4-Benzyl-3-(2-fur­yl)-1H-1,2,4-triazole-5(4H)-thione hemihydrate

Muhammad Zareef; Rashid Iqbal; Masood Parvez

doi:10.1107/S1600536808012361

. 2008 May 3;64(Pt 6):o952–o953. doi: 10.1107/S1600536808012361

4-Benzyl-3-(2-furyl)-1H-1,2,4-triazole-5(4H)-thione hemihydrate

Muhammad Zareef ^a,^*, Rashid Iqbal ^a, Masood Parvez ^b

PMCID: PMC2961370 PMID: 21202686

Abstract

In the asymmetric unit of the title compound, C₁₃H₁₁N₃OS·0.5H₂O, there are two independent molecules of 4-benzyl-3-(2-furyl)-1H-1,2,4-triazole-5(4H)-thione and a water molecule of hydration. The conformation of the two organic molecules is slightly different, the dihedral angles formed by the furyl and triazole rings being 5.63 (15) and 17.66 (13)°. The water molecule of hydration links three adjacent triazole molecules to form a cluster via intermolecular O—H⋯S, N—H⋯S and N—H⋯O hydrogen bonds, generating a 10-membered ring of graph set R ³ ₃(10). The crystal structure is further stabilized by intra- and intermolecular C—H⋯S, C—H⋯O and C—H⋯N hydrogen bonds and by π–π stacking interactions involving the furyl and triazole rings of centrosymmetrically related molecules, with a centroid–centroid separation of 3.470 (2) Å.

Related literature

For related literature, see: Ahmad et al. (2001 ▶); Altman & Solomost (1993 ▶); Chai et al. (2003 ▶); Dege et al. (2004 ▶); Hashimoto et al. (1990 ▶); Kanazawa et al. (1988 ▶); Öztürk et al. (2004 ▶); Yıldırım et al. (2004 ▶); Bernstein et al. (1995 ▶); Etter (1990 ▶).

Experimental

Crystal data

C₁₃H₁₁N₃OS·0.5H₂O
M _r = 266.33
Triclinic,
a = 6.082 (2) Å
b = 12.069 (4) Å
c = 17.818 (5) Å
α = 92.43 (2)°
β = 94.35 (2)°
γ = 103.83 (2)°
V = 1263.9 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 173 (2) K
0.18 × 0.16 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T _min = 0.956, T _max = 0.990
10729 measured reflections
5735 independent reflections
4365 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.096
S = 1.03
5735 reflections
347 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012361/rz2207sup1.cif

e-64-0o952-sup1.cif^{(24.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012361/rz2207Isup2.hkl

e-64-0o952-Isup2.hkl^{(275.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯N5ⁱ	0.85 (2)	2.08 (2)	2.906 (2)	165 (2)
N1—H1A⋯S2ⁱⁱ	0.88 (2)	2.47 (2)	3.267 (2)	151 (2)
N4—H4A⋯O3ⁱⁱⁱ	0.89 (2)	1.81 (2)	2.697 (2)	174 (2)
C7—H7A⋯N2^iv	0.99	2.60	3.304 (3)	128
C7—H7B⋯O1^iv	0.99	2.59	3.440 (2)	144
O3—H3B⋯S1	0.85 (2)	2.50 (2)	3.320 (2)	162 (2)
C7—H7A⋯S1	0.99	2.74	3.237 (2)	112
C9—H9⋯N3	0.95	2.56	2.893 (2)	101
C26—H26⋯N6	0.95	2.58	2.903 (3)	100
C20—H20B⋯S2	0.99	2.78	3.214 (2)	107

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

supplementary crystallographic information

Comment

Recently, much attention has been focused on disubstituted 1,2,4-triazole derivatives for their broad-spectrum biological and pharmacological activities, such as fungicidal, herbicidal, anticonvulsant, antitumoral and inhibition of cholesterol (Chai et al., 2003; Kanazawa et al., 1988; Hashimoto et al., 1990). In addition, they have many applications in agriculture domain (Altman & Solomost, 1993). In this paper, we report the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound is composed of two independent molecules (hereafter called A and B) depicted in Fig. 1 and 2, respectively, and a water molecule of hydration. The furyl and triazole rings in molecule A are substantially planar (maximum deviation 0.0586 (13) Å for atom N2), with the S1 atom 0.1980 (16) Å out of this plane; the mean-planes of the furyl and triazole form a dihedral angle of 5.63 (15)°. The corresponding furyl and triazole rings in molecule B are far from planar with atoms O2 and C17 deviating from the plane by 0.2571 (11) and -0.1633 (15) Å, respectively. The mean-planes of the five-membered rings in molecule B form an angle 17.66 (13)°. In both molecules, the benzyl rings are oriented at 80.72 (4) and 80.70 (4)°, from the planes formed by the ten atoms of the furyl and triazole rings in the molecules A and B, respectively. Bond distances and angles in the two molecules agree well with each other. Similar bond distances and bond angles have been reported in compounds closely related to the title compound, e.g., 4-chlorophenyl analogue (Öztürk et al., 2004), 4-methoxyphenyl analogue (Yıldırım et al., 2004) and 4-p-tolyl (Dege et al., 2004); in all these compounds, the mean-planes of the phenyl rings and those of the furyl and triazole rings lie close to right angles. The water molecule of hydration links three adjacent molecules of the title compound to form a cluster via intermolecular hydrogen bonds (Fig. 3, Table 1), forming a 10-membered ring of graph set R³₃(10) (Etter, 1990; Bernstein et al., 1995). Nonconventional intermolecular C—H···N and C—H···O H-bonds are also present in addition to intramolecular C—H···S and C—H···N hydrogen interactions (Table 1). The crystal structure is further stabilized by π-π stacking interactions involving centrosymmetrically related furyl and triazole rings at (x, y, z) and (1-x, -y, -z) with a centroid-centroid separation of 3.470 (2) Å.

Experimental

The title compound was prepared from the corresponding thiosemicarbazide by following the reported procedure (Ahmad et al., 2001). 4-Benzyl-1-(2-furoyl)thiosemicarbazide (10 mmol) was dissolved in an aqueous 4 N sodium hydroxide solution (50 ml). The solution was heated to reflux for 7 h, cooled and filtered. The filtrate was acidified to pH of 4–5, with 4 N hydrochloric acid. The solid crude product was filtered off, washed with water and recrystallized from aqueous ethanol (60%). Crystals of the title compound were grown by slow evaporation of an ethanol solution over 11 days at room temperature (yield 81%).