Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104019730/av1196sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104019730/av1196Isup2.hkl |
CCDC reference: 254932
For the synthesis of (I), to 6-(3,4-difluorobenzoyl)-2-benzothiazolinone (2.5 mmol) was added 4-vinylpyridine (7.5 mmol), and the reaction mixture was heated under reflux in an oil bath until molten and then for an additional 2 h at 353 K. On addition of a cold alchol–water mixture, the product separated, and the resulting precipitate was collected by filtration (Gökhan et al., 1999). Yield: 61.41%. M.p: 399–401 K. The crude product was recrystallized from ethanol–water. IR (KBr, cm−1): n 1692 (lactam C=O), 1649 (arom. ket.). 1H NMR (CDCl3): d 3.071–3.109 (t, 2H, CH2—Ar), 4.243–4.280 (t, 2H, N—CH2), 7.026–7.047 (d, J = 8.4 Hz, 1H, 2-benzothiazolinone H-4), 7.162–7.173 (d, J = 4.4 Hz, 2H, pyridine H-2, H-6), 7.315–7.339 (t, 1H, benzene H-5'), 7.53–7.57 (s, 1H, benzene H-2'), 7.624–7.674 (t, 1H, benzene H-6'), 7.728–7.754 (d, J = 10 Hz, 2-benzothiazolinone H-5), 7.922–7.926 (s, 1H, benzothiazolinone H-7), 8.529–8.543 (d, J = 8 Hz, 2H, pyridine H-3, H-5). Analysis calulate for C21H14F2N2O2S (MW = 396): N 7.07, S 8.09%; found: N 6.93, S 7.81%).
H atoms were placed in idealized positions and refined using a riding model [Ueq(H) = 1.3Ueq(C), C—H = 0.93 Å (aromatic) and C—H = 0.97 Å (ethyl)].
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
| Figure 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level. Figure 2. The crystal packing of (I), projected on to the bc plane. |
C21H14F2N2O2S | F(000) = 816 |
Mr = 396.4 | Dx = 1.468 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 7.2985 (15) Å | θ = 11–18.1° |
b = 19.4347 (19) Å | µ = 0.22 mm−1 |
c = 12.6638 (16) Å | T = 295 K |
β = 93.020 (1)° | Prism, colourless |
V = 1793.8 (5) Å3 | 0.54 × 0.42 × 0.12 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.020 |
non–profiled ω/2θ scans | θmax = 26.3°, θmin = 2.6° |
Absorption correction: ψ scan (North et al., 1968) | h = −9→0 |
Tmin = 0.852, Tmax = 0.974 | k = −24→0 |
3924 measured reflections | l = −15→15 |
3636 independent reflections | 3 standard reflections every 120 min |
2575 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo2) + (0.0601P)2 + 0.5076P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.120 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.22 e Å−3 |
3636 reflections | Δρmin = −0.20 e Å−3 |
253 parameters |
