Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029571/ym2060sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029571/ym2060Isup2.hkl |
CCDC reference: 655010
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.003 Å
- R factor = 0.052
- wR factor = 0.173
- Data-to-parameter ratio = 17.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT230_ALERT_2_C Hirshfeld Test Diff for C15 - C16 .. 6.46 su PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For general backgroud, see: Zabriskie et al. (1988); Metzger (1984); Kornis (1984); Comba (1993); Chohan et al. (2002); Florin et al. (1980); Rau (1990); Bach et al. (1996); Biswas & Umapathy (2000); Ochiai et al. (1986); Tsuda et al. (2000); Allen et al. (1987). For related literature, see: Bruni et al. (1995); Seferoğlu et al. (2006a,b,c, 2007a,b,c; Seferoğlu, Hökelek, Şahin et al. (2006); Hökelek et al. (2007).
For the preparation of the title compound, 2-amino-5-methylthiazole (230 mg, 2 mmol) was dissolved in a hot glacial acetic acid-propionic acid mixture (2:1, 8 ml). The solution was rapidly cooled in an ice-salt bath and then added dropwise with stirring to a cold solution of nitrosylsulfuric acid (3 ml) over a period of 30 min. The mixture was stirred for an additional 2 h at 273 K. The resulting diazonium salt was cooled in an ice-salt bath and then added dropwise with stirring to 1-methyl-2-phenylindole (414 mg, 2 mmol) in an acetic acid-propionic acid mixture (3:1, 8 ml). The solution was stirred at 273–278 K for 2 h and the pH of the reaction mixture was maintained at 4–6 by the addition of a saturated sodium carbonate solution (40 ml). The mixture was stirred for a further 1 h. The resulting solid was filtered, washed with cold water and crystallized from ethanol (yield; 550 mg, 84%, 495–497 K).
H atoms were located in difference syntheses and refined isotropically [C—H = 0.89 (3)–1.04 (3) Å and Uiso(H) = 0.062 (6)–0.110 (10) Å2].
Heterocycles containing the 1,3-thiazole ring system exhibit a wide spectrum of biological activities, including acting as antiviral and antifungal agents, and that ring has been identified as a central structural element of a number of biologically active natural products (Zabriskie et al., 1988) and of pharmacologically active compounds (Metzger, 1984). The bioactivity of S,N-thiazoles is mainly due to their structural similarities with proteins' imidazolyl entities (Kornis, 1984) as well as their biological, structural, electronic and spectroscopic properties (Comba, 1993). Their existence may modify the bioactive and pharmaceutical characteristics of the adducts (Chohan et al., 2002).
Indole and its derivatives form a class of toxic recalcitrant N-heterocyclic compounds that are considered as pollutants (Florin et al., 1980). Azo derivatives are used extensively in analytical chemistry and in dyestuff industry as metallochromic and acid-base indicators (Rau, 1990). They are also used in the fields of non-linear optics and optical data storage (Bach et al., 1996). Azo dyes have wide applicability as optical materials and their structures have also attracted considerable attention (Biswas & Umapathy, 2000). Many azo-dye breakdown products are carcinogenic, toxic or mutagenic to life (Ochiai et al., 1986). Although there are many publications on the industrial applications of azo dyes (Tsuda et al., 2000), to the best of our knowledge, few structures of azoindole derivatives have been reported to date (Bruni et al., 1995; Seferoğlu et al., 2006a,b,c; Seferoğlu et al., 2006; Seferoğlu et al., 2007a,b,c; Hökelek et al., 2007). The present study was undertaken in order to ascertain the crystal structure of the title compound, (I).
The molecular structure of (I), is shown in Fig. 1. The bond lengths and angles are in normal ranges (Allen et al., 1987).
