We present the crystal and molecular structures of two new N-phthalyl-3-amino-2-arylpropionic acid pantolactonyl ester derivatives with 4-fluorophenyl and 3,4-dimethoxyphenyl as the aryl group, 2,3,4,5-tetrahydro-4,4-dimethyl-2-oxofuran-3-yl 3-phthalimido-2-(4-fluorophenyl)propanoate, C23H20FNO6, and 2,3,4,5-tetrahydro-4,4-dimethyl-2-oxofuran-3-yl 3-phthalimido-2-(3,4-dimethoxyphenyl)propanoate ethyl acetate hemisolvate, C25H25NO8·0.5C4H8O2. This structural study confirms the S configuration of the C2 and validates the stereospecificity of our synthesis strategy.
Supporting information
CCDC references: 136875; 144625; 144626
Ces trois composés ont été synthetisés à partir des acides
3-amino-2-arylpropanoïques racémiques via l'addition
diastéréoselective de la (R)-pantolactone à leurs cétènes.
Cette réaction permet la préparation d'esters pantolactoniques
énantiomériquement purs des acides
(S)—N-Phtaloyl-3-amino-2-(4-fluorophényl,
4-méthoxyphényl et 3,4-dimethoxyphenyl)propanoïques. Les
cristallizations des trois composés ont été effectuées à
température ambiante à partir d'un mélange d'acétate d'éthyle
et d'hexane.
Pour le composé (III), les listes des coordonnées des atomes, des facteurs
d'agitation thermique anisotrope, des facteurs de structure et des distances
et angles ont été déposées au dépôt d'archives de Cambridge
Crystallographic Data Centre (Reference CCDC 136875). On peut en obtenir des
copies en s'addressant a: CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44
1223 336033 or e-mail: deposit@ccdc.cam.ac.uk). Le composé (II) cristallize
avec une demi molécule d'acétate d'éthyle (confirmé par 1H
RMN des cristaux). Cette demi molécule de solvant a été rajoutée dans
la formule brute, ce qui explique un désorde de 50%. Il n'a pas été
possible d'assigner les hydrogènes de cette molécule de solvant.
For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: maXus (Mackay et al., 1999); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: maXus.
Crystal data top
C23H20FNO6 | Dx = 1.31 Mg m−3 |
Mr = 425.41 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 14895 reflections |
a = 9.5666 (3) Å | θ = 1.0–25.4° |
b = 11.1026 (2) Å | µ = 0.1 mm−1 |
c = 20.3200 (6) Å | T = 298 K |
V = 2158.3 (2) Å3 | Prism, colorless |
Z = 4 | 0.32 × 0.27 × 0.10 mm |
Data collection top
KappaCCD diffractometer | Rint = 0.028 |
phi–scan | θmax = 25.4° |
13240 measured reflections | h = −11→11 |
2362 independent reflections | k = −12→12 |
2209 reflections with refl_observed_if_I_ > _3.00_σ(I) | l = −24→25 |
Refinement top
Refinement on F | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(F) + 0.03F2] |
wR(F2) = 0.052 | (Δ/σ)max = 0.007 |
S = 1.22 | Δρmax = 0.10 e Å−3 |
2209 reflections | Δρmin = −0.10 e Å−3 |
273 parameters | |
Crystal data top
C23H20FNO6 | V = 2158.3 (2) Å3 |
Mr = 425.41 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.5666 (3) Å | µ = 0.1 mm−1 |
b = 11.1026 (2) Å | T = 298 K |
c = 20.3200 (6) Å | 0.32 × 0.27 × 0.10 mm |
Data collection top
KappaCCD diffractometer | 2209 reflections with refl_observed_if_I_ > _3.00_σ(I) |
13240 measured reflections | Rint = 0.028 |
2362 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 273 parameters |
wR(F2) = 0.052 | H-atom parameters not refined |
S = 1.22 | Δρmax = 0.10 e Å−3 |
2209 reflections | Δρmin = −0.10 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
F1 | −0.34540 (4) | −0.88610 (4) | −0.50450 (2) | 0.0941 (2) | |
O1 | −0.71590 (5) | −0.43500 (4) | −0.35980 (2) | 0.0480 (2) | |
O2 | −0.71550 (4) | −0.37200 (5) | −0.46500 (2) | 0.0522 (2) | |
O3 | −0.57870 (6) | −0.13430 (6) | −0.51940 (3) | 0.0494 (3) | |
O4 | −0.35670 (5) | −0.21880 (4) | −0.32620 (2) | 0.0684 (2) | |
O5 | −0.89860 (6) | −0.63200 (6) | −0.33060 (3) | 0.0913 (3) | |
O6 | −1.04710 (6) | −0.49290 (4) | −0.29440 (3) | 0.0787 (3) | |
