4-[(5-Bromo-2-hy­droxy­benzyl­idene)amino]-3-ethyl-1H-1,2,4-triazole-5(4H)-thione

Yuan, C.-X.; Lan, S.-F.; Liu, X.-Y.; Zhu, M.-L.

doi:10.1107/S1600536814016833

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 8| August 2014| Pages o881-o882

doi:10.1107/S1600536814016833

Open

access

4-[(5-Bromo-2-hydroxybenzylidene)amino]-3-ethyl-1H-1,2,4-triazole-5(4H)-thione

Cai-Xia Yuan,^a Shu-Fen Lan,^a Xin-Yu Liu ^a and Miao-Li Zhu ^a ^*

^aInstitute of Molecular Science, Key Laboratory of Chemical Biology and Molecular, Engineering of the Education Ministry, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China
^*Correspondence e-mail: miaoli@sxu.edu.cn

Edited by L. Fabian, University of East Anglia, England (Received 3 April 2014; accepted 21 July 2014; online 26 July 2014)

The title compound, C₁₁H₁₁BrN₄OS, crystallized as a racemic twin with two symmetry-independent molecules in the asymmetric unit. The dihedral angles between the benzene and triazole rings of the two independent molecules are 56.41 (18) and 54.48 (18)°. An intramolecular O—H⋯N hydrogen bond occurs in each molecule. In the crystal, pairs of symmetry-independent molecules are linked by pairs of almost linear N—H⋯S hydrogen bonds, forming cyclic dimers characterized by an R₂²(8) motif. There are weak π–π interactions between the benzene rings of symmetry-independent molecules, with a centroid–centroid distance of 3.874 (3) Å.

Keywords: crystal structure.

CCDC reference: 1015277

Related literature

For background to the biological activity of related compounds, see: Demirbas (2004 ); Demirbas et al. (2009 ); Todoulou et al. (1994 ); Kumar et al. (2008 ); Kochikyan et al. (2011 ); Singhal et al. (2011 ); Popiołek et al. (2013 ); Sraa (2012 ). For similar structures, see: Wu et al. (2012 ); Pannu & Hundal (2011 ). For standard bond lengths, see: Allen et al. (1987 ). For graph-sets of hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₁H₁₁BrN₄OS
M_r = 327.21
Monoclinic, P 2₁
a = 6.323 (4) Å
b = 16.459 (11) Å
c = 12.461 (8) Å
β = 90.330 (9)°
V = 1296.8 (15) Å³
Z = 4
Mo Kα radiation
μ = 3.32 mm⁻¹
T = 298 K
0.40 × 0.35 × 0.30 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ) T_min = 0.350, T_max = 0.435
14802 measured reflections
5222 independent reflections
4285 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.065
S = 1.01
5222 reflections
328 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.45 e Å⁻³
Absolute structure: Flack (1983 ), 2514 Friedel pairs
Absolute structure parameter: 0.581 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S2ⁱ	0.86	2.45	3.309 (3)	176
N5—H5A⋯S1ⁱⁱ	0.86	2.44	3.302 (3)	177
O1—H1A⋯N4	0.82	2.02	2.712 (4)	141
O2—H2⋯N8	0.82	1.99	2.695 (4)	143
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

CCDC reference: 1015277

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814016833/fy2115sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814016833/fy2115Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814016833/fy2115Isup3.cml

checkCIF report

Comment top

Recently, 1,2,4-triazoles and their derivatives have been the focus of a great deal of attention owing to their effective biological activities such as antimicrobial, antiviral, analgesic, anti-inflammatory, anticancer and antioxidant properties (Demirbas et al., 2004 and 2009; Kochikyan et al., 2011; Kumar et al., 2008; Singhal et al., 2011; Todoulou et al., 1994). As a result, a number of attempts were made to improve the activity of these compounds by varying the substituents on the 1,2,4-triazole nucleus (Popiołek et al., 2013; Sraa et al., 2012). Among these, the amino- and mercapto-group substituted 1,2,4-triazole ring systems represent an important group of compounds that are promising for practical application. Therefore, the title compound (I), has been synthesized and its crystal structure has been determinined.

