In the structures of 2-(4-chlorophenyl)-4-(2-hydroxyphenyl)-2,3-dihydro-1,5-benzothiazepine, C21H16ClNOS, 4-(2-hydroxyphenyl)-2-(4-tolyl)-2,3-dihydro-1,5-benzothiazepine, C22H19NOS, and 4-(2-hydroxyphenyl)-2-(3-methoxyphenyl)-2,3-dihydro-1,5-benzothiazepine, C22H19NO2S, the central seven-membered heterocyclic rings adopt twist-boat conformations in which the N atoms are involved in strong intramolecular hydrogen bonds with the hydroxyl H atoms, resulting in six-membered rings.
Supporting information
CCDC references: 214392; 214393; 214394
Syntheses of the chalcones, (III), were carried out according to the procedures described by Furniss et al. (1989). Aqueous solutions of NaOH (60.0 ml, 4.0 M) were added to rectified spirit (35.0 ml) in conical flasks fitted with mechanical stirrers. The flasks were cooled in an ice bath and freshly distilled o-hydroxy acetophenone, (I), (0.01 mol) was added to each. To these solutions were added, while stirring, substituted benzaldehydes, (II), (0.01 mol). The temperature was kept at about 298 K and the reaction mixtures were stirred vigorously for 2–3 h until the mixtures became thick. The reaction mixtures were kept at 273–277 K overnight. The solid masses thus obtained were neutralized with HCl, and the precipitates separated were crystallized from equeous ethanol. The benzothiazepine derivatives (IVa)–(IVc) were synthesized according to the procedure reported by Svetlik et al. (1989). To the corresponding solutions of chalcones, (III), (0.02 mol) in dry methanol (100–150 ml), which were acidified by adding conconcentrated HCl (five drops), was added o-amino thiophenol (0.02 mol). The mixtures were refluxed until crystalline solids separated out. After cooling, solid benzothiazepine derivatives were collected, washed with ether and cold methanol, and recrystallized from aqueous ethanol.
For the three structures, the H atoms were located from difference Fourier syntheses and were included in the refinements at idealized positions, with C—H distances of 0.95–1.00 and an O—H distance of 0.84 Å and with isotropic thermal displacement parameters of 1.5 (hydroxyl H atoms) or 1.2 (the remaining H atoms) times the equivalent thermal displacement parameters of the parent atoms. The methyl H atoms in (IVb) were disordered over six sites and were included in the refinement using the DFIX 123 command in SHELXL97. The final difference maps were free of any chemically significant features.
For all compounds, data collection: COLLECT (Hooft, 1998); cell refinement: HKL DENZO (Otwinowski & Minor, 1997). Data reduction: HKL SCALEPACK (Otwinowski & Minor, 1997) for (IVa); SCALEPACK (Otwinowski & Minor, 1997) for (IVb), (IVc). For all compounds, program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
(IVa) 2-(4-chlorophenyl)-4-(2-hydroxylphenyl)-2-phenyl-2,3-dihydro-1,5- benzothiazepine
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Crystal data top
C21H16ClNOS | F(000) = 760 |
Mr = 365.86 | Dx = 1.419 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9054 reflections |
a = 18.036 (9) Å | θ = 4.1–25.0° |
b = 4.836 (2) Å | µ = 0.35 mm−1 |
c = 19.790 (11) Å | T = 173 K |
β = 97.02 (2)° | Needle, yellow |
V = 1713.2 (15) Å3 | 0.15 × 0.08 × 0.06 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD Area Detector diffractometer | 2987 independent reflections |
Radiation source: fine-focus sealed tube | 2093 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ω and ϕ scans | θmax = 25.0°, θmin = 4.1° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −21→20 |
Tmin = 0.901, Tmax = 0.982 | k = −5→5 |
9054 measured reflections | l = −23→23 |
Refinement top
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.058P)2] where P = (Fo2 + 2Fc2)/3 |
2987 reflections | (Δ/σ)max = 0.001 |
227 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
C21H16ClNOS | V = 1713.2 (15) Å3 |
Mr = 365.86 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.036 (9) Å | µ = 0.35 mm−1 |
b = 4.836 (2) Å | T = 173 K |
c = 19.790 (11) Å | 0.15 × 0.08 × 0.06 mm |
β = 97.02 (2)° | |
Data collection top
Nonius KappaCCD Area Detector diffractometer | 2987 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 2093 reflections with I > 2σ(I) |
Tmin = 0.901, Tmax = 0.982 | Rint = 0.064 |
9054 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.21 e Å−3 |
2987 reflections | Δρmin = −0.32 e Å−3 |
227 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.89138 (13) | 0.3863 (5) | 0.59156 (12) | 0.0292 (6) | |
C2 | 0.85176 (13) | 0.3364 (5) | 0.64726 (13) | 0.0289 (6) | |
S3 | 0.78231 (3) | 0.07528 (13) | 0.64579 (3) | 0.0319 (2) | |
C4 | 0.70901 (13) | 0.1897 (5) | 0.57907 (13) | 0.0293 (6) | |
H4 | 0.6878 | 0.0189 | 0.5557 | 0.035* | |
C5 | 0.74426 (13) | 0.3586 (5) | 0.52527 (13) | 0.0307 (6) | |
H5A | 0.7058 | 0.3970 | 0.4863 | 0.037* | |
H5B | 0.7620 | 0.5379 | 0.5452 | 0.037* | |
C6 | 0.80873 (13) | 0.2076 (5) | 0.50029 (13) | 0.0293 (6) | |
N7 | 0.87641 (11) | 0.2375 (4) | 0.52969 (10) | 0.0307 (5) | |
C8 | 0.95000 (14) | 0.5748 (5) | 0.59769 (13) | 0.0333 (6) | |
H8 | 0.9772 | 0.6067 | 0.5602 | 0.040* | |
C9 | 0.96897 (14) | 0.7162 (5) | 0.65808 (14) | 0.0345 (6) | |
H9 | 1.0079 | 0.8494 | 0.6614 | 0.041* | |
