Three thiochromeno[4,3-b]pyrrole esters have very similar conformations. Structurally two of the compounds differ only by the substituent on the benzene ring, i.e. 4-isopropylphenyl and o-tolyl, while two of the compounds differ only in that one has a pyrrole ring and one has an isoxazole ring.
Keywords: crystal structure, thiochromene, isoxazole, pyrrole, chromenopyrrole, thiopyran, C—H⋯π interactions
Abstract
In the title compounds, C23H27NO2S, (I), and C21H23NO2S, (II), the pyrrole rings have envelope conformations with the C atom substituted by the benzene ring as the flap. In the third title compound, C20H21NO3S, (III), the isoxazole ring has a twisted conformation on the C—C bond substituted by the benzene ring and the carboxylate group. In all three compounds, the thiopyran ring has a half-chair conformation. The mean plane of the pyrrole ring is inclined to the mean plane of the thiopyran ring by 57.07 (9), 58.98 (9) and 60.34 (12)° in (I), (II) and (III), respectively. The benzene rings are inclined to one another by 73.26 (10)° in (I), 65.781)° in (II) and 63.37 (13)° in (III). In the crystals of all three compounds, there are no classical hydrogen bonds present. Only in the crystal of compound (I) are molecules linked by a pair of C—H⋯π interactions, forming inversion dimers. The isopropyl group in compound (I) is disordered over two sets of sites and has a refined occupancy ratio of 0.586 (13):0.414 (13).
Chemical context
Pyrrole derivatives are of considerable synthetic importance due to their extensive use in drug discovery (Toja et al., 1987 ▸) which is linked to their pharmacological activity such as anti-inflammatory (Muchowski et al., 1985 ▸), cytotoxicity (Dannhardt et al., 2000 ▸) and their use in the treatment of hyperlipidemias (Holub et al., 2004 ▸) and as antitumour agents (Krowicki et al., 1988 ▸). Other pyrrole-containing heterocyclic compounds have been reported previously for biological studies (Almerico et al., 1998 ▸). Pyrrole derivatives have biological activity such as COX-1/COX-2 inhibitors (Dannhardt et al., 2000 ▸) as well as cytotoxic activity against a variety of marine and human tumour models (Evans et al., 2003 ▸). Isoxazoline derivatives have been shown to be efficient precursors for the preparation of many synthetic intermediates including γ-amino alcohols and β-hydroxy ketones (Kozikowski, 1984 ▸). They display interesting biological properties such as herbicidal, plant-growth regulatory and antitumour activities (Howe & Shelton, 1990 ▸). Chromenopyrrole compounds are used in the treatment of impulsive disorders (Caine & Koob, 1993 ▸). Continuing our interest in such compounds, we have synthesized the title compounds and report herein on their crystal structures.
Structural commentary
The title compounds (I) and (II) differ only by the substituent on the benzene ring; 4-isopropylphenyl in (I) and o-tolyl in (II). Compounds (II) and (III) differ only in that (II) has a pyrrole ring while (III) has an isoxazole ring.
The molecular structure of compound (I) is shown in Fig. 1 ▸. The five-membered methyl-substituted pyrrole ring adopts an envelope conformation with atom C9 as the flap, deviating from the mean plane defined by the plane of the other ring atoms by 0.0167 Å. The puckering parameters of this ring are q 2 = 0.4713 (15) Å and φ2 = 41.27 (19)°. The thiopyran ring has a half-chair conformation, with the lowest asymmetry parameters ΔC2(S1—C7) = 8.34 (16) Å. The mean plane of the pyrrole ring makes dihedral angles of 57.07 (9) and 63.29 (10)° with the mean plane of the thiopyran ring and the benzene ring, respectively.
Figure 1.
The molecular structure of compound (I), showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
The molecular structure of the compound (II) is illustrated in Fig. 2 ▸. The bond lengths and bond angles are similar to those in compound (I). The pyrrole ring (N1/C8–C12) adopts an envelope conformation with atom C9 atom as the flap having asymmetry parameters (Nardelli, 1983 ▸) ΔCS(C9) = 4.51 Å and with puckering parameters q 2 = 0.4673 (18) Å, φ2 = 223.5 (2)°. As in (I), the thiopyran ring has a half-chair conformation. The mean plane of the pyrrole ring is inclined to thiopyran ring mean plane and the benzene ring by 58.98 (9) and 67.75 (11)°, respectively. The carboxylate group assumes an extended conformation, as can be seen from the C8—C13—O2—C14 torsion angle of 175.4 (2)°.
Figure 2.
The molecular structure of compound (II), showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
The molecular structure of molecule (III) is shown in Fig. 3 ▸. The isoxazole ring (N1/O3/C11/C8/C9) has a twist conformation about bond C9–C8: puckering parameters q 2 = 0.466 (2) Å, φ2 = 275.7 (3)°. As in (I) and (II), the thiopyran ring has a half-chair conformation. The dihedral angles between the mean plane of the isoxazole ring and the thiopyran ring mean plane and the benzene ring are 60.34 (12) and 61.30 (14)°, respectively. The geometric parameters of molecule (III) agree well with those reported for (I) and (II), and a closely related structure, 1-methyl-3-(naphthalen-1-yl)-3,3a,4,9b-tetrahydro-1H-chromeno[4,3-c]isoxazole-3a-carbonitrile (Gangadharan et al., 2011 ▸).
Figure 3.
The molecular structure of compound (III), showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
Supramolecular features
In the crystals of compounds (I), (II) and (III), there are no classical hydrogen bonds present. Only in compound (I) is there a C—H⋯π interaction present, and molecules are linked by a pair of these interactions forming inversion dimers (Table 1 ▸ and Fig. 4 ▸).
Table 1. Hydrogen-bond geometry (Å, °) for (I) .
Cg3 is the centroid of the C1–C6 ring.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C17—H17⋯Cg3i | 0.93 | 2.91 | 3.695 (2) | 143 |
Symmetry code: (i) 
.
Figure 4.
A view along the b axis of the crystal packing of compound (I). The dashed cyan lines represent the C—H⋯centroid distances (see Table 1 ▸).
Database survey
While a search of the Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014 ▸) for chromenoisoxazole derivatives revealed over 30 hits, there were no hits for thiochromenopyrroles or thiochromenoisoxazoles.
Synthesis and crystallization
Compound (I): To a solution of methyl (E)-2-{[(2-formylphenyl)thio]methyl}-3-phenylacrylate (1 mmol) and sarcosine (1.2 mmol) in acetonitrile (10 ml), was added pyridine (0.2 mmol) and the mixture was refluxed until completion of the reaction (monitored by TLC). The crude product was subjected to column chromatography on silica gel (100–200 mesh) using petroleum ether–ethyl acetate (9:1) as eluent, which successfully provided the pure product as a colourless solid. The product was dissolved in chloroform and heated for 2 min. The resulting solution were allowed to evaporate slowly at room temperature and yielded colourless block-like crystals of compound (I).
Compound (II): Here methyl (E)-2-{[(2-formylphenyl)thio]methyl}-3-(o-tolyl) acrylate (1 mmol) and sarcosine (1.2 mmol) in acetonitrile (10 ml) were reacted with pyridine following the same procedure as for compound (I), and colourless crystals of compound (II) were obtained.
Compound (III): Here methyl (E)-2-{[(2-formylphenyl)thio]methyl}-3-(o-tolyl) acrylate(1 mmol) and N-methyl hydroxylamine hydrochloride (1.1 mmol) in acetonitrile (10 ml) were reacted with pyridine following the same procedure as for compounds (I) and (II), and colourless crystals of compound (III) were obtained.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The C-bound H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and allowed to ride on their parent atoms, with U iso(H) = 1.5U eq(C) for methyl H atoms and 1.2U eq(C) for other H atoms. The isopropyl group in compound (I), atoms C19–C21, is disordered over two sets of sites and has a refined occupancy ratio of 0.586 (13):0.414 (13).
Table 2. Experimental details.
| (I) | (II) | (III) | |
|---|---|---|---|
| Crystal data | |||
| Chemical formula | C23H27NO2S | C21H21NO2S | C20H21NO3S |
| M r | 381.52 | 351.45 | 355.44 |
| Crystal system, space group | Monoclinic, P21/n | Triclinic, P
|
Orthorhombic, P b c a |
| Temperature (K) | 293 | 293 | 293 |
| a, b, c (Å) | 10.7330 (3), 7.7568 (2), 24.9436 (7) | 8.1882 (3), 10.4987 (4), 10.9594 (4) | 11.2629 (11), 13.2117 (11), 24.041 (3) |
| α, β, γ (°) | 90, 98.485 (1), 90 | 104.554 (1), 90.983 (1), 90.134 (1) | 90, 90, 90 |
| V (Å3) | 2053.92 (10) | 911.74 (6) | 3577.3 (6) |
| Z | 4 | 2 | 8 |
| Radiation type | Mo Kα | Mo Kα | Mo Kα |
| μ (mm−1) | 0.18 | 0.19 | 0.20 |
| Crystal size (mm) | 0.35 × 0.30 × 0.25 | 0.35 × 0.30 × 0.25 | 0.35 × 0.30 × 0.25 |
| Data collection | |||
| Diffractometer | Bruker SMART APEXII CCD | Bruker SMART APEXII CCD | Bruker SMART APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2008 ▸) | Multi-scan (SADABS; Bruker, 2008 ▸) | Multi-scan (SADABS; Bruker, 2008 ▸) |
| T min, T max | 0.941, 0.958 | 0.935, 0.953 | 0.932, 0.951 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 16824, 3616, 3170 | 19010, 3210, 2790 | 37913, 3151, 2536 |
| R int | 0.019 | 0.020 | 0.033 |
| (sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.595 |
| Refinement | |||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.041, 0.111, 1.06 | 0.038, 0.115, 1.07 | 0.046, 0.111, 1.12 |
| No. of reflections | 3616 | 3210 | 3151 |
| No. of parameters | 272 | 229 | 229 |
| No. of restraints | 107 | 0 | 0 |
| H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.24, −0.27 | 0.26, −0.32 | 0.22, −0.22 |
Supplementary Material
Crystal structure: contains datablock(s) global, I, II, III. DOI: 10.1107/S2056989015008063/su5106sup1.cif
e-71-00574-sup1.cif (61.1KB, cif)
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008063/su5106Isup2.hkl
e-71-00574-Isup2.hkl (177.3KB, hkl)
Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989015008063/su5106IIsup3.hkl
e-71-00574-IIsup3.hkl (157.5KB, hkl)
Structure factors: contains datablock(s) III. DOI: 10.1107/S2056989015008063/su5106IIIsup4.hkl
e-71-00574-IIIsup4.hkl (154.7KB, hkl)
Click here for additional data file. (7.7KB, cml)
Supporting information file. DOI: 10.1107/S2056989015008063/su5106Isup5.cml
Click here for additional data file. (7.2KB, cml)
Supporting information file. DOI: 10.1107/S2056989015008063/su5106IIsup6.cml
Click here for additional data file. (7KB, cml)
Supporting information file. DOI: 10.1107/S2056989015008063/su5106IIIsup7.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank the Department of Chemistry, IIT, Chennai, India, for the X-ray intensity data collection.
