Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007190/wn6145sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007190/wn6145Isup2.hkl |
CCDC reference: 214603
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.044
- wR factor = 0.146
- Data-to-parameter ratio = 12.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound was synthesized by irradiation (254 nm) of 4-(2-chlorobenzyl)-5-phenyl-1,2,4-triazole-3-thione, according to a reported method (Park et al., 1999), using CH3CN/NaOH as solvent. After completion of the reaction, removal of solvent and chromatographic separation on a silica-gel column by elution with a petroleum ether-ethyl acetate (1:1) mixture afforded the title compound.
The H atoms were positioned geometrically and were treated as riding on their parent C atoms, with aromatic C—H distances of 0.93 Å and other C—H distances of 0.97 Å,
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, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997) and PLATON (Spek, 1997); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
C15H11N3S | Dx = 1.395 Mg m−3 |
Mr = 265.33 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 26 reflections |
a = 11.5674 (15) Å | θ = 5–20° |
b = 10.1948 (19) Å | µ = 0.24 mm−1 |
c = 21.433 (3) Å | T = 293 K |
V = 2527.5 (7) Å3 | Block, colorless |
Z = 8 | 0.46 × 0.26 × 0.23 mm |
F(000) = 1104 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.015 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.6° |
Graphite monochromator | h = −2→13 |
ω/2θ scans | k = −2→12 |
2197 measured reflections | l = −25→5 |
2110 independent reflections | 2 standard reflections every 200 reflections |
1457 reflections with I > 2σ(I) | intensity decay: <1.5% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.146 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.88 | (Δ/σ)max < 0.001 |
2110 reflections | Δρmax = 0.19 e Å−3 |
173 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0065 (13) |
C15H11N3S | V = 2527.5 (7) Å3 |
Mr = 265.33 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.5674 (15) Å | µ = 0.24 mm−1 |
b = 10.1948 (19) Å | T = 293 K |
c = 21.433 (3) Å | 0.46 × 0.26 × 0.23 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.015 |
2197 measured reflections | 2 standard reflections every 200 reflections |
2110 independent reflections | intensity decay: <1.5% |
1457 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.19 e Å−3 |
2110 reflections | Δρmin = −0.19 e Å−3 |
173 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.21009 (7) | 0.03609 (8) | 0.40577 (4) | 0.0493 (3) | |
N1 | 0.21175 (18) | 0.2360 (2) | 0.32144 (10) | 0.0352 (6) | |
C9 | 0.2885 (2) | 0.2893 (3) | 0.28026 (13) | 0.0373 (7) | |
N2 | 0.3885 (2) | 0.2296 (3) | 0.28482 (12) | 0.0460 (7) | |
N3 | 0.3791 (2) | 0.1331 (3) | 0.33051 (13) | 0.0485 (7) | |
C7 | 0.0683 (2) | 0.2548 (3) | 0.40579 (13) | 0.0392 (7) | |
C1 | 0.2721 (2) | 0.1397 (3) | 0.35089 (13) | 0.0393 (7) | |
C10 | 0.2625 (2) | 0.3935 (3) | 0.23477 (12) | 0.0369 (7) | |