C10 | 0.93128 (14) | 0.6641 (5) | 0.71396 (14) | 0.0346 (6) | |
H10 | 0.9453 | 0.7583 | 0.7557 | 0.041* | |
C11 | 0.87314 (14) | 0.4741 (5) | 0.70867 (13) | 0.0324 (6) | |
H11 | 0.8477 | 0.4374 | 0.7470 | 0.039* | |
C12 | 0.64449 (13) | 0.3399 (5) | 0.60472 (13) | 0.0302 (6) | |
C13 | 0.57203 (14) | 0.2881 (6) | 0.57518 (14) | 0.0405 (7) | |
H13 | 0.5638 | 0.1559 | 0.5396 | 0.049* | |
C14 | 0.51160 (15) | 0.4246 (6) | 0.59638 (15) | 0.0442 (7) | |
H14 | 0.4623 | 0.3870 | 0.5756 | 0.053* | |
C15 | 0.52385 (14) | 0.6161 (6) | 0.64814 (14) | 0.0371 (7) | |
C16 | 0.59512 (14) | 0.6760 (5) | 0.67793 (14) | 0.0364 (6) | |
H16 | 0.6031 | 0.8114 | 0.7128 | 0.044* | |
C17 | 0.65493 (13) | 0.5363 (5) | 0.65639 (13) | 0.0326 (6) | |
H17 | 0.7041 | 0.5753 | 0.6773 | 0.039* | |
C18 | 0.79630 (14) | 0.0132 (5) | 0.44247 (12) | 0.0296 (6) | |
C19 | 0.72434 (14) | −0.0415 (6) | 0.41025 (13) | 0.0369 (6) | |
H19 | 0.6833 | 0.0567 | 0.4244 | 0.044* | |
C20 | 0.71120 (16) | −0.2336 (6) | 0.35868 (13) | 0.0417 (7) | |
H20 | 0.6619 | −0.2660 | 0.3374 | 0.050* | |
C21 | 0.77109 (17) | −0.3793 (6) | 0.33824 (14) | 0.0425 (7) | |
H21 | 0.7625 | −0.5134 | 0.3031 | 0.051* | |
C22 | 0.84269 (16) | −0.3304 (6) | 0.36864 (14) | 0.0406 (7) | |
H22 | 0.8832 | −0.4308 | 0.3542 | 0.049* | |
C23 | 0.85631 (14) | −0.1354 (5) | 0.42036 (13) | 0.0325 (6) | |
O24 | 0.92787 (9) | −0.0941 (4) | 0.44721 (9) | 0.0414 (5) | |
H24 | 0.9291 | 0.0131 | 0.4807 | 0.062* | |
Cl25 | 0.44800 (4) | 0.78184 (17) | 0.67724 (4) | 0.0541 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0245 (13) | 0.0320 (14) | 0.0307 (14) | 0.0054 (11) | 0.0023 (10) | −0.0001 (11) |
C2 | 0.0229 (13) | 0.0306 (14) | 0.0324 (14) | 0.0038 (10) | −0.0002 (11) | 0.0041 (11) |
S3 | 0.0287 (4) | 0.0313 (4) | 0.0349 (4) | 0.0005 (3) | 0.0007 (3) | 0.0059 (3) |
C4 | 0.0288 (13) | 0.0289 (14) | 0.0295 (14) | 0.0014 (11) | 0.0005 (11) | −0.0023 (11) |
C5 | 0.0300 (13) | 0.0316 (14) | 0.0297 (14) | 0.0035 (11) | 0.0007 (11) | 0.0014 (11) |
C6 | 0.0288 (13) | 0.0291 (14) | 0.0299 (14) | 0.0034 (11) | 0.0036 (11) | 0.0049 (11) |
N7 | 0.0287 (11) | 0.0334 (12) | 0.0303 (12) | −0.0017 (9) | 0.0043 (9) | −0.0003 (10) |
C8 | 0.0284 (13) | 0.0352 (15) | 0.0361 (15) | 0.0010 (12) | 0.0034 (11) | 0.0042 (12) |
C9 | 0.0271 (13) | 0.0341 (15) | 0.0414 (16) | −0.0015 (11) | 0.0005 (12) | −0.0021 (13) |
C10 | 0.0325 (14) | 0.0328 (15) | 0.0364 (16) | 0.0048 (12) | −0.0036 (12) | −0.0007 (12) |
C11 | 0.0323 (14) | 0.0327 (15) | 0.0315 (15) | 0.0063 (12) | 0.0014 (11) | 0.0043 (12) |
C12 | 0.0290 (13) | 0.0303 (14) | 0.0311 (15) | −0.0010 (11) | 0.0023 (11) | 0.0049 (11) |
C13 | 0.0308 (15) | 0.0483 (17) | 0.0406 (17) | 0.0020 (13) | −0.0028 (12) | −0.0065 (13) |
C14 | 0.0260 (14) | 0.0544 (19) | 0.0504 (18) | 0.0010 (13) | −0.0024 (12) | −0.0062 (15) |
C15 | 0.0282 (14) | 0.0394 (16) | 0.0449 (17) | 0.0061 (12) | 0.0091 (12) | 0.0039 (13) |
C16 | 0.0375 (15) | 0.0354 (15) | 0.0370 (16) | 0.0015 (12) | 0.0072 (12) | −0.0016 (12) |
C17 | 0.0227 (13) | 0.0344 (15) | 0.0407 (16) | −0.0021 (11) | 0.0033 (11) | −0.0006 (12) |
C18 | 0.0322 (14) | 0.0304 (14) | 0.0264 (14) | 0.0002 (11) | 0.0049 (11) | 0.0025 (11) |
C19 | 0.0358 (15) | 0.0433 (16) | 0.0315 (15) | 0.0032 (12) | 0.0040 (12) | −0.0002 (13) |
C20 | 0.0435 (16) | 0.0443 (17) | 0.0352 (16) | −0.0016 (13) | −0.0039 (13) | −0.0034 (14) |
C21 | 0.0585 (19) | 0.0412 (17) | 0.0277 (15) | −0.0022 (14) | 0.0052 (13) | −0.0048 (13) |
C22 | 0.0485 (17) | 0.0408 (16) | 0.0348 (16) | 0.0026 (13) | 0.0138 (13) | −0.0025 (13) |
C23 | 0.0349 (15) | 0.0362 (15) | 0.0274 (14) | −0.0007 (12) | 0.0077 (11) | 0.0064 (11) |
O24 | 0.0331 (10) | 0.0493 (12) | 0.0432 (12) | 0.0031 (9) | 0.0100 (8) | −0.0089 (9) |
Cl25 | 0.0342 (4) | 0.0629 (5) | 0.0673 (6) | 0.0121 (3) | 0.0146 (4) | −0.0054 (4) |
Geometric parameters (Å, º) top
C1—C8 | 1.390 (3) | C12—C17 | 1.391 (4) |
C1—C2 | 1.406 (4) | C13—C14 | 1.382 (4) |
C1—N7 | 1.418 (3) | C13—H13 | 0.9500 |
C2—C11 | 1.398 (3) | C14—C15 | 1.378 (4) |
C2—S3 | 1.776 (3) | C14—H14 | 0.9500 |
S3—C4 | 1.836 (2) | C15—C16 | 1.378 (4) |
C4—C12 | 1.511 (4) | C15—Cl25 | 1.743 (3) |
C4—C5 | 1.540 (4) | C16—C17 | 1.383 (4) |
C4—H4 | 1.0000 | C16—H16 | 0.9500 |
C5—C6 | 1.507 (3) | C17—H17 | 0.9500 |
C5—H5A | 0.9900 | C18—C19 | 1.400 (3) |
C5—H5B | 0.9900 | C18—C23 | 1.413 (4) |
C6—N7 | 1.295 (3) | C19—C20 | 1.379 (4) |
C6—C18 | 1.477 (3) | C19—H19 | 0.9500 |
C8—C9 | 1.383 (4) | C20—C21 | 1.390 (4) |
C8—H8 | 0.9500 | C20—H20 | 0.9500 |
C9—C10 | 1.390 (4) | C21—C22 | 1.377 (4) |
C9—H9 | 0.9500 | C21—H21 | 0.9500 |
C10—C11 | 1.389 (4) | C22—C23 | 1.391 (4) |
C10—H10 | 0.9500 | C22—H22 | 0.9500 |
C11—H11 | 0.9500 | C23—O24 | 1.349 (3) |
C12—C13 | 1.388 (3) | O24—H24 | 0.8400 |
| | | |
C8—C1—C2 | 119.9 (2) | C13—C12—C4 | 119.7 (2) |
C8—C1—N7 | 118.1 (2) | C17—C12—C4 | 122.3 (2) |
C2—C1—N7 | 121.9 (2) | C14—C13—C12 | 121.5 (3) |
C11—C2—C1 | 119.1 (2) | C14—C13—H13 | 119.2 |
C11—C2—S3 | 118.15 (19) | C12—C13—H13 | 119.2 |
C1—C2—S3 | 122.30 (19) | C15—C14—C13 | 119.0 (2) |
C2—S3—C4 | 103.99 (12) | C15—C14—H14 | 120.5 |
C12—C4—C5 | 112.2 (2) | C13—C14—H14 | 120.5 |
C12—C4—S3 | 114.81 (18) | C16—C15—C14 | 121.0 (2) |
C5—C4—S3 | 109.59 (17) | C16—C15—Cl25 | 119.4 (2) |