supplementary crystallographic information
(I) Methyl 3-(4-isopropylphenyl)-1-methyl-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Crystal data
| C23H27NO2S | F(000) = 816 |
| Mr = 381.52 | Dx = 1.234 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 3170 reflections |
| a = 10.7330 (3) Å | θ = 1.7–25.0° |
| b = 7.7568 (2) Å | µ = 0.18 mm−1 |
| c = 24.9436 (7) Å | T = 293 K |
| β = 98.485 (1)° | Block, colourless |
| V = 2053.92 (10) Å3 | 0.35 × 0.30 × 0.25 mm |
| Z = 4 |
(I) Methyl 3-(4-isopropylphenyl)-1-methyl-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Data collection
| Bruker SMART APEXII CCD diffractometer | 3616 independent reflections |
| Radiation source: fine-focus sealed tube | 3170 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.019 |
| ω and φ scans | θmax = 25.0°, θmin = 1.7° |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −12→12 |
| Tmin = 0.941, Tmax = 0.958 | k = −9→9 |
| 16824 measured reflections | l = −24→29 |
(I) Methyl 3-(4-isopropylphenyl)-1-methyl-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Refinement
| 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.111 | H-atom parameters constrained |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.050P)2 + 1.0371P] where P = (Fo2 + 2Fc2)/3 |
| 3616 reflections | (Δ/σ)max < 0.001 |
| 272 parameters | Δρmax = 0.24 e Å−3 |
| 107 restraints | Δρmin = −0.27 e Å−3 |
(I) Methyl 3-(4-isopropylphenyl)-1-methyl-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Special details
| 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. |
(I) Methyl 3-(4-isopropylphenyl)-1-methyl-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| C1 | 0.64364 (15) | 0.4800 (2) | 0.14949 (7) | 0.0333 (4) | |
| C2 | 0.60663 (18) | 0.4940 (3) | 0.20060 (8) | 0.0468 (5) | |
| H2 | 0.5834 | 0.6015 | 0.2124 | 0.056* | |
| C3 | 0.6033 (2) | 0.3533 (3) | 0.23429 (9) | 0.0584 (6) | |
| H3 | 0.5765 | 0.3660 | 0.2679 | 0.070* | |
| C4 | 0.6398 (2) | 0.1946 (3) | 0.21793 (9) | 0.0606 (6) | |
| H4 | 0.6379 | 0.0994 | 0.2405 | 0.073* | |
| C5 | 0.67929 (19) | 0.1762 (3) | 0.16824 (9) | 0.0511 (5) | |
| H5 | 0.7052 | 0.0687 | 0.1576 | 0.061* | |
| C6 | 0.68086 (16) | 0.3175 (2) | 0.13353 (7) | 0.0361 (4) | |
| C7 | 0.70294 (16) | 0.4766 (2) | 0.03604 (7) | 0.0327 (4) | |
| H7A | 0.7507 | 0.4820 | 0.0060 | 0.039* | |
| H7B | 0.6142 | 0.4775 | 0.0212 | 0.039* | |
| C8 | 0.73260 (14) | 0.6355 (2) | 0.07149 (6) | 0.0279 (4) | |
| C9 | 0.64648 (14) | 0.6410 (2) | 0.11561 (7) | 0.0301 (4) | |
| H9 | 0.6724 | 0.7380 | 0.1399 | 0.036* | |
| C10 | 0.42438 (19) | 0.7312 (3) | 0.11351 (10) | 0.0568 (6) | |
| H10A | 0.4083 | 0.6368 | 0.1364 | 0.085* | |
| H10B | 0.3492 | 0.7573 | 0.0889 | 0.085* | |
| H10C | 0.4495 | 0.8305 | 0.1354 | 0.085* | |
| C11 | 0.55213 (17) | 0.8256 (2) | 0.04721 (8) | 0.0399 (4) | |
| H11A | 0.5384 | 0.9360 | 0.0636 | 0.048* | |
| H11B | 0.4980 | 0.8183 | 0.0125 | 0.048* | |
| C12 | 0.69127 (16) | 0.8060 (2) | 0.03967 (7) | 0.0324 (4) | |
| H12 | 0.7370 | 0.9003 | 0.0600 | 0.039* | |
| C13 | 0.87070 (15) | 0.6497 (2) | 0.09487 (7) | 0.0347 (4) | |
| C14 | 1.07866 (18) | 0.6040 (4) | 0.07703 (11) | 0.0687 (7) | |
| H14A | 1.1210 | 0.5552 | 0.0493 | 0.103* | |
| H14B | 1.1034 | 0.5433 | 0.1105 | 0.103* | |
| H14C | 1.1010 | 0.7234 | 0.0818 | 0.103* | |
| C15 | 0.72199 (16) | 0.8169 (2) | −0.01743 (7) | 0.0333 (4) | |
| C16 | 0.64436 (17) | 0.7505 (2) | −0.06219 (7) | 0.0420 (4) | |
| H16 | 0.5687 | 0.6984 | −0.0575 | 0.050* | |
| C17 | 0.67758 (19) | 0.7603 (3) | −0.11355 (8) | 0.0486 (5) | |
| H17 | 0.6232 | 0.7158 | −0.1428 | 0.058* | |
| C18 | 0.7893 (2) | 0.8346 (3) | −0.12255 (8) | 0.0515 (5) | |
| C19 | 0.8153 (7) | 0.8254 (11) | −0.1815 (2) | 0.0583 (18) | 0.586 (13) |
| H19 | 0.7602 | 0.7432 | −0.2035 | 0.070* | 0.586 (13) |
| C20 | 0.8006 (10) | 1.0118 (12) | −0.2041 (3) | 0.102 (3) | 0.586 (13) |
| H20A | 0.7144 | 1.0475 | −0.2061 | 0.153* | 0.586 (13) |
| H20B | 0.8248 | 1.0152 | −0.2396 | 0.153* | 0.586 (13) |
| H20C | 0.8536 | 1.0882 | −0.1805 | 0.153* | 0.586 (13) |
| C21 | 0.9546 (11) | 0.7867 (18) | −0.1814 (5) | 0.091 (3) | 0.586 (13) |
| H21A | 0.9717 | 0.7809 | −0.2181 | 0.137* | 0.586 (13) |
| H21B | 0.9752 | 0.6784 | −0.1637 | 0.137* | 0.586 (13) |
| H21C | 1.0044 | 0.8765 | −0.1624 | 0.137* | 0.586 (13) |
| C19' | 0.8449 (11) | 0.8718 (19) | −0.1752 (3) | 0.073 (3) | 0.414 (13) |
| H19' | 0.8974 | 0.9752 | −0.1685 | 0.087* | 0.414 (13) |
| C20' | 0.7403 (12) | 0.915 (2) | −0.2199 (4) | 0.104 (4) | 0.414 (13) |
| H20D | 0.6884 | 1.0039 | −0.2079 | 0.156* | 0.414 (13) |
| H20E | 0.6902 | 0.8143 | −0.2295 | 0.156* | 0.414 (13) |
| H20F | 0.7753 | 0.9552 | −0.2509 | 0.156* | 0.414 (13) |
| C21' | 0.9299 (17) | 0.728 (2) | −0.1893 (8) | 0.088 (4) | 0.414 (13) |
| H21D | 0.9944 | 0.7061 | −0.1591 | 0.132* | 0.414 (13) |
| H21E | 0.9681 | 0.7605 | −0.2203 | 0.132* | 0.414 (13) |
| H21F | 0.8810 | 0.6248 | −0.1976 | 0.132* | 0.414 (13) |
| C22 | 0.8668 (2) | 0.9020 (3) | −0.07806 (9) | 0.0568 (6) | |
| H22 | 0.9427 | 0.9532 | −0.0829 | 0.068* | |
| C23 | 0.83327 (18) | 0.8944 (3) | −0.02667 (8) | 0.0462 (5) | |
| H23 | 0.8865 | 0.9422 | 0.0023 | 0.055* | |
| N1 | 0.52473 (13) | 0.68409 (19) | 0.08280 (6) | 0.0361 (3) | |
| O1 | 0.90964 (14) | 0.7164 (3) | 0.13667 (7) | 0.0840 (7) | |
| O2 | 0.94460 (11) | 0.5889 (2) | 0.06139 (6) | 0.0505 (4) | |
| S1 | 0.73931 (5) | 0.27778 (6) | 0.07238 (2) | 0.04255 (16) |
(I) Methyl 3-(4-isopropylphenyl)-1-methyl-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0291 (8) | 0.0381 (9) | 0.0328 (9) | −0.0026 (7) | 0.0045 (7) | 0.0019 (7) |
| C2 | 0.0467 (11) | 0.0570 (12) | 0.0382 (10) | −0.0011 (9) | 0.0113 (8) | 0.0033 (9) |
| C3 | 0.0558 (12) | 0.0821 (17) | 0.0382 (11) | −0.0046 (12) | 0.0099 (9) | 0.0161 (11) |
| C4 | 0.0603 (13) | 0.0663 (15) | 0.0530 (13) | −0.0048 (11) | 0.0011 (10) | 0.0293 (12) |
| C5 | 0.0538 (12) | 0.0402 (11) | 0.0565 (13) | −0.0005 (9) | −0.0007 (10) | 0.0140 (9) |
| C6 | 0.0327 (9) | 0.0353 (9) | 0.0387 (10) | −0.0027 (7) | 0.0000 (7) | 0.0054 (8) |
