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3-(4-Nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione
Article in Acta Crystallographica Section E Structure Reports Online · September 2011
DOI: 10.1107/S1600536811033952 · Source: PubMed
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Ching Kheng Quah Dr. Nithin Chandra
Universiti Sains Malaysia Forensic Science Laboratory, Bangalore
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organic compounds
Acta Crystallographica Section E b = 8.2109 (1) Å Mo K radiation
Structure Reports c = 14.6757 (3) Å = 0.33 mm1
= 101.302 (1) T = 100 K
Online V = 924.29 (2) Å3 0.35 0.27 0.17 mm
ISSN 1600-5368 Z=4
Data collection
3-(4-Nitrophenyl)-1H-1,2,4-triazole- Bruker SMART APEXII CCD 8521 measured reflections
diffractometer 1988 independent reflections
5(4H)-thione Absorption correction: multi-scan 1789 reflections with I > 2(I)
(SADABS; Bruker, 2009) Rint = 0.021
Tmin = 0.892, Tmax = 0.947
Hoong-Kun Fun,a*‡Ching Kheng Quah,a§ Nithinchandrab
and Balakrishna Kallurayab Refinement
a
R[F 2 > 2(F 2)] = 0.042 H atoms treated by a mixture of
X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 wR(F 2) = 0.109 independent and constrained
USM, Penang, Malaysia, and bDepartment of Studies in Chemistry, Mangalore S = 1.17 refinement
University, Mangalagangotri, Mangalore 574 199, India 1988 reflections max = 0.42 e Å3
Correspondence e-mail: hkfun@[Link] 144 parameters min = 0.29 e Å3
Received 18 August 2011; accepted 19 August 2011
Key indicators: single-crystal X-ray study; T = 100 K; mean (C–C) = 0.003 Å;
Table 1
Hydrogen-bond geometry (Å, ).
R factor = 0.042; wR factor = 0.109; data-to-parameter ratio = 13.8.
D—H A D—H H A D A D—H A
i
N1—H1N1 S1 0.84 (3) 2.48 (3) 3.295 (3) 164 (3)
In the title compound, C8H6N4O2S, the 1,2,4-triazole ring and N2—H1N2 S1ii 0.80 (3) 2.50 (3) 3.285 (3) 168 (3)
the nitro group form dihedral angles of 6.26 (13) and 9.5 (3) ,
Symmetry codes: (i) x þ 1; y þ 12; z þ 12; (ii) x þ 1; y 12; z þ 12.
respectively, with the phenyl ring. In the crystal, the molecules
are linked via pairs of N—H S hydrogen bonds, generating Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT
[010] chains which contain R22 (8) ring motifs. The crystal (Bruker, 2009); data reduction: SAINT; program(s) used to solve
structure is further stabilized by – stacking [centroid– structure: SHELXTL (Sheldrick, 2008); program(s) used to refine
centroid distance = 3.5491 (14) Å] interactions. structure: SHELXTL; molecular graphics: SHELXTL; software used
to prepare material for publication: SHELXTL and PLATON (Spek,
2009).
Related literature
For general background to and the biological activity of 1,2,4- HKF and CKQ thank Universiti Sains Malaysia for the
triazole derivatives, see: Shujuan et al. (2004); Clemons et al. Research University Grant (No. 1001/PFIZIK/811160).
(2004); Johnston (2002); Wei et al. (2007). For standard bond-
length data, see: Allen et al. (1987). For the stability of the Supplementary data and figures for this paper are available from the
temperature controller used for the data collection, see: IUCr electronic archives (Reference: HB6376).
Cosier & Glazer (1986). For hydrogen-bond motifs, see:
Bernstein et al. (1995). For related structures, see: Fun et al. References
(2010, 2011).
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Clemons, M., Coleman, R. E. & Verma, S. (2004). Cancer Treat. Rev. 30, 325–
332.
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.
Fun, H.-K., Quah, C. K., Nithinchandra & Kalluraya B. (2011). Acta Cryst.
E67, hb6375.
Fun, H.-K., Quah, C. K., Vijesh, A. M., Malladi, S. & Isloor, A. M. (2010). Acta
Cryst. E66, o29–o30.
Johnston, G. A. R. (2002). Curr. Top. Med. Chem. 2, 903–913.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Experimental Shujuan, S., Hongxiang, L., Gao, Y., Fan, P., Ma, B., Ge, W. & Wang, X. (2004).