N1 | −0.46280 (6) | −0.20720 (6) | −0.42760 (3) | 0.0380 (3) | |
C1 | −0.65380 (7) | −0.40690 (5) | −0.41750 (3) | 0.0375 (3) | |
C2 | −0.49750 (6) | −0.42570 (5) | −0.41350 (3) | 0.0396 (3) | |
C3 | −0.42230 (6) | −0.32550 (5) | −0.45200 (3) | 0.0430 (3) | |
C4 | −0.45700 (7) | −0.54950 (6) | −0.43880 (3) | 0.0432 (3) | |
C5 | −0.37050 (6) | −0.62290 (5) | −0.40170 (3) | 0.0567 (3) | |
C6 | −0.33230 (8) | −0.73670 (7) | −0.42400 (4) | 0.0694 (4) | |
C7 | −0.38160 (6) | −0.77430 (5) | −0.48320 (3) | 0.0644 (3) | |
C8 | −0.46590 (8) | −0.70540 (6) | −0.52170 (4) | 0.0639 (4) | |
C9 | −0.50380 (7) | −0.59170 (6) | −0.49890 (3) | 0.0535 (3) | |
C10 | −0.43020 (9) | −0.16530 (7) | −0.36500 (4) | 0.0445 (4) | |
C11 | −0.50340 (7) | −0.04880 (7) | −0.35750 (4) | 0.0479 (4) | |
C12 | −0.51490 (6) | 0.02830 (5) | −0.30430 (3) | 0.0678 (3) | |
C13 | −0.59790 (9) | 0.13030 (7) | −0.31310 (5) | 0.0818 (5) | |
C14 | −0.66450 (8) | 0.15370 (6) | −0.37110 (5) | 0.0773 (4) | |
C15 | −0.65290 (7) | 0.07730 (8) | −0.42400 (4) | 0.0593 (4) | |
C16 | −0.57170 (9) | −0.02440 (8) | −0.41590 (6) | 0.0427 (5) | |
C17 | −0.54290 (8) | −0.12360 (8) | −0.46270 (4) | 0.0378 (4) | |
C18 | −0.9323 (1) | −0.5288 (1) | −0.32720 (4) | 0.0595 (6) | |
C19 | −0.86400 (7) | −0.41830 (7) | −0.35630 (4) | 0.0426 (3) | |
C20 | −0.9103 (1) | −0.31630 (9) | −0.31100 (5) | 0.0491 (6) | |
C21 | −1.0581 (1) | −0.36220 (8) | −0.29660 (4) | 0.0682 (5) | |
C22 | −0.82430 (9) | −0.31310 (9) | −0.24830 (4) | 0.0839 (5) | |
C23 | −0.91320 (7) | −0.19420 (6) | −0.34460 (3) | 0.0738 (3) | |
H2 | −0.4701 (7) | −0.4180 (5) | −0.3682 (3) | 0.05930* | |
H3A | −0.3200 (7) | −0.3375 (6) | −0.4484 (3) | 0.06300* | |
H3B | −0.4492 (8) | −0.3307 (7) | −0.4984 (4) | 0.06300* | |
H5 | −0.3467 (6) | −0.5972 (5) | −0.3620 (4) | 0.07670* | |
H6 | −0.279 (1) | −0.7936 (8) | −0.3986 (5) | 0.08940* | |
H8 | −0.4944 (9) | −0.7311 (8) | −0.5640 (5) | 0.08390* | |
H9 | −0.5618 (9) | −0.5406 (8) | −0.5247 (4) | 0.07350* | |
H12 | −0.4672 (9) | 0.0080 (9) | −0.2671 (5) | 0.08780* | |
H13 | −0.602 (1) | 0.169 (1) | −0.2758 (6) | 0.10180* | |
H14 | −0.7211 (9) | 0.2283 (8) | −0.3755 (5) | 0.09730* | |
H15 | −0.698 (1) | 0.089 (1) | −0.4688 (6) | 0.07930* | |
H19 | −0.90060 | −0.40580 | −0.40080 | 0.06260* | |
H21A | −1.09910 | −0.33490 | −0.25660 | 0.08820* | |
H21B | −1.12170 | −0.33460 | −0.33220 | 0.08820* | |
H22A | −0.8251 (9) | −0.3916 (7) | −0.2285 (4) | 0.10400* | |
H22B | −0.864 (1) | −0.2557 (9) | −0.2183 (5) | 0.10400* | |
H22C | −0.72980 | −0.29060 | −0.25830 | 0.10400* | |
H23A | −0.96800 | −0.19840 | −0.38410 | 0.09380* | |
H23B | −0.81930 | −0.17080 | −0.35540 | 0.09380* | |
H23C | −0.9534 (8) | −0.1359 (7) | −0.3153 (4) | 0.09380* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.0829 (2) | 0.0454 (3) | 0.1540 (2) | 0.0116 (2) | 0.0345 (2) | −0.0171 (2) |
O1 | 0.0356 (2) | 0.0673 (3) | 0.0410 (2) | 0.0126 (2) | 0.0085 (2) | 0.0065 (2) |
O2 | 0.0390 (2) | 0.0707 (3) | 0.0469 (2) | 0.0025 (2) | 0.0023 (2) | 0.0130 (2) |
O3 | 0.0458 (3) | 0.0607 (4) | 0.0416 (3) | −0.0018 (3) | −0.0061 (3) | 0.0040 (3) |
O4 | 0.0716 (3) | 0.0793 (3) | 0.0542 (3) | 0.0118 (2) | −0.0202 (2) | 0.0063 (2) |
O5 | 0.1035 (3) | 0.0546 (4) | 0.1158 (3) | 0.0090 (3) | 0.0386 (2) | 0.0050 (3) |
O6 | 0.0598 (3) | 0.0747 (3) | 0.1016 (5) | 0.0047 (2) | 0.0390 (3) | 0.0160 (3) |
N1 | 0.0340 (4) | 0.0408 (4) | 0.0391 (4) | 0.0025 (3) | −0.0016 (3) | −0.0007 (3) |
C1 | 0.0380 (3) | 0.0350 (3) | 0.0395 (3) | 0.0044 (2) | 0.0080 (3) | 0.0010 (3) |
C2 | 0.0344 (3) | 0.0424 (3) | 0.0421 (4) | 0.0059 (2) | 0.0041 (3) | 0.0001 (3) |
C3 | 0.0362 (3) | 0.0441 (3) | 0.0487 (3) | 0.0036 (3) | 0.0094 (3) | −0.0024 (3) |
C4 | 0.0328 (3) | 0.0407 (4) | 0.0560 (3) | 0.0045 (3) | 0.0100 (3) | 0.0010 (3) |
C5 | 0.0506 (3) | 0.0559 (3) | 0.0637 (3) | 0.0132 (2) | 0.0049 (2) | 0.0071 (2) |
