N-[(E)-(5-Methyl­thio­phen-2-yl)methyl­idene]-1H-1,2,4-triazol-3-amine

Chohan, Z.H.; Hanif, M.; Tahir, M.N.

doi:10.1107/S1600536808041494

organic compounds

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Volume 65| Part 1| January 2009| Page o117

doi:10.1107/S1600536808041494

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N-[(E)-(5-Methylthiophen-2-yl)methylidene]-1H-1,2,4-triazol-3-amine

Zahid H. Chohan,^a Muhammad Hanif ^a and M. Nawaz Tahir ^b ^*

^aDepartment of Chemistry, Bahauddin Zakariya University, Multan-60800, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 4 December 2008; accepted 8 December 2008; online 13 December 2008)

In the title Schiff base, C₈H₈N₄S, a condensation product of 5-methylthiophene-2-carboxaldehyde and 3-amino-1,2,4-triazole, the dihedral angle between the triazolyl and thienyl rings is 6.44 (14)°. The compound exists as a polymeric chain arising from intermolecular N—H⋯N bonding.

Related literature

For a related comound, see: Chohan et al. (2009 ). For the biological properties of such compounds, see: Foroumadi et al. (2003 ); Manfredini et al. (2000 ).

Experimental

Crystal data

C₈H₈N₄S
M_r = 192.24
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.2570 (7) Å
b = 8.9522 (8) Å
c = 14.2930 (15) Å
V = 928.56 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 (2) K
0.24 × 0.16 × 0.14 mm

Data collection

Bruker KAPPA APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.928, T_max = 0.956
5793 measured reflections
2206 independent reflections
1859 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.097
S = 1.05
2206 reflections
134 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 854 Friedel pairs
Flack parameter: −0.02 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3n⋯N1ⁱ	0.85 (3)	2.12 (3)	2.963 (2)	172 (2)
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks text, I. DOI: 10.1107/S1600536808041494/ng2524sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041494/ng2524Isup2.hkl

checkCIF report

Comment top

Compounds derived from triazole possess antimicrobial, analgesic, anti-inflammatory, local anesthetic, antineoplastic and antimalarial properties (Foroumadi et al., 2003). Some triazole Schiff bases also exhibited antiproliferative and anticancer activity (Manfredini et al., 2000). Due to their significant biological applications they have gained much attention in bioinorganic and metal-based drug discovery. In view of its structural and biological importance, we have synthesized (Chohan et al., 2009), series of triazole derived Schiff bases along with the title compound (I). We report herein, its preperation and crystal structure.

In the molecule of title compound, (Fig 1), the bond lengths and angles are within normal ranges. In this molecule 5-methylthiophen ring is attached to 5-membered ring of triazole moiety through the Schiff bond C=N. The dihedral angle between ring A(S1/C1—C4) and B(C7/N2/N3/C8/N4) is 6.44 (14)°. There exist intramolecular as well as an intermolecular H-bonds as given in Table 1. The molecules are connected to each other through intermolecular H-bonds of N–H···N type in a helical way (Fig 2).

Related literature top

For a similar comound, see: Chohan et al. (2009). For the biological properties of such compounds, see: Foroumadi et al. (2003); Manfredini et al. (2000).

Experimental top

A mixture of 5-methylthiophene-2-carboxaldehyde (1.09 ml, 0.01 M) and 3-amino-1,2,4-triazole (0.84 g, 0.01 M) in 1:1 molar proportions in methanol (40 ml) was boiled under reflux for 5 h by monitoring through TLC. The reaction mixture was cooled at room temperature and filtered; within an hour a light brown solid product separated from the clear solution. It was filtered, washed with methanol, dried and recrystallized from a mixture of ethanol:methanol (1:1).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2003)..

Figures top

	Fig. 1. ORTEP-3 for Windows (Farrugia, 1997) drawing of the title compound, C₈H₈N₄S, with the atom numbering scheme. The thermal ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii. The intramolecular H-bonding is shown by dashed lines.
	Fig. 2. The partial unit cell packing of (I) (Spek, 2003) showing the interamolecular and intermolecular hydrogen bonding showing that polymeric sheets are formed.

