The structures of the novel triazolobenzothiazines 2,4-dihydro-1
H-benzo[
b][1,2,4]triazolo[4,3-
d][1,4]thiazin-1-one (IDPH-791), C
9H
7N
3OS, (I), a potential muscle relaxant, its benzoyl derivative, 2-(2-oxo-2-phenylethyl)-2,4-dihydro-1
H-benzo[
b][1,2,4]triazolo[4,3-
d][1,4]thiazin-1-one, C
20H
17N
3O
4S, (II), and the
-keto ester derivative, ethyl 3-oxo-2-(1-oxo-2,4-dihydro-1
H-benzo[
b][1,2,4]triazolo[4,3-
d][1,4]thiazin-2-yl)-3-phenylpropanoate, C
17H
13N
3O
2S, (III), are the first examples of benzothiazine-fused triazoles in the crystallographic literature. The heterocyclic thiazine rings in all three structures adopt a distorted half-chair conformation. Compound (III) exists in the
trans-
-diketo form. Other than N-H
O hydrogen bonds in (I) forming dimers, no formal intermolecular hydrogen bonds are involved in the crystal packing of any of the three structures, which is dominated by C-H
O/N and
-
stacking interactions.
Supporting information
CCDC references: 914661; 914662; 914663
The synthesis of (I) and (II) (SMS Pharma Research Centre, Hyderabad) was
reported previously (Reddy Sastry et al., 1991). They were
recrystallized from solutions in methanol (30 ml) for (I) and ethylacetate (30 ml) for (II) by slow evaporation. Compound (III) (SMS Pharma Research Centre,
Hyderabad) was prepared by heating a mixture of (I) (100 mmol) and
ethyl-2-bromo-3-oxo-3-phenyl propanoate (105 mmol) in acetonitrile (20 ml)
containing anhydrous K2CO3 (200 mmol) and tetrabutylammonium bromide (10 mmol) for 3 h under stirring and refluxing conditions. The reaction mixture
was then cooled to room temperature, filtered, concentrated, triturated with
ether (10 ml) and again filtered to yield (III). Suitable single crystals of
(III) were grown by slow evaporation of a solution in methanol (30 ml).
In (III), the atoms O4, C19 and C20 are disordered over two sites and the
site-occupancy factors refined to 0.596 (15) and 0.404 (15). The anisotropic
displacement parameters of the disordered atoms were restrained to be similar
[SIMU instruction in SHELXL97 (Sheldrick, 2008)], and the
direction of
motion along the axis between these atoms was also restrained (DELU
instruction in SHELXL97). The C—C distances of the disordered groups
were restrained to be 1.55 (2) Å and the C18—O4 and O4—C19 distances to
be 1.33 (2) and 1.45 (2) Å. The N-bound H atoms of (I) were located in a
difference Fourier map and their positions and isotropic displacement
parameters were refined. The C-bound H atoms of (I), (II) and (III) were
located in difference density maps, but were positioned geometrically and
included as riding atoms, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene), and with Uiso(H) = 1.5Ueq(C) for the methyl
groups or 1.2Ueq(C) otherwise. The methyl groups were allowed to
rotate but not to tip.
For all compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(I) 4
H-1,2,4-Triazolo[3,4-
c][1,4]benzothiazin-1(2
H)-one
top
Crystal data top
C9H7N3OS | F(000) = 1696 |
Mr = 205.24 | Dx = 1.548 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 7940 reflections |
a = 14.6307 (11) Å | θ = 2.8–27.9° |
b = 8.5718 (7) Å | µ = 0.33 mm−1 |
c = 28.083 (2) Å | T = 294 K |
V = 3521.9 (5) Å3 | Block, colourless |
Z = 16 | 0.18 × 0.16 × 0.07 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2895 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −17→17 |
23641 measured reflections | k = −10→10 |
3092 independent reflections | l = −33→33 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0472P)2 + 1.2353P] where P = (Fo2 + 2Fc2)/3 |
3092 reflections | (Δ/σ)max = 0.002 |
261 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C9H7N3OS | V = 3521.9 (5) Å3 |
Mr = 205.24 | Z = 16 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.6307 (11) Å | µ = 0.33 mm−1 |
b = 8.5718 (7) Å | T = 294 K |
c = 28.083 (2) Å | 0.18 × 0.16 × 0.07 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2895 reflections with I > 2σ(I) |
23641 measured reflections | Rint = 0.020 |
3092 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.24 e Å−3 |
3092 reflections | Δρmin = −0.18 e Å−3 |
261 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.84019 (11) | −0.11143 (18) | 0.61793 (6) | 0.0445 (4) | |
H1A | 0.8313 | −0.2029 | 0.6007 | 0.053* | |
C2A | 0.85524 (10) | 0.02781 (17) | 0.59376 (5) | 0.0357 (3) | |
C3A | 0.82292 (12) | 0.2168 (2) | 0.51776 (6) | 0.0469 (4) | |
H3A | 0.8329 | 0.2402 | 0.4844 | 0.056* | |
H3B | 0.7578 | 0.2214 | 0.5240 | 0.056* | |
C4A | 0.87140 (10) | 0.33258 (18) | 0.54789 (5) | 0.0395 (3) | |
C5A | 0.86734 (9) | 0.16437 (16) | 0.62042 (5) | 0.0323 (3) | |
C6A | 0.86333 (10) | 0.15985 (18) | 0.66991 (5) | 0.0391 (3) | |
H6A | 0.8697 | 0.2512 | 0.6875 | 0.047* | |
C7A | 0.84988 (11) | 0.0189 (2) | 0.69286 (6) | 0.0456 (4) | |
H7A | 0.8487 | 0.0153 | 0.7260 | 0.055* | |
C8A | 0.83823 (11) | −0.1162 (2) | 0.66694 (6) | 0.0483 (4) | |
H8A | 0.8291 | −0.2106 | 0.6825 | 0.058* | |
C9A | 0.93332 (10) | 0.43507 (17) | 0.61350 (5) | 0.0390 (3) | |
N1A | 0.90420 (10) | 0.46461 (16) | 0.53405 (5) | 0.0499 (4) | |
N2A | 0.94070 (10) | 0.52891 (16) | 0.57515 (5) | 0.0473 (3) | |
N3A | 0.88573 (8) | 0.30624 (13) | 0.59590 (4) | 0.0342 (3) | |
H1N | 0.9754 (13) | 0.608 (2) | 0.5746 (6) | 0.057 (5)* | |
O1A | 0.96071 (9) | 0.45606 (13) | 0.65440 (4) | 0.0504 (3) | |
S1A | 0.86581 (3) | 0.02384 (5) | 0.531275 (14) | 0.04670 (14) | |
C1B | 1.18683 (11) | 1.36233 (19) | 0.63302 (6) | 0.0453 (4) | |
H1B | 1.2178 | 1.4384 | 0.6502 | 0.054* | |
C2B | 1.16244 (10) | 1.22315 (17) | 0.65508 (5) | 0.0352 (3) | |
C3B | 1.09811 (12) | 1.07916 (19) | 0.73374 (5) | 0.0444 (4) | |
H3C | 1.1078 | 1.0400 | 0.7657 | 0.053* | |
H3D | 1.0444 | 1.1454 | 0.7340 | 0.053* | |
C4B | 1.08442 (10) | 0.94730 (17) | 0.70038 (5) | 0.0352 (3) | |
C5B | 1.11430 (9) | 1.11109 (16) | 0.62890 (5) | 0.0312 (3) | |