C6 | 0.0643 (4) | 0.0527 (4) | 0.0912 (5) | 0.0216 (3) | 0.0168 (3) | 0.0166 (4) |
C7 | 0.0511 (3) | 0.0390 (3) | 0.1032 (3) | 0.0039 (2) | 0.0255 (3) | −0.0046 (2) |
C8 | 0.0472 (5) | 0.0574 (4) | 0.0870 (5) | −0.0012 (4) | 0.0089 (4) | −0.0218 (3) |
C9 | 0.0403 (3) | 0.0537 (4) | 0.0664 (3) | 0.0064 (3) | 0.0003 (3) | −0.0089 (3) |
C10 | 0.0415 (4) | 0.0517 (5) | 0.0403 (4) | −0.0001 (3) | −0.0035 (4) | 0.0014 (3) |
C11 | 0.0457 (4) | 0.0505 (4) | 0.0474 (4) | −0.0040 (3) | 0.0064 (3) | −0.0056 (3) |
C12 | 0.0724 (3) | 0.0733 (3) | 0.0577 (3) | −0.0130 (2) | 0.0097 (2) | −0.0202 (2) |
C13 | 0.0847 (5) | 0.0672 (4) | 0.0935 (6) | −0.0091 (3) | 0.0294 (5) | −0.0397 (4) |
C14 | 0.0643 (4) | 0.0562 (4) | 0.1113 (7) | 0.0093 (3) | 0.0174 (4) | −0.0188 (4) |
C15 | 0.0453 (4) | 0.0468 (5) | 0.0858 (6) | 0.0055 (3) | 0.0058 (4) | −0.0015 (4) |
C16 | 0.0334 (5) | 0.0429 (5) | 0.0519 (8) | −0.0019 (4) | 0.0032 (5) | −0.0005 (5) |
C17 | 0.0304 (4) | 0.0419 (6) | 0.0410 (5) | −0.0040 (4) | 0.0019 (4) | 0.0035 (4) |
C18 | 0.0543 (6) | 0.0568 (8) | 0.0673 (5) | 0.0053 (5) | 0.0187 (4) | 0.0056 (5) |
C19 | 0.0318 (3) | 0.0540 (4) | 0.0419 (5) | 0.0062 (3) | 0.0069 (3) | 0.0019 (3) |
C20 | 0.0432 (6) | 0.0604 (5) | 0.0437 (7) | 0.0128 (5) | 0.0066 (5) | −0.0039 (5) |
C21 | 0.0518 (6) | 0.0790 (5) | 0.0738 (5) | 0.0208 (4) | 0.0225 (5) | 0.0060 (4) |
C22 | 0.0793 (5) | 0.1143 (5) | 0.0581 (4) | 0.0322 (4) | −0.0087 (4) | −0.0266 (4) |
C23 | 0.0880 (4) | 0.0587 (4) | 0.0746 (4) | 0.0130 (3) | 0.0116 (3) | −0.0058 (3) |
Geometric parameters (Å, º) top
F1—C7 | 1.359 (1) | C5—C6 | 1.391 (1) |
O1—C1 | 1.351 (1) | C6—C7 | 1.358 (2) |
O1—C19 | 1.431 (1) | C7—C8 | 1.359 (1) |
O2—C1 | 1.196 (1) | C8—C9 | 1.393 (1) |
O4—C10 | 1.212 (1) | C10—C11 | 1.479 (2) |
O3—C17 | 1.208 (2) | C11—C12 | 1.383 (1) |
O5—C18 | 1.192 (2) | C11—C16 | 1.382 (2) |
O6—C18 | 1.345 (2) | C12—C13 | 1.395 (1) |
O6—C21 | 1.456 (1) | C13—C14 | 1.365 (2) |
N1—C3 | 1.456 (1) | C14—C15 | 1.374 (2) |
N1—C10 | 1.390 (2) | C15—C16 | 1.380 (2) |
N1—C17 | 1.399 (2) | C16—C17 | 1.481 (2) |
C1—C2 | 1.512 (1) | C18—C19 | 1.511 (2) |
C2—C3 | 1.539 (1) | C19—C20 | 1.525 (2) |
C2—C4 | 1.518 (1) | C20—C21 | 1.531 (2) |
C4—C5 | 1.385 (1) | C20—C22 | 1.517 (2) |
C4—C9 | 1.383 (1) | C20—C23 | 1.518 (2) |
| | | |
C1—O1—C19 | 116.7 (1) | C10—C11—C16 | 107.9 (1) |
C18—O6—C21 | 109.8 (1) | C12—C11—C16 | 120.8 (1) |
C3—N1—C10 | 123.6 (1) | C11—C12—C13 | 116.6 (1) |
C3—N1—C17 | 124.8 (1) | C12—C13—C14 | 122.1 (1) |
C10—N1—C17 | 111.6 (1) | C13—C14—C15 | 121.4 (1) |
O1—C1—O2 | 123.9 (1) | C14—C15—C16 | 117.2 (1) |
O1—C1—C2 | 110.9 (1) | C11—C16—C15 | 121.9 (1) |
O2—C1—C2 | 125.2 (1) | C11—C16—C17 | 108.5 (1) |
C1—C2—C3 | 109.6 (1) | C15—C16—C17 | 129.5 (1) |
C1—C2—C4 | 111.1 (1) | O3—C17—N1 | 125.2 (1) |
C3—C2—C4 | 111.3 (1) | O3—C17—C16 | 129.3 (1) |
N1—C3—C2 | 110.8 (1) | N1—C17—C16 | 105.5 (1) |
C2—C4—C5 | 120.1 (1) | O5—C18—O6 | 122.3 (1) |
C2—C4—C9 | 121.6 (1) | O5—C18—C19 | 129.9 (1) |
C5—C4—C9 | 118.4 (1) | O6—C18—C19 | 107.8 (1) |
C4—C5—C6 | 120.9 (1) | O1—C19—C18 | 110.0 (1) |
C5—C6—C7 | 118.5 (1) | O1—C19—C20 | 114.4 (1) |
F1—C7—C6 | 118.3 (1) | C18—C19—C20 | 104.0 (1) |
F1—C7—C8 | 118.8 (1) | C19—C20—C21 | 97.8 (1) |
C6—C7—C8 | 122.9 (1) | C19—C20—C22 | 111.5 (1) |
C7—C8—C9 | 118.2 (1) | C19—C20—C23 | 113.4 (1) |
C4—C9—C8 | 121.1 (1) | C21—C20—C22 | 110.4 (1) |
O4—C10—N1 | 124.2 (1) | C21—C20—C23 | 111.5 (1) |
O4—C10—C11 | 129.5 (1) | C22—C20—C23 | 111.5 (1) |
N1—C10—C11 | 106.3 (1) | O6—C21—C20 | 105.7 (1) |
C10—C11—C12 | 131.3 (1) | | |
| | | |
C19—O1—C1—O2 | −1.6 (1) | C6—C7—C8—C9 | −0.5 (1) |
C19—O1—C1—C2 | 178.5 (1) | C7—C8—C9—C4 | 0.1 (1) |
C1—O1—C19—C18 | 132.2 (1) | O4—C10—C11—C12 | −3.6 (1) |
C1—O1—C19—C20 | −111.2 (1) | O4—C10—C11—C16 | 178.8 (2) |
C21—O6—C18—O5 | 177.7 (2) | N1—C10—C11—C12 | 175.6 (2) |
C21—O6—C18—C19 | −2.8 (1) | N1—C10—C11—C16 | −2.0 (1) |