An examination of the deviations from the least-squares planes through the individual rings shows that all the rings are planar. The indole ring system is planar, with a dihedral angle of 0.72 (6)° between rings A (C5—C10) and B (N4/C4/C5/C10/C11). In the closely related compounds 3-(4-chlorophenyldiazenyl)-1-methyl-2-phenyl-1H-indole, (II) (Seferoğlu et al., 2006a), N-{4-[(2-phenyl-1H-indol-3-yl)diazenyl]phenyl}acetamide, (III) (Seferoğlu et al., 2006b), ethyl[2-(2-phenyl-1H-indol-3-yldiazenyl)-1,3 -thiazol-4-yl]acetate, (IV) (Seferoğlu et al., 2006c), ethyl-2-{2-[(1-methyl-2-phenyl-1H-indol-3-yl)diazenyl]thiazol-4-yl}acetate, (V) (Seferoğlu et al., 2006), 1-methyl-2-phenyl-3-(1,3,4-thiadiazol-2-yldiazenyl)-1H-indole, (VI) (Seferoğlu et al., 2007a), 1,2-dimethyl-3-(thiazol-2-yldazenyl)-1H-indole, (VII) (Seferoğlu et al., 2007b), 3-(5-ethyl-1,3,4-thiadiazol-2-yldiazenyl)-1-Methyl-2-phenyl-1H-indole, (VIII) (Seferoğlu et al., 2007c) and 3-(6-methoxybenzothiazol-2-yldiazenyl)-1-methyl -2-phenyl-1H-indole, (IX) (Hökelek et al., 2007), the observed A/B and/or A'/B' dihedral angles are 1.56 (11) and 0.77 (12)° in (II), 1.63 (14)° in (III), 0.99 (10)° in (IV) and 0.59 (7)° in (V), 4.26 (7)° in (VI), 2.07 (9) and 2.04 (9)° in (VII), 0.59 (12)° in (VIII) and 1.16 (7)° in (IX). The orientations of rings C (S1/N1/C1—C3) and D (C12—C17) with respect to the indole ring system may be described by the dihedral angles of 13.97 (4) and 47.79 (6)°, respectively.
As can be seen from the packing diagram (Fig. 2), the molecules of (I) are stacked along the a axis and elongated along the b axis. Dipole-dipole and van der Waals interactions are effective in the molecular packing.
For general backgroud, see: Zabriskie et al. (1988); Metzger (1984); Kornis (1984); Comba (1993); Chohan et al. (2002); Florin et al. (1980); Rau (1990); Bach et al. (1996); Biswas & Umapathy (2000); Ochiai et al. (1986); Tsuda et al. (2000); Allen et al. (1987). For related literature, see: Bruni et al. (1995); Seferoğlu et al. (2006a,b,c, 2007a,b,c; Seferoğlu, Hökelek, Şahin et al. (2006); Hökelek et al. (2007).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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).
C19H16N4S | Z = 2 |
Mr = 332.42 | F(000) = 348 |
Triclinic, P1 | Dx = 1.338 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2514 (7) Å | Cell parameters from 5548 reflections |
b = 9.2745 (5) Å | θ = 2.1–30.6° |
c = 11.0971 (6) Å | µ = 0.20 mm−1 |
α = 106.259 (1)° | T = 294 K |
β = 106.542 (2)° | Rod-shaped, red |
γ = 103.337 (2)° | 0.35 × 0.20 × 0.15 mm |
V = 824.90 (9) Å3 |
Rigaku R-AXIS RAPID-S diffractometer | 5029 independent reflections |
Radiation source: fine-focus sealed tube | 3726 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
ω scans | θmax = 30.6°, θmin = 2.1° |
