


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048465/bh2135sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048465/bh2135Isup2.hkl |
CCDC reference: 667316
2-Methyl-11-(4-fluorophenyl)-4-[(E)-(4-fluorophenyl)methylidene]- 1,2,3,4,11,11a-hexahydro-pyrido[3,4-c][1,5]benzothiazepine (1 mmol) and 4-chloro-N-hydroxybenzenecarboxymidoyl chloride (1 mmol) were dissolved in benzene (15 ml). Triethylamine (1 mmol) was added to the above mixture and refluxed for 30 min. After completion of the reaction the triethylamine hydrochloride was filtered off, solvent evaporated, and the product was purified by column chromatography using petroleum ether:ethyl acetate (90:10 v/v) mixture and finally recrystallized from ethyl acetate to obtain pure 1-(4-chlorophenyl)-8-(4-fluorophenyl)-4-[(E)-(4-fluorophenyl)methylidene]- 6-methyl-4,5,6,7,7a,8-hexahydro[1,2,4]oxadiazolo[5,4-d]pyrido[3,4-c][1,5] benzothiazepine as colourless crystals.
H atoms were placed geometrically and refined using a riding model with C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).
The title compound, C33H26N3OF2SCl, belongs to an important class of heterocycles which are expected to possess antihypertensive properties, and is made of three fused ring systems viz. a benzothiazepine, an oxadiazole and a methyl piperidine ring. Interestingly, benzothiazepines have been established as a class of calcium channel blockers (Budriesi et al., 2007), oxadiazole derivatives have been found to possess antimicrobial activity (Şahin et al., 2002) and piperidine ring occurs in many natural alkaloids and are constituents of a number of pharmaceutical drugs. Also, the role of non-conventional hydrogen bonds viz. C—H···X (X= N, O, Cl, F, etc.) can be accurately assessed through precise single-crystal structure determinations of these compounds which, in turn, may provide insights into design of drugs with a wide range of biological activities.
Least-squares plane calculations show that the 4-fluorophenyl attached to thiazepine, 4-flurophenyl attached to piperidine and 4-chlorophenyl rings make dihedral angles of 40.0 (1), 67.6 (1) and 71.5 (1)°, respectively, with respect to the benzene fused to the thiazepine ring. The torsion angles about the methylidene bond C4—C40—C41—C42 = -39.7 (3)° and C4—C40—C41—C46 = 144.01 (19)° indicate a significant twist of the 4-fluorophenyl ring which may be attributed to steric factors. The oxadiazole, piperidine and benzothiazepine rings adopt the envelope [Q = 0.299 (2) Å, φ = 150.5 (3)°] (Cremer & Pople, 1975), chair [Q = 0.597 (2) Å, θ = 1.6 (2)°, φ = 251 (5)°] (Boeyens, 1978) and twist-boat conformations, respectively. The molecular aggregation is characterized by linear chains of centrosymmetrically related pairs extending along the [010] axis, connected through a C—H···F and a C—H···N bonds (Table 1). The interactions between these linear chains are purely van der Waal's in nature. No significant π···π and C—H···π interactions were found in the crystal structure.
For biological properties of related compounds, see: Budriesi et al., 2007; Şahin et al., 2002. For conformational analysis of ring systems, see: Cremer & Pople, 1975; Boeyens, 1978.