| C7 | 0.0379 (9) | 0.0283 (8) | 0.0321 (9) | −0.0001 (7) | 0.0060 (7) | −0.0029 (7) |
| C8 | 0.0293 (8) | 0.0258 (8) | 0.0297 (8) | 0.0000 (6) | 0.0075 (6) | −0.0021 (7) |
| C9 | 0.0293 (8) | 0.0287 (8) | 0.0336 (9) | −0.0008 (7) | 0.0087 (7) | −0.0037 (7) |
| C10 | 0.0387 (10) | 0.0608 (13) | 0.0763 (15) | 0.0117 (10) | 0.0258 (10) | 0.0141 (12) |
| C11 | 0.0406 (10) | 0.0338 (9) | 0.0469 (11) | 0.0094 (8) | 0.0122 (8) | 0.0075 (8) |
| C12 | 0.0366 (9) | 0.0247 (8) | 0.0367 (9) | −0.0019 (7) | 0.0079 (7) | −0.0007 (7) |
| C13 | 0.0316 (9) | 0.0373 (9) | 0.0362 (10) | −0.0008 (7) | 0.0086 (7) | −0.0024 (8) |
| C14 | 0.0303 (10) | 0.0772 (17) | 0.1015 (19) | 0.0028 (11) | 0.0199 (11) | −0.0011 (15) |
| C15 | 0.0360 (9) | 0.0279 (8) | 0.0361 (9) | −0.0006 (7) | 0.0055 (7) | 0.0050 (7) |
| C16 | 0.0374 (9) | 0.0444 (11) | 0.0431 (11) | −0.0042 (8) | 0.0022 (8) | 0.0043 (8) |
| C17 | 0.0507 (11) | 0.0549 (12) | 0.0377 (11) | 0.0014 (10) | −0.0015 (9) | 0.0009 (9) |
| C18 | 0.0574 (12) | 0.0605 (13) | 0.0378 (11) | 0.0086 (10) | 0.0110 (9) | 0.0093 (10) |
| C19 | 0.056 (3) | 0.082 (4) | 0.037 (3) | −0.016 (3) | 0.010 (2) | −0.003 (2) |
| C20 | 0.128 (6) | 0.122 (6) | 0.063 (4) | 0.034 (5) | 0.039 (4) | 0.048 (4) |
| C21 | 0.100 (6) | 0.128 (8) | 0.057 (5) | 0.017 (5) | 0.046 (5) | 0.013 (5) |
| C19' | 0.090 (6) | 0.088 (6) | 0.043 (4) | −0.009 (5) | 0.018 (4) | 0.001 (4) |
| C20' | 0.127 (8) | 0.132 (9) | 0.053 (5) | 0.016 (6) | 0.012 (5) | 0.031 (5) |
| C21' | 0.085 (7) | 0.122 (10) | 0.058 (5) | 0.015 (7) | 0.016 (5) | −0.012 (6) |
| C22 | 0.0504 (12) | 0.0700 (15) | 0.0533 (13) | −0.0146 (11) | 0.0186 (10) | 0.0108 (11) |
| C23 | 0.0446 (10) | 0.0521 (12) | 0.0418 (11) | −0.0145 (9) | 0.0059 (8) | 0.0025 (9) |
| N1 | 0.0288 (7) | 0.0338 (8) | 0.0468 (9) | 0.0040 (6) | 0.0097 (6) | 0.0054 (7) |
| O1 | 0.0382 (8) | 0.1496 (19) | 0.0630 (10) | −0.0111 (9) | 0.0038 (7) | −0.0553 (12) |
| O2 | 0.0319 (6) | 0.0652 (9) | 0.0575 (8) | 0.0022 (6) | 0.0169 (6) | −0.0123 (7) |
| S1 | 0.0551 (3) | 0.0263 (2) | 0.0470 (3) | 0.00570 (19) | 0.0104 (2) | −0.00152 (19) |
(I) Methyl 3-(4-isopropylphenyl)-1-methyl-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Geometric parameters (Å, º)
| C1—C2 | 1.394 (2) | C14—H14A | 0.9600 |
| C1—C6 | 1.398 (2) | C14—H14B | 0.9600 |
| C1—C9 | 1.510 (2) | C14—H14C | 0.9600 |
| C2—C3 | 1.382 (3) | C15—C23 | 1.386 (2) |
| C2—H2 | 0.9300 | C15—C16 | 1.390 (2) |
| C3—C4 | 1.372 (4) | C16—C17 | 1.382 (3) |
| C3—H3 | 0.9300 | C16—H16 | 0.9300 |
| C4—C5 | 1.375 (3) | C17—C18 | 1.378 (3) |
| C4—H4 | 0.9300 | C17—H17 | 0.9300 |
| C5—C6 | 1.398 (3) | C18—C22 | 1.387 (3) |
| C5—H5 | 0.9300 | C18—C19 | 1.539 (5) |
| C6—S1 | 1.7599 (19) | C18—C19' | 1.546 (7) |
| C7—C8 | 1.523 (2) | C19—C21 | 1.524 (12) |
| C7—S1 | 1.8024 (17) | C19—C20 | 1.551 (11) |
| C7—H7A | 0.9700 | C19—H19 | 0.9800 |
| C7—H7B | 0.9700 | C20—H20A | 0.9600 |
| C8—C13 | 1.515 (2) | C20—H20B | 0.9600 |
| C8—C9 | 1.539 (2) | C20—H20C | 0.9600 |
| C8—C12 | 1.572 (2) | C21—H21A | 0.9600 |
| C9—N1 | 1.474 (2) | C21—H21B | 0.9600 |
| C9—H9 | 0.9800 | C21—H21C | 0.9600 |
| C10—N1 | 1.457 (2) | C19'—C20' | 1.500 (14) |
| C10—H10A | 0.9600 | C19'—C21' | 1.519 (15) |
| C10—H10B | 0.9600 | C19'—H19' | 0.9800 |
| C10—H10C | 0.9600 | C20'—H20D | 0.9600 |
| C11—N1 | 1.468 (2) | C20'—H20E | 0.9600 |
| C11—C12 | 1.540 (2) | C20'—H20F | 0.9600 |
| C11—H11A | 0.9700 | C21'—H21D | 0.9600 |
| C11—H11B | 0.9700 | C21'—H21E | 0.9600 |
| C12—C15 | 1.511 (2) | C21'—H21F | 0.9600 |
| C12—H12 | 0.9800 | C22—C23 | 1.383 (3) |
| C13—O1 | 1.184 (2) | C22—H22 | 0.9300 |
| C13—O2 | 1.321 (2) | C23—H23 | 0.9300 |
| C14—O2 | 1.439 (2) | ||
| C2—C1—C6 | 117.55 (17) | C23—C15—C16 | 117.15 (16) |
| C2—C1—C9 | 118.63 (16) | C23—C15—C12 | 119.62 (15) |
| C6—C1—C9 | 123.77 (15) | C16—C15—C12 | 123.22 (15) |
| C3—C2—C1 | 122.1 (2) | C17—C16—C15 | 121.20 (17) |
| C3—C2—H2 | 119.0 | C17—C16—H16 | 119.4 |
| C1—C2—H2 | 119.0 | C15—C16—H16 | 119.4 |
| C4—C3—C2 | 119.6 (2) | C18—C17—C16 | 121.59 (18) |
| C4—C3—H3 | 120.2 | C18—C17—H17 | 119.2 |
| C2—C3—H3 | 120.2 | C16—C17—H17 | 119.2 |
| C3—C4—C5 | 120.0 (2) | C17—C18—C22 | 117.43 (18) |
| C3—C4—H4 | 120.0 | C17—C18—C19 | 114.9 (3) |
| C5—C4—H4 | 120.0 | C22—C18—C19 | 127.6 (3) |
| C4—C5—C6 | 120.7 (2) | C17—C18—C19' | 132.0 (5) |
| C4—C5—H5 | 119.7 | C22—C18—C19' | 110.4 (5) |
| C6—C5—H5 | 119.7 | C19—C18—C19' | 18.3 (5) |
| C1—C6—C5 | 120.03 (18) | C21—C19—C18 | 108.9 (7) |
| C1—C6—S1 | 123.93 (13) | C21—C19—C20 | 103.4 (9) |
| C5—C6—S1 | 115.96 (15) | C18—C19—C20 | 106.3 (6) |
| C8—C7—S1 | 112.92 (11) | C21—C19—H19 | 112.6 |
| C8—C7—H7A | 109.0 | C18—C19—H19 | 112.6 |
| S1—C7—H7A | 109.0 | C20—C19—H19 | 112.6 |
| C8—C7—H7B | 109.0 | C19—C20—H20A | 109.5 |
| S1—C7—H7B | 109.0 | C19—C20—H20B | 109.5 |
| H7A—C7—H7B | 107.8 | H20A—C20—H20B | 109.5 |
| C13—C8—C7 | 113.01 (13) | C19—C20—H20C | 109.5 |
| C13—C8—C9 | 112.32 (13) | H20A—C20—H20C | 109.5 |
| C7—C8—C9 | 109.95 (13) | H20B—C20—H20C | 109.5 |
| C13—C8—C12 | 108.71 (13) | C19—C21—H21A | 109.5 |
| C7—C8—C12 | 111.61 (13) | C19—C21—H21B | 109.5 |
| C9—C8—C12 | 100.59 (12) | H21A—C21—H21B | 109.5 |
| N1—C9—C1 | 114.12 (13) | C19—C21—H21C | 109.5 |
| N1—C9—C8 | 100.71 (13) | H21A—C21—H21C | 109.5 |
| C1—C9—C8 | 116.20 (13) | H21B—C21—H21C | 109.5 |
| N1—C9—H9 | 108.5 | C20'—C19'—C21' | 113.7 (14) |
| C1—C9—H9 | 108.5 | C20'—C19'—C18 | 109.5 (8) |
| C8—C9—H9 | 108.5 | C21'—C19'—C18 | 112.4 (12) |
| N1—C10—H10A | 109.5 | C20'—C19'—H19' | 107.0 |
| N1—C10—H10B | 109.5 | C21'—C19'—H19' | 107.0 |
| H10A—C10—H10B | 109.5 | C18—C19'—H19' | 107.0 |
| N1—C10—H10C | 109.5 | C19'—C20'—H20D | 109.5 |
| H10A—C10—H10C | 109.5 | C19'—C20'—H20E | 109.5 |
| H10B—C10—H10C | 109.5 | H20D—C20'—H20E | 109.5 |
| N1—C11—C12 | 106.52 (13) | C19'—C20'—H20F | 109.5 |
| N1—C11—H11A | 110.4 | H20D—C20'—H20F | 109.5 |
| C12—C11—H11A | 110.4 | H20E—C20'—H20F | 109.5 |
| N1—C11—H11B | 110.4 | C19'—C21'—H21D | 109.5 |
| C12—C11—H11B | 110.4 | C19'—C21'—H21E | 109.5 |
| H11A—C11—H11B | 108.6 | H21D—C21'—H21E | 109.5 |