C12—C4—H4 | 106.6 | C14—C15—Cl25 | 119.6 (2) |
C5—C4—H4 | 106.6 | C15—C16—C17 | 119.2 (3) |
S3—C4—H4 | 106.6 | C15—C16—H16 | 120.4 |
C6—C5—C4 | 111.7 (2) | C17—C16—H16 | 120.4 |
C6—C5—H5A | 109.3 | C16—C17—C12 | 121.3 (2) |
C4—C5—H5A | 109.3 | C16—C17—H17 | 119.4 |
C6—C5—H5B | 109.3 | C12—C17—H17 | 119.4 |
C4—C5—H5B | 109.3 | C19—C18—C23 | 117.8 (2) |
H5A—C5—H5B | 107.9 | C19—C18—C6 | 121.2 (2) |
N7—C6—C18 | 117.7 (2) | C23—C18—C6 | 121.0 (2) |
N7—C6—C5 | 121.4 (2) | C20—C19—C18 | 122.0 (2) |
C18—C6—C5 | 120.8 (2) | C20—C19—H19 | 119.0 |
C6—N7—C1 | 121.0 (2) | C18—C19—H19 | 119.0 |
C9—C8—C1 | 120.3 (2) | C19—C20—C21 | 119.2 (2) |
C9—C8—H8 | 119.8 | C19—C20—H20 | 120.4 |
C1—C8—H8 | 119.8 | C21—C20—H20 | 120.4 |
C8—C9—C10 | 120.3 (2) | C22—C21—C20 | 120.4 (2) |
C8—C9—H9 | 119.9 | C22—C21—H21 | 119.8 |
C10—C9—H9 | 119.9 | C20—C21—H21 | 119.8 |
C11—C10—C9 | 119.9 (2) | C21—C22—C23 | 120.6 (3) |
C11—C10—H10 | 120.1 | C21—C22—H22 | 119.7 |
C9—C10—H10 | 120.1 | C23—C22—H22 | 119.7 |
C10—C11—C2 | 120.4 (2) | O24—C23—C22 | 117.7 (2) |
C10—C11—H11 | 119.8 | O24—C23—C18 | 122.3 (2) |
C2—C11—H11 | 119.8 | C22—C23—C18 | 120.0 (2) |
C13—C12—C17 | 117.9 (2) | C23—O24—H24 | 109.5 |
| | | |
C8—C1—C2—C11 | −1.3 (3) | S3—C4—C12—C17 | 42.2 (3) |
N7—C1—C2—C11 | 174.9 (2) | C17—C12—C13—C14 | −0.5 (4) |
C8—C1—C2—S3 | −173.85 (19) | C4—C12—C13—C14 | −178.9 (3) |
N7—C1—C2—S3 | 2.3 (3) | C12—C13—C14—C15 | −0.1 (4) |
C11—C2—S3—C4 | 122.96 (19) | C13—C14—C15—C16 | 1.1 (4) |
C1—C2—S3—C4 | −64.4 (2) | C13—C14—C15—Cl25 | −178.0 (2) |
C2—S3—C4—C12 | −97.9 (2) | C14—C15—C16—C17 | −1.5 (4) |
C2—S3—C4—C5 | 29.3 (2) | Cl25—C15—C16—C17 | 177.6 (2) |
C12—C4—C5—C6 | 179.7 (2) | C15—C16—C17—C12 | 0.9 (4) |
S3—C4—C5—C6 | 51.0 (2) | C13—C12—C17—C16 | 0.1 (4) |
C4—C5—C6—N7 | −90.1 (3) | C4—C12—C17—C16 | 178.5 (2) |
C4—C5—C6—C18 | 88.0 (3) | N7—C6—C18—C19 | 176.6 (2) |
C18—C6—N7—C1 | −170.2 (2) | C5—C6—C18—C19 | −1.5 (4) |
C5—C6—N7—C1 | 7.9 (3) | N7—C6—C18—C23 | 0.2 (4) |
C8—C1—N7—C6 | −135.1 (2) | C5—C6—C18—C23 | −177.9 (2) |
C2—C1—N7—C6 | 48.7 (3) | C23—C18—C19—C20 | 0.1 (4) |
C2—C1—C8—C9 | −0.8 (4) | C6—C18—C19—C20 | −176.4 (2) |
N7—C1—C8—C9 | −177.1 (2) | C18—C19—C20—C21 | 0.5 (4) |
C1—C8—C9—C10 | 2.2 (4) | C19—C20—C21—C22 | −0.6 (4) |
C8—C9—C10—C11 | −1.5 (4) | C20—C21—C22—C23 | 0.2 (4) |
C9—C10—C11—C2 | −0.6 (4) | C21—C22—C23—O24 | −178.9 (2) |
C1—C2—C11—C10 | 2.0 (3) | C21—C22—C23—C18 | 0.4 (4) |
S3—C2—C11—C10 | 174.86 (18) | C19—C18—C23—O24 | 178.7 (2) |
C5—C4—C12—C13 | 94.6 (3) | C6—C18—C23—O24 | −4.8 (4) |
S3—C4—C12—C13 | −139.4 (2) | C19—C18—C23—C22 | −0.6 (4) |
C5—C4—C12—C17 | −83.7 (3) | C6—C18—C23—C22 | 175.9 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O24—H24···N7 | 0.84 | 1.80 | 2.543 (3) | 146 |
(IVb) 4-(2-hydroxylphenyl)-2-phenyl-2-(4-tolyl)-2,3-dihydro-1,5-benzothiazepine
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Crystal data top
C22H19NOS | F(000) = 728 |
Mr = 345.44 | Dx = 1.335 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8207 reflections |
a = 4.8678 (11) Å | θ = 3.6–30.0° |
b = 17.563 (3) Å | µ = 0.20 mm−1 |
c = 20.129 (5) Å | T = 173 K |
β = 93.078 (8)° | Needle, yellow |
V = 1718.4 (6) Å3 | 0.22 × 0.12 × 0.08 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD Area Detector diffractometer | 4972 independent reflections |
Radiation source: fine-focus sealed tube | 3195 reflections with I > 2.0σ(I) |
Graphite monochromator | Rint = 0.037 |
ω and ϕ scans | θmax = 30.0°, θmin = 3.6° |
Absorption correction: multi-scan SORTAV: (Blessing, 1997) | h = −6→6 |
Tmin = 0.906, Tmax = 0.988 | k = −21→24 |
8207 measured reflections | l = −28→28 |
Refinement top
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) = 0.121 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.2349P] where P = (Fo2 + 2Fc2)/3 |
4972 reflections | (Δ/σ)max = 0.001 |
228 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
C22H19NOS | V = 1718.4 (6) Å3 |
Mr = 345.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.8678 (11) Å | µ = 0.20 mm−1 |
b = 17.563 (3) Å | T = 173 K |
c = 20.129 (5) Å | 0.22 × 0.12 × 0.08 mm |
β = 93.078 (8)° | |
Data collection top
Nonius KappaCCD Area Detector diffractometer | 4972 independent reflections |
Absorption correction: multi-scan SORTAV: (Blessing, 1997) | 3195 reflections with I > 2.0σ(I) |
Tmin = 0.906, Tmax = 0.988 | Rint = 0.037 |
8207 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.23 e Å−3 |
4972 reflections | Δρmin = −0.32 e Å−3 |
228 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S3 | 0.75407 (8) | 0.97332 (2) | 0.76225 (2) | 0.02867 (12) | |
O24 | 0.4199 (2) | 1.08023 (7) | 0.53490 (6) | 0.0372 (3) | |
H24 | 0.5355 | 1.0484 | 0.5502 | 0.056* | |
N7 | 0.7929 (3) | 1.02570 (7) | 0.61496 (7) | 0.0286 (3) | |
C1 | 0.9544 (3) | 0.96218 (8) | 0.63529 (8) | 0.0275 (4) | |
C2 | 0.9610 (3) | 0.93421 (8) | 0.70116 (8) | 0.0261 (3) | |
C4 | 0.8922 (3) | 1.07002 (8) | 0.77382 (8) | 0.0248 (3) | |
H4 | 0.7334 | 1.1038 | 0.7830 | 0.030* | |
C5 | 1.0070 (3) | 1.09768 (8) | 0.70857 (7) | 0.0241 (3) | |
H5A | 1.0568 | 1.1522 | 0.7130 | 0.029* | |
H5B | 1.1766 | 1.0689 | 0.7003 | 0.029* | |
C6 | 0.8036 (3) | 1.08796 (8) | 0.64949 (8) | 0.0255 (3) | |
C8 | 1.1034 (4) | 0.92505 (9) | 0.58796 (9) | 0.0337 (4) | |