C6B | 1.09161 (10) | 1.13879 (18) | 0.58181 (5) | 0.0374 (3) | |
H6B | 1.0589 | 1.0648 | 0.5646 | 0.045* | |
C7B | 1.11793 (11) | 1.2773 (2) | 0.56047 (6) | 0.0457 (4) | |
H7B | 1.1034 | 1.2954 | 0.5287 | 0.055* | |
C8B | 1.16549 (12) | 1.38856 (19) | 0.58584 (6) | 0.0505 (4) | |
H8B | 1.1831 | 1.4811 | 0.5712 | 0.061* | |
C9B | 1.06956 (10) | 0.82465 (16) | 0.63058 (5) | 0.0359 (3) | |
N1B | 1.06615 (9) | 0.80492 (15) | 0.71179 (4) | 0.0421 (3) | |
N2B | 1.05896 (9) | 0.72947 (15) | 0.66834 (5) | 0.0426 (3) | |
N3B | 1.08893 (8) | 0.96891 (13) | 0.65165 (4) | 0.0320 (3) | |
H2N | 1.0370 (12) | 0.634 (2) | 0.6670 (6) | 0.054 (5)* | |
O1B | 1.06371 (8) | 0.79255 (12) | 0.58797 (4) | 0.0466 (3) | |
S1B | 1.19697 (3) | 1.19015 (5) | 0.714522 (14) | 0.04555 (14) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.0450 (8) | 0.0329 (8) | 0.0556 (10) | −0.0063 (7) | −0.0041 (7) | −0.0022 (7) |
C2A | 0.0336 (7) | 0.0351 (8) | 0.0384 (8) | −0.0025 (6) | −0.0004 (6) | −0.0035 (6) |
C3A | 0.0514 (9) | 0.0545 (10) | 0.0347 (8) | −0.0057 (8) | −0.0059 (7) | 0.0021 (7) |
C4A | 0.0423 (8) | 0.0397 (8) | 0.0365 (8) | −0.0004 (7) | −0.0011 (6) | 0.0042 (6) |
C5A | 0.0310 (7) | 0.0306 (7) | 0.0353 (7) | −0.0015 (6) | 0.0020 (5) | −0.0001 (6) |
C6A | 0.0441 (8) | 0.0382 (8) | 0.0349 (8) | −0.0009 (7) | 0.0029 (6) | −0.0027 (6) |
C7A | 0.0473 (9) | 0.0521 (10) | 0.0375 (8) | −0.0018 (7) | 0.0035 (7) | 0.0085 (7) |
C8A | 0.0483 (9) | 0.0408 (9) | 0.0559 (10) | −0.0058 (7) | −0.0006 (8) | 0.0150 (7) |
C9A | 0.0447 (8) | 0.0306 (7) | 0.0417 (8) | −0.0034 (6) | 0.0047 (6) | −0.0026 (6) |
N1A | 0.0581 (9) | 0.0465 (8) | 0.0450 (8) | −0.0050 (7) | −0.0045 (6) | 0.0118 (6) |
N2A | 0.0581 (9) | 0.0331 (7) | 0.0507 (8) | −0.0098 (6) | −0.0014 (6) | 0.0052 (6) |
N3A | 0.0396 (6) | 0.0298 (6) | 0.0333 (6) | −0.0023 (5) | 0.0015 (5) | 0.0004 (5) |
O1A | 0.0686 (8) | 0.0412 (6) | 0.0414 (6) | −0.0170 (5) | 0.0016 (5) | −0.0068 (5) |
S1A | 0.0572 (3) | 0.0463 (2) | 0.0366 (2) | −0.00550 (18) | 0.00072 (17) | −0.01162 (17) |
C1B | 0.0451 (9) | 0.0338 (8) | 0.0571 (10) | −0.0073 (7) | 0.0042 (7) | −0.0038 (7) |
C2B | 0.0348 (7) | 0.0323 (7) | 0.0385 (7) | 0.0002 (6) | 0.0024 (6) | −0.0042 (6) |
C3B | 0.0562 (9) | 0.0444 (9) | 0.0327 (8) | −0.0037 (7) | 0.0056 (7) | −0.0050 (7) |
C4B | 0.0383 (7) | 0.0368 (7) | 0.0304 (7) | −0.0021 (6) | 0.0025 (6) | −0.0007 (6) |
C5B | 0.0304 (7) | 0.0280 (7) | 0.0351 (7) | 0.0001 (5) | 0.0049 (5) | −0.0010 (6) |
C6B | 0.0386 (7) | 0.0380 (8) | 0.0354 (7) | −0.0017 (6) | 0.0024 (6) | −0.0004 (6) |
C7B | 0.0508 (9) | 0.0462 (9) | 0.0401 (8) | 0.0036 (7) | 0.0064 (7) | 0.0090 (7) |
C8B | 0.0561 (10) | 0.0353 (8) | 0.0600 (10) | −0.0036 (7) | 0.0112 (8) | 0.0103 (7) |
C9B | 0.0394 (8) | 0.0305 (7) | 0.0378 (8) | −0.0042 (6) | 0.0016 (6) | −0.0032 (6) |
N1B | 0.0526 (8) | 0.0394 (7) | 0.0343 (7) | −0.0066 (6) | 0.0001 (5) | 0.0024 (5) |
N2B | 0.0578 (8) | 0.0307 (7) | 0.0394 (7) | −0.0096 (6) | −0.0013 (6) | 0.0001 (5) |
N3B | 0.0376 (6) | 0.0283 (6) | 0.0301 (6) | −0.0039 (5) | 0.0020 (5) | −0.0022 (5) |
O1B | 0.0658 (7) | 0.0385 (6) | 0.0355 (6) | −0.0128 (5) | 0.0034 (5) | −0.0075 (4) |
S1B | 0.0524 (3) | 0.0455 (2) | 0.0388 (2) | −0.00944 (17) | −0.00671 (16) | −0.00798 (16) |
Geometric parameters (Å, º) top
C1A—C8A | 1.377 (2) | C1B—C8B | 1.380 (2) |
C1A—C2A | 1.391 (2) | C1B—C2B | 1.391 (2) |
C1A—H1A | 0.9300 | C1B—H1B | 0.9300 |
C2A—C5A | 1.401 (2) | C2B—C5B | 1.400 (2) |
C2A—S1A | 1.7619 (15) | C2B—S1B | 1.7668 (15) |
C3A—C4A | 1.485 (2) | C3B—C4B | 1.482 (2) |
C3A—S1A | 1.8092 (18) | C3B—S1B | 1.8133 (17) |
C3A—H3A | 0.9700 | C3B—H3C | 0.9700 |
C3A—H3B | 0.9700 | C3B—H3D | 0.9700 |
C4A—N1A | 1.289 (2) | C4B—N1B | 1.2898 (19) |
C4A—N3A | 1.3831 (18) | C4B—N3B | 1.3826 (18) |
C5A—C6A | 1.392 (2) | C5B—C6B | 1.384 (2) |
C5A—N3A | 1.4231 (18) | C5B—N3B | 1.4252 (17) |
C6A—C7A | 1.383 (2) | C6B—C7B | 1.384 (2) |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C7A—C8A | 1.379 (2) | C7B—C8B | 1.379 (2) |
C7A—H7A | 0.9300 | C7B—H7B | 0.9300 |
C8A—H8A | 0.9300 | C8B—H8B | 0.9300 |
C9A—O1A | 1.2299 (18) | C9B—O1B | 1.2310 (18) |
C9A—N2A | 1.348 (2) | C9B—N2B | 1.347 (2) |
C9A—N3A | 1.3959 (19) | C9B—N3B | 1.3998 (18) |
N1A—N2A | 1.386 (2) | N1B—N2B | 1.3849 (18) |
N2A—H1N | 0.85 (2) | N2B—H2N | 0.88 (2) |
| | | |
C8A—C1A—C2A | 121.10 (15) | C8B—C1B—C2B | 120.63 (15) |
C8A—C1A—H1A | 119.4 | C8B—C1B—H1B | 119.7 |
C2A—C1A—H1A | 119.4 | C2B—C1B—H1B | 119.7 |
C1A—C2A—C5A | 118.45 (14) | C1B—C2B—C5B | 118.93 (14) |
C1A—C2A—S1A | 118.90 (11) | C1B—C2B—S1B | 119.00 (12) |
C5A—C2A—S1A | 122.51 (11) | C5B—C2B—S1B | 122.02 (11) |
C4A—C3A—S1A | 109.02 (11) | C4B—C3B—S1B | 108.66 (10) |
C4A—C3A—H3A | 109.9 | C4B—C3B—H3C | 110.0 |
S1A—C3A—H3A | 109.9 | S1B—C3B—H3C | 110.0 |
C4A—C3A—H3B | 109.9 | C4B—C3B—H3D | 110.0 |
S1A—C3A—H3B | 109.9 | S1B—C3B—H3D | 110.0 |
H3A—C3A—H3B | 108.3 | H3C—C3B—H3D | 108.3 |
N1A—C4A—N3A | 112.38 (14) | N1B—C4B—N3B | 112.49 (12) |
N1A—C4A—C3A | 126.36 (14) | N1B—C4B—C3B | 126.36 (13) |
N3A—C4A—C3A | 121.25 (13) | N3B—C4B—C3B | 121.14 (13) |
C6A—C5A—C2A | 120.35 (13) | C6B—C5B—C2B | 120.32 (13) |
C6A—C5A—N3A | 120.99 (13) | C6B—C5B—N3B | 120.84 (13) |
C2A—C5A—N3A | 118.64 (12) | C2B—C5B—N3B | 118.84 (12) |
C7A—C6A—C5A | 119.71 (14) | C5B—C6B—C7B | 119.61 (14) |
C7A—C6A—H6A | 120.1 | C5B—C6B—H6B | 120.2 |
C5A—C6A—H6A | 120.1 | C7B—C6B—H6B | 120.2 |
C8A—C7A—C6A | 120.35 (14) | C8B—C7B—C6B | 120.65 (15) |
C8A—C7A—H7A | 119.8 | C8B—C7B—H7B | 119.7 |
C6A—C7A—H7A | 119.8 | C6B—C7B—H7B | 119.7 |
C1A—C8A—C7A | 120.00 (15) | C7B—C8B—C1B | 119.84 (15) |
C1A—C8A—H8A | 120.0 | C7B—C8B—H8B | 120.1 |
C7A—C8A—H8A | 120.0 | C1B—C8B—H8B | 120.1 |
O1A—C9A—N2A | 129.24 (14) | O1B—C9B—N2B | 128.46 (13) |
O1A—C9A—N3A | 127.51 (14) | O1B—C9B—N3B | 128.49 (13) |
N2A—C9A—N3A | 103.25 (13) | N2B—C9B—N3B | 103.04 (12) |
C4A—N1A—N2A | 103.97 (13) | C4B—N1B—N2B | 103.81 (12) |
