supplementary materials


hg5308 scheme

Acta Cryst. (2013). E69, o697    [ doi:10.1107/S1600536813009501 ]

4-Benzyl-3-(thiophen-2-yl)-4,5-dihydro-1H-1,2,4-triazole-5-thione

M. M. Al-Shehri, A. A. El-Emam, N. R. El-Brollosy, S. W. Ng and E. R. T. Tiekink

Abstract top

In the title compound, C13H11N3S2, the triazole and thiophene rings are coplanar [dihedral angle = 6.22 (13)°]. By contrast, the phenyl ring is perpendicular to the triazole ring [dihedral angle = 85.58 (13)°], so that the molecule has an L-shape. The thiophene S atom is syn with the ring imine N atom. In the crystal, eight-membered {...HNCS}2 synthons form between centrosymmetrically related molecules, leading to dimeric aggregates that are connected into a supramolecular layer parallel to (101) by [pi]-[pi] interactions between centrosymmetrically related triazole rings [centroid-centroid distance = 3.6091 (15) Å] and C-H...[pi] interactions.

Comment top

In continuation of research into the chemical and pharmacological properties of 1,2,4-triazole derivatives (El-Emam & Ibrahim, 1991; Navidpour et al., 2006; Kumar et al., 2010; Wang et al., 2011), we describe herein the X-ray crystal structure determination of the title compound, (I).

In (I), Fig. 1, the triazole ring is plane (r.m.s. deviation = 0.008 Å) and the thione-S2 atom lies 0.030 (1) Å out of the plane. The thiophene ring is co-planar with the triazole ring [dihedral angle = 6.22 (13)°] and the latter forms a dihedral of 85.58 (13)° with the phenyl ring. The thiophene-S1 atom is syn with the ring imine-N2 atom. Overall, the molecule has the shape of the letter L. A similar conformation was found in the analogous furanyl compound for which two molecules comprise the asymmetric unit and which was characterized as an hydrate (Zareef et al., 2008).

In the crystal packing, centrosymmetrically related molecules aggregate into dimers via N—H···S hydrogen bonds that lead to eight-membered {···HNCS}2 synthons, Table 1. The dimers are connected into rows along the b axis by ππ interactions between centrosymmetrically related triazole rings [inter-centroid distance = 3.6091 (15) Å for symmetry operation: 1 - x, 1 - y, 1 - z]. Projecting out on either side of the row are the phenyl groups that inter-digitate with translationally related rows to enable the formation of edge-to-face C—H···π interactions, Table 1, that result in a supramolecular layer parallel to (1 0 1), Fig. 2. Layers stack with no specific interactions between them, Fig. 3.

Related literature top

For the pharmacological properties (anti-inflammatory, anti-microbial and anti-cancer) of 1,2,4-triazole derivatives, see: El-Emam & Ibrahim (1991); Navidpour et al. (2006); Kumar et al. (2010); Wang et al. (2011). For a related structure, see: Zareef et al. (2008).

Experimental top

A mixture of thiophene-2-carbohydrazide (1.42 g, 0.01 mol), benzyl isothiocyanate (1.49 g, 0.01 mol), in ethanol (10 ml) was heated under reflux with stirring for 1 h after which the solvent was distilled off in vacuo. Aqueous sodium hydroxide solution (10%, 15 ml) was added to the residue and the mixture was heated under reflux for 2 h then filtered hot. On cooling, the mixture was acidified with hydrochloric acid and the precipitated crude product was filtered, washed with water, dried and crystallized from aqueous ethanol to yield 2.32 g (85%) of the title compound as colourless crystals. M.pt: 515–517 K. Single crystals suitable for X-ray analysis were obtained by slow evaporation of its CHCl3:EtOH (1:1; 10 ml) solution at room temperature. 1H NMR (DMSO-d6, 500.13 MHz): δ 5.51 (s, 2H, CH2), 7.13–7.14 (m, 3H, Ar—H), 7.27–7.40 (m, 4H, Ar—H & thiophene-H), 7.77 (d, 1H, thiophene-H, J = 4.0 Hz), 14.21 (s, 1H, SH, thiol tautomer). 13C NMR (DMSO-d6, 125.76 MHz): δ 46.74 (CH2), 126.15, 126.33, 127.51, 128.19, 128.72, 128.86, 129.90, 135.40 (Ar—C & thiophene-C), 146.31 (triazole C-3), 168.31 (triazole C-5).

