4-[(E)-4-Bromo­benzyl­ideneamino]-3-methyl-1H-1,2,4-triazole-5(4H)-thione

Fun, H.-K.; Jebas, S.R.; Sujith, K.V.; Patil, P.S.; Kalluraya, B.; Muralidharan, A.; Dharmaprakash, S.M.

doi:10.1107/S1600536808021636

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1509

doi:10.1107/S1600536808021636

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4-[(E)-4-Bromobenzylideneamino]-3-methyl-1H-1,2,4-triazole-5(4H)-thione

Hoong-Kun Fun,^a ^* Samuel Robinson Jebas,^a ‡ K. V. Sujith,^b P. S. Patil,^c B. Kalluraya,^b A. Muralidharan ^d and S. M. Dharmaprakash ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India, ^cDepartment of Studies in Physics, Mangalore University, Mangalagangotri, Mangalore 574 199, India, and ^dDepartment of Chemistry, Nehru Arts and Science College, Kanhangad, Kerala 671 328, India
^*Correspondence e-mail: hkfun@usm.my

(Received 8 July 2008; accepted 11 July 2008; online 16 July 2008)

In the title molecule, C₁₀H₉BrN₄S, the dihedral angle between the triazole and benzene rings is 12.32 (19)°. An intramolecular C—H⋯S hydrogen bond generates an S(6) ring motif. In the crystal packing, centrosymmetrically related molecules are linked into a dimer by N—H⋯S hydrogen bonds, and the dimers are linked into a chain running along [1 $[\overline{1}]$ 1] by Br⋯N short contacts [3.187 (3) Å]. The crystal packing is further strengthened by π–π interactions involving the triazole ring [centroid–centroid distance = 3.322 (2) Å].

Related literature

For the pharmacological activity of triazole compounds, see: Bekircan et al. (2006 ); Brandt et al. (2007 ); Holla et al. (1996 , 2002 ); Yale et al. (1966 ). For bond-length data, see: Allen et al. (1987 ). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₉BrN₄S
M_r = 297.18
Triclinic, $[P \overline 1]$
a = 6.9239 (5) Å
b = 7.6072 (5) Å
c = 11.5982 (8) Å
α = 82.453 (5)°
β = 88.339 (5)°
γ = 68.204 (4)°
V = 562.18 (7) Å³
Z = 2
Mo Kα radiation
μ = 3.82 mm⁻¹
T = 100.0 (1) K
0.32 × 0.31 × 0.12 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.265, T_max = 0.629
13535 measured reflections
3252 independent reflections
2538 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.121
S = 1.09
3252 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −1.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯S1ⁱ	0.87	2.48	3.321 (4)	164
C7—H7A⋯S1	0.93	2.50	3.223 (4)	134
Symmetry code: (i) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); 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, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021636/ci2629sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021636/ci2629Isup2.hkl

checkCIF report

Comment top

Various 1,2,4-triazole derivatives are found to be associated with diverse pharmacological activity (Holla et al., 1996,2002). Schiff bases of 1,2,4-triazoles find diverse applications and extensive biological activity. Schiff bases derived from 3-substituted-4-amino-5-mercapto-1,2,4 triazoles show antiinflammatory, analgesic, antimicrobial and antidepressant activities (Yale et al., 1966; Bekircan et al., 2006). The incorporation of the 1,2,4-triazole unit into Schiff-base macrocycles is of considerable current interest as complexes of 1,2,4-triazoles are being developed for potential use in applications such as magnetic materials and photochemically driven molecular devices (Brandt et al., 2007). These applications prompted us to synthesize a novel Schiff base, derived from the reaction of 4-amino-5-methyl-2,4-dihydro-3H-1,2,4- triazole-3-thione with 4-bromo benzaldehyde.

In the title compound (Fig.1), the bond lengths and angles are found to have normal values (Allen et al., 1987). The dihedral angle between the triazole ring (N2/C8/N3/N4/C9) and the benzene ring (C1-C6) is 12.32 (19)°, indicating that they are slightly twisted from each other. An intramolecular C—H···S hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995).