H8 | 1.0946 | 0.9429 | 0.5433 | 0.040* | |
C9 | 1.2640 (4) | 0.86245 (10) | 0.60509 (9) | 0.0372 (4) | |
H9 | 1.3693 | 0.8386 | 0.5726 | 0.045* | |
C10 | 1.2719 (4) | 0.83440 (9) | 0.66957 (9) | 0.0357 (4) | |
H10 | 1.3813 | 0.7911 | 0.6812 | 0.043* | |
C11 | 1.1193 (3) | 0.86986 (8) | 0.71693 (8) | 0.0300 (4) | |
H11 | 1.1227 | 0.8500 | 0.7609 | 0.036* | |
C12 | 1.1067 (3) | 1.08076 (9) | 0.83093 (8) | 0.0261 (3) | |
C13 | 1.1624 (4) | 1.15475 (10) | 0.85255 (9) | 0.0356 (4) | |
H13 | 1.0621 | 1.1959 | 0.8325 | 0.043* | |
C14 | 1.3616 (4) | 1.16946 (10) | 0.90279 (9) | 0.0415 (4) | |
H14 | 1.3929 | 1.2204 | 0.9172 | 0.050* | |
C15 | 1.5161 (3) | 1.11078 (11) | 0.93230 (8) | 0.0385 (4) | |
C16 | 1.4609 (4) | 1.03739 (11) | 0.91070 (9) | 0.0381 (4) | |
H16 | 1.5636 | 0.9963 | 0.9302 | 0.046* | |
C17 | 1.2574 (3) | 1.02219 (9) | 0.86084 (8) | 0.0310 (4) | |
H17 | 1.2223 | 0.9711 | 0.8474 | 0.037* | |
C18 | 0.6112 (3) | 1.14960 (8) | 0.63026 (8) | 0.0254 (3) | |
C19 | 0.5986 (3) | 1.21651 (9) | 0.66801 (8) | 0.0302 (4) | |
H19 | 0.7206 | 1.2224 | 0.7061 | 0.036* | |
C20 | 0.4140 (4) | 1.27421 (9) | 0.65152 (9) | 0.0353 (4) | |
H20 | 0.4087 | 1.3188 | 0.6781 | 0.042* | |
C21 | 0.2370 (4) | 1.26611 (10) | 0.59573 (9) | 0.0388 (4) | |
H21 | 0.1103 | 1.3056 | 0.5838 | 0.047* | |
C22 | 0.2431 (3) | 1.20111 (10) | 0.55730 (9) | 0.0372 (4) | |
H22 | 0.1210 | 1.1964 | 0.5191 | 0.045* | |
C23 | 0.4259 (3) | 1.14234 (9) | 0.57384 (8) | 0.0287 (4) | |
C25 | 1.7345 (4) | 1.12760 (13) | 0.98684 (9) | 0.0541 (6) | |
H25A | 1.7426 | 1.1826 | 0.9950 | 0.081* | 0.50 |
H25B | 1.9136 | 1.1098 | 0.9731 | 0.081* | 0.50 |
H25C | 1.6886 | 1.1013 | 1.0277 | 0.081* | 0.50 |
H25D | 1.8206 | 1.0799 | 1.0022 | 0.081* | 0.50 |
H25E | 1.6496 | 1.1526 | 1.0241 | 0.081* | 0.50 |
H25F | 1.8746 | 1.1612 | 0.9695 | 0.081* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S3 | 0.0290 (2) | 0.0248 (2) | 0.0324 (2) | −0.00593 (16) | 0.00292 (16) | −0.00182 (16) |
O24 | 0.0432 (7) | 0.0354 (6) | 0.0317 (7) | 0.0064 (5) | −0.0106 (5) | −0.0039 (5) |
N7 | 0.0311 (7) | 0.0258 (7) | 0.0284 (7) | 0.0027 (6) | −0.0029 (6) | −0.0014 (6) |
C1 | 0.0287 (8) | 0.0236 (7) | 0.0294 (9) | −0.0008 (6) | −0.0048 (7) | −0.0024 (6) |
C2 | 0.0264 (8) | 0.0220 (7) | 0.0297 (9) | −0.0034 (6) | −0.0015 (6) | −0.0023 (6) |
C4 | 0.0251 (7) | 0.0210 (7) | 0.0280 (8) | −0.0018 (6) | −0.0020 (6) | −0.0012 (6) |
C5 | 0.0241 (7) | 0.0217 (7) | 0.0262 (8) | −0.0009 (6) | −0.0017 (6) | 0.0003 (6) |
C6 | 0.0257 (8) | 0.0245 (8) | 0.0259 (8) | −0.0016 (6) | −0.0014 (6) | 0.0022 (6) |
C8 | 0.0435 (10) | 0.0282 (8) | 0.0292 (9) | 0.0038 (7) | −0.0009 (8) | −0.0013 (7) |
C9 | 0.0450 (10) | 0.0292 (8) | 0.0378 (10) | 0.0075 (8) | 0.0051 (8) | −0.0043 (7) |
C10 | 0.0385 (9) | 0.0250 (8) | 0.0432 (11) | 0.0051 (7) | −0.0020 (8) | 0.0021 (7) |
C11 | 0.0358 (9) | 0.0226 (8) | 0.0312 (9) | −0.0028 (7) | −0.0022 (7) | 0.0015 (7) |
C12 | 0.0254 (8) | 0.0299 (8) | 0.0230 (8) | −0.0032 (6) | 0.0012 (6) | 0.0005 (6) |
C13 | 0.0432 (10) | 0.0294 (9) | 0.0337 (10) | −0.0062 (7) | −0.0038 (8) | 0.0012 (7) |
C14 | 0.0486 (11) | 0.0421 (10) | 0.0332 (10) | −0.0178 (9) | −0.0024 (8) | −0.0053 (8) |
C15 | 0.0321 (9) | 0.0597 (12) | 0.0235 (9) | −0.0124 (8) | 0.0001 (7) | −0.0014 (8) |
C16 | 0.0328 (9) | 0.0521 (11) | 0.0290 (9) | 0.0025 (8) | −0.0030 (7) | 0.0032 (8) |
C17 | 0.0308 (8) | 0.0334 (9) | 0.0287 (9) | 0.0007 (7) | 0.0003 (7) | −0.0007 (7) |
C18 | 0.0252 (8) | 0.0251 (7) | 0.0258 (8) | −0.0006 (6) | −0.0009 (6) | 0.0028 (6) |
C19 | 0.0314 (9) | 0.0261 (8) | 0.0325 (9) | 0.0004 (7) | −0.0036 (7) | −0.0006 (7) |
C20 | 0.0375 (9) | 0.0270 (8) | 0.0413 (10) | 0.0036 (7) | −0.0002 (8) | −0.0027 (7) |
C21 | 0.0342 (9) | 0.0345 (9) | 0.0470 (11) | 0.0091 (7) | −0.0031 (8) | 0.0059 (8) |
C22 | 0.0352 (9) | 0.0393 (10) | 0.0361 (10) | 0.0041 (8) | −0.0090 (8) | 0.0069 (8) |
C23 | 0.0300 (8) | 0.0303 (8) | 0.0257 (9) | −0.0011 (7) | −0.0004 (7) | 0.0022 (7) |
C25 | 0.0434 (11) | 0.0857 (16) | 0.0322 (11) | −0.0225 (11) | −0.0087 (9) | −0.0034 (10) |
Geometric parameters (Å, º) top
S3—C2 | 1.7696 (17) | C13—C14 | 1.387 (2) |
S3—C4 | 1.8368 (15) | C13—H13 | 0.9500 |
O24—C23 | 1.3427 (19) | C14—C15 | 1.390 (3) |
O24—H24 | 0.8400 | C14—H14 | 0.9500 |
N7—C6 | 1.2952 (19) | C15—C16 | 1.382 (3) |
N7—C1 | 1.4128 (19) | C15—C25 | 1.516 (2) |
C1—C8 | 1.390 (2) | C16—C17 | 1.397 (2) |
C1—C2 | 1.413 (2) | C16—H16 | 0.9500 |
C2—C11 | 1.395 (2) | C17—H17 | 0.9500 |
C4—C12 | 1.523 (2) | C18—C19 | 1.403 (2) |
C4—C5 | 1.534 (2) | C18—C23 | 1.418 (2) |
C4—H4 | 1.0000 | C19—C20 | 1.383 (2) |
C5—C6 | 1.516 (2) | C19—H19 | 0.9500 |
C5—H5A | 0.9900 | C20—C21 | 1.386 (2) |
C5—H5B | 0.9900 | C20—H20 | 0.9500 |
C6—C18 | 1.470 (2) | C21—C22 | 1.380 (2) |
C8—C9 | 1.382 (2) | C21—H21 | 0.9500 |
C8—H8 | 0.9500 | C22—C23 | 1.392 (2) |
C9—C10 | 1.387 (2) | C22—H22 | 0.9500 |
C9—H9 | 0.9500 | C25—H25A | 0.9800 |
C10—C11 | 1.387 (2) | C25—H25B | 0.9800 |
C10—H10 | 0.9500 | C25—H25C | 0.9800 |
C11—H11 | 0.9500 | C25—H25D | 0.9800 |
C12—C17 | 1.383 (2) | C25—H25E | 0.9800 |
C12—C13 | 1.392 (2) | C25—H25F | 0.9800 |
| | | |
C2—S3—C4 | 103.23 (7) | C14—C15—C25 | 120.50 (18) |
C23—O24—H24 | 109.5 | C15—C16—C17 | 121.49 (17) |