Absorption correction: multi-scan (Blessing, 1995) | h = −11→13 |
Tmin = 0.932, Tmax = 0.970 | k = −13→13 |
24972 measured reflections | l = −15→15 |
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)] = 0.052 | All H-atom parameters refined |
wR(F2) = 0.173 | w = 1/[σ2(Fo2) + (0.0946P)2 + 0.0434P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
5029 reflections | Δρmax = 0.32 e Å−3 |
282 parameters | Δρmin = −0.23 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: 0.062 (8) |
C19H16N4S | γ = 103.337 (2)° |
Mr = 332.42 | V = 824.90 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2514 (7) Å | Mo Kα radiation |
b = 9.2745 (5) Å | µ = 0.20 mm−1 |
c = 11.0971 (6) Å | T = 294 K |
α = 106.259 (1)° | 0.35 × 0.20 × 0.15 mm |
β = 106.542 (2)° |
Rigaku R-AXIS RAPID-S diffractometer | 5029 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3726 reflections with I > 2σ(I) |
Tmin = 0.932, Tmax = 0.970 | Rint = 0.058 |
24972 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.173 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.32 e Å−3 |
5029 reflections | Δρmin = −0.23 e Å−3 |
282 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 | 0.48122 (5) | 0.83549 (5) | 0.31455 (4) | 0.05207 (17) | |
N1 | 0.57518 (19) | 1.0153 (2) | 0.19243 (15) | 0.0583 (4) | |
N2 | 0.76648 (16) | 1.08163 (17) | 0.41078 (14) | 0.0493 (3) | |
N3 | 0.79155 (15) | 1.01851 (16) | 0.50037 (13) | 0.0453 (3) | |
N4 | 1.10746 (17) | 1.14326 (17) | 0.81588 (13) | 0.0493 (3) | |
C1 | 0.6195 (2) | 0.98952 (19) | 0.30474 (17) | 0.0475 (4) | |
C2 | 0.4254 (2) | 0.9083 (2) | 0.10821 (19) | 0.0590 (4) | |
C3 | 0.3545 (2) | 0.8044 (2) | 0.15525 (18) | 0.0532 (4) | |
C4 | 0.92786 (19) | 1.10103 (19) | 0.61325 (16) | 0.0450 (3) | |
C5 | 1.05265 (19) | 1.25219 (19) | 0.65531 (16) | 0.0457 (3) | |
C6 | 1.0817 (2) | 1.3684 (2) | 0.5996 (2) | 0.0543 (4) | |
C7 | 1.2172 (2) | 1.5033 (2) | 0.6738 (2) | 0.0648 (5) | |
C8 | 1.3228 (3) | 1.5235 (3) | 0.8000 (2) | 0.0686 (5) | |
C9 | 1.2963 (2) | 1.4093 (3) | 0.8561 (2) | 0.0629 (5) | |
C10 | 1.16079 (19) | 1.2736 (2) | 0.78208 (17) | 0.0476 (4) | |
C11 | 0.96765 (19) | 1.0384 (2) | 0.71412 (16) | 0.0456 (3) | |
C12 | 0.8817 (2) | 0.8837 (2) | 0.71330 (16) | 0.0475 (4) | |
C13 | 0.7158 (2) | 0.8344 (2) | 0.67463 (19) | 0.0557 (4) | |
C14 | 0.6323 (3) | 0.6842 (3) | 0.6636 (2) | 0.0708 (6) | |
C15 | 0.7136 (3) | 0.5829 (3) | 0.6911 (2) | 0.0767 (6) | |
C16 | 0.8769 (3) | 0.6300 (3) | 0.7305 (2) | 0.0674 (5) | |
C17 | 0.9622 (3) | 0.7798 (2) | 0.74165 (19) | 0.0575 (4) | |
C18 | 1.1814 (3) | 1.1384 (3) | 0.9485 (2) | 0.0619 (5) | |
C19 | 0.1894 (3) | 0.6815 (3) | 0.0887 (3) | 0.0685 (5) | |
H2 | 0.375 (3) | 0.910 (3) | 0.019 (2) | 0.077 (7)* | |
H6 | 1.009 (3) | 1.358 (3) | 0.515 (2) | 0.075 (7)* | |
H7 | 1.238 (3) | 1.586 (3) | 0.637 (3) | 0.084 (7)* | |
H8 | 1.418 (4) | 1.629 (4) | 0.853 (3) | 0.108 (9)* | |