Data collection: APEXII (Bruker–Nonius, 2004); cell refinement: SAINT (Bruker–Nonius, 2004); data reduction: SAINT (Bruker–Nonius, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C33H26ClF2N3OS | F(000) = 1216 |
Mr = 586.08 | Dx = 1.370 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5122 reflections |
a = 10.836 (5) Å | θ = 2.0–30.0° |
b = 11.366 (4) Å | µ = 0.25 mm−1 |
c = 23.100 (3) Å | T = 298 K |
β = 92.63 (1)° | Plate, colourless |
V = 2842.0 (17) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Bruker Kappa-APEX2 CCD diffractometer | 8394 independent reflections |
Radiation source: fine-focus sealed tube | 5384 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω and φ scans | θmax = 30.2°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −14→15 |
Tmin = 0.93, Tmax = 0.96 | k = −16→15 |
36502 measured reflections | l = −32→30 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0498P)2 + 0.8797P] where P = (Fo2 + 2Fc2)/3 |
8394 reflections | (Δ/σ)max = 0.001 |
370 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C33H26ClF2N3OS | V = 2842.0 (17) Å3 |
Mr = 586.08 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.836 (5) Å | µ = 0.25 mm−1 |
b = 11.366 (4) Å | T = 298 K |
c = 23.100 (3) Å | 0.30 × 0.20 × 0.20 mm |
β = 92.63 (1)° |
Bruker Kappa-APEX2 CCD diffractometer | 8394 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 5384 reflections with I > 2σ(I) |
Tmin = 0.93, Tmax = 0.96 | Rint = 0.029 |
36502 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.32 e Å−3 |
8394 reflections | Δρmin = −0.34 e Å−3 |
370 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.26565 (15) | −0.17757 (14) | 0.62165 (7) | 0.0415 (3) | |
N2 | 0.18066 (13) | −0.16509 (12) | 0.65790 (6) | 0.0463 (3) | |
O3 | 0.13128 (10) | −0.04971 (10) | 0.64893 (5) | 0.0464 (3) | |
C3A | 0.22839 (14) | 0.01637 (13) | 0.62121 (6) | 0.0391 (3) | |
C4 | 0.31070 (15) | 0.06934 (13) | 0.66958 (6) | 0.0399 (3) | |
C5 | 0.23745 (16) | 0.14586 (15) | 0.70822 (7) | 0.0458 (4) | |
H5A | 0.1761 | 0.0986 | 0.7268 | 0.055* | |
H5B | 0.2920 | 0.1797 | 0.7383 | 0.055* | |
N6 | 0.17576 (14) | 0.24050 (13) | 0.67469 (6) | 0.0491 (3) | |
C7 | 0.09347 (16) | 0.19098 (16) | 0.62914 (7) | 0.0481 (4) | |
H7A | 0.0515 | 0.2543 | 0.6081 | 0.058* | |
H7B | 0.0313 | 0.1427 | 0.6466 | 0.058* | |
C7A | 0.16481 (14) | 0.11610 (13) | 0.58675 (6) | 0.0390 (3) | |
H71A | 0.1059 | 0.0818 | 0.5580 | 0.047* | |
C8 | 0.25323 (15) | 0.19818 (13) | 0.55535 (7) | 0.0406 (3) | |
H8 | 0.2868 | 0.2524 | 0.5851 | 0.049* | |
S9 | 0.38729 (4) | 0.12699 (4) | 0.525049 (19) | 0.04702 (12) | |
C9A | 0.31578 (15) | 0.00373 (15) | 0.49202 (7) | 0.0429 (4) | |
C10 | 0.30426 (17) | −0.00698 (17) | 0.43211 (7) | 0.0517 (4) | |
H10 | 0.3324 | 0.0532 | 0.4088 | 0.062* | |
C11 | 0.25179 (19) | −0.10530 (18) | 0.40693 (8) | 0.0582 (5) | |