| C15—C12—C11 | 117.38 (14) | C19'—C21'—H21F | 109.5 |
| C15—C12—C8 | 116.04 (13) | H21D—C21'—H21F | 109.5 |
| C11—C12—C8 | 103.18 (13) | H21E—C21'—H21F | 109.5 |
| C15—C12—H12 | 106.5 | C23—C22—C18 | 121.21 (19) |
| C11—C12—H12 | 106.5 | C23—C22—H22 | 119.4 |
| C8—C12—H12 | 106.5 | C18—C22—H22 | 119.4 |
| O1—C13—O2 | 123.11 (16) | C22—C23—C15 | 121.41 (18) |
| O1—C13—C8 | 124.68 (16) | C22—C23—H23 | 119.3 |
| O2—C13—C8 | 112.07 (14) | C15—C23—H23 | 119.3 |
| O2—C14—H14A | 109.5 | C10—N1—C11 | 111.09 (15) |
| O2—C14—H14B | 109.5 | C10—N1—C9 | 115.36 (15) |
| H14A—C14—H14B | 109.5 | C11—N1—C9 | 105.37 (13) |
| O2—C14—H14C | 109.5 | C13—O2—C14 | 117.99 (16) |
| H14A—C14—H14C | 109.5 | C6—S1—C7 | 101.98 (8) |
| H14B—C14—H14C | 109.5 | ||
| C6—C1—C2—C3 | −1.5 (3) | C8—C12—C15—C23 | −93.3 (2) |
| C9—C1—C2—C3 | −179.07 (17) | C11—C12—C15—C16 | −36.9 (2) |
| C1—C2—C3—C4 | 1.4 (3) | C8—C12—C15—C16 | 85.7 (2) |
| C2—C3—C4—C5 | −0.1 (3) | C23—C15—C16—C17 | 0.5 (3) |
| C3—C4—C5—C6 | −1.0 (3) | C12—C15—C16—C17 | −178.64 (17) |
| C2—C1—C6—C5 | 0.4 (3) | C15—C16—C17—C18 | 0.7 (3) |
| C9—C1—C6—C5 | 177.81 (16) | C16—C17—C18—C22 | −1.0 (3) |
| C2—C1—C6—S1 | −176.06 (13) | C16—C17—C18—C19 | 176.5 (4) |
| C9—C1—C6—S1 | 1.3 (2) | C16—C17—C18—C19' | −175.7 (7) |
| C4—C5—C6—C1 | 0.8 (3) | C17—C18—C19—C21 | −140.0 (8) |
| C4—C5—C6—S1 | 177.59 (16) | C22—C18—C19—C21 | 37.2 (10) |
| S1—C7—C8—C13 | 61.01 (16) | C19'—C18—C19—C21 | 58 (2) |
| S1—C7—C8—C9 | −65.37 (15) | C17—C18—C19—C20 | 109.2 (7) |
| S1—C7—C8—C12 | −176.10 (11) | C22—C18—C19—C20 | −73.6 (8) |
| C2—C1—C9—N1 | −86.08 (19) | C19'—C18—C19—C20 | −52 (2) |
| C6—C1—C9—N1 | 96.55 (19) | C17—C18—C19'—C20' | 33.7 (16) |
| C2—C1—C9—C8 | 157.34 (15) | C22—C18—C19'—C20' | −141.3 (12) |
| C6—C1—C9—C8 | −20.0 (2) | C19—C18—C19'—C20' | 57 (2) |
| C13—C8—C9—N1 | 161.82 (13) | C17—C18—C19'—C21' | −93.5 (12) |
| C7—C8—C9—N1 | −71.42 (15) | C22—C18—C19'—C21' | 91.4 (13) |
| C12—C8—C9—N1 | 46.38 (14) | C19—C18—C19'—C21' | −71 (2) |
| C13—C8—C9—C1 | −74.36 (18) | C17—C18—C22—C23 | 0.2 (3) |
| C7—C8—C9—C1 | 52.41 (18) | C19—C18—C22—C23 | −177.0 (4) |
| C12—C8—C9—C1 | 170.21 (13) | C19'—C18—C22—C23 | 176.0 (6) |
| N1—C11—C12—C15 | 132.25 (15) | C18—C22—C23—C15 | 1.0 (3) |
| N1—C11—C12—C8 | 3.27 (17) | C16—C15—C23—C22 | −1.3 (3) |
| C13—C8—C12—C15 | 81.94 (17) | C12—C15—C23—C22 | 177.85 (19) |
| C7—C8—C12—C15 | −43.37 (18) | C12—C11—N1—C10 | 152.28 (16) |
| C9—C8—C12—C15 | −159.95 (14) | C12—C11—N1—C9 | 26.68 (18) |
| C13—C8—C12—C11 | −148.26 (14) | C1—C9—N1—C10 | 65.7 (2) |
| C7—C8—C12—C11 | 86.43 (16) | C8—C9—N1—C10 | −169.06 (15) |
| C9—C8—C12—C11 | −30.15 (15) | C1—C9—N1—C11 | −171.39 (14) |
| C7—C8—C13—O1 | −150.6 (2) | C8—C9—N1—C11 | −46.15 (16) |
| C9—C8—C13—O1 | −25.5 (3) | O1—C13—O2—C14 | 0.5 (3) |
| C12—C8—C13—O1 | 84.9 (2) | C8—C13—O2—C14 | 176.23 (17) |
| C7—C8—C13—O2 | 33.7 (2) | C1—C6—S1—C7 | −11.94 (17) |
| C9—C8—C13—O2 | 158.85 (15) | C5—C6—S1—C7 | 171.45 (14) |
| C12—C8—C13—O2 | −90.74 (17) | C8—C7—S1—C6 | 43.36 (13) |
| C11—C12—C15—C23 | 144.07 (17) |
(I) Methyl 3-(4-isopropylphenyl)-1-methyl-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Hydrogen-bond geometry (Å, º)
Cg3 is the centroid of the C1–C6 ring.
| D—H···A | D—H | H···A | D···A | D—H···A |
| C17—H17···Cg3i | 0.93 | 2.91 | 3.695 (2) | 143 |
Symmetry code: (i) −x+1, −y+1, −z.
(II) Methyl 1-methyl-3-(o-tolyl)-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Crystal data
| C21H21NO2S | Z = 2 |
| Mr = 351.45 | F(000) = 372 |
| Triclinic, P1 | Dx = 1.280 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.1882 (3) Å | Cell parameters from 2790 reflections |
| b = 10.4987 (4) Å | θ = 1.9–25.0° |
| c = 10.9594 (4) Å | µ = 0.19 mm−1 |
| α = 104.554 (1)° | T = 293 K |
| β = 90.983 (1)° | Block, colourless |
| γ = 90.134 (1)° | 0.35 × 0.30 × 0.25 mm |
| V = 911.74 (6) Å3 |
(II) Methyl 1-methyl-3-(o-tolyl)-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Data collection
| Bruker SMART APEXII CCD diffractometer | 3210 independent reflections |
| Radiation source: fine-focus sealed tube | 2790 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.020 |
| ω and φ scans | θmax = 25.0°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −9→9 |
| Tmin = 0.935, Tmax = 0.953 | k = −12→12 |
| 19010 measured reflections | l = −13→13 |
(II) Methyl 1-methyl-3-(o-tolyl)-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Refinement
| 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.115 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.0591P)2 + 0.2766P] where P = (Fo2 + 2Fc2)/3 |
| 3210 reflections | (Δ/σ)max < 0.001 |
| 229 parameters | Δρmax = 0.26 e Å−3 |
| 0 restraints | Δρmin = −0.32 e Å−3 |
(II) Methyl 1-methyl-3-(o-tolyl)-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Special details
| 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. |
(II) Methyl 1-methyl-3-(o-tolyl)-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.1321 (2) | 0.62046 (16) | 0.33099 (15) | 0.0424 (4) | |
| C2 | 0.0560 (3) | 0.6916 (2) | 0.43961 (18) | 0.0589 (5) | |
| H2 | −0.0253 | 0.6509 | 0.4748 | 0.071* | |
| C3 | 0.0976 (3) | 0.8203 (2) | 0.4965 (2) | 0.0759 (7) | |
| H3 | 0.0434 | 0.8661 | 0.5679 | 0.091* | |
| C4 | 0.2199 (4) | 0.8801 (2) | 0.4468 (2) | 0.0768 (7) | |
| H4 | 0.2487 | 0.9670 | 0.4845 | 0.092* | |
| C5 | 0.2994 (3) | 0.81250 (19) | 0.3421 (2) | 0.0614 (5) | |
| H5 | 0.3836 | 0.8534 | 0.3102 | 0.074* | |
| C6 | 0.2560 (2) | 0.68236 (17) | 0.28217 (16) | 0.0444 (4) | |
| C7 | 0.2650 (2) | 0.45327 (17) | 0.09015 (16) | 0.0435 (4) | |
| H7A | 0.1727 | 0.4687 | 0.0392 | 0.052* | |
| H7B | 0.3373 | 0.3921 | 0.0356 | 0.052* | |
| C8 | 0.20327 (18) | 0.39039 (15) | 0.19172 (15) | 0.0389 (4) | |
| C9 | 0.07923 (18) | 0.48030 (16) | 0.27409 (15) | 0.0397 (4) | |
| H9 | 0.0487 | 0.4408 | 0.3426 | 0.048* | |
| C10 | −0.2119 (2) | 0.5208 (2) | 0.2449 (2) | 0.0627 (5) | |
| H10A | −0.3002 | 0.4990 | 0.1844 | 0.094* | |
| H10B | −0.2028 | 0.6148 | 0.2747 | 0.094* | |
| H10C | −0.2328 | 0.4835 | 0.3146 | 0.094* | |
