4-(5-Bromo-2-hydroxy-benzyl-idene-amino)-3-methyl-1H-1,2,4-triazole-5(4H)-thione.

In the title compound, C(10)H(9)BrN(4)OS, the triazole ring forms a dihedral angle of 72.05 (14)° with the benzene ring. The conformation of the mol-ecule is stabilized by intra-molecular O-H⋯·N hydrogen bonding. The crystal packing is determined by inter-molecular N-H⋯S inter-actions, a short Br⋯S contact of 3.4464 (13) Å and π-π stacking of the triazole rings and of the benzene rings (centroid-centroid distances of 3.4109 and 3.569 Å, respectively).

Related literature

For related literature, see: Allen et al. (1987 ▶); Awad et al. (1991 ▶); Eweiss et al. (1986 ▶); Ji et al. (2002 ▶); Mohan (1983 ▶); Xu et al. (2002 ▶).

Experimental

Crystal data

C10H9BrN4OS

M = 313.18

Triclinic,

a = 6.9780 (8) Å

b = 7.1529 (8) Å

c = 12.3119 (14) Å

α = 83.561 (2)°

β = 88.820 (2)°

γ = 79.987 (2)°

V = 601.35 (12) Å3

Z = 2

Mo Kα radiation

μ = 3.58 mm−1

T = 293 (2) K

0.30 × 0.28 × 0.26 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (Blessing; 1995 ▶) T min = 0.404, T max = 0.519 (expected range = 0.307–0.394)

4340 measured reflections

2560 independent reflections

1977 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.111

S = 1.10

2560 reflections

161 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.59 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 2001 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062149/gk2112sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062149/gk2112Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C10H9BrN4OS	Z = 2
Mr = 313.18	F000 = 312
Triclinic, P1	Dx = 1.730 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 6.9780 (8) Å	Cell parameters from 1728 reflections
b = 7.1529 (8) Å	θ = 2.9–26.2º
c = 12.3119 (14) Å	µ = 3.58 mm−1
α = 83.561 (2)º	T = 293 (2) K
β = 88.820 (2)º	Plate, yellow
γ = 79.987 (2)º	0.30 × 0.28 × 0.26 mm
V = 601.35 (12) Å3

Bruker SMART CCD diffractometer	2560 independent reflections
Radiation source: fine-focus sealed tube	1977 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
T = 293(2) K	θmax = 27.0º
ω scans	θmin = 1.7º
Absorption correction: multi-scan(Blessing; 1995)	h = −8→8
Tmin = 0.404, Tmax = 0.519	k = −9→8
4340 measured reflections	l = −13→15

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.111	w = 1/[σ2(Fo2) + (0.0416P)2 + 0.455P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max = 0.001
2560 reflections	Δρmax = 0.42 e Å−3
161 parameters	Δρmin = −0.58 e Å−3
2 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq
Br1	0.79546 (7)	0.36351 (7)	0.64076 (4)	0.05088 (18)
C1	0.2803 (6)	0.3219 (6)	0.0688 (3)	0.0386 (9)
C2	0.5585 (6)	0.2362 (6)	−0.0218 (3)	0.0383 (9)
C3	0.7615 (6)	0.1524 (7)	−0.0409 (4)	0.0500 (11)
H3A	0.7832	0.1481	−0.1178	0.075*
H3B	0.7886	0.0253	−0.0038	0.075*
H3C	0.8457	0.2290	−0.0134	0.075*
C4	0.5834 (6)	0.2340 (6)	0.2504 (3)	0.0387 (9)
H4	0.5514	0.3663	0.2371	0.046*
C5	0.6609 (5)	0.1469 (6)	0.3552 (3)	0.0350 (9)
C6	0.6983 (5)	−0.0480 (6)	0.3857 (3)	0.0377 (9)
C7	0.7585 (6)	−0.1188 (6)	0.4911 (3)	0.0415 (10)
H7	0.7807	−0.2500	0.5114	0.050*
C8	0.7855 (6)	0.0030 (6)	0.5659 (3)	0.0422 (10)
H8	0.8259	−0.0456	0.6365	0.051*
C9	0.7521 (5)	0.2008 (6)	0.5355 (3)	0.0356 (9)
C10	0.6892 (6)	0.2752 (6)	0.4322 (3)	0.0384 (9)
H10	0.6654	0.4065	0.4126	0.046*
N1	0.4330 (5)	0.3251 (5)	−0.0963 (3)	0.0419 (8)
N2	0.2652 (5)	0.3746 (5)	−0.0387 (3)	0.0372 (8)
N3	0.4714 (5)	0.2332 (4)	0.0799 (3)	0.0355 (8)
N4	0.5586 (5)	0.1292 (5)	0.1755 (3)	0.0398 (8)
O1	0.6727 (5)	−0.1790 (4)	0.3183 (3)	0.0500 (8)
S1	0.10932 (16)	0.35060 (17)	0.16652 (9)	0.0457 (3)
H2	0.161 (5)	0.440 (6)	−0.069 (4)	0.069*
H1	0.640 (8)	−0.123 (7)	0.258 (2)	0.069*