C21H14F2N2O2S | V = 1793.8 (5) Å3 |
Mr = 396.4 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.2985 (15) Å | µ = 0.22 mm−1 |
b = 19.4347 (19) Å | T = 295 K |
c = 12.6638 (16) Å | 0.54 × 0.42 × 0.12 mm |
β = 93.020 (1)° |
Enraf–Nonius CAD-4 diffractometer | 2575 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.020 |
Tmin = 0.852, Tmax = 0.974 | 3 standard reflections every 120 min |
3924 measured reflections | intensity decay: none |
3636 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.22 e Å−3 |
3636 reflections | Δρmin = −0.20 e Å−3 |
253 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3487 (3) | 0.19388 (12) | 0.92523 (17) | 0.0517 (5) | |
C10 | 0.8748 (3) | 0.23074 (12) | 1.13913 (15) | 0.0474 (5) | |
C11 | 0.9403 (3) | 0.16475 (12) | 1.15321 (18) | 0.0562 (6) | |
C12 | 1.1193 (3) | 0.15461 (13) | 1.1900 (2) | 0.0632 (6) | |
C13 | 1.1752 (3) | 0.26674 (13) | 1.1952 (2) | 0.0682 (7) | |
C14 | 0.9989 (3) | 0.28276 (12) | 1.1598 (2) | 0.0605 (6) | |
C15 | 0.1012 (3) | 0.49966 (11) | 0.86825 (18) | 0.0526 (5) | |
C16 | −0.0555 (3) | 0.50812 (10) | 0.78782 (17) | 0.0490 (5) | |
C17 | −0.0463 (3) | 0.48641 (12) | 0.68443 (18) | 0.0578 (6) | |
C18 | −0.1855 (4) | 0.50253 (13) | 0.6099 (2) | 0.0686 (7) | |
C19 | −0.3334 (4) | 0.53844 (13) | 0.6410 (2) | 0.0677 (7) | |
C2 | 0.2085 (3) | 0.31080 (10) | 0.88687 (15) | 0.0404 (4) | |
C20 | −0.3480 (3) | 0.55728 (12) | 0.7441 (2) | 0.0634 (6) | |
C21 | −0.2092 (3) | 0.54415 (11) | 0.81764 (19) | 0.0578 (6) | |
C3 | 0.1127 (3) | 0.37026 (10) | 0.86199 (15) | 0.0425 (5) | |
C4 | 0.2005 (3) | 0.43338 (10) | 0.87735 (16) | 0.0458 (5) | |
C5 | 0.3856 (3) | 0.43468 (12) | 0.91406 (17) | 0.0521 (5) | |
C6 | 0.4821 (3) | 0.37588 (12) | 0.93701 (16) | 0.0508 (5) | |
C7 | 0.3927 (3) | 0.31298 (11) | 0.92419 (15) | 0.0423 (4) | |
C8 | 0.6569 (3) | 0.23639 (13) | 0.98100 (17) | 0.0537 (6) | |
C9 | 0.6797 (3) | 0.24464 (15) | 1.10050 (17) | 0.0596 (6) | |
F1 | −0.4717 (3) | 0.55545 (9) | 0.57044 (15) | 0.1065 (6) | |
F2 | −0.5002 (2) | 0.59065 (9) | 0.77139 (15) | 0.0998 (6) | |
N1 | 0.4668 (2) | 0.24848 (9) | 0.94270 (14) | 0.0480 (4) | |
N2 | 1.2385 (3) | 0.20429 (11) | 1.21157 (17) | 0.0635 (5) | |
O1 | 0.3860 (2) | 0.13405 (9) | 0.93881 (16) | 0.0759 (5) | |
O2 | 0.1432 (2) | 0.54769 (8) | 0.92658 (15) | 0.0744 (5) | |
S1 | 0.13058 (7) | 0.22595 (3) | 0.87782 (4) | 0.04813 (17) | |
H11 | 0.8642 | 0.1273 | 1.138 | 0.067* | |
H12 | 1.1588 | 0.1095 | 1.2004 | 0.076* | |