(I) top

Crystal data top

C₈H₈N₄S	F(000) = 400
M_r = 192.24	D_x = 1.375 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2206 reflections
a = 7.2570 (7) Å	θ = 2.7–28.3°
b = 8.9522 (8) Å	µ = 0.31 mm⁻¹
c = 14.2930 (15) Å	T = 296 K
V = 928.56 (16) Å³	Prismatic, light brown
Z = 4	0.24 × 0.16 × 0.14 mm

Data collection top

Bruker KAPPA APEXII CCD diffractometer	2206 independent reflections
Radiation source: fine-focus sealed tube	1859 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 7.4 pixels mm^-1	θ_max = 28.3°, θ_min = 2.7°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −11→11
T_min = 0.928, T_max = 0.956	l = −17→19
5793 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0562P)² + 0.0383P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2206 reflections	Δρ_max = 0.20 e Å⁻³
134 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 854 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (10)

Crystal data top

C₈H₈N₄S	V = 928.56 (16) Å³
M_r = 192.24	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.2570 (7) Å	µ = 0.31 mm⁻¹
b = 8.9522 (8) Å	T = 296 K
c = 14.2930 (15) Å	0.24 × 0.16 × 0.14 mm

Data collection top

Bruker KAPPA APEXII CCD diffractometer	2206 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1859 reflections with I > 2σ(I)
T_min = 0.928, T_max = 0.956	R_int = 0.034
5793 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.097	Δρ_max = 0.20 e Å⁻³
S = 1.05	Δρ_min = −0.23 e Å⁻³
2206 reflections	Absolute structure: Flack (1983), 854 Friedel pairs
134 parameters	Absolute structure parameter: −0.02 (10)
0 restraints

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.48892 (7)	−0.18020 (5)	0.00175 (3)	0.0512 (2)
N1	0.5269 (2)	0.13362 (16)	0.09627 (10)	0.0456 (4)
N2	0.4898 (2)	0.29617 (16)	0.22417 (10)	0.0498 (5)
N3	0.5397 (2)	0.43946 (17)	0.23930 (11)	0.0502 (5)
N4	0.6332 (3)	0.39225 (19)	0.09806 (13)	0.0659 (7)
C1	0.5665 (3)	−0.0136 (2)	−0.04286 (12)	0.0460 (5)
C2	0.6222 (3)	−0.0303 (3)	−0.13344 (14)	0.0565 (7)
C3	0.6008 (3)	−0.1767 (3)	−0.16735 (14)	0.0562 (7)
C4	0.5306 (3)	−0.2720 (2)	−0.10199 (12)	0.0497 (5)
C5	0.4937 (4)	−0.4350 (3)	−0.11161 (16)	0.0737 (9)
C6	0.5724 (3)	0.1226 (2)	0.00957 (13)	0.0473 (5)
C7	0.5491 (3)	0.27297 (19)	0.13780 (12)	0.0432 (5)
C8	0.6228 (3)	0.4940 (3)	0.16478 (17)	0.0654 (8)
H2	0.663 (3)	0.048 (2)	−0.1784 (19)	0.0678*
H3	0.629 (3)	−0.210 (3)	−0.2327 (18)	0.0675*
H3N	0.515 (3)	0.488 (3)	0.2891 (17)	0.0602*
H5A	0.52067	−0.48427	−0.05354	0.1103*
H5B	0.57023	−0.47560	−0.16015	0.1103*
H5C	0.36648	−0.45026	−0.12734	0.1103*
H6	0.621 (3)	0.209 (2)	−0.0237 (15)	0.0567*
H8	0.671 (4)	0.595 (2)	0.1599 (17)	0.0785*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0642 (3)	0.0540 (3)	0.0354 (2)	−0.0070 (2)	0.0078 (2)	−0.0047 (2)
N1	0.0516 (8)	0.0465 (7)	0.0386 (7)	0.0015 (7)	−0.0023 (7)	−0.0011 (6)
N2	0.0668 (10)	0.0434 (7)	0.0392 (7)	0.0024 (7)	0.0000 (8)	0.0002 (5)
N3	0.0644 (10)	0.0439 (8)	0.0422 (8)	0.0024 (7)	−0.0020 (8)	−0.0053 (6)
N4	0.0895 (14)	0.0554 (10)	0.0529 (10)	−0.0181 (9)	0.0184 (10)	−0.0072 (8)
C1	0.0475 (9)	0.0518 (10)	0.0388 (8)	−0.0018 (7)	0.0027 (8)	−0.0017 (7)
C2	0.0641 (13)	0.0637 (13)	0.0418 (10)	−0.0064 (9)	0.0110 (9)	0.0012 (9)
C3	0.0605 (12)	0.0706 (13)	0.0376 (9)	0.0014 (10)	0.0098 (9)	−0.0096 (9)
C4	0.0515 (10)	0.0573 (10)	0.0404 (8)	−0.0008 (8)	0.0011 (8)	−0.0092 (7)
C5	0.100 (2)	0.0629 (12)	0.0582 (12)	−0.0099 (13)	0.0055 (13)	−0.0160 (10)
C6	0.0521 (9)	0.0499 (9)	0.0398 (8)	−0.0004 (8)	−0.0003 (8)	0.0008 (7)
C7	0.0475 (9)	0.0431 (8)	0.0391 (8)	0.0031 (7)	−0.0022 (8)	0.0003 (7)
C8	0.0827 (16)	0.0504 (11)	0.0630 (13)	−0.0152 (11)	0.0126 (12)	−0.0079 (10)

