4-[(3-Nitro­benzyl­idene)amino]-3-(pyridin-4-yl)-1H-1,2,4-triazole-5(4H)-thione

Li, T.-B.; Yang, M.-S.; Yin, B.-S.

doi:10.1107/S1600536811054444

organic compounds

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Volume 68| Part 2| February 2012| Page o279

doi:10.1107/S1600536811054444

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4-[(3-Nitrobenzylidene)amino]-3-(pyridin-4-yl)-1H-1,2,4-triazole-5(4H)-thione

Tian-Bao Li,^a ^* Ming-Sheng Yang ^a and Bang-Shao Yin ^a

^aCollege of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, People's Republic of China
^*Correspondence e-mail: yinbangshao@yahoo.cn

(Received 16 December 2011; accepted 18 December 2011; online 7 January 2012)

In the title compound, C₁₄H₁₀N₆O₂S, the dihedral angle between the pyridine and triazole rings is 3.21 (10)°. The molecule is significantly twisted about the N_t—N_b (t = triazole and b = benzylidene) bond [C—N_t—N_b=C = 151.64 (17)°]. In the crystal, molecules are linked by weak N—H⋯N hydrogen bonds, generating C(8) chains propagating in [10 $[\overline{1}]$ ].

Related literature

For further details of the synthesis, see: Wang et al. (2010 ). For the biological activity of related compounds, see: Liu et al. (2011 ).

Experimental

Crystal data

C₁₄H₁₀N₆O₂S
M_r = 326.34
Monoclinic, P 2₁ /n
a = 3.7989 (13) Å
b = 24.334 (9) Å
c = 15.208 (6) Å
β = 93.035 (5)°
V = 1403.9 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.10 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.952, T_max = 0.975
14478 measured reflections
3317 independent reflections
2807 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.103
S = 1.07
3317 reflections
212 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N1ⁱ	0.90 (1)	1.96 (1)	2.815 (2)	158 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks gllobal, I. DOI: 10.1107/S1600536811054444/hb6570sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054444/hb6570Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811054444/hb6570Isup3.cml

checkCIF report

Related literature top

For further details of the synthesis, see: Wang et al. (2010). For the biological activity of related compounds, see: Liu et al. (2011).

Experimental top

The title complex was prepared according to the literature procedures (Wang et al. (2010)). Colourless prisms were recrystallised from dimethylformamide solution at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing for (I).

4-[(3-Nitrobenzylidene)amino]-3-(pyridin-4-yl)-1H-1,2,4-triazole- 5(4H)-thione top

Crystal data top

C₁₄H₁₀N₆O₂S	F(000) = 672
M_r = 326.34	D_x = 1.544 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 3.7989 (13) Å	Cell parameters from 4572 reflections
b = 24.334 (9) Å	θ = 1.6–28.0°
c = 15.208 (6) Å	µ = 0.25 mm⁻¹
β = 93.035 (5)°	T = 113 K
V = 1403.9 (9) Å³	Prism, colorless
Z = 4	0.20 × 0.18 × 0.10 mm

Data collection top

Rigaku Saturn724 CCD diffractometer	3317 independent reflections
Radiation source: rotating anode	2807 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.056
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.9°, θ_min = 1.6°
ω and ϕ scans	h = −4→4
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −32→32
T_min = 0.952, T_max = 0.975	l = −19→20
14478 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0391P)² + 0.3217P] where P = (F_o² + 2F_c²)/3
3317 reflections	(Δ/σ)_max = 0.002
212 parameters	Δρ_max = 0.30 e Å⁻³
7 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₄H₁₀N₆O₂S	V = 1403.9 (9) Å³
M_r = 326.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.7989 (13) Å	µ = 0.25 mm⁻¹
b = 24.334 (9) Å	T = 113 K
c = 15.208 (6) Å	0.20 × 0.18 × 0.10 mm
β = 93.035 (5)°