H13 | 1.256 | 0.3031 | 1.2085 | 0.082* | |
H14 | 0.964 | 0.3284 | 1.1499 | 0.073* | |
H17 | 0.0539 | 0.4608 | 0.6647 | 0.069* | |
H18 | −0.1779 | 0.489 | 0.5398 | 0.082* | |
H21 | −0.2172 | 0.5591 | 0.887 | 0.069* | |
H3 | −0.0084 | 0.3683 | 0.8354 | 0.051* | |
H5 | 0.4443 | 0.4769 | 0.923 | 0.062* | |
H6 | 0.6047 | 0.3778 | 0.9607 | 0.061* | |
H8A | 0.7367 | 0.2687 | 0.9474 | 0.064* | |
H8B | 0.6932 | 0.1903 | 0.9617 | 0.064* | |
H9A | 0.646 | 0.2911 | 1.1199 | 0.072* | |
H9B | 0.5984 | 0.2129 | 1.1342 | 0.072* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0432 (12) | 0.0570 (13) | 0.0544 (13) | 0.0084 (10) | −0.0018 (9) | 0.0022 (10) |
C10 | 0.0372 (10) | 0.0657 (13) | 0.0389 (11) | 0.0089 (10) | −0.0005 (8) | 0.0023 (10) |
C11 | 0.0468 (12) | 0.0568 (13) | 0.0643 (14) | 0.0000 (10) | −0.0036 (11) | 0.0004 (11) |
C12 | 0.0567 (14) | 0.0573 (14) | 0.0751 (16) | 0.0194 (12) | −0.0011 (12) | 0.0055 (12) |
C13 | 0.0523 (14) | 0.0633 (15) | 0.0872 (19) | −0.0054 (12) | −0.0152 (13) | 0.0009 (13) |
C14 | 0.0564 (14) | 0.0503 (13) | 0.0732 (16) | 0.0117 (11) | −0.0118 (12) | 0.0045 (11) |
C15 | 0.0503 (13) | 0.0462 (12) | 0.0603 (13) | −0.0064 (10) | −0.0060 (11) | −0.0025 (10) |
C16 | 0.0486 (12) | 0.0411 (11) | 0.0565 (13) | −0.0049 (9) | −0.0043 (10) | 0.0053 (9) |
C17 | 0.0560 (14) | 0.0582 (13) | 0.0592 (14) | −0.0008 (11) | 0.0019 (11) | 0.0007 (11) |
C18 | 0.0801 (18) | 0.0694 (16) | 0.0551 (14) | −0.0037 (14) | −0.0081 (13) | 0.0035 (12) |
C19 | 0.0725 (17) | 0.0539 (14) | 0.0736 (17) | 0.0028 (12) | −0.0247 (14) | 0.0088 (12) |
C2 | 0.0320 (9) | 0.0513 (11) | 0.0375 (10) | −0.0061 (8) | −0.0030 (8) | −0.0008 (8) |
C20 | 0.0560 (14) | 0.0484 (13) | 0.0848 (19) | 0.0090 (11) | −0.0074 (13) | 0.0016 (12) |
C21 | 0.0630 (15) | 0.0495 (12) | 0.0600 (14) | 0.0056 (11) | −0.0044 (11) | −0.0010 (10) |
C3 | 0.0305 (9) | 0.0505 (11) | 0.0457 (11) | −0.0024 (8) | −0.0060 (8) | −0.0016 (9) |
C4 | 0.0398 (11) | 0.0493 (11) | 0.0473 (11) | −0.0050 (9) | −0.0080 (9) | −0.0029 (9) |
C5 | 0.0440 (12) | 0.0546 (13) | 0.0563 (13) | −0.0126 (10) | −0.0097 (10) | −0.0066 (10) |
C6 | 0.0313 (10) | 0.0667 (14) | 0.0531 (12) | −0.0081 (9) | −0.0103 (9) | −0.0058 (10) |
C7 | 0.0316 (10) | 0.0568 (12) | 0.0379 (10) | 0.0016 (9) | −0.0039 (8) | −0.0006 (9) |
C8 | 0.0359 (11) | 0.0767 (16) | 0.0481 (12) | 0.0143 (10) | −0.0026 (9) | 0.0006 (11) |
C9 | 0.0402 (12) | 0.0899 (17) | 0.0481 (13) | 0.0161 (11) | −0.0027 (9) | 0.0008 (11) |