| C11 | −0.0773 (2) | 0.3283 (2) | 0.1264 (2) | 0.0678 (6) | |
| H11A | −0.1131 | 0.3147 | 0.0392 | 0.081* | |
| H11B | −0.1569 | 0.2884 | 0.1702 | 0.081* | |
| C12 | 0.0921 (2) | 0.26691 (17) | 0.13364 (18) | 0.0475 (4) | |
| H12 | 0.0856 | 0.2166 | 0.1976 | 0.057* | |
| C15 | 0.1522 (2) | 0.17354 (16) | 0.01548 (17) | 0.0480 (4) | |
| C16 | 0.1305 (3) | 0.2006 (2) | −0.10163 (19) | 0.0648 (6) | |
| H14 | 0.0742 | 0.2760 | −0.1067 | 0.078* | |
| C17 | 0.1898 (3) | 0.1190 (2) | −0.2106 (2) | 0.0800 (7) | |
| H15 | 0.1722 | 0.1387 | −0.2878 | 0.096* | |
| C18 | 0.2745 (3) | 0.0093 (2) | −0.2041 (2) | 0.0790 (7) | |
| H16 | 0.3181 | −0.0447 | −0.2767 | 0.095* | |
| C19 | 0.2953 (3) | −0.02130 (19) | −0.0912 (2) | 0.0669 (6) | |
| H17 | 0.3519 | −0.0972 | −0.0884 | 0.080* | |
| C20 | 0.2343 (2) | 0.05785 (17) | 0.02048 (19) | 0.0520 (4) | |
| C21 | 0.2546 (3) | 0.0131 (2) | 0.1378 (2) | 0.0727 (6) | |
| H19A | 0.3050 | −0.0719 | 0.1187 | 0.109* | |
| H19B | 0.1495 | 0.0075 | 0.1738 | 0.109* | |
| H19C | 0.3223 | 0.0748 | 0.1969 | 0.109* | |
| C13 | 0.3469 (2) | 0.34856 (16) | 0.26130 (16) | 0.0431 (4) | |
| C14 | 0.4427 (3) | 0.3058 (3) | 0.4510 (2) | 0.0920 (9) | |
| H21A | 0.4697 | 0.2173 | 0.4077 | 0.138* | |
| H21B | 0.4048 | 0.3074 | 0.5338 | 0.138* | |
| H21C | 0.5379 | 0.3609 | 0.4579 | 0.138* | |
| N1 | −0.06074 (15) | 0.46851 (14) | 0.18600 (14) | 0.0455 (4) | |
| O1 | 0.47275 (15) | 0.30893 (14) | 0.21352 (13) | 0.0592 (4) | |
| O2 | 0.31503 (18) | 0.35417 (16) | 0.38084 (13) | 0.0709 (4) | |
| S1 | 0.37215 (5) | 0.60605 (5) | 0.15186 (5) | 0.05272 (17) |
(II) Methyl 1-methyl-3-(o-tolyl)-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0429 (9) | 0.0469 (9) | 0.0392 (9) | 0.0106 (7) | −0.0039 (7) | 0.0146 (7) |
| C2 | 0.0667 (12) | 0.0659 (12) | 0.0451 (10) | 0.0183 (10) | 0.0044 (9) | 0.0155 (9) |
| C3 | 0.1017 (18) | 0.0676 (14) | 0.0490 (12) | 0.0260 (13) | −0.0033 (12) | −0.0027 (11) |
| C4 | 0.112 (2) | 0.0520 (12) | 0.0602 (14) | 0.0051 (13) | −0.0200 (13) | 0.0042 (10) |
| C5 | 0.0735 (13) | 0.0514 (11) | 0.0618 (12) | −0.0055 (10) | −0.0200 (10) | 0.0202 (10) |
| C6 | 0.0452 (9) | 0.0454 (9) | 0.0445 (9) | 0.0049 (7) | −0.0109 (7) | 0.0158 (7) |
| C7 | 0.0355 (8) | 0.0514 (10) | 0.0436 (9) | 0.0035 (7) | 0.0040 (7) | 0.0118 (7) |
| C8 | 0.0316 (8) | 0.0413 (8) | 0.0440 (9) | 0.0044 (6) | −0.0002 (6) | 0.0113 (7) |
| C9 | 0.0332 (8) | 0.0478 (9) | 0.0423 (9) | 0.0069 (7) | 0.0036 (6) | 0.0187 (7) |
| C10 | 0.0335 (9) | 0.0740 (13) | 0.0857 (15) | 0.0107 (9) | 0.0090 (9) | 0.0290 (11) |
| C11 | 0.0379 (10) | 0.0607 (12) | 0.0978 (16) | 0.0003 (9) | −0.0111 (10) | 0.0075 (11) |
| C12 | 0.0390 (9) | 0.0453 (9) | 0.0590 (11) | −0.0005 (7) | −0.0042 (8) | 0.0148 (8) |
| C15 | 0.0458 (9) | 0.0391 (9) | 0.0579 (11) | −0.0027 (7) | −0.0109 (8) | 0.0109 (8) |
| C16 | 0.0859 (15) | 0.0476 (11) | 0.0579 (12) | 0.0018 (10) | −0.0216 (11) | 0.0093 (9) |
| C17 | 0.114 (2) | 0.0635 (14) | 0.0567 (13) | −0.0073 (13) | −0.0173 (13) | 0.0061 (11) |
| C18 | 0.0939 (18) | 0.0674 (14) | 0.0630 (14) | −0.0041 (12) | −0.0038 (12) | −0.0067 (11) |
| C19 | 0.0627 (13) | 0.0398 (10) | 0.0896 (16) | 0.0022 (9) | −0.0081 (11) | 0.0011 (10) |
| C20 | 0.0483 (10) | 0.0390 (9) | 0.0684 (12) | −0.0046 (7) | −0.0104 (8) | 0.0138 (8) |
| C21 | 0.0836 (16) | 0.0532 (12) | 0.0876 (16) | 0.0003 (11) | −0.0119 (12) | 0.0305 (11) |
| C13 | 0.0373 (9) | 0.0401 (9) | 0.0509 (10) | 0.0046 (7) | −0.0028 (7) | 0.0100 (7) |
| C14 | 0.0858 (17) | 0.131 (2) | 0.0647 (14) | 0.0513 (16) | −0.0112 (12) | 0.0354 (15) |
| N1 | 0.0286 (7) | 0.0527 (8) | 0.0573 (9) | 0.0047 (6) | −0.0002 (6) | 0.0176 (7) |
| O1 | 0.0374 (7) | 0.0683 (9) | 0.0731 (9) | 0.0151 (6) | 0.0019 (6) | 0.0197 (7) |
| O2 | 0.0618 (9) | 0.1045 (12) | 0.0516 (8) | 0.0386 (8) | 0.0005 (6) | 0.0289 (8) |
| S1 | 0.0402 (3) | 0.0558 (3) | 0.0645 (3) | −0.00397 (19) | 0.0072 (2) | 0.0190 (2) |
(II) Methyl 1-methyl-3-(o-tolyl)-1,2,3,3a,4,9b-hexahydrothiochromeno[4,3-b]pyrrole-3a-carboxylate . Geometric parameters (Å, º)
| C1—C6 | 1.389 (3) | C11—C12 | 1.540 (2) |
| C1—C2 | 1.394 (2) | C11—H11A | 0.9700 |
| C1—C9 | 1.506 (2) | C11—H11B | 0.9700 |
| C2—C3 | 1.377 (3) | C12—C15 | 1.505 (3) |
| C2—H2 | 0.9300 | C12—H12 | 0.9800 |
| C3—C4 | 1.372 (4) | C15—C16 | 1.391 (3) |
| C3—H3 | 0.9300 | C15—C20 | 1.402 (2) |
| C4—C5 | 1.364 (3) | C16—C17 | 1.380 (3) |
| C4—H4 | 0.9300 | C16—H14 | 0.9300 |
| C5—C6 | 1.401 (3) | C17—C18 | 1.362 (4) |
| C5—H5 | 0.9300 | C17—H15 | 0.9300 |
| C6—S1 | 1.7495 (18) | C18—C19 | 1.362 (3) |
| C7—C8 | 1.522 (2) | C18—H16 | 0.9300 |
| C7—S1 | 1.7967 (17) | C19—C20 | 1.397 (3) |
| C7—H7A | 0.9700 | C19—H17 | 0.9300 |
| C7—H7B | 0.9700 | C20—C21 | 1.483 (3) |
| C8—C13 | 1.516 (2) | C21—H19A | 0.9600 |
| C8—C9 | 1.531 (2) | C21—H19B | 0.9600 |
| C8—C12 | 1.573 (2) | C21—H19C | 0.9600 |
| C9—N1 | 1.470 (2) | C13—O1 | 1.192 (2) |
| C9—H9 | 0.9800 | C13—O2 | 1.327 (2) |
| C10—N1 | 1.450 (2) | C14—O2 | 1.453 (2) |
| C10—H10A | 0.9600 | C14—H21A | 0.9600 |
| C10—H10B | 0.9600 | C14—H21B | 0.9600 |
| C10—H10C | 0.9600 | C14—H21C | 0.9600 |
| C11—N1 | 1.458 (2) | ||
| C6—C1—C2 | 117.86 (17) | C12—C11—H11B | 110.3 |
| C6—C1—C9 | 123.26 (15) | H11A—C11—H11B | 108.6 |
| C2—C1—C9 | 118.87 (16) | C15—C12—C11 | 117.07 (16) |
| C3—C2—C1 | 122.0 (2) | C15—C12—C8 | 116.40 (14) |
| C3—C2—H2 | 119.0 | C11—C12—C8 | 102.78 (13) |
| C1—C2—H2 | 119.0 | C15—C12—H12 | 106.6 |
| C4—C3—C2 | 119.3 (2) | C11—C12—H12 | 106.6 |
| C4—C3—H3 | 120.3 | C8—C12—H12 | 106.6 |
| C2—C3—H3 | 120.3 | C16—C15—C20 | 118.02 (18) |
| C5—C4—C3 | 120.2 (2) | C16—C15—C12 | 121.01 (16) |
| C5—C4—H4 | 119.9 | C20—C15—C12 | 120.96 (17) |
| C3—C4—H4 | 119.9 | C17—C16—C15 | 122.0 (2) |
| C4—C5—C6 | 120.9 (2) | C17—C16—H14 | 119.0 |
| C4—C5—H5 | 119.5 | C15—C16—H14 | 119.0 |
| C6—C5—H5 | 119.5 | C18—C17—C16 | 119.5 (2) |
| C1—C6—C5 | 119.60 (18) | C18—C17—H15 | 120.2 |
| C1—C6—S1 | 124.27 (13) | C16—C17—H15 | 120.2 |
| C5—C6—S1 | 116.06 (15) | C19—C18—C17 | 119.9 (2) |
| C8—C7—S1 | 113.57 (12) | C19—C18—H16 | 120.1 |