C9A—N2A—N1A | 113.39 (13) | C9B—N2B—N1B | 113.71 (12) |
C9A—N2A—H1N | 122.6 (13) | C9B—N2B—H2N | 124.8 (12) |
N1A—N2A—H1N | 122.3 (12) | N1B—N2B—H2N | 120.1 (12) |
C4A—N3A—C9A | 106.95 (12) | C4B—N3B—C9B | 106.88 (11) |
C4A—N3A—C5A | 125.63 (12) | C4B—N3B—C5B | 124.80 (11) |
C9A—N3A—C5A | 126.80 (12) | C9B—N3B—C5B | 128.22 (11) |
C2A—S1A—C3A | 99.26 (7) | C2B—S1B—C3B | 97.88 (7) |
| | | |
C8A—C1A—C2A—C5A | −0.8 (2) | C8B—C1B—C2B—C5B | −1.2 (2) |
C8A—C1A—C2A—S1A | 175.12 (12) | C8B—C1B—C2B—S1B | 176.39 (13) |
S1A—C3A—C4A—N1A | 135.55 (15) | S1B—C3B—C4B—N1B | 135.70 (14) |
S1A—C3A—C4A—N3A | −44.59 (18) | S1B—C3B—C4B—N3B | −45.50 (18) |
C1A—C2A—C5A—C6A | −0.6 (2) | C1B—C2B—C5B—C6B | 0.1 (2) |
S1A—C2A—C5A—C6A | −176.39 (11) | S1B—C2B—C5B—C6B | −177.41 (11) |
C1A—C2A—C5A—N3A | 177.98 (13) | C1B—C2B—C5B—N3B | −179.66 (13) |
S1A—C2A—C5A—N3A | 2.23 (19) | S1B—C2B—C5B—N3B | 2.84 (18) |
C2A—C5A—C6A—C7A | 1.8 (2) | C2B—C5B—C6B—C7B | 0.9 (2) |
N3A—C5A—C6A—C7A | −176.78 (14) | N3B—C5B—C6B—C7B | −179.36 (13) |
C5A—C6A—C7A—C8A | −1.6 (2) | C5B—C6B—C7B—C8B | −0.8 (2) |
C2A—C1A—C8A—C7A | 1.0 (2) | C6B—C7B—C8B—C1B | −0.3 (3) |
C6A—C7A—C8A—C1A | 0.2 (3) | C2B—C1B—C8B—C7B | 1.3 (3) |
N3A—C4A—N1A—N2A | −0.83 (18) | N3B—C4B—N1B—N2B | 0.40 (17) |
C3A—C4A—N1A—N2A | 179.04 (15) | C3B—C4B—N1B—N2B | 179.30 (15) |
O1A—C9A—N2A—N1A | 177.94 (16) | O1B—C9B—N2B—N1B | −177.27 (15) |
N3A—C9A—N2A—N1A | −2.56 (18) | N3B—C9B—N2B—N1B | 2.78 (17) |
C4A—N1A—N2A—C9A | 2.19 (19) | C4B—N1B—N2B—C9B | −2.08 (18) |
N1A—C4A—N3A—C9A | −0.68 (18) | N1B—C4B—N3B—C9B | 1.26 (17) |
C3A—C4A—N3A—C9A | 179.44 (14) | C3B—C4B—N3B—C9B | −177.70 (14) |
N1A—C4A—N3A—C5A | −172.14 (14) | N1B—C4B—N3B—C5B | −175.30 (13) |
C3A—C4A—N3A—C5A | 8.0 (2) | C3B—C4B—N3B—C5B | 5.7 (2) |
O1A—C9A—N3A—C4A | −178.59 (16) | O1B—C9B—N3B—C4B | 177.70 (15) |
N2A—C9A—N3A—C4A | 1.90 (16) | N2B—C9B—N3B—C4B | −2.35 (15) |
O1A—C9A—N3A—C5A | −7.3 (2) | O1B—C9B—N3B—C5B | −5.9 (3) |
N2A—C9A—N3A—C5A | 173.22 (13) | N2B—C9B—N3B—C5B | 174.06 (13) |
C6A—C5A—N3A—C4A | −164.62 (14) | C6B—C5B—N3B—C4B | −160.55 (13) |
C2A—C5A—N3A—C4A | 16.8 (2) | C2B—C5B—N3B—C4B | 19.2 (2) |
C6A—C5A—N3A—C9A | 25.6 (2) | C6B—C5B—N3B—C9B | 23.6 (2) |
C2A—C5A—N3A—C9A | −153.01 (14) | C2B—C5B—N3B—C9B | −156.61 (14) |
C1A—C2A—S1A—C3A | 150.82 (13) | C1B—C2B—S1B—C3B | 146.30 (13) |
C5A—C2A—S1A—C3A | −33.45 (14) | C5B—C2B—S1B—C3B | −36.20 (13) |
C4A—C3A—S1A—C2A | 50.69 (12) | C4B—C3B—S1B—C2B | 53.54 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2B—H2N···O1A | 0.88 (2) | 1.93 (2) | 2.7771 (17) | 163.4 (17) |
N2A—H1N···O1B | 0.85 (2) | 2.08 (2) | 2.9112 (18) | 168.4 (17) |
C3A—H3A···O1Bi | 0.97 | 2.55 | 3.402 (2) | 147 |
C3B—H3C···O1Aii | 0.97 | 2.56 | 3.4238 (19) | 149 |
C3B—H3D···N1Bii | 0.97 | 2.61 | 3.444 (2) | 144 |
C6A—H6A···O1A | 0.93 | 2.39 | 2.9438 (19) | 118 |
C6B—H6B···O1B | 0.93 | 2.43 | 3.0009 (19) | 120 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, y+1/2, −z+3/2. |
(II) 2-(2-Oxo-2-phenylethyl)-4
H-1,2,4-triazolo[3,4-
c][1,4]benzothiazin-1(2
H)-one
top
Crystal data top
C17H13N3O2S | F(000) = 672 |
Mr = 323.36 | Dx = 1.477 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3459 reflections |
a = 11.6248 (18) Å | θ = 2.7–24.8° |
b = 14.920 (2) Å | µ = 0.24 mm−1 |
c = 8.5909 (13) Å | T = 294 K |
β = 102.564 (3)° | Needle, colourless |
V = 1454.3 (4) Å3 | 0.21 × 0.12 × 0.08 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2175 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 25.0°, θmin = 1.8° |
ω scans | h = −13→13 |
13803 measured reflections | k = −17→17 |
2562 independent reflections | l = −10→10 |
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) = 0.110 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0521P)2 + 0.4963P] where P = (Fo2 + 2Fc2)/3 |
2562 reflections | (Δ/σ)max < 0.001 |
208 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
Crystal data top
C17H13N3O2S | V = 1454.3 (4) Å3 |
Mr = 323.36 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.6248 (18) Å | µ = 0.24 mm−1 |
b = 14.920 (2) Å | T = 294 K |
c = 8.5909 (13) Å | 0.21 × 0.12 × 0.08 mm |
β = 102.564 (3)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2175 reflections with I > 2σ(I) |
13803 measured reflections | Rint = 0.035 |
2562 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.29 e Å−3 |
2562 reflections | Δρmin = −0.15 e Å−3 |
208 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.4068 (2) | 0.09302 (16) | 1.1514 (3) | 0.0476 (6) | |
H1 | 0.3310 | 0.1167 | 1.1253 | 0.057* | |
C2 | 0.49454 (18) | 0.12968 (14) | 1.0841 (2) | 0.0385 (5) | |
C3 | 0.59868 (19) | 0.27745 (14) | 0.9999 (3) | 0.0430 (5) | |
H3A | 0.5992 | 0.3281 | 0.9293 | 0.052* | |
H3B | 0.6110 | 0.2996 | 1.1084 | 0.052* | |
C4 | 0.69294 (18) | 0.21352 (14) | 0.9852 (3) | 0.0380 (5) | |
C5 | 0.60792 (17) | 0.09307 (13) | 1.1240 (2) | 0.0347 (5) | |
C6 | 0.6323 (2) | 0.02331 (14) | 1.2319 (3) | 0.0416 (5) | |
H6 | 0.7082 | 0.0000 | 1.2604 | 0.050* | |
C7 | 0.5428 (2) | −0.01189 (16) | 1.2975 (3) | 0.0482 (6) | |
H7 | 0.5591 | −0.0589 | 1.3700 | 0.058* | |
C8 | 0.4305 (2) | 0.02227 (17) | 1.2560 (3) | 0.0509 (6) | |
H8 | 0.3706 | −0.0024 | 1.2986 | 0.061* | |
C9 | 0.79549 (18) | 0.08501 (14) | 1.0186 (2) | 0.0378 (5) | |
C10 | 0.94467 (19) | 0.13928 (16) | 0.8692 (3) | 0.0458 (6) | |
H10A | 0.9951 | 0.0922 | 0.9245 | 0.055* | |
H10B | 0.9892 | 0.1948 | 0.8831 | 0.055* | |
C11 | 0.91012 (19) | 0.11681 (14) | 0.6929 (3) | 0.0408 (5) | |
C12 | 1.00213 (18) | 0.12699 (14) | 0.5969 (3) | 0.0392 (5) | |
C13 | 1.11552 (19) | 0.15584 (15) | 0.6638 (3) | 0.0454 (6) | |
H13 | 1.1364 | 0.1689 | 0.7722 | 0.055* | |
C14 | 1.1977 (2) | 0.16532 (17) | 0.5704 (3) | 0.0532 (6) | |
H14 | 1.2733 | 0.1854 | 0.6157 | 0.064* | |
C15 | 1.1678 (2) | 0.14515 (17) | 0.4112 (3) | 0.0552 (7) | |
H15 | 1.2233 | 0.1517 | 0.3486 | 0.066* | |
