(2E)-2-(5-Bromo-2-hy-droxy-3-meth-oxy-benzyl-idene)-N-cyclo-hexyl-hydrazine-carbothio-amide.

The title compound, C(15)H(20)BrN(3)O(2)S, crystallizes in the thio-amide form and adopts an E,E conformation with respect to the azomethine and hydrazinic bonds, respectively. The mol-ecules are paired through N-H⋯O and O-H⋯S hydrogen bonds, leading to the formation of centrosymmetric dimers in the crystal. These dimers are stacked along the a axis and are inter-connected through N-H⋯S hydrogen bonds to generate polymeric chains. The structure also features C-H⋯π interactions. An intra-molecular O-H⋯O bond is also present.

Related literature

For applications of hydrazinecarbothio­amide and its derivatives, see: Barber et al. (1992 ▶); Parrilha et al. (2011 ▶). For the synthesis, see: Klayman et al. (1979 ▶). For related structures, see: Dutta et al. (1997 ▶); Seena et al. (2006 ▶, 2008 ▶); Nisha et al. (2011 ▶). For standard bond-length data, see: Huheey et al. (1993 ▶); March (1992 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C15H20BrN3O2S

M = 386.31

Triclinic,

a = 5.7883 (4) Å

b = 11.412 (1) Å

c = 13.1312 (12) Å

α = 75.194 (4)°

β = 86.493 (3)°

γ = 83.489 (3)°

V = 832.72 (12) Å3

Z = 2

Mo Kα radiation

μ = 2.60 mm−1

T = 296 K

0.30 × 0.25 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.509, T max = 0.562

12149 measured reflections

2923 independent reflections

2521 reflections with I > 2σ(I)

R int = 0.070

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.098

S = 1.12

2923 reflections

213 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.41 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) global, I. DOI: 10.1107/S1600536812007039/fj2514sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007039/fj2514Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812007039/fj2514Isup3.cml

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

C15H20BrN3O2S	Z = 2
Mr = 386.31	F(000) = 396
Triclinic, P1	Dx = 1.541 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7883 (4) Å	Cell parameters from 6391 reflections
b = 11.412 (1) Å	θ = 2.7–27.9°
c = 13.1312 (12) Å	µ = 2.60 mm−1
α = 75.194 (4)°	T = 296 K
β = 86.493 (3)°	Block, colourless
γ = 83.489 (3)°	0.30 × 0.25 × 0.25 mm
V = 832.72 (12) Å3

Bruker APEXII CCD diffractometer	2923 independent reflections
Radiation source: fine-focus sealed tube	2521 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
Detector resolution: 8.33 pixels mm-1	θmax = 25.0°, θmin = 2.7°
ω and φ scan	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −13→13
Tmin = 0.509, Tmax = 0.562	l = −15→15
12149 measured reflections

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098	w = 1/[σ2(Fo2) + (0.0194P)2 + 0.6265P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max = 0.001
2923 reflections	Δρmax = 0.27 e Å−3
213 parameters	Δρmin = −0.41 e Å−3
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0142 (18)