C18—O6—C21—C20 | −21.6 (1) | C10—C11—C12—C13 | −177.4 (2) |
C3—N1—C10—O4 | 5.5 (1) | C10—C11—C16—C15 | 178.3 (2) |
C10—N1—C3—C2 | 66.2 (1) | C10—C11—C16—C17 | −0.7 (1) |
C3—N1—C10—C11 | −173.7 (1) | C16—C11—C12—C13 | −0.1 (1) |
C3—N1—C17—O3 | −6.6 (1) | C12—C11—C16—C15 | 0.5 (1) |
C17—N1—C3—C2 | −111.4 (1) | C12—C11—C16—C17 | −178.6 (2) |
C3—N1—C17—C16 | 173.3 (1) | C11—C12—C13—C14 | −0.1 (1) |
C17—N1—C10—O4 | −176.6 (2) | C12—C13—C14—C15 | 0.0 (1) |
C10—N1—C17—O3 | 175.6 (2) | C13—C14—C15—C16 | 0.3 (1) |
C17—N1—C10—C11 | 4.1 (1) | C14—C15—C16—C11 | −0.6 (1) |
C10—N1—C17—C16 | −4.5 (1) | C14—C15—C16—C17 | 178.2 (2) |
O1—C1—C2—C3 | −142.1 (1) | C11—C16—C17—O3 | −177.0 (2) |
O1—C1—C2—C4 | 94.5 (1) | C11—C16—C17—N1 | 3.1 (1) |
O2—C1—C2—C3 | 38.0 (1) | C15—C16—C17—O3 | 4.1 (1) |
O2—C1—C2—C4 | −85.4 (1) | C15—C16—C17—N1 | −175.8 (2) |
C1—C2—C3—N1 | 56.3 (1) | O5—C18—C19—O1 | −31.5 (1) |
C1—C2—C4—C5 | −130.2 (1) | O5—C18—C19—C20 | −154.5 (2) |
C1—C2—C4—C9 | 50.2 (1) | O6—C18—C19—O1 | 149.0 (1) |
C4—C2—C3—N1 | 179.6 (1) | O6—C18—C19—C20 | 26.0 (1) |
C3—C2—C4—C5 | 107.4 (1) | O1—C19—C20—C21 | −156.1 (1) |
C3—C2—C4—C9 | −72.2 (1) | O1—C19—C20—C22 | −40.5 (1) |
C2—C4—C5—C6 | 179.9 (1) | O1—C19—C20—C23 | 86.4 (1) |
C2—C4—C9—C8 | 179.9 (1) | C18—C19—C20—C21 | −36.0 (1) |
C9—C4—C5—C6 | −0.5 (1) | C18—C19—C20—C22 | 79.6 (1) |
C5—C4—C9—C8 | 0.3 (1) | C18—C19—C20—C23 | −153.6 (1) |
C4—C5—C6—C7 | 0.1 (1) | C19—C20—C21—O6 | 35.2 (1) |
C5—C6—C7—F1 | −179.2 (1) | C22—C20—C21—O6 | −81.3 (1) |
C5—C6—C7—C8 | 0.4 (1) | C23—C20—C21—O6 | 154.2 (1) |
F1—C7—C8—C9 | 179.1 (1) | | |
Crystal data top
C25H25NO8·0.5C4H8O2 | Dx = 1.29 Mg m−3 |
Mr = 511.53 | Mo Kα radiation, λ = 0.71073 Å |
Monoclinic, P21 | Cell parameters from 11342 reflections |
a = 11.560 (1) Å | θ = 1–25.4° |
b = 8.400 (1) Å | µ = 0.10 mm−1 |
c = 13.954 (1) Å | T = 298 K |
β = 103.41 (1)° | Prism, colorless |
V = 1318.1 (4) Å3 | 0.4 × 0.3 × 0.3 mm |
Z = 2 | |
Data collection top
KappaCCD diffractometer | Rint = 0.028 |
phi–scan | θmax = 25.4° |
10968 measured reflections | h = −13→14 |
2742 independent reflections | k = −8→9 |
2547 reflections with refl_observed_if_I_ > _1.00_σ(I) | l = −17→16 |
Refinement top
Refinement on F | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.062 | w = 1/[σ2(F) + 0.05F2] |
wR(F2) = 0.098 | (Δ/σ)max = 0.047 |
S = 1.65 | Δρmax = 0.23 e Å−3 |
2547 reflections | Δρmin = −0.25 e Å−3 |
313 parameters | |
Crystal data top
C25H25NO8·0.5C4H8O2 | V = 1318.1 (4) Å3 |
Mr = 511.53 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 11.560 (1) Å | µ = 0.10 mm−1 |
b = 8.400 (1) Å | T = 298 K |
c = 13.954 (1) Å | 0.4 × 0.3 × 0.3 mm |
β = 103.41 (1)° | |
Data collection top
KappaCCD diffractometer | 2547 reflections with refl_observed_if_I_ > _1.00_σ(I) |
10968 measured reflections | Rint = 0.028 |
2742 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.062 | 313 parameters |
wR(F2) = 0.098 | H-atom parameters not refined |
S = 1.65 | Δρmax = 0.23 e Å−3 |
2547 reflections | Δρmin = −0.25 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1 | 0.3230 (2) | 0.18300 | 0.3084 (1) | 0.047 (1) | |
O2 | 0.2266 (2) | 0.1958 (3) | 0.1492 (1) | 0.062 (1) | |
O3 | −0.0848 (2) | 0.0758 (3) | 0.3483 (2) | 0.070 (1) | |
O4 | −0.0353 (2) | 0.0082 (3) | 0.0357 (1) | 0.068 (1) | |
O7 | 0.1844 (2) | 0.8305 (3) | 0.2152 (2) | 0.047 (1) | |
O8 | 0.1717 (2) | 0.9066 (3) | 0.3914 (2) | 0.055 (1) | |
O6 | 0.6241 (2) | 0.2507 (3) | 0.3099 (2) | 0.101 (1) | |
O5 | 0.4753 (2) | 0.4319 (3) | 0.2730 (2) | 0.131 (1) | |
O9 | 0.4952 (2) | 0.2054 (4) | −0.0006 (2) | 0.250 (1) | 0.50 |
O10 | 0.5002 (2) | 0.4256 (4) | −0.0592 (2) | 0.250 (1) | 0.50 |
N1 | −0.0415 (2) | 0.0765 (4) | 0.1955 (2) | 0.040 (1) | |
C1 | 0.2271 (2) | 0.2088 (4) | 0.2346 (2) | 0.043 (2) | |
C2 | 0.1222 (2) | 0.2588 (4) | 0.2759 (2) | 0.041 (1) | |
C3 | 0.0040 (2) | 0.2402 (4) | 0.1998 (2) | 0.050 (2) | |
