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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o618.
Published online 2009 February 28. doi:  10.1107/S1600536809006394
PMCID: PMC2968424

3-[1-(4-Isobutyl­phen­yl)eth­yl]-1H-1,2,4-triazole-5(4H)-thione

Abstract

In the title compound, C14H19N3S, the dihedral angle between the mean planes of the five- and six-membered rings is 74.69 (4)°. Pairs of inter­molecular N—H(...)S inter­actions link neighbouring mol­ecules into dimers with R 2 2(8) ring motifs. These dimers are then linked together by the same type of inter­actions into an infinite one-dimensional chain along the b axis.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]). For the biomedical applications compounds containing 1,2,4-triazole rings, see, for example: Shujuan et al. (2004 [triangle]); Clemons et al. (2004 [triangle]); Johnston et al. (2002 [triangle]); Wei et al. (2007 [triangle]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o618-scheme1.jpg

Experimental

Crystal data

  • C14H19N3S
  • M r = 261.38
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o618-efi1.jpg
  • a = 12.0905 (2) Å
  • b = 8.4408 (1) Å
  • c = 14.3189 (2) Å
  • β = 98.365 (1)°
  • V = 1445.75 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.21 mm−1
  • T = 100 K
  • 0.51 × 0.36 × 0.20 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.900, T max = 0.959
  • 27376 measured reflections
  • 6797 independent reflections
  • 5688 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.108
  • S = 1.03
  • 6797 reflections
  • 174 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.68 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006394/cs2108sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006394/cs2108Isup2.hkl

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

Acknowledgments

HKF, RK and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK and SRJ thank Universiti Sains Malaysia for post-doctoral research fellowships. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

The 1,2,4-triazole nucleus has been incorporated into a wide variety of therapeutically interesting compounds. Several compounds containing 1,2,4-triazole rings are well known as drugs. For example, fluconazole is used as an antimicrobial drug (Shujuan et al., 2004), while vorozole, letrozole and anastrozole are non-steroidal drugs used for the threatment of cancer (Clemons et al., 2004) and loreclezole is used as an anticonvulsant (Johnston et al., 2002). Similarly substituted derivatives of triazole possess comprehensive bioactivities such as antimicrobial, anti-inflammatory, analgesic, antihypertensive, anticonvulsant and antiviral activities (Wei et al., 2007). Due to the progress that occurs in dealing with the chemistry of 1,2,4-triazoles as well as their biological activity, we synthesized and reported the crystal structure of the title compound.

The title compound, Fig. 1, comprises a single molcule in the asymmetric unit. The dihedral angle between the mean planes of the five- and six-membered rings is 74.69 (4)°. Pairs of intermolecular N—H···S interactions link neighbouring molecules into dimers with R22(8) ring motifs (Bernstein et al., 1995). These dimers are linked together into an infinite 1-D chains along the b axis.

Experimental

A mixture of 2-[2-(4-isobutylphenyl)propanoyl]hydrazinecarbothioamide (0.01 mole) and 10% KOH (10 ml) was refluxed for 3 h. After the mixture was cooled to room temperature, it was then neutralized by the gradual addition of glacial acetic acid. The solid product obtained was collected by filtration, washed with ethanol and dried. It was then recrystallized using ethanol. Crystals suitable for X-ray analysis were obtained from ethanol solution by slow evaporation (Yield 71%; m.p. 473–474 K).

Refinement

Hydrogen atoms bound to N1 and N2 were located from the difference Fourier map and refined freely; see Table. 1. The rest of the H atoms were positioned geometrically and refined with a riding model approximation with C—H = 0.95–1.00 Å and Uiso(H) = 1.2 & 1.5 Ueq(C). A rotating group model were used for the methyl groups. The highest peak (0.71 e. Å-3) is located 0.71 Å from C4 and the deepest hole (-0.29 e. Å-3) is located 1.07 Å from N2.