The crystal structure is illustrated in Fig. 1. The title compound (I) crystallizes in the monoclinic space group P2₁ with two symmetry-independent molecules in the unit cell. The bond lengths of N4–C5 [1.274 (5) Å] and N8–C16 [1.272 (5) Å] confirm them as double bonds, which is similar to those reported in other Schiff bases (Pannu et al., 2011; Wu et al., 2012;). The molecule of (I) exists in the thione tautometic form, with C═S distances of 1.673 (4) and 1.672 (4) Å, which indicates a substantial double-bond character (Allen et al., 1987).

The packing arrangement in the crystal structure of (I) is shown in Fig. 2. As a common feature of o-hydroxysalicylidene systems, the azomethine group in title compound forms intramolecular O–H···N hydrogen bonds with the neighbouring hydroxyl groups. Moreover, the crystal structure also contains intermolecular N–H···S hydrogen bonds between both independent molecules with cyclic motifs [graph set R₂²(8)] (Bernstein et al., 1995). The molecules are further linked via weak π-π interactions between benzene rings (Cg1 and Cg2). The hydrogen bonds and π-π interactions link the molecules into ribbon structures.

Related literature top

For background to the biological activity of related compounds, see: Demirbas (2004); Demirbas et al. (2009);Todoulou et al. (1994); Kumar et al. (2008); Kochikyan et al. (2011); Singhal et al. (2011); Popiołek et al. (2013); Sraa (2012). For similar structures, see: Wu et al. (2012); Pannu & Hundal (2011). For standard bond lengths, see: Allen et al. (1987). For graph-sets of hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

The title compound was synthesized by condensation of 4-amino-3-ethyl- 1H-1,2,4-triazole-5(4H)-thione and 5-Br-salicylaldehyde. 0.5 mmol of 4-amino-3-ethyl-1,2,4-triazole-5-thione was thoroughly dissolved in 20 ml of ethanol with a constant stirring at 353 K. Then 0.5 mmol of 5-bromosalicylaldehyde in 10 ml ethanol was added dropwise to a solution of the above. The mixture was further refluxed for 2 h. The resulting yellow solution was filtered and the filtrate was left to stand at room temperature. The yellow crystals of compound (I) were received from the filtrate with slowly evaporating the solvent for a few days. Yield: 78%. Anal. Calcd. for C₁₁H₁₁BrN₄OS: C 40.38, H 3.39, N 17.12%. Found: C 40.31, H 3.45, N 17.07%. IR (ν/cm^-1): 3109, 3055, 2958, 1603, 1588, 1513, 1416, 1352, 1288, 1165, 1174, 967, 817, 627. UV/vis in DMSO, λ_max/nm (ε 10³/M^-1 cm^-1): 265(13.9), 343(7.77).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. View of the structure with displacement ellipsoids drawn at the 30% probability level. Dotted lines represent hydrogen bonds and π–π interactions.
	Fig. 2. A part of the crystal structure, showing the formation of a chain of R₂²(8) hydrogen-bonded rings and π-π stacking between the benzene rings rings; Cg1: C6/C7/C8/C9/C10/C11, Cg2: C17/C18/C19/C20/C21/C22. Symmetry codes: i) x - 1, y. z + 1; ii) x + 1, y, z - 1. H atoms without H-bonds have been omitted for clarity.