H9 | 1.365 (3) | 1.424 (3) | 0.940 (2) | 0.065 (6)* | |
H13 | 0.662 (3) | 0.902 (2) | 0.658 (2) | 0.062 (6)* | |
H14 | 0.526 (3) | 0.651 (3) | 0.634 (3) | 0.086 (8)* | |
H15 | 0.662 (4) | 0.485 (4) | 0.686 (3) | 0.101 (9)* | |
H16 | 0.932 (3) | 0.561 (3) | 0.747 (3) | 0.091 (8)* | |
H17 | 1.085 (3) | 0.813 (3) | 0.773 (2) | 0.074 (6)* | |
H181 | 1.118 (4) | 1.059 (4) | 0.962 (3) | 0.100 (9)* | |
H182 | 1.192 (3) | 1.232 (4) | 1.017 (3) | 0.096 (8)* | |
H183 | 1.276 (4) | 1.116 (3) | 0.953 (3) | 0.100 (9)* | |
H191 | 0.125 (4) | 0.688 (3) | 0.001 (3) | 0.108 (9)* | |
H192 | 0.128 (4) | 0.698 (3) | 0.140 (3) | 0.100 (9)* | |
H193 | 0.190 (4) | 0.578 (4) | 0.068 (3) | 0.110 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0495 (3) | 0.0518 (3) | 0.0478 (2) | 0.00908 (18) | 0.01069 (18) | 0.02237 (19) |
N1 | 0.0554 (8) | 0.0677 (9) | 0.0510 (8) | 0.0151 (7) | 0.0142 (7) | 0.0311 (7) |
N2 | 0.0450 (7) | 0.0531 (8) | 0.0468 (7) | 0.0119 (6) | 0.0126 (6) | 0.0227 (6) |
N3 | 0.0424 (7) | 0.0468 (7) | 0.0430 (7) | 0.0133 (6) | 0.0128 (5) | 0.0163 (5) |
N4 | 0.0436 (7) | 0.0558 (8) | 0.0403 (7) | 0.0129 (6) | 0.0092 (5) | 0.0159 (6) |
C1 | 0.0452 (8) | 0.0503 (8) | 0.0461 (8) | 0.0145 (7) | 0.0132 (7) | 0.0215 (7) |
C2 | 0.0541 (10) | 0.0712 (12) | 0.0465 (9) | 0.0185 (9) | 0.0087 (8) | 0.0266 (8) |
C3 | 0.0459 (9) | 0.0564 (9) | 0.0488 (9) | 0.0152 (7) | 0.0103 (7) | 0.0165 (7) |
C4 | 0.0416 (8) | 0.0460 (8) | 0.0428 (8) | 0.0119 (6) | 0.0128 (6) | 0.0151 (6) |
C5 | 0.0407 (8) | 0.0473 (8) | 0.0445 (8) | 0.0118 (6) | 0.0144 (6) | 0.0142 (6) |
C6 | 0.0510 (9) | 0.0526 (9) | 0.0574 (10) | 0.0134 (7) | 0.0193 (8) | 0.0221 (8) |
C7 | 0.0569 (11) | 0.0582 (11) | 0.0746 (13) | 0.0075 (9) | 0.0262 (10) | 0.0258 (10) |
C8 | 0.0523 (11) | 0.0608 (11) | 0.0710 (13) | −0.0014 (9) | 0.0177 (10) | 0.0151 (10) |
C9 | 0.0458 (10) | 0.0660 (11) | 0.0548 (10) | 0.0032 (8) | 0.0103 (8) | 0.0118 (9) |
C10 | 0.0388 (8) | 0.0518 (8) | 0.0457 (8) | 0.0108 (7) | 0.0139 (6) | 0.0144 (7) |
C11 | 0.0420 (8) | 0.0499 (8) | 0.0420 (7) | 0.0145 (6) | 0.0138 (6) | 0.0157 (6) |
C12 | 0.0498 (9) | 0.0519 (8) | 0.0411 (7) | 0.0159 (7) | 0.0172 (7) | 0.0182 (6) |
C13 | 0.0505 (9) | 0.0583 (10) | 0.0568 (10) | 0.0130 (8) | 0.0194 (8) | 0.0240 (8) |
C14 | 0.0588 (12) | 0.0717 (13) | 0.0704 (13) | 0.0028 (10) | 0.0203 (10) | 0.0293 (11) |
C15 | 0.0989 (17) | 0.0528 (11) | 0.0704 (13) | 0.0077 (11) | 0.0295 (12) | 0.0279 (10) |
C16 | 0.0893 (16) | 0.0596 (11) | 0.0649 (12) | 0.0292 (11) | 0.0328 (11) | 0.0324 (10) |
C17 | 0.0655 (11) | 0.0630 (10) | 0.0547 (10) | 0.0270 (9) | 0.0260 (9) | 0.0292 (8) |
C18 | 0.0565 (11) | 0.0760 (13) | 0.0433 (9) | 0.0171 (10) | 0.0090 (8) | 0.0220 (9) |
C19 | 0.0500 (11) | 0.0691 (13) | 0.0620 (12) | 0.0072 (9) | 0.0079 (9) | 0.0129 (10) |
S1—C1 | 1.7355 (17) | C10—C9 | 1.392 (2) |
