4-[(E)-(3-Methyl-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-4-yl)imino­meth­yl]benzonitrile

Zhao, Y.-Y.; Zhao, H.; Wang, W.-X.; Xiao, J.

doi:10.1107/S1600536808017613

organic compounds

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Volume 64| Part 7| July 2008| Page o1273

doi:10.1107/S1600536808017613

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4-[(E)-(3-Methyl-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-4-yl)iminomethyl]benzonitrile

Yu-Yuan Zhao,^a ^* Hong Zhao,^a Wen-Xiang Wang ^a and Jie Xiao ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: zhaohong@seu.edu.cn

(Received 11 April 2008; accepted 11 June 2008; online 13 June 2008)

In the title compound, C₁₁H₉N₅S, the dihedral angle between the mean planes of the thione-substituted triazole ring and benzonitrile ring is 4.28 (3)°. Intermolecular N—H⋯S hydrogen bonds link the molecules together into characteristic dimers.

Related literature

For the application of benzotriazole compounds in industry, see: Sharma & Bahel (1982 ); Grasso (1988 ); Eweiss et al. (1986 ); Awad et al. (1991 ); Pillard et al. (2001 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₉N₅S
M_r = 243.29
Triclinic, $[P \overline 1]$
a = 6.975 (2) Å
b = 7.682 (2) Å
c = 11.412 (2) Å
α = 90.262 (7)°
β = 94.328 (14)°
γ = 104.713 (17)°
V = 589.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 (2) K
0.70 × 0.50 × 0.50 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.854, T_max = 0.901
5954 measured reflections
2659 independent reflections
2178 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.115
S = 1.05
2659 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3D⋯N5ⁱ	0.86	2.11	2.934 (2)	162
Symmetry code: (i) x, y+1, z-1.

Data collection: CrystalClear (Rigaku, 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017613/rn2041sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017613/rn2041Isup2.hkl

checkCIF report

Comment top

It has been found that 1,2,4-thiadiazoles possess a broad spectrum of biological activities and can be widely used as fungicides (Sharma & Bahel, 1982) and insecticides (Grasso, 1988). In addition, amine- and thione-substituted triazoles have been studied as anti-inflammatory and antimicrobial agents (Eweiss et al., 1986; Awad et al., 1991). Benzotriazole and its derivatives comprise an important class of corrosion inhibitors, typically used as trace additives in industrial chemical mixtures, such as coolants, cutting fluids and hydraulic fluids (Pillard et al., 2001). We present its crystal structure here. The molecule exists in the thione tautomeric form, with an S···C distance of 1.6752 (3) A °, which indicates substantial double-bond character for this bond [1.671 (24) A °, Allen et al., 1987]. The dihedral angle between thione-substituted triazole ring and benzonitrile ring is 4.28 (3) °. N-H···N hydrogen bonds are observed in the crystal structure which link the molecules into dimers.

Related literature top

For the application of benzotriazole compounds in industry, see: Sharma & Bahel (1982); Grasso (1988); Eweiss et al. (1986); Awad et al. (1991); Pillard et al. (2001). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of 4-amino-3-methanyl-1H-1,2,4-triazole-5(4H)- thione (0.02 mol) and 4-formylbenzonitrile (0.02 mol) was refluxed at 391 K for 20 min in methanol. The mixture was then filtered and crystallized from ethanol to afford the target material (yield 89%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. A packing diagram of the title compound, viewed down the a axis.