Geometric parameters (Å, º) top

S1—C1	1.7169 (19)	C1—C6	1.432 (3)
S1—C4	1.7220 (18)	C2—C3	1.406 (4)
N1—C6	1.286 (2)	C3—C4	1.364 (3)
N1—C7	1.391 (2)	C4—C5	1.490 (3)
N2—N3	1.350 (2)	C2—H2	1.00 (2)
N2—C7	1.324 (2)	C3—H3	1.00 (3)
N3—C8	1.318 (3)	C5—H5A	0.9600
N4—C7	1.355 (3)	C5—H5B	0.9600
N4—C8	1.321 (3)	C5—H5C	0.9600
N3—H3N	0.85 (3)	C6—H6	0.974 (19)
C1—C2	1.365 (3)	C8—H8	0.97 (2)

S1···N1	3.1295 (15)	N4···H5A^vii	2.5700
S1···C4ⁱ	3.647 (2)	N4···H6	2.39 (2)
N1···S1	3.1295 (15)	C1···N4^v	3.419 (3)
N1···N3ⁱⁱ	2.963 (2)	C4···S1^viii	3.647 (2)
N2···N4	2.252 (2)	C8···N2ⁱⁱⁱ	3.241 (3)
N2···C8ⁱⁱ	3.241 (3)	C7···H3^vi	3.03 (2)
N2···N3ⁱⁱ	3.243 (2)	C7···H3Nⁱⁱ	2.80 (3)
N3···N1ⁱⁱⁱ	2.963 (2)	H2···N2^iv	2.83 (2)
N3···N4	2.171 (2)	H2···N3^iv	2.87 (2)
N3···N2ⁱⁱⁱ	3.243 (2)	H3···N2^ix	2.94 (2)
N4···C1^iv	3.419 (3)	H3···C7^ix	3.03 (2)
N4···N3	2.171 (2)	H3N···N1ⁱⁱⁱ	2.12 (3)
N1···H3Nⁱⁱ	2.12 (3)	H3N···N2ⁱⁱⁱ	2.77 (3)
N2···H8ⁱⁱ	2.71 (2)	H3N···C7ⁱⁱⁱ	2.80 (3)
N2···H2^v	2.83 (2)	H5A···N4^x	2.5700
N2···H3^vi	2.94 (2)	H6···N4	2.39 (2)
N2···H3Nⁱⁱ	2.77 (3)	H8···N2ⁱⁱⁱ	2.71 (2)
N3···H2^v	2.87 (2)