S1—C3 | 1.7209 (18) | C11—N4 | 1.366 (2) |
N1—C2 | 1.374 (2) | C11—C4 | 1.398 (2) |
N2—C1 | 1.398 (2) | C11—C12 | 1.467 (2) |
N3—N2 | 1.2815 (18) | C12—C13 | 1.393 (3) |
N3—C4 | 1.365 (2) | C12—C17 | 1.396 (2) |
N4—C10 | 1.389 (2) | C13—C14 | 1.381 (3) |
N4—C18 | 1.454 (2) | C13—H13 | 0.91 (2) |
C1—N1 | 1.304 (2) | C14—C15 | 1.378 (4) |
C2—H2 | 0.97 (2) | C14—H14 | 0.89 (3) |
C3—C2 | 1.348 (3) | C15—H15 | 0.90 (3) |
C3—C19 | 1.503 (3) | C16—C15 | 1.370 (4) |
C5—C4 | 1.448 (2) | C16—H16 | 0.93 (3) |
C5—C6 | 1.397 (2) | C17—C16 | 1.383 (3) |
C5—C10 | 1.404 (2) | C17—H17 | 1.03 (2) |
C6—C7 | 1.388 (3) | C18—H181 | 0.91 (3) |
C6—H6 | 0.95 (2) | C18—H182 | 0.94 (3) |
C7—H7 | 0.97 (2) | C18—H183 | 0.94 (3) |
C8—C7 | 1.393 (3) | C19—H191 | 1.01 (3) |
C8—C9 | 1.381 (3) | C19—H192 | 0.92 (3) |
C8—H8 | 1.04 (3) | C19—H193 | 0.92 (3) |
C9—H9 | 0.91 (2) | ||
C3—S1—C1 | 88.89 (8) | N4—C10—C5 | 109.22 (14) |
C1—N1—C2 | 109.34 (15) | C9—C10—C5 | 121.98 (17) |
N3—N2—C1 | 110.10 (13) | N4—C11—C4 | 108.74 (15) |
N2—N3—C4 | 116.17 (14) | N4—C11—C12 | 123.71 (14) |
C10—N4—C18 | 122.69 (16) | C4—C11—C12 | 127.50 (15) |
C11—N4—C10 | 109.02 (13) | C13—C12—C17 | 119.12 (17) |
C11—N4—C18 | 127.68 (16) | C13—C12—C11 | 119.75 (15) |
N1—C1—N2 | 122.33 (15) | C17—C12—C11 | 120.98 (16) |
N1—C1—S1 | 115.24 (13) | C12—C13—H13 | 120.2 (14) |
N2—C1—S1 | 122.42 (12) | C14—C13—C12 | 120.29 (19) |
N1—C2—H2 | 119.9 (14) | C14—C13—H13 | 119.5 (14) |
C3—C2—N1 | 117.12 (16) | C13—C14—H14 | 119.7 (16) |
C3—C2—H2 | 123.0 (14) | C15—C14—C13 | 119.8 (2) |
C2—C3—C19 | 128.42 (18) | C15—C14—H14 | 120.4 (16) |
C2—C3—S1 | 109.41 (14) | C14—C15—H15 | 121 (2) |
C19—C3—S1 | 122.13 (16) | C16—C15—C14 | 120.7 (2) |
N3—C4—C11 | 120.07 (15) | C16—C15—H15 | 118 (2) |
N3—C4—C5 | 132.33 (15) | C15—C16—C17 | 120.2 (2) |
C11—C4—C5 | 107.59 (14) | C15—C16—H16 | 120.9 (17) |
C6—C5—C10 | 119.65 (15) | C17—C16—H16 | 118.9 (17) |
C6—C5—C4 | 134.94 (16) | C16—C17—C12 | 119.9 (2) |
C10—C5—C4 | 105.41 (14) | C16—C17—H17 | 118.5 (12) |
C7—C6—C5 | 118.10 (19) | C12—C17—H17 | 121.6 (12) |
C7—C6—H6 | 120.6 (15) | N4—C18—H182 | 110.1 (16) |
C5—C6—H6 | 121.3 (15) | N4—C18—H183 | 108.3 (17) |
C6—C7—C8 | 121.6 (2) | H182—C18—H183 | 116 (3) |
C6—C7—H7 | 119.2 (16) | N4—C18—H181 | 111.5 (19) |
C8—C7—H7 | 119.2 (16) | H182—C18—H181 | 104 (2) |
C9—C8—C7 | 121.03 (19) | H183—C18—H181 | 107 (2) |
C9—C8—H8 | 120.6 (16) | C3—C19—H193 | 113 (2) |
C7—C8—H8 | 118.3 (16) | C3—C19—H192 | 111.8 (19) |
C8—C9—C10 | 117.64 (19) | H193—C19—H192 | 110 (3) |
C8—C9—H9 | 120.4 (15) | C3—C19—H191 | 112.3 (18) |
C10—C9—H9 | 121.9 (14) | H193—C19—H191 | 106 (2) |
N4—C10—C9 | 128.80 (17) | H192—C19—H191 | 103 (2) |
C3—S1—C1—N1 | −0.12 (15) | C4—C5—C10—C9 | −178.63 (17) |
C3—S1—C1—N2 | 178.57 (15) | C5—C6—C7—C8 | 0.3 (3) |
C1—S1—C3—C2 | 0.76 (15) | C9—C8—C7—C6 | 0.1 (3) |