C4 | 0.1374 (2) | 0.4321 (4) | 0.3096 (2) | 0.039 (1) | |
C5 | 0.1575 (2) | 0.5498 (4) | 0.2454 (2) | 0.038 (1) | |
C6 | 0.1674 (2) | 0.7069 (4) | 0.2739 (2) | 0.034 (2) | |
C7 | 0.1583 (2) | 0.7477 (4) | 0.3688 (2) | 0.039 (1) | |
C8 | 0.1378 (3) | 0.6314 (4) | 0.4326 (2) | 0.042 (2) | |
C9 | 0.1273 (2) | 0.4744 (3) | 0.4010 (2) | 0.044 (1) | |
C10 | −0.0582 (2) | −0.0234 (4) | 0.1142 (2) | 0.044 (2) | |
C11 | −0.1126 (3) | −0.1722 (4) | 0.1433 (2) | 0.041 (2) | |
C16 | −0.1284 (3) | −0.1507 (4) | 0.2367 (2) | 0.041 (2) | |
C17 | −0.0834 (3) | 0.0094 (4) | 0.2711 (2) | 0.044 (2) | |
C19 | 0.4318 (3) | 0.1480 (4) | 0.2814 (3) | 0.052 (2) | |
C20 | 0.5133 (3) | 0.0328 (5) | 0.3501 (3) | 0.054 (2) | |
C24 | 0.2096 (3) | 0.7907 (4) | 0.1216 (2) | 0.060 (2) | |
C12 | −0.1472 (3) | −0.3096 (5) | 0.0918 (3) | 0.055 (2) | |
C13 | −0.2009 (3) | −0.4239 (4) | 0.1364 (2) | 0.061 (2) | |
C14 | −0.2171 (3) | −0.4053 (5) | 0.2306 (2) | 0.072 (2) | |
C15 | −0.1797 (3) | −0.2670 (5) | 0.2835 (3) | 0.060 (2) | |
C18 | 0.5075 (3) | 0.2968 (4) | 0.2876 (3) | 0.088 (2) | |
C21 | 0.6298 (3) | 0.0805 (5) | 0.3256 (3) | 0.076 (2) | |
C22 | 0.5158 (4) | 0.0706 (6) | 0.4571 (3) | 0.085 (3) | |
C23 | 0.485 (1) | −0.141 (1) | 0.3256 (7) | 0.08 (4) | |
C25 | 0.1737 (9) | 0.951 (2) | 0.492 (1) | 0.07 (5) | |
C26 | 0.466 (1) | 0.367 (1) | −0.002 (1) | 0.25 (5) | 0.50 |
C28 | 0.5549 (8) | 0.089 (2) | 0.008 (1) | 0.25 (3) | 0.50 |
C27 | 0.423 (1) | 0.471 (3) | 0.070 (2) | 0.25 (8) | 0.50 |
C29 | 0.662 (2) | 0.152 (1) | 0.078 (2) | 0.25 (5) | 0.50 |
H2 | 0.122 (5) | 0.193 (9) | 0.325 (5) | 0.05970* | |
H3A | −0.060 (6) | 0.298 (9) | 0.220 (5) | 0.06730* | |
H3B | 0.007 (5) | 0.278 (8) | 0.126 (5) | 0.06730* | |
H5 | 0.154 (5) | 0.506 (8) | 0.187 (5) | 0.05710* | |
H8 | 0.121 (5) | 0.655 (9) | 0.496 (5) | 0.06140* | |
H9 | 0.112 (4) | 0.392 (7) | 0.437 (4) | 0.06360* | |
H12 | −0.126 (7) | −0.34 (1) | 0.031 (6) | 0.07360* | |
H13 | −0.205 (8) | −0.51 (1) | 0.100 (7) | 0.07840* | |
H14 | −0.254 (5) | −0.524 (8) | 0.262 (4) | 0.09020* | |
H15 | −0.195 (5) | −0.240 (8) | 0.334 (5) | 0.07930* | |
H19 | 0.413 (7) | 0.11 (1) | 0.216 (5) | 0.07140* | |
H21A | 0.708 (6) | 0.06 (1) | 0.368 (5) | 0.09440* | |
H21B | 0.63 (1) | 0.01 (2) | 0.266 (8) | 0.09440* | |
H22A | 0.530 (8) | 0.21 (1) | 0.480 (7) | 0.10300* | |
H22B | 0.578 (8) | −0.03 (1) | 0.499 (6) | 0.10300* | |
H22C | 0.437 (6) | 0.054 (9) | 0.466 (5) | 0.10300* | |
H23A | 0.482 (7) | −0.15 (1) | 0.243 (6) | 0.09520* | |
H23B | 0.393 (5) | −0.195 (8) | 0.346 (5) | 0.09520* | |
H23C | 0.554 (7) | −0.21 (1) | 0.388 (6) | 0.09520* | |
H24A | 0.207 (9) | 0.90 (1) | 0.092 (7) | 0.07960* | |
H24B | 0.114 (9) | 0.74 (1) | 0.073 (8) | 0.07960* | |
H24C | 0.276 (8) | 0.74 (1) | 0.135 (6) | 0.07960* | |
H25A | 0.171 (8) | 1.07 (1) | 0.496 (6) | 0.09050* | |
H25B | 0.252 (8) | 0.92 (1) | 0.554 (6) | 0.09050* | |
H25C | 0.095 (7) | 0.92 (1) | 0.506 (5) | 0.09050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.035 (1) | 0.056 (1) | 0.049 (1) | 0.0049 (9) | 0.0094 (9) | 0.0010 (9) |
O2 | 0.066 (2) | 0.074 (1) | 0.041 (1) | 0.0126 (9) | 0.005 (1) | −0.0007 (9) |
O3 | 0.053 (2) | 0.089 (1) | 0.068 (1) | −0.013 (1) | 0.026 (1) | −0.038 (1) |
O4 | 0.083 (1) | 0.072 (1) | 0.045 (1) | −0.0162 (9) | 0.016 (1) | 0.0120 (9) |
O7 | 0.067 (1) | 0.034 (1) | 0.039 (1) | −0.002 (1) | 0.020 (1) | 0.001 (1) |
O8 | 0.077 (1) | 0.039 (2) | 0.046 (2) | 0.002 (1) | 0.018 (1) | −0.007 (1) |
O6 | 0.054 (1) | 0.101 (1) | 0.144 (1) | −0.023 (1) | 0.030 (1) | 0.002 (1) |
O5 | 0.128 (2) | 0.060 (2) | 0.205 (2) | −0.008 (1) | 0.072 (1) | 0.025 (1) |
O9 | 0.246 (2) | 0.246 (1) | 0.246 (1) | 0.000 (1) | 0.057 (1) | 0.000 (1) |
O10 | 0.246 (2) | 0.246 (2) | 0.246 (2) | 0.000 (1) | 0.057 (1) | 0.000 (1) |
N1 | 0.034 (2) | 0.041 (2) | 0.043 (2) | −0.007 (1) | 0.007 (1) | −0.005 (1) |
C1 | 0.041 (2) | 0.032 (2) | 0.051 (2) | 0.002 (1) | −0.001 (1) | 0.002 (1) |