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	−0.42662 (6)	0.51878 (3)	0.63154 (3)	0.05382 (17)
S1	0.75115 (13)	0.88705 (7)	0.80347 (7)	0.0448 (2)
O1	−0.1322 (4)	0.2029 (2)	0.97526 (18)	0.0520 (6)
O2	0.1901 (4)	0.3362 (2)	0.99890 (19)	0.0471 (6)
N1	0.2789 (4)	0.6672 (2)	0.8130 (2)	0.0377 (6)
N2	0.4703 (4)	0.7170 (2)	0.8316 (2)	0.0398 (6)
N3	0.3358 (5)	0.8967 (2)	0.7247 (2)	0.0407 (6)
C1	−0.0696 (5)	0.5340 (3)	0.7638 (2)	0.0384 (7)
H1	−0.0523	0.6089	0.7167	0.046*
C2	−0.2371 (5)	0.4647 (3)	0.7502 (2)	0.0391 (7)
C3	−0.2709 (5)	0.3530 (3)	0.8186 (2)	0.0405 (7)
H3	−0.3877	0.3081	0.8082	0.049*
C4	−0.1268 (5)	0.3105 (3)	0.9024 (2)	0.0379 (7)
C5	0.0459 (5)	0.3795 (3)	0.9177 (2)	0.0358 (7)
C6	0.0749 (5)	0.4910 (3)	0.8492 (2)	0.0360 (7)
C7	0.2600 (5)	0.5588 (3)	0.8659 (2)	0.0370 (7)
H7	0.3681	0.5218	0.9169	0.044*
C8	0.5028 (5)	0.8331 (3)	0.7839 (2)	0.0350 (7)
C9	0.3347 (5)	1.0238 (3)	0.6669 (2)	0.0387 (7)
H9	0.4949	1.0399	0.6439	0.046*
C10	0.1921 (7)	1.0438 (3)	0.5704 (3)	0.0517 (9)
H10A	0.0369	1.0206	0.5918	0.062*
H10B	0.2626	0.9922	0.5262	0.062*
C11	0.1758 (8)	1.1755 (4)	0.5079 (3)	0.0687 (11)
H11A	0.3286	1.1957	0.4788	0.082*
H11B	0.0734	1.1866	0.4496	0.082*
C12	0.0842 (8)	1.2596 (4)	0.5760 (4)	0.0710 (12)
H12A	−0.0747	1.2451	0.5992	0.085*
H12B	0.0838	1.3435	0.5351	0.085*
C13	0.2320 (7)	1.2397 (3)	0.6707 (3)	0.0602 (10)
H13A	0.1675	1.2930	0.7145	0.072*
H13B	0.3882	1.2601	0.6476	0.072*
C14	0.2423 (6)	1.1085 (3)	0.7344 (3)	0.0481 (8)
H14A	0.3423	1.0969	0.7936	0.058*
H14B	0.0878	1.0898	0.7620	0.058*
C15	−0.2900 (7)	0.1217 (3)	0.9629 (3)	0.0551 (9)
H15A	−0.4466	0.1577	0.9693	0.083*
H15B	−0.2659	0.0468	1.0165	0.083*
H15C	−0.2643	0.1055	0.8947	0.083*
H3'	0.211 (4)	0.866 (3)	0.723 (3)	0.041 (9)*
H2	0.576 (5)	0.672 (3)	0.868 (2)	0.040 (9)*
H2'	0.144 (6)	0.277 (2)	1.042 (2)	0.055 (11)*

	U11	U22	U33	U12	U13	U23
Br1	0.0582 (3)	0.0553 (3)	0.0480 (2)	−0.01859 (17)	−0.01714 (16)	−0.00386 (17)
S1	0.0339 (4)	0.0390 (5)	0.0610 (5)	−0.0161 (3)	−0.0082 (4)	−0.0048 (4)
O1	0.0655 (15)	0.0405 (13)	0.0502 (14)	−0.0291 (11)	−0.0122 (11)	0.0010 (11)
O2	0.0522 (14)	0.0394 (13)	0.0484 (14)	−0.0181 (11)	−0.0168 (11)	0.0008 (11)
N1	0.0335 (13)	0.0323 (14)	0.0491 (15)	−0.0107 (10)	−0.0055 (11)	−0.0096 (12)
N2	0.0335 (14)	0.0287 (14)	0.0568 (17)	−0.0083 (11)	−0.0134 (12)	−0.0050 (12)
N3	0.0372 (15)	0.0336 (14)	0.0506 (16)	−0.0158 (11)	−0.0100 (12)	−0.0019 (12)
C1	0.0387 (16)	0.0334 (16)	0.0433 (17)	−0.0078 (13)	−0.0013 (13)	−0.0081 (14)
C2	0.0411 (17)	0.0388 (17)	0.0390 (17)	−0.0107 (13)	−0.0054 (13)	−0.0088 (14)
C3	0.0400 (17)	0.0419 (18)	0.0435 (18)	−0.0168 (13)	−0.0023 (13)	−0.0123 (14)
C4	0.0413 (17)	0.0338 (16)	0.0396 (17)	−0.0147 (13)	0.0013 (13)	−0.0068 (13)
C5	0.0368 (16)	0.0323 (16)	0.0402 (17)	−0.0090 (12)	−0.0027 (13)	−0.0097 (13)
C6	0.0351 (16)	0.0311 (16)	0.0443 (17)	−0.0081 (12)	−0.0020 (13)	−0.0117 (13)
C7	0.0358 (16)	0.0312 (16)	0.0451 (18)	−0.0089 (12)	−0.0047 (13)	−0.0083 (14)
C8	0.0333 (15)	0.0342 (16)	0.0393 (17)	−0.0099 (12)	0.0014 (12)	−0.0103 (13)
C9	0.0399 (16)	0.0325 (16)	0.0429 (17)	−0.0129 (12)	−0.0049 (13)	−0.0030 (13)
C10	0.066 (2)	0.044 (2)	0.0432 (19)	−0.0136 (16)	−0.0122 (16)	−0.0028 (15)
C11	0.094 (3)	0.050 (2)	0.054 (2)	−0.014 (2)	−0.016 (2)	0.0069 (19)
C12	0.067 (3)	0.044 (2)	0.086 (3)	−0.0003 (18)	0.001 (2)	0.010 (2)
C13	0.071 (3)	0.0349 (19)	0.075 (3)	−0.0115 (17)	0.014 (2)	−0.0166 (18)
C14	0.057 (2)	0.0419 (19)	0.048 (2)	−0.0148 (15)	0.0006 (16)	−0.0106 (15)
C15	0.064 (2)	0.044 (2)	0.060 (2)	−0.0312 (17)	−0.0025 (18)	−0.0071 (17)