J. Pharm. Biomed. Anal. 34, 1117–1124.
Crystal data Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Wei, T.-B., Tang, J., Liu, H. & Zhang, Y.-M. (2007). Phosphorus Sulfur Silicon,
C8H6N4O2S Monoclinic, P21 =c
182, 1581–1587.
Mr = 222.23 a = 7.8221 (1) Å
‡ Thomson Reuters ResearcherID: A-3561-2009
§ Thomson Reuters ResearcherID: A-5525-2009
Acta Cryst. (2011). E67, o2413 doi:10.1107/S1600536811033952 Fun et al. o2413
supplementary materials
supplementary materials
Acta Cryst. (2011). E67, o2413 [ doi:10.1107/S1600536811033952 ]
3-(4-Nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione
H.-K. Fun, C. K. Quah, Nithinchandra and B. Kalluraya
Comment
The 1,2,4-triazole nucleus has been incorporated into a wide variety of therapeutically interesting compounds. Several com-
pounds containing 1,2,4-triazole rings are well known as drugs. For example, fluconazole is used as an antimicrobial drug
(Shujuan et al., 2004), whereas vorozole, letrozole and anastrozole are non-steroidal drugs used for the treatment of cancer
(Clemons et al., 2004) and loreclezole is used as an anticonvulsant (Johnston, 2002). Similarly substituted derivatives of
triazole possess comprehensive bioactivities such as antimicrobial, anti-inflammatory, analgesic, antihypertensive, anticon-
vulsant 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.
In the title molecule, Fig. 1, the 1,2,4-triazole ring (N1-N3/C1/C2, maximum deviation of 0.002 (2) Å at atoms N3
and C2) and the nitro group (O1/O2/N4) form dihedral angles of 6.26 (13) and 9.5 (3)°, respectively, with the phenyl ring
(C3-C8). Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures
(Fun et al., 2010, 2011).
In the crystal structure, the molecules are linked via intermolecular N1–H1N1···S1 and N2–H1N2···S1 hydrogen bonds
(Table 1), generating R22 (8) ring motifs (Bernstein et al., 1995) and are further linked into one-dimensional chains along
[010] via adjacent ring motifs. π-π stacking interactions between the centroids of C3-C8 phenyl ring (Cg1) and N1-N3/C1/C2
triazole ring (Cg2), with Cg1···Cg2iii distance of 3.5491 (14) Å [symmetry code: (iii) 1-X,1-Y,1-Z] are observed.
Experimental
A mixture of 2-[(4-nitrophenyl)carbonyl]hydrazinecarbothioamide (0.01 mol) 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.
Yellow blocks of (I) were obtained from ethanol solution by slow evaporation.
Refinement
Atoms H1N1 and H1N2 were located from the difference Fourier map and refined freely [N–H = 0.80 (3) or 0.84 (3) Å].
The remaining H atoms were positioned geometrically and refined using a riding model with C–H = 0.95 Å and Uiso(H)
= 1.2 Ueq(C).
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Figures
Fig. 1. The molecular structure of the title compound showing 50% probability displacement
ellipsoids for non-H atoms.
Fig. 2. The crystal structure of the title compound, viewed along the a axis. H atoms not in-
volved in hydrogen bonds (dashed lines) have been omitted for clarity.
3-(4-Nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione
Crystal data
C8H6N4O2S F(000) = 456
Mr = 222.23 Dx = 1.597 Mg m−3
Monoclinic, P21/c Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc Cell parameters from 6061 reflections
a = 7.8221 (1) Å θ = 2.7–32.7°
b = 8.2109 (1) Å µ = 0.33 mm−1
c = 14.6757 (3) Å T = 100 K
β = 101.302 (1)° Block, yellow
V = 924.29 (2) Å3 0.35 × 0.27 × 0.17 mm
Z=4
Data collection
Bruker SMART APEXII CCD
1988 independent reflections
diffractometer
Radiation source: fine-focus sealed tube 1789 reflections with I > 2σ(I)
graphite Rint = 0.021
φ and ω scans θmax = 27.0°, θmin = 2.7°
Absorption correction: multi-scan
h = −9→8
(SADABS; Bruker, 2009)
Tmin = 0.892, Tmax = 0.947 k = −10→10
8521 measured reflections l = −15→18
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Refinement
Primary atom site location: structure-invariant direct
Refinement on F2 methods
Least-squares matrix: full Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring
R[F2 > 2σ(F2)] = 0.042 sites
H atoms treated by a mixture of independent and
wR(F2) = 0.109 constrained refinement
w = 1/[σ2(Fo2) + (0.023P)2 + 1.7764P]
S = 1.17
where P = (Fo2 + 2Fc2)/3
1988 reflections (Δ/σ)max = 0.001
144 parameters Δρmax = 0.42 e Å−3
0 restraints Δρmin = −0.29 e Å−3
Special details
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier &
Glazer, 1986) operating at 100.0 (1) K.