C2 | 0.040 (1) | 0.032 (2) | 0.047 (2) | 0.002 (1) | 0.004 (1) | 0.005 (1) |
C3 | 0.039 (2) | 0.038 (2) | 0.065 (2) | 0.000 (1) | −0.001 (1) | 0.001 (1) |
C4 | 0.032 (2) | 0.036 (2) | 0.046 (2) | −0.001 (1) | 0.005 (1) | 0.004 (1) |
C5 | 0.041 (2) | 0.038 (1) | 0.032 (2) | 0.003 (1) | 0.004 (1) | 0.000 (1) |
C6 | 0.037 (2) | 0.031 (2) | 0.032 (2) | 0.002 (1) | 0.008 (2) | 0.004 (1) |
C7 | 0.035 (2) | 0.034 (2) | 0.046 (2) | 0.002 (1) | 0.006 (1) | −0.004 (1) |
C8 | 0.045 (2) | 0.045 (2) | 0.034 (2) | 0.001 (1) | 0.012 (1) | 0.006 (1) |
C9 | 0.047 (2) | 0.043 (1) | 0.041 (2) | 0.001 (1) | 0.011 (1) | 0.009 (1) |
C10 | 0.041 (2) | 0.047 (2) | 0.040 (3) | −0.002 (1) | 0.008 (2) | 0.004 (2) |
C11 | 0.040 (3) | 0.044 (2) | 0.034 (2) | −0.001 (1) | 0.004 (2) | 0.002 (1) |
C16 | 0.030 (2) | 0.050 (2) | 0.042 (2) | −0.004 (1) | 0.009 (1) | 0.002 (1) |
C17 | 0.032 (2) | 0.056 (2) | 0.043 (2) | −0.001 (1) | 0.009 (1) | −0.006 (2) |
C19 | 0.043 (3) | 0.058 (2) | 0.053 (4) | −0.001 (2) | 0.017 (3) | 0.001 (2) |
C20 | 0.036 (2) | 0.065 (2) | 0.056 (3) | 0.001 (2) | 0.004 (2) | 0.000 (2) |
C24 | 0.086 (2) | 0.044 (2) | 0.049 (2) | −0.004 (1) | 0.025 (2) | 0.006 (1) |
C12 | 0.059 (2) | 0.048 (3) | 0.055 (3) | −0.004 (2) | 0.013 (2) | −0.009 (2) |
C13 | 0.069 (3) | 0.045 (2) | 0.062 (2) | −0.003 (2) | 0.004 (2) | −0.006 (2) |
C14 | 0.062 (2) | 0.055 (2) | 0.095 (2) | −0.014 (2) | 0.017 (2) | 0.018 (2) |
C15 | 0.054 (2) | 0.065 (2) | 0.059 (3) | −0.012 (2) | 0.021 (2) | 0.002 (2) |
C18 | 0.072 (2) | 0.080 (2) | 0.112 (2) | −0.017 (2) | 0.040 (2) | 0.000 (2) |
C21 | 0.044 (2) | 0.089 (3) | 0.090 (2) | 0.002 (2) | 0.016 (2) | 0.000 (2) |
C22 | 0.071 (3) | 0.123 (3) | 0.056 (4) | 0.027 (2) | 0.013 (3) | 0.004 (2) |
C23 | 0.06 (6) | 0.06 (4) | 0.11 (3) | 0.01 (3) | 0.00 (3) | 0.01 (3) |
C25 | 0.12 (7) | 0.05 (6) | 0.04 (4) | 0.01 (5) | 0.02 (5) | −0.01 (4) |
C26 | 0.25 (4) | 0.25 (7) | 0.25 (7) | 0.00 (4) | 0.06 (5) | 0.00 (5) |
C28 | 0.25 (4) | 0.25 (6) | 0.25 (4) | 0.00 (3) | 0.06 (3) | 0.00 (3) |
C27 | 0.25 (8) | 0.2 (1) | 0.25 (5) | 0.00 (7) | 0.06 (5) | 0.00 (6) |
C29 | 0.25 (6) | 0.25 (6) | 0.25 (5) | 0.00 (4) | 0.06 (4) | 0.00 (4) |
Geometric parameters (Å, º) top
O1—C1 | 1.344 (4) | C4—C9 | 1.355 (4) |
O1—C19 | 1.425 (4) | C5—C6 | 1.375 (5) |
O2—C1 | 1.195 (4) | C6—C7 | 1.395 (4) |
O3—C17 | 1.217 (4) | C7—C8 | 1.379 (5) |
O4—C10 | 1.214 (4) | C8—C9 | 1.387 (5) |
O7—C6 | 1.365 (4) | C10—C11 | 1.497 (5) |
O7—C24 | 1.442 (4) | C11—C16 | 1.369 (5) |
O8—C7 | 1.372 (5) | C11—C12 | 1.369 (6) |
O8—C25 | 1.45 (2) | C16—C17 | 1.481 (5) |
O6—C18 | 1.367 (4) | C16—C15 | 1.383 (5) |
O6—C21 | 1.446 (6) | C19—C20 | 1.525 (6) |
O5—C18 | 1.197 (5) | C19—C18 | 1.517 (5) |
O9—C26 | 1.40 (2) | C20—C21 | 1.518 (6) |
O9—C28 | 1.19 (2) | C20—C22 | 1.520 (6) |
N1—C3 | 1.468 (5) | C20—C23 | 1.52 (2) |
N1—C10 | 1.388 (5) | C12—C13 | 1.369 (6) |
N1—C17 | 1.379 (5) | C13—C14 | 1.379 (5) |
C1—C2 | 1.518 (4) | C14—C15 | 1.390 (6) |
C2—C3 | 1.532 (4) | C26—C27 | 1.50 (3) |
C2—C4 | 1.527 (5) | C28—C27i | 1.54 (3) |
C4—C5 | 1.389 (5) | C28—C29 | 1.48 (3) |
| | | |
C1—O1—C19 | 116.9 (3) | C10—C11—C12 | 130.6 (4) |
C6—O7—C24 | 117.1 (3) | C16—C11—C12 | 121.6 (4) |
C7—O8—C25 | 116.5 (6) | C11—C16—C17 | 108.3 (3) |
C18—O6—C21 | 108.8 (3) | C11—C16—C15 | 121.5 (4) |
C26—O9—C28 | 159.0 (10) | C17—C16—C15 | 130.2 (3) |
C3—N1—C10 | 125.5 (3) | O3—C17—N1 | 124.7 (4) |
C3—N1—C17 | 122.5 (3) | O3—C17—C16 | 128.9 (3) |
C10—N1—C17 | 111.8 (3) | N1—C17—C16 | 106.4 (3) |
O1—C1—O2 | 124.2 (3) | O1—C19—C20 | 114.8 (3) |
O1—C1—C2 | 110.1 (3) | O1—C19—C18 | 110.4 (3) |
O2—C1—C2 | 125.8 (3) | C20—C19—C18 | 102.9 (3) |
C1—C2—C3 | 111.8 (3) | C19—C20—C21 | 98.2 (3) |
C1—C2—C4 | 109.6 (3) | C19—C20—C22 | 110.7 (4) |
C3—C2—C4 | 109.3 (3) | C19—C20—C23 | 113.6 (5) |
N1—C3—C2 | 112.2 (3) | C21—C20—C22 | 110.5 (4) |
