Methyl (E)-3-(2-bromo-4,5-dimeth-oxy-benzyl-idene)dithio-carbazate.

The title compound, C(11)H(13)BrN(2)O(2)S(2), was obtained from the condensation reaction of methyl dithio-carbazate and 2-bromo-4,5-dimeth-oxy-benzaldehyde. In the mol-ecule, the benzene ring and dithio-carbazate fragment are located on opposite sides of the C=N bond, showing an E conformation. The dithio-carbazate fragment is approximately planar (r.m.s deviation = 0.0281 Å) and the mean plane is oriented at a dihedral angle of 11.38 (15)° with respect to the benzene ring. In the crystal, pairs of N-H⋯S hydrogen bonds link the mol-ecules into centrosymmetric dimers.

Related literature

For applications of hydrazone and its derivatives in the biological field, see: Okabe et al. (1993 ▶); Hu et al. (2001 ▶). For related structures, see: Shan et al. (2008a ▶,b ▶,c ▶). For the synthesis, see: Hu et al. (2001 ▶).

Experimental

Crystal data

C11H13BrN2O2S2

M = 349.26

Triclinic,

a = 5.2460 (12) Å

b = 11.781 (5) Å

c = 12.400 (5) Å

α = 102.347 (3)°

β = 100.930 (4)°

γ = 101.874 (4)°

V = 710.4 (4) Å3

Z = 2

Mo Kα radiation

μ = 3.18 mm−1

T = 293 K

0.42 × 0.28 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.73, T max = 0.82

5185 measured reflections

2553 independent reflections

2051 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.079

S = 1.02

2553 reflections

166 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.35 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811039304/xu5332sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811039304/xu5332Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811039304/xu5332Isup3.cml

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

C11H13BrN2O2S2	Z = 2
Mr = 349.26	F(000) = 352
Triclinic, P1	Dx = 1.633 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2460 (12) Å	Cell parameters from 2553 reflections
b = 11.781 (5) Å	θ = 2.8–25.2°
c = 12.400 (5) Å	µ = 3.18 mm−1
α = 102.347 (3)°	T = 293 K
β = 100.930 (4)°	Prism, colorless
γ = 101.874 (4)°	0.42 × 0.28 × 0.25 mm
V = 710.4 (4) Å3

Rigaku R-AXIS RAPID IP diffractometer	2553 independent reflections
Radiation source: fine-focus sealed tube	2051 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 10.0 pixels mm-1	θmax = 25.2°, θmin = 2.8°
ω scans	h = −5→6
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→11
Tmin = 0.73, Tmax = 0.82	l = −14→14
5185 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.037P)2] where P = (Fo2 + 2Fc2)/3
2553 reflections	(Δ/σ)max = 0.001
166 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.35 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
Br	0.29930 (7)	0.52287 (3)	0.29304 (3)	0.06212 (15)
S1	1.14891 (18)	0.35920 (7)	−0.09979 (7)	0.0586 (2)
S2	0.95417 (16)	0.13601 (7)	−0.02534 (7)	0.0499 (2)
N1	0.7198 (5)	0.2821 (2)	0.11142 (18)	0.0411 (5)
N2	0.8444 (5)	0.3398 (2)	0.04224 (18)	0.0438 (6)
H2N	0.8360	0.4121	0.0428	0.053*
O1	0.3795 (4)	0.0498 (2)	0.38554 (17)	0.0620 (6)
O2	0.1403 (4)	0.1803 (2)	0.49916 (17)	0.0676 (6)
C1	0.3386 (5)	0.3734 (3)	0.3172 (2)	0.0438 (7)
C2	0.2229 (5)	0.3338 (3)	0.3994 (2)	0.0487 (7)
H2	0.1332	0.3810	0.4402	0.058*
C3	0.2405 (6)	0.2269 (3)	0.4200 (2)	0.0480 (7)
C4	0.3727 (5)	0.1538 (3)	0.3573 (2)	0.0459 (7)
C5	0.4848 (5)	0.1938 (3)	0.2762 (2)	0.0424 (7)
H5	0.5721	0.1457	0.2348	0.051*
C6	0.4722 (5)	0.3035 (2)	0.2539 (2)	0.0399 (6)
C7	0.6023 (5)	0.3466 (3)	0.1714 (2)	0.0418 (6)
H7	0.6001	0.4227	0.1621	0.050*
C8	0.9769 (5)	0.2856 (2)	−0.0251 (2)	0.0392 (6)
C9	1.1501 (7)	0.0933 (3)	−0.1230 (3)	0.0603 (9)
H9A	1.0899	0.1146	−0.1923	0.090*
H9B	1.1296	0.0081	−0.1393	0.090*
H9C	1.3358	0.1345	−0.0899	0.090*
C10	0.5363 (7)	−0.0214 (3)	0.3356 (3)	0.0635 (9)
H10A	0.4618	−0.0497	0.2548	0.095*
H10B	0.5356	−0.0888	0.3675	0.095*
H10C	0.7174	0.0263	0.3506	0.095*
C11	0.0060 (7)	0.2495 (4)	0.5675 (3)	0.0780 (12)
H11A	0.1296	0.3245	0.6114	0.117*
H11B	−0.0597	0.2057	0.6179	0.117*
H11C	−0.1419	0.2648	0.5192	0.117*