Data collection top

Rigaku Saturn724 CCD diffractometer	3317 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2807 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.975	R_int = 0.056
14478 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	7 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.30 e Å⁻³
3317 reflections	Δρ_min = −0.28 e Å⁻³
212 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.79238 (13)	0.064958 (19)	−0.05911 (3)	0.01910 (14)
O1	1.3928 (4)	0.08135 (6)	0.49993 (9)	0.0325 (4)
O2	1.2099 (6)	0.14915 (7)	0.41988 (12)	0.0631 (7)
N1	0.0656 (4)	0.30533 (6)	0.24207 (10)	0.0201 (4)
N2	0.3124 (4)	0.20542 (6)	−0.04085 (10)	0.0176 (3)
N3	0.4482 (4)	0.16171 (6)	−0.08450 (10)	0.0169 (3)
N4	0.5138 (4)	0.14148 (6)	0.05152 (9)	0.0144 (3)
N5	0.6482 (4)	0.12137 (6)	0.13193 (10)	0.0163 (3)
N6	1.2412 (5)	0.10008 (7)	0.43334 (11)	0.0270 (4)
C1	0.2990 (5)	0.21757 (8)	0.20265 (12)	0.0203 (4)
H1	0.3918	0.1830	0.2216	0.024*
C2	0.2005 (5)	0.25621 (8)	0.26337 (12)	0.0221 (4)
H2	0.2308	0.2472	0.3241	0.027*
C3	0.0267 (5)	0.31683 (8)	0.15567 (12)	0.0217 (4)
H3	−0.0704	0.3515	0.1387	0.026*
C4	0.1197 (5)	0.28122 (8)	0.09009 (12)	0.0198 (4)
H4	0.0884	0.2915	0.0299	0.024*
C5	0.2600 (5)	0.23011 (7)	0.11340 (12)	0.0153 (4)
C6	0.3606 (5)	0.19291 (7)	0.04253 (11)	0.0152 (4)
C7	0.5807 (5)	0.12176 (7)	−0.03166 (12)	0.0152 (4)
C8	0.6464 (5)	0.06903 (7)	0.14201 (12)	0.0160 (4)
H8	0.5481	0.0453	0.0976	0.019*
C9	0.8035 (5)	0.04757 (8)	0.22553 (11)	0.0158 (4)
C10	0.8222 (5)	−0.00903 (8)	0.24024 (12)	0.0176 (4)
H10	0.7268	−0.0337	0.1968	0.021*
C11	0.9793 (5)	−0.02948 (8)	0.31800 (12)	0.0205 (4)
H11	0.9920	−0.0681	0.3271	0.025*
C12	1.1176 (5)	0.00569 (8)	0.38243 (12)	0.0197 (4)
H12	1.2262	−0.0081	0.4356	0.024*
C13	1.0928 (5)	0.06162 (8)	0.36685 (12)	0.0189 (4)
C14	0.9407 (5)	0.08343 (8)	0.29021 (12)	0.0186 (4)
H14	0.9297	0.1221	0.2816	0.022*
H3A	0.461 (5)	0.1634 (9)	−0.1431 (7)	0.025 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0194 (3)	0.0182 (2)	0.0198 (3)	0.00006 (19)	0.00267 (19)	−0.00447 (18)
O1	0.0432 (10)	0.0331 (8)	0.0195 (8)	0.0039 (7)	−0.0132 (7)	0.0013 (6)
O2	0.1174 (18)	0.0204 (8)	0.0460 (11)	−0.0044 (10)	−0.0482 (11)	−0.0003 (7)
N1	0.0243 (10)	0.0202 (8)	0.0160 (8)	0.0027 (7)	0.0030 (7)	−0.0009 (6)
N2	0.0213 (9)	0.0165 (8)	0.0150 (8)	0.0000 (7)	0.0015 (6)	−0.0010 (6)
N3	0.0231 (9)	0.0172 (8)	0.0108 (7)	−0.0001 (7)	0.0029 (7)	−0.0004 (6)
N4	0.0163 (8)	0.0149 (7)	0.0118 (7)	0.0001 (6)	−0.0009 (6)	0.0009 (6)
N5	0.0183 (8)	0.0190 (8)	0.0114 (7)	0.0024 (6)	−0.0017 (6)	0.0005 (6)
N6	0.0354 (11)	0.0249 (9)	0.0196 (9)	0.0001 (8)	−0.0082 (8)	0.0013 (7)
C1	0.0266 (11)	0.0173 (9)	0.0171 (9)	0.0038 (8)	0.0016 (8)	0.0023 (7)
C2	0.0312 (12)	0.0219 (10)	0.0135 (9)	0.0044 (9)	0.0030 (8)	0.0008 (7)
C3	0.0241 (11)	0.0206 (10)	0.0204 (10)	0.0050 (8)	0.0003 (8)	0.0006 (7)
C4	0.0239 (11)	0.0194 (9)	0.0162 (9)	0.0024 (8)	0.0014 (8)	0.0022 (7)
C5	0.0135 (9)	0.0164 (8)	0.0158 (9)	−0.0015 (7)	0.0002 (7)	−0.0003 (7)
C6	0.0155 (10)	0.0153 (8)	0.0144 (9)	−0.0010 (7)	−0.0011 (7)	0.0008 (7)
C7	0.0132 (9)	0.0184 (9)	0.0140 (9)	−0.0054 (7)	0.0012 (7)	−0.0020 (7)
C8	0.0144 (10)	0.0180 (9)	0.0155 (9)	−0.0003 (7)	0.0006 (7)	−0.0003 (7)
C9	0.0143 (10)	0.0187 (9)	0.0146 (9)	0.0008 (7)	0.0020 (7)	0.0010 (7)
C10	0.0168 (10)	0.0182 (9)	0.0180 (9)	0.0014 (8)	0.0037 (7)	−0.0021 (7)
C11	0.0224 (11)	0.0171 (9)	0.0221 (10)	0.0029 (8)	0.0027 (8)	0.0023 (7)
C12	0.0177 (10)	0.0247 (10)	0.0166 (9)	0.0027 (8)	0.0001 (8)	0.0056 (7)
C13	0.0188 (10)	0.0216 (9)	0.0161 (9)	0.0008 (8)	−0.0010 (8)	−0.0007 (7)
C14	0.0213 (11)	0.0170 (9)	0.0174 (9)	0.0006 (8)	−0.0001 (8)	0.0012 (7)