4-[(E)-(3-Methyl-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-4- yl)iminomethyl]benzonitrile top

Crystal data top

C₁₁H₉N₅S	Z = 2
M_r = 243.29	F(000) = 252
Triclinic, P1	D_x = 1.371 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.975 (2) Å	Cell parameters from 1492 reflections
b = 7.682 (2) Å	θ = 3.0–27.4°
c = 11.412 (2) Å	µ = 0.26 mm⁻¹
α = 90.262 (7)°	T = 293 K
β = 94.328 (14)°	Block, colorless
γ = 104.713 (17)°	0.70 × 0.50 × 0.50 mm
V = 589.5 (3) Å³

Data collection top

Rigaku Mercury2 diffractometer	2659 independent reflections
Radiation source: fine-focus sealed tube	2178 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
CCD_Profile_fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.854, T_max = 0.901	l = −14→14
5954 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0532P)² + 0.1343P] where P = (F_o² + 2F_c²)/3
2659 reflections	(Δ/σ)_max = 0.002
155 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₉N₅S	γ = 104.713 (17)°
M_r = 243.29	V = 589.5 (3) Å³
Triclinic, P1	Z = 2
a = 6.975 (2) Å	Mo Kα radiation
b = 7.682 (2) Å	µ = 0.26 mm⁻¹
c = 11.412 (2) Å	T = 293 K
α = 90.262 (7)°	0.70 × 0.50 × 0.50 mm
β = 94.328 (14)°

Data collection top

Rigaku Mercury2 diffractometer	2659 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2178 reflections with I > 2σ(I)
T_min = 0.854, T_max = 0.901	R_int = 0.022
5954 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.05	Δρ_max = 0.18 e Å⁻³
2659 reflections	Δρ_min = −0.21 e Å⁻³
155 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
C1	0.2635 (2)	1.3033 (2)	0.27180 (13)	0.0379 (3)
C2	0.1665 (3)	1.0264 (2)	0.18636 (14)	0.0439 (4)
C3	0.1029 (4)	0.8280 (3)	0.17603 (17)	0.0617 (5)
H3A	0.0629	0.7922	0.0953	0.093*
H3B	−0.0070	0.7840	0.2230	0.093*
H3C	0.2115	0.7789	0.2030	0.093*
C4	0.2745 (2)	1.1001 (2)	0.49268 (13)	0.0400 (4)
H4	0.3196	1.2248	0.4992	0.048*
C5	0.2738 (2)	0.9871 (2)	0.59672 (13)	0.0371 (3)
C6	0.3299 (3)	1.0685 (2)	0.70682 (14)	0.0487 (4)
H6	0.3678	1.1934	0.7142	0.058*
C7	0.3300 (3)	0.9654 (3)	0.80588 (15)	0.0539 (5)
H7	0.3652	1.0206	0.8798	0.065*
C8	0.2773 (3)	0.7799 (2)	0.79417 (15)	0.0476 (4)
C9	0.2227 (3)	0.6970 (2)	0.68453 (16)	0.0514 (4)
H9	0.1879	0.5721	0.6772	0.062*
C10	0.2200 (3)	0.8001 (2)	0.58632 (15)	0.0461 (4)
H10	0.1821	0.7445	0.5127	0.055*
C11	0.2800 (3)	0.6704 (3)	0.89609 (17)	0.0601 (5)
N1	0.21505 (19)	1.11995 (17)	0.29285 (10)	0.0362 (3)
N2	0.1847 (2)	1.1369 (2)	0.10000 (12)	0.0524 (4)
N3	0.2429 (2)	1.3038 (2)	0.15394 (12)	0.0485 (4)
H3D	0.2647	1.4017	0.1151	0.058*
N4	0.2117 (2)	1.02188 (17)	0.39419 (11)	0.0385 (3)
N5	0.2817 (3)	0.5822 (3)	0.97577 (16)	0.0811 (6)
S1	0.32744 (8)	1.48037 (6)	0.36283 (4)	0.05691 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0412 (8)	0.0381 (8)	0.0336 (8)	0.0090 (6)	0.0012 (6)	0.0115 (6)
C2	0.0541 (10)	0.0461 (9)	0.0328 (8)	0.0162 (7)	−0.0013 (7)	0.0027 (6)
C3	0.0905 (15)	0.0456 (10)	0.0494 (11)	0.0217 (10)	−0.0072 (10)	−0.0044 (8)
C4	0.0457 (9)	0.0390 (8)	0.0350 (8)	0.0100 (7)	0.0031 (6)	0.0111 (6)
C5	0.0366 (8)	0.0433 (8)	0.0325 (7)	0.0115 (6)	0.0048 (6)	0.0131 (6)
C6	0.0612 (11)	0.0433 (9)	0.0377 (8)	0.0070 (8)	0.0003 (7)	0.0109 (7)
C7	0.0647 (11)	0.0623 (11)	0.0325 (8)	0.0130 (9)	0.0007 (7)	0.0134 (8)
C8	0.0463 (9)	0.0592 (11)	0.0412 (9)	0.0186 (8)	0.0096 (7)	0.0259 (8)
C9	0.0628 (11)	0.0426 (9)	0.0525 (10)	0.0180 (8)	0.0112 (8)	0.0191 (8)
C10	0.0576 (10)	0.0443 (9)	0.0382 (9)	0.0160 (8)	0.0048 (7)	0.0102 (7)
C11	0.0646 (12)	0.0709 (13)	0.0517 (11)	0.0264 (10)	0.0144 (9)	0.0305 (10)
N1	0.0438 (7)	0.0370 (7)	0.0279 (6)	0.0105 (5)	0.0016 (5)	0.0089 (5)
N2	0.0719 (10)	0.0542 (9)	0.0308 (7)	0.0172 (8)	−0.0013 (6)	0.0065 (6)
N3	0.0652 (9)	0.0451 (8)	0.0328 (7)	0.0103 (7)	0.0016 (6)	0.0154 (6)
N4	0.0465 (7)	0.0389 (7)	0.0312 (6)	0.0125 (6)	0.0041 (5)	0.0136 (5)
N5	0.1056 (16)	0.0881 (14)	0.0603 (11)	0.0394 (12)	0.0213 (10)	0.0456 (10)
S1	0.0794 (4)	0.0363 (2)	0.0488 (3)	0.0070 (2)	−0.0080 (2)	0.00552 (19)