H11 | 0.2471 | −0.1128 | 0.3668 | 0.070* | |
C12 | 0.20602 (17) | −0.19283 (17) | 0.44107 (8) | 0.0544 (4) | |
H12 | 0.1700 | −0.2592 | 0.4239 | 0.065* | |
C13 | 0.21341 (16) | −0.18245 (15) | 0.50082 (7) | 0.0469 (4) | |
H13 | 0.1800 | −0.2407 | 0.5236 | 0.056* | |
C13A | 0.27046 (14) | −0.08553 (14) | 0.52684 (7) | 0.0404 (3) | |
N14 | 0.28845 (12) | −0.07636 (11) | 0.58843 (5) | 0.0396 (3) | |
C1E | 0.47422 (19) | −0.48916 (16) | 0.60873 (8) | 0.0560 (5) | |
C2E | 0.36580 (19) | −0.49215 (15) | 0.63745 (8) | 0.0535 (4) | |
H2E | 0.3392 | −0.5617 | 0.6541 | 0.064* | |
C3E | 0.29710 (17) | −0.39048 (14) | 0.64122 (7) | 0.0470 (4) | |
H3E | 0.2230 | −0.3917 | 0.6600 | 0.056* | |
C4E | 0.33800 (16) | −0.28603 (14) | 0.61706 (7) | 0.0426 (4) | |
C5E | 0.44779 (17) | −0.28544 (16) | 0.58912 (8) | 0.0546 (4) | |
H5E | 0.4760 | −0.2157 | 0.5733 | 0.066* | |
C6E | 0.51637 (19) | −0.38703 (17) | 0.58441 (9) | 0.0611 (5) | |
H6E | 0.5898 | −0.3865 | 0.5651 | 0.073* | |
C40 | 0.43178 (15) | 0.04950 (14) | 0.67434 (7) | 0.0438 (4) | |
H40 | 0.4622 | −0.0044 | 0.6483 | 0.053* | |
C41 | 0.52401 (16) | 0.10201 (17) | 0.71562 (7) | 0.0492 (4) | |
C42 | 0.5219 (2) | 0.21982 (18) | 0.73168 (9) | 0.0641 (5) | |
H42 | 0.4578 | 0.2676 | 0.7174 | 0.077* | |
C43 | 0.6129 (2) | 0.2676 (2) | 0.76843 (11) | 0.0807 (7) | |
H43 | 0.6101 | 0.3463 | 0.7792 | 0.097* | |
C44 | 0.7058 (2) | 0.1977 (3) | 0.78831 (11) | 0.0828 (7) | |
C45 | 0.7134 (2) | 0.0817 (3) | 0.77427 (10) | 0.0809 (7) | |
H45 | 0.7784 | 0.0356 | 0.7890 | 0.097* | |
C46 | 0.62175 (17) | 0.0339 (2) | 0.73741 (9) | 0.0619 (5) | |
H46 | 0.6260 | −0.0451 | 0.7272 | 0.074* | |
C61 | 0.1071 (2) | 0.3164 (2) | 0.71289 (9) | 0.0737 (6) | |
H61A | 0.1624 | 0.3477 | 0.7427 | 0.111* | |
H61B | 0.0436 | 0.2714 | 0.7303 | 0.111* | |
H61C | 0.0702 | 0.3798 | 0.6908 | 0.111* | |
C81 | 0.18678 (15) | 0.27456 (14) | 0.51049 (7) | 0.0405 (3) | |
C82 | 0.11326 (16) | 0.22881 (16) | 0.46533 (7) | 0.0507 (4) | |
H82 | 0.1009 | 0.1479 | 0.4630 | 0.061* | |
C83 | 0.05769 (18) | 0.3015 (2) | 0.42351 (8) | 0.0603 (5) | |
H83 | 0.0090 | 0.2702 | 0.3931 | 0.072* | |
C84 | 0.0760 (2) | 0.4192 (2) | 0.42803 (9) | 0.0670 (6) | |
C85 | 0.1463 (2) | 0.46790 (19) | 0.47118 (11) | 0.0792 (7) | |
H85 | 0.1573 | 0.5490 | 0.4731 | 0.095* | |
C86 | 0.2018 (2) | 0.39493 (16) | 0.51271 (9) | 0.0622 (5) | |
H86 | 0.2504 | 0.4279 | 0.5428 | 0.075* | |
F1 | 0.79600 (16) | 0.24504 (19) | 0.82413 (8) | 0.1296 (7) | |
F2 | 0.02109 (15) | 0.49074 (14) | 0.38734 (6) | 0.1075 (5) | |
CL1 | 0.55743 (6) | −0.61865 (5) | 0.60066 (3) | 0.0882 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0473 (9) | 0.0431 (8) | 0.0338 (8) | −0.0042 (7) | −0.0001 (7) | 0.0055 (6) |
N2 | 0.0513 (8) | 0.0449 (7) | 0.0429 (8) | −0.0018 (6) | 0.0041 (6) | 0.0078 (6) |