C16 | 1.0565 (2) | 0.11529 (18) | 0.3433 (3) | 0.0586 (7) | |
H16 | 1.0371 | 0.1007 | 0.2355 | 0.070* | |
C17 | 0.9732 (2) | 0.10688 (16) | 0.4353 (3) | 0.0500 (6) | |
H17 | 0.8974 | 0.0877 | 0.3887 | 0.060* | |
N1 | 0.77836 (17) | 0.22750 (12) | 0.9143 (2) | 0.0466 (5) | |
N2 | 0.84323 (16) | 0.14868 (12) | 0.9388 (2) | 0.0456 (5) | |
N3 | 0.69649 (14) | 0.12901 (11) | 1.05118 (19) | 0.0349 (4) | |
O1 | 0.83143 (13) | 0.00975 (10) | 1.05492 (19) | 0.0483 (4) | |
O2 | 0.81152 (14) | 0.09055 (12) | 0.6344 (2) | 0.0599 (5) | |
S1 | 0.45916 (5) | 0.21922 (4) | 0.94660 (7) | 0.0491 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0356 (12) | 0.0601 (15) | 0.0513 (14) | −0.0071 (11) | 0.0185 (11) | −0.0126 (12) |
C2 | 0.0360 (11) | 0.0436 (12) | 0.0382 (11) | −0.0042 (9) | 0.0129 (9) | −0.0081 (9) |
C3 | 0.0449 (13) | 0.0395 (12) | 0.0483 (13) | 0.0035 (10) | 0.0183 (10) | 0.0024 (10) |
C4 | 0.0393 (12) | 0.0375 (11) | 0.0400 (12) | 0.0003 (9) | 0.0149 (9) | 0.0010 (9) |
C5 | 0.0339 (11) | 0.0393 (11) | 0.0350 (11) | −0.0047 (9) | 0.0161 (9) | −0.0056 (9) |
C6 | 0.0423 (12) | 0.0420 (12) | 0.0437 (12) | −0.0004 (10) | 0.0161 (10) | 0.0000 (10) |
C7 | 0.0581 (15) | 0.0461 (13) | 0.0470 (13) | −0.0074 (11) | 0.0258 (11) | 0.0011 (11) |
C8 | 0.0516 (14) | 0.0569 (15) | 0.0529 (14) | −0.0192 (12) | 0.0307 (12) | −0.0110 (12) |
C9 | 0.0320 (11) | 0.0429 (12) | 0.0409 (12) | 0.0009 (9) | 0.0130 (9) | −0.0001 (10) |
C10 | 0.0368 (12) | 0.0519 (14) | 0.0553 (14) | 0.0019 (10) | 0.0242 (10) | 0.0048 (11) |
C11 | 0.0348 (12) | 0.0358 (11) | 0.0551 (14) | 0.0009 (9) | 0.0171 (10) | 0.0076 (10) |
C12 | 0.0380 (12) | 0.0352 (11) | 0.0475 (13) | 0.0018 (9) | 0.0160 (10) | 0.0044 (9) |
C13 | 0.0402 (12) | 0.0552 (14) | 0.0442 (13) | −0.0009 (11) | 0.0163 (10) | 0.0015 (11) |
C14 | 0.0384 (13) | 0.0649 (16) | 0.0613 (16) | −0.0015 (11) | 0.0216 (11) | 0.0047 (13) |
C15 | 0.0531 (15) | 0.0637 (16) | 0.0582 (16) | 0.0097 (12) | 0.0326 (13) | 0.0083 (13) |
C16 | 0.0686 (18) | 0.0667 (17) | 0.0446 (14) | 0.0063 (14) | 0.0215 (13) | −0.0011 (12) |
C17 | 0.0456 (13) | 0.0531 (15) | 0.0516 (14) | −0.0020 (11) | 0.0111 (11) | −0.0027 (11) |
N1 | 0.0469 (11) | 0.0433 (11) | 0.0566 (12) | 0.0031 (9) | 0.0266 (9) | 0.0075 (9) |
N2 | 0.0401 (10) | 0.0443 (11) | 0.0607 (12) | 0.0060 (8) | 0.0294 (9) | 0.0082 (9) |
N3 | 0.0324 (9) | 0.0366 (9) | 0.0392 (10) | 0.0000 (7) | 0.0157 (7) | 0.0017 (7) |
O1 | 0.0435 (9) | 0.0432 (9) | 0.0630 (10) | 0.0098 (7) | 0.0222 (8) | 0.0093 (8) |
O2 | 0.0381 (9) | 0.0722 (12) | 0.0709 (12) | −0.0120 (8) | 0.0155 (8) | 0.0020 (9) |
S1 | 0.0369 (3) | 0.0576 (4) | 0.0528 (4) | 0.0076 (3) | 0.0098 (3) | 0.0049 (3) |
Geometric parameters (Å, º) top
C1—C8 | 1.375 (3) | C9—N3 | 1.405 (3) |
C1—C2 | 1.389 (3) | C10—N2 | 1.440 (3) |
C1—H1 | 0.9300 | C10—C11 | 1.518 (3) |
C2—C5 | 1.399 (3) | C10—H10A | 0.9700 |
C2—S1 | 1.772 (2) | C10—H10B | 0.9700 |
C3—C4 | 1.479 (3) | C11—O2 | 1.212 (3) |
C3—S1 | 1.809 (2) | C11—C12 | 1.494 (3) |
C3—H3A | 0.9700 | C12—C13 | 1.387 (3) |
C3—H3B | 0.9700 | C12—C17 | 1.388 (3) |
C4—N1 | 1.290 (3) | C13—C14 | 1.382 (3) |
C4—N3 | 1.379 (3) | C13—H13 | 0.9300 |
C5—C6 | 1.381 (3) | C14—C15 | 1.370 (4) |
C5—N3 | 1.421 (2) | C14—H14 | 0.9300 |
C6—C7 | 1.389 (3) | C15—C16 | 1.373 (4) |
C6—H6 | 0.9300 | C15—H15 | 0.9300 |
C7—C8 | 1.374 (3) | C16—C17 | 1.382 (3) |
C7—H7 | 0.9300 | C16—H16 | 0.9300 |
C8—H8 | 0.9300 | C17—H17 | 0.9300 |
C9—O1 | 1.215 (3) | N1—N2 | 1.388 (3) |
C9—N2 | 1.358 (3) | | |
| | | |
C8—C1—C2 | 120.9 (2) | N2—C10—H10B | 109.2 |
C8—C1—H1 | 119.6 | C11—C10—H10B | 109.2 |
C2—C1—H1 | 119.6 | H10A—C10—H10B | 107.9 |
C1—C2—C5 | 118.8 (2) | O2—C11—C12 | 122.0 (2) |
C1—C2—S1 | 119.30 (17) | O2—C11—C10 | 120.42 (19) |
C5—C2—S1 | 121.83 (16) | C12—C11—C10 | 117.57 (18) |
C4—C3—S1 | 108.00 (15) | C13—C12—C17 | 118.9 (2) |
C4—C3—H3A | 110.1 | C13—C12—C11 | 122.2 (2) |
S1—C3—H3A | 110.1 | C17—C12—C11 | 118.9 (2) |
C4—C3—H3B | 110.1 | C14—C13—C12 | 120.4 (2) |
S1—C3—H3B | 110.1 | C14—C13—H13 | 119.8 |
H3A—C3—H3B | 108.4 | C12—C13—H13 | 119.8 |
N1—C4—N3 | 112.62 (18) | C15—C14—C13 | 120.0 (2) |
N1—C4—C3 | 126.63 (19) | C15—C14—H14 | 120.0 |
N3—C4—C3 | 120.75 (18) | C13—C14—H14 | 120.0 |
C6—C5—C2 | 120.21 (19) | C14—C15—C16 | 120.4 (2) |
C6—C5—N3 | 121.15 (18) | C14—C15—H15 | 119.8 |
C2—C5—N3 | 118.64 (18) | C16—C15—H15 | 119.8 |
C5—C6—C7 | 119.6 (2) | C15—C16—C17 | 120.0 (2) |
C5—C6—H6 | 120.2 | C15—C16—H16 | 120.0 |
C7—C6—H6 | 120.2 | C17—C16—H16 | 120.0 |
C8—C7—C6 | 120.5 (2) | C16—C17—C12 | 120.3 (2) |
C8—C7—H7 | 119.8 | C16—C17—H17 | 119.8 |
C6—C7—H7 | 119.8 | C12—C17—H17 | 119.8 |
C7—C8—C1 | 119.9 (2) | C4—N1—N2 | 103.88 (17) |
C7—C8—H8 | 120.1 | C9—N2—N1 | 113.63 (16) |
C1—C8—H8 | 120.1 | C9—N2—C10 | 127.04 (19) |
O1—C9—N2 | 128.37 (19) | N1—N2—C10 | 119.11 (17) |
O1—C9—N3 | 129.14 (19) | C4—N3—C9 | 107.32 (16) |
N2—C9—N3 | 102.48 (18) | C4—N3—C5 | 124.48 (17) |
N2—C10—C11 | 111.90 (19) | C9—N3—C5 | 127.94 (17) |
N2—C10—H10A | 109.2 | C2—S1—C3 | 97.36 (10) |
C11—C10—H10A | 109.2 | | |
| | | |
C8—C1—C2—C5 | 0.3 (3) | C11—C12—C17—C16 | −179.8 (2) |
C8—C1—C2—S1 | 178.64 (17) | N3—C4—N1—N2 | −1.6 (2) |
S1—C3—C4—N1 | 132.3 (2) | C3—C4—N1—N2 | 178.2 (2) |
S1—C3—C4—N3 | −47.9 (2) | O1—C9—N2—N1 | 179.0 (2) |
C1—C2—C5—C6 | −1.8 (3) | N3—C9—N2—N1 | −2.4 (2) |
S1—C2—C5—C6 | 179.94 (16) | O1—C9—N2—C10 | 4.4 (4) |
C1—C2—C5—N3 | 178.11 (18) | N3—C9—N2—C10 | −177.0 (2) |
S1—C2—C5—N3 | −0.2 (3) | C4—N1—N2—C9 | 2.6 (3) |
C2—C5—C6—C7 | 1.7 (3) | C4—N1—N2—C10 | 177.6 (2) |
N3—C5—C6—C7 | −178.20 (19) | C11—C10—N2—C9 | 95.9 (3) |
C5—C6—C7—C8 | −0.1 (3) | C11—C10—N2—N1 | −78.4 (3) |
C6—C7—C8—C1 | −1.4 (3) | N1—C4—N3—C9 | 0.2 (2) |
C2—C1—C8—C7 | 1.3 (3) | C3—C4—N3—C9 | −179.6 (2) |
N2—C10—C11—O2 | −15.5 (3) | N1—C4—N3—C5 | −174.29 (19) |
N2—C10—C11—C12 | 165.41 (18) | C3—C4—N3—C5 | 5.9 (3) |
O2—C11—C12—C13 | −179.1 (2) | O1—C9—N3—C4 | 179.9 (2) |