C6—N7—C1 | 120.37 (13) | C15—C16—H16 | 119.3 |
C8—C1—C2 | 119.59 (14) | C17—C16—H16 | 119.3 |
C8—C1—N7 | 118.32 (14) | C12—C17—C16 | 120.65 (15) |
C2—C1—N7 | 122.05 (14) | C12—C17—H17 | 119.7 |
C11—C2—C1 | 118.67 (15) | C16—C17—H17 | 119.7 |
C11—C2—S3 | 118.97 (13) | C19—C18—C23 | 117.71 (14) |
C1—C2—S3 | 122.16 (12) | C19—C18—C6 | 121.35 (14) |
C12—C4—C5 | 109.91 (12) | C23—C18—C6 | 120.92 (14) |
C12—C4—S3 | 116.21 (10) | C20—C19—C18 | 122.05 (15) |
C5—C4—S3 | 109.39 (10) | C20—C19—H19 | 119.0 |
C12—C4—H4 | 107.0 | C18—C19—H19 | 119.0 |
C5—C4—H4 | 107.0 | C19—C20—C21 | 119.15 (16) |
S3—C4—H4 | 107.0 | C19—C20—H20 | 120.4 |
C6—C5—C4 | 112.55 (12) | C21—C20—H20 | 120.4 |
C6—C5—H5A | 109.1 | C22—C21—C20 | 120.52 (16) |
C4—C5—H5A | 109.1 | C22—C21—H21 | 119.7 |
C6—C5—H5B | 109.1 | C20—C21—H21 | 119.7 |
C4—C5—H5B | 109.1 | C21—C22—C23 | 120.81 (15) |
H5A—C5—H5B | 107.8 | C21—C22—H22 | 119.6 |
N7—C6—C18 | 118.29 (13) | C23—C22—H22 | 119.6 |
N7—C6—C5 | 121.45 (13) | O24—C23—C22 | 117.99 (14) |
C18—C6—C5 | 120.26 (13) | O24—C23—C18 | 122.26 (14) |
C9—C8—C1 | 120.73 (16) | C22—C23—C18 | 119.75 (15) |
C9—C8—H8 | 119.6 | C15—C25—H25A | 109.5 |
C1—C8—H8 | 119.6 | C15—C25—H25B | 109.5 |
C8—C9—C10 | 120.20 (17) | H25A—C25—H25B | 109.5 |
C8—C9—H9 | 119.9 | C15—C25—H25C | 109.5 |
C10—C9—H9 | 119.9 | H25A—C25—H25C | 109.5 |
C11—C10—C9 | 119.65 (15) | H25B—C25—H25C | 109.5 |
C11—C10—H10 | 120.2 | C15—C25—H25D | 109.5 |
C9—C10—H10 | 120.2 | H25A—C25—H25D | 141.1 |
C10—C11—C2 | 121.13 (15) | H25B—C25—H25D | 56.3 |
C10—C11—H11 | 119.4 | H25C—C25—H25D | 56.3 |
C2—C11—H11 | 119.4 | C15—C25—H25E | 109.5 |
C17—C12—C13 | 117.94 (14) | H25A—C25—H25E | 56.3 |
C17—C12—C4 | 124.27 (14) | H25B—C25—H25E | 141.1 |
C13—C12—C4 | 117.75 (13) | H25C—C25—H25E | 56.3 |
C14—C13—C12 | 121.21 (16) | H25D—C25—H25E | 109.5 |
C14—C13—H13 | 119.4 | C15—C25—H25F | 109.5 |
C12—C13—H13 | 119.4 | H25A—C25—H25F | 56.3 |
C13—C14—C15 | 120.97 (16) | H25B—C25—H25F | 56.3 |
C13—C14—H14 | 119.5 | H25C—C25—H25F | 141.1 |
C15—C14—H14 | 119.5 | H25D—C25—H25F | 109.5 |
C16—C15—C14 | 117.73 (15) | H25E—C25—H25F | 109.5 |
C16—C15—C25 | 121.77 (18) | | |
| | | |
C6—N7—C1—C8 | −132.86 (17) | S3—C4—C12—C13 | −163.34 (13) |
C6—N7—C1—C2 | 49.3 (2) | C17—C12—C13—C14 | −0.3 (3) |
C8—C1—C2—C11 | 0.3 (2) | C4—C12—C13—C14 | −177.81 (16) |
N7—C1—C2—C11 | 178.15 (13) | C12—C13—C14—C15 | 1.3 (3) |
C8—C1—C2—S3 | −174.43 (12) | C13—C14—C15—C16 | −1.1 (3) |
N7—C1—C2—S3 | 3.4 (2) | C13—C14—C15—C25 | 179.60 (18) |
C4—S3—C2—C11 | 119.20 (12) | C14—C15—C16—C17 | 0.1 (3) |
C4—S3—C2—C1 | −66.04 (13) | C25—C15—C16—C17 | 179.36 (17) |
C2—S3—C4—C12 | −95.17 (13) | C13—C12—C17—C16 | −0.7 (3) |
C2—S3—C4—C5 | 29.98 (11) | C4—C12—C17—C16 | 176.61 (16) |
C12—C4—C5—C6 | 179.56 (12) | C15—C16—C17—C12 | 0.8 (3) |
S3—C4—C5—C6 | 50.84 (14) | N7—C6—C18—C19 | 175.68 (15) |
C1—N7—C6—C18 | −173.78 (14) | C5—C6—C18—C19 | −4.0 (2) |
C1—N7—C6—C5 | 5.9 (2) | N7—C6—C18—C23 | −2.4 (2) |
C4—C5—C6—N7 | −89.00 (18) | C5—C6—C18—C23 | 177.92 (14) |
C4—C5—C6—C18 | 90.67 (17) | C23—C18—C19—C20 | −0.2 (3) |
C2—C1—C8—C9 | −1.9 (2) | C6—C18—C19—C20 | −178.36 (16) |
N7—C1—C8—C9 | −179.79 (15) | C18—C19—C20—C21 | −0.4 (3) |
C1—C8—C9—C10 | 2.0 (3) | C19—C20—C21—C22 | 0.4 (3) |
C8—C9—C10—C11 | −0.5 (3) | C20—C21—C22—C23 | 0.3 (3) |
C9—C10—C11—C2 | −1.1 (2) | C21—C22—C23—O24 | 179.30 (17) |
C1—C2—C11—C10 | 1.1 (2) | C21—C22—C23—C18 | −0.9 (3) |
S3—C2—C11—C10 | 176.09 (12) | C19—C18—C23—O24 | −179.35 (15) |
C5—C4—C12—C17 | −105.51 (17) | C6—C18—C23—O24 | −1.2 (2) |
S3—C4—C12—C17 | 19.4 (2) | C19—C18—C23—C22 | 0.9 (2) |
C5—C4—C12—C13 | 71.78 (18) | C6—C18—C23—C22 | 179.05 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O24—H24···N7 | 0.84 | 1.80 | 2.5489 (17) | 147 |
(IVc) 4-(2-hydroxylphenyl)-2-(4-methoxyphenyl)-2-phenyl-2,3-dihydro-1,5- benzothiazepine
top
Crystal data top
C22H19NO2S | F(000) = 760 |
Mr = 361.44 | Dx = 1.340 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7583 reflections |
a = 11.973 (2) Å | θ = 3.7–27.5° |
b = 16.224 (4) Å | µ = 0.20 mm−1 |
c = 9.250 (3) Å | T = 173 K |
β = 94.437 (9)° | Needle, yellow |
V = 1791.4 (8) Å3 | 0.35 × 0.08 × 0.07 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD Area Detector diffractometer | 4081 independent reflections |
Radiation source: fine-focus sealed tube | 3007 reflections with I > 2.0σ(I) |
Graphite monochromator | Rint = 0.031 |
ω and ϕ scans | θmax = 27.5°, θmin = 3.7° |
Absorption correction: multi-scan SORTAV: (Blessing, 1997) | h = −15→15 |
Tmin = 0.908, Tmax = 0.990 | k = −21→21 |
7583 measured reflections | l = −11→12 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.05P)2 + 0.404P] where P = (Fo2 + 2Fc2)/3 |
4081 reflections | (Δ/σ)max < 0.001 |
237 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C22H19NO2S | V = 1791.4 (8) Å3 |
Mr = 361.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.973 (2) Å | µ = 0.20 mm−1 |
b = 16.224 (4) Å | T = 173 K |
c = 9.250 (3) Å | 0.35 × 0.08 × 0.07 mm |
β = 94.437 (9)° | |
Data collection top
Nonius KappaCCD Area Detector diffractometer | 4081 independent reflections |
Absorption correction: multi-scan SORTAV: (Blessing, 1997) | 3007 reflections with I > 2.0σ(I) |
Tmin = 0.908, Tmax = 0.990 | Rint = 0.031 |