4-[(5-Bromo-2-hydroxybenzylidene)amino]-3-ethyl-1H-1,2,4-triazole-5(4H)-thione top

Crystal data top

C₁₁H₁₁BrN₄OS	F(000) = 656
M_r = 327.21	D_x = 1.676 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4187 reflections
a = 6.323 (4) Å	θ = 2.5–25.3°
b = 16.459 (11) Å	µ = 3.32 mm⁻¹
c = 12.461 (8) Å	T = 298 K
β = 90.330 (9)°	Block, yellow
V = 1296.8 (15) Å³	0.40 × 0.35 × 0.30 mm
Z = 4

Data collection top

Bruker SMART APEXII diffractometer	5222 independent reflections
Radiation source: fine-focus sealed tube	4285 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 26.3°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −7→7
T_min = 0.350, T_max = 0.435	k = −20→20
14802 measured reflections	l = −15→15

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)] = 0.031	H-atom parameters constrained
wR(F²) = 0.065	w = 1/[σ²(F_o²) + (0.031P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
5222 reflections	Δρ_max = 0.28 e Å⁻³
328 parameters	Δρ_min = −0.45 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 2514 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.581 (7)

Crystal data top

C₁₁H₁₁BrN₄OS	V = 1296.8 (15) Å³
M_r = 327.21	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 6.323 (4) Å	µ = 3.32 mm⁻¹
b = 16.459 (11) Å	T = 298 K
c = 12.461 (8) Å	0.40 × 0.35 × 0.30 mm
β = 90.330 (9)°

Data collection top

Bruker SMART APEXII diffractometer	5222 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	4285 reflections with I > 2σ(I)
T_min = 0.350, T_max = 0.435	R_int = 0.033
14802 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.065	Δρ_max = 0.28 e Å⁻³
S = 1.01	Δρ_min = −0.45 e Å⁻³
5222 reflections	Absolute structure: Flack (1983), 2514 Friedel pairs
328 parameters	Absolute structure parameter: 0.581 (7)
1 restraint