C2—C4—C5 | 120.3 (3) | C21—C20—C23 | 111.0 (6) |
C2—C4—C9 | 120.7 (3) | C22—C20—C23 | 112.1 (5) |
C5—C4—C9 | 119.0 (3) | C11—C12—C13 | 117.4 (4) |
C4—C5—C6 | 120.8 (3) | C12—C13—C14 | 122.0 (4) |
O7—C6—C5 | 124.8 (3) | C13—C14—C15 | 120.4 (4) |
O7—C6—C7 | 115.8 (3) | C16—C15—C14 | 117.0 (4) |
C5—C6—C7 | 119.4 (3) | O6—C18—O5 | 124.0 (4) |
O8—C7—C6 | 115.3 (3) | O6—C18—C19 | 107.8 (3) |
O8—C7—C8 | 124.6 (3) | O5—C18—C19 | 128.2 (4) |
C6—C7—C8 | 120.1 (3) | O6—C21—C20 | 106.5 (3) |
C7—C8—C9 | 118.9 (3) | O9—C26—C27 | 132.5 (16) |
C4—C9—C8 | 121.9 (3) | O9—C28—C27i | 130.2 (13) |
O4—C10—N1 | 125.9 (4) | O9—C28—C29 | 98.6 (11) |
O4—C10—C11 | 128.3 (4) | C27i—C28—C29 | 116.3 (12) |
N1—C10—C11 | 105.7 (3) | C26—C27—C28i | 76.2 (13) |
C10—C11—C16 | 107.8 (3) | | |
| | | |
C19—O1—C1—O2 | 4.2 (3) | O7—C6—C7—C8 | 178.2 (5) |
C19—O1—C1—C2 | −174.9 (4) | C5—C6—C7—O8 | 178.7 (5) |
C1—O1—C19—C20 | −146.4 (4) | C5—C6—C7—C8 | −1.0 (3) |
C1—O1—C19—C18 | 98.0 (4) | O8—C7—C8—C9 | −179.2 (5) |
C24—O7—C6—C5 | −8.7 (3) | C6—C7—C8—C9 | 0.4 (3) |
C24—O7—C6—C7 | 172.1 (4) | C7—C8—C9—C4 | 0.4 (3) |
C25—O8—C7—C6 | −174.5 (7) | O4—C10—C11—C16 | −176.4 (5) |
C25—O8—C7—C8 | 5.2 (7) | O4—C10—C11—C12 | 1.8 (4) |
C21—O6—C18—O5 | 178.2 (5) | N1—C10—C11—C16 | 1.9 (3) |
C21—O6—C18—C19 | −4.0 (3) | N1—C10—C11—C12 | −179.9 (5) |
C18—O6—C21—C20 | −21.5 (3) | C10—C11—C16—C17 | −1.0 (3) |
C28—O9—C26—C27 | −103 (3) | C10—C11—C16—C15 | 178.6 (5) |
C26—O9—C28—C29 | 26 (2) | C10—C11—C12—C13 | −176.5 (6) |
C3—N1—C10—O4 | 1.8 (3) | C12—C11—C16—C17 | −179.3 (5) |
C10—N1—C3—C2 | −117.0 (4) | C16—C11—C12—C13 | 1.5 (4) |
C3—N1—C10—C11 | −176.6 (4) | C12—C11—C16—C15 | 0.2 (4) |
C3—N1—C17—O3 | −1.6 (3) | C11—C16—C17—O3 | 177.3 (5) |
C17—N1—C3—C2 | 69.3 (4) | C11—C16—C17—N1 | −0.4 (3) |
C3—N1—C17—C16 | 176.2 (4) | C11—C16—C15—C14 | −1.5 (4) |
C10—N1—C17—O3 | −176.1 (5) | C15—C16—C17—O3 | −2.2 (4) |
C17—N1—C10—O4 | 176.1 (5) | C15—C16—C17—N1 | −179.9 (5) |
C17—N1—C10—C11 | −2.3 (3) | C17—C16—C15—C14 | 178.0 (6) |
C10—N1—C17—C16 | 1.7 (3) | O1—C19—C20—C21 | −157.3 (4) |
O1—C1—C2—C3 | −162.5 (4) | O1—C19—C20—C22 | −41.7 (4) |
O1—C1—C2—C4 | 76.1 (3) | O1—C19—C20—C23 | 85.5 (6) |
O2—C1—C2—C3 | 18.4 (3) | O1—C19—C18—O6 | 150.4 (4) |
O2—C1—C2—C4 | −103.0 (4) | O1—C19—C18—O5 | −32.0 (4) |
C1—C2—C3—N1 | 83.0 (3) | C20—C19—C18—O6 | 27.5 (3) |
C1—C2—C4—C5 | 53.4 (3) | C20—C19—C18—O5 | −154.9 (5) |
C1—C2—C4—C9 | −129.0 (4) | C18—C19—C20—C21 | −37.4 (3) |
C4—C2—C3—N1 | −155.4 (4) | C18—C19—C20—C22 | 78.2 (4) |
C3—C2—C4—C5 | −69.5 (3) | C18—C19—C20—C23 | −154.6 (6) |
C3—C2—C4—C9 | 108.1 (4) | C19—C20—C21—O6 | 36.5 (3) |
C2—C4—C5—C6 | 177.8 (5) | C22—C20—C21—O6 | −79.3 (4) |
C2—C4—C9—C8 | −178.4 (5) | C23—C20—C21—O6 | 155.7 (6) |
C9—C4—C5—C6 | 0.2 (3) | C11—C12—C13—C14 | −1.9 (4) |
C5—C4—C9—C8 | −0.8 (3) | C12—C13—C14—C15 | 0.6 (4) |
C4—C5—C6—O7 | −178.4 (5) | C13—C14—C15—C16 | 1.1 (4) |
C4—C5—C6—C7 | 0.7 (3) | C27—C28—O9—C26 | −110 (3) |
O7—C6—C7—O8 | −2.1 (3) | C28—C27—C26—O9 | 174 (2) |
Symmetry code: (i) −x+1, y+1/2, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C23H20FNO6 | C25H25NO8·0.5C4H8O2 |
Mr | 425.41 | 511.53 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 9.5666 (3), 11.1026 (2), 20.3200 (6) | 11.560 (1), 8.400 (1), 13.954 (1) |
α, β, γ (°) | 90.00 (1), 90.00 (1), 90.00 (1) | 90.00 (1), 103.41 (1), 90.00 (1) |
V (Å3) | 2158.3 (2) | 1318.1 (4) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.1 | 0.10 |
Crystal size (mm) | 0.32 × 0.27 × 0.10 | 0.4 × 0.3 × 0.3 |
|
Data collection |
Diffractometer | KappaCCD diffractometer | KappaCCD diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed reflections | 13240, 2362, 2209 [refl_observed_if_I_ > _3.00_σ(I)] | 10968, 2742, 2547 [refl_observed_if_I_ > _1.00_σ(I)] |
Rint | 0.028 | 0.028 |
(sin θ/λ)max (Å−1) | 0.604 | 0.604 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.052, 1.22 | 0.062, 0.098, 1.65 |