7583 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.23 e Å−3 |
4081 reflections | Δρmin = −0.36 e Å−3 |
237 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.69018 (13) | 0.08409 (10) | 0.37331 (16) | 0.0276 (3) | |
C2 | 0.80306 (13) | 0.05878 (10) | 0.39202 (16) | 0.0298 (4) | |
S3 | 0.91453 (3) | 0.12995 (3) | 0.42612 (4) | 0.03332 (14) | |
C4 | 0.91081 (12) | 0.19439 (10) | 0.26106 (15) | 0.0258 (3) | |
H4 | 0.9315 | 0.2517 | 0.2929 | 0.031* | |
C5 | 0.79075 (12) | 0.19788 (10) | 0.19215 (15) | 0.0254 (3) | |
H5A | 0.7869 | 0.2379 | 0.1111 | 0.031* | |
H5B | 0.7699 | 0.1431 | 0.1515 | 0.031* | |
C6 | 0.70767 (12) | 0.22256 (10) | 0.29877 (15) | 0.0249 (3) | |
N7 | 0.65848 (10) | 0.16807 (8) | 0.37436 (13) | 0.0270 (3) | |
C8 | 0.60551 (15) | 0.02496 (11) | 0.36624 (17) | 0.0356 (4) | |
H8 | 0.5294 | 0.0418 | 0.3535 | 0.043* | |
C9 | 0.63128 (18) | −0.05791 (12) | 0.37763 (19) | 0.0454 (5) | |
H9 | 0.5730 | −0.0978 | 0.3712 | 0.054* | |
C10 | 0.74195 (18) | −0.08290 (12) | 0.39839 (19) | 0.0450 (5) | |
H10 | 0.7595 | −0.1398 | 0.4082 | 0.054* | |
C11 | 0.82705 (16) | −0.02487 (11) | 0.40485 (17) | 0.0379 (4) | |
H11 | 0.9028 | −0.0425 | 0.4182 | 0.046* | |
C12 | 0.99582 (13) | 0.16724 (9) | 0.15730 (16) | 0.0256 (3) | |
C13 | 0.96555 (13) | 0.12219 (10) | 0.03311 (17) | 0.0315 (4) | |
H13 | 0.8897 | 0.1062 | 0.0119 | 0.038* | |
C14 | 1.04633 (14) | 0.10037 (11) | −0.06055 (17) | 0.0353 (4) | |
H14 | 1.0250 | 0.0698 | −0.1459 | 0.042* | |
C15 | 1.15660 (14) | 0.12261 (11) | −0.03077 (18) | 0.0336 (4) | |
H15 | 1.2111 | 0.1078 | −0.0956 | 0.040* | |
C16 | 1.18799 (13) | 0.16686 (10) | 0.09443 (17) | 0.0304 (4) | |
C17 | 1.10791 (13) | 0.18948 (10) | 0.18856 (17) | 0.0285 (3) | |
H17 | 1.1294 | 0.2200 | 0.2739 | 0.034* | |
C18 | 0.68103 (12) | 0.30969 (10) | 0.32035 (15) | 0.0259 (3) | |
C19 | 0.73321 (14) | 0.37229 (10) | 0.24504 (17) | 0.0317 (4) | |
H19 | 0.7819 | 0.3574 | 0.1730 | 0.038* | |
C20 | 0.71591 (14) | 0.45478 (11) | 0.27241 (18) | 0.0360 (4) | |
H20 | 0.7521 | 0.4959 | 0.2199 | 0.043* | |
C21 | 0.64493 (15) | 0.47677 (11) | 0.37760 (19) | 0.0382 (4) | |
H21 | 0.6335 | 0.5334 | 0.3983 | 0.046* | |
C22 | 0.59088 (14) | 0.41730 (11) | 0.45220 (18) | 0.0356 (4) | |
H22 | 0.5420 | 0.4333 | 0.5233 | 0.043* | |
C23 | 0.60698 (13) | 0.33411 (10) | 0.42478 (16) | 0.0290 (4) | |
O24 | 0.55363 (10) | 0.27899 (8) | 0.50447 (12) | 0.0354 (3) | |
H24 | 0.5718 | 0.2310 | 0.4815 | 0.053* | |
O25 | 1.29948 (9) | 0.18624 (8) | 0.11383 (13) | 0.0420 (3) | |
C26 | 1.34418 (15) | 0.21132 (12) | 0.2539 (2) | 0.0410 (4) | |
H26A | 1.4257 | 0.2171 | 0.2541 | 0.049* | |
H26B | 1.3264 | 0.1698 | 0.3255 | 0.049* | |
H26C | 1.3113 | 0.2643 | 0.2785 | 0.049* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0303 (8) | 0.0327 (9) | 0.0200 (7) | 0.0024 (7) | 0.0025 (6) | 0.0013 (6) |
C2 | 0.0323 (9) | 0.0374 (9) | 0.0198 (7) | 0.0056 (7) | 0.0039 (6) | 0.0015 (6) |
S3 | 0.0248 (2) | 0.0517 (3) | 0.0231 (2) | 0.00411 (18) | −0.00084 (15) | 0.00421 (17) |
C4 | 0.0238 (8) | 0.0320 (8) | 0.0218 (7) | 0.0020 (6) | 0.0027 (6) | −0.0022 (6) |
C5 | 0.0247 (8) | 0.0316 (8) | 0.0200 (7) | 0.0040 (6) | 0.0021 (6) | −0.0010 (6) |
C6 | 0.0214 (7) | 0.0337 (9) | 0.0192 (7) | 0.0026 (6) | −0.0016 (5) | 0.0001 (6) |
N7 | 0.0227 (7) | 0.0332 (7) | 0.0248 (6) | 0.0028 (5) | 0.0015 (5) | 0.0008 (6) |
C8 | 0.0365 (10) | 0.0405 (10) | 0.0299 (9) | −0.0035 (8) | 0.0021 (7) | 0.0006 (7) |
C9 | 0.0627 (13) | 0.0383 (11) | 0.0352 (10) | −0.0119 (9) | 0.0040 (8) | −0.0031 (8) |
C10 | 0.0713 (14) | 0.0326 (10) | 0.0317 (9) | 0.0079 (9) | 0.0081 (9) | 0.0006 (8) |
C11 | 0.0459 (11) | 0.0417 (10) | 0.0267 (8) | 0.0149 (8) | 0.0061 (7) | 0.0014 (7) |
C12 | 0.0254 (8) | 0.0268 (8) | 0.0250 (8) | 0.0033 (6) | 0.0044 (6) | 0.0003 (6) |
C13 | 0.0268 (8) | 0.0390 (10) | 0.0288 (8) | 0.0006 (7) | 0.0029 (6) | −0.0066 (7) |
C14 | 0.0376 (10) | 0.0414 (10) | 0.0271 (8) | 0.0045 (8) | 0.0038 (7) | −0.0075 (7) |
C15 | 0.0341 (9) | 0.0390 (10) | 0.0291 (8) | 0.0062 (7) | 0.0119 (7) | 0.0006 (7) |
C16 | 0.0255 (8) | 0.0336 (9) | 0.0327 (9) | 0.0001 (7) | 0.0074 (6) | 0.0029 (7) |
C17 | 0.0280 (8) | 0.0312 (9) | 0.0266 (8) | −0.0006 (7) | 0.0040 (6) | −0.0033 (7) |
C18 | 0.0224 (8) | 0.0331 (9) | 0.0217 (7) | 0.0067 (6) | −0.0010 (6) | 0.0011 (6) |
C19 | 0.0334 (9) | 0.0354 (9) | 0.0264 (8) | 0.0038 (7) | 0.0034 (6) | 0.0010 (7) |
C20 | 0.0373 (9) | 0.0331 (9) | 0.0377 (9) | 0.0028 (7) | 0.0036 (7) | 0.0041 (7) |
C21 | 0.0390 (10) | 0.0326 (9) | 0.0422 (10) | 0.0099 (8) | −0.0015 (8) | −0.0027 (8) |
C22 | 0.0327 (9) | 0.0400 (10) | 0.0345 (9) | 0.0118 (7) | 0.0049 (7) | −0.0039 (8) |
C23 | 0.0234 (8) | 0.0386 (9) | 0.0248 (8) | 0.0050 (7) | 0.0004 (6) | 0.0019 (7) |
O24 | 0.0312 (6) | 0.0401 (7) | 0.0362 (6) | 0.0060 (5) | 0.0122 (5) | 0.0017 (5) |
O25 | 0.0250 (6) | 0.0590 (8) | 0.0432 (7) | −0.0044 (6) | 0.0102 (5) | −0.0079 (6) |
C26 | 0.0275 (9) | 0.0489 (11) | 0.0464 (11) | −0.0025 (8) | 0.0014 (8) | 0.0012 (8) |
Geometric parameters (Å, º) top
C1—C8 | 1.394 (2) | C13—H13 | 0.9500 |
C1—C2 | 1.410 (2) | C14—C15 | 1.376 (2) |
C1—N7 | 1.414 (2) | C14—H14 | 0.9500 |
C2—C11 | 1.390 (2) | C15—C16 | 1.389 (2) |
C2—S3 | 1.775 (2) | C15—H15 | 0.9500 |