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The
cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds
in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used
for estimating esds 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, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculat-
ing 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)
x y z Uiso*/Ueq
S1 0.48563 (8) 0.37379 (7) 0.18859 (4) 0.02226 (18)
O1 0.0046 (3) 0.9832 (3) 0.65011 (15) 0.0430 (6)
O2 0.0293 (3) 0.7834 (3) 0.74650 (13) 0.0364 (5)
N1 0.3673 (3) 0.5040 (3) 0.33704 (14) 0.0184 (4)
N2 0.3841 (3) 0.2469 (3) 0.34126 (15) 0.0227 (5)
N3 0.3212 (3) 0.2888 (3) 0.41922 (14) 0.0227 (5)
N4 0.0471 (3) 0.8436 (3) 0.67295 (14) 0.0265 (5)
C1 0.4131 (3) 0.3742 (3) 0.29010 (16) 0.0192 (5)
C2 0.3128 (3) 0.4479 (3) 0.41483 (16) 0.0187 (5)
C3 0.2506 (3) 0.5522 (3) 0.48290 (16) 0.0186 (5)
C4 0.2100 (3) 0.4814 (3) 0.56284 (16) 0.0206 (5)
H4A 0.2269 0.3680 0.5738 0.025*
C5 0.1450 (3) 0.5774 (3) 0.62606 (16) 0.0218 (5)
H5A 0.1165 0.5310 0.6805 0.026*
C6 0.1226 (3) 0.7419 (3) 0.60807 (16) 0.0223 (5)
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C7 0.1638 (3) 0.8162 (3) 0.53043 (17) 0.0235 (5)
H7A 0.1490 0.9301 0.5208 0.028*
C8 0.2272 (3) 0.7193 (3) 0.46708 (16) 0.0210 (5)
H8A 0.2548 0.7668 0.4127 0.025*
H1N1 0.384 (4) 0.601 (4) 0.323 (2) 0.026 (8)*
H1N2 0.400 (4) 0.154 (4) 0.329 (2) 0.033 (9)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
S1 0.0335 (3) 0.0136 (3) 0.0225 (3) −0.0009 (2) 0.0124 (2) −0.0021 (2)
O1 0.0675 (15) 0.0288 (12) 0.0374 (11) 0.0141 (11) 0.0220 (10) −0.0025 (9)
O2 0.0480 (12) 0.0404 (13) 0.0235 (9) 0.0060 (10) 0.0140 (8) −0.0005 (9)
N1 0.0223 (10) 0.0137 (11) 0.0204 (10) 0.0009 (8) 0.0070 (8) −0.0006 (8)
N2 0.0280 (11) 0.0160 (11) 0.0271 (11) 0.0011 (9) 0.0128 (9) −0.0006 (9)
N3 0.0262 (10) 0.0192 (11) 0.0255 (10) 0.0011 (8) 0.0118 (8) −0.0001 (9)
N4 0.0292 (11) 0.0280 (13) 0.0229 (10) 0.0014 (9) 0.0063 (8) −0.0047 (9)
C1 0.0185 (10) 0.0170 (12) 0.0222 (11) −0.0003 (9) 0.0045 (9) −0.0029 (10)
C2 0.0149 (10) 0.0207 (13) 0.0207 (11) 0.0002 (9) 0.0040 (8) 0.0016 (10)
C3 0.0146 (10) 0.0217 (13) 0.0198 (11) 0.0000 (9) 0.0040 (8) −0.0044 (10)
C4 0.0188 (10) 0.0205 (13) 0.0220 (11) −0.0007 (9) 0.0026 (9) 0.0014 (10)