C10—C11—C12—C13 | 0.0 (3) | N2—C9—N3—C4 | 1.3 (2) |
O2—C11—C12—C17 | 0.9 (3) | O1—C9—N3—C5 | −5.8 (4) |
C10—C11—C12—C17 | 180.0 (2) | N2—C9—N3—C5 | 175.59 (19) |
C17—C12—C13—C14 | 0.7 (3) | C6—C5—N3—C4 | −158.2 (2) |
C11—C12—C13—C14 | −179.3 (2) | C2—C5—N3—C4 | 21.9 (3) |
C12—C13—C14—C15 | −0.8 (4) | C6—C5—N3—C9 | 28.4 (3) |
C13—C14—C15—C16 | −0.1 (4) | C2—C5—N3—C9 | −151.4 (2) |
C14—C15—C16—C17 | 1.1 (4) | C1—C2—S1—C3 | 146.39 (18) |
C15—C16—C17—C12 | −1.1 (4) | C5—C2—S1—C3 | −35.34 (19) |
C13—C12—C17—C16 | 0.2 (4) | C4—C3—S1—C2 | 55.21 (17) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1 | 0.93 | 2.51 | 3.040 (3) | 117 |
C10—H10A···O1i | 0.97 | 2.50 | 3.377 (3) | 150 |
Symmetry code: (i) −x+2, −y, −z+2. |
(III) Ethyl 3-oxo-2-(1-oxo-1
H,4
H-1,2,4-triazolo[3,4-
c][1,4]benzothiazin-2-yl)-3-phenylpropanoate
top
Crystal data top
C20H17N3O4S | F(000) = 1648 |
Mr = 395.43 | Dx = 1.380 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.6533 (14) Å | Cell parameters from 8703 reflections |
b = 12.7279 (13) Å | θ = 2.2–27.6° |
c = 22.2927 (19) Å | µ = 0.20 mm−1 |
β = 100.601 (3)° | T = 294 K |
V = 3807.9 (6) Å3 | Plate, colourless |
Z = 8 | 0.16 × 0.14 × 0.05 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2804 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.048 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
ω scans | h = −16→16 |
17579 measured reflections | k = −15→15 |
3355 independent reflections | l = −26→26 |
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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0585P)2 + 5.1188P] where P = (Fo2 + 2Fc2)/3 |
3355 reflections | (Δ/σ)max < 0.001 |
283 parameters | Δρmax = 0.46 e Å−3 |
52 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
C20H17N3O4S | V = 3807.9 (6) Å3 |
Mr = 395.43 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.6533 (14) Å | µ = 0.20 mm−1 |
b = 12.7279 (13) Å | T = 294 K |
c = 22.2927 (19) Å | 0.16 × 0.14 × 0.05 mm |
β = 100.601 (3)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2804 reflections with I > 2σ(I) |
17579 measured reflections | Rint = 0.048 |
3355 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.064 | 52 restraints |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.46 e Å−3 |
3355 reflections | Δρmin = −0.28 e Å−3 |
283 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.1257 (3) | 0.6780 (3) | 0.49936 (17) | 0.0713 (9) | |
H1 | 0.1707 | 0.7171 | 0.5270 | 0.086* | |
C2 | 0.1566 (2) | 0.5858 (2) | 0.47527 (14) | 0.0561 (8) | |
C3 | 0.2717 (2) | 0.4125 (3) | 0.49316 (17) | 0.0663 (9) | |
H3A | 0.3365 | 0.3798 | 0.4959 | 0.080* | |
H3B | 0.2449 | 0.3923 | 0.5289 | 0.080* | |
C4 | 0.2046 (2) | 0.3758 (2) | 0.43767 (14) | 0.0508 (7) | |
C5 | 0.0868 (2) | 0.5255 (2) | 0.43667 (13) | 0.0479 (7) | |
C6 | −0.0116 (2) | 0.5580 (3) | 0.42121 (15) | 0.0583 (8) | |
H6 | −0.0584 | 0.5167 | 0.3963 | 0.070* | |
C7 | −0.0390 (3) | 0.6533 (3) | 0.44355 (19) | 0.0731 (10) | |
H7 | −0.1040 | 0.6774 | 0.4319 | 0.088* | |
C8 | 0.0284 (3) | 0.7121 (3) | 0.48249 (19) | 0.0786 (11) | |
H8 | 0.0088 | 0.7753 | 0.4977 | 0.094* | |
C9 | 0.0701 (2) | 0.3720 (2) | 0.36308 (14) | 0.0512 (7) | |
C10 | 0.1045 (2) | 0.1956 (3) | 0.32654 (15) | 0.0570 (8) | |
H10 | 0.0648 | 0.2151 | 0.2869 | 0.068* | |
C11 | 0.1969 (2) | 0.1345 (3) | 0.31531 (15) | 0.0588 (8) | |
C12 | 0.2457 (2) | 0.1677 (3) | 0.26426 (15) | 0.0588 (8) | |
C13 | 0.2119 (3) | 0.2520 (3) | 0.22691 (17) | 0.0736 (10) | |
H13 | 0.1581 | 0.2916 | 0.2342 | 0.088* | |
C14 | 0.2591 (4) | 0.2773 (4) | 0.1783 (2) | 0.0971 (13) | |
H14 | 0.2368 | 0.3338 | 0.1530 | 0.117* | |
C15 | 0.3389 (4) | 0.2178 (5) | 0.1682 (2) | 0.1049 (16) | |
H15 | 0.3703 | 0.2342 | 0.1357 | 0.126* | |
C16 | 0.3723 (3) | 0.1355 (5) | 0.2052 (2) | 0.0965 (14) | |
H16 | 0.4269 | 0.0969 | 0.1981 | 0.116* | |
C17 | 0.3264 (3) | 0.1085 (3) | 0.25296 (17) | 0.0759 (10) | |
H17 | 0.3489 | 0.0512 | 0.2776 | 0.091* | |
C18 | 0.0409 (3) | 0.1266 (3) | 0.35988 (17) | 0.0711 (9) | |
C19 | −0.0499 (11) | −0.0273 (12) | 0.3580 (5) | 0.108 (4) | 0.596 (15) |
H19A | −0.0983 | 0.0121 | 0.3757 | 0.129* | 0.596 (15) |
H19B | −0.0074 | −0.0663 | 0.3900 | 0.129* | 0.596 (15) |
C20 | −0.1003 (9) | −0.0990 (9) | 0.3092 (5) | 0.125 (5) | 0.596 (15) |
H20A | −0.1326 | −0.0583 | 0.2750 | 0.188* | 0.596 (15) |
H20B | −0.1489 | −0.1405 | 0.3246 | 0.188* | 0.596 (15) |
H20C | −0.0517 | −0.1445 | 0.2966 | 0.188* | 0.596 (15) |
C191 | −0.0936 (11) | −0.0043 (9) | 0.3354 (8) | 0.086 (3) | 0.404 (15) |
H19C | −0.1499 | −0.0133 | 0.3023 | 0.103* | 0.404 (15) |
H19D | −0.1177 | 0.0216 | 0.3710 | 0.103* | 0.404 (15) |
C201 | −0.0385 (14) | −0.1068 (13) | 0.3497 (11) | 0.129 (7) | 0.404 (15) |
H20D | −0.0022 | −0.1229 | 0.3178 | 0.194* | 0.404 (15) |
H20E | −0.0854 | −0.1620 | 0.3525 | 0.194* | 0.404 (15) |
H20F | 0.0071 | −0.1007 | 0.3878 | 0.194* | 0.404 (15) |
N1 | 0.21558 (17) | 0.2914 (2) | 0.40800 (13) | 0.0592 (7) | |
N2 | 0.13419 (17) | 0.2904 (2) | 0.36024 (12) | 0.0578 (7) | |
N3 | 0.11885 (16) | 0.42965 (18) | 0.41295 (11) | 0.0474 (6) | |
O1 | −0.00803 (16) | 0.3894 (2) | 0.32908 (10) | 0.0698 (7) | |
O2 | 0.2266 (2) | 0.0622 (2) | 0.34810 (13) | 0.0842 (8) | |
O3 | 0.03282 (19) | 0.1373 (3) | 0.41169 (12) | 0.0878 (8) | |
O4 | 0.0093 (8) | 0.0430 (8) | 0.3264 (5) | 0.091 (3) | 0.596 (15) |
O41 | −0.0202 (9) | 0.0687 (9) | 0.3178 (6) | 0.073 (3) | 0.404 (15) |
S1 | 0.28467 (6) | 0.55313 (7) | 0.49131 (5) | 0.0726 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.090 (3) | 0.055 (2) | 0.073 (2) | −0.0011 (18) | 0.0260 (19) | −0.0096 (17) |
C2 | 0.0635 (18) | 0.0490 (17) | 0.0590 (18) | 0.0027 (14) | 0.0198 (15) | 0.0010 (14) |
C3 | 0.0559 (19) | 0.0572 (19) | 0.079 (2) | 0.0015 (15) | −0.0043 (16) | −0.0038 (17) |
C4 | 0.0424 (15) | 0.0464 (16) | 0.0624 (18) | 0.0051 (12) | 0.0067 (13) | 0.0011 (14) |
C5 | 0.0512 (16) | 0.0467 (15) | 0.0503 (16) | 0.0045 (12) | 0.0212 (13) | 0.0035 (13) |
