19) | 0.0455 (5) | |
C12 | 0.3202 (3) | 0.3247 (3) | −0.0289 (2) | 0.0639 (7) | |
H12A | 0.3757 | 0.3703 | −0.0769 | 0.077* | |
C13 | 0.3237 (4) | 0.1821 (3) | −0.0198 (3) | 0.0783 (9) | |
H13A | 0.3814 | 0.1163 | −0.0609 | 0.094* | |
C14 | 0.2296 (4) | 0.1605 (3) | 0.0579 (3) | 0.0748 (9) | |
H14A | 0.2103 | 0.0751 | 0.0809 | 0.090* | |
C15 | 0.3991 (3) | 0.4169 (3) | 0.20421 (18) | 0.0424 (5) | |
C16 | 0.5786 (3) | 0.1584 (3) | 0.2504 (3) | 0.0682 (7) | |
H16A | 0.6463 | 0.1679 | 0.2991 | 0.082* | |
H16B | 0.6175 | 0.1696 | 0.1762 | 0.082* | |
C17 | 0.5761 (4) | 0.0088 (4) | 0.2949 (4) | 0.0978 (12) | |
H17A | 0.6797 | −0.0701 | 0.2992 | 0.147* | |
H17B | 0.5091 | 0.0004 | 0.2459 | 0.147* | |
H17C | 0.5378 | −0.0013 | 0.3684 | 0.147* | |
C18 | 0.1366 (3) | 0.4932 (3) | 0.28685 (19) | 0.0456 (5) | |
C19 | −0.1125 (5) | 0.5277 (7) | 0.3508 (4) | 0.131 (2) | |
H19A | −0.0538 | 0.4939 | 0.4220 | 0.158* | |
H19B | −0.1969 | 0.6275 | 0.3434 | 0.158* | |
C20 | −0.1741 (6) | 0.4272 (6) | 0.3504 (5) | 0.142 (2) | |
H20A | −0.2565 | 0.4387 | 0.4004 | 0.213* | |
H20B | −0.0938 | 0.3250 | 0.3748 | 0.213* | |
H20C | −0.2145 | 0.4485 | 0.2758 | 0.213* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0686 (4) | 0.0664 (4) | 0.0601 (4) | −0.0267 (3) | −0.0157 (3) | −0.0195 (3) |
Cl2 | 0.1109 (7) | 0.0846 (6) | 0.0944 (6) | −0.0125 (5) | −0.0190 (5) | −0.0597 (5) |
O1 | 0.0856 (13) | 0.0478 (10) | 0.0493 (10) | −0.0353 (9) | 0.0058 (9) | −0.0084 (8) |
O2 | 0.0650 (11) | 0.0591 (11) | 0.0696 (12) | −0.0392 (9) | 0.0051 (9) | −0.0175 (9) |
O3 | 0.0453 (9) | 0.0632 (11) | 0.0779 (12) | −0.0306 (8) | 0.0167 (8) | −0.0274 (9) |
O4 | 0.0488 (9) | 0.0462 (9) | 0.0588 (10) | −0.0202 (7) | −0.0017 (7) | −0.0092 (8) |
O5 | 0.0713 (12) | 0.1050 (16) | 0.0385 (10) | −0.0395 (11) | 0.0077 (9) | −0.0084 (10) |
O6 | 0.0581 (12) | 0.170 (2) | 0.0598 (12) | −0.0676 (14) | 0.0266 (9) | −0.0485 (14) |
N1 | 0.0486 (10) | 0.0433 (10) | 0.0365 (9) | −0.0233 (8) | 0.0015 (8) | −0.0110 (8) |
C1 | 0.0480 (12) | 0.0472 (13) | 0.0402 (12) | −0.0224 (10) | 0.0039 (9) | −0.0101 (10) |
C2 | 0.0562 (13) | 0.0536 (13) | 0.0376 (12) | −0.0293 (11) | 0.0048 (10) | −0.0133 (10) |
C3 | 0.0418 (11) | 0.0517 (13) | 0.0395 (11) | −0.0249 (10) | 0.0020 (9) | −0.0143 (10) |
C4 | 0.0410 (11) | 0.0448 (12) | 0.0372 (11) | −0.0240 (9) | 0.0039 (8) | −0.0120 (9) |
C5 | 0.0457 (12) | 0.0442 (12) | 0.0380 (11) | −0.0215 (10) | 0.0044 (9) | −0.0121 (9) |