C1—S1—C4	92.13 (9)	N1—C7—N4	125.46 (16)
C6—N1—C7	116.76 (15)	N2—C7—N4	114.44 (16)
N3—N2—C7	102.19 (14)	N3—C8—N4	110.7 (2)
N2—N3—C8	110.20 (17)	C1—C2—H2	128.6 (14)
C7—N4—C8	102.42 (18)	C3—C2—H2	117.8 (14)
C8—N3—H3N	125.6 (17)	C2—C3—H3	125.2 (15)
N2—N3—H3N	124.1 (17)	C4—C3—H3	121.9 (15)
S1—C1—C6	123.72 (14)	C4—C5—H5A	109.00
C2—C1—C6	125.52 (19)	C4—C5—H5B	109.00
S1—C1—C2	110.75 (16)	C4—C5—H5C	110.00
C1—C2—C3	113.4 (2)	H5A—C5—H5B	109.00
C2—C3—C4	112.85 (18)	H5A—C5—H5C	109.00
S1—C4—C3	110.91 (15)	H5B—C5—H5C	109.00
C3—C4—C5	128.07 (19)	N1—C6—H6	120.2 (12)
S1—C4—C5	121.02 (15)	C1—C6—H6	115.6 (12)
N1—C6—C1	124.19 (17)	N3—C8—H8	124.6 (15)
N1—C7—N2	120.07 (16)	N4—C8—H8	124.7 (15)

C1—S1—C4—C3	−0.12 (18)	C8—N4—C7—N2	−0.4 (3)
C4—S1—C1—C2	−0.28 (18)	C7—N4—C8—N3	0.4 (2)
C4—S1—C1—C6	−179.69 (19)	C8—N4—C7—N1	−178.6 (2)
C1—S1—C4—C5	178.8 (2)	C2—C1—C6—N1	−176.6 (2)
C6—N1—C7—N4	−7.9 (3)	S1—C1—C2—C3	0.6 (2)
C7—N1—C6—C1	177.03 (19)	C6—C1—C2—C3	−180.0 (2)
C6—N1—C7—N2	173.91 (18)	S1—C1—C6—N1	2.7 (3)
C7—N2—N3—C8	0.1 (2)	C1—C2—C3—C4	−0.7 (3)
N3—N2—C7—N1	178.54 (17)	C2—C3—C4—S1	0.5 (2)
N3—N2—C7—N4	0.2 (2)	C2—C3—C4—C5	−178.4 (2)
N2—N3—C8—N4	−0.3 (2)

Symmetry codes: (i) x−1/2, −y−1/2, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x+1/2, −y+1/2, −z; (v) x−1/2, −y+1/2, −z; (vi) −x+3/2, −y, z+1/2; (vii) x, y+1, z; (viii) x+1/2, −y−1/2, −z; (ix) −x+3/2, −y, z−1/2; (x) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3n···N1ⁱⁱⁱ	0.85 (3)	2.12 (3)	2.963 (2)	172 (2)
C6—H6···N4	0.974 (19)	2.39 (2)	2.761 (3)	101.7 (15)

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

Experimental details

Crystal data
Chemical formula	C₈H₈N₄S
M_r	192.24
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	7.2570 (7), 8.9522 (8), 14.2930 (15)
V (Å³)	928.56 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.24 × 0.16 × 0.14

Data collection
Diffractometer	Bruker KAPPA APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.928, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	5793, 2206, 1859
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.097, 1.05
No. of reflections	2206
No. of parameters	134
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.23
Absolute structure	Flack (1983), 854 Friedel pairs
Absolute structure parameter	−0.02 (10)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2003)..

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3n···N1ⁱ	0.85 (3)	2.12 (3)	2.963 (2)	172 (2)

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

Acknowledgements

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore.

References

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