Br1—C2	1.891 (3)	C7—H7	0.9300
S1—C8	1.685 (3)	C9—C14	1.506 (4)
O1—C4	1.352 (4)	C9—C10	1.508 (4)
O1—C15	1.417 (4)	C9—H9	0.9800
O2—C5	1.351 (4)	C10—C11	1.513 (5)
O2—H2'	0.826 (19)	C10—H10A	0.9700
N1—C7	1.267 (4)	C10—H10B	0.9700
N1—N2	1.363 (3)	C11—C12	1.507 (6)
N2—C8	1.342 (4)	C11—H11A	0.9700
N2—H2	0.840 (18)	C11—H11B	0.9700
N3—C8	1.308 (4)	C12—C13	1.507 (6)
N3—C9	1.454 (4)	C12—H12A	0.9700
N3—H3'	0.842 (18)	C12—H12B	0.9700
C1—C2	1.366 (4)	C13—C14	1.513 (5)
C1—C6	1.392 (4)	C13—H13A	0.9700
C1—H1	0.9300	C13—H13B	0.9700
C2—C3	1.385 (4)	C14—H14A	0.9700
C3—C4	1.374 (4)	C14—H14B	0.9700
C3—H3	0.9300	C15—H15A	0.9600
C4—C5	1.394 (4)	C15—H15B	0.9600
C5—C6	1.379 (4)	C15—H15C	0.9600
C6—C7	1.449 (4)
C4—O1—C15	118.5 (3)	C10—C9—H9	108.5
C5—O2—H2'	113 (3)	C9—C10—C11	111.4 (3)
C7—N1—N2	115.6 (3)	C9—C10—H10A	109.3
C8—N2—N1	120.9 (2)	C11—C10—H10A	109.3
C8—N2—H2	120 (2)	C9—C10—H10B	109.3
N1—N2—H2	119 (2)	C11—C10—H10B	109.3
C8—N3—C9	125.6 (2)	H10A—C10—H10B	108.0
C8—N3—H3'	119 (2)	C12—C11—C10	111.1 (3)
C9—N3—H3'	115 (2)	C12—C11—H11A	109.4
C2—C1—C6	119.1 (3)	C10—C11—H11A	109.4
C2—C1—H1	120.4	C12—C11—H11B	109.4
C6—C1—H1	120.4	C10—C11—H11B	109.4
C1—C2—C3	122.6 (3)	H11A—C11—H11B	108.0
C1—C2—Br1	119.6 (2)	C11—C12—C13	110.8 (3)
C3—C2—Br1	117.8 (2)	C11—C12—H12A	109.5
C4—C3—C2	118.1 (3)	C13—C12—H12A	109.5
C4—C3—H3	120.9	C11—C12—H12B	109.5
C2—C3—H3	120.9	C13—C12—H12B	109.5
O1—C4—C3	126.0 (3)	H12A—C12—H12B	108.1
O1—C4—C5	113.8 (3)	C12—C13—C14	110.8 (3)
C3—C4—C5	120.2 (3)	C12—C13—H13A	109.5
O2—C5—C6	119.3 (3)	C14—C13—H13A	109.5
O2—C5—C4	120.0 (3)	C12—C13—H13B	109.5
C6—C5—C4	120.7 (3)	C14—C13—H13B	109.5
C5—C6—C1	119.2 (3)	H13A—C13—H13B	108.1
C5—C6—C7	119.2 (3)	C9—C14—C13	110.4 (3)
C1—C6—C7	121.5 (3)	C9—C14—H14A	109.6
N1—C7—C6	121.9 (3)	C13—C14—H14A	109.6
