3-[(4-Phen­oxy­phen­yl)sulfan­yl]-5-phenyl-1H-1,2,4-triazole

Raja Ben Othman; Mathieu Marchivie; Franck Suzenet; Sylvain Routier

doi:10.1107/S1600536814008204

. 2014 Apr 30;70(Pt 5):o622–o623. doi: 10.1107/S1600536814008204

3-[(4-Phenoxyphenyl)sulfanyl]-5-phenyl-1H-1,2,4-triazole

Raja Ben Othman ^a,^b, Mathieu Marchivie ^c,^*, Franck Suzenet ^b, Sylvain Routier ^b

PMCID: PMC4011301 PMID: 24860412

Abstract

The title compound, C₂₀H₁₅N₃OS, is V-shaped. In the 4-phenoxyphenyl group, the two rings are inclined to one another by 74.52 (13)°. These rings are inclined to the triazole ring by 72.20 (15) and 72.30 (15)°, respectively. The phenyl ring is inclined to the triazole ring by 10.85 (12)°. In the crystal, molecules are linked via N—H⋯N hydrogen bonds, forming chains propagating along [010]. These chains are linked via pairs of C—H⋯S hydrogen bonds, forming sheets lying parallel to the ac plane.

Related literature

For the synthesis, properties and various biological activities of functionalizated 1,2,4-triazole derivatives, see: Holla et al. (2002 ▶, 2003 ▶); Walczak et al. (2004 ▶); Zitouni et al. (2005 ▶); Prasad et al. (2009 ▶); Wael et al. (2012 ▶); Almasirad et al. (2004 ▶); Amir & Shikha (2004 ▶); Kane et al. (1988 ▶); Akhtar et al. (2010 ▶). For the crystal structures of related N-free triazole derivatives, see for example: Qadeer et al. (2007 ▶); and for N-subsituted derivatives, see for example: Zhao et al. (2010 ▶); Wu et al. (2009 ▶). Working with sulfur-containing heterocycles may provide unexpected results and the title compound was obtained within an unprecedented series of results, see: Ben Othman et al. (2014 ▶). graphic file with name e-70-0o622-scheme1.jpg

Experimental

Crystal data

C₂₀H₁₅N₃OS
M _r = 345.41
Monoclinic,
a = 16.6112 (12) Å
b = 5.8445 (5) Å
c = 17.5415 (10) Å
β = 93.131 (5)°
V = 1700.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 293 K
0.35 × 0.25 × 0.12 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.932, T _max = 0.976
44120 measured reflections
3099 independent reflections
2333 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.152
S = 1.02
3099 reflections
207 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: COLLECT (Bruker–Nonius, 1998) ▶; cell refinement: DIRAX/LSQ (Duisenberg, 1992 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814008204/su2718sup1.cif

e-70-0o622-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008204/su2718Isup2.hkl

e-70-0o622-Isup2.hkl^{(170.2KB, hkl)}

Click here for additional data file.^{(6.4KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814008204/su2718Isup3.cml

CCDC reference: 991904

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯N2ⁱ	0.91 (3)	2.05 (3)	2.944 (3)	170 (2)
C16—H16⋯S1ⁱⁱ	0.93	2.77	3.694 (2)	170

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This result is part of a larger research program that was supported by grants from the Région Centre and the Labex IRON (ANR-11-LABX-0018–01).

supplementary crystallographic information

1. Comment

From a medicinal chemistry point of view, it is of great interest to develop efficient methods for the synthesis and the functionalization of 1,2,4-triazoles, as they are known to possess a wide range of biological activities, such as, as anticancer (Holla et al., 2002, 2003) antitubercular (Walczak et al., 2004), antimicrobial (Zitouni et al., 2005; Prasad et al., 2009; Wael et al., 2012), anticonvulsant (Almasirad et al., 2004), anti-inflammatory, analgesic (Amir & Shikha, 2004), antidepressant (Kane et al., 1988), and urease inhibitors (Akhtar et al., 2010). Thus, the synthesis of 1,2,4-triazoles and the investigation of their chemical and biological behaviour have acquired more importance in recent decades for these reasons.

An efficient and convenient method was developed for the formation of substituted thiotriazoles via an organometallic addition and subsequent ring opening sequence of 3-substituted-[1,2,4]triazolo[3,4-][1,3,4]thiadiazole. This method is applicable to a wide range of substrates containing different functional groups and furnishes excellent yields of the corresponding unsubstituted 3 or 5-alkyl, aryl, alkynyl and alkenyl sulfanyl-1,2,4-triazole products.

Interestingly, working with sulfur-containing heterocycles may provide unexpected results and we report herein on the crystal structure of one derivative obtained within an unprecedented series of results (Ben Othman et al., 2014).

The molecular structure of the title molecule is illustrated in Fig. 1. The molecule is V-shaped about atom S1. In the 4-phenoxyphenyl group the two rings (C9-C14 and C15-C20) are inclined to one another by 74.52 (13) °. These rings are inclined to the triazole ring (N1-N3/C7/C8) by 72.20 (15) and 72.30 (15) °, respectively. The phenyl ring (C1-C6) is inclined to the triazole ring by 10.85 (12) °.

In the crystal, molecules are linked via N-H···N hydrogen bonds forming chains propagating along [010]; see Table 1 and Fig. 2. These chains are linked via pairs of C-H···S hydrogen bonds forming sheets lying parallel to the ac plane (Table 1 and Fig. 2).

2. Experimental

For the synthesis of the title compound, see Fig. 3. In a 25 ml flask, phenyl ZnBr solution in THF (1.5 mmol, 0.5M) was added drop wise under argon at room temperature to a solution of 3-Phenyl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole (0.5 mmol) in THF (5 ml), and the mixture was stirred for 25 min (see Fig 3). At the end of the reaction, the mixture was quenched with 15 mL of an aqueous solution of saturated NH₄Cl, and extracted with CH₂Cl₂ (2 × 20 ml). The extract was dried over magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (eluent 6:4 petroleum ether/AcOEt). The title compound was obtained as a white solid in 80% yield. R_f = 0.60 (petroleum ether/EtOAc, 6:4); M.p. 318-320 K. HRMS (EI—MS): m/z calcd for C₂₀H₁₅N₃OS: 346.10086 [M + H]⁺, found: 346.10112. Crystals of the title compound were obtained by vapor diffusion of petroleum ether into a solution of the title compound in a CH₂Cl₂/Et₂O/pentane mixture. Spectroscopic data for the title compound is available in the archived CIF.