Figures

Fig. 1.
The molecular structure of (I) with atom labels and 50% probability ellipsoids for non-H atoms.
Fig. 2.
A crystal packing detail of (I), viewed down the (001) direction, showing 1-D infinite chains along (0 1 0) direction connected through intermolecular N—H···S contacts with R22(8) motifs, indicated in dashed lines.

Crystal data

C14H19N3SF(000) = 560
Mr = 261.38Dx = 1.201 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9932 reflections
a = 12.0905 (2) Åθ = 2.8–38.1°
b = 8.4408 (1) ŵ = 0.21 mm1
c = 14.3189 (2) ÅT = 100 K
β = 98.365 (1)°Block, colourless
V = 1445.75 (4) Å30.51 × 0.36 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer6797 independent reflections
Radiation source: fine-focus sealed tube5688 reflections with I > 2σ(I)
graphiteRint = 0.027
[var phi] and ω scansθmax = 36.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −19→19
Tmin = 0.900, Tmax = 0.959k = −13→13
27376 measured reflectionsl = −23→23

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.059P)2 + 0.2413P] where P = (Fo2 + 2Fc2)/3
6797 reflections(Δ/σ)max = 0.001
174 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = −0.29 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S11.028285 (17)0.45561 (2)0.304961 (13)0.02021 (6)
N10.93584 (6)0.32637 (7)0.13580 (4)0.01752 (11)
N20.93093 (6)0.57817 (8)0.13587 (5)0.01827 (11)
N30.88205 (6)0.53370 (7)0.04670 (5)0.01893 (12)
C10.96400 (6)0.45407 (8)0.19170 (5)0.01660 (12)
C20.88639 (6)0.37897 (8)0.04886 (5)0.01656 (12)
C30.84388 (6)0.26915 (9)−0.03029 (5)0.01834 (13)
H3A0.91010.2190−0.05290.022*
C40.77413 (6)0.13752 (9)0.00436 (5)0.01678 (12)
C50.69207 (7)0.17148 (9)0.06075 (5)0.02042 (13)
H5A0.68180.27750.08000.025*
C60.62523 (7)0.05153 (9)0.08897 (6)0.02088 (14)
H6A0.57010.07690.12760.025*
C70.63774 (6)−0.10552 (9)0.06156 (5)0.01780 (12)
C80.72006 (7)−0.13874 (9)0.00540 (5)0.01903 (13)
H8A0.7302−0.2447−0.01410.023*
C90.78770 (7)−0.01891 (9)−0.02255 (5)0.01853 (13)