Refinement top

The C-bound H-atoms were placed in calculated positions [C—H = 0.93 to 0.97 Å, Uiso(H) = 1.2Ueq(C)] and were included in the refinement in the riding model approximation. The N-bound H-atom was refined with the distance restraint N—H = 0.88±0.01 Å.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.
[Figure 2] Fig. 2. A view of the supramolecular layer in (I), which is sustained by N—H···S hydrogen bonds as well as by ππ and C—H···π interactions shown as orange, blue and purple dashed lines, respectively.
[Figure 3] Fig. 3. View of the unit-cell contents in projection down the b axis of (I), highlighting the stacking of layers. The N—H···S hydrogen bonds as well as by ππ and C—H···π interactions shown as orange, blue and purple dashed lines, respectively.
4-Benzyl-3-(thiophen-2-yl)-4,5-dihydro-1H-1,2,4-triazole-5-thione top
Crystal data top
C13H11N3S2F(000) = 568
Mr = 273.37Dx = 1.425 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1615 reflections
a = 13.422 (2) Åθ = 3.0–27.5°
b = 6.1670 (7) ŵ = 0.40 mm1
c = 16.596 (2) ÅT = 295 K
β = 111.972 (15)°Prism, colourless
V = 1273.9 (3) Å30.30 × 0.05 × 0.05 mm
Z = 4
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector
2937 independent reflections
Radiation source: SuperNova (Mo) X-ray Source2088 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.036
Detector resolution: 10.4041 pixels mm-1θmax = 27.6°, θmin = 3.3°
ω scanh = 1217
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 85
Tmin = 0.806, Tmax = 1.000l = 2119
6460 measured reflections
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0415P)2 + 0.2539P]
where P = (Fo2 + 2Fc2)/3
2937 reflections(Δ/σ)max < 0.001
167 parametersΔρmax = 0.24 e Å3
1 restraintΔρmin = 0.27 e Å3
Crystal data top
C13H11N3S2V = 1273.9 (3) Å3
Mr = 273.37Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.422 (2) ŵ = 0.40 mm1
b = 6.1670 (7) ÅT = 295 K
c = 16.596 (2) Å0.30 × 0.05 × 0.05 mm
β = 111.972 (15)°
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector
2937 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
2088 reflections with I > 2σ(I)
Tmin = 0.806, Tmax = 1.000Rint = 0.036
6460 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109Δρmax = 0.24 e Å3
S = 1.02Δρmin = 0.27 e Å3
2937 reflectionsAbsolute structure: ?
167 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
S10.21756 (5)0.78528 (13)0.30574 (4)0.0548 (2)
S20.47823 (5)0.12218 (10)0.62298 (3)0.03891 (18)
N10.34574 (15)0.4060 (3)0.39839 (11)0.0395 (5)
N20.40554 (15)0.2515 (3)0.45408 (12)0.0383 (5)