N1—C7—H7	119.1	C9—C14—H14B	109.6
C6—C7—H7	119.1	C13—C14—H14B	109.6
N3—C8—N2	116.6 (3)	H14A—C14—H14B	108.1
N3—C8—S1	124.5 (2)	O1—C15—H15A	109.5
N2—C8—S1	118.8 (2)	O1—C15—H15B	109.5
N3—C9—C14	111.7 (3)	H15A—C15—H15B	109.5
N3—C9—C10	108.2 (2)	O1—C15—H15C	109.5
C14—C9—C10	111.4 (3)	H15A—C15—H15C	109.5
N3—C9—H9	108.5	H15B—C15—H15C	109.5
C14—C9—H9	108.5
C7—N1—N2—C8	−176.8 (3)	C2—C1—C6—C7	178.1 (3)
C6—C1—C2—C3	0.5 (5)	N2—N1—C7—C6	−175.5 (3)
C6—C1—C2—Br1	−177.5 (2)	C5—C6—C7—N1	−172.0 (3)
C1—C2—C3—C4	−1.0 (5)	C1—C6—C7—N1	10.1 (5)
Br1—C2—C3—C4	177.1 (2)	C9—N3—C8—N2	179.5 (3)
C15—O1—C4—C3	3.8 (5)	C9—N3—C8—S1	−0.6 (5)
C15—O1—C4—C5	−175.5 (3)	N1—N2—C8—N3	4.1 (4)
C2—C3—C4—O1	−178.6 (3)	N1—N2—C8—S1	−175.9 (2)
C2—C3—C4—C5	0.7 (5)	C8—N3—C9—C14	−86.2 (4)
O1—C4—C5—O2	0.7 (4)	C8—N3—C9—C10	150.8 (3)
C3—C4—C5—O2	−178.7 (3)	N3—C9—C10—C11	178.1 (3)
O1—C4—C5—C6	179.4 (3)	C14—C9—C10—C11	54.9 (4)
C3—C4—C5—C6	0.0 (5)	C9—C10—C11—C12	−54.6 (5)
O2—C5—C6—C1	178.2 (3)	C10—C11—C12—C13	55.9 (5)
C4—C5—C6—C1	−0.4 (5)	C11—C12—C13—C14	−57.4 (4)
O2—C5—C6—C7	0.2 (4)	N3—C9—C14—C13	−177.2 (3)
C4—C5—C6—C7	−178.4 (3)	C10—C9—C14—C13	−56.0 (4)
C2—C1—C6—C5	0.2 (5)	C12—C13—C14—C9	57.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2′···O1	0.83 (2)	2.21 (4)	2.616 (3)	110 (3)
O2—H2′···S1i	0.83 (2)	2.43 (3)	3.142 (2)	145 (3)
N2—H2···O2i	0.84 (2)	2.25 (2)	2.959 (3)	142 (3)
N3—H3′···S1ii	0.84 (2)	2.81 (3)	3.483 (3)	138 (3)
C13—H13A···Cg1iii	0.97	2.71	3.664 (4)	168

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2′⋯O1	0.83 (2)	2.21 (4)	2.616 (3)	110 (3)
O2—H2′⋯S1i	0.83 (2)	2.43 (3)	3.142 (2)	145 (3)
N2—H2⋯O2i	0.84 (2)	2.25 (2)	2.959 (3)	142 (3)
N3—H3′⋯S1ii	0.84 (2)	2.81 (3)	3.483 (3)	138 (3)
C13—H13A⋯Cg1iii	0.97	2.71	3.664 (4)	168

Symmetry codes: (i) ; (ii) ; (iii) .