C5 0.0193 (11) 0.0287 (14) 0.0170 (11) −0.0006 (10) 0.0030 (9) 0.0014 (10)
C6 0.0197 (11) 0.0272 (14) 0.0202 (11) 0.0015 (10) 0.0046 (9) −0.0060 (10)
C7 0.0264 (12) 0.0187 (12) 0.0258 (12) 0.0037 (10) 0.0065 (10) −0.0002 (10)
C8 0.0241 (11) 0.0199 (13) 0.0205 (11) −0.0005 (9) 0.0079 (9) −0.0003 (10)
Geometric parameters (Å, °)
S1—C1 1.695 (2) C2—C3 1.469 (3)
O1—N4 1.222 (3) C3—C8 1.398 (3)
O2—N4 1.220 (3) C3—C4 1.400 (3)
N1—C1 1.355 (3) C4—C5 1.387 (3)
N1—C2 1.375 (3) C4—H4A 0.9500
N1—H1N1 0.84 (3) C5—C6 1.380 (4)
N2—C1 1.332 (3) C5—H5A 0.9500
N2—N3 1.375 (3) C6—C7 1.385 (3)
N2—H1N2 0.80 (3) C7—C8 1.387 (3)
N3—C2 1.309 (3) C7—H7A 0.9500
N4—C6 1.474 (3) C8—H8A 0.9500
C1—N1—C2 108.3 (2) C8—C3—C2 120.6 (2)
C1—N1—H1N1 124 (2) C4—C3—C2 119.2 (2)
C2—N1—H1N1 127 (2) C5—C4—C3 119.8 (2)
C1—N2—N3 113.7 (2) C5—C4—H4A 120.1
C1—N2—H1N2 125 (2) C3—C4—H4A 120.1
N3—N2—H1N2 122 (2) C6—C5—C4 118.5 (2)
C2—N3—N2 103.4 (2) C6—C5—H5A 120.8
O2—N4—O1 123.4 (2) C4—C5—H5A 120.8
O2—N4—C6 118.1 (2) C5—C6—C7 123.2 (2)
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O1—N4—C6 118.4 (2) C5—C6—N4 118.8 (2)
N2—C1—N1 103.9 (2) C7—C6—N4 118.0 (2)
N2—C1—S1 128.14 (19) C6—C7—C8 118.1 (2)
N1—C1—S1 127.98 (19) C6—C7—H7A 121.0
N3—C2—N1 110.8 (2) C8—C7—H7A 121.0
N3—C2—C3 124.6 (2) C7—C8—C3 120.3 (2)
N1—C2—C3 124.6 (2) C7—C8—H8A 119.9
C8—C3—C4 120.2 (2) C3—C8—H8A 119.9
C1—N2—N3—C2 −0.3 (3) C2—C3—C4—C5 −177.6 (2)
N3—N2—C1—N1 0.1 (3) C3—C4—C5—C6 −0.2 (3)
N3—N2—C1—S1 −178.54 (17) C4—C5—C6—C7 −0.7 (4)
C2—N1—C1—N2 0.1 (2) C4—C5—C6—N4 177.6 (2)
C2—N1—C1—S1 178.73 (18) O2—N4—C6—C5 9.9 (3)
N2—N3—C2—N1 0.3 (3) O1—N4—C6—C5 −169.7 (2)
N2—N3—C2—C3 179.3 (2) O2—N4—C6—C7 −171.7 (2)
C1—N1—C2—N3 −0.2 (3) O1—N4—C6—C7 8.7 (3)
C1—N1—C2—C3 −179.2 (2) C5—C6—C7—C8 1.3 (4)
N3—C2—C3—C8 −172.6 (2) N4—C6—C7—C8 −177.0 (2)
N1—C2—C3—C8 6.3 (3) C6—C7—C8—C3 −0.9 (4)
N3—C2—C3—C4 5.6 (4) C4—C3—C8—C7 0.0 (3)
N1—C2—C3—C4 −175.6 (2) C2—C3—C8—C7 178.2 (2)
C8—C3—C4—C5 0.5 (3)
Hydrogen-bond geometry (Å, °)
D—H···A D—H H···A D···A D—H···A
i 0.84 (3) 2.48 (3) 3.295 (3) 164 (3)
N1—H1N1···S1
ii 0.80 (3) 2.50 (3) 3.285 (3) 168 (3)
N2—H1N2···S1
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.
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