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
Br1	0.19835 (6)	0.61341 (2)	−0.42475 (3)	0.05443 (12)
S1	0.10279 (14)	0.43885 (6)	0.11498 (7)	0.0394 (2)
O1	0.8327 (4)	0.49113 (17)	−0.10062 (19)	0.0511 (7)
H1A	0.8001	0.5035	−0.0391	0.077*
N1	0.2852 (5)	0.50342 (19)	0.2940 (2)	0.0425 (8)
H1	0.1906	0.4848	0.3368	0.051*
N2	0.4568 (5)	0.5484 (2)	0.3291 (2)	0.0423 (8)
N3	0.4567 (4)	0.53213 (17)	0.1540 (2)	0.0313 (7)
N4	0.5457 (4)	0.53192 (18)	0.0511 (2)	0.0360 (7)
C1	0.2787 (5)	0.4913 (2)	0.1880 (3)	0.0325 (8)
C2	0.5590 (5)	0.5653 (2)	0.2428 (3)	0.0337 (8)
C3	0.7562 (6)	0.6128 (3)	0.2360 (3)	0.0438 (9)
H3A	0.7331	0.6594	0.1898	0.053*
H3B	0.8655	0.5795	0.2039	0.053*
C4	0.8317 (7)	0.6420 (2)	0.3461 (3)	0.0529 (11)
H4A	0.7232	0.6744	0.3786	0.079*
H4B	0.9574	0.6741	0.3380	0.079*
H4C	0.8619	0.5960	0.3909	0.079*
C5	0.4165 (6)	0.5478 (2)	−0.0249 (3)	0.0332 (8)
H5	0.2777	0.5616	−0.0087	0.040*
C6	0.4824 (5)	0.5449 (2)	−0.1370 (3)	0.0305 (8)
C7	0.6786 (5)	0.5157 (2)	−0.1695 (3)	0.0343 (8)
C8	0.7249 (6)	0.5113 (2)	−0.2784 (3)	0.0404 (10)
H8	0.8531	0.4893	−0.3004	0.048*
C9	0.5816 (6)	0.5393 (2)	−0.3542 (3)	0.0390 (9)
H9	0.6142	0.5370	−0.4268	0.047*
C10	0.3887 (6)	0.5707 (2)	−0.3211 (3)	0.0362 (9)
C11	0.3376 (6)	0.5723 (2)	−0.2137 (3)	0.0342 (8)
H11	0.2063	0.5917	−0.1923	0.041*
Br2	0.85545 (7)	0.24611 (3)	0.99904 (3)	0.06106 (14)
S2	0.93822 (14)	0.42617 (6)	0.46355 (7)	0.0375 (2)
O2	0.2087 (4)	0.36500 (17)	0.6796 (2)	0.0480 (8)
H2	0.2556	0.3672	0.6184	0.072*
N5	0.7520 (5)	0.36383 (19)	0.2834 (2)	0.0390 (8)
H5A	0.8466	0.3827	0.2409	0.047*
N6	0.5811 (5)	0.3204 (2)	0.2478 (2)	0.0401 (8)
N7	0.5821 (4)	0.33383 (18)	0.4232 (2)	0.0314 (7)
N8	0.4955 (4)	0.33164 (19)	0.5266 (2)	0.0321 (7)
C12	0.7603 (5)	0.3746 (2)	0.3909 (3)	0.0319 (8)
C13	0.4769 (5)	0.3032 (2)	0.3348 (3)	0.0315 (8)
C14	0.2795 (5)	0.2556 (2)	0.3413 (3)	0.0400 (8)
H14A	0.1713	0.2884	0.3750	0.048*
H14B	0.3037	0.2083	0.3863	0.048*
C15	0.1996 (6)	0.2275 (2)	0.2317 (3)	0.0472 (10)
H15A	0.1887	0.2735	0.1845	0.071*
H15B	0.0630	0.2028	0.2393	0.071*
H15C	0.2967	0.1887	0.2023	0.071*
C16	0.6252 (6)	0.3124 (2)	0.6007 (3)	0.0353 (9)
H16	0.7633	0.2985	0.5832	0.042*
C17	0.5601 (6)	0.3117 (2)	0.7123 (3)	0.0328 (8)
C18	0.3609 (6)	0.3392 (2)	0.7470 (3)	0.0361 (9)
C19	0.3173 (6)	0.3417 (2)	0.8567 (3)	0.0443 (9)
H19	0.1881	0.3620	0.8797	0.053*
C20	0.4612 (6)	0.3147 (2)	0.9307 (3)	0.0462 (10)
H20	0.4296	0.3165	1.0034	0.055*
C21	0.6543 (6)	0.2846 (2)	0.8971 (3)	0.0423 (9)
C22	0.7078 (6)	0.2850 (2)	0.7897 (3)	0.0403 (9)
H22	0.8411	0.2675	0.7685	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0537 (2)	0.0799 (3)	0.02963 (19)	0.0011 (2)	−0.00409 (16)	0.0045 (2)