C6 | 0.0474 (12) | 0.0422 (12) | 0.0458 (12) | −0.0177 (10) | 0.0001 (10) | −0.0135 (10) |
C7 | 0.0531 (13) | 0.0482 (13) | 0.0428 (12) | −0.0238 (11) | −0.0034 (10) | −0.0105 (10) |
C8 | 0.0696 (16) | 0.0563 (15) | 0.0513 (14) | −0.0228 (13) | 0.0007 (12) | −0.0262 (12) |
C9 | 0.0614 (16) | 0.0567 (15) | 0.0630 (17) | −0.0042 (12) | −0.0040 (13) | −0.0286 (13) |
C10 | 0.0484 (13) | 0.0576 (15) | 0.0505 (14) | −0.0146 (11) | −0.0028 (10) | −0.0176 (11) |
C11 | 0.0506 (13) | 0.0511 (13) | 0.0427 (12) | −0.0290 (11) | −0.0011 (10) | −0.0134 (10) |
C12 | 0.0799 (19) | 0.0614 (16) | 0.0566 (16) | −0.0338 (14) | 0.0147 (14) | −0.0234 (13) |
C13 | 0.103 (2) | 0.0608 (18) | 0.071 (2) | −0.0278 (17) | 0.0056 (18) | −0.0316 (15) |
C14 | 0.095 (2) | 0.0506 (16) | 0.087 (2) | −0.0379 (16) | −0.0075 (18) | −0.0202 (15) |
C15 | 0.0461 (12) | 0.0487 (13) | 0.0378 (11) | −0.0239 (10) | 0.0038 (9) | −0.0154 (9) |
C16 | 0.0575 (16) | 0.0576 (16) | 0.0765 (19) | −0.0138 (13) | −0.0015 (14) | −0.0181 (14) |
C17 | 0.094 (2) | 0.0527 (18) | 0.133 (3) | −0.0200 (17) | −0.013 (2) | −0.0218 (19) |
C18 | 0.0499 (13) | 0.0536 (13) | 0.0423 (13) | −0.0306 (11) | 0.0106 (10) | −0.0157 (10) |
C19 | 0.111 (3) | 0.269 (6) | 0.102 (3) | −0.136 (4) | 0.074 (3) | −0.107 (4) |
C20 | 0.167 (5) | 0.142 (4) | 0.153 (4) | −0.104 (4) | 0.095 (4) | −0.053 (3) |
Cl1—C7 | 1.731 (2) | C6—C7 | 1.381 (3) |
Cl2—C8 | 1.729 (2) | C6—H6A | 0.9300 |
O1—C1 | 1.212 (3) | C7—C8 | 1.384 (3) |
O2—C11 | 1.368 (3) | C8—C9 | 1.382 (4) |
O2—C14 | 1.370 (3) | C9—C10 | 1.377 (3) |
O3—C15 | 1.199 (3) | C9—H9A | 0.9300 |
O4—C15 | 1.317 (3) | C10—H10A | 0.9300 |
O4—C16 | 1.459 (3) | C11—C12 | 1.334 (4) |
O5—C18 | 1.181 (3) | C12—C13 | 1.416 (4) |
O6—C18 | 1.306 (3) | C12—H12A | 0.9300 |
O6—C19 | 1.466 (4) | C13—C14 | 1.316 (5) |
N1—C1 | 1.378 (3) | C13—H13A | 0.9300 |
N1—C5 | 1.429 (3) | C14—H14A | 0.9300 |
N1—C4 | 1.466 (3) | C16—C17 | 1.476 (4) |
C1—C2 | 1.499 (3) | C16—H16A | 0.9700 |
C2—C3 | 1.526 (3) | C16—H16B | 0.9700 |
C2—H2A | 0.9700 | C17—H17A | 0.9600 |
C2—H2B | 0.9700 | C17—H17B | 0.9600 |
C3—C11 | 1.481 (3) | C17—H17C | 0.9600 |
C3—C4 | 1.577 (3) | C19—C20 | 1.390 (6) |
C3—H3A | 0.9800 | C19—H19A | 0.9700 |
C4—C15 | 1.535 (3) | C19—H19B | 0.9700 |
C4—C18 | 1.535 (3) | C20—H20A | 0.9600 |
C5—C10 | 1.383 (3) | C20—H20B | 0.9600 |
C5—C6 | 1.385 (3) | C20—H20C | 0.9600 |