C1—S1—C3—C19 | −177.22 (18) | C7—C8—C9—C10 | 0.1 (3) |
C1—N1—C2—C3 | 1.2 (3) | N4—C10—C9—C8 | −179.68 (18) |
N3—N2—C1—N1 | −170.58 (16) | C5—C10—C9—C8 | −0.6 (3) |
N3—N2—C1—S1 | 10.8 (2) | C4—C11—N4—C10 | −0.63 (18) |
C4—N3—N2—C1 | −176.83 (13) | C12—C11—N4—C10 | 177.05 (15) |
N2—N3—C4—C11 | −177.78 (14) | C4—C11—N4—C18 | 170.57 (18) |
N2—N3—C4—C5 | 1.5 (3) | C12—C11—N4—C18 | −11.8 (3) |
C11—N4—C10—C9 | 179.16 (18) | N4—C11—C12—C13 | 136.47 (17) |
C18—N4—C10—C9 | 7.4 (3) | C4—C11—C12—C13 | −46.3 (3) |
C11—N4—C10—C5 | −0.01 (18) | N4—C11—C12—C17 | −48.0 (2) |
C18—N4—C10—C5 | −171.73 (17) | C4—C11—C12—C17 | 129.21 (19) |
N2—C1—N1—C2 | −179.24 (16) | N4—C11—C4—N3 | −179.52 (14) |
S1—C1—N1—C2 | −0.5 (2) | C12—C11—C4—N3 | 2.9 (3) |
C19—C3—C2—N1 | 176.5 (2) | N4—C11—C4—C5 | 1.00 (18) |
S1—C3—C2—N1 | −1.3 (2) | C12—C11—C4—C5 | −176.57 (16) |
C6—C5—C4—N3 | 0.1 (3) | C13—C12—C17—C16 | 0.3 (3) |
C10—C5—C4—N3 | 179.63 (17) | C11—C12—C17—C16 | −175.25 (17) |
C6—C5—C4—C11 | 179.47 (19) | C17—C12—C13—C14 | −0.5 (3) |
C10—C5—C4—C11 | −0.97 (17) | C11—C12—C13—C14 | 175.09 (18) |
C10—C5—C6—C7 | −0.8 (3) | C12—C13—C14—C15 | 0.1 (3) |
C4—C5—C6—C7 | 178.67 (19) | C13—C14—C15—C16 | 0.6 (4) |
C6—C5—C10—N4 | −179.76 (15) | C17—C16—C15—C14 | −0.8 (4) |
C4—C5—C10—N4 | 0.60 (17) | C12—C17—C16—C15 | 0.4 (3) |
C6—C5—C10—C9 | 1.0 (3) |
Experimental details
Crystal data | |
Chemical formula | C19H16N4S |
Mr | 332.42 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 9.2514 (7), 9.2745 (5), 11.0971 (6) |
α, β, γ (°) | 106.259 (1), 106.542 (2), 103.337 (2) |
V (Å3) | 824.90 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.35 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID-S |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.932, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24972, 5029, 3726 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.715 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.173, 1.06 |
No. of reflections | 5029 |
No. of parameters | 282 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.32, −0.23 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
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Heterocycles containing the 1,3-thiazole ring system exhibit a wide spectrum of biological activities, including acting as antiviral and antifungal agents, and that ring has been identified as a central structural element of a number of biologically active natural products (Zabriskie et al., 1988) and of pharmacologically active compounds (Metzger, 1984). The bioactivity of S,N-thiazoles is mainly due to their structural similarities with proteins' imidazolyl entities (Kornis, 1984) as well as their biological, structural, electronic and spectroscopic properties (Comba, 1993). Their existence may modify the bioactive and pharmaceutical characteristics of the adducts (Chohan et al., 2002).