	U11	U22	U33	U12	U13	U23
Br	0.0681 (3)	0.0539 (2)	0.0700 (2)	0.02466 (17)	0.02423 (18)	0.01301 (17)
S1	0.0871 (6)	0.0518 (5)	0.0646 (5)	0.0304 (4)	0.0508 (5)	0.0325 (4)
S2	0.0635 (5)	0.0409 (4)	0.0588 (5)	0.0197 (4)	0.0304 (4)	0.0217 (4)
N1	0.0497 (14)	0.0445 (14)	0.0364 (12)	0.0116 (11)	0.0202 (11)	0.0177 (11)
N2	0.0615 (16)	0.0401 (13)	0.0443 (13)	0.0190 (12)	0.0286 (12)	0.0215 (11)
O1	0.0794 (16)	0.0694 (15)	0.0599 (13)	0.0274 (12)	0.0413 (12)	0.0352 (12)
O2	0.0721 (15)	0.0933 (17)	0.0550 (13)	0.0250 (13)	0.0420 (12)	0.0298 (12)
C1	0.0391 (16)	0.0493 (17)	0.0406 (15)	0.0114 (13)	0.0083 (13)	0.0083 (13)
C2	0.0431 (17)	0.070 (2)	0.0359 (15)	0.0200 (15)	0.0177 (13)	0.0067 (15)
C3	0.0424 (17)	0.070 (2)	0.0361 (15)	0.0117 (15)	0.0180 (13)	0.0177 (15)
C4	0.0435 (17)	0.0566 (19)	0.0369 (15)	0.0064 (14)	0.0137 (13)	0.0139 (14)
C5	0.0459 (17)	0.0515 (18)	0.0346 (14)	0.0148 (14)	0.0190 (13)	0.0112 (13)
C6	0.0382 (15)	0.0470 (17)	0.0354 (14)	0.0094 (13)	0.0133 (12)	0.0106 (13)
C7	0.0481 (17)	0.0421 (16)	0.0391 (15)	0.0117 (13)	0.0159 (13)	0.0142 (13)
C8	0.0474 (16)	0.0425 (16)	0.0346 (14)	0.0158 (13)	0.0144 (13)	0.0166 (12)
C9	0.073 (2)	0.0517 (19)	0.073 (2)	0.0287 (17)	0.0390 (18)	0.0213 (17)
C10	0.083 (2)	0.062 (2)	0.064 (2)	0.0289 (19)	0.0369 (19)	0.0264 (17)
C11	0.067 (2)	0.124 (3)	0.0492 (19)	0.024 (2)	0.0377 (18)	0.016 (2)

Br—C1	1.893 (3)	C3—C4	1.411 (4)
S1—C8	1.662 (3)	C4—C5	1.376 (4)
S2—C8	1.741 (3)	C5—C6	1.390 (4)
S2—C9	1.789 (3)	C5—H5	0.9300
N1—C7	1.280 (3)	C6—C7	1.454 (4)
N1—N2	1.381 (3)	C7—H7	0.9300
N2—C8	1.328 (3)	C9—H9A	0.9600
N2—H2N	0.8600	C9—H9B	0.9600
O1—C4	1.349 (3)	C9—H9C	0.9600
O1—C10	1.421 (4)	C10—H10A	0.9600
O2—C3	1.360 (3)	C10—H10B	0.9600
O2—C11	1.431 (4)	C10—H10C	0.9600
C1—C2	1.395 (4)	C11—H11A	0.9600
C1—C6	1.398 (4)	C11—H11B	0.9600
C2—C3	1.355 (4)	C11—H11C	0.9600
C2—H2	0.9300
C8—S2—C9	101.93 (13)	N1—C7—C6	121.3 (3)
C7—N1—N2	113.4 (2)	N1—C7—H7	119.3
C8—N2—N1	121.0 (2)	C6—C7—H7	119.3
C8—N2—H2N	119.5	N2—C8—S1	120.9 (2)
N1—N2—H2N	119.5	N2—C8—S2	114.23 (19)
C4—O1—C10	118.1 (2)	S1—C8—S2	124.83 (16)
C3—O2—C11	117.8 (3)	S2—C9—H9A	109.5
C2—C1—C6	120.9 (3)	S2—C9—H9B	109.5
C2—C1—Br	117.3 (2)	H9A—C9—H9B	109.5
C6—C1—Br	121.8 (2)	S2—C9—H9C	109.5
C3—C2—C1	120.3 (3)	H9A—C9—H9C	109.5
C3—C2—H2	119.8	H9B—C9—H9C	109.5
C1—C2—H2	119.8	O1—C10—H10A	109.5
C2—C3—O2	125.5 (3)	O1—C10—H10B	109.5
C2—C3—C4	120.3 (2)	H10A—C10—H10B	109.5
O2—C3—C4	114.2 (3)	O1—C10—H10C	109.5
O1—C4—C5	126.1 (3)	H10A—C10—H10C	109.5
O1—C4—C3	115.1 (2)	H10B—C10—H10C	109.5
C5—C4—C3	118.7 (3)	O2—C11—H11A	109.5
C4—C5—C6	122.3 (3)	O2—C11—H11B	109.5
C4—C5—H5	118.9	H11A—C11—H11B	109.5
C6—C5—H5	118.9	O2—C11—H11C	109.5
C5—C6—C1	117.5 (2)	H11A—C11—H11C	109.5
C5—C6—C7	121.5 (2)	H11B—C11—H11C	109.5
C1—C6—C7	121.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···S1i	0.86	2.62	3.456 (4)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯S1i	0.86	2.62	3.456 (4)	166

Symmetry code: (i) .