S1	0.0403 (5)	0.0497 (6)	0.0281 (4)	−0.0051 (4)	0.0038 (4)	0.0017 (4)
O1	0.0457 (16)	0.074 (2)	0.0334 (14)	0.0183 (14)	0.0076 (12)	0.0048 (14)
N1	0.0402 (18)	0.064 (2)	0.0238 (16)	−0.0095 (16)	0.0092 (13)	0.0011 (15)
N2	0.0442 (18)	0.058 (2)	0.0251 (15)	−0.0021 (16)	0.0042 (14)	−0.0043 (14)
N3	0.0337 (16)	0.0378 (18)	0.0226 (15)	0.0022 (14)	0.0057 (12)	0.0023 (13)
N4	0.0364 (17)	0.047 (2)	0.0252 (16)	0.0010 (14)	0.0102 (13)	0.0031 (14)
C1	0.034 (2)	0.036 (2)	0.0277 (19)	0.0065 (16)	0.0038 (15)	0.0053 (15)
C2	0.035 (2)	0.036 (2)	0.0300 (19)	0.0093 (16)	0.0040 (15)	−0.0019 (15)
C3	0.047 (2)	0.044 (2)	0.041 (2)	−0.002 (2)	0.0050 (16)	0.003 (2)
C4	0.062 (3)	0.047 (3)	0.049 (2)	−0.013 (2)	−0.008 (2)	0.0012 (19)
C5	0.0341 (19)	0.033 (2)	0.033 (2)	0.0020 (16)	0.0075 (16)	0.0027 (16)
C6	0.0342 (19)	0.031 (2)	0.0260 (18)	−0.0051 (16)	0.0071 (15)	0.0024 (15)
C7	0.036 (2)	0.035 (2)	0.0315 (19)	0.0044 (16)	0.0048 (16)	0.0009 (15)
C8	0.043 (2)	0.043 (2)	0.035 (2)	0.0007 (18)	0.0164 (19)	−0.0040 (17)
C9	0.048 (2)	0.047 (2)	0.0228 (18)	−0.0021 (19)	0.0103 (16)	−0.0042 (16)
C10	0.043 (2)	0.040 (2)	0.0249 (18)	−0.0066 (17)	0.0016 (16)	0.0001 (16)
C11	0.0327 (19)	0.043 (2)	0.0275 (19)	−0.0011 (16)	0.0046 (15)	−0.0031 (16)
Br2	0.0659 (3)	0.0819 (3)	0.0352 (2)	−0.0148 (2)	−0.01050 (19)	0.0139 (2)
S2	0.0369 (5)	0.0487 (6)	0.0268 (4)	−0.0048 (4)	0.0045 (4)	−0.0016 (4)
O2	0.0395 (16)	0.067 (2)	0.0380 (16)	0.0097 (14)	0.0065 (12)	0.0014 (14)
N5	0.0415 (19)	0.053 (2)	0.0224 (16)	−0.0015 (15)	0.0075 (13)	0.0009 (14)
N6	0.0423 (19)	0.055 (2)	0.0233 (16)	−0.0035 (16)	0.0007 (14)	−0.0044 (14)
N7	0.0297 (16)	0.0400 (18)	0.0248 (15)	0.0023 (14)	0.0068 (12)	−0.0010 (13)
N8	0.0317 (16)	0.0435 (19)	0.0213 (16)	−0.0013 (14)	0.0081 (13)	−0.0012 (13)
C12	0.0308 (19)	0.042 (2)	0.0233 (17)	0.0038 (16)	0.0039 (14)	0.0010 (15)
C13	0.034 (2)	0.037 (2)	0.0237 (18)	0.0016 (16)	−0.0003 (15)	−0.0048 (15)
C14	0.0397 (19)	0.043 (2)	0.0373 (19)	−0.0010 (18)	0.0062 (15)	−0.0065 (17)
C15	0.054 (2)	0.041 (3)	0.047 (2)	−0.0062 (19)	−0.0110 (19)	−0.0010 (19)
C16	0.042 (2)	0.038 (2)	0.0264 (19)	0.0009 (17)	0.0117 (17)	0.0011 (16)
C17	0.039 (2)	0.034 (2)	0.0251 (18)	−0.0053 (16)	0.0059 (15)	0.0012 (15)
C18	0.043 (2)	0.033 (2)	0.032 (2)	−0.0094 (17)	0.0074 (17)	−0.0015 (16)
C19	0.049 (2)	0.052 (2)	0.032 (2)	−0.0018 (19)	0.0139 (18)	−0.0057 (18)
C20	0.059 (3)	0.053 (3)	0.0261 (19)	−0.015 (2)	0.0159 (18)	−0.0049 (17)
C21	0.053 (2)	0.049 (2)	0.0247 (18)	−0.0162 (19)	−0.0019 (17)	0.0030 (16)
C22	0.041 (2)	0.043 (2)	0.037 (2)	0.0005 (18)	0.0072 (17)	0.0034 (17)