H9A0.8436−0.0444−0.06030.022*
C100.56594 (7)−0.23645 (10)0.09233 (6)0.02152 (14)
H10A0.5276−0.29100.03550.026*
H10B0.5077−0.18870.12550.026*
C110.63088 (7)−0.35955 (10)0.15737 (6)0.02271 (14)
H11A0.6886−0.40800.12280.027*
C120.55200 (9)−0.49136 (12)0.18006 (8)0.0324 (2)
H12A0.5165−0.54050.12120.049*
H12B0.4944−0.44650.21380.049*
H12C0.5946−0.57150.21970.049*
C130.69077 (9)−0.28392 (15)0.24717 (6)0.0358 (2)
H13A0.7396−0.19880.23070.054*
H13B0.7358−0.36410.28480.054*
H13C0.6355−0.24010.28380.054*
C140.77858 (8)0.35945 (11)−0.11351 (6)0.02686 (16)
H14A0.82600.4429−0.13410.040*
H14B0.71180.4072−0.09380.040*
H14C0.75620.2860−0.16580.040*
H1N20.9359 (11)0.6745 (17)0.1514 (9)0.032 (3)*
H1N10.9456 (11)0.2302 (18)0.1541 (10)0.037 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.02875 (10)0.00993 (8)0.02066 (9)−0.00165 (6)−0.00069 (7)0.00020 (5)
N10.0229 (3)0.0097 (2)0.0194 (2)0.0000 (2)0.0011 (2)0.00087 (18)
N20.0215 (3)0.0097 (2)0.0230 (3)0.0005 (2)0.0011 (2)0.00087 (19)
N30.0215 (3)0.0128 (2)0.0220 (3)0.0011 (2)0.0017 (2)0.0013 (2)
C10.0185 (3)0.0102 (3)0.0212 (3)−0.0005 (2)0.0032 (2)0.0005 (2)
C20.0177 (3)0.0129 (3)0.0192 (3)0.0001 (2)0.0031 (2)0.0015 (2)
C30.0216 (3)0.0159 (3)0.0177 (3)−0.0010 (2)0.0034 (2)0.0005 (2)
C40.0192 (3)0.0152 (3)0.0156 (3)−0.0007 (2)0.0014 (2)−0.0001 (2)
C50.0224 (3)0.0163 (3)0.0232 (3)0.0012 (3)0.0054 (2)−0.0010 (2)
C60.0207 (3)0.0191 (3)0.0235 (3)0.0010 (3)0.0053 (3)0.0000 (2)
C70.0183 (3)0.0168 (3)0.0174 (3)−0.0009 (2)−0.0006 (2)0.0018 (2)
C80.0240 (3)0.0149 (3)0.0179 (3)−0.0009 (3)0.0020 (2)−0.0008 (2)
C90.0230 (3)0.0161 (3)0.0168 (3)−0.0004 (3)0.0038 (2)−0.0016 (2)
C100.0206 (3)0.0206 (3)0.0228 (3)−0.0024 (3)0.0012 (2)0.0031 (3)
C110.0250 (3)0.0214 (3)0.0232 (3)0.0027 (3)0.0083 (3)0.0058 (3)
C120.0369 (5)0.0247 (4)0.0393 (5)0.0001 (4)0.0183 (4)0.0085 (4)
C130.0374 (5)0.0468 (6)0.0216 (4)−0.0011 (4)−0.0006 (3)0.0079 (4)
C140.0317 (4)0.0269 (4)0.0208 (3)−0.0036 (3)−0.0005 (3)0.0062 (3)