Geometric parameters (Å, º) top

S1—C7	1.6634 (19)	C3—C4	1.381 (3)
O1—N6	1.226 (2)	C3—H3	0.9500
O2—N6	1.216 (2)	C4—C5	1.392 (2)
N1—C2	1.334 (2)	C4—H4	0.9500
N1—C3	1.344 (2)	C5—C6	1.473 (2)
N2—C6	1.308 (2)	C8—C9	1.470 (2)
N2—N3	1.369 (2)	C8—H8	0.9500
N3—C7	1.342 (2)	C9—C14	1.395 (2)
N3—H3A	0.896 (9)	C9—C10	1.396 (3)
N4—C6	1.384 (2)	C10—C11	1.388 (3)
N4—N5	1.389 (2)	C10—H10	0.9500
N4—C7	1.389 (2)	C11—C12	1.383 (3)
N5—C8	1.283 (2)	C11—H11	0.9500
N6—C13	1.468 (2)	C12—C13	1.384 (3)
C1—C2	1.383 (3)	C12—H12	0.9500
C1—C5	1.391 (3)	C13—C14	1.379 (3)
C1—H1	0.9500	C14—H14	0.9500
C2—H2	0.9500

C2—N1—C3	116.43 (16)	N2—C6—N4	110.06 (16)
C6—N2—N3	104.61 (15)	N2—C6—C5	122.55 (16)
C7—N3—N2	114.30 (15)	N4—C6—C5	127.40 (16)
C7—N3—H3A	126.1 (14)	N3—C7—N4	102.37 (15)
N2—N3—H3A	119.3 (13)	N3—C7—S1	128.51 (14)
C6—N4—N5	122.59 (14)	N4—C7—S1	129.03 (14)
C6—N4—C7	108.58 (15)	N5—C8—C9	116.82 (16)
N5—N4—C7	127.12 (15)	N5—C8—H8	121.6
C8—N5—N4	116.80 (15)	C9—C8—H8	121.6
O2—N6—O1	122.78 (18)	C14—C9—C10	119.34 (17)
O2—N6—C13	118.63 (16)	C14—C9—C8	120.42 (17)
O1—N6—C13	118.58 (17)	C10—C9—C8	120.23 (16)
C2—C1—C5	118.91 (18)	C11—C10—C9	120.39 (17)
C2—C1—H1	120.5	C11—C10—H10	119.8
C5—C1—H1	120.5	C9—C10—H10	119.8
N1—C2—C1	124.13 (18)	C12—C11—C10	120.77 (17)
N1—C2—H2	117.9	C12—C11—H11	119.6
C1—C2—H2	117.9	C10—C11—H11	119.6
N1—C3—C4	123.79 (18)	C11—C12—C13	117.85 (17)
N1—C3—H3	118.1	C11—C12—H12	121.1
C4—C3—H3	118.1	C13—C12—H12	121.1
C3—C4—C5	119.07 (17)	C14—C13—C12	123.01 (18)
C3—C4—H4	120.5	C14—C13—N6	117.72 (17)
C5—C4—H4	120.5	C12—C13—N6	119.25 (16)
C1—C5—C4	117.65 (17)	C13—C14—C9	118.64 (17)
C1—C5—C6	124.09 (17)	C13—C14—H14	120.7
C4—C5—C6	118.25 (16)	C9—C14—H14	120.7