Geometric parameters (Å, º) top

Br1—C10	1.896 (4)	Br2—C21	1.901 (4)
S1—C1	1.673 (4)	S2—C12	1.672 (4)
O1—C7	1.356 (4)	O2—C18	1.343 (4)
O1—H1A	0.8200	O2—H2	0.8200
N1—C1	1.336 (4)	N5—C12	1.352 (4)
N1—N2	1.383 (4)	N5—N6	1.367 (4)
N1—H1	0.8600	N5—H5A	0.8600
N2—C2	1.288 (4)	N6—C13	1.303 (4)
N3—C1	1.380 (4)	N7—C12	1.374 (4)
N3—C2	1.391 (4)	N7—C13	1.379 (4)
N3—N4	1.403 (4)	N7—N8	1.404 (4)
N4—C5	1.275 (4)	N8—C16	1.271 (4)
C2—C3	1.474 (5)	C13—C14	1.476 (5)
C3—C4	1.527 (5)	C14—C15	1.525 (5)
C3—H3A	0.9700	C14—H14A	0.9700
C3—H3B	0.9700	C14—H14B	0.9700
C4—H4A	0.9600	C15—H15A	0.9600
C4—H4B	0.9600	C15—H15B	0.9600
C4—H4C	0.9600	C15—H15C	0.9600
C5—C6	1.461 (5)	C16—C17	1.453 (5)
C5—H5	0.9300	C16—H16	0.9300
C6—C7	1.393 (5)	C17—C18	1.408 (5)
C6—C11	1.394 (5)	C17—C22	1.409 (5)
C7—C8	1.392 (5)	C18—C19	1.396 (5)
C8—C9	1.384 (5)	C19—C20	1.366 (5)
C8—H8	0.9300	C19—H19	0.9300
C9—C10	1.390 (5)	C20—C21	1.384 (5)
C9—H9	0.9300	C20—H20	0.9300
C10—C11	1.379 (5)	C21—C22	1.382 (5)
C11—H11	0.9300	C22—H22	0.9300

C7—O1—H1A	109.5	C18—O2—H2	109.5
C1—N1—N2	114.3 (3)	C12—N5—N6	114.6 (3)
C1—N1—H1	122.8	C12—N5—H5A	122.7
N2—N1—H1	122.8	N6—N5—H5A	122.7
C2—N2—N1	104.4 (3)	C13—N6—N5	104.3 (3)
C1—N3—C2	108.9 (3)	C12—N7—C13	109.7 (3)
C1—N3—N4	127.7 (3)	C12—N7—N8	127.4 (3)
C2—N3—N4	122.8 (3)	C13—N7—N8	122.3 (3)
C5—N4—N3	114.8 (3)	C16—N8—N7	114.8 (3)
N1—C1—N3	102.2 (3)	N5—C12—N7	101.5 (3)
N1—C1—S1	129.1 (3)	N5—C12—S2	128.7 (3)
N3—C1—S1	128.7 (3)	N7—C12—S2	129.8 (3)
N2—C2—N3	110.2 (3)	N6—C13—N7	109.9 (3)
N2—C2—C3	126.3 (3)	N6—C13—C14	126.4 (3)
N3—C2—C3	123.5 (3)	N7—C13—C14	123.7 (3)
C2—C3—C4	112.1 (3)	C13—C14—C15	112.8 (3)
C2—C3—H3A	109.2	C13—C14—H14A	109.0
C4—C3—H3A	109.2	C15—C14—H14A	109.0
C2—C3—H3B	109.2	C13—C14—H14B	109.0
C4—C3—H3B	109.2	C15—C14—H14B	109.0
H3A—C3—H3B	107.9	H14A—C14—H14B	107.8
C3—C4—H4A	109.5	C14—C15—H15A	109.5
C3—C4—H4B	109.5	C14—C15—H15B	109.5
H4A—C4—H4B	109.5	H15A—C15—H15B	109.5
C3—C4—H4C	109.5	C14—C15—H15C	109.5
H4A—C4—H4C	109.5	H15A—C15—H15C	109.5
H4B—C4—H4C	109.5	H15B—C15—H15C	109.5
N4—C5—C6	121.3 (3)	N8—C16—C17	120.8 (3)
N4—C5—H5	119.4	N8—C16—H16	119.6
C6—C5—H5	119.4	C17—C16—H16	119.6
C7—C6—C11	119.7 (3)	C18—C17—C22	118.7 (3)
C7—C6—C5	123.2 (3)	C18—C17—C16	123.3 (3)
C11—C6—C5	117.0 (3)	C22—C17—C16	117.9 (3)
O1—C7—C8	116.6 (3)	O2—C18—C19	117.3 (3)
O1—C7—C6	123.9 (3)	O2—C18—C17	123.3 (3)
C8—C7—C6	119.6 (3)	C19—C18—C17	119.4 (4)
C9—C8—C7	120.5 (3)	C20—C19—C18	121.1 (4)
C9—C8—H8	119.7	C20—C19—H19	119.4
C7—C8—H8	119.7	C18—C19—H19	119.4
C8—C9—C10	119.6 (3)	C19—C20—C21	119.8 (3)
C8—C9—H9	120.2	C19—C20—H20	120.1
C10—C9—H9	120.2	C21—C20—H20	120.1
C11—C10—C9	120.4 (3)	C22—C21—C20	120.8 (4)
C11—C10—Br1	120.2 (3)	C22—C21—Br2	118.8 (3)
C9—C10—Br1	119.4 (3)	C20—C21—Br2	120.3 (3)
C10—C11—C6	120.1 (3)	C21—C22—C17	119.9 (3)
C10—C11—H11	119.9	C21—C22—H22	120.0
C6—C11—H11	119.9	C17—C22—H22	120.0

