3-(4-Nitro­phen­yl)-1H-1,2,4-triazole-5(4H)-thione

Fun, H.-K.; Quah, C.K.; Nithinchandra; Kalluraya, B.

doi:10.1107/S1600536811033952

organic compounds

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Volume 67| Part 9| September 2011| Page o2413

doi:10.1107/S1600536811033952

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3-(4-Nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Nithinchandra ^b and Balakrishna Kalluraya ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 18 August 2011; accepted 19 August 2011; online 27 August 2011)

In the title compound, C₈H₆N₄O₂S, the 1,2,4-triazole ring and the nitro group form dihedral angles of 6.26 (13) and 9.5 (3)°, respectively, with the phenyl ring. In the crystal, the molecules are linked via pairs of N—H⋯S hydrogen bonds, generating [010] chains which contain R²₂ (8) ring motifs. The crystal structure is further stabilized by π–π stacking [centroid–centroid distance = 3.5491 (14) Å] interactions.

Related literature

For general background to and the biological activity of 1,2,4-triazole derivatives, see: Shujuan et al. (2004 ); Clemons et al. (2004 ); Johnston (2002 ); Wei et al. (2007 ). For standard bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For related structures, see: Fun et al. (2010 , 2011 ).

Experimental

Crystal data

C₈H₆N₄O₂S
M_r = 222.23
Monoclinic, P 2₁ /c
a = 7.8221 (1) Å
b = 8.2109 (1) Å
c = 14.6757 (3) Å
β = 101.302 (1)°
V = 924.29 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 K
0.35 × 0.27 × 0.17 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.892, T_max = 0.947
8521 measured reflections
1988 independent reflections
1789 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.109
S = 1.17
1988 reflections
144 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯S1ⁱ	0.84 (3)	2.48 (3)	3.295 (3)	164 (3)
N2—H1N2⋯S1ⁱⁱ	0.80 (3)	2.50 (3)	3.285 (3)	168 (3)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811033952/hb6376sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033952/hb6376Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811033952/hb6376Isup3.cml

checkCIF report

Comment top

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), 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, 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.

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.

Related literature top

For general background to and the biological activity of 1,2,4-triazole derivatives, see: Shujuan et al. (2004); Clemons et al. (2004); Johnston (2002); Wei et al. (2007). For standard bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures, see: Fun et al. (2010, 2011).

Experimental top

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.

Computing details top

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

Figures top

	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 involved in hydrogen bonds (dashed lines) have been omitted for clarity.

3-(4-Nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione top

Crystal data top

C₈H₆N₄O₂S	F(000) = 456
M_r = 222.23	D_x = 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 top

Bruker SMART APEXII CCD diffractometer	1988 independent reflections
Radiation source: fine-focus sealed tube	1789 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→8
T_min = 0.892, T_max = 0.947	k = −10→10
8521 measured reflections	l = −15→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.023P)² + 1.7764P] where P = (F_o² + 2F_c²)/3
1988 reflections	(Δ/σ)_max = 0.001
144 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₈H₆N₄O₂S	V = 924.29 (2) Å³
M_r = 222.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.8221 (1) Å	µ = 0.33 mm⁻¹
b = 8.2109 (1) Å	T = 100 K
c = 14.6757 (3) Å	0.35 × 0.27 × 0.17 mm
β = 101.302 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	1988 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1789 reflections with I > 2σ(I)
T_min = 0.892, T_max = 0.947	R_int = 0.021
8521 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 0.42 e Å⁻³
1988 reflections	Δρ_min = −0.29 e Å⁻³
144 parameters

Special details top

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, conventional 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 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

	x	y	z	U_iso*/U_eq
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)
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) top

	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, º) top

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)
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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1ⁱ	0.84 (3)	2.48 (3)	3.295 (3)	164 (3)
N2—H1N2···S1ⁱⁱ	0.80 (3)	2.50 (3)	3.285 (3)	168 (3)

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

Experimental details

Crystal data
Chemical formula	C₈H₆N₄O₂S
M_r	222.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.8221 (1), 8.2109 (1), 14.6757 (3)
β (°)	101.302 (1)
V (Å³)	924.29 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.35 × 0.27 × 0.17

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.892, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	8521, 1988, 1789
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.109, 1.17
No. of reflections	1988
No. of parameters	144
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.29

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1ⁱ	0.84 (3)	2.48 (3)	3.295 (3)	164 (3)
N2—H1N2···S1ⁱⁱ	0.80 (3)	2.50 (3)	3.285 (3)	168 (3)

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009

§Thomson Reuters ResearcherID: A-5525-2009

Acknowledgements

HKF and CKQ thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160).

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