| C8—C7—H7A | 108.9 | C17—C18—H16 | 120.1 |
| S1—C7—H7A | 108.9 | C18—C19—C20 | 122.1 (2) |
| C8—C7—H7B | 108.9 | C18—C19—H17 | 119.0 |
| S1—C7—H7B | 108.9 | C20—C19—H17 | 119.0 |
| H7A—C7—H7B | 107.7 | C19—C20—C15 | 118.43 (19) |
| C13—C8—C7 | 109.75 (13) | C19—C20—C21 | 118.35 (18) |
| C13—C8—C9 | 115.80 (13) | C15—C20—C21 | 123.19 (19) |
| C7—C8—C9 | 110.26 (13) | C20—C21—H19A | 109.5 |
| C13—C8—C12 | 109.12 (13) | C20—C21—H19B | 109.5 |
| C7—C8—C12 | 111.39 (14) | H19A—C21—H19B | 109.5 |
| C9—C8—C12 | 100.21 (12) | C20—C21—H19C | 109.5 |
| N1—C9—C1 | 113.43 (13) | H19A—C21—H19C | 109.5 |
| N1—C9—C8 | 101.16 (13) | H19B—C21—H19C | 109.5 |
| C1—C9—C8 | 116.72 (13) | O1—C13—O2 | 122.96 (16) |
| N1—C9—H9 | 108.4 | O1—C13—C8 | 124.25 (16) |
| C1—C9—H9 | 108.4 | O2—C13—C8 | 112.71 (14) |
| C8—C9—H9 | 108.4 | O2—C14—H21A | 109.5 |
| N1—C10—H10A | 109.5 | O2—C14—H21B | 109.5 |
| N1—C10—H10B | 109.5 | H21A—C14—H21B | 109.5 |
| H10A—C10—H10B | 109.5 | O2—C14—H21C | 109.5 |
| N1—C10—H10C | 109.5 | H21A—C14—H21C | 109.5 |
| H10A—C10—H10C | 109.5 | H21B—C14—H21C | 109.5 |
| H10B—C10—H10C | 109.5 | C10—N1—C11 | 110.79 (15) |
| N1—C11—C12 | 106.89 (14) | C10—N1—C9 | 114.21 (15) |
| N1—C11—H11A | 110.3 | C11—N1—C9 | 105.48 (13) |
| C12—C11—H11A | 110.3 | C13—O2—C14 | 115.82 (16) |
| N1—C11—H11B | 110.3 | C6—S1—C7 | 102.79 (8) |
| C6—C1—C2—C3 | 1.6 (3) | C11—C12—C15—C16 | 41.8 (3) |
| C9—C1—C2—C3 | −179.75 (17) | C8—C12—C15—C16 | −80.2 (2) |
| C1—C2—C3—C4 | −1.4 (3) | C11—C12—C15—C20 | −139.27 (18) |
| C2—C3—C4—C5 | −0.1 (3) | C8—C12—C15—C20 | 98.65 (19) |
| C3—C4—C5—C6 | 1.3 (3) | C20—C15—C16—C17 | −1.4 (3) |
| C2—C1—C6—C5 | −0.4 (2) | C12—C15—C16—C17 | 177.5 (2) |
| C9—C1—C6—C5 | −178.98 (15) | C15—C16—C17—C18 | −0.9 (4) |
| C2—C1—C6—S1 | 176.50 (12) | C16—C17—C18—C19 | 2.1 (4) |
| C9—C1—C6—S1 | −2.1 (2) | C17—C18—C19—C20 | −1.0 (4) |
| C4—C5—C6—C1 | −1.0 (3) | C18—C19—C20—C15 | −1.3 (3) |
| C4—C5—C6—S1 | −178.16 (16) | C18—C19—C20—C21 | 176.6 (2) |
| S1—C7—C8—C13 | −66.15 (15) | C16—C15—C20—C19 | 2.5 (3) |
| S1—C7—C8—C9 | 62.56 (15) | C12—C15—C20—C19 | −176.46 (17) |
| S1—C7—C8—C12 | 172.89 (10) | C16—C15—C20—C21 | −175.41 (19) |
| C6—C1—C9—N1 | −94.84 (18) | C12—C15—C20—C21 | 5.7 (3) |
| C2—C1—C9—N1 | 86.56 (18) | C7—C8—C13—O1 | −34.2 (2) |
| C6—C1—C9—C8 | 22.2 (2) | C9—C8—C13—O1 | −159.81 (16) |
| C2—C1—C9—C8 | −156.42 (15) | C12—C8—C13—O1 | 88.1 (2) |
| C13—C8—C9—N1 | −163.87 (13) | C7—C8—C13—O2 | 149.08 (15) |
| C7—C8—C9—N1 | 70.79 (15) | C9—C8—C13—O2 | 23.5 (2) |
| C12—C8—C9—N1 | −46.69 (14) | C12—C8—C13—O2 | −88.61 (17) |
| C13—C8—C9—C1 | 72.56 (18) | C12—C11—N1—C10 | −149.04 (17) |
| C7—C8—C9—C1 | −52.78 (18) | C12—C11—N1—C9 | −25.0 (2) |
| C12—C8—C9—C1 | −170.27 (13) | C1—C9—N1—C10 | −66.85 (19) |
| N1—C11—C12—C15 | −133.89 (17) | C8—C9—N1—C10 | 167.34 (14) |
| N1—C11—C12—C8 | −5.0 (2) | C1—C9—N1—C11 | 171.26 (15) |
| C13—C8—C12—C15 | −77.38 (18) | C8—C9—N1—C11 | 45.45 (17) |
| C7—C8—C12—C15 | 43.94 (19) | O1—C13—O2—C14 | −1.3 (3) |
| C9—C8—C12—C15 | 160.58 (14) | C8—C13—O2—C14 | 175.43 (19) |
| C13—C8—C12—C11 | 153.30 (16) | C1—C6—S1—C7 | 10.31 (16) |
| C7—C8—C12—C11 | −85.38 (18) | C5—C6—S1—C7 | −172.73 (13) |
| C9—C8—C12—C11 | 31.27 (17) | C8—C7—S1—C6 | −40.14 (13) |
(III) Methyl 1-methyl-3-(o-tolyl)-3,3a,4,9b-tetrahydro-1H-thiochromeno[4,3-c]isoxazole-3a-carboxylate . Crystal data
| C20H21NO3S | F(000) = 1504 |
| Mr = 355.44 | Dx = 1.320 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 2536 reflections |
| a = 11.2629 (11) Å | θ = 1.7–25.0° |
| b = 13.2117 (11) Å | µ = 0.20 mm−1 |
| c = 24.041 (3) Å | T = 293 K |
| V = 3577.3 (6) Å3 | Block, colourless |
| Z = 8 | 0.35 × 0.30 × 0.25 mm |
(III) Methyl 1-methyl-3-(o-tolyl)-3,3a,4,9b-tetrahydro-1H-thiochromeno[4,3-c]isoxazole-3a-carboxylate . Data collection
| Bruker SMART APEXII CCD diffractometer | 3151 independent reflections |
| Radiation source: fine-focus sealed tube | 2536 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.033 |
| ω and φ scans | θmax = 25.0°, θmin = 1.7° |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −13→13 |
| Tmin = 0.932, Tmax = 0.951 | k = −15→15 |
| 37913 measured reflections | l = −25→28 |
(III) Methyl 1-methyl-3-(o-tolyl)-3,3a,4,9b-tetrahydro-1H-thiochromeno[4,3-c]isoxazole-3a-carboxylate . Refinement
| 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) = 0.111 | H-atom parameters constrained |
| S = 1.12 | w = 1/[σ2(Fo2) + (0.0267P)2 + 3.6376P] where P = (Fo2 + 2Fc2)/3 |
| 3151 reflections | (Δ/σ)max < 0.001 |
| 229 parameters | Δρmax = 0.22 e Å−3 |
| 0 restraints | Δρmin = −0.22 e Å−3 |
(III) Methyl 1-methyl-3-(o-tolyl)-3,3a,4,9b-tetrahydro-1H-thiochromeno[4,3-c]isoxazole-3a-carboxylate . Special details
| 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. |
(III) Methyl 1-methyl-3-(o-tolyl)-3,3a,4,9b-tetrahydro-1H-thiochromeno[4,3-c]isoxazole-3a-carboxylate . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| C6 | 0.1021 (2) | 0.96898 (18) | 0.15232 (10) | 0.0414 (6) | |
| C5 | 0.1663 (3) | 1.0558 (2) | 0.16587 (11) | 0.0554 (8) | |
| H2 | 0.2488 | 1.0549 | 0.1644 | 0.067* | |
| C4 | 0.1082 (4) | 1.1428 (2) | 0.18133 (13) | 0.0682 (9) | |
| H3 | 0.1516 | 1.2001 | 0.1908 | 0.082* | |
| C3 | −0.0133 (4) | 1.1458 (2) | 0.18285 (13) | 0.0661 (9) | |
| H4 | −0.0524 | 1.2051 | 0.1928 | 0.079* | |
| C2 | −0.0774 (3) | 1.0602 (2) | 0.16959 (11) | 0.0532 (7) | |
| H5 | −0.1599 | 1.0627 | 0.1704 | 0.064* | |
| C1 | −0.0216 (2) | 0.96998 (17) | 0.15496 (9) | 0.0387 (6) | |
| C9 | −0.0973 (2) | 0.87834 (17) | 0.14347 (9) | 0.0349 (5) | |
| H7 | −0.1701 | 0.8994 | 0.1244 | 0.042* | |
| C8 | −0.0406 (2) | 0.79039 (17) | 0.11168 (9) | 0.0339 (5) | |
| C7 | 0.0803 (2) | 0.76400 (18) | 0.13613 (10) | 0.0396 (6) | |
| H9A | 0.1108 | 0.7038 | 0.1179 | 0.048* | |
| H9B | 0.0713 | 0.7489 | 0.1754 | 0.048* | |
| C12 | −0.0283 (2) | 0.80429 (18) | 0.04923 (10) | 0.0402 (6) | |
| C13 | −0.1085 (4) | 0.8784 (3) | −0.03165 (13) | 0.1103 (17) | |
| H11A | −0.0351 | 0.9079 | −0.0439 | 0.165* | |
| H11B | −0.1734 | 0.9211 | −0.0425 | 0.165* | |
