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

Abstract

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 R ² ₂ (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,

• a = 7.8221 (1) Å

• b = 8.2109 (1) Å

• c = 14.6757 (3) Å

• β = 101.302 (1)°

• V = 924.29 (2) ų

• 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[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811033952/hb6376Isup3.cml

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
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) ; (ii) .

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), 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.

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 U_iso(H) = 1.2 U_eq(C).

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

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 diffractometer	1988 independent reflections
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 (SADABS; Bruker, 2009)	h = −9→8
Tmin = 0.892, Tmax = 0.947	k = −10→10
8521 measured reflections	l = −15→18

Refinement

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(Fo2) + (0.023P)2 + 1.7764P] 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, 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 (Ų)

	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)
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 (Ų)

	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)
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
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.