(2E)-2-(5-Bromo-2-hy-droxy-3-meth-oxy-benzyl-idene)-N-phenyl-hydrazine-carbo-thio-amide.

The title compound, C(15)H(14)BrN(3)O(2)S, adopts an E,E conformation with respect to the azomethine and hydrazinic bonds and exists in the thio-amide form. The two rings in the mol-ecule are twisted away from each other, making a dihedral angle of 69.13 (13)°. In the crystal, mol-ecules are linked through pairs of N-H⋯O and O-H⋯S hydrogen bonds, leading to the formation of inversion dimers which are stacked along the a axis. Intra-molecular N-H⋯N, O-H⋯O and C-H⋯π inter-actions are also present.

Related literature

For applications of hydrazinecarbothio­amide and its derivatives, see: Barber et al. (1992 ▶); Parrilha et al. (2011 ▶). For the synthesis, see: Joseph et al. (2006 ▶). For related structures, see: Dutta et al. (1997 ▶); Seena et al. (2006 ▶, 2008 ▶); Nisha et al. (2011 ▶); Jacob & Kurup (2012 ▶). For C=S and C=N double-bond lengths, see: Allen et al. (1987) ▶.

Experimental

Crystal data

C15H14BrN3O2S

M = 380.26

Triclinic,

a = 6.1046 (5) Å

b = 11.0329 (8) Å

c = 12.4303 (9) Å

α = 101.175 (3)°

β = 91.323 (2)°

γ = 104.759 (2)°

V = 791.91 (10) Å3

Z = 2

Mo Kα radiation

μ = 2.74 mm−1

T = 296 K

0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.399, T max = 0.504

11624 measured reflections

2774 independent reflections

2338 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.068

S = 1.01

2774 reflections

212 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.44 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812022520/fj2553sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812022520/fj2553Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812022520/fj2553Isup3.cml

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

C15H14BrN3O2S	Z = 2
Mr = 380.26	F(000) = 384.0
Triclinic, P1	Dx = 1.595 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1046 (5) Å	Cell parameters from 4882 reflections
b = 11.0329 (8) Å	θ = 2.8–25.9°
c = 12.4303 (9) Å	µ = 2.74 mm−1
α = 101.175 (3)°	T = 296 K
β = 91.323 (2)°	Block, yellow
γ = 104.759 (2)°	0.35 × 0.30 × 0.25 mm
V = 791.91 (10) Å3

Bruker Kappa APEXII CCD diffractometer	2774 independent reflections
Radiation source: fine-focus sealed tube	2338 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 8.33 pixels mm-1	θmax = 25.0°, θmin = 2.8°
ω and φ scan	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −13→13
Tmin = 0.399, Tmax = 0.504	l = −14→14
11624 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0256P)2 + 0.4209P] where P = (Fo2 + 2Fc2)/3
2774 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.40 e Å−3
3 restraints	Δρmin = −0.44 e Å−3