Indole and its derivatives form a class of toxic recalcitrant N-heterocyclic compounds that are considered as pollutants (Florin et al., 1980). Azo derivatives are used extensively in analytical chemistry and in dyestuff industry as metallochromic and acid-base indicators (Rau, 1990). They are also used in the fields of non-linear optics and optical data storage (Bach et al., 1996). Azo dyes have wide applicability as optical materials and their structures have also attracted considerable attention (Biswas & Umapathy, 2000). Many azo-dye breakdown products are carcinogenic, toxic or mutagenic to life (Ochiai et al., 1986). Although there are many publications on the industrial applications of azo dyes (Tsuda et al., 2000), to the best of our knowledge, few structures of azoindole derivatives have been reported to date (Bruni et al., 1995; Seferoğlu et al., 2006a,b,c; Seferoğlu et al., 2006; Seferoğlu et al., 2007a,b,c; Hökelek et al., 2007). The present study was undertaken in order to ascertain the crystal structure of the title compound, (I).
The molecular structure of (I), is shown in Fig. 1. The bond lengths and angles are in normal ranges (Allen et al., 1987).
An examination of the deviations from the least-squares planes through the individual rings shows that all the rings are planar. The indole ring system is planar, with a dihedral angle of 0.72 (6)° between rings A (C5—C10) and B (N4/C4/C5/C10/C11). In the closely related compounds 3-(4-chlorophenyldiazenyl)-1-methyl-2-phenyl-1H-indole, (II) (Seferoğlu et al., 2006a), N-{4-[(2-phenyl-1H-indol-3-yl)diazenyl]phenyl}acetamide, (III) (Seferoğlu et al., 2006b), ethyl[2-(2-phenyl-1H-indol-3-yldiazenyl)-1,3 -thiazol-4-yl]acetate, (IV) (Seferoğlu et al., 2006c), ethyl-2-{2-[(1-methyl-2-phenyl-1H-indol-3-yl)diazenyl]thiazol-4-yl}acetate, (V) (Seferoğlu et al., 2006), 1-methyl-2-phenyl-3-(1,3,4-thiadiazol-2-yldiazenyl)-1H-indole, (VI) (Seferoğlu et al., 2007a), 1,2-dimethyl-3-(thiazol-2-yldazenyl)-1H-indole, (VII) (Seferoğlu et al., 2007b), 3-(5-ethyl-1,3,4-thiadiazol-2-yldiazenyl)-1-Methyl-2-phenyl-1H-indole, (VIII) (Seferoğlu et al., 2007c) and 3-(6-methoxybenzothiazol-2-yldiazenyl)-1-methyl -2-phenyl-1H-indole, (IX) (Hökelek et al., 2007), the observed A/B and/or A'/B' dihedral angles are 1.56 (11) and 0.77 (12)° in (II), 1.63 (14)° in (III), 0.99 (10)° in (IV) and 0.59 (7)° in (V), 4.26 (7)° in (VI), 2.07 (9) and 2.04 (9)° in (VII), 0.59 (12)° in (VIII) and 1.16 (7)° in (IX). The orientations of rings C (S1/N1/C1—C3) and D (C12—C17) with respect to the indole ring system may be described by the dihedral angles of 13.97 (4) and 47.79 (6)°, respectively.
As can be seen from the packing diagram (Fig. 2), the molecules of (I) are stacked along the a axis and elongated along the b axis. Dipole-dipole and van der Waals interactions are effective in the molecular packing.