Geometric parameters (Å, °)

S1—C11.6934 (8)C7—C101.5101 (11)
N1—C11.3561 (9)C8—C91.3954 (11)
N1—C21.3741 (9)C8—H8A0.9500
N1—H1N10.856 (15)C9—H9A0.9500
N2—C11.3429 (10)C10—C111.5332 (11)
N2—N31.3786 (9)C10—H10A0.9900
N2—H1N20.843 (15)C10—H10B0.9900
N3—C21.3073 (10)C11—C131.5212 (14)
C2—C31.4961 (10)C11—C121.5307 (13)
C3—C41.5210 (10)C11—H11A1.0000
C3—C141.5332 (11)C12—H12A0.9800
C3—H3A1.0000C12—H12B0.9800
C4—C91.3918 (10)C12—H12C0.9800
C4—C51.3970 (10)C13—H13A0.9800
C5—C61.3915 (11)C13—H13B0.9800
C5—H5A0.9500C13—H13C0.9800
C6—C71.3969 (11)C14—H14A0.9800
C6—H6A0.9500C14—H14B0.9800
C7—C81.3960 (10)C14—H14C0.9800
C1—N1—C2108.46 (6)C4—C9—C8120.71 (7)
C1—N1—H1N1124.2 (10)C4—C9—H9A119.6
C2—N1—H1N1127.3 (10)C8—C9—H9A119.6
C1—N2—N3112.91 (6)C7—C10—C11114.07 (6)
C1—N2—H1N2126.2 (9)C7—C10—H10A108.7
N3—N2—H1N2120.8 (9)C11—C10—H10A108.7
C2—N3—N2103.88 (6)C7—C10—H10B108.7
N2—C1—N1103.96 (6)C11—C10—H10B108.7
N2—C1—S1128.29 (6)H10A—C10—H10B107.6
N1—C1—S1127.75 (5)C13—C11—C12111.11 (7)
N3—C2—N1110.79 (6)C13—C11—C10111.58 (8)
N3—C2—C3126.37 (7)C12—C11—C10109.98 (7)
N1—C2—C3122.85 (6)C13—C11—H11A108.0
C2—C3—C4110.56 (6)C12—C11—H11A108.0
C2—C3—C14111.23 (6)C10—C11—H11A108.0
C4—C3—C14111.68 (6)C11—C12—H12A109.5
C2—C3—H3A107.7C11—C12—H12B109.5
C4—C3—H3A107.7H12A—C12—H12B109.5
C14—C3—H3A107.7C11—C12—H12C109.5
C9—C4—C5118.48 (7)H12A—C12—H12C109.5
C9—C4—C3120.63 (6)H12B—C12—H12C109.5
C5—C4—C3120.84 (7)C11—C13—H13A109.5
C6—C5—C4120.65 (7)C11—C13—H13B109.5
C6—C5—H5A119.7H13A—C13—H13B109.5
C4—C5—H5A119.7C11—C13—H13C109.5
C5—C6—C7121.18 (7)H13A—C13—H13C109.5
C5—C6—H6A119.4H13B—C13—H13C109.5
C7—C6—H6A119.4C3—C14—H14A109.5
C8—C7—C6117.90 (7)C3—C14—H14B109.5
C8—C7—C10120.62 (7)H14A—C14—H14B109.5
C6—C7—C10121.48 (7)C3—C14—H14C109.5
C9—C8—C7121.08 (7)H14A—C14—H14C109.5
C9—C8—H8A119.5H14B—C14—H14C109.5
C7—C8—H8A119.5
C1—N2—N3—C2−0.33 (8)C14—C3—C4—C5−77.63 (9)
N3—N2—C1—N10.44 (8)C9—C4—C5—C6−0.25 (11)
N3—N2—C1—S1179.36 (5)C3—C4—C5—C6177.25 (7)
C2—N1—C1—N2−0.36 (8)C4—C5—C6—C7−0.29 (12)
C2—N1—C1—S1−179.29 (6)C5—C6—C7—C80.43 (11)
N2—N3—C2—N10.08 (8)C5—C6—C7—C10179.67 (7)
N2—N3—C2—C3179.70 (7)C6—C7—C8—C9−0.03 (11)
C1—N1—C2—N30.18 (9)C10—C7—C8—C9−179.28 (7)
C1—N1—C2—C3−179.45 (6)C5—C4—C9—C80.64 (11)
N3—C2—C3—C4−132.25 (8)C3—C4—C9—C8−176.86 (7)
N1—C2—C3—C447.32 (9)C7—C8—C9—C4−0.51 (11)
N3—C2—C3—C14−7.57 (10)C8—C7—C10—C1164.45 (9)
N1—C2—C3—C14172.00 (7)C6—C7—C10—C11−114.77 (8)
C2—C3—C4—C9−135.76 (7)C7—C10—C11—C1359.28 (9)
C14—C3—C4—C999.82 (8)C7—C10—C11—C12−176.94 (7)
C2—C3—C4—C546.79 (9)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H1N2···S1i0.843 (14)2.476 (14)3.3150 (7)173.9 (12)
N1—H1N1···S1ii0.856 (15)2.400 (15)3.2549 (6)176.4 (13)

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CS2108).

References

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  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Clemons, M., Coleman, R. E. & Verma, S. (2004). Cancer Treat. Rev.30, 325–332. [PubMed]
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst.19, 105–107.
  • Johnston, G. A. R. (2002). Curr. Top. Med. Chem.2, 903–913. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shujuan, S., Hongxiang, L., Gao, Y., Fan, P., Ma, B., Ge, W. & Wang, X. (2004). J. Pharm. Biomed. Anal.34, 1117–1124. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Wei, T.-B., Tang, J., Liu, H. & Zhang, Y.-M. (2007). Phosphorus Sulfur Silicon, 182, 1581–1587.

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