C8 | 0.0920 (2) | 0.2712 (3) | 0.33722 (13) | 0.0402 (7) | |
H8A | 0.0394 | 0.2162 | 0.3136 | 0.048* | |
H8B | 0.0780 | 0.3617 | 0.3254 | 0.048* | |
C12 | 0.1362 (3) | 0.4963 (3) | 0.16003 (15) | 0.0473 (8) | |
H12 | 0.0641 | 0.5024 | 0.1411 | 0.057* | |
C15 | 0.3497 (3) | 0.4804 (3) | 0.21702 (15) | 0.0448 (8) | |
H15 | 0.4215 | 0.4765 | 0.2364 | 0.054* | |
C11 | 0.1551 (3) | 0.4026 (3) | 0.20527 (14) | 0.0408 (7) | |
H11 | 0.0961 | 0.3450 | 0.2162 | 0.049* | |
C2 | 0.1163 (3) | 0.1526 (3) | 0.44058 (13) | 0.0412 (7) | |
C13 | 0.2235 (3) | 0.5811 (3) | 0.14273 (16) | 0.0545 (9) | |
H13 | 0.2103 | 0.6441 | 0.1121 | 0.065* | |
C6 | −0.0062 (3) | 0.3396 (3) | 0.43578 (15) | 0.0531 (9) | |
H6 | −0.0379 | 0.4095 | 0.4137 | 0.064* | |
C4 | 0.0145 (3) | 0.2220 (4) | 0.53150 (16) | 0.0637 (10) | |
H4 | −0.0037 | 0.2111 | 0.5734 | 0.076* | |
C3 | 0.0902 (3) | 0.1376 (3) | 0.50339 (15) | 0.0543 (9) | |
H3 | 0.1240 | 0.0704 | 0.5263 | 0.065* | |
C14 | 0.3299 (3) | 0.5721 (3) | 0.17092 (16) | 0.0527 (9) | |
H14 | 0.3892 | 0.6283 | 0.1588 | 0.063* | |
C5 | −0.0349 (3) | 0.3230 (4) | 0.49828 (17) | 0.0647 (10) | |
H5 | −0.0870 | 0.3796 | 0.5175 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0526 (6) | 0.0450 (5) | 0.0502 (5) | 0.0078 (4) | 0.0009 (4) | 0.0007 (4) |
N1 | 0.0288 (12) | 0.0432 (14) | 0.0336 (12) | −0.0003 (11) | −0.0013 (11) | −0.0057 (11) |
C9 | 0.0305 (15) | 0.0460 (18) | 0.0354 (16) | −0.0012 (14) | 0.0003 (12) | −0.0091 (14) |
N2 | 0.0318 (14) | 0.0587 (17) | 0.0475 (16) | 0.0010 (13) | 0.0019 (12) | −0.0053 (13) |
N3 | 0.0355 (15) | 0.0625 (18) | 0.0474 (16) | 0.0082 (13) | −0.0016 (12) | −0.0039 (14) |
C7 | 0.0357 (16) | 0.0431 (16) | 0.0386 (16) | −0.0037 (14) | 0.0029 (13) | −0.0019 (14) |
C1 | 0.0355 (17) | 0.0433 (17) | 0.0391 (17) | 0.0053 (15) | −0.0056 (14) | −0.0090 (14) |
C10 | 0.0343 (16) | 0.0434 (17) | 0.0331 (15) | −0.0029 (14) | 0.0060 (13) | −0.0094 (13) |
C8 | 0.0279 (15) | 0.0499 (18) | 0.0428 (18) | 0.0013 (14) | 0.0017 (13) | 0.0009 (15) |
C12 | 0.0438 (18) | 0.056 (2) | 0.0427 (18) | 0.0049 (16) | −0.0015 (15) | −0.0063 (16) |
C15 | 0.0346 (17) | 0.0499 (19) | 0.0500 (19) | −0.0039 (15) | 0.0071 (14) | −0.0117 (16) |
C11 | 0.0361 (16) | 0.0473 (17) | 0.0392 (16) | −0.0056 (15) | 0.0043 (14) | −0.0053 (15) |
C2 | 0.0406 (17) | 0.0445 (17) | 0.0384 (17) | −0.0057 (15) | 0.0012 (13) | −0.0035 (14) |
C13 | 0.067 (2) | 0.0466 (19) | 0.0495 (19) | 0.0073 (19) | 0.0128 (18) | 0.0015 (16) |
C6 | 0.051 (2) | 0.053 (2) | 0.055 (2) | 0.0089 (17) | 0.0120 (16) | 0.0007 (17) |
C4 | 0.085 (3) | 0.067 (2) | 0.0392 (19) | −0.005 (2) | 0.0178 (19) | −0.0014 (18) |
C3 | 0.070 (2) | 0.052 (2) | 0.0408 (19) | −0.0003 (18) | 0.0020 (18) | 0.0001 (16) |
C14 | 0.050 (2) | 0.0450 (19) | 0.063 (2) | −0.0071 (17) | 0.0113 (18) | −0.0026 (18) |
C5 | 0.076 (3) | 0.059 (2) | 0.058 (2) | 0.007 (2) | 0.029 (2) | −0.009 (2) |
S1—C1 | 1.736 (3) | C12—C13 | 1.380 (5) |
S1—C2 | 1.773 (3) | C12—H12 | 0.9300 |
N1—C9 | 1.364 (3) | C15—C14 | 1.379 (5) |