O3 | 0.0455 (6) | 0.0478 (6) | 0.0465 (6) | −0.0002 (5) | 0.0097 (5) | 0.0072 (5) |
C3A | 0.0404 (8) | 0.0430 (8) | 0.0341 (8) | 0.0006 (6) | 0.0042 (6) | 0.0043 (6) |
C4 | 0.0457 (9) | 0.0423 (8) | 0.0315 (7) | 0.0019 (6) | 0.0007 (6) | 0.0066 (6) |
C5 | 0.0497 (9) | 0.0533 (9) | 0.0342 (8) | 0.0067 (7) | 0.0008 (7) | 0.0020 (7) |
N6 | 0.0583 (9) | 0.0519 (8) | 0.0370 (7) | 0.0130 (7) | 0.0009 (6) | −0.0011 (6) |
C7 | 0.0459 (9) | 0.0579 (10) | 0.0407 (9) | 0.0104 (7) | 0.0027 (7) | 0.0055 (7) |
C7A | 0.0385 (8) | 0.0455 (8) | 0.0326 (8) | 0.0007 (6) | −0.0020 (6) | 0.0033 (6) |
C8 | 0.0441 (9) | 0.0414 (8) | 0.0362 (8) | 0.0009 (6) | −0.0013 (7) | 0.0018 (6) |
S9 | 0.0408 (2) | 0.0489 (2) | 0.0518 (3) | −0.00048 (17) | 0.00653 (18) | 0.01041 (18) |
C9A | 0.0408 (8) | 0.0493 (9) | 0.0392 (8) | 0.0071 (7) | 0.0081 (7) | 0.0073 (7) |
C10 | 0.0529 (10) | 0.0627 (11) | 0.0402 (9) | 0.0078 (8) | 0.0111 (8) | 0.0107 (8) |
C11 | 0.0636 (12) | 0.0768 (13) | 0.0341 (9) | 0.0095 (10) | 0.0024 (8) | 0.0012 (8) |
C12 | 0.0583 (11) | 0.0605 (11) | 0.0438 (10) | 0.0031 (8) | −0.0054 (8) | −0.0053 (8) |
C13 | 0.0494 (10) | 0.0504 (9) | 0.0408 (9) | −0.0002 (7) | 0.0011 (7) | 0.0026 (7) |
C13A | 0.0411 (8) | 0.0464 (8) | 0.0338 (8) | 0.0055 (6) | 0.0036 (6) | 0.0034 (6) |
N14 | 0.0473 (7) | 0.0382 (6) | 0.0332 (7) | 0.0015 (5) | 0.0028 (5) | 0.0048 (5) |
C1E | 0.0650 (12) | 0.0476 (9) | 0.0547 (11) | 0.0095 (8) | −0.0054 (9) | 0.0014 (8) |
C2E | 0.0753 (13) | 0.0404 (8) | 0.0445 (9) | −0.0027 (8) | −0.0010 (9) | 0.0055 (7) |
C3E | 0.0601 (10) | 0.0447 (9) | 0.0363 (8) | −0.0046 (7) | 0.0046 (7) | 0.0032 (6) |
C4E | 0.0518 (9) | 0.0417 (8) | 0.0339 (8) | −0.0013 (7) | −0.0016 (7) | 0.0042 (6) |
C5E | 0.0556 (11) | 0.0474 (9) | 0.0611 (11) | −0.0006 (8) | 0.0065 (9) | 0.0116 (8) |
C6E | 0.0558 (11) | 0.0600 (11) | 0.0682 (13) | 0.0070 (9) | 0.0092 (10) | 0.0086 (9) |
C40 | 0.0447 (9) | 0.0484 (9) | 0.0383 (8) | 0.0022 (7) | 0.0012 (7) | 0.0066 (7) |
C41 | 0.0446 (9) | 0.0627 (11) | 0.0400 (9) | −0.0014 (8) | −0.0004 (7) | 0.0105 (7) |
C42 | 0.0634 (12) | 0.0601 (12) | 0.0675 (13) | −0.0060 (9) | −0.0096 (10) | 0.0087 (10) |
C43 | 0.0832 (16) | 0.0760 (15) | 0.0812 (16) | −0.0228 (13) | −0.0137 (13) | −0.0014 (12) |
C44 | 0.0693 (15) | 0.110 (2) | 0.0672 (14) | −0.0264 (14) | −0.0187 (12) | 0.0072 (14) |
C45 | 0.0529 (12) | 0.116 (2) | 0.0717 (15) | 0.0024 (13) | −0.0179 (11) | 0.0199 (14) |
C46 | 0.0501 (11) | 0.0755 (13) | 0.0597 (12) | 0.0049 (9) | −0.0027 (9) | 0.0105 (10) |
C61 | 0.0951 (17) | 0.0759 (14) | 0.0501 (11) | 0.0348 (12) | 0.0032 (11) | −0.0070 (10) |
C81 | 0.0426 (8) | 0.0442 (8) | 0.0350 (8) | 0.0034 (6) | 0.0040 (7) | 0.0042 (6) |
C82 | 0.0543 (10) | 0.0515 (10) | 0.0455 (10) | −0.0002 (8) | −0.0044 (8) | 0.0032 (7) |
C83 | 0.0560 (11) | 0.0831 (14) | 0.0412 (10) | 0.0075 (10) | −0.0055 (8) | 0.0089 (9) |