C6 | 0.0512 (17) | 0.0616 (19) | 0.0671 (19) | 0.0080 (14) | 0.0239 (14) | 0.0053 (16) |
C7 | 0.066 (2) | 0.070 (2) | 0.093 (3) | 0.0186 (18) | 0.041 (2) | 0.006 (2) |
C8 | 0.097 (3) | 0.056 (2) | 0.096 (3) | 0.014 (2) | 0.051 (2) | −0.009 (2) |
C9 | 0.0418 (15) | 0.0578 (18) | 0.0547 (17) | 0.0035 (13) | 0.0110 (13) | −0.0003 (14) |
C10 | 0.0527 (16) | 0.0626 (19) | 0.0563 (18) | 0.0011 (14) | 0.0115 (14) | −0.0158 (15) |
C11 | 0.0608 (19) | 0.0549 (19) | 0.0608 (19) | 0.0033 (15) | 0.0114 (15) | −0.0112 (16) |
C12 | 0.0554 (17) | 0.063 (2) | 0.0593 (19) | 0.0015 (15) | 0.0144 (14) | −0.0100 (16) |
C13 | 0.078 (2) | 0.077 (2) | 0.069 (2) | 0.0050 (19) | 0.0207 (18) | 0.0039 (19) |
C14 | 0.119 (4) | 0.098 (3) | 0.079 (3) | −0.006 (3) | 0.028 (3) | 0.010 (2) |
C15 | 0.105 (3) | 0.141 (5) | 0.079 (3) | −0.025 (3) | 0.043 (3) | −0.015 (3) |
C16 | 0.076 (3) | 0.142 (4) | 0.078 (3) | 0.009 (3) | 0.032 (2) | −0.024 (3) |
C17 | 0.065 (2) | 0.093 (3) | 0.072 (2) | 0.0142 (19) | 0.0188 (18) | −0.019 (2) |
C18 | 0.065 (2) | 0.085 (2) | 0.068 (2) | −0.0078 (17) | 0.0224 (17) | −0.0222 (18) |
C19 | 0.109 (9) | 0.122 (8) | 0.096 (7) | −0.053 (7) | 0.030 (6) | −0.012 (6) |
C20 | 0.125 (9) | 0.110 (7) | 0.132 (8) | −0.061 (6) | 0.000 (7) | −0.001 (6) |
C191 | 0.084 (8) | 0.086 (7) | 0.087 (9) | −0.014 (4) | 0.011 (6) | 0.006 (6) |
C201 | 0.124 (13) | 0.100 (8) | 0.161 (17) | 0.002 (8) | 0.018 (12) | 0.044 (11) |
N1 | 0.0419 (13) | 0.0564 (15) | 0.0753 (17) | 0.0074 (11) | −0.0001 (12) | −0.0112 (13) |
N2 | 0.0450 (13) | 0.0596 (15) | 0.0659 (16) | 0.0069 (11) | 0.0031 (11) | −0.0143 (13) |
N3 | 0.0415 (12) | 0.0463 (13) | 0.0546 (14) | 0.0039 (10) | 0.0099 (10) | −0.0015 (11) |
O1 | 0.0531 (13) | 0.0799 (16) | 0.0703 (15) | 0.0147 (11) | −0.0047 (11) | −0.0089 (12) |
O2 | 0.101 (2) | 0.0672 (16) | 0.0906 (18) | 0.0221 (14) | 0.0334 (15) | 0.0120 (14) |
O3 | 0.0776 (17) | 0.124 (2) | 0.0666 (16) | −0.0106 (15) | 0.0268 (13) | −0.0198 (15) |
O4 | 0.099 (6) | 0.100 (6) | 0.085 (5) | −0.042 (5) | 0.040 (4) | −0.030 (4) |
O41 | 0.075 (6) | 0.065 (4) | 0.082 (5) | −0.010 (4) | 0.027 (4) | −0.019 (4) |
S1 | 0.0596 (5) | 0.0562 (5) | 0.0978 (7) | −0.0064 (4) | 0.0033 (5) | −0.0099 (5) |
Geometric parameters (Å, º) top
C1—C8 | 1.382 (5) | C12—C17 | 1.396 (5) |
C1—C2 | 1.388 (5) | C13—C14 | 1.396 (6) |
C1—H1 | 0.9300 | C13—H13 | 0.9300 |
C2—C5 | 1.392 (4) | C14—C15 | 1.380 (7) |
C2—S1 | 1.769 (3) | C14—H14 | 0.9300 |
C3—C4 | 1.473 (4) | C15—C16 | 1.359 (7) |
C3—S1 | 1.800 (3) | C15—H15 | 0.9300 |
C3—H3A | 0.9700 | C16—C17 | 1.375 (6) |
C3—H3B | 0.9700 | C16—H16 | 0.9300 |
C4—N1 | 1.284 (4) | C17—H17 | 0.9300 |
C4—N3 | 1.382 (3) | C18—O3 | 1.188 (4) |
C5—C6 | 1.387 (4) | C18—O4 | 1.325 (7) |
C5—N3 | 1.429 (4) | C18—O41 | 1.354 (9) |
C6—C7 | 1.388 (5) | C19—O4 | 1.469 (8) |
C6—H6 | 0.9300 | C19—C20 | 1.488 (9) |
C7—C8 | 1.367 (5) | C19—H19A | 0.9700 |
C7—H7 | 0.9300 | C19—H19B | 0.9700 |
C8—H8 | 0.9300 | C20—H20A | 0.9600 |
C9—O1 | 1.210 (3) | C20—H20B | 0.9600 |
C9—N2 | 1.367 (4) | C20—H20C | 0.9600 |
C9—N3 | 1.394 (4) | C191—O41 | 1.473 (9) |
C10—N2 | 1.439 (4) | C191—C201 | 1.510 (9) |
C10—C18 | 1.522 (5) | C191—H19C | 0.9700 |
C10—C11 | 1.541 (4) | C191—H19D | 0.9700 |
C10—H10 | 0.9800 | C201—H20D | 0.9600 |
C11—O2 | 1.198 (4) | C201—H20E | 0.9600 |
C11—C12 | 1.482 (5) | C201—H20F | 0.9600 |
C12—C13 | 1.384 (5) | N1—N2 | 1.390 (3) |
| | | |
C8—C1—C2 | 120.4 (4) | C15—C14—C13 | 119.4 (5) |
C8—C1—H1 | 119.8 | C15—C14—H14 | 120.3 |
C2—C1—H1 | 119.8 | C13—C14—H14 | 120.3 |
C1—C2—C5 | 119.0 (3) | C16—C15—C14 | 120.7 (4) |
C1—C2—S1 | 118.7 (3) | C16—C15—H15 | 119.6 |
C5—C2—S1 | 122.2 (2) | C14—C15—H15 | 119.6 |
C4—C3—S1 | 110.2 (2) | C15—C16—C17 | 120.9 (4) |
C4—C3—H3A | 109.6 | C15—C16—H16 | 119.6 |
S1—C3—H3A | 109.6 | C17—C16—H16 | 119.6 |
C4—C3—H3B | 109.6 | C16—C17—C12 | 119.5 (4) |
S1—C3—H3B | 109.6 | C16—C17—H17 | 120.3 |
H3A—C3—H3B | 108.1 | C12—C17—H17 | 120.3 |
N1—C4—N3 | 112.3 (3) | O3—C18—O4 | 124.1 (6) |
N1—C4—C3 | 125.8 (3) | O3—C18—O41 | 125.5 (8) |
N3—C4—C3 | 121.8 (3) | O3—C18—C10 | 124.9 (3) |
C6—C5—C2 | 120.6 (3) | O4—C18—C10 | 110.2 (5) |
C6—C5—N3 | 120.7 (3) | O41—C18—C10 | 108.0 (7) |
C2—C5—N3 | 118.6 (3) | O4—C19—C20 | 104.2 (7) |
C5—C6—C7 | 119.0 (3) | O4—C19—H19A | 110.9 |
C5—C6—H6 | 120.5 | C20—C19—H19A | 110.9 |
C7—C6—H6 | 120.5 | O4—C19—H19B | 110.9 |
C8—C7—C6 | 120.8 (3) | C20—C19—H19B | 110.9 |
C8—C7—H7 | 119.6 | H19A—C19—H19B | 108.9 |
C6—C7—H7 | 119.6 | O41—C191—C201 | 105.3 (12) |
C7—C8—C1 | 120.1 (3) | O41—C191—H19C | 110.7 |
C7—C8—H8 | 119.9 | C201—C191—H19C | 110.7 |
C1—C8—H8 | 119.9 | O41—C191—H19D | 110.7 |
O1—C9—N2 | 127.4 (3) | C201—C191—H19D | 110.7 |
O1—C9—N3 | 129.7 (3) | H19C—C191—H19D | 108.8 |
N2—C9—N3 | 102.8 (2) | C191—C201—H20D | 109.5 |
N2—C10—C18 | 111.1 (3) | C191—C201—H20E | 109.5 |
N2—C10—C11 | 110.3 (2) | H20D—C201—H20E | 109.5 |
C18—C10—C11 | 110.2 (3) | C191—C201—H20F | 109.5 |
N2—C10—H10 | 108.4 | H20D—C201—H20F | 109.5 |
C18—C10—H10 | 108.4 | H20E—C201—H20F | 109.5 |
C11—C10—H10 | 108.4 | C4—N1—N2 | 104.5 (2) |
O2—C11—C12 | 122.6 (3) | C9—N2—N1 | 112.7 (2) |
O2—C11—C10 | 118.9 (3) | C9—N2—C10 | 122.7 (2) |
C12—C11—C10 | 118.5 (3) | N1—N2—C10 | 121.1 (2) |
C13—C12—C17 | 119.8 (3) | C4—N3—C9 | 107.6 (2) |
C13—C12—C11 | 122.5 (3) | C4—N3—C5 | 124.8 (2) |
C17—C12—C11 | 117.7 (3) | C9—N3—C5 | 127.6 (2) |
C12—C13—C14 | 119.8 (4) | C18—O4—C19 | 111.8 (8) |
C12—C13—H13 | 120.1 | C18—O41—C191 | 121.4 (13) |
C14—C13—H13 | 120.1 | C2—S1—C3 | 98.09 (15) |
| | | |
C8—C1—C2—C5 | −3.6 (5) | N3—C4—N1—N2 | 1.5 (3) |
C8—C1—C2—S1 | 172.9 (3) | C3—C4—N1—N2 | 179.4 (3) |
S1—C3—C4—N1 | 141.6 (3) | O1—C9—N2—N1 | −177.5 (3) |
S1—C3—C4—N3 | −40.6 (4) | N3—C9—N2—N1 | 4.1 (3) |
C1—C2—C5—C6 | 1.6 (4) | O1—C9—N2—C10 | −18.7 (5) |
S1—C2—C5—C6 | −174.7 (2) | N3—C9—N2—C10 | 162.9 (3) |