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	1.28630 (5)	0.08118 (3)	0.45166 (3)	0.05852 (12)
S1	0.16123 (11)	0.32832 (7)	0.12714 (5)	0.05073 (19)
O1	1.1158 (3)	0.42448 (18)	0.77355 (13)	0.0518 (5)
O2	0.8043 (3)	0.47160 (18)	0.65009 (14)	0.0457 (4)
N1	0.6514 (3)	0.31281 (18)	0.32779 (15)	0.0366 (5)
N2	0.4670 (4)	0.3403 (2)	0.28201 (16)	0.0416 (5)
N3	0.5318 (4)	0.2386 (2)	0.11374 (17)	0.0454 (5)
C1	0.9885 (4)	0.2399 (2)	0.44657 (19)	0.0373 (5)
H1	0.9594	0.2004	0.3726	0.045*
C2	1.1446 (4)	0.2114 (2)	0.5112 (2)	0.0391 (6)
C3	1.1985 (4)	0.2702 (2)	0.6213 (2)	0.0421 (6)
H3	1.3079	0.2503	0.6629	0.051*
C4	1.0856 (4)	0.3588 (2)	0.66732 (19)	0.0380 (5)
C5	0.9203 (4)	0.3875 (2)	0.60356 (19)	0.0347 (5)
C6	0.8726 (4)	0.3296 (2)	0.49340 (18)	0.0330 (5)
C7	0.6955 (4)	0.3582 (2)	0.43026 (18)	0.0364 (5)
H7	0.6119	0.4114	0.4660	0.044*
C8	0.3980 (4)	0.2983 (2)	0.17484 (19)	0.0372 (5)
C9	0.4879 (4)	0.1782 (2)	0.00017 (19)	0.0389 (6)
C10	0.2884 (5)	0.0890 (3)	−0.0380 (2)	0.0575 (8)
H10	0.1770	0.0683	0.0101	0.069*
C11	0.2513 (5)	0.0295 (3)	−0.1473 (2)	0.0637 (8)
H11	0.1133	−0.0299	−0.1728	0.076*
C12	0.4137 (5)	0.0565 (3)	−0.2185 (2)	0.0577 (8)
H12	0.3883	0.0155	−0.2922	0.069*
C13	0.6148 (6)	0.1446 (4)	−0.1802 (2)	0.0722 (10)
H13	0.7274	0.1633	−0.2282	0.087*
C14	0.6525 (5)	0.2064 (3)	−0.0708 (2)	0.0616 (8)
H14	0.7893	0.2669	−0.0456	0.074*
C15	1.2722 (5)	0.3963 (3)	0.8467 (2)	0.0618 (8)
H15A	1.2241	0.3073	0.8500	0.093*
H15B	1.2761	0.4477	0.9188	0.093*
H15C	1.4211	0.4150	0.8203	0.093*
H3'	0.653 (3)	0.240 (3)	0.146 (2)	0.055 (8)*
H2	0.389 (4)	0.380 (2)	0.3232 (19)	0.046 (8)*
H2'	0.856 (5)	0.507 (3)	0.7130 (17)	0.072 (10)*

	U11	U22	U33	U12	U13	U23
Br1	0.0572 (2)	0.05035 (17)	0.0776 (2)	0.03025 (13)	0.01961 (15)	0.01303 (14)
S1	0.0438 (4)	0.0760 (5)	0.0333 (3)	0.0295 (3)	−0.0088 (3)	−0.0032 (3)
O1	0.0632 (12)	0.0653 (12)	0.0328 (9)	0.0318 (9)	−0.0119 (8)	0.0058 (9)
O2	0.0525 (11)	0.0583 (11)	0.0301 (9)	0.0324 (9)	−0.0068 (8)	−0.0039 (8)
N1	0.0374 (11)	0.0452 (11)	0.0296 (11)	0.0165 (9)	−0.0017 (8)	0.0066 (9)
N2	0.0406 (12)	0.0588 (13)	0.0292 (11)	0.0268 (10)	−0.0020 (9)	0.0006 (10)
N3	0.0448 (13)	0.0649 (14)	0.0293 (11)	0.0278 (11)	−0.0056 (10)	0.0002 (10)
C1	0.0396 (14)	0.0383 (13)	0.0334 (13)	0.0114 (10)	0.0044 (11)	0.0045 (11)
C2	0.0381 (13)	0.0375 (13)	0.0467 (15)	0.0172 (10)	0.0074 (11)	0.0104 (11)
C3	0.0392 (14)	0.0457 (14)	0.0469 (15)	0.0167 (11)	−0.0028 (11)	0.0156 (12)
C4	0.0415 (14)	0.0429 (13)	0.0308 (13)	0.0129 (11)	−0.0038 (10)	0.0090 (11)
C5	0.0345 (13)	0.0379 (12)	0.0343 (13)	0.0145 (10)	0.0015 (10)	0.0075 (10)
C6	0.0315 (12)	0.0378 (12)	0.0308 (12)	0.0112 (10)	0.0003 (10)	0.0072 (10)
C7	0.0389 (13)	0.0415 (13)	0.0296 (12)	0.0162 (10)	−0.0015 (10)	0.0026 (10)
C8	0.0397 (14)	0.0424 (13)	0.0292 (12)	0.0135 (11)	−0.0024 (10)	0.0036 (10)
C9	0.0459 (15)	0.0467 (14)	0.0287 (12)	0.0245 (12)	−0.0014 (11)	0.0027 (11)
C10	0.0643 (19)	0.0545 (17)	0.0432 (16)	0.0037 (14)	0.0135 (14)	−0.0002 (14)
C11	0.066 (2)	0.0541 (17)	0.0534 (18)	0.0012 (15)	0.0036 (16)	−0.0103 (15)
C12	0.070 (2)	0.0685 (19)	0.0329 (14)	0.0286 (16)	−0.0015 (14)	−0.0053 (13)
C13	0.059 (2)	0.112 (3)	0.0384 (16)	0.0219 (19)	0.0125 (14)	−0.0017 (17)
C14	0.0383 (15)	0.092 (2)	0.0448 (16)	0.0143 (15)	−0.0023 (13)	−0.0035 (16)
C15	0.076 (2)	0.0678 (19)	0.0430 (16)	0.0209 (16)	−0.0209 (15)	0.0144 (14)