S3—C4 | 1.848 (2) | C16—O25 | 1.370 (2) |
C4—C12 | 1.517 (2) | C16—C17 | 1.393 (2) |
C4—C5 | 1.528 (2) | C17—H17 | 0.9500 |
C4—H4 | 1.0000 | C18—C19 | 1.405 (2) |
C5—C6 | 1.508 (2) | C18—C23 | 1.417 (2) |
C5—H5A | 0.9900 | C19—C20 | 1.381 (2) |
C5—H5B | 0.9900 | C19—H19 | 0.9500 |
C6—N7 | 1.297 (2) | C20—C21 | 1.387 (2) |
C6—C18 | 1.466 (2) | C20—H20 | 0.9500 |
C8—C9 | 1.382 (3) | C21—C22 | 1.377 (3) |
C8—H8 | 0.9500 | C21—H21 | 0.9500 |
C9—C10 | 1.385 (3) | C22—C23 | 1.390 (2) |
C9—H9 | 0.9500 | C22—H22 | 0.9500 |
C10—C11 | 1.385 (3) | C23—O24 | 1.351 (2) |
C10—H10 | 0.9500 | O24—H24 | 0.8400 |
C11—H11 | 0.9500 | O25—C26 | 1.422 (2) |
C12—C13 | 1.386 (2) | C26—H26A | 0.9800 |
C12—C17 | 1.398 (2) | C26—H26B | 0.9800 |
C13—C14 | 1.393 (2) | C26—H26C | 0.9800 |
| | | |
C8—C1—C2 | 119.47 (15) | C14—C13—H13 | 120.0 |
C8—C1—N7 | 117.96 (14) | C15—C14—C13 | 120.70 (15) |
C2—C1—N7 | 122.32 (14) | C15—C14—H14 | 119.7 |
C11—C2—C1 | 118.97 (16) | C13—C14—H14 | 119.7 |
C11—C2—S3 | 118.19 (13) | C14—C15—C16 | 119.73 (15) |
C1—C2—S3 | 122.19 (13) | C14—C15—H15 | 120.1 |
C2—S3—C4 | 104.57 (7) | C16—C15—H15 | 120.1 |
C12—C4—C5 | 113.73 (12) | O25—C16—C17 | 124.64 (15) |
C12—C4—S3 | 112.57 (10) | O25—C16—C15 | 115.20 (14) |
C5—C4—S3 | 109.11 (10) | C17—C16—C15 | 120.14 (15) |
C12—C4—H4 | 107.0 | C16—C17—C12 | 119.91 (14) |
C5—C4—H4 | 107.0 | C16—C17—H17 | 120.0 |
S3—C4—H4 | 107.0 | C12—C17—H17 | 120.0 |
C6—C5—C4 | 112.58 (12) | C19—C18—C23 | 117.48 (15) |
C6—C5—H5A | 109.1 | C19—C18—C6 | 121.31 (14) |
C4—C5—H5A | 109.1 | C23—C18—C6 | 121.09 (14) |
C6—C5—H5B | 109.1 | C20—C19—C18 | 122.08 (15) |
C4—C5—H5B | 109.1 | C20—C19—H19 | 119.0 |
H5A—C5—H5B | 107.8 | C18—C19—H19 | 119.0 |
N7—C6—C18 | 118.12 (14) | C19—C20—C21 | 119.12 (16) |
N7—C6—C5 | 121.45 (14) | C19—C20—H20 | 120.4 |
C18—C6—C5 | 120.43 (14) | C21—C20—H20 | 120.4 |
C6—N7—C1 | 121.32 (13) | C22—C21—C20 | 120.57 (16) |
C9—C8—C1 | 120.60 (17) | C22—C21—H21 | 119.7 |
C9—C8—H8 | 119.7 | C20—C21—H21 | 119.7 |
C1—C8—H8 | 119.7 | C21—C22—C23 | 120.80 (16) |
C8—C9—C10 | 120.08 (18) | C21—C22—H22 | 119.6 |
C8—C9—H9 | 120.0 | C23—C22—H22 | 119.6 |
C10—C9—H9 | 120.0 | O24—C23—C22 | 117.73 (14) |
C9—C10—C11 | 119.98 (17) | O24—C23—C18 | 122.29 (15) |
C9—C10—H10 | 120.0 | C22—C23—C18 | 119.92 (15) |
C11—C10—H10 | 120.0 | C23—O24—H24 | 109.5 |
C2—C11—C10 | 120.89 (17) | C16—O25—C26 | 118.63 (13) |
C2—C11—H11 | 119.6 | O25—C26—H26A | 109.5 |
C10—C11—H11 | 119.6 | O25—C26—H26B | 109.5 |
C13—C12—C17 | 119.52 (14) | H26A—C26—H26B | 109.5 |
C13—C12—C4 | 122.16 (14) | O25—C26—H26C | 109.5 |
C17—C12—C4 | 118.32 (13) | H26A—C26—H26C | 109.5 |
C12—C13—C14 | 119.99 (15) | H26B—C26—H26C | 109.5 |
C12—C13—H13 | 120.0 | | |
| | | |
C8—C1—C2—C11 | −0.8 (2) | C17—C12—C13—C14 | −0.9 (2) |
N7—C1—C2—C11 | 173.35 (14) | C4—C12—C13—C14 | 178.49 (15) |
C8—C1—C2—S3 | −171.44 (12) | C12—C13—C14—C15 | 0.4 (3) |
N7—C1—C2—S3 | 2.7 (2) | C13—C14—C15—C16 | 0.4 (3) |
C11—C2—S3—C4 | 125.51 (12) | C14—C15—C16—O25 | −179.76 (15) |
C1—C2—S3—C4 | −63.79 (13) | C14—C15—C16—C17 | −0.8 (3) |
C2—S3—C4—C12 | −98.63 (12) | O25—C16—C17—C12 | 179.20 (15) |
C2—S3—C4—C5 | 28.61 (12) | C15—C16—C17—C12 | 0.3 (2) |
C12—C4—C5—C6 | 178.28 (13) | C13—C12—C17—C16 | 0.5 (2) |
S3—C4—C5—C6 | 51.70 (15) | C4—C12—C17—C16 | −178.90 (14) |
C4—C5—C6—N7 | −90.11 (17) | N7—C6—C18—C19 | 178.34 (14) |
C4—C5—C6—C18 | 89.42 (16) | C5—C6—C18—C19 | −1.2 (2) |
C18—C6—N7—C1 | −171.87 (12) | N7—C6—C18—C23 | 2.4 (2) |
C5—C6—N7—C1 | 7.7 (2) | C5—C6—C18—C23 | −177.14 (13) |
C8—C1—N7—C6 | −137.86 (15) | C23—C18—C19—C20 | 1.4 (2) |
C2—C1—N7—C6 | 47.9 (2) | C6—C18—C19—C20 | −174.72 (14) |
C2—C1—C8—C9 | 0.1 (2) | C18—C19—C20—C21 | 0.1 (3) |
N7—C1—C8—C9 | −174.31 (14) | C19—C20—C21—C22 | −1.1 (3) |
C1—C8—C9—C10 | 0.9 (2) | C20—C21—C22—C23 | 0.6 (3) |
C8—C9—C10—C11 | −1.3 (3) | C21—C22—C23—O24 | 178.32 (15) |
C1—C2—C11—C10 | 0.5 (2) | C21—C22—C23—C18 | 0.9 (2) |
S3—C2—C11—C10 | 171.49 (13) | C19—C18—C23—O24 | −179.13 (14) |
C9—C10—C11—C2 | 0.6 (2) | C6—C18—C23—O24 | −3.0 (2) |
C5—C4—C12—C13 | −22.2 (2) | C19—C18—C23—C22 | −1.8 (2) |
S3—C4—C12—C13 | 102.57 (15) | C6—C18—C23—C22 | 174.26 (14) |
C5—C4—C12—C17 | 157.21 (14) | C17—C16—O25—C26 | 17.6 (2) |
S3—C4—C12—C17 | −78.05 (16) | C15—C16—O25—C26 | −163.49 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O24—H24···N7 | 0.84 | 1.81 | 2.5489 (18) | 147 |
Experimental details
| (IVa) | (IVb) | (IVc) |
Crystal data |
Chemical formula | C21H16ClNOS | C22H19NOS | C22H19NO2S |
Mr | 365.86 | 345.44 | 361.44 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 173 | 173 | 173 |
a, b, c (Å) | 18.036 (9), 4.836 (2), 19.790 (11) | 4.8678 (11), 17.563 (3), 20.129 (5) | 11.973 (2), 16.224 (4), 9.250 (3) |
β (°) | 97.02 (2) | 93.078 (8) | 94.437 (9) |
V (Å3) | 1713.2 (15) | 1718.4 (6) | 1791.4 (8) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.35 | 0.20 | 0.20 |
Crystal size (mm) | 0.15 × 0.08 × 0.06 | 0.22 × 0.12 × 0.08 | 0.35 × 0.08 × 0.07 |
|
Data collection |
Diffractometer | Nonius KappaCCD Area Detector diffractometer | Nonius KappaCCD Area Detector diffractometer | Nonius KappaCCD Area Detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) | Multi-scan SORTAV: (Blessing, 1997) | Multi-scan SORTAV: (Blessing, 1997) |