In the crystal packing, centrosymmetrically related molecules are linked into a dimer by N—H···S hydrogen bonds (Table 1). The dimers are linked into a chain running along the [1 1 1] by Br1···N4(1+x, -1+y, 1+z) short contacts [3.187 (3) Å]. The crystal packing is further strengthened by π-π interactions between the N2/C8/N3/N4/C9 (centroid Cg1) rings of the molecules at (x, y, z) and (1-x, 1-y, z) [centroid-centroid distance = 3.322 (2) Å].

Related literature top

For the pharmacological activity of triazole compounds, see: Bekircan et al. (2006); Brandt et al. (2007); Holla et al. (1996, 2002); Yale et al. (1966). For bond-length data, see: Allen et al. (1987). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995).

Experimental top

A mixture of 4-amino-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-thione (0.01 mol), 4-bromobenzaldehyde (0.01 mol) in ethanol (30 ml) and 2 drops of concentrated H₂SO₄ was refluxed for 3 h. The solid product obtained was collected by filtration, washed with ethanol and dried. Single crystals suitable for X-ray analysis were obtained from ethanol by slow evaporation.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005; data reduction: SAINT (Bruker, 2005); 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, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. The dashed line indicates a hydrogen bond.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis. Hydrogen bonds and Br···N short contacts are shown as dashed lines.

4-[(E)-4-Bromobenzylideneamino]-3-methyl-1H-1,2,4-triazole- 5(4H)-thione top

Crystal data top

C₁₀H₉BrN₄S	Z = 2
M_r = 297.18	F(000) = 296
Triclinic, P1	D_x = 1.756 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9239 (5) Å	Cell parameters from 5175 reflections
b = 7.6072 (5) Å	θ = 2.9–33.2°
c = 11.5982 (8) Å	µ = 3.82 mm⁻¹
α = 82.453 (5)°	T = 100 K
β = 88.339 (5)°	Plate, colourless
γ = 68.204 (4)°	0.32 × 0.31 × 0.12 mm
V = 562.18 (7) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3252 independent reflections
Radiation source: fine-focus sealed tube	2538 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ϕ and ω scans	θ_max = 30.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.265, T_max = 0.629	k = −10→10
13535 measured reflections	l = −16→16

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0635P)² + 0.1826P] where P = (F_o² + 2F_c²)/3
3252 reflections	(Δ/σ)_max = 0.001
146 parameters	Δρ_max = 1.20 e Å⁻³
0 restraints	Δρ_min = −1.50 e Å⁻³

Crystal data top

C₁₀H₉BrN₄S	γ = 68.204 (4)°
M_r = 297.18	V = 562.18 (7) Å³
Triclinic, P1	Z = 2
a = 6.9239 (5) Å	Mo Kα radiation
b = 7.6072 (5) Å	µ = 3.82 mm⁻¹
c = 11.5982 (8) Å	T = 100 K
α = 82.453 (5)°	0.32 × 0.31 × 0.12 mm
β = 88.339 (5)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3252 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2538 reflections with I > 2σ(I)
T_min = 0.265, T_max = 0.629	R_int = 0.059
13535 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.09	Δρ_max = 1.20 e Å⁻³
3252 reflections	Δρ_min = −1.50 e Å⁻³
146 parameters