| H11C | −0.1179 | 0.8128 | −0.0483 | 0.165* | |
| C11 | −0.1353 (2) | 0.70812 (18) | 0.12471 (10) | 0.0405 (6) | |
| H12 | −0.2058 | 0.7209 | 0.1019 | 0.049* | |
| C15 | −0.0373 (2) | 0.5505 (2) | 0.15990 (12) | 0.0485 (7) | |
| H13 | −0.0221 | 0.5846 | 0.1930 | 0.058* | |
| C16 | 0.0011 (3) | 0.4518 (2) | 0.15331 (15) | 0.0626 (9) | |
| H14 | 0.0427 | 0.4197 | 0.1817 | 0.075* | |
| C17 | −0.0226 (3) | 0.4015 (2) | 0.10480 (16) | 0.0698 (10) | |
| H15 | 0.0041 | 0.3355 | 0.1000 | 0.084* | |
| C18 | −0.0850 (3) | 0.4478 (2) | 0.06366 (14) | 0.0638 (8) | |
| H16 | −0.1015 | 0.4122 | 0.0312 | 0.077* | |
| C19 | −0.1248 (2) | 0.5466 (2) | 0.06874 (12) | 0.0483 (7) | |
| C20 | −0.1961 (3) | 0.5916 (3) | 0.02205 (13) | 0.0751 (10) | |
| H18A | −0.1985 | 0.5450 | −0.0086 | 0.113* | |
| H18B | −0.1600 | 0.6538 | 0.0102 | 0.113* | |
| H18C | −0.2755 | 0.6048 | 0.0347 | 0.113* | |
| C14 | −0.0983 (2) | 0.59892 (18) | 0.11741 (10) | 0.0382 (6) | |
| C10 | −0.2337 (3) | 0.8711 (2) | 0.22232 (12) | 0.0608 (8) | |
| H20A | −0.2966 | 0.8737 | 0.1954 | 0.091* | |
| H20B | −0.2167 | 0.9382 | 0.2353 | 0.091* | |
| H20C | −0.2576 | 0.8295 | 0.2531 | 0.091* | |
| N1 | −0.12874 (18) | 0.82867 (15) | 0.19689 (8) | 0.0399 (5) | |
| O3 | −0.1645 (2) | 0.72567 (14) | 0.18158 (8) | 0.0649 (6) | |
| O1 | 0.04071 (18) | 0.75906 (16) | 0.02133 (8) | 0.0600 (5) | |
| O2 | −0.1069 (2) | 0.86808 (17) | 0.02891 (7) | 0.0757 (7) | |
| S1 | 0.18494 (6) | 0.86516 (5) | 0.12793 (3) | 0.04623 (19) |
(III) Methyl 1-methyl-3-(o-tolyl)-3,3a,4,9b-tetrahydro-1H-thiochromeno[4,3-c]isoxazole-3a-carboxylate . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C6 | 0.0534 (15) | 0.0403 (14) | 0.0303 (13) | −0.0046 (12) | −0.0061 (11) | 0.0067 (11) |
| C5 | 0.0688 (19) | 0.0493 (17) | 0.0482 (16) | −0.0181 (15) | −0.0132 (14) | 0.0071 (13) |
| C4 | 0.105 (3) | 0.0420 (18) | 0.0574 (19) | −0.0220 (18) | −0.0143 (19) | −0.0011 (14) |
| C3 | 0.105 (3) | 0.0359 (16) | 0.0576 (19) | 0.0024 (17) | −0.0008 (18) | −0.0053 (14) |
| C2 | 0.0725 (19) | 0.0397 (15) | 0.0472 (16) | 0.0070 (14) | −0.0027 (14) | 0.0022 (12) |
| C1 | 0.0539 (15) | 0.0339 (13) | 0.0282 (12) | 0.0021 (11) | −0.0056 (11) | 0.0023 (10) |
| C9 | 0.0377 (12) | 0.0378 (13) | 0.0293 (12) | 0.0064 (10) | −0.0032 (10) | 0.0017 (10) |
| C8 | 0.0361 (12) | 0.0333 (12) | 0.0325 (12) | 0.0029 (10) | 0.0010 (10) | −0.0002 (10) |
| C7 | 0.0386 (13) | 0.0366 (13) | 0.0436 (14) | 0.0013 (11) | −0.0005 (11) | 0.0016 (11) |
| C12 | 0.0456 (14) | 0.0384 (14) | 0.0364 (13) | −0.0014 (12) | 0.0023 (12) | −0.0044 (11) |
| C13 | 0.171 (4) | 0.129 (3) | 0.0311 (17) | 0.072 (3) | 0.005 (2) | 0.0142 (19) |
| C11 | 0.0380 (13) | 0.0393 (13) | 0.0441 (14) | 0.0005 (11) | 0.0040 (11) | −0.0018 (11) |
| C15 | 0.0466 (15) | 0.0459 (16) | 0.0531 (17) | −0.0084 (13) | −0.0029 (13) | 0.0046 (13) |
| C16 | 0.0490 (16) | 0.0498 (18) | 0.089 (2) | 0.0048 (14) | 0.0027 (16) | 0.0217 (17) |
| C17 | 0.067 (2) | 0.0392 (16) | 0.103 (3) | 0.0065 (15) | 0.025 (2) | −0.0020 (18) |
| C18 | 0.072 (2) | 0.0492 (17) | 0.070 (2) | −0.0109 (16) | 0.0155 (17) | −0.0181 (16) |
| C19 | 0.0443 (15) | 0.0470 (15) | 0.0536 (17) | −0.0096 (12) | 0.0025 (13) | −0.0044 (13) |
| C20 | 0.087 (2) | 0.074 (2) | 0.064 (2) | −0.0162 (19) | −0.0271 (19) | −0.0084 (17) |
| C14 | 0.0329 (12) | 0.0365 (13) | 0.0451 (14) | −0.0043 (10) | 0.0030 (11) | −0.0009 (11) |
| C10 | 0.0687 (19) | 0.0627 (19) | 0.0510 (16) | 0.0175 (16) | 0.0203 (15) | 0.0000 (14) |
| N1 | 0.0433 (11) | 0.0410 (12) | 0.0355 (11) | 0.0055 (9) | 0.0023 (9) | 0.0018 (9) |
| O3 | 0.0916 (16) | 0.0424 (11) | 0.0607 (13) | −0.0102 (10) | 0.0396 (12) | −0.0064 (9) |
| O1 | 0.0646 (12) | 0.0726 (13) | 0.0428 (11) | 0.0123 (11) | 0.0081 (10) | −0.0140 (10) |
| O2 | 0.1102 (18) | 0.0868 (16) | 0.0301 (10) | 0.0516 (14) | 0.0040 (11) | 0.0056 (10) |
| S1 | 0.0383 (3) | 0.0485 (4) | 0.0519 (4) | −0.0047 (3) | −0.0019 (3) | 0.0028 (3) |
(III) Methyl 1-methyl-3-(o-tolyl)-3,3a,4,9b-tetrahydro-1H-thiochromeno[4,3-c]isoxazole-3a-carboxylate . Geometric parameters (Å, º)
| C6—C5 | 1.395 (4) | C13—H11B | 0.9600 |
| C6—C1 | 1.395 (4) | C13—H11C | 0.9600 |
| C6—S1 | 1.759 (3) | C11—O3 | 1.425 (3) |
| C5—C4 | 1.374 (4) | C11—C14 | 1.512 (3) |
| C5—H2 | 0.9300 | C11—H12 | 0.9800 |
| C4—C3 | 1.369 (5) | C15—C16 | 1.383 (4) |
| C4—H3 | 0.9300 | C15—C14 | 1.387 (4) |
| C3—C2 | 1.379 (4) | C15—H13 | 0.9300 |
| C3—H4 | 0.9300 | C16—C17 | 1.368 (5) |
| C2—C1 | 1.392 (4) | C16—H14 | 0.9300 |
| C2—H5 | 0.9300 | C17—C18 | 1.359 (5) |
| C1—C9 | 1.506 (3) | C17—H15 | 0.9300 |
| C9—N1 | 1.485 (3) | C18—C19 | 1.385 (4) |
| C9—C8 | 1.531 (3) | C18—H16 | 0.9300 |
| C9—H7 | 0.9800 | C19—C14 | 1.392 (4) |
| C8—C12 | 1.519 (3) | C19—C20 | 1.503 (4) |
| C8—C7 | 1.523 (3) | C20—H18A | 0.9600 |
| C8—C11 | 1.555 (3) | C20—H18B | 0.9600 |
| C7—S1 | 1.793 (2) | C20—H18C | 0.9600 |
| C7—H9A | 0.9700 | C10—N1 | 1.444 (3) |
| C7—H9B | 0.9700 | C10—H20A | 0.9600 |
| C12—O1 | 1.188 (3) | C10—H20B | 0.9600 |
| C12—O2 | 1.317 (3) | C10—H20C | 0.9600 |
| C13—O2 | 1.462 (3) | N1—O3 | 1.466 (3) |
| C13—H11A | 0.9600 | ||
| C5—C6—C1 | 119.9 (3) | H11B—C13—H11C | 109.5 |
| C5—C6—S1 | 116.4 (2) | O3—C11—C14 | 109.3 (2) |
| C1—C6—S1 | 123.51 (19) | O3—C11—C8 | 103.74 (19) |
| C4—C5—C6 | 120.3 (3) | C14—C11—C8 | 117.02 (19) |
| C4—C5—H2 | 119.9 | O3—C11—H12 | 108.8 |
| C6—C5—H2 | 119.9 | C14—C11—H12 | 108.8 |
| C3—C4—C5 | 120.5 (3) | C8—C11—H12 | 108.8 |
| C3—C4—H3 | 119.8 | C16—C15—C14 | 120.4 (3) |
| C5—C4—H3 | 119.8 | C16—C15—H13 | 119.8 |
| C4—C3—C2 | 119.5 (3) | C14—C15—H13 | 119.8 |
| C4—C3—H4 | 120.2 | C17—C16—C15 | 119.6 (3) |
| C2—C3—H4 | 120.2 | C17—C16—H14 | 120.2 |
| C3—C2—C1 | 121.6 (3) | C15—C16—H14 | 120.2 |
| C3—C2—H5 | 119.2 | C18—C17—C16 | 120.2 (3) |
| C1—C2—H5 | 119.2 | C18—C17—H15 | 119.9 |
| C2—C1—C6 | 118.1 (2) | C16—C17—H15 | 119.9 |
| C2—C1—C9 | 118.6 (2) | C17—C18—C19 | 121.8 (3) |
| C6—C1—C9 | 123.3 (2) | C17—C18—H16 | 119.1 |
| N1—C9—C1 | 109.36 (18) | C19—C18—H16 | 119.1 |
| N1—C9—C8 | 101.30 (18) | C18—C19—C14 | 118.2 (3) |