H20.4302 (18)0.138 (3)0.4349 (15)0.052 (8)*
N30.35676 (13)0.4651 (3)0.53331 (10)0.0304 (4)
C10.14130 (18)0.9997 (4)0.31144 (16)0.0475 (6)
H10.10541.09040.26480.057*
C20.1387 (2)1.0233 (4)0.39097 (16)0.0492 (6)
H2A0.10081.13300.40540.059*
C30.19944 (19)0.8647 (4)0.45051 (14)0.0426 (6)
H30.20540.85740.50810.051*
C40.24840 (16)0.7233 (4)0.41373 (13)0.0346 (5)
C50.31583 (17)0.5357 (4)0.44809 (13)0.0323 (5)
C60.41379 (16)0.2783 (3)0.53621 (13)0.0315 (5)
C70.34971 (17)0.5686 (4)0.61041 (13)0.0344 (5)
H7A0.35860.72380.60650.041*
H7B0.40850.51680.66140.041*
C80.24552 (17)0.5271 (4)0.62246 (12)0.0344 (5)
C90.1871 (2)0.3419 (5)0.59316 (17)0.0534 (7)
H90.21100.23910.56350.064*
C100.0931 (2)0.3049 (5)0.6069 (2)0.0708 (9)
H100.05400.17870.58630.085*
C110.0579 (2)0.4550 (6)0.65120 (19)0.0665 (8)
H110.00560.43160.66020.080*
C120.1160 (2)0.6383 (5)0.68195 (17)0.0595 (8)
H120.09280.73870.71290.071*
C130.2092 (2)0.6763 (4)0.66753 (15)0.0474 (6)
H130.24790.80290.68820.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0569 (4)0.0694 (5)0.0403 (3)0.0206 (4)0.0206 (3)0.0166 (3)
S20.0448 (3)0.0349 (3)0.0365 (3)0.0064 (3)0.0146 (2)0.0030 (3)
N10.0467 (11)0.0384 (11)0.0365 (10)0.0075 (9)0.0190 (8)0.0045 (9)
N20.0453 (11)0.0369 (11)0.0369 (10)0.0088 (9)0.0204 (9)0.0021 (9)
N30.0335 (9)0.0279 (9)0.0318 (9)0.0017 (8)0.0145 (7)0.0002 (8)
C10.0385 (13)0.0476 (15)0.0501 (14)0.0047 (12)0.0095 (10)0.0177 (12)
C20.0478 (14)0.0404 (14)0.0561 (15)0.0098 (12)0.0155 (12)0.0040 (12)
C30.0500 (14)0.0378 (13)0.0386 (12)0.0104 (12)0.0148 (10)0.0046 (11)
C40.0328 (11)0.0346 (12)0.0355 (11)0.0007 (10)0.0117 (9)0.0036 (10)
C50.0345 (11)0.0308 (11)0.0313 (10)0.0024 (10)0.0120 (9)0.0009 (10)
C60.0309 (11)0.0301 (11)0.0355 (11)0.0029 (9)0.0148 (9)0.0015 (9)
C70.0371 (12)0.0337 (12)0.0314 (10)0.0001 (10)0.0116 (9)0.0031 (9)
C80.0371 (12)0.0363 (12)0.0307 (10)0.0035 (10)0.0137 (9)0.0008 (10)
C90.0547 (16)0.0503 (16)0.0651 (16)0.0097 (13)0.0339 (13)0.0164 (13)
C100.0595 (18)0.073 (2)0.092 (2)0.0239 (17)0.0418 (17)0.0182 (19)
C110.0493 (16)0.089 (2)0.0722 (18)0.0006 (17)0.0350 (14)0.0030 (18)
C120.0588 (17)0.073 (2)0.0550 (15)0.0159 (16)0.0313 (13)0.0069 (15)
C130.0531 (15)0.0455 (15)0.0458 (13)0.0023 (12)0.0211 (11)0.0120 (12)
Geometric parameters (Å, º) top
S1—C11.696 (3)C4—C51.448 (3)
S1—C41.725 (2)C7—C81.507 (3)
S2—C61.678 (2)C7—H7A0.9700
N1—C51.315 (3)C7—H7B0.9700
N1—N21.361 (3)C8—C91.368 (3)
N2—C61.336 (3)C8—C131.384 (3)
N2—H20.881 (10)C9—C101.382 (4)
N3—C61.374 (3)C9—H90.9300
N3—C51.382 (2)C10—C111.372 (4)
N3—C71.464 (2)C10—H100.9300