Special details top

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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
Br1	1.07281 (6)	0.01690 (5)	0.76969 (3)	0.02379 (13)
S1	0.13495 (15)	0.36883 (13)	0.17836 (8)	0.0247 (2)
N1	0.5353 (5)	0.4917 (4)	0.2620 (2)	0.0212 (6)
N2	0.4008 (5)	0.5702 (4)	0.1661 (2)	0.0201 (6)
N3	0.1919 (5)	0.6408 (4)	0.0225 (3)	0.0243 (6)
N4	0.3110 (5)	0.7506 (4)	−0.0027 (3)	0.0236 (6)
C1	0.8184 (6)	0.3339 (5)	0.4542 (3)	0.0237 (7)
H1A	0.8534	0.4121	0.3957	0.028*
C2	0.9486 (6)	0.2514 (5)	0.5516 (3)	0.0246 (7)
H2A	1.0698	0.2751	0.5590	0.029*
C3	0.8955 (6)	0.1335 (5)	0.6374 (3)	0.0214 (7)
C4	0.7153 (6)	0.0956 (5)	0.6288 (3)	0.0230 (7)
H4A	0.6830	0.0140	0.6862	0.028*
C5	0.5843 (6)	0.1829 (5)	0.5321 (3)	0.0224 (7)
H5A	0.4606	0.1626	0.5265	0.027*
C6	0.6348 (5)	0.2997 (5)	0.4439 (3)	0.0199 (7)
C7	0.4924 (5)	0.3838 (5)	0.3443 (3)	0.0199 (7)
H7A	0.3710	0.3592	0.3407	0.024*
C8	0.2417 (6)	0.5275 (5)	0.1234 (3)	0.0217 (7)
C9	0.4376 (6)	0.7049 (5)	0.0860 (3)	0.0211 (7)
C10	0.5990 (6)	0.7828 (5)	0.1022 (3)	0.0249 (7)
H10A	0.6335	0.8346	0.0280	0.037*
H10B	0.7209	0.6828	0.1377	0.037*
H10C	0.5478	0.8818	0.1514	0.037*
H1N3	0.1157	0.6542	−0.0384	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0287 (2)	0.02116 (18)	0.01825 (18)	−0.00691 (14)	−0.00647 (13)	0.00315 (12)
S1	0.0301 (5)	0.0264 (4)	0.0191 (4)	−0.0150 (4)	−0.0050 (3)	0.0069 (3)
N1	0.0242 (15)	0.0186 (13)	0.0177 (14)	−0.0058 (12)	−0.0047 (11)	0.0029 (11)
N2	0.0251 (14)	0.0185 (13)	0.0154 (13)	−0.0085 (12)	−0.0020 (11)	0.0041 (10)
N3	0.0318 (16)	0.0226 (14)	0.0179 (14)	−0.0120 (13)	−0.0029 (12)	0.0058 (11)
N4	0.0259 (15)	0.0242 (15)	0.0203 (14)	−0.0109 (13)	0.0003 (12)	0.0040 (11)
C1	0.0278 (18)	0.0222 (16)	0.0194 (16)	−0.0094 (14)	0.0024 (14)	0.0028 (13)
C2	0.0227 (17)	0.0252 (17)	0.0243 (18)	−0.0076 (14)	−0.0052 (14)	−0.0009 (14)
C3	0.0253 (17)	0.0167 (15)	0.0164 (15)	−0.0024 (13)	−0.0035 (13)	0.0022 (12)
C4	0.0307 (19)	0.0178 (15)	0.0188 (16)	−0.0083 (14)	0.0018 (14)	0.0007 (12)
C5	0.0255 (17)	0.0198 (16)	0.0225 (17)	−0.0100 (14)	−0.0034 (14)	0.0002 (13)
C6	0.0237 (16)	0.0176 (15)	0.0173 (15)	−0.0074 (13)	−0.0001 (13)	0.0003 (12)
C7	0.0239 (16)	0.0191 (15)	0.0158 (15)	−0.0079 (13)	−0.0044 (13)	0.0009 (12)
C8	0.0229 (16)	0.0210 (16)	0.0182 (16)	−0.0057 (14)	−0.0004 (13)	0.0006 (12)
C9	0.0252 (17)	0.0181 (15)	0.0195 (16)	−0.0088 (14)	−0.0006 (13)	0.0013 (12)
C10	0.0285 (18)	0.0230 (17)	0.0228 (17)	−0.0116 (15)	−0.0006 (14)	0.0047 (13)

Geometric parameters (Å, º) top

Br1—C3	1.895 (3)	C2—C3	1.386 (5)
S1—C8	1.686 (4)	C2—H2A	0.93
N1—C7	1.278 (4)	C3—C4	1.390 (5)
N1—N2	1.390 (4)	C4—C5	1.392 (5)
N2—C8	1.380 (5)	C4—H4A	0.93
N2—C9	1.381 (4)	C5—C6	1.390 (5)
N3—C8	1.331 (4)	C5—H5A	0.93
N3—N4	1.377 (4)	C6—C7	1.455 (4)
N3—H1N3	0.87	C7—H7A	0.93
N4—C9	1.296 (5)	C9—C10	1.473 (5)
C1—C2	1.391 (5)	C10—H10A	0.96
C1—C6	1.400 (5)	C10—H10B	0.96
C1—H1A	0.93	C10—H10C	0.96