C1—N1—N2—C2	0.5 (4)	C12—N5—N6—C13	0.2 (4)
C1—N3—N4—C5	51.3 (5)	C12—N7—N8—C16	−51.8 (5)
C2—N3—N4—C5	−139.1 (4)	C13—N7—N8—C16	138.0 (4)
N2—N1—C1—N3	−0.7 (4)	N6—N5—C12—N7	0.7 (4)
N2—N1—C1—S1	178.4 (3)	N6—N5—C12—S2	−177.9 (3)
C2—N3—C1—N1	0.6 (4)	C13—N7—C12—N5	−1.3 (4)
N4—N3—C1—N1	171.4 (3)	N8—N7—C12—N5	−172.5 (3)
C2—N3—C1—S1	−178.5 (3)	C13—N7—C12—S2	177.3 (3)
N4—N3—C1—S1	−7.7 (5)	N8—N7—C12—S2	6.1 (5)
N1—N2—C2—N3	−0.1 (4)	N5—N6—C13—N7	−1.0 (4)
N1—N2—C2—C3	179.9 (3)	N5—N6—C13—C14	−179.0 (3)
C1—N3—C2—N2	−0.4 (4)	C12—N7—C13—N6	1.6 (4)
N4—N3—C2—N2	−171.7 (3)	N8—N7—C13—N6	173.3 (3)
C1—N3—C2—C3	179.7 (3)	C12—N7—C13—C14	179.6 (3)
N4—N3—C2—C3	8.3 (5)	N8—N7—C13—C14	−8.7 (5)
N2—C2—C3—C4	−0.3 (6)	N6—C13—C14—C15	−1.0 (6)
N3—C2—C3—C4	179.6 (3)	N7—C13—C14—C15	−178.7 (3)
N3—N4—C5—C6	−176.1 (3)	N7—N8—C16—C17	176.8 (3)
N4—C5—C6—C7	7.9 (6)	N8—C16—C17—C18	−6.3 (6)
N4—C5—C6—C11	−172.8 (3)	N8—C16—C17—C22	176.1 (3)
C11—C6—C7—O1	177.0 (3)	C22—C17—C18—O2	−179.2 (3)
C5—C6—C7—O1	−3.7 (6)	C16—C17—C18—O2	3.3 (6)
C11—C6—C7—C8	−2.4 (5)	C22—C17—C18—C19	2.0 (6)
C5—C6—C7—C8	176.9 (3)	C16—C17—C18—C19	−175.6 (4)
O1—C7—C8—C9	−176.4 (3)	O2—C18—C19—C20	178.4 (4)
C6—C7—C8—C9	3.1 (6)	C17—C18—C19—C20	−2.8 (6)
C7—C8—C9—C10	−1.1 (6)	C18—C19—C20—C21	0.3 (6)
C8—C9—C10—C11	−1.6 (6)	C19—C20—C21—C22	3.0 (6)
C8—C9—C10—Br1	177.2 (3)	C19—C20—C21—Br2	−179.5 (3)
C9—C10—C11—C6	2.2 (6)	C20—C21—C22—C17	−3.7 (6)
Br1—C10—C11—C6	−176.5 (3)	Br2—C21—C22—C17	178.8 (3)
C7—C6—C11—C10	−0.2 (5)	C18—C17—C22—C21	1.2 (5)
C5—C6—C11—C10	−179.5 (3)	C16—C17—C22—C21	178.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S2ⁱ	0.86	2.45	3.309 (3)	176
N5—H5A···S1ⁱⁱ	0.86	2.44	3.302 (3)	177
O1—H1A···N4	0.82	2.02	2.712 (4)	141
O2—H2···N8	0.82	1.99	2.695 (4)	143