C84 | 0.0723 (14) | 0.0732 (13) | 0.0556 (12) | 0.0189 (11) | 0.0033 (10) | 0.0271 (10) |
C85 | 0.1073 (19) | 0.0467 (11) | 0.0828 (16) | 0.0116 (11) | −0.0055 (14) | 0.0163 (10) |
C86 | 0.0826 (14) | 0.0457 (10) | 0.0573 (12) | −0.0001 (9) | −0.0093 (10) | 0.0019 (8) |
F1 | 0.1032 (12) | 0.1675 (18) | 0.1129 (13) | −0.0444 (12) | −0.0530 (10) | −0.0030 (12) |
F2 | 0.1228 (12) | 0.1098 (11) | 0.0883 (10) | 0.0369 (10) | −0.0117 (9) | 0.0513 (9) |
CL1 | 0.0964 (4) | 0.0586 (3) | 0.1103 (5) | 0.0258 (3) | 0.0137 (4) | 0.0067 (3) |
C1—N2 | 1.281 (2) | C1E—CL1 | 1.740 (2) |
C1—N14 | 1.4108 (19) | C2E—C3E | 1.380 (3) |
C1—C4E | 1.467 (2) | C2E—H2E | 0.9300 |
N2—O3 | 1.4279 (18) | C3E—C4E | 1.393 (2) |
O3—C3A | 1.4639 (19) | C3E—H3E | 0.9300 |
C3A—N14 | 1.467 (2) | C4E—C5E | 1.379 (3) |
C3A—C4 | 1.521 (2) | C5E—C6E | 1.380 (3) |
C3A—C7A | 1.531 (2) | C5E—H5E | 0.9300 |
C4—C40 | 1.331 (2) | C6E—H6E | 0.9300 |
C4—C5 | 1.499 (2) | C40—C41 | 1.475 (2) |
C5—N6 | 1.468 (2) | C40—H40 | 0.9300 |
C5—H5A | 0.9700 | C41—C46 | 1.388 (3) |
C5—H5B | 0.9700 | C41—C42 | 1.390 (3) |
N6—C7 | 1.461 (2) | C42—C43 | 1.383 (3) |
N6—C61 | 1.461 (2) | C42—H42 | 0.9300 |
C7—C7A | 1.533 (2) | C43—C44 | 1.346 (4) |
C7—H7A | 0.9700 | C43—H43 | 0.9300 |
C7—H7B | 0.9700 | C44—C45 | 1.361 (4) |
C7A—C8 | 1.542 (2) | C44—F1 | 1.362 (3) |
C7A—H71A | 0.9800 | C45—C46 | 1.389 (3) |
C8—C81 | 1.509 (2) | C45—H45 | 0.9300 |
C8—S9 | 1.8298 (17) | C46—H46 | 0.9300 |
C8—H8 | 0.9800 | C61—H61A | 0.9600 |
S9—C9A | 1.7582 (19) | C61—H61B | 0.9600 |
C9A—C10 | 1.389 (2) | C61—H61C | 0.9600 |
C9A—C13A | 1.398 (2) | C81—C86 | 1.379 (2) |
C10—C11 | 1.371 (3) | C81—C82 | 1.385 (2) |
C10—H10 | 0.9300 | C82—C83 | 1.388 (2) |
C11—C12 | 1.376 (3) | C82—H82 | 0.9300 |
C11—H11 | 0.9300 | C83—C84 | 1.356 (3) |
C12—C13 | 1.384 (2) | C83—H83 | 0.9300 |
C12—H12 | 0.9300 | C84—C85 | 1.345 (3) |
C13—C13A | 1.387 (2) | C84—F2 | 1.359 (2) |
C13—H13 | 0.9300 | C85—C86 | 1.385 (3) |
C13A—N14 | 1.431 (2) | C85—H85 | 0.9300 |
C1E—C2E | 1.376 (3) | C86—H86 | 0.9300 |
C1E—C6E | 1.377 (3) | ||
N2—C1—N14 | 114.48 (14) | C2E—C1E—C6E | 121.62 (17) |
N2—C1—C4E | 122.87 (14) | C2E—C1E—CL1 | 119.26 (15) |
N14—C1—C4E | 122.57 (14) | C6E—C1E—CL1 | 119.08 (16) |
C1—N2—O3 | 106.42 (12) | C1E—C2E—C3E | 119.01 (16) |
N2—O3—C3A | 105.22 (11) | C1E—C2E—H2E | 120.5 |
O3—C3A—N14 | 101.65 (12) | C3E—C2E—H2E | 120.5 |
O3—C3A—C4 | 106.91 (12) | C2E—C3E—C4E | 120.40 (17) |
N14—C3A—C4 | 113.85 (13) | C2E—C3E—H3E | 119.8 |
O3—C3A—C7A | 106.98 (12) | C4E—C3E—H3E | 119.8 |
N14—C3A—C7A | 117.59 (12) | C5E—C4E—C3E | 119.26 (16) |
C4—C3A—C7A | 108.88 (13) | C5E—C4E—C1 | 120.32 (15) |
C40—C4—C5 | 126.58 (15) | C3E—C4E—C1 | 120.42 (16) |
C40—C4—C3A | 122.42 (15) | C4E—C5E—C6E | 120.79 (17) |
C5—C4—C3A | 110.99 (14) | C4E—C5E—H5E | 119.6 |