C11—O2—C14 | 105.9 (2) | C5—C10—H10A | 120.2 |
C15—O4—C16 | 116.20 (19) | C12—C11—O2 | 109.5 (2) |
C18—O6—C19 | 117.2 (3) | C12—C11—C3 | 133.4 (2) |
C1—N1—C5 | 121.07 (18) | O2—C11—C3 | 117.0 (2) |
C1—N1—C4 | 113.36 (17) | C11—C12—C13 | 107.1 (3) |
C5—N1—C4 | 125.31 (17) | C11—C12—H12A | 126.4 |
O1—C1—N1 | 124.8 (2) | C13—C12—H12A | 126.4 |
O1—C1—C2 | 127.2 (2) | C14—C13—C12 | 106.7 (3) |
N1—C1—C2 | 107.91 (19) | C14—C13—H13A | 126.7 |
C1—C2—C3 | 104.95 (18) | C12—C13—H13A | 126.7 |
C1—C2—H2A | 110.8 | C13—C14—O2 | 110.7 (3) |
C3—C2—H2A | 110.8 | C13—C14—H14A | 124.6 |
C1—C2—H2B | 110.8 | O2—C14—H14A | 124.6 |
C3—C2—H2B | 110.8 | O3—C15—O4 | 125.0 (2) |
H2A—C2—H2B | 108.8 | O3—C15—C4 | 123.5 (2) |
C11—C3—C2 | 112.61 (19) | O4—C15—C4 | 111.28 (18) |
C11—C3—C4 | 117.58 (18) | O4—C16—C17 | 107.8 (3) |
C2—C3—C4 | 102.83 (16) | O4—C16—H16A | 110.1 |
C11—C3—H3A | 107.8 | C17—C16—H16A | 110.1 |
C2—C3—H3A | 107.8 | O4—C16—H16B | 110.1 |
C4—C3—H3A | 107.8 | C17—C16—H16B | 110.1 |
N1—C4—C15 | 111.08 (17) | H16A—C16—H16B | 108.5 |
N1—C4—C18 | 108.84 (17) | C16—C17—H17A | 109.5 |
C15—C4—C18 | 110.97 (18) | C16—C17—H17B | 109.5 |
N1—C4—C3 | 100.97 (16) | H17A—C17—H17B | 109.5 |
C15—C4—C3 | 108.53 (17) | C16—C17—H17C | 109.5 |
C18—C4—C3 | 116.04 (17) | H17A—C17—H17C | 109.5 |
C10—C5—C6 | 120.2 (2) | H17B—C17—H17C | 109.5 |
C10—C5—N1 | 118.38 (19) | O5—C18—O6 | 125.3 (2) |
C6—C5—N1 | 121.35 (19) | O5—C18—C4 | 123.1 (2) |
C7—C6—C5 | 119.9 (2) | O6—C18—C4 | 111.4 (2) |
C7—C6—H6A | 120.1 | C20—C19—O6 | 111.6 (4) |
C5—C6—H6A | 120.1 | C20—C19—H19A | 109.3 |
C6—C7—C8 | 119.8 (2) | O6—C19—H19A | 109.3 |
C6—C7—Cl1 | 118.98 (18) | C20—C19—H19B | 109.3 |
C8—C7—Cl1 | 121.20 (18) | O6—C19—H19B | 109.3 |
C9—C8—C7 | 120.0 (2) | H19A—C19—H19B | 108.0 |
C9—C8—Cl2 | 119.2 (2) | C19—C20—H20A | 109.5 |
C7—C8—Cl2 | 120.77 (19) | C19—C20—H20B | 109.5 |
C10—C9—C8 | 120.4 (2) | H20A—C20—H20B | 109.5 |
C10—C9—H9A | 119.8 | C19—C20—H20C | 109.5 |
C8—C9—H9A | 119.8 | H20A—C20—H20C | 109.5 |
C9—C10—C5 | 119.6 (2) | H20B—C20—H20C | 109.5 |
C9—C10—H10A | 120.2 | ||
C5—N1—C1—O1 | 1.7 (3) | Cl2—C8—C9—C10 | 179.0 (2) |
C4—N1—C1—O1 | −172.8 (2) | C8—C9—C10—C5 | −1.4 (4) |
C5—N1—C1—C2 | −179.18 (18) | C6—C5—C10—C9 | 1.9 (4) |
C4—N1—C1—C2 | 6.4 (2) | N1—C5—C10—C9 | −176.3 (2) |
O1—C1—C2—C3 | −166.2 (2) | C14—O2—C11—C12 | −0.5 (3) |
N1—C1—C2—C3 | 14.7 (2) | C14—O2—C11—C3 | 176.5 (2) |