F1 | 0.1055 (14) | 0.1027 (13) | 0.1048 (13) | 0.0269 (11) | −0.0544 (11) | 0.0002 (10) |
F2 | 0.0762 (11) | 0.0969 (12) | 0.1247 (15) | 0.0370 (10) | −0.0110 (10) | −0.0061 (10) |
N1 | 0.0345 (9) | 0.0608 (11) | 0.0477 (10) | 0.0058 (8) | −0.0058 (7) | −0.0005 (8) |
N2 | 0.0410 (10) | 0.0719 (14) | 0.0763 (14) | 0.0119 (9) | −0.0084 (9) | 0.0041 (10) |
O1 | 0.0650 (11) | 0.0573 (10) | 0.1041 (14) | 0.0145 (9) | −0.0069 (10) | 0.0060 (10) |
O2 | 0.0748 (12) | 0.0542 (10) | 0.0913 (13) | 0.0008 (8) | −0.0241 (10) | −0.0182 (9) |
S1 | 0.0354 (3) | 0.0474 (3) | 0.0610 (3) | −0.0031 (2) | −0.0036 (2) | 0.0009 (2) |
S1—C2 | 1.746 (2) | C6—H6 | 0.93 |
S1—C1 | 1.784 (2) | C11—C10 | 1.377 (3) |
C7—N1 | 1.380 (3) | C11—C12 | 1.378 (3) |
C7—C6 | 1.391 (3) | C11—H11 | 0.93 |
C7—C2 | 1.402 (3) | C16—C17 | 1.381 (3) |
N1—C1 | 1.377 (3) | C16—C21 | 1.392 (3) |
N1—C8 | 1.464 (2) | C8—C9 | 1.522 (3) |
C3—C2 | 1.378 (3) | C8—H8A | 0.97 |
C3—C4 | 1.393 (3) | C8—H8B | 0.97 |
C3—H3 | 0.93 | C12—H12 | 0.93 |
O1—C1 | 1.204 (3) | F1—C19 | 1.353 (3) |
C5—C6 | 1.366 (3) | C10—C9 | 1.505 (3) |
C5—C4 | 1.406 (3) | C9—H9A | 0.97 |
C5—H5 | 0.93 | C9—H9B | 0.97 |
O2—C15 | 1.219 (2) | C20—C21 | 1.364 (3) |
C15—C4 | 1.480 (3) | C20—C19 | 1.365 (4) |
C15—C16 | 1.500 (3) | C19—C18 | 1.361 (4) |
N2—C13 | 1.311 (3) | C13—H13 | 0.93 |
N2—C12 | 1.319 (3) | C21—H21 | 0.93 |
F2—C20 | 1.347 (3) | C17—C18 | 1.385 (3) |
C14—C10 | 1.373 (3) | C17—H17 | 0.93 |
C14—C13 | 1.376 (3) | C18—H18 | 0.93 |
C14—H14 | 0.93 | ||
C2—S1—C1 | 91.49 (10) | N1—C1—S1 | 108.94 (15) |
N1—C7—C6 | 126.97 (17) | N1—C8—C9 | 111.37 (17) |
N1—C7—C2 | 112.95 (17) | N1—C8—H8A | 109.4 |
C6—C7—C2 | 120.07 (18) | C9—C8—H8A | 109.4 |
C1—N1—C7 | 115.86 (16) | N1—C8—H8B | 109.4 |
C1—N1—C8 | 120.22 (18) | C9—C8—H8B | 109.4 |
C7—N1—C8 | 123.90 (18) | H8A—C8—H8B | 108 |
C2—C3—C4 | 118.86 (17) | N2—C12—C11 | 124.7 (2) |
C2—C3—H3 | 120.6 | N2—C12—H12 | 117.7 |
C4—C3—H3 | 120.6 | C11—C12—H12 | 117.7 |
C3—C2—C7 | 121.16 (18) | C14—C10—C11 | 116.13 (19) |
C3—C2—S1 | 128.12 (14) | C14—C10—C9 | 122.2 (2) |
C7—C2—S1 | 110.72 (15) | C11—C10—C9 | 121.7 (2) |
C6—C5—C4 | 122.07 (19) | C10—C9—C8 | 110.87 (17) |
C6—C5—H5 | 119 | C10—C9—H9A | 109.5 |
C4—C5—H5 | 119 | C8—C9—H9A | 109.5 |
O2—C15—C4 | 120.84 (19) | C10—C9—H9B | 109.5 |
O2—C15—C16 | 119.1 (2) | C8—C9—H9B | 109.5 |
C4—C15—C16 | 120.08 (18) | H9A—C9—H9B | 108.1 |
C13—N2—C12 | 115.0 (2) | F2—C20—C21 | 120.5 (2) |
C3—C4—C5 | 119.27 (19) | F2—C20—C19 | 118.8 (2) |