| C1—C9—C8 | 117.7 (2) | C18—C19—C20 | 118.7 (3) |
| N1—C9—H7 | 109.3 | C14—C19—C20 | 123.1 (3) |
| C1—C9—H7 | 109.3 | C19—C20—H18A | 109.5 |
| C8—C9—H7 | 109.3 | C19—C20—H18B | 109.5 |
| C12—C8—C7 | 109.1 (2) | H18A—C20—H18B | 109.5 |
| C12—C8—C9 | 116.09 (19) | C19—C20—H18C | 109.5 |
| C7—C8—C9 | 110.75 (19) | H18A—C20—H18C | 109.5 |
| C12—C8—C11 | 110.23 (19) | H18B—C20—H18C | 109.5 |
| C7—C8—C11 | 112.07 (19) | C15—C14—C19 | 119.7 (2) |
| C9—C8—C11 | 98.24 (18) | C15—C14—C11 | 119.4 (2) |
| C8—C7—S1 | 111.98 (16) | C19—C14—C11 | 120.8 (2) |
| C8—C7—H9A | 109.2 | N1—C10—H20A | 109.5 |
| S1—C7—H9A | 109.2 | N1—C10—H20B | 109.5 |
| C8—C7—H9B | 109.2 | H20A—C10—H20B | 109.5 |
| S1—C7—H9B | 109.2 | N1—C10—H20C | 109.5 |
| H9A—C7—H9B | 107.9 | H20A—C10—H20C | 109.5 |
| O1—C12—O2 | 123.6 (2) | H20B—C10—H20C | 109.5 |
| O1—C12—C8 | 123.8 (2) | C10—N1—O3 | 104.0 (2) |
| O2—C12—C8 | 112.5 (2) | C10—N1—C9 | 112.9 (2) |
| O2—C13—H11A | 109.5 | O3—N1—C9 | 104.98 (17) |
| O2—C13—H11B | 109.5 | C11—O3—N1 | 109.19 (17) |
| H11A—C13—H11B | 109.5 | C12—O2—C13 | 115.9 (2) |
| O2—C13—H11C | 109.5 | C6—S1—C7 | 101.32 (12) |
| H11A—C13—H11C | 109.5 | ||
| C1—C6—C5—C4 | −0.6 (4) | C9—C8—C11—O3 | −40.3 (2) |
| S1—C6—C5—C4 | 175.2 (2) | C12—C8—C11—C14 | 77.5 (3) |
| C6—C5—C4—C3 | −0.9 (5) | C7—C8—C11—C14 | −44.3 (3) |
| C5—C4—C3—C2 | 1.0 (5) | C9—C8—C11—C14 | −160.7 (2) |
| C4—C3—C2—C1 | 0.5 (5) | C14—C15—C16—C17 | −0.7 (4) |
| C3—C2—C1—C6 | −2.0 (4) | C15—C16—C17—C18 | −1.0 (5) |
| C3—C2—C1—C9 | 177.3 (2) | C16—C17—C18—C19 | 1.1 (5) |
| C5—C6—C1—C2 | 2.0 (4) | C17—C18—C19—C14 | 0.6 (4) |
| S1—C6—C1—C2 | −173.48 (18) | C17—C18—C19—C20 | −178.4 (3) |
| C5—C6—C1—C9 | −177.2 (2) | C16—C15—C14—C19 | 2.3 (4) |
| S1—C6—C1—C9 | 7.3 (3) | C16—C15—C14—C11 | −177.7 (2) |
| C2—C1—C9—N1 | −82.6 (3) | C18—C19—C14—C15 | −2.2 (4) |
| C6—C1—C9—N1 | 96.7 (3) | C20—C19—C14—C15 | 176.6 (3) |
| C2—C1—C9—C8 | 162.6 (2) | C18—C19—C14—C11 | 177.8 (2) |
| C6—C1—C9—C8 | −18.1 (3) | C20—C19—C14—C11 | −3.3 (4) |
| N1—C9—C8—C12 | 163.35 (19) | O3—C11—C14—C15 | −34.3 (3) |
| C1—C9—C8—C12 | −77.5 (3) | C8—C11—C14—C15 | 83.1 (3) |
| N1—C9—C8—C7 | −71.5 (2) | O3—C11—C14—C19 | 145.6 (2) |
| C1—C9—C8—C7 | 47.7 (3) | C8—C11—C14—C19 | −96.9 (3) |
| N1—C9—C8—C11 | 46.0 (2) | C1—C9—N1—C10 | 86.3 (3) |
| C1—C9—C8—C11 | 165.10 (19) | C8—C9—N1—C10 | −148.7 (2) |
| C12—C8—C7—S1 | 64.2 (2) | C1—C9—N1—O3 | −161.01 (19) |
| C9—C8—C7—S1 | −64.8 (2) | C8—C9—N1—O3 | −36.0 (2) |
| C11—C8—C7—S1 | −173.41 (16) | C14—C11—O3—N1 | 145.05 (19) |
| C7—C8—C12—O1 | 32.1 (3) | C8—C11—O3—N1 | 19.5 (2) |
| C9—C8—C12—O1 | 158.1 (2) | C10—N1—O3—C11 | 129.1 (2) |
| C11—C8—C12—O1 | −91.4 (3) | C9—N1—O3—C11 | 10.3 (2) |
| C7—C8—C12—O2 | −151.3 (2) | O1—C12—O2—C13 | 2.2 (5) |
| C9—C8—C12—O2 | −25.3 (3) | C8—C12—O2—C13 | −174.4 (3) |
| C11—C8—C12—O2 | 85.2 (3) | C5—C6—S1—C7 | 163.25 (19) |
| C12—C8—C11—O3 | −162.1 (2) | C1—C6—S1—C7 | −21.1 (2) |
| C7—C8—C11—O3 | 76.1 (2) | C8—C7—S1—C6 | 48.96 (19) |
References
- Almerico, A. M., Diana, P., Barraja, P., Dattolo, G., Mingoia, F., Loi, A. G., Scintu, F., Milia, C., Puddu, I. & La Colla, P. (1998). Farmaco, 53, 33–40. [DOI] [PubMed]
- Bruker (2008). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
- Caine, B. & Koob, G. F. (1993). Science, 260, 1814–1816. [DOI] [PubMed]
- Dannhardt, G., Kiefer, W., Krämer, G., Maehrlein, S., Nowe, U. & Fiebich, B. (2000). Eur. J. Med. Chem. 35, 499–510. [DOI] [PubMed]
- Evans, M. A., Smith, D. C., Holub, J. M., Argenti, A., Hoff, M., Dalglish, G. A., Wilson, D. L., Taylor, B. M., Berkowitz, J. D., Burnham, B. S., Krumpe, K., Gupton, J. T., Scarlett, T. C., Durham, R. W. Jr & Hall, I. H. (2003). Arch. Pharm. Pharm. Med. Chem. 336, 181–190. [DOI] [PubMed]
- Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
- Gangadharan, R., SethuSankar, K., Murugan, G. & Bakthadoss, M. (2011). Acta Cryst. E67, o942. [DOI] [PMC free article] [PubMed]
- Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. [DOI] [PubMed]
- Holub, J. M., O’Toole-Colin, K., Getzel, A., Argenti, A., Evans, M. A., Smith, D. C., Dalglish, G. A., Rifat, S., Wilson, D. L., Taylor, B. M., Miott, U., Glersaye, J., Suet Lam, K., McCranor, B. J., Berkowitz, J. D., Miller, R. B., Lukens, J. R., Krumpe, K., Gupton, J. T. & Burnham, B. S. (2004). Molecules, 9, 135–157. [DOI] [PMC free article] [PubMed]
- Howe, R. K. & Shelton, B. R. (1990). J. Org. Chem. 55, 4603–4607.
- Kozikowski, A. P. (1984). Acc. Chem. Res. 17, 410–416.
- Krowicki, K., Balzarini, J., De Clercq, E., Newman, R. A. & Lown, J. W. (1988). J. Med. Chem. 31, 341–345. [DOI] [PubMed]
- Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.
- Muchowski, J. M., Unger, S. H., Ackrell, J., Cheung, P., Cook, J., Gallegra, P., Halpern, O., Koehler, R. & Kluge, A. F. (1985). J. Med. Chem. 28, 1037–1049. [DOI] [PubMed]
- Nardelli, M. (1983). Acta Cryst. C39, 1141–1142.
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
- Spek, A. L. (2009). Acta Cryst. D65, 148–155. [DOI] [PMC free article] [PubMed]
- Toja, E., Depaoli, A., Tuan, G. & Kettenring, J. (1987). Synthesis, pp. 272–274.
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, I, II, III. DOI: 10.1107/S2056989015008063/su5106sup1.cif
e-71-00574-sup1.cif (61.1KB, cif)
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008063/su5106Isup2.hkl
e-71-00574-Isup2.hkl (177.3KB, hkl)
Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989015008063/su5106IIsup3.hkl
e-71-00574-IIsup3.hkl (157.5KB, hkl)
Structure factors: contains datablock(s) III. DOI: 10.1107/S2056989015008063/su5106IIIsup4.hkl
e-71-00574-IIIsup4.hkl (154.7KB, hkl)
Click here for additional data file. (7.7KB, cml)
Supporting information file. DOI: 10.1107/S2056989015008063/su5106Isup5.cml
Click here for additional data file. (7.2KB, cml)
Supporting information file. DOI: 10.1107/S2056989015008063/su5106IIsup6.cml
Click here for additional data file. (7KB, cml)
Supporting information file. DOI: 10.1107/S2056989015008063/su5106IIIsup7.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report