C1—C2—C3—C11 | −155.48 (18) | C2—C3—C11—C12 | 11.8 (4) |
C1—C2—C3—C4 | −27.9 (2) | C4—C3—C11—C12 | −107.5 (3) |
C1—N1—C4—C15 | 91.3 (2) | C2—C3—C11—O2 | −164.31 (19) |
C5—N1—C4—C15 | −82.8 (2) | C4—C3—C11—O2 | 76.4 (2) |
C1—N1—C4—C18 | −146.20 (18) | O2—C11—C12—C13 | 0.6 (3) |
C5—N1—C4—C18 | 39.6 (3) | C3—C11—C12—C13 | −175.7 (3) |
C1—N1—C4—C3 | −23.6 (2) | C11—C12—C13—C14 | −0.4 (4) |
C5—N1—C4—C3 | 162.24 (18) | C12—C13—C14—O2 | 0.1 (4) |
C11—C3—C4—N1 | 154.83 (18) | C11—O2—C14—C13 | 0.2 (3) |
C2—C3—C4—N1 | 30.5 (2) | C16—O4—C15—O3 | −5.5 (3) |
C11—C3—C4—C15 | 38.0 (2) | C16—O4—C15—C4 | 169.97 (19) |
C2—C3—C4—C15 | −86.3 (2) | N1—C4—C15—O3 | −13.9 (3) |
C11—C3—C4—C18 | −87.7 (2) | C18—C4—C15—O3 | −135.1 (2) |
C2—C3—C4—C18 | 147.96 (19) | C3—C4—C15—O3 | 96.3 (2) |
C1—N1—C5—C10 | 62.2 (3) | N1—C4—C15—O4 | 170.59 (17) |
C4—N1—C5—C10 | −124.0 (2) | C18—C4—C15—O4 | 49.4 (2) |
C1—N1—C5—C6 | −115.9 (2) | C3—C4—C15—O4 | −79.3 (2) |
C4—N1—C5—C6 | 57.8 (3) | C15—O4—C16—C17 | −178.4 (2) |
C10—C5—C6—C7 | −0.5 (4) | C19—O6—C18—O5 | 1.1 (5) |
N1—C5—C6—C7 | 177.7 (2) | C19—O6—C18—C4 | −173.7 (3) |
C5—C6—C7—C8 | −1.5 (4) | N1—C4—C18—O5 | −91.7 (3) |
C5—C6—C7—Cl1 | 179.61 (18) | C15—C4—C18—O5 | 30.8 (3) |
C6—C7—C8—C9 | 2.0 (4) | C3—C4—C18—O5 | 155.3 (2) |
Cl1—C7—C8—C9 | −179.1 (2) | N1—C4—C18—O6 | 83.3 (2) |
C6—C7—C8—Cl2 | −177.5 (2) | C15—C4—C18—O6 | −154.2 (2) |
Cl1—C7—C8—Cl2 | 1.4 (3) | C3—C4—C18—O6 | −29.7 (3) |
C7—C8—C9—C10 | −0.6 (4) | C18—O6—C19—C20 | −116.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O3i | 0.97 | 2.43 | 3.355 (3) | 159 |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C20H20FNO6 | C20H19Cl2NO6 |
Mr | 389.37 | 440.26 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 293 | 298 |
a, b, c (Å) | 9.582 (3), 10.157 (3), 11.384 (4) | 9.5478 (9), 10.2319 (9), 12.5088 (11) |
α, β, γ (°) | 90.305 (6), 105.358 (6), 112.405 (5) | 72.749 (2), 86.206 (2), 64.310 (2) |
V (Å3) | 980.6 (5) | 1048.91 (16) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.35 |
Crystal size (mm) | 0.39 × 0.36 × 0.22 | 0.23 × 0.19 × 0.15 |
Data collection | ||
Diffractometer | Bruker CCD area-detector diffractometer | Bruker CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.885, 0.978 | 0.875, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6019, 4167, 2936 | 6438, 4450, 3184 |
Rint | 0.015 | 0.018 |
(sin θ/λ)max (Å−1) | 0.639 | 0.639 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.130, 1.03 | 0.048, 0.140, 1.05 |