N6—C5—C4 | 110.59 (13) | C6E—C5E—H5E | 119.6 |
N6—C5—H5A | 109.5 | C1E—C6E—C5E | 118.91 (19) |
C4—C5—H5A | 109.5 | C1E—C6E—H6E | 120.5 |
N6—C5—H5B | 109.5 | C5E—C6E—H6E | 120.5 |
C4—C5—H5B | 109.5 | C4—C40—C41 | 128.37 (16) |
H5A—C5—H5B | 108.1 | C4—C40—H40 | 115.8 |
C7—N6—C61 | 110.58 (15) | C41—C40—H40 | 115.8 |
C7—N6—C5 | 110.23 (14) | C46—C41—C42 | 117.55 (18) |
C61—N6—C5 | 110.24 (14) | C46—C41—C40 | 119.45 (18) |
N6—C7—C7A | 111.41 (14) | C42—C41—C40 | 122.90 (16) |
N6—C7—H7A | 109.3 | C43—C42—C41 | 121.5 (2) |
C7A—C7—H7A | 109.3 | C43—C42—H42 | 119.3 |
N6—C7—H7B | 109.3 | C41—C42—H42 | 119.3 |
C7A—C7—H7B | 109.3 | C44—C43—C42 | 118.6 (2) |
H7A—C7—H7B | 108.0 | C44—C43—H43 | 120.7 |
C3A—C7A—C7 | 107.88 (12) | C42—C43—H43 | 120.7 |
C3A—C7A—C8 | 114.71 (13) | C43—C44—C45 | 122.8 (2) |
C7—C7A—C8 | 107.87 (13) | C43—C44—F1 | 118.6 (3) |
C3A—C7A—H71A | 108.7 | C45—C44—F1 | 118.5 (2) |
C7—C7A—H71A | 108.7 | C44—C45—C46 | 118.4 (2) |
C8—C7A—H71A | 108.7 | C44—C45—H45 | 120.8 |
C81—C8—C7A | 112.57 (13) | C46—C45—H45 | 120.8 |
C81—C8—S9 | 110.72 (11) | C41—C46—C45 | 121.1 (2) |
C7A—C8—S9 | 115.70 (11) | C41—C46—H46 | 119.5 |
C81—C8—H8 | 105.7 | C45—C46—H46 | 119.5 |
C7A—C8—H8 | 105.7 | N6—C61—H61A | 109.5 |
S9—C8—H8 | 105.7 | N6—C61—H61B | 109.5 |
C9A—S9—C8 | 100.17 (8) | H61A—C61—H61B | 109.5 |
C10—C9A—C13A | 119.46 (16) | N6—C61—H61C | 109.5 |
C10—C9A—S9 | 121.32 (13) | H61A—C61—H61C | 109.5 |
C13A—C9A—S9 | 119.22 (12) | H61B—C61—H61C | 109.5 |
C11—C10—C9A | 120.71 (17) | C86—C81—C82 | 117.63 (16) |
C11—C10—H10 | 119.6 | C86—C81—C8 | 119.57 (15) |
C9A—C10—H10 | 119.6 | C82—C81—C8 | 122.77 (15) |
C10—C11—C12 | 119.95 (17) | C81—C82—C83 | 121.15 (18) |
C10—C11—H11 | 120.0 | C81—C82—H82 | 119.4 |
C12—C11—H11 | 120.0 | C83—C82—H82 | 119.4 |
C11—C12—C13 | 120.28 (18) | C84—C83—C82 | 118.47 (19) |
C11—C12—H12 | 119.9 | C84—C83—H83 | 120.8 |
C13—C12—H12 | 119.9 | C82—C83—H83 | 120.8 |
C12—C13—C13A | 120.28 (16) | C85—C84—C83 | 122.59 (18) |
C12—C13—H13 | 119.9 | C85—C84—F2 | 118.8 (2) |
C13A—C13—H13 | 119.9 | C83—C84—F2 | 118.6 (2) |
C13—C13A—C9A | 119.24 (15) | C84—C85—C86 | 118.7 (2) |
C13—C13A—N14 | 121.77 (14) | C84—C85—H85 | 120.6 |
C9A—C13A—N14 | 118.94 (14) | C86—C85—H85 | 120.6 |
C1—N14—C13A | 117.52 (13) | C81—C86—C85 | 121.44 (19) |
C1—N14—C3A | 102.24 (12) | C81—C86—H86 | 119.3 |
C13A—N14—C3A | 121.47 (12) | C85—C86—H86 | 119.3 |
N14—C1—N2—O3 | 3.69 (18) | C13—C13A—N14—C3A | −116.19 (17) |
C4E—C1—N2—O3 | −179.38 (14) | C9A—C13A—N14—C3A | 66.2 (2) |
C1—N2—O3—C3A | −22.32 (15) | O3—C3A—N14—C1 | −27.85 (14) |
N2—O3—C3A—N14 | 31.02 (13) | C4—C3A—N14—C1 | 86.72 (15) |
N2—O3—C3A—C4 | −88.59 (14) | C7A—C3A—N14—C1 | −144.21 (14) |
N2—O3—C3A—C7A | 154.89 (12) | O3—C3A—N14—C13A | 105.57 (14) |
O3—C3A—C4—C40 | 123.58 (16) | C4—C3A—N14—C13A | −139.87 (14) |