C3—C4—C15 | 122.43 (18) | C21—C20—C19 | 120.7 (2) |
C5—C4—C15 | 117.93 (18) | F1—C19—C18 | 120.7 (3) |
C10—C14—C13 | 119.4 (2) | F1—C19—C20 | 118.2 (3) |
C10—C14—H14 | 120.3 | C18—C19—C20 | 121.1 (2) |
C13—C14—H14 | 120.3 | N2—C13—C14 | 125.2 (2) |
C5—C6—C7 | 118.53 (17) | N2—C13—H13 | 117.4 |
C5—C6—H6 | 120.7 | C14—C13—H13 | 117.4 |
C7—C6—H6 | 120.7 | C20—C21—C16 | 119.3 (2) |
C10—C11—C12 | 119.6 (2) | C20—C21—H21 | 120.4 |
C10—C11—H11 | 120.2 | C16—C21—H21 | 120.4 |
C12—C11—H11 | 120.2 | C16—C17—C18 | 120.4 (2) |
C17—C16—C21 | 119.4 (2) | C16—C17—H17 | 119.8 |
C17—C16—C15 | 122.5 (2) | C18—C17—H17 | 119.8 |
C21—C16—C15 | 117.9 (2) | C19—C18—C17 | 118.9 (2) |
O1—C1—N1 | 125.9 (2) | C19—C18—H18 | 120.5 |
O1—C1—S1 | 125.16 (19) | C17—C18—H18 | 120.5 |
C6—C7—N1—C1 | 179.2 (2) | C8—N1—C1—S1 | −179.33 (15) |
C2—C7—N1—C1 | −2.0 (2) | C2—S1—C1—O1 | 179.3 (2) |
C6—C7—N1—C8 | 0.7 (3) | C2—S1—C1—N1 | −1.22 (15) |
C2—C7—N1—C8 | 179.43 (18) | C1—N1—C8—C9 | −96.6 (2) |
C4—C3—C2—C7 | −1.8 (3) | C7—N1—C8—C9 | 81.9 (3) |
C4—C3—C2—S1 | 178.61 (16) | C13—N2—C12—C11 | −0.2 (4) |
N1—C7—C2—C3 | −178.69 (17) | C10—C11—C12—N2 | −1.5 (4) |
C6—C7—C2—C3 | 0.2 (3) | C13—C14—C10—C11 | −1.7 (3) |
N1—C7—C2—S1 | 1.0 (2) | C13—C14—C10—C9 | 179.9 (2) |
C6—C7—C2—S1 | 179.82 (16) | C12—C11—C10—C14 | 2.4 (3) |
C1—S1—C2—C3 | 179.78 (19) | C12—C11—C10—C9 | −179.2 (2) |
C1—S1—C2—C7 | 0.16 (15) | C14—C10—C9—C8 | 98.3 (3) |
C2—C3—C4—C5 | 2.3 (3) | C11—C10—C9—C8 | −80.1 (3) |
C2—C3—C4—C15 | −170.59 (19) | N1—C8—C9—C10 | 178.9 (2) |
C6—C5—C4—C3 | −1.1 (3) | F2—C20—C19—F1 | 1.2 (4) |
C6—C5—C4—C15 | 172.0 (2) | C21—C20—C19—F1 | −177.1 (2) |
O2—C15—C4—C3 | 143.6 (2) | F2—C20—C19—C18 | −177.7 (2) |
C16—C15—C4—C3 | −35.4 (3) | C21—C20—C19—C18 | 4.0 (4) |
O2—C15—C4—C5 | −29.4 (3) | C12—N2—C13—C14 | 0.9 (4) |
C16—C15—C4—C5 | 151.7 (2) | C10—C14—C13—N2 | 0.1 (4) |
C4—C5—C6—C7 | −0.5 (3) | F2—C20—C21—C16 | 178.5 (2) |
N1—C7—C6—C5 | 179.7 (2) | C19—C20—C21—C16 | −3.2 (4) |
C2—C7—C6—C5 | 1.0 (3) | C17—C16—C21—C20 | 0.0 (3) |
O2—C15—C16—C17 | 135.3 (2) | C15—C16—C21—C20 | 175.0 (2) |
C4—C15—C16—C17 | −45.7 (3) | C21—C16—C17—C18 | 2.5 (3) |
O2—C15—C16—C21 | −39.5 (3) | C15—C16—C17—C18 | −172.3 (2) |
C4—C15—C16—C21 | 139.5 (2) | F1—C19—C18—C17 | 179.7 (2) |
C7—N1—C1—O1 | −178.4 (2) | C20—C19—C18—C17 | −1.4 (4) |
C8—N1—C1—O1 | 0.2 (3) | C16—C17—C18—C19 | −1.8 (4) |
C7—N1—C1—S1 | 2.1 (2) |
Experimental details
Crystal data | |
Chemical formula | C21H14F2N2O2S |