C1—C2—C5—N3 | −178.9 (3) | C4—N1—N2—C9 | −3.6 (4) |
S1—C2—C5—N3 | 4.8 (4) | C4—N1—N2—C10 | −162.8 (3) |
C2—C5—C6—C7 | 1.7 (5) | C18—C10—N2—C9 | −74.8 (4) |
N3—C5—C6—C7 | −177.8 (3) | C11—C10—N2—C9 | 162.6 (3) |
C5—C6—C7—C8 | −3.1 (5) | C18—C10—N2—N1 | 82.3 (3) |
C6—C7—C8—C1 | 1.1 (6) | C11—C10—N2—N1 | −40.3 (4) |
C2—C1—C8—C7 | 2.3 (6) | N1—C4—N3—C9 | 1.0 (3) |
N2—C10—C11—O2 | 98.8 (4) | C3—C4—N3—C9 | −177.0 (3) |
C18—C10—C11—O2 | −24.3 (4) | N1—C4—N3—C5 | 179.3 (3) |
N2—C10—C11—C12 | −81.1 (4) | C3—C4—N3—C5 | 1.3 (4) |
C18—C10—C11—C12 | 155.8 (3) | O1—C9—N3—C4 | 178.6 (3) |
O2—C11—C12—C13 | −179.2 (3) | N2—C9—N3—C4 | −3.0 (3) |
C10—C11—C12—C13 | 0.7 (5) | O1—C9—N3—C5 | 0.4 (5) |
O2—C11—C12—C17 | 3.0 (5) | N2—C9—N3—C5 | 178.7 (3) |
C10—C11—C12—C17 | −177.1 (3) | C6—C5—N3—C4 | −160.9 (3) |
C17—C12—C13—C14 | −0.2 (6) | C2—C5—N3—C4 | 19.6 (4) |
C11—C12—C13—C14 | −177.9 (4) | C6—C5—N3—C9 | 17.1 (4) |
C12—C13—C14—C15 | 0.0 (7) | C2—C5—N3—C9 | −162.4 (3) |
C13—C14—C15—C16 | −0.4 (7) | O3—C18—O4—C19 | 8.5 (12) |
C14—C15—C16—C17 | 1.0 (8) | O41—C18—O4—C19 | −93 (3) |
C15—C16—C17—C12 | −1.2 (7) | C10—C18—O4—C19 | 178.2 (8) |
C13—C12—C17—C16 | 0.8 (6) | C20—C19—O4—C18 | 165.6 (16) |
C11—C12—C17—C16 | 178.6 (3) | O3—C18—O41—C191 | −11.8 (15) |
N2—C10—C18—O3 | −14.2 (5) | O4—C18—O41—C191 | 83 (3) |
C11—C10—C18—O3 | 108.4 (4) | C10—C18—O41—C191 | −178.2 (9) |
N2—C10—C18—O4 | 176.1 (7) | C201—C191—O41—C18 | −88 (2) |
C11—C10—C18—O4 | −61.2 (7) | C1—C2—S1—C3 | 146.7 (3) |
N2—C10—C18—O41 | 152.3 (7) | C5—C2—S1—C3 | −37.0 (3) |
C11—C10—C18—O41 | −85.1 (7) | C4—C3—S1—C2 | 51.2 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O3i | 0.97 | 2.47 | 3.153 (4) | 127 |
C6—H6···O1 | 0.93 | 2.39 | 2.977 (4) | 121 |
C8—H8···O3ii | 0.93 | 2.46 | 3.265 (4) | 145 |
C13—H13···O1iii | 0.93 | 2.58 | 3.330 (4) | 138 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, −y+1, −z+1; (iii) −x, y, −z+1/2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C9H7N3OS | C17H13N3O2S | C20H17N3O4S |
Mr | 205.24 | 323.36 | 395.43 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, P21/c | Monoclinic, C2/c |
Temperature (K) | 294 | 294 | 294 |
a, b, c (Å) | 14.6307 (11), 8.5718 (7), 28.083 (2) | 11.6248 (18), 14.920 (2), 8.5909 (13) | 13.6533 (14), 12.7279 (13), 22.2927 (19) |
α, β, γ (°) | 90, 90, 90 | 90, 102.564 (3), 90 | 90, 100.601 (3), 90 |
V (Å3) | 3521.9 (5) | 1454.3 (4) | 3807.9 (6) |
Z | 16 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.33 | 0.24 | 0.20 |
Crystal size (mm) | 0.18 × 0.16 × 0.07 | 0.21 × 0.12 × 0.08 | 0.16 × 0.14 × 0.05 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23641, 3092, 2895 | 13803, 2562, 2175 | 17579, 3355, 2804 |
Rint | 0.020 | 0.035 | 0.048 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.083, 1.03 | 0.046, 0.110, 1.09 | 0.064, 0.166, 1.19 |
No. of reflections | 3092 | 2562 | 3355 |
No. of parameters | 261 | 208 | 283 |
No. of restraints | 0 | 0 | 52 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.18 | 0.29, −0.15 | 0.46, −0.28 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2B—H2N···O1A | 0.88 (2) | 1.93 (2) | 2.7771 (17) | 163.4 (17) |
N2A—H1N···O1B | 0.85 (2) | 2.08 (2) | 2.9112 (18) | 168.4 (17) |
C3A—H3A···O1Bi | 0.97 | 2.55 | 3.402 (2) | 146.9 |
C3B—H3C···O1Aii | 0.97 | 2.56 | 3.4238 (19) | 148.5 |
C3B—H3D···N1Bii | 0.97 | 2.61 | 3.444 (2) | 144.4 |
C6A—H6A···O1A | 0.93 | 2.39 | 2.9438 (19) | 117.9 |
C6B—H6B···O1B | 0.93 | 2.43 | 3.0009 (19) | 120.0 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, y+1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1 | 0.93 | 2.51 | 3.040 (3) | 116.5 |
C10—H10A···O1i | 0.97 | 2.50 | 3.377 (3) | 150.1 |
Symmetry code: (i) −x+2, −y, −z+2. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O3i | 0.97 | 2.47 | 3.153 (4) | 126.9 |
C6—H6···O1 | 0.93 | 2.39 | 2.977 (4) | 120.8 |
C8—H8···O3ii | 0.93 | 2.46 | 3.265 (4) | 144.5 |
C13—H13···O1iii | 0.93 | 2.58 | 3.330 (4) | 137.7 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, −y+1, −z+1; (iii) −x, y, −z+1/2. |
Selected geometric parameters (Å ,° ) for (I), (II) and (III) topParameter | (IA) | (IB) | (II) | (III) |
C2-S1 | 1.762 (2) | 1.767 (2) | 1.772 (2) | 1.769 (3) |
C3-S1 | 1.809 (2) | 1.813 (2) | 1.809 (2) | 1.800 (3) |
C4-N3 | 1.383 (2) | 1.383 (2) | 1.379 (3) | 1.382 (3) |
C5-N3 | 1.423 (2) | 1.425 (2) | 1.421 (2) | 1.429 (4) |
C9-N2 | 1.348 (2) | 1.347 (2) | 1.358 (3) | 1.367 (4) |
C4-N3-C9 | 106.95 (12) | 106.88 (11) | 107.32 (16) | 107.6 (2) |
C4-N3-C5 | 125.63 (12) | 124.80 (11) | 124.48 (17) | 124.8 (2) |
C9-N3-C5 | 126.80 (12) | 128.22 (11) | 127.94 (17) | 127.6 (2) |
The triazole scaffold, one of the most important and well known heterocycles, is a common and integral feature of a variety of natural products and medicinal agents. It is present as an important structural component in an array of drug categories such as antimicrobial (Girmenia, 2009), analgesic (Hafez et al., 2008), anticonvulsant (Guan et al., 2007), antimalarial (Gujjar et al., 2009), antiviral (Johns et al., 2009) and anticancer agents (Duran et al., 2002). In the last few decades, the structure–activity relationships of triazole derivatives have revealed that the substituents on the triazole ring can be varied but the greatest difference, both structurally and in terms of properties, is exerted by the groups attached to the N atom (Liu et al., 2008). The triazole ring is an attractive connecting unit, since it is stable to metabolic degradation and capable of hydrogen bonding, which can be favourable in the binding of biomolecular targets and in improving solubility (Dalvie et al., 2002; Horne et al., 2004). The synthesis of triazoles fused to another heterocyclic ring has attracted widespread attention due to possible diverse applications in therapeutics and as pesticides, herbicides, dyes, lubricants and analytical reagents (Holla et al., 2001, 2002).