C7—N1—N2	119.6 (3)	C6—C5—H5A	119.4
C8—N2—C9	108.5 (3)	C4—C5—H5A	119.4
C8—N2—N1	133.0 (3)	C5—C6—C1	119.2 (3)
C9—N2—N1	118.1 (3)	C5—C6—C7	118.3 (3)
C8—N3—N4	114.1 (3)	C1—C6—C7	122.5 (3)
C8—N3—H1N3	137.0	N1—C7—C6	119.6 (3)
N4—N3—H1N3	108.1	N1—C7—H7A	120.2
C9—N4—N3	104.3 (3)	C6—C7—H7A	120.2
C2—C1—C6	120.3 (3)	N3—C8—N2	102.7 (3)
C2—C1—H1A	119.8	N3—C8—S1	126.6 (3)
C6—C1—H1A	119.8	N2—C8—S1	130.6 (3)
C3—C2—C1	119.2 (4)	N4—C9—N2	110.4 (3)
C3—C2—H2A	120.4	N4—C9—C10	126.1 (3)
C1—C2—H2A	120.4	N2—C9—C10	123.5 (3)
C2—C3—C4	121.7 (3)	C9—C10—H10A	109.5
C2—C3—Br1	119.8 (3)	C9—C10—H10B	109.5
C4—C3—Br1	118.5 (3)	H10A—C10—H10B	109.5
C3—C4—C5	118.4 (3)	C9—C10—H10C	109.5
C3—C4—H4A	120.8	H10A—C10—H10C	109.5
C5—C4—H4A	120.8	H10B—C10—H10C	109.5
C6—C5—C4	121.2 (3)

C7—N1—N2—C8	−16.6 (6)	C5—C6—C7—N1	−179.9 (3)
C7—N1—N2—C9	171.9 (3)	C1—C6—C7—N1	0.7 (5)
C8—N3—N4—C9	−0.5 (4)	N4—N3—C8—N2	0.9 (4)
C6—C1—C2—C3	0.7 (5)	N4—N3—C8—S1	−177.3 (3)
C1—C2—C3—C4	−0.1 (5)	C9—N2—C8—N3	−1.0 (4)
C1—C2—C3—Br1	179.1 (3)	N1—N2—C8—N3	−173.0 (3)
C2—C3—C4—C5	−1.4 (5)	C9—N2—C8—S1	177.2 (3)
Br1—C3—C4—C5	179.4 (3)	N1—N2—C8—S1	5.1 (6)
C3—C4—C5—C6	2.3 (5)	N3—N4—C9—N2	−0.2 (4)
C4—C5—C6—C1	−1.7 (5)	N3—N4—C9—C10	180.0 (3)
C4—C5—C6—C7	179.0 (3)	C8—N2—C9—N4	0.8 (4)
C2—C1—C6—C5	0.1 (5)	N1—N2—C9—N4	174.2 (3)
C2—C1—C6—C7	179.5 (3)	C8—N2—C9—C10	−179.4 (3)
N2—N1—C7—C6	179.2 (3)	N1—N2—C9—C10	−6.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···S1ⁱ	0.87	2.48	3.321 (4)	164
C7—H7A···S1	0.93	2.50	3.223 (4)	134

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₉BrN₄S
M_r	297.18
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.9239 (5), 7.6072 (5), 11.5982 (8)
α, β, γ (°)	82.453 (5), 88.339 (5), 68.204 (4)
V (Å³)	562.18 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.82
Crystal size (mm)	0.32 × 0.31 × 0.12

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.265, 0.629
No. of measured, independent and observed [I > 2σ(I)] reflections	13535, 3252, 2538
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.121, 1.09
No. of reflections	3252
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.20, −1.50

Computer programs: APEX2 (Bruker, 2005), APEX2 (Bruker, 2005, SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···S1ⁱ	0.87	2.48	3.321 (4)	164
C7—H7A···S1	0.93	2.50	3.223 (4)	134

Symmetry code: (i) −x, −y+1, −z.

Footnotes

‡Permanent address: Department of Physics, Karunya University, Karunya Nagar, Coimbatore 641 114, India.

Acknowledgements

HKF and SRJ thank the Malaysian government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks the Universiti Sains Malaysia for a post-doctoral research fellowship.

References

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