C6—N2—N3—C7	0.1 (2)	N2—N3—C7—S1	−175.14 (13)
C6—N4—N5—C8	151.64 (17)	C6—N4—C7—N3	−2.68 (19)
C7—N4—N5—C8	−44.9 (2)	N5—N4—C7—N3	−167.98 (16)
C3—N1—C2—C1	−0.1 (3)	C6—N4—C7—S1	174.07 (14)
C5—C1—C2—N1	0.6 (3)	N5—N4—C7—S1	8.8 (3)
C2—N1—C3—C4	−0.4 (3)	N4—N5—C8—C9	177.27 (15)
N1—C3—C4—C5	0.5 (3)	N5—C8—C9—C14	1.1 (3)
C2—C1—C5—C4	−0.5 (3)	N5—C8—C9—C10	−177.83 (17)
C2—C1—C5—C6	178.91 (18)	C14—C9—C10—C11	−0.7 (3)
C3—C4—C5—C1	0.0 (3)	C8—C9—C10—C11	178.18 (17)
C3—C4—C5—C6	−179.44 (17)	C9—C10—C11—C12	0.5 (3)
N3—N2—C6—N4	−1.9 (2)	C10—C11—C12—C13	0.2 (3)
N3—N2—C6—C5	178.17 (16)	C11—C12—C13—C14	−0.7 (3)
N5—N4—C6—N2	169.09 (15)	C11—C12—C13—N6	−179.16 (17)
C7—N4—C6—N2	3.0 (2)	O2—N6—C13—C14	3.3 (3)
N5—N4—C6—C5	−10.9 (3)	O1—N6—C13—C14	−176.44 (19)
C7—N4—C6—C5	−177.05 (17)	O2—N6—C13—C12	−178.2 (2)
C1—C5—C6—N2	178.28 (18)	O1—N6—C13—C12	2.1 (3)
C4—C5—C6—N2	−2.3 (3)	C12—C13—C14—C9	0.4 (3)
C1—C5—C6—N4	−1.7 (3)	N6—C13—C14—C9	178.92 (17)
C4—C5—C6—N4	177.75 (18)	C10—C9—C14—C13	0.3 (3)
N2—N3—C7—N4	1.6 (2)	C8—C9—C14—C13	−178.61 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1ⁱ	0.90 (1)	1.96 (1)	2.815 (2)	158 (2)

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀N₆O₂S
M_r	326.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	3.7989 (13), 24.334 (9), 15.208 (6)
β (°)	93.035 (5)
V (Å³)	1403.9 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.20 × 0.18 × 0.10

Data collection
Diffractometer	Rigaku Saturn724 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.952, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	14478, 3317, 2807
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.103, 1.07
No. of reflections	3317
No. of parameters	212
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.28

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1ⁱ	0.896 (9)	1.964 (12)	2.815 (2)	157.9 (19)

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Acknowledgements

This work was supported by the start-up foundation of Hunan Normal University.

References

Liu, X. H., Tan, C. X. & Jian, Q. W. (2011). Phosphorus Sulfur Silicon Relat. Elem. 186, 558–564. Web of Science CSD CrossRef CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc. The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, B. L., Shi, Y. X., Ma, Y., Liu, X. H., Li, Y. H., Song, H. B., Li, B. J. & Li, Z. M. (2010). J. Agric. Food Chem. 58, 5515–5520. Web of Science CrossRef CAS PubMed Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-[(3-Nitro­benzyl­­idene)amino]-3-(pyridin-4-yl)-1H-1,2,4-triazole-5(4H)-thione

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-[(3-Nitrobenzylidene)amino]-3-(pyridin-4-yl)-1H-1,2,4-triazole-5(4H)-thione