N1—C1 | 1.360 (4) | C15—H15 | 0.9300 |
N1—C8 | 1.470 (3) | C11—H11 | 0.9300 |
C9—N2 | 1.311 (4) | C2—C3 | 1.388 (4) |
C9—C10 | 1.473 (4) | C13—C14 | 1.375 (5) |
N2—N3 | 1.393 (4) | C13—H13 | 0.9300 |
N3—C1 | 1.314 (4) | C6—C5 | 1.391 (5) |
C7—C6 | 1.380 (4) | C6—H6 | 0.9300 |
C7—C2 | 1.397 (4) | C4—C5 | 1.376 (5) |
C7—C8 | 1.504 (4) | C4—C3 | 1.367 (5) |
C10—C15 | 1.396 (4) | C4—H4 | 0.9300 |
C10—C11 | 1.396 (4) | C3—H3 | 0.9300 |
C8—H8A | 0.9700 | C14—H14 | 0.9300 |
C8—H8B | 0.9700 | C5—H5 | 0.9300 |
C12—C11 | 1.379 (4) | ||
C1—S1—C2 | 97.49 (14) | C10—C15—C14 | 120.4 (3) |
C9—N1—C1 | 104.7 (2) | C10—C15—H15 | 119.8 |
C9—N1—C8 | 131.6 (2) | C14—C15—H15 | 119.8 |
C1—N1—C8 | 123.6 (2) | C12—C11—C10 | 120.4 (3) |
N2—C9—N1 | 110.0 (3) | C12—C11—H11 | 119.8 |
N2—C9—C10 | 124.3 (3) | C10—C11—H11 | 119.8 |
N1—C9—C10 | 125.6 (2) | C3—C2—C7 | 120.9 (3) |
C9—N2—N3 | 108.1 (2) | C3—C2—S1 | 117.9 (3) |
C1—N3—N2 | 105.7 (2) | C7—C2—S1 | 121.2 (2) |
C6—C7—C2 | 117.8 (3) | C14—C13—C12 | 119.7 (3) |
C6—C7—C8 | 120.0 (3) | C14—C13—H13 | 120.2 |
C2—C7—C8 | 122.2 (3) | C12—C13—H13 | 120.2 |
N3—C1—N1 | 111.5 (3) | C7—C6—C5 | 121.5 (3) |
N3—C1—S1 | 125.7 (2) | C7—C6—H6 | 119.3 |
N1—C1—S1 | 122.8 (2) | C5—C6—H6 | 119.3 |
C15—C10—C11 | 118.5 (3) | C5—C4—C3 | 120.6 (3) |
C15—C10—C9 | 119.4 (3) | C5—C4—H4 | 119.7 |
C11—C10—C9 | 121.9 (3) | C3—C4—H4 | 119.7 |
N1—C8—C7 | 111.7 (2) | C2—C3—C4 | 119.9 (3) |
N1—C8—H8A | 109.3 | C2—C3—H3 | 120.1 |
C7—C8—H8A | 109.3 | C4—C3—H3 | 120.1 |
N1—C8—H8B | 109.3 | C13—C14—C15 | 120.6 (3) |
C7—C8—H8B | 109.3 | C13—C14—H14 | 119.7 |
H8A—C8—H8B | 107.9 | C15—C14—H14 | 119.7 |
C11—C12—C13 | 120.4 (3) | C4—C5—C6 | 119.4 (3) |
C11—C12—H12 | 119.8 | C4—C5—H5 | 120.3 |
C13—C12—H12 | 119.8 | C6—C5—H5 | 120.3 |
C1—N1—C9—N2 | −0.3 (3) | C2—C7—C8—N1 | −36.8 (4) |
C8—N1—C9—N2 | 176.2 (3) | C11—C10—C15—C14 | −0.6 (4) |
C1—N1—C9—C10 | 176.6 (3) | C9—C10—C15—C14 | 174.8 (3) |
C8—N1—C9—C10 | −6.9 (4) | C13—C12—C11—C10 | 0.9 (4) |
N1—C9—N2—N3 | 0.0 (3) | C15—C10—C11—C12 | −0.6 (4) |
C10—C9—N2—N3 | −177.0 (2) | C9—C10—C11—C12 | −175.9 (3) |
C9—N2—N3—C1 | 0.4 (3) | C6—C7—C2—C3 | −0.4 (4) |
N2—N3—C1—N1 | −0.6 (3) | C8—C7—C2—C3 | −178.1 (3) |
N2—N3—C1—S1 | 176.7 (2) | C6—C7—C2—S1 | 178.4 (2) |
C9—N1—C1—N3 | 0.6 (3) | C8—C7—C2—S1 | 0.7 (4) |
C8—N1—C1—N3 | −176.3 (2) | C1—S1—C2—C3 | −149.2 (3) |
C9—N1—C1—S1 | −176.8 (2) | C1—S1—C2—C7 | 32.0 (3) |
C8—N1—C1—S1 | 6.3 (4) | C11—C12—C13—C14 | −0.1 (5) |
C2—S1—C1—N3 | 146.8 (3) | C2—C7—C6—C5 | −1.3 (5) |
C2—S1—C1—N1 | −36.1 (3) | C8—C7—C6—C5 | 176.5 (3) |
N2—C9—C10—C15 | −33.5 (4) | C7—C2—C3—C4 | 1.5 (5) |
N1—C9—C10—C15 | 150.0 (3) | S1—C2—C3—C4 | −177.3 (3) |
N2—C9—C10—C11 | 141.8 (3) | C5—C4—C3—C2 | −0.9 (5) |
N1—C9—C10—C11 | −34.7 (4) | C12—C13—C14—C15 | −1.1 (5) |
C9—N1—C8—C7 | −142.3 (3) | C10—C15—C14—C13 | 1.4 (5) |
C1—N1—C8—C7 | 33.7 (4) | C3—C4—C5—C6 | −0.7 (6) |
C6—C7—C8—N1 | 145.6 (3) | C7—C6—C5—C4 | 1.9 (6) |
Experimental details
Crystal data | |
Chemical formula | C15H11N3S |