Br1—C2	1.900 (2)	C4—C5	1.404 (3)
S1—C8	1.682 (2)	C5—C6	1.384 (3)
O1—C4	1.361 (3)	C6—C7	1.454 (3)
O1—C15	1.434 (3)	C7—H7	0.9300
O2—C5	1.358 (3)	C9—C10	1.363 (4)
O2—H2'	0.819 (18)	C9—C14	1.369 (4)
N1—C7	1.270 (3)	C10—C11	1.376 (4)
N1—N2	1.376 (3)	C10—H10	0.9300
N2—C8	1.342 (3)	C11—C12	1.359 (4)
N2—H2	0.843 (17)	C11—H11	0.9300
N3—C8	1.337 (3)	C12—C13	1.365 (4)
N3—C9	1.427 (3)	C12—H12	0.9300
N3—H3'	0.830 (17)	C13—C14	1.383 (4)
C1—C2	1.366 (3)	C13—H13	0.9300
C1—C6	1.404 (3)	C14—H14	0.9300
C1—H1	0.9300	C15—H15A	0.9600
C2—C3	1.389 (3)	C15—H15B	0.9600
C3—C4	1.379 (3)	C15—H15C	0.9600
C3—H3	0.9300
C4—O1—C15	117.7 (2)	C6—C7—H7	119.0
C5—O2—H2'	112 (2)	N3—C8—N2	115.7 (2)
C7—N1—N2	114.91 (19)	N3—C8—S1	125.34 (18)
C8—N2—N1	122.0 (2)	N2—C8—S1	118.95 (18)
C8—N2—H2	118.8 (18)	C10—C9—C14	119.4 (2)
N1—N2—H2	119.1 (18)	C10—C9—N3	121.1 (2)
C8—N3—C9	126.3 (2)	C14—C9—N3	119.4 (2)
C8—N3—H3'	115 (2)	C9—C10—C11	120.3 (3)
C9—N3—H3'	118 (2)	C9—C10—H10	119.9
C2—C1—C6	119.1 (2)	C11—C10—H10	119.9
C2—C1—H1	120.4	C12—C11—C10	120.8 (3)
C6—C1—H1	120.4	C12—C11—H11	119.6
C1—C2—C3	122.6 (2)	C10—C11—H11	119.6
C1—C2—Br1	119.52 (18)	C11—C12—C13	119.0 (3)
C3—C2—Br1	117.78 (17)	C11—C12—H12	120.5
C4—C3—C2	118.3 (2)	C13—C12—H12	120.5
C4—C3—H3	120.8	C12—C13—C14	120.6 (3)
C2—C3—H3	120.8	C12—C13—H13	119.7
O1—C4—C3	126.1 (2)	C14—C13—H13	119.7
O1—C4—C5	113.7 (2)	C9—C14—C13	119.8 (3)
C3—C4—C5	120.2 (2)	C9—C14—H14	120.1
O2—C5—C6	119.51 (19)	C13—C14—H14	120.1
O2—C5—C4	120.0 (2)	O1—C15—H15A	109.5
C6—C5—C4	120.5 (2)	O1—C15—H15B	109.5
C5—C6—C1	119.2 (2)	H15A—C15—H15B	109.5