No. of reflections | 4167 | 4450 |
No. of parameters | 255 | 264 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.25 | 0.37, −0.41 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1997), SHELXTL (Sheldrick, 1997a), SHELXTL.
C7—C8 | 1.351 (3) | C13—C14 | 1.309 (4) |
C8—C9 | 1.361 (3) | C19—C20 | 1.463 (4) |
C11—C12 | 1.333 (3) | ||
N1—C4—C3 | 101.46 (12) | ||
C1—N1—C5—C10 | −66.6 (2) | C19—O6—C18—C4 | −176.75 (16) |
C16—O4—C15—C4 | −167.98 (14) | C18—O6—C19—C20 | 96.1 (2) |
C15—O4—C16—C17 | 177.24 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···O3i | 0.97 | 2.49 | 3.457 (2) | 174 |
C14—H14A···O1ii | 0.93 | 2.43 | 3.220 (3) | 143 |
C19—H19A···O1iii | 0.97 | 2.60 | 3.410 (3) | 141 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z; (iii) x+1, y, z. |
C7—C8 | 1.384 (3) | C13—C14 | 1.316 (5) |
C8—C9 | 1.382 (4) | C19—C20 | 1.390 (6) |
C11—C12 | 1.334 (4) | ||
N1—C4—C3 | 100.97 (16) | ||
C1—N1—C5—C10 | 62.2 (3) | C19—O6—C18—C4 | −173.7 (3) |
C16—O4—C15—C4 | 169.97 (19) | C18—O6—C19—C20 | −116.5 (5) |
C15—O4—C16—C17 | −178.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O3i | 0.97 | 2.43 | 3.355 (3) | 159 |
Symmetry code: (i) −x+1, −y+1, −z. |
Bioactivity of the lactam compounds depends on their ability to acylate several proteins to inhibit the cross-linking of bacterial cell walls (Baldwin et al., 1991), which in turn is dependent on the presense of a suitably substituted and activated lactam ring (Baldwin et al.,1984). It has been observed that N-phenyl-γ-lactam derivatives exhibit Gram-positive and Gram-negative antibacterial activities, and the replacement of the phenyl group by a 2-furyl moiety at the 4-position of the γ-lactam ring causes this compound to be moderately active (Ray et al.,1994). In the variation of N-aryl substituents, the replacement of the N-phenyl by the N-4-chlorophenyl group increased the antibacterial activity significantly (Kar et al.,1998). It has also been found that the introduction of fluorine in the aryl moiety alters the activity of many organic compounds abnormally, by affecting the half life of the drug. The title compounds, (I) and (II), were synthesized in order to obtain novel γ-lactam analogues with potential bioactivity. The crystal structure determinations of (I) and (II) were carried out in order to elucidate their molecular conformation.