Tmin, Tmax | 0.901, 0.982 | 0.906, 0.988 | 0.908, 0.990 |
No. of measured, independent and observed reflections | 9054, 2987, 2093 [I > 2σ(I)] | 8207, 4972, 3195 [I > 2.0σ(I)] | 7583, 4081, 3007 [I > 2.0σ(I)] |
Rint | 0.064 | 0.037 | 0.031 |
(sin θ/λ)max (Å−1) | 0.595 | 0.703 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.113, 1.02 | 0.046, 0.121, 0.99 | 0.040, 0.107, 1.02 |
No. of reflections | 2987 | 4972 | 4081 |
No. of parameters | 227 | 228 | 237 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.32 | 0.23, −0.32 | 0.23, −0.36 |
Selected geometric parameters (Å, º) for (IVa) topC1—N7 | 1.418 (3) | C6—N7 | 1.295 (3) |
C2—S3 | 1.776 (3) | C15—Cl25 | 1.743 (3) |
S3—C4 | 1.836 (2) | C23—O24 | 1.349 (3) |
| | | |
C2—S3—C4 | 103.99 (12) | C6—N7—C1 | 121.0 (2) |
Hydrogen-bond geometry (Å, º) for (IVa) top
D—H···A | D—H | H···A | D···A | D—H···A |
O24—H24···N7 | 0.84 | 1.80 | 2.543 (3) | 146 |
Selected geometric parameters (Å, º) for (IVb) topS3—C2 | 1.7696 (17) | N7—C6 | 1.2952 (19) |
S3—C4 | 1.8368 (15) | N7—C1 | 1.4128 (19) |
O24—C23 | 1.3427 (19) | | |
| | | |
C2—S3—C4 | 103.23 (7) | C6—N7—C1 | 120.37 (13) |
C23—O24—H24 | 109.5 | | |
Hydrogen-bond geometry (Å, º) for (IVb) top
D—H···A | D—H | H···A | D···A | D—H···A |
O24—H24···N7 | 0.84 | 1.80 | 2.5489 (17) | 147 |
Selected geometric parameters (Å, º) for (IVc) topC1—N7 | 1.414 (2) | C6—N7 | 1.297 (2) |
C2—S3 | 1.775 (2) | C23—O24 | 1.351 (2) |
S3—C4 | 1.848 (2) | | |
| | | |
C2—S3—C4 | 104.57 (7) | C6—N7—C1 | 121.32 (13) |
Hydrogen-bond geometry (Å, º) for (IVc) top
D—H···A | D—H | H···A | D···A | D—H···A |
O24—H24···N7 | 0.84 | 1.81 | 2.5489 (18) | 147 |
Many chemotherapeutic applications have been associated with benzothiazepine derivatives, such as diltiazem, which is used as a calcium channel blocker (Chaffman & Brogden, 1985), an angiotensin-converting enzyme inhibitor (Itoh et al., 1986), and an anticonvulsant and tranquilizing agent (Bock et al., 1989). Calcium channel blockers are important cardiovascular drugs for the management of angina pectoris and hypertension and may have applications in additional therapeutic areas (Godfraind et al., 1986). The importance of the methoxyphenyl moiety in biologically active compounds belonging to the benzothiazepine series of drugs has also been reported (Pant et al., 1994). Following these studies and continuing our investigations in this area (Ansari et al., 2002), we have reacted 2-hydroxy acetophenone, (I), with substituted benzaldehyde, (II), (see Scheme; R = Cl, CH3 or H and R' = H, H, or OCH3, respectively). The reaction yielded chalcones, (III), which on treatment with o-aminothiophenol in equimolar quantities in acidified methanol led to the formation of 4-chlorophenyl, 4-toluyl and 3-methoxyphenyl derivatives of 4-(2'-hydroxylphenyl)-2-phenyl −2,3-dihydro-1,5-benzothiazepine, (IVa)–(IVc), respectively. In this paper, we report the crystal structures of (IVa)–(IVc).
The Figs. 1–3 show the structures of (IVa)–(IVc), respectively. In all three structures, the central seven-membered heterocyclic rings adopt twist- boat conformations, such that atoms C1, C5, C6 and N7 are essentially planar and the remaining atoms lie above this plane. The distances of the remaining atoms of the heterocyclic ring from the planes in (IVa)–(IVc) are, respectively, 0.997 (4), 0.983 (3) and 0.983 (3) Å for atom C2; 2.287 (3), 2.283 (2) and 2.268 (4) Å for atom S3; and 1.393 (4), 1.388 (3) and 1.375 (2) Å for atom C4. Atoms C1, C5, C6 and N7 of the heterocyclic rings are coplanar with the hydroxyphenyl rings in the three structures, with atoms C1 and O24 lying on the opposite sides of the mean planes passing through these atoms (plane 1), the maximum deviations for C1 being 0.181 (2), 0.1307 (12) and 0.1531 (11) Å and for O24 being 0.095 (2), 0.0591 (11) and 0.0590 (10) Å for (IVa)–(IVc), respectively. Moreover, the C12–C17 phenyl ring (plane 2) is almost coplanar with plane 1 in (IVa) [the angle between the mean planes? is 3.48 (12)°] and is inclined at 18.39 (7) and 65.88 (5)° in (IVb) and (IVc), respectively. The angles between the mean planes formed by the C1/C2/C8–C11 (plane 3) and C12–C17 (plane 4) phenyl rings are 51.3 (9), 63.68 (5) and 64.05 (6)°, respectively, while the C18—C23 phenyl ring (plane 5) is oriented with respect to plane 3 at 52.94 (9), 48.71 (6) and 52.49 (5)° in (IVa)–(IVc), respectively.
In all three structures, atom N7 of the heterocyclic ring is involved in intramolecular hydrogen bonds with the hydroxyl H atom, resulting in a six-membered ring; details of hydrogen-bonding geometry are provided in Tables 2, 4 and 6 for (IVa)-(IVc), respectively. Note that in (IVb), atom S3 is involved in short intramolecular contacts with a phenyl H atom [S3···H17 = 2.78 Å]. The corresponding contact in (IVa) is 2.91 Å, while (IVc) displays no such contact. Crystal-packing forces and the orientation of the phenyl rings are probably responsible for these observations.
The molecular dimensions in the three structures are unexceptional. A search of the November 2002 release of the Cambridge Structural Database (Allen, 2002) showed only five structures containing a heterocyclic seven- membered ring analogous to that in (IVa)–(IVc).