C5—C6—C7	119.2 (2)	O1—C15—H15C	109.5
C1—C6—C7	121.5 (2)	H15A—C15—H15C	109.5
N1—C7—C6	122.1 (2)	H15B—C15—H15C	109.5
N1—C7—H7	119.0
C7—N1—N2—C8	−179.5 (2)	C2—C1—C6—C7	−176.4 (2)
C6—C1—C2—C3	−1.7 (4)	N2—N1—C7—C6	174.8 (2)
C6—C1—C2—Br1	175.39 (17)	C5—C6—C7—N1	176.6 (2)
C1—C2—C3—C4	1.4 (4)	C1—C6—C7—N1	−6.6 (4)
Br1—C2—C3—C4	−175.76 (18)	C9—N3—C8—N2	175.5 (2)
C15—O1—C4—C3	−2.7 (4)	C9—N3—C8—S1	−6.8 (4)
C15—O1—C4—C5	176.6 (2)	N1—N2—C8—N3	−5.9 (4)
C2—C3—C4—O1	179.5 (2)	N1—N2—C8—S1	176.19 (18)
C2—C3—C4—C5	0.2 (4)	C8—N3—C9—C10	−52.8 (4)
O1—C4—C5—O2	−1.6 (3)	C8—N3—C9—C14	129.9 (3)
C3—C4—C5—O2	177.8 (2)	C14—C9—C10—C11	−1.2 (4)
O1—C4—C5—C6	179.1 (2)	N3—C9—C10—C11	−178.4 (3)
C3—C4—C5—C6	−1.5 (4)	C9—C10—C11—C12	1.4 (5)
O2—C5—C6—C1	−178.2 (2)	C10—C11—C12—C13	−0.5 (5)
C4—C5—C6—C1	1.2 (4)	C11—C12—C13—C14	−0.4 (5)
O2—C5—C6—C7	−1.2 (3)	C10—C9—C14—C13	0.2 (4)
C4—C5—C6—C7	178.1 (2)	N3—C9—C14—C13	177.5 (3)
C2—C1—C6—C5	0.4 (3)	C12—C13—C14—C9	0.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3′···N1	0.83 (2)	2.25 (3)	2.654 (3)	110 (2)
N2—H2···O2i	0.84 (2)	2.23 (2)	2.983 (3)	149 (2)
O2—H2′···O1	0.82 (2)	2.20 (3)	2.631 (2)	113 (3)
O2—H2′···S1i	0.82 (2)	2.44 (2)	3.1547 (18)	146 (3)
C15—H15A···Cg2ii	0.96	2.90	3.649 (3)	135
C7—H7···O2	0.93	2.44	2.764 (3)	101

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3′⋯N1	0.83 (2)	2.25 (3)	2.654 (3)	110 (2)
N2—H2⋯O2i	0.84 (2)	2.23 (2)	2.983 (3)	149 (2)
O2—H2′⋯O1	0.82 (2)	2.20 (3)	2.631 (2)	113 (3)
O2—H2′⋯S1i	0.82 (2)	2.44 (2)	3.1547 (18)	146 (3)
C15—H15A⋯Cg2ii	0.96	2.90	3.649 (3)	135

Symmetry codes: (i) ; (ii) .