	U11	U22	U33	U12	U13	U23
Br1	0.0587 (3)	0.0552 (3)	0.0373 (3)	−0.0031 (2)	−0.0109 (2)	−0.0079 (2)
C1	0.044 (2)	0.037 (2)	0.035 (2)	−0.0072 (18)	−0.0095 (18)	−0.0040 (18)
C2	0.043 (2)	0.033 (2)	0.041 (2)	−0.0098 (18)	−0.0050 (18)	−0.0098 (18)
C3	0.047 (3)	0.047 (3)	0.055 (3)	−0.004 (2)	−0.003 (2)	−0.005 (2)
C4	0.038 (2)	0.040 (2)	0.036 (2)	−0.0030 (18)	−0.0052 (17)	−0.0012 (18)
C5	0.0302 (19)	0.041 (2)	0.034 (2)	−0.0083 (17)	−0.0078 (16)	0.0013 (18)
C6	0.0279 (19)	0.033 (2)	0.047 (2)	0.0047 (16)	−0.0057 (17)	0.0024 (19)
C7	0.039 (2)	0.036 (2)	0.045 (2)	−0.0042 (18)	−0.0069 (19)	0.0075 (19)
C8	0.035 (2)	0.050 (3)	0.036 (2)	−0.0016 (19)	−0.0069 (17)	0.010 (2)
C9	0.0286 (19)	0.040 (2)	0.038 (2)	−0.0015 (16)	−0.0091 (16)	−0.0059 (18)
C10	0.038 (2)	0.033 (2)	0.039 (2)	0.0024 (17)	−0.0083 (18)	0.0067 (18)
N1	0.046 (2)	0.046 (2)	0.0337 (18)	−0.0062 (17)	−0.0059 (16)	−0.0034 (16)
N2	0.0391 (19)	0.0380 (19)	0.0325 (18)	−0.0021 (15)	−0.0100 (15)	−0.0007 (15)
N3	0.0396 (18)	0.0323 (18)	0.0345 (18)	−0.0054 (15)	−0.0119 (14)	−0.0024 (14)
N4	0.0440 (19)	0.0285 (17)	0.0389 (19)	0.0097 (14)	−0.0155 (15)	0.0086 (15)
O1	0.062 (2)	0.0376 (17)	0.0481 (19)	−0.0034 (15)	−0.0136 (16)	−0.0005 (15)
S1	0.0458 (6)	0.0541 (7)	0.0325 (6)	0.0015 (5)	−0.0055 (4)	0.0006 (5)