C1—C21.341 (3)C11—C121.359 (4)
C1—H10.9300C11—H110.9300
C2—C31.412 (3)C12—C131.379 (4)
C2—H2A0.9300C12—H120.9300
C3—C41.366 (3)C13—H130.9300
C3—H30.9300
C1—S1—C491.71 (11)N3—C6—S2127.78 (15)
C5—N1—N2103.94 (17)N3—C7—C8114.11 (17)
C6—N2—N1114.13 (18)N3—C7—H7A108.7
C6—N2—H2124.6 (16)C8—C7—H7A108.7
N1—N2—H2121.0 (16)N3—C7—H7B108.7
C6—N3—C5107.63 (16)C8—C7—H7B108.7
C6—N3—C7123.51 (17)H7A—C7—H7B107.6
C5—N3—C7128.77 (18)C9—C8—C13118.4 (2)
C2—C1—S1112.20 (18)C9—C8—C7122.1 (2)
C2—C1—H1123.9C13—C8—C7119.4 (2)
S1—C1—H1123.9C8—C9—C10121.1 (3)
C1—C2—C3113.1 (2)C8—C9—H9119.5
C1—C2—H2A123.4C10—C9—H9119.5
C3—C2—H2A123.4C11—C10—C9119.7 (3)
C4—C3—C2112.2 (2)C11—C10—H10120.1
C4—C3—H3123.9C9—C10—H10120.1
C2—C3—H3123.9C12—C11—C10119.9 (3)
C3—C4—C5131.97 (19)C12—C11—H11120.1
C3—C4—S1110.76 (16)C10—C11—H11120.1
C5—C4—S1117.24 (16)C11—C12—C13120.4 (3)
N1—C5—N3110.66 (19)C11—C12—H12119.8
N1—C5—C4122.11 (18)C13—C12—H12119.8
N3—C5—C4127.23 (19)C12—C13—C8120.4 (3)
N2—C6—N3103.62 (17)C12—C13—H13119.8
N2—C6—S2128.59 (17)C8—C13—H13119.8
C5—N1—N2—C60.3 (3)N1—N2—C6—N31.0 (2)
C4—S1—C1—C20.2 (2)N1—N2—C6—S2178.98 (16)
S1—C1—C2—C30.2 (3)C5—N3—C6—N21.3 (2)
C1—C2—C3—C40.7 (3)C7—N3—C6—N2175.41 (18)
C2—C3—C4—C5178.7 (2)C5—N3—C6—S2178.73 (16)
C2—C3—C4—S10.8 (3)C7—N3—C6—S24.6 (3)
C1—S1—C4—C30.61 (19)C6—N3—C7—C8102.1 (2)
C1—S1—C4—C5178.87 (18)C5—N3—C7—C881.9 (3)
N2—N1—C5—N30.5 (2)N3—C7—C8—C929.0 (3)
N2—N1—C5—C4179.08 (19)N3—C7—C8—C13153.6 (2)
C6—N3—C5—N11.2 (2)C13—C8—C9—C100.9 (4)
C7—N3—C5—N1175.28 (19)C7—C8—C9—C10178.3 (2)
C6—N3—C5—C4178.4 (2)C8—C9—C10—C110.5 (5)
C7—N3—C5—C45.1 (3)C9—C10—C11—C120.6 (5)
C3—C4—C5—N1172.4 (2)C10—C11—C12—C131.2 (5)
S1—C4—C5—N15.4 (3)C11—C12—C13—C80.8 (4)
C3—C4—C5—N37.2 (4)C9—C8—C13—C120.3 (3)
S1—C4—C5—N3175.03 (17)C7—C8—C13—C12177.8 (2)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C8–C13 ring.
D—H···AD—HH···AD···AD—H···A
N2—H2···S2i0.88 (1)2.43 (1)3.297 (2)169 (2)
C13—H13···Cg1ii0.932.943.636 (3)133
Symmetry codes: (i) x+1, y, z+1; (ii) x+1/2, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C8–C13 ring.
D—H···AD—HH···AD···AD—H···A
N2—H2···S2i0.881 (10)2.429 (11)3.297 (2)169 (2)
C13—H13···Cg1ii0.932.943.636 (3)133
Symmetry codes: (i) x+1, y, z+1; (ii) x+1/2, y+1/2, z+3/2.
Acknowledgements top

The financial support of the Deanship of Scientific Research and the Research Center for Female Scientific and Medical Colleges, King Saud University, is greatly appreciated. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/03).

references
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