No. of reflections | 2209 | 2547 |
No. of parameters | 273 | 313 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters not refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.10, −0.10 | 0.23, −0.25 |
Selected geometric parameters (Å, º) for (I) topO1—C1 | 1.351 (1) | C1—C2 | 1.512 (1) |
O1—C19 | 1.431 (1) | C2—C3 | 1.539 (1) |
O2—C1 | 1.196 (1) | C2—C4 | 1.518 (1) |
N1—C3 | 1.456 (1) | | |
| | | |
C1—O1—C19 | 116.7 (1) | C1—C2—C3 | 109.6 (1) |
O1—C1—O2 | 123.9 (1) | C1—C2—C4 | 111.1 (1) |
O1—C1—C2 | 110.9 (1) | C3—C2—C4 | 111.3 (1) |
O2—C1—C2 | 125.2 (1) | N1—C3—C2 | 110.8 (1) |
| | | |
C19—O1—C1—C2 | 178.5 (1) | O1—C1—C2—C3 | −142.1 (1) |
Selected geometric parameters (Å, º) for (II) topO1—C1 | 1.344 (4) | C1—C2 | 1.518 (4) |
O1—C19 | 1.425 (4) | C2—C3 | 1.532 (4) |
O2—C1 | 1.195 (4) | C2—C4 | 1.527 (5) |
N1—C3 | 1.468 (5) | | |
| | | |
C1—O1—C19 | 116.9 (3) | C1—C2—C3 | 111.8 (3) |
O1—C1—O2 | 124.2 (3) | C1—C2—C4 | 109.6 (3) |
O1—C1—C2 | 110.1 (3) | C3—C2—C4 | 109.3 (3) |
O2—C1—C2 | 125.8 (3) | N1—C3—C2 | 112.2 (3) |
| | | |
C19—O1—C1—C2 | −174.9 (4) | O1—C1—C2—C3 | −162.5 (4) |
Les β-amino acides et leurs dérivés forment une famille importante de composés pour le développement de pseudopeptides (Xie et al., 1989) et de β-lactames fonctionnalisés (Salzmann et al., 1980). Incorporés dans un peptide ou sous forme libre, ils présentent des activités biologiques intéressantes, (Juaristi, 1997). Dans le but d'extrapoler les résultats obtenus par notre équipe dans la série des acides 3-amino-2-arylpropanoïques (Calmès & Escale, 1998), nous décrivons ici la structure de deux nouveaux dérivés de cet acide. La synthèse des esters (R)-pantolactonyl des acides (S)—N-phtaloyl-3-amino-2-(4-fluorophényl)propanoïque, (I), (S)—N-phtaloyl-3-amino-2-(3,4-diméthoxyphényl)propanoïque, (II), et (S)—N-phtaloyl-3-amino-2-(4-méthoxyphényl)propanoïque, (III) (Calmès et al., 1999) a été réalisée en utilisant les mêmes méthodes que lors de la préparation de l'acide (S)-3-amino-2-phénylpropanoïque (Calmès & Escale, 1998). L'analyse spectrale par RMN 1H (400 MHz) ne nous permettant pas d'attribuer la stéréochimie du carbone C2, l'étude de ces trois composés a été effectuée par diffraction des rayons X. Nous présentons ici les structures des composés (I) et (II). \sch
Les molécules (I) et (II) sont représentées respectivement sur les Figures 1 e t 2. Ces structures montrent que pour les deux composés la configuration absolue du carbone α C2 établie à partir de la configuration connue R du carbone C19 de la pantolactone est dans tous les cas de configuration S. La structure du composé (III) donne la même configuration S pour le carbone C2, elle n'est pas décrite ici montrant peu de différence avec le composé (I). Pour les deux composés les deux cycles aromatiques, le phényle constitué des atomes C4—C5—C6—C7—C8—C9 et le N-phtalyle constitué des atomes N1—C10—C11—C12—C13—C14—C15—C16—C17 sont approximativement dans le même plan. Les angles entre les deux plans moyens sont respectivement de 8,5(4)° et 16,9(4)° pour les composés (I) et (II). L'angle plus important pour le produit (II) est dû à la présence d'une demi molécule d'acétate d'éthyle dans la maille. On notera que les angles de torsion C19—O1—C1—C2 sont similaires, 178,5(1)° pour (I) et -174,9(4)° pour (II). Seul l'angle de torsion O1—C1—C2—C3 varie de 162,5(4)° pour le produit (II) comparé à -142,1(1)° pour le produit (I). La variation majeure de géométrie entre les composés est une rotation autour de la liaison C1—C2. Les cycles pantolactoniques C18—C19—C20—C21—O6 sont dans des conformations enveloppe, le carbone C20 étant distant respectivement de 0,599 (1) e t 0,612 (3) Å du plan moyen formé par les atomes C18, C19, C21 et O6 des composés (I) et (II). L'atome C24 du substituant méthoxy de (II) est dans le même plan que le phényl qui le supporte.