Both compounds contain one phenyl ring (C5–C10), one furan ring (C11–C14/O2) and one pyrrolidine ring (C1–C4/N1; Figs. 1 and 2). The pyrrolidine ring is intermediate between envelope and half-chair conformations, with a local pesudo-mirror running through atom C3 and the midpoint of the C1—N1 bond, and a local pseudo-twofold axis running through atom C1 and the midpoint of the C3—C4 bond (Duax et al., 1976). Atom C3 deviates from the mean plane passing through the remaining atoms in the ring by 0.476 Å in (I) and 0.492 Å in (II). The conformation of the pyrrolidin ring is dictated by the existence of intramolecular contacts [C11···O4 = 2.878 (2) Å in (I) and 2.876 (3) Å in (II)]. The distortion of the pyrrolidine ring also affects the N1—C4—C3 ring angle [101.46 (12)° in (I) and 100.97 (16)° in (II)]. The plane of the phenyl group is twisted from the plane of the furan ring by 74.01 (7) and 84.46 (9)° in (I) and (II), respectively. The dihedral angle between the phenyl ring and the pyrrolidine ring is 69.79 (8)° in (I) and 64.05 (8)° in (II), and the angle between the pyrrolidine and furan rings is 56.42 (10)° in (I) and 46.38 (12)° in (II).
In both compounds, one of the ethyl acetate chains is completely extended, with all of the non-H atoms coplanar [the mean deviation from the C4/C15/O3/O4/C16/C17 plane is 0.060 Å for (I) and 0.050 Å for (II)]. The other ethyl acetate chain is twisted, the C18—O6—C19—C20 torsion angle being 96.1 (2)° for (I) and −116.5 (5)° for (II). In this chain in (II), a weak attractive intramolecular contact (O6···H3A =2.35 Å) is found. Also in the twisted ethyl acetate chain, a bit more marked for compound II, Slight disorder, which is more marked in (II), is also apparent at the end of the twisted ethyl acetate chain (C19/C20), as evidenced by the Ueq values and the short C19—C20 distance [1.390 (6) Å for (II); Table 2].
The C11—C12 and C13—C14 distances (Tables 1 and 2) confirm the double-bond character of these linkages. These distances are shorter than those found in the corresponding compounds when the tiophen ring replaces the furan ring. [(I): Usman et al., 2001; (II): Ray et al. 1998] In both compounds, the intermolecular interaction between atoms H14A and O1 shortens the nearest C═C double bond in the furan ring [C13═C14 = 1.309 (4) Å in (I) and 1.316 (5) Å in (II)]. The presence of the F atom in (I) provokes a shortening of the nearest C—C bonds [C7—C8 = 1.351 (3) Å and C8—C9 = 1.361 (3) Å]. On the other hand, a short intermolecular contact between atoms Cl1 and O5 [Cl1···O5 = 3.164 (2) Å] is found in (II). In both compounds centrosymetric pairs are formed. As has been found in related compounds, weak hydrogen bonds (Tables 3 and 4) and van der Waals interactions stabilize the crystal structures (Figs. 3 and 4)