N14—C3A—C4—C40 | 12.2 (2) | C7A—C3A—N14—C13A | −10.8 (2) |
C7A—C3A—C4—C40 | −121.17 (16) | C6E—C1E—C2E—C3E | 0.9 (3) |
O3—C3A—C4—C5 | −57.68 (16) | CL1—C1E—C2E—C3E | −176.81 (14) |
N14—C3A—C4—C5 | −169.09 (12) | C1E—C2E—C3E—C4E | −1.0 (3) |
C7A—C3A—C4—C5 | 57.57 (16) | C2E—C3E—C4E—C5E | 0.2 (3) |
C40—C4—C5—N6 | 120.48 (18) | C2E—C3E—C4E—C1 | −179.30 (15) |
C3A—C4—C5—N6 | −58.19 (18) | N2—C1—C4E—C5E | −162.90 (17) |
C4—C5—N6—C7 | 59.06 (18) | N14—C1—C4E—C5E | 13.8 (2) |
C4—C5—N6—C61 | −178.59 (17) | N2—C1—C4E—C3E | 16.6 (2) |
C61—N6—C7—C7A | 177.10 (15) | N14—C1—C4E—C3E | −166.68 (15) |
C5—N6—C7—C7A | −60.75 (17) | C3E—C4E—C5E—C6E | 0.7 (3) |
O3—C3A—C7A—C7 | 58.34 (16) | C1—C4E—C5E—C6E | −179.80 (17) |
N14—C3A—C7A—C7 | 171.77 (13) | C2E—C1E—C6E—C5E | 0.0 (3) |
C4—C3A—C7A—C7 | −56.86 (16) | CL1—C1E—C6E—C5E | 177.70 (16) |
O3—C3A—C7A—C8 | 178.57 (12) | C4E—C5E—C6E—C1E | −0.8 (3) |
N14—C3A—C7A—C8 | −67.99 (18) | C5—C4—C40—C41 | −4.0 (3) |
C4—C3A—C7A—C8 | 63.37 (16) | C3A—C4—C40—C41 | 174.52 (15) |
N6—C7—C7A—C3A | 59.72 (17) | C4—C40—C41—C46 | 144.01 (19) |
N6—C7—C7A—C8 | −64.73 (16) | C4—C40—C41—C42 | −39.7 (3) |
C3A—C7A—C8—C81 | 165.43 (13) | C46—C41—C42—C43 | −0.6 (3) |
C7—C7A—C8—C81 | −74.34 (16) | C40—C41—C42—C43 | −176.99 (19) |
C3A—C7A—C8—S9 | 36.72 (17) | C41—C42—C43—C44 | 0.7 (4) |
C7—C7A—C8—S9 | 156.96 (11) | C42—C43—C44—C45 | −0.7 (4) |
C81—C8—S9—C9A | −84.45 (12) | C42—C43—C44—F1 | 179.5 (2) |
C7A—C8—S9—C9A | 45.15 (12) | C43—C44—C45—C46 | 0.6 (4) |
C8—S9—C9A—C10 | 110.28 (14) | F1—C44—C45—C46 | −179.6 (2) |
C8—S9—C9A—C13A | −70.17 (14) | C42—C41—C46—C45 | 0.5 (3) |
C13A—C9A—C10—C11 | −1.6 (3) | C40—C41—C46—C45 | 177.01 (19) |
S9—C9A—C10—C11 | 177.92 (14) | C44—C45—C46—C41 | −0.5 (3) |
C9A—C10—C11—C12 | 2.3 (3) | C7A—C8—C81—C86 | 125.69 (18) |
C10—C11—C12—C13 | −0.4 (3) | S9—C8—C81—C86 | −103.06 (17) |
C11—C12—C13—C13A | −2.0 (3) | C7A—C8—C81—C82 | −56.5 (2) |
C12—C13—C13A—C9A | 2.6 (2) | S9—C8—C81—C82 | 74.79 (18) |
C12—C13—C13A—N14 | −174.97 (16) | C86—C81—C82—C83 | 0.6 (3) |
C10—C9A—C13A—C13 | −0.8 (2) | C8—C81—C82—C83 | −177.30 (16) |
S9—C9A—C13A—C13 | 179.63 (12) | C81—C82—C83—C84 | −0.6 (3) |
C10—C9A—C13A—N14 | 176.86 (14) | C82—C83—C84—C85 | 0.4 (3) |
S9—C9A—C13A—N14 | −2.7 (2) | C82—C83—C84—F2 | −179.60 (18) |
N2—C1—N14—C13A | −119.50 (16) | C83—C84—C85—C86 | −0.2 (4) |
C4E—C1—N14—C13A | 63.6 (2) | F2—C84—C85—C86 | 179.8 (2) |
N2—C1—N14—C3A | 16.18 (17) | C82—C81—C86—C85 | −0.4 (3) |
C4E—C1—N14—C3A | −160.76 (14) | C8—C81—C86—C85 | 177.58 (19) |
C13—C13A—N14—C1 | 10.6 (2) | C84—C85—C86—C81 | 0.2 (4) |
C9A—C13A—N14—C1 | −166.97 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C61—H61C···F2i | 0.96 | 2.50 | 3.435 (3) | 166 |
C83—H83···N2ii | 0.93 | 2.61 | 3.488 (3) | 157 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C33H26ClF2N3OS |