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S2ⁱ	0.86	2.45	3.309 (3)	176.4
N5—H5A···S1ⁱⁱ	0.86	2.44	3.302 (3)	177.4
O1—H1A···N4	0.82	2.02	2.712 (4)	141.4
O2—H2···N8	0.82	1.99	2.695 (4)	143.2

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z.

Acknowledgements

The authors acknowledge the National Natural Science Foundation of China (grant Nos. 21001070 and 21271121) and the Province Natural Science Foundation of Shanxi Province of China (grant No. 2011021006–2).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orapen, G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Demirbas, N. (2004). Eur. J. Med. Chem. 39, 793–804. Web of Science CrossRef PubMed CAS Google Scholar
Demirbas, A., Sahin, D., Demirbas, N. & Alpay-Karaoglu, S. (2009). Eur. J. Med. Chem. 44, 2896–2903. Web of Science CrossRef PubMed CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kochikyan, T. V., Samvelyan, M. A., Arutyunyan, E. V., Arutyunyan, V. S., Avetisyan, A. A., Malakyan, M. G., Vardevanyan, L. A. & Badzhinyan, S. A. (2011). Pharm. Chem. J. 44, 525–527. Web of Science CrossRef CAS Google Scholar
Kumar, H., Javed, A. S., Khan, A. S. & Amir, M. (2008). Eur. J. Med. Chem. 43, 2688–2698. Web of Science CrossRef PubMed CAS Google Scholar
Pannu, A. P. S. & Hundal, M. S. (2011). J. Chem. Crystallogr. 41, 1447–1450. Web of Science CSD CrossRef CAS Google Scholar
Popiołek, Ł., Kosikowska, U., Mazur, L., Dobosz, M. & Malm, A. (2013). Med. Chem. Res. 22, 3134–3147. PubMed Google Scholar
Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Singhal, N., Sharma, P. K., Dudhe, R. & Kumar, N. (2011). J. Chem. Pharm. Res. 3, 126–133. CAS Google Scholar
Sraa, A. M. (2012). Spectrochim. Acta A Mol. Biomol. Spectrosc. 96, 898–905. Web of Science PubMed Google Scholar
Todoulou, O., Papadaki-Valiraki, A., Ikeda, S. & De Clercq, E. (1994). Eur. J. Med. Chem. 29E, 611–620. CrossRef Web of Science Google Scholar
Wu, X., Yuan, C.-X., Ma, L., Zhai, K.-L. & Zhu, M.-L. (2012). Acta Cryst. E68, o1674. CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 8| August 2014| Pages o881-o882

doi:10.1107/S1600536814016833

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

4-[(5-Bromo-2-hy­dr­oxy­benzyl­­idene)amino]-3-ethyl-1H-1,2,4-triazole-5(4H)-thione

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-[(5-Bromo-2-hydroxybenzylidene)amino]-3-ethyl-1H-1,2,4-triazole-5(4H)-thione