Geometric parameters (Å, º) top

C1—N3	1.3420 (19)	C6—C7	1.383 (2)
C1—N1	1.3887 (19)	C6—H6	0.9300
C1—S1	1.6546 (17)	C7—C8	1.382 (3)
C2—N2	1.296 (2)	C7—H7	0.9300
C2—N1	1.384 (2)	C8—C9	1.383 (3)
C2—C3	1.477 (2)	C8—C11	1.440 (2)
C3—H3A	0.9600	C9—C10	1.377 (2)
C3—H3B	0.9600	C9—H9	0.9300
C3—H3C	0.9600	C10—H10	0.9300
C4—N4	1.266 (2)	C11—N5	1.137 (2)
C4—C5	1.4735 (19)	N1—N4	1.3815 (16)
C4—H4	0.9300	N2—N3	1.371 (2)
C5—C6	1.384 (2)	N3—H3D	0.8600
C5—C10	1.391 (2)

N3—C1—N1	101.52 (13)	C8—C7—C6	119.51 (17)
N3—C1—S1	127.16 (12)	C8—C7—H7	120.2
N1—C1—S1	131.32 (11)	C6—C7—H7	120.2
N2—C2—N1	110.55 (15)	C7—C8—C9	120.50 (15)
N2—C2—C3	126.08 (16)	C7—C8—C11	120.31 (18)
N1—C2—C3	123.37 (15)	C9—C8—C11	119.20 (18)
C2—C3—H3A	109.5	C10—C9—C8	119.79 (17)
C2—C3—H3B	109.5	C10—C9—H9	120.1
H3A—C3—H3B	109.5	C8—C9—H9	120.1
C2—C3—H3C	109.5	C9—C10—C5	120.33 (16)
H3A—C3—H3C	109.5	C9—C10—H10	119.8
H3B—C3—H3C	109.5	C5—C10—H10	119.8
N4—C4—C5	117.83 (15)	N5—C11—C8	179.2 (2)
N4—C4—H4	121.1	N4—N1—C2	118.04 (13)
C5—C4—H4	121.1	N4—N1—C1	133.14 (13)
C6—C5—C10	119.33 (14)	C2—N1—C1	108.80 (13)
C6—C5—C4	119.41 (15)	C2—N2—N3	104.07 (13)
C10—C5—C4	121.26 (14)	C1—N3—N2	115.04 (13)
C7—C6—C5	120.52 (17)	C1—N3—H3D	122.5
C7—C6—H6	119.7	N2—N3—H3D	122.5
C5—C6—H6	119.7	C4—N4—N1	120.55 (13)