Mr | 586.08 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 10.836 (5), 11.366 (4), 23.100 (3) |
β (°) | 92.63 (1) |
V (Å3) | 2842.0 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker Kappa-APEX2 CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.93, 0.96 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36502, 8394, 5384 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.707 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.128, 1.01 |
No. of reflections | 8394 |
No. of parameters | 370 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.34 |
Computer programs: APEXII (Bruker–Nonius, 2004), SAINT (Bruker–Nonius, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLUTON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C61—H61C···F2i | 0.96 | 2.50 | 3.435 (3) | 165.5 |
C83—H83···N2ii | 0.93 | 2.61 | 3.488 (3) | 157.4 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z+1. |
The title compound, C33H26N3OF2SCl, belongs to an important class of heterocycles which are expected to possess antihypertensive properties, and is made of three fused ring systems viz. a benzothiazepine, an oxadiazole and a methyl piperidine ring. Interestingly, benzothiazepines have been established as a class of calcium channel blockers (Budriesi et al., 2007), oxadiazole derivatives have been found to possess antimicrobial activity (Şahin et al., 2002) and piperidine ring occurs in many natural alkaloids and are constituents of a number of pharmaceutical drugs. Also, the role of non-conventional hydrogen bonds viz. C—H···X (X= N, O, Cl, F, etc.) can be accurately assessed through precise single-crystal structure determinations of these compounds which, in turn, may provide insights into design of drugs with a wide range of biological activities.
Least-squares plane calculations show that the 4-fluorophenyl attached to thiazepine, 4-flurophenyl attached to piperidine and 4-chlorophenyl rings make dihedral angles of 40.0 (1), 67.6 (1) and 71.5 (1)°, respectively, with respect to the benzene fused to the thiazepine ring. The torsion angles about the methylidene bond C4—C40—C41—C42 = -39.7 (3)° and C4—C40—C41—C46 = 144.01 (19)° indicate a significant twist of the 4-fluorophenyl ring which may be attributed to steric factors. The oxadiazole, piperidine and benzothiazepine rings adopt the envelope [Q = 0.299 (2) Å, φ = 150.5 (3)°] (Cremer & Pople, 1975), chair [Q = 0.597 (2) Å, θ = 1.6 (2)°, φ = 251 (5)°] (Boeyens, 1978) and twist-boat conformations, respectively. The molecular aggregation is characterized by linear chains of centrosymmetrically related pairs extending along the [010] axis, connected through a C—H···F and a C—H···N bonds (Table 1). The interactions between these linear chains are purely van der Waal's in nature. No significant π···π and C—H···π interactions were found in the crystal structure.