Mr | 396.4 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 7.2985 (15), 19.4347 (19), 12.6638 (16) |
β (°) | 93.020 (1) |
V (Å3) | 1793.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.54 × 0.42 × 0.12 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.852, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3924, 3636, 2575 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.623 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.120, 1.02 |
No. of reflections | 3636 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.20 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
S1—C2 | 1.746 (2) | C15—C16 | 1.500 (3) |
S1—C1 | 1.784 (2) | N2—C13 | 1.311 (3) |
C7—N1 | 1.380 (3) | N2—C12 | 1.319 (3) |
N1—C1 | 1.377 (3) | F2—C20 | 1.347 (3) |
N1—C8 | 1.464 (2) | C8—C9 | 1.522 (3) |
O1—C1 | 1.204 (3) | F1—C19 | 1.353 (3) |
O2—C15 | 1.219 (2) | C10—C9 | 1.505 (3) |
C15—C4 | 1.480 (3) | ||
C2—S1—C1 | 91.49 (10) | O1—C1—N1 | 125.9 (2) |
N1—C7—C2 | 112.95 (17) | N1—C1—S1 | 108.94 (15) |
C1—N1—C7 | 115.86 (16) | N1—C8—C9 | 111.37 (17) |
C7—C2—S1 | 110.72 (15) | N2—C12—C11 | 124.7 (2) |
C13—N2—C12 | 115.0 (2) | C14—C10—C11 | 116.13 (19) |
C10—C11—C12 | 119.6 (2) | N2—C13—C14 | 125.2 (2) |
C16—C15—C4—C3 | −35.4 (3) | C7—N1—C8—C9 | 81.9 (3) |
C4—C15—C16—C17 | −45.7 (3) | C14—C10—C9—C8 | 98.3 (3) |
C1—N1—C8—C9 | −96.6 (2) | N1—C8—C9—C10 | 178.9 (2) |
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Benzothiazole derivatives possess a broad spectrum of pharmacological activitie, such as antibacterial, antifungal (Delmas et al., 2002; Kanoongo et al., 1990; Karalı et al., 2004; Lakhan et al., 2000), dopaminergic (Weinstock et al., 1987;), anticonvulsant (Chopade et al., 2002), antiadrenergic (Di Nunno et al., 2000) and analgesic anti-inflammatory activities (Gökhan et al., 2004; Khedekar et al., 2003). The immunological importance of these derivatives prompted us to synthesize a 3-substituted-2-benzothiazolinone derivative and clarify its structure.
It has been stated that 2-hydroxybenzothiazole may also exist in the tautomeric form (Katritzky, 1985). The vinylpyridine group therefore may be bonded to the 6-acyl-2-benzothiazolinone moiety through both the N and the O atoms depending on whether the molecule existed in the hydroxy or the one form, and a mixture of N-substituted or O-substituted benzothiazolinone derivatives may be generated. The present work has been carried out in order to determine the stereochemistry of the reactive tautomeric form.