Mr | 265.33 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 11.5674 (15), 10.1948 (19), 21.433 (3) |
V (Å3) | 2527.5 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.46 × 0.26 × 0.23 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2197, 2110, 1457 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.146, 0.88 |
No. of reflections | 2110 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.19 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997) and PLATON (Spek, 1997), SHELXL97 and PARST (Nardelli, 1995).
S1—C1 | 1.736 (3) | N1—C1 | 1.360 (4) |
S1—C2 | 1.773 (3) | C9—C10 | 1.473 (4) |
N1—C9 | 1.364 (3) | N2—N3 | 1.393 (4) |
C1—S1—C2 | 97.49 (14) | N2—C9—N1 | 110.0 (3) |
C9—N1—C8 | 131.6 (2) | N1—C9—C10 | 125.6 (2) |
C1—N1—C8 | 123.6 (2) | C9—N2—N3 | 108.1 (2) |
Triazole derivatives exhibit antimicrobial (Habib et al., 1997), antiviral (Ergen et al., 1996), anti-HIV-1 (Invidiata et al., 1996), antifungal, antimycobacterial and anticonvulsant (Gulerman et al., 1997) activities. It is also a highly potent eosinophilia inhibitor (Naito et al., 1996), fungicide (Croften, 1996) and herbicide (Tada et al., 1995). Some of the benzothiazine derivatives are most active against the Gram-positive Bacillus subtilis (Armenize et al., 1991). It also possesses neuroleptic activities (Grol & Rollema, 1975). The X-ray crystal structure analysis of the title compound, (I), was carried out as part of our studies on triazole derivatives.
The N—N, C—N and C—S bond distances in the fused fragment system are comparable with those found in a related structure, viz. 3-amino-6,7-dihydro-6-hydroxy-5H-1,2,4-trizolo[3,4-b][1,3]thiazine (Glowka, 1994). The S1—C1 [1.736 (3) Å], C1—N1 [1.360 (4) Å] and C1—N3 [1.314 (4) Å] bond distances clearly reflect the resonance of the thiourea system (Valle et al., 1970). The C1—S1—C2 angle of 97.5 (1)° suggests that the S atom uses only p-orbitals to form bonds with atom C1 and C2. In order to minimize the steric repulsion between the H atoms at C8 and C11, the relevant bond angles, viz. C8—N1—C9 and N1—C9—C10, are widened.
In the title compound, (I) (Fig. 1), the benzene ring (A) is planar, with a maximum deviation of 0.010 (4) Å for C5. The thiazine ring (B) is in a boat conformation with puckering parameters (Cremer & Pople, 1975) q2 = 0.547 (2), Q3 = −0.054 (3), QT = 0.549 (2), Φ = 124° and θ = 96°, and asymmetry parameters (Nardelli, 1983) ΔS(C8) = 0.024 (1) and ΔS(N1—C1) = 0.030 (1). Atoms S1 and C8 deviate by 0.552 (1) and 0.400 (3) Å, respectively, from the weighted least-squares plane through the remaining four atoms C1, N1, C7 and C2. The dihedral angle between the benzene (A), triazole (C) and phenyl (D) rings are: A/C 38.5 (1) A/D 70.9 (1) and C/D 34.3 (1)°.
In addition to van der Waals interactions, π···π interactions are possibly involved to ensure cohesion between the molecules. There is a π–π interaction between the triazole ring at (x, y, z) and the phenyl ring at (1/2 − x, −1/2 + y, z), the centroids of the two rings being separated by 3.531 (2) Å.