N4—C4—C5—C6	−176.05 (15)	C3—C2—N1—N4	2.8 (2)
N4—C4—C5—C10	4.7 (2)	N2—C2—N1—C1	1.31 (19)
C10—C5—C6—C7	−0.9 (3)	C3—C2—N1—C1	−178.55 (17)
C4—C5—C6—C7	179.80 (16)	N3—C1—N1—N4	177.34 (15)
C5—C6—C7—C8	1.3 (3)	S1—C1—N1—N4	−3.4 (3)
C6—C7—C8—C9	−0.7 (3)	N3—C1—N1—C2	−0.99 (17)
C6—C7—C8—C11	178.86 (17)	S1—C1—N1—C2	178.25 (13)
C7—C8—C9—C10	−0.3 (3)	N1—C2—N2—N3	−0.99 (19)
C11—C8—C9—C10	−179.81 (17)	C3—C2—N2—N3	178.87 (18)
C8—C9—C10—C5	0.6 (3)	N1—C1—N3—N2	0.42 (19)
C6—C5—C10—C9	−0.1 (3)	S1—C1—N3—N2	−178.87 (13)
C4—C5—C10—C9	179.22 (16)	C2—N2—N3—C1	0.3 (2)
C7—C8—C11—N5	−176 (100)	C5—C4—N4—N1	−177.73 (12)
C9—C8—C11—N5	4 (17)	C2—N1—N4—C4	172.61 (15)
N2—C2—N1—N4	−177.30 (14)	C1—N1—N4—C4	−5.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3D···N5ⁱ	0.86	2.11	2.934 (2)	162

Symmetry code: (i) x, y+1, z−1.

Experimental details

Crystal data
Chemical formula	C₁₁H₉N₅S
M_r	243.29
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.975 (2), 7.682 (2), 11.412 (2)
α, β, γ (°)	90.262 (7), 94.328 (14), 104.713 (17)
V (Å³)	589.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.70 × 0.50 × 0.50

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.854, 0.901
No. of measured, independent and observed [I > 2σ(I)] reflections	5954, 2659, 2178
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.115, 1.05
No. of reflections	2659
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.21

Computer programs: CrystalClear (Rigaku, 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—H3D···N5ⁱ	0.86	2.11	2.934 (2)	161.7

Symmetry code: (i) x, y+1, z−1.

Acknowledgements

This work was supported by a Start-up Grant from SEU to Professor Ren-Gen Xiong.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Awad, I., Abdel-Rahman, A. & Bakite, E. (1991). J. Chem. Technol. Biotechnol. 51, 483–486. CrossRef CAS Google Scholar
Eweiss, N., Bahajaj, A. & Elsherbini, E. (1986). J. Heterocycl. Chem. 23, 1451–1458. CrossRef CAS Google Scholar
Grasso, S. A. (1988). Farm. Ed. Sci. 43, 851–854. CAS Google Scholar
Pillard, D. A., Cornell, J. S., Dufresne, D. L. & Hernandez, M. T. (2001). Water Res. 35, 557–560. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sharma, R. S. & Bahel, S. C. (1982). J. Indian Chem. Soc. 59, 877–879. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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

4-[(E)-(3-Methyl-5-thioxo-4,5-di­hydro-1H-1,2,4-triazol-4-yl)imino­meth­yl]benzo­nitrile

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-[(E)-(3-Methyl-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-4-yl)iminomethyl]benzonitrile