1,4-Benzothiazines, structural analogues of phenothiazines, possess a wide range of pharmacological activities (Fringuelli et al., 1998; Matsumoto et al., 2000; Kobayashi et al., 1997), and the presence of a fold along the N···S axis is considered to be one of the structural features to impart these activities (Silverman, 2004; Gupta & Ojha, 1988). A novel series of triazolobenzothiazines was synthesized by Reddy Sastry et al. (1991) and they were reported to be potential centrally acting muscle relaxant agents. Among these, the compound IDPH-791, (I), was stated as exhibiting significant muscle relaxant activity, being twice as potent and with a longer duration of action than mephenesin (Junnarkar et al., 1992). Recently, we have reported the crystal structures of triazolobenzoxazines (Ravikumar et al., 2012). In continuation of our work on the structural elucidation of bioactive molecules (Ravikumar & Sridhar, 2010; Ravikumar et al., 2011), we report here the crystal structures of three novel 1,4-benzothiazine-fused triazoles, IDPH-791, (I), and its N-substituted derivatives, (II) and (III).
The structures of (I)–(III) (Figs. 1–3) consist of a tricyclic core, with triazole and benzene rings sharing the thiazine ring. The interatomic distances and angles are unexceptional and are comparable with those reported for related structures (de Meester et al., 1986; Pilati & Simonetta, 1986). In (III), atoms O4, C19 and C20 of the propanoate side chain are disordered over two sites with occupancies of 0.596 (15) and 0.404 (15).
The two crystallographically independent molecules in the asymmetric unit of (I), labelled with the suffixes A and B, are related by a pseudo-inversion centre which lies at (0.0, 0.62,0.63), and the r.m.s. deviation for the mutual fit of the two molecules is 0.047 Å. Dimers with pseudo-inversion centres are formed by hydrogen bonds between the triazole NH group of one molecule in the asymmetric unit and the carbonyl O atom of the other, generating an R22(8) graph-set ring motif (Etter, 1990; Etter et al., 1990; Bernstein et al., 1995).
Significant structural similarities are seen in (I)–(III). In the thiazine ring the two S—C and N—C bond lengths (Table 1) are not equal, owing to different environments. The C2—S1—C3 angles of 99.3 (1) and 97.9 (1)° in (I), 97.4 (1)° in (II) and 98.1 (2)° in (III) suggest that atom S1 uses only its p-orbitals to form bonds with C2 and C3 (Aravindan et al., 2003). Thiazine atom N3 shows planarity, as the sums of the C—N3—C bond angles are 359.4 (1) and 359.9 (1)° in (I), 359.7 (2)° in (II) and 360.0 (2)° in (III).
In all three structures the tricyclic ring system is conformationally similar (Fig. 4). The thiazine ring is in a distorted half-chair conformation, with atoms S1 and C2 displaced by 1.057 (1) and -1.122 (1) and 0.473 (2) and -0.488 (2) Å, respectively, in (I), 1.177 (1) and 0.547 (2) Å, respectively, in (II), and 1.076 (1) and 0.428 (2) Å, respectively, in (III), from the plane defined by atoms C3/C4/N3/C5 (Nardelli, 1983). The dihedral angles between the triazole and benzene rings are 22.1 (1) and 21.8 (1)° in (I), 25.2 (1)° in (II) and 18.4 (1)° in (III), reflecting the twist created by the central thiazine ring in the tricyclic ring system. Another feature common to all three structures is an intramolecular interaction in the tricyclic ring system, observed between carbonyl atom O1 and atom C6 of the benzene ring, generating an S(6) graph-set motif.
The presence of bulky benzylol [in (II)] and phenylpropanoate [in (III)] substituents on N2 of the triazole ring is the cause of asymmetry in the angles around N2 (Table 1). In (II), the orientation of the phenyl ring with respect to the tricylic ring system is defined by the torsion angle N2—C10—C11—C12 = 165.4 (2)°, which also reflects the overall conformation of the molecule in extended form. On the other hand, in (III) the phenyl ring is in an almost perpendicular orientation [-81.1 (4)°], perhaps due to the propanoate substitution at C10. Compound (III) exists in the trans β-diketo form. As suggested by Bertolasi et al. (2008) on keto–enol tautomerization of β-diketones from X-ray structure data and density functional theory calculations, the steric hindrance of bulky group substituents plays a role in shifting the more common β-keto–enol tautomer to the β-diketo form. Furthermore, they also reported that the occurrence of the trans β-diketo form in crystal structures can be interpreted in terms of the existence of a high activation energy in the mechanism to attain the β-keto–enol form. The O atoms of both the ketone (O2) and the ester (O3) carbonyl groups do not point in the same direction. The dihedral angle between the planes defined by atoms O2/C11/C10 and O3/C18/C10 is 81.2 (3)°. The carbonyl atom O2 of the ketone group and the benzene ring are coplanar [O2—C11—C12—C17 = 0.9 (3)° in (II) and 3.0 (5)° in (III)].
The packing diagrams for (I)–(III) are given in Figs. 5–7. In the absence of conventional hydrogen bonds, other than N—H···O hydrogen bonds in (I) as mentioned earlier, the crystal packing of (I)–(III) is essentially governed by C—H···O/N and π–π stacking interactions (Tables 2–4).
In (I), dimers related to each other by an inversion centre are linked alternately in a head-to-tail manner via C—H···O interactions (C3A—H···O1Bi; details and symmetry code in Table 2), forming an R24(14) ring motif. These dimers are further linked by C—H···N and C—H···O interactions (C3B—H3D···N1Bii and C3B—H3C···O1Aii; details and symmetry code in Table 2), generating an R32(7) ring motif and forming a two-dimensional network in the [011] direction. A π–π stacking interaction is observed between the triazole and benzene ring systems [ring-centroid separation = 3.673 (2) Å; symmetry code: x, y - 1, z].
The molecules of (II) are linked together by paired C10—H···O1i (details and symmetry code in Table 3) interactions, forming a centrosymmetric R22(10) dimer. We believe this could be facilitated by the extended conformation of the molecule mentioned earlier. The face-to-face orientation of the two benzene rings, centrosymmetrically related, results in a π–π stacking interaction [ring-centroid separation = 3.651 (1) Å; symmetry code: ? Please complete] and links the dimers.
In (III) there are more intermolecular C—H···O interactions than in (II), due to the presence of the additional propanoate group. The molecules are linked by paired C3—H···O3i, C8—H···O3ii and C13—H···O1iii interactions (details and symmetry codes Table 4), forming centrosymmetric R22(16), R22(22) and R22(16) dimers, which are interconnected. As also seen in (II), there is a π–π stacking interaction between centrosymmetrically related benzene rings [ring-centroid separation = 3.987 (2) Å; symmetry code: ? Please complete].
In conclusion, this is the first report presenting the crystal structures of benzothiazine-fused triazoles. The tricyclic ring system generates an S(6) graph-set motif in all three title crystal structures. Crystallographic study shows that the N2 substitution has no significant effect on the conformation of the tricyclic ring system. The validity of the postulate that C—H···O/N interactions play a significant role in molecular assembly and crystal packing (Desiraju, 2005) has been illustrated. These structures are a useful addition to current knowledge of weak interactions and their role in supramolecular networks, molecular recognition and crystal engineering.