Br1—C9	1.898 (4)	C5—C10	1.431 (5)
C1—N2	1.336 (5)	C6—O1	1.356 (5)
C1—N3	1.375 (5)	C6—C7	1.385 (6)
C1—S1	1.681 (4)	C7—C8	1.373 (6)
C2—N1	1.312 (5)	C7—H7	0.9300
C2—N3	1.381 (5)	C8—C9	1.402 (6)
C2—C3	1.463 (6)	C8—H8	0.9300
C3—H3A	0.9600	C9—C10	1.372 (5)
C3—H3B	0.9600	C10—H10	0.9300
C3—H3C	0.9600	N1—N2	1.370 (5)
C4—N4	1.285 (5)	N2—H2	0.862 (19)
C4—C5	1.440 (5)	N3—N4	1.409 (4)
C4—H4	0.9300	O1—H1	0.821 (19)
C5—C6	1.383 (5)
N2—C1—N3	102.6 (3)	C8—C7—C6	120.5 (4)
N2—C1—S1	129.2 (3)	C8—C7—H7	119.7
N3—C1—S1	128.2 (3)	C6—C7—H7	119.7
N1—C2—N3	109.8 (4)	C7—C8—C9	119.9 (4)
N1—C2—C3	126.3 (4)	C7—C8—H8	120.1
N3—C2—C3	123.9 (4)	C9—C8—H8	120.1
C2—C3—H3A	109.5	C10—C9—C8	120.8 (4)
C2—C3—H3B	109.5	C10—C9—Br1	120.7 (3)
H3A—C3—H3B	109.5	C8—C9—Br1	118.4 (3)
C2—C3—H3C	109.5	C9—C10—C5	118.8 (4)
H3A—C3—H3C	109.5	C9—C10—H10	120.6
H3B—C3—H3C	109.5	C5—C10—H10	120.6
N4—C4—C5	120.0 (4)	C2—N1—N2	104.2 (3)
N4—C4—H4	120.0	C1—N2—N1	114.4 (3)
C5—C4—H4	120.0	C1—N2—H2	123 (3)
C6—C5—C10	119.7 (4)	N1—N2—H2	122 (3)
C6—C5—C4	124.2 (4)	C1—N3—C2	109.0 (3)
C10—C5—C4	116.0 (4)	C1—N3—N4	126.2 (3)
O1—C6—C5	123.4 (4)	C2—N3—N4	124.1 (3)
O1—C6—C7	116.3 (4)	C4—N4—N3	113.7 (3)
C5—C6—C7	120.3 (4)	C6—O1—H1	109 (4)
N4—C4—C5—C6	−5.4 (6)	C3—C2—N1—N2	179.5 (4)
N4—C4—C5—C10	178.1 (4)	N3—C1—N2—N1	0.2 (4)
C10—C5—C6—O1	179.1 (3)	S1—C1—N2—N1	−178.5 (3)
C4—C5—C6—O1	2.6 (6)	C2—N1—N2—C1	0.5 (4)
C10—C5—C6—C7	1.5 (6)	N2—C1—N3—C2	−0.7 (4)
C4—C5—C6—C7	−174.9 (4)	S1—C1—N3—C2	178.0 (3)
O1—C6—C7—C8	−179.0 (4)	N2—C1—N3—N4	−171.4 (3)
C5—C6—C7—C8	−1.3 (6)	S1—C1—N3—N4	7.3 (6)
C6—C7—C8—C9	0.0 (6)	N1—C2—N3—C1	1.1 (4)
C7—C8—C9—C10	1.2 (6)	C3—C2—N3—C1	−179.3 (4)
C7—C8—C9—Br1	−179.0 (3)	N1—C2—N3—N4	172.1 (3)
C8—C9—C10—C5	−0.9 (6)	C3—C2—N3—N4	−8.4 (6)
Br1—C9—C10—C5	179.2 (3)	C5—C4—N4—N3	176.5 (3)
C6—C5—C10—C9	−0.4 (6)	C1—N3—N4—C4	−71.7 (5)
C4—C5—C10—C9	176.3 (3)	C2—N3—N4—C4	118.9 (4)
N3—C2—N1—N2	−0.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1i	0.862 (19)	2.44 (2)	3.295 (3)	173 (5)
O1—H1···N4	0.821 (19)	1.97 (4)	2.676 (4)	144 (5)
O1—H1···N1ii	0.821 (19)	2.69 (5)	3.178 (5)	120 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1i	0.862 (19)	2.44 (2)	3.295 (3)	173 (5)
O1—H1⋯N4	0.821 (19)	1.97 (4)	2.676 (4)	144 (5)
O1—H1⋯N1ii	0.821 (19)	2.69 (5)	3.178 (5)	120 (5)

Symmetry codes: (i) ; (ii) .