The title compound, (I), was synthesized by the reaction of 6-(3,4-difluorobenzoyl)-2- benzothiazolinone with 4-vinylpyridine. The structure of (I) was suggested by IR, 1H NMR and elementary analysis. In order to obtain information about the stereochemistry of the molecule and to confirm the assigned structure, X-ray analysis was undertaken. The biological activity of (I) is under investigation.
The molecular structure and atom-numbering scheme are shown in Fig. 1, and the arrangement of the molecules in the unit cell is given in Fig. 2. Selected bond lengths and angles are listed in Table 1. The benzothiazole ring system is planar, the greatest deviations from the least-squares plane of the system being those of atoms C3 [−0.016 (2) Å] and C1 [0.0142 (2) Å]. The dihedral angle between the planes associated with the benzene and thiazole rings is only 0.55 (8)°. This value is close to those found for other structures including a benzothiazole ring system [e.g. 0.3 (1)° (Ćaleta et al., 2004) and 2.3 (4)° (Castiñeiras et al., 2000)].
The pyridylethyl moiety at atom N1 is rotated around the N1—C8 and C9—C10 bonds, giving C7—N1—C8—C9 and C8—C9—C10—C14 torsion angles of 81.9 (3) and 98.3 (3)°. The dihedral angle between the ring planes is 1.08 (9)°, so that the pyridine ring is almost parallel to the benzothiazole ring system. The difluorobenzene moiety is nearly planar, and atoms F1 and F2 lie −0.043 (2) and 0.56 (2) Å from the mean plane of the benzene ring atoms. The carbonyl group at atom C4 is inclined with respect to the benzothiazole system; atom O2 departs 0.853 (2) Å from the mean ring plane. The dihedral angle between the plane defined by atoms O2, C4, C15 and C16 and the plane of the benzene ring is 33.3 (1)°.
In the thiazole ring, the S1—C1 bond is longer than the S1—C2 bond [1.784 (2) Å versus 1.746 (2) Å] and is also longer than the accepted value for an S—Csp2 single bond [1.762 Å for O=C—S—C#; Allen et al., 1987]. The difference between the S1—C1 and S1—C2 bond lengths can be attributed to the fact that carbonyl atom O1 is bonded to atom C1, whereas atom C2 belongs to the aromatic ring. The S—C distances are in agreement with those found for other structures containing benzothiazolinone, such as 2-hydroxybenzothiazole [1.7767 (13) and 1.7479 (13) Å; Flakus et al., 2002] and methyl-3-(5-choloro-2-oxo-1,3-benzothiazol-3(2H)-yl)propanoate [1.776 (3) and 1.742 (3) Å; Aydın et al., 2002]. The N1—C1 [1.377 (3) Å] and N1—C7 [1.380 (3) Å] bond lengths are within the usual range for Csp2—Nsp2 bonds, while the N1—C8 bond length [1.464 (2) Å] is close to the average length of Csp3—Nsp2 bonds (Allen et al., 1987). These values are comparable to those of other structures [1.3589 (16) and 1.3911 (16) Å in 2-hydroxybenzothiazole, and 1.362 (4), 1.401 (4) and 1.469 (3) Å in methyl-3-(5-choloro-2-oxo- 1,3-benzothiazol-3(2H)-yl)propanoate]. The sum of the angles about atom N1 (360°) indicates a planar sp2 environment.
In this structure, the orientations of carbonyl atoms O2 and O1 toward the benzothiazole and ethyl groups, respectively, are consistent with an intramolecular hydrogen-type interaction. In this manner, carbonyl groups are involved in the formation of a five-membered ring structure [C5···O2 = 2.830 (3) Å, C5—H5···O2 = 94.9°, C8···O1 = 2.835 (3) Å and C8—H8B···O1 = 100.3°]. The crystal packing of (I) is shown in Fig. 2. There are no intermolecular hydrogen bonds, but the F atoms of the phenyl substituent are involved in short intermolecular contacts [F1···F1i = 2.814 (3) Å and S1···F2ii = 3.347 (2) Å; symmetry codes: (i) −x, −y, −z; (ii) 1/2 − x, 1/2 + y, 1/2 − z].