Crystal structure of 4-{[(1H-1,2,4-triazol-1-yl)meth­yl]sulfan­yl}phenol

Yong-Le Zhang; Chuang Zhang; Wei Guo; Jing Wang

doi:10.1107/S1600536814019965

. 2014 Sep 13;70(Pt 10):o1106. doi: 10.1107/S1600536814019965

Crystal structure of 4-{[(1H-1,2,4-triazol-1-yl)methyl]sulfanyl}phenol

Yong-Le Zhang ^a, Chuang Zhang ^a, Wei Guo ^a, Jing Wang ^a,^*

PMCID: PMC4257201 PMID: 25484697

Abstract

In the title compound, C₉H₉N₃OS, the plane of the benzene ring forms a dihedral angle of 33.40 (5)° with that of the triazole group. In the crystal, molecules are linked by O—H⋯N hydrogen bonds involving the phenol –OH group and one of the unsubstituted N atoms of the triazole ring, resulting in chains along [010]. These chains are further extended into a layer parallel to (001) by weak C—H⋯N hydrogen-bond interactions. Aromatic π–π stacking [centroid–centroid separation = 3.556 (1) Å] between the triazole rings links the layers into a three-dimensional network.

Keywords: crystal structure; 1,2,4-triazole derivative; hydrogen bonding; π–π stacking; biological activity

Related literature

For the biological activity of related compounds, see: Sidwell et al. (1972 ▶); Khan et al. (2010 ▶); Xu et al. (2011 ▶); Jubie et al. (2011 ▶); Patel et al. (2013 ▶); Salgın-Gökşen et al. (2007 ▶); Lin et al. (2005 ▶); Coucouvanis (2007 ▶). graphic file with name e-70-o1106-scheme1.jpg

Experimental

Crystal data

C₉H₉N₃OS
M _r = 207.25
Monoclinic,
a = 5.3975 (10) Å
b = 10.0099 (19) Å
c = 18.311 (3) Å
β = 91.010 (3)°
V = 989.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 296 K
0.28 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.922, T _max = 0.943
4977 measured reflections
1755 independent reflections
1453 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.077
S = 1.05
1755 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: APEX2; 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814019965/ds2243sup1.cif

e-70-o1106-sup1.cif^{(15.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019965/ds2243Isup2.hkl

e-70-o1106-Isup2.hkl^{(86.5KB, hkl)}

Click here for additional data file.^{(3.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814019965/ds2243Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S1600536814019965/ds2243fig1.tif

The molecular structure of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 40% probability level.

Click here for additional data file.^{(1.7MB, tif)}

. DOI: 10.1107/S1600536814019965/ds2243fig2.tif

A view of the hydrogen bonded polymeric layer. The hydrogen bonds are shown as dashed lines.

CCDC reference: 1022888

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
O1—H1⋯N3ⁱ	0.82	1.91	2.7290 (19)	173
C2—H2⋯N2ⁱⁱ	0.93	2.55	3.318 (2)	140

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

Acknowledgments

The authors graterfully acknowledge financial support for this work from the Fund of research and development in Science and Technology of Hebei Province of China (grant No. 12276402D), and the National Natural Science Funds of China (NSFC grant No. 81202504).

supplementary crystallographic information

S1. Comment

1,2,4-triazole derivatives and sulfur-containing compounds have attracted much attention recently, owing to their fascinating and effective biological activities, for instance, antiviral, antimicrobial, anticancer, analgesic, antioxidant as well as antiinflammatory properties(Sidwell et al.,1972; Khan et al., 2010; Xu et al., 2011; Jubie et al., 2011; Patel et al., 2013; Salgın-Gökşen et al., 2007; Lin et al., 2005). As a result, much effort has been devoted to improve the activity of these compounds by modulating or introducing the substituents on the 1,2,4-triazole species. Among these, the thioether substituted 1,2,4-triazol ring systems represent an attractive group of substance that are promising for particular applications, such as bioinspired materials and biocatalysts (Coucouvanis, 2007). In this work, the title compound has been prepared and its crystal structure has been determined.

The crystal structure is illustrated in Fig. 1. Single crystal X-ray analysis reveals this compound crystallizes in monoclinic system with space group P2₁/n. The bond lengths of C1—N2 [1.308 (2) Å] and C2—N3 [1.317 (2) Å] confirm they are double bonds. The dihedral angle formed by the benzene ring system and triazole plane is 33.396 (53)°, and the torsion angle of C4—S1—C3—N1 is 55.531 (131) Å.

Further analysis of crystal packing shows that these molecules are head-to-tail linked by O—H···N hydrogen bonds (Fig. 2, red dashed lines) between the phenolic hydroxyl groups and the triazole rings, forming a zigzag chain along the [010] axis. These one dimensional motifs are further extended to a two dimensional layer via weak C—H···N interactions (Fig. 2, black dashed lines). The layers arrange in an ABAB fashion along [001] direction and eventually constructed a three dimensional supramolecular framework by virtue of π···π forces between the parallel triazole rings of neighbering molecules, with the centroid-to-centroid distance of 3.556 Å.

S2. Experimental

1-chloromethyl-1,2,4-triazole hydrochloride (28 g, 0.18 mol), 4-mercaptophenol (22.7 g, 0.18 mol) and NaOH (24 g, 0.6 mol) were dissolved in 100 ml ethanol/water (v/v = 1/4) solution. The mixture was stirred at room temperature for 2 h, and further refluxed for 2 h longer. After the reaction was cooled to room temperature, 150 ml water was added to dissolve the generated precipitate. The mixture was acidified to pH 4 by dropwise addition of concd. hydrochloric acid. The resulting voluminous white precipitate was filtered off, washed throughly with water and dried in air. The colorless strip crystals of the title compound were obtained by recrystallizing the powder samples from ethanol solution (yield 77%, m.p. 480-482 K).

S3. Refinement

H atoms bonded to C were positioned with idealized geometry using a riding model with the aromatic C—H = 0.93 Å and methylene C—H = 0.97 Å, respectively. The H atom attached to O atom was found in difference electron-density maps and fixed O—H = 0.82 Å bond length. All H atoms were refined with isotropic displacement parameters set at U_iso(H) = 1.2 U_eq(C) and U_iso(H) =1.5 U_eq(O) of the parent atom.