organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

aSchool of Pharmaceutial Science, Hebei Medical University, Shijiazhuang 050017, People's Republic of China
*Correspondence e-mail: jingwang@home.ipe.ac.cn

Edited by P. Dastidar, Indian Association for the Cultivation of Science, India (Received 1 August 2014; accepted 4 September 2014; online 13 September 2014)

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 ππ stacking [centroid–centroid separation = 3.556 (1) Å] between the triazole rings links the layers into a three-dimensional network.

1. Related literature

For the biological activity of related compounds, see: Sidwell et al. (1972[Sidwell, R. W., Huffman, J. H., GP Khare, L., Allen, B., JT Witkowski, R. & Robins, K. (1972). Science, 177, 705-706.]); Khan et al. (2010[Khan, I., Ali, S., Hameed, S., Rama, N. H., Hussain, M. T., Wadood, A. & Choudhary, M. I. (2010). Eur. J. Med. Chem. 45, 5200-5207.]); Xu et al. (2011[Xu, J., Cao, Y., Zhang, J., Yu, S., Zou, Y., Chai, X. & Sun, Q. (2011). Eur. J. Med. Chem. 46, 3142-3148.]); Jubie et al. (2011[Jubie, S., Sikdar, P., Antony, S., Kalirajan, R., Gowramma, B., Gomathy, S. & Elango, K. (2011). Pak. J. Pharm. Sci. 24, 109-112.]); Patel et al. (2013[Patel, N. B., Khan, I. H., Pannecouque, C. & De Clercq, E. (2013). Med. Chem. Res. 22, 1320-1329.]); Salgın-Gökşen et al. (2007[Salgın-Gökşen, U., Gökhan-Kelekçi, N., Göktaş, Ö., Köysal, Y., Kılıç, E., Işık, Ş. & Özalp, M. (2007). Bioorg. Med. Chem. 15, 5738-5751.]); Lin et al. (2005[Lin, R., Connolly, P. J., Huang, S., Wetter, S. K., Lu, Y., Murray, W. V. & Jolliffe, L. K. (2005). J. Med. Chem. 48, 4208-4211.]); Coucouvanis (2007[Coucouvanis, D. (2007). J. Biol. Inorg. Chem. 12, S157-S177.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C9H9N3OS

  • Mr = 207.25

  • Monoclinic, P 21 /n

  • 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

2.2. Data collection

  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.922, Tmax = 0.943

  • 4977 measured reflections

  • 1755 independent reflections

  • 1453 reflections with I > 2σ(I)

  • Rint = 0.020

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.032

  • wR(F2) = 0.077

  • S = 1.05

  • 1755 reflections

  • 128 parameters

  • H-atom parameters constrained

  • Δρmax = 0.14 e Å−3

  • Δρmin = −0.17 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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
Symmetry codes: (i) [-x+{\script{5\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2003[Bruker (2003). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2001[Bruker (2001). SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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.

Experimental top

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).

Refinement top

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 Uiso(H) = 1.2 Ueq(C) and Uiso(H) =1.5 Ueq(O) of the parent atom.

Related literature top

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).

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 (Bruker, 2003); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. A view of the hydrogen bonded polymeric layer. The hydrogen bonds are shown as dashed lines.
4-{[(1H-1,2,4-Triazol-1-yl)methyl]sulfanyl}phenol top
Crystal data top
C9H9N3OSF(000) = 432
Mr = 207.25Dx = 1.392 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1691 reflections
a = 5.3975 (10) Åθ = 2.3–23.8°
b = 10.0099 (19) ŵ = 0.30 mm1
c = 18.311 (3) ÅT = 296 K
β = 91.010 (3)°Strip, colorless
V = 989.2 (3) Å30.28 × 0.22 × 0.20 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1755 independent reflections
Radiation source: fine-focus sealed tube1453 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
phi and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 66
Tmin = 0.922, Tmax = 0.943k = 1111
4977 measured reflectionsl = 1821
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0294P)2 + 0.2664P]
where P = (Fo2 + 2Fc2)/3
1755 reflections(Δ/σ)max < 0.001
128 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C9H9N3OSV = 989.2 (3) Å3
Mr = 207.25Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.3975 (10) ŵ = 0.30 mm1
b = 10.0099 (19) ÅT = 296 K
c = 18.311 (3) Å0.28 × 0.22 × 0.20 mm
β = 91.010 (3)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1755 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1453 reflections with I > 2σ(I)
Tmin = 0.922, Tmax = 0.943Rint = 0.020
4977 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.077H-atom parameters constrained
S = 1.05Δρmax = 0.14 e Å3
1755 reflectionsΔρmin = 0.17 e Å3
128 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.66005 (10)0.44273 (5)0.08502 (3)0.05715 (18)
O11.2294 (3)0.31388 (12)0.35509 (7)0.0530 (4)
H11.32330.37470.36710.080*
N10.8498 (2)0.20284 (13)0.04543 (7)0.0369 (3)
N20.6462 (2)0.12317 (15)0.04545 (8)0.0450 (4)
N30.9755 (3)0.01570 (15)0.09366 (8)0.0475 (4)
C10.7326 (3)0.01291 (19)0.07461 (9)0.0461 (4)
H1A0.63390.06200.08170.055*
C21.0418 (3)0.13729 (18)0.07465 (9)0.0440 (4)
H21.20040.17240.08080.053*
C30.8344 (3)0.34022 (18)0.02238 (10)0.0483 (5)
H3A0.75610.34420.02570.058*
H3B1.00060.37620.01850.058*
C40.8297 (3)0.40921 (17)0.16692 (9)0.0436 (4)
C50.7646 (3)0.30194 (19)0.21040 (10)0.0487 (5)
H50.62810.24990.19740.058*
C60.9001 (4)0.27158 (18)0.27266 (10)0.0487 (5)
H60.85490.19900.30120.058*
C71.1036 (3)0.34846 (16)0.29307 (9)0.0403 (4)
C81.1682 (3)0.45690 (18)0.25025 (10)0.0458 (4)
H81.30350.50960.26360.055*
C91.0315 (4)0.48657 (18)0.18780 (10)0.0477 (5)
H91.07570.55950.15940.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0629 (3)0.0550 (3)0.0531 (3)0.0208 (2)0.0116 (2)0.0047 (2)
O10.0666 (9)0.0444 (7)0.0476 (7)0.0068 (6)0.0120 (6)0.0013 (6)
N10.0317 (7)0.0419 (8)0.0370 (8)0.0003 (6)0.0013 (6)0.0019 (6)
N20.0338 (8)0.0530 (9)0.0481 (9)0.0058 (7)0.0062 (6)0.0003 (7)
N30.0478 (9)0.0500 (9)0.0443 (9)0.0054 (7)0.0067 (7)0.0001 (7)
C10.0470 (11)0.0484 (11)0.0427 (10)0.0062 (8)0.0011 (8)0.0010 (8)
C20.0309 (9)0.0542 (12)0.0466 (10)0.0011 (8)0.0041 (7)0.0057 (9)
C30.0553 (11)0.0473 (11)0.0424 (10)0.0003 (9)0.0001 (8)0.0043 (8)
C40.0471 (10)0.0402 (10)0.0434 (10)0.0082 (8)0.0015 (8)0.0072 (8)
C50.0476 (10)0.0489 (11)0.0496 (11)0.0088 (8)0.0010 (8)0.0080 (9)
C60.0609 (12)0.0402 (10)0.0449 (10)0.0115 (9)0.0023 (9)0.0005 (8)
C70.0473 (10)0.0369 (9)0.0366 (9)0.0017 (8)0.0012 (7)0.0057 (7)
C80.0463 (10)0.0414 (10)0.0495 (11)0.0077 (8)0.0002 (8)0.0027 (8)
C90.0583 (11)0.0376 (10)0.0473 (11)0.0001 (8)0.0044 (9)0.0021 (8)
Geometric parameters (Å, º) top
S1—C41.7753 (18)C3—H3A0.9700
S1—C31.8146 (18)C3—H3B0.9700
O1—C71.358 (2)C4—C91.385 (3)
O1—H10.8200C4—C51.386 (3)
N1—C21.331 (2)C5—C61.378 (3)
N1—N21.3578 (18)C5—H50.9300
N1—C31.440 (2)C6—C71.387 (2)
N2—C11.308 (2)C6—H60.9300
N3—C21.317 (2)C7—C81.387 (2)
N3—C11.351 (2)C8—C91.382 (2)
C1—H1A0.9300C8—H80.9300
C2—H20.9300C9—H90.9300
C4—S1—C399.29 (8)C9—C4—C5118.74 (17)
C7—O1—H1109.5C9—C4—S1121.27 (14)
C2—N1—N2109.56 (14)C5—C4—S1119.97 (14)
C2—N1—C3128.98 (15)C6—C5—C4120.68 (17)
N2—N1—C3121.22 (14)C6—C5—H5119.7
C1—N2—N1102.31 (13)C4—C5—H5119.7
C2—N3—C1102.59 (15)C5—C6—C7120.46 (17)
N2—C1—N3115.15 (16)C5—C6—H6119.8
N2—C1—H1A122.4C7—C6—H6119.8
N3—C1—H1A122.4O1—C7—C6117.77 (15)
N3—C2—N1110.40 (15)O1—C7—C8123.04 (15)
N3—C2—H2124.8C6—C7—C8119.19 (16)
N1—C2—H2124.8C9—C8—C7120.00 (17)
N1—C3—S1112.49 (12)C9—C8—H8120.0
N1—C3—H3A109.1C7—C8—H8120.0
S1—C3—H3A109.1C8—C9—C4120.93 (17)
N1—C3—H3B109.1C8—C9—H9119.5
S1—C3—H3B109.1C4—C9—H9119.5
H3A—C3—H3B107.8
C2—N1—N2—C10.58 (18)C3—S1—C4—C588.92 (16)
C3—N1—N2—C1175.34 (14)C9—C4—C5—C60.9 (3)
N1—N2—C1—N30.3 (2)S1—C4—C5—C6177.54 (14)
C2—N3—C1—N20.1 (2)C4—C5—C6—C70.3 (3)
C1—N3—C2—N10.45 (19)C5—C6—C7—O1179.81 (16)
N2—N1—C2—N30.68 (19)C5—C6—C7—C80.4 (3)
C3—N1—C2—N3174.91 (15)O1—C7—C8—C9179.87 (16)
C2—N1—C3—S1105.58 (18)C6—C7—C8—C90.5 (3)
N2—N1—C3—S168.07 (18)C7—C8—C9—C40.1 (3)
C4—S1—C3—N155.54 (14)C5—C4—C9—C80.8 (3)
C3—S1—C4—C989.51 (16)S1—C4—C9—C8177.62 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N3i0.821.912.7290 (19)173
C2—H2···N2ii0.932.553.318 (2)140
Symmetry codes: (i) x+5/2, y+1/2, z+1/2; (ii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N3i0.821.912.7290 (19)173.2
C2—H2···N2ii0.932.553.318 (2)140.1
Symmetry codes: (i) x+5/2, y+1/2, z+1/2; (ii) x+1, y, z.
 

Acknowledgements

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).

References

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