Methyl (E)-3-(2-bromo-4,5-dimeth­oxy­benzyl­idene)dithio­carbazate

Fan, Z.; Huang, Y.-L.; Tong, F.; Huang, Y.-W.; Shan, S.

doi:10.1107/S1600536811039304

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2919

doi:10.1107/S1600536811039304

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Methyl (E)-3-(2-bromo-4,5-dimethoxybenzylidene)dithiocarbazate

Zheng Fan,^a Yan-Lan Huang,^b Fang Tong,^b Yi-Wei Huang ^b and Shang Shan ^b ^*

^aCollege of Biological and Environmental Engineering, Zhejiang University of Technology, People's Republic of China, and ^bCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, People's Republic of China
^*Correspondence e-mail: shanshang@mail.hz.zj.cn

(Received 23 September 2011; accepted 25 September 2011; online 12 October 2011)

The title compound, C₁₁H₁₃BrN₂O₂S₂, was obtained from the condensation reaction of methyl dithiocarbazate and 2-bromo-4,5-dimethoxybenzaldehyde. In the molecule, the benzene ring and dithiocarbazate fragment are located on opposite sides of the C=N bond, showing an E conformation. The dithiocarbazate 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 molecules 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_r = 349.26
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.079
S = 1.02
2553 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.35 e Å⁻³

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) -x+2, -y+1, -z.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811039304/xu5332sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811039304/xu5332Isup3.cml

checkCIF report

Comment top

Hydrazone and its derivatives have shown the potential application in the biological field (Okabe et al., 1993; Hu et al., 2001). As part of the ongoing investigation on anti-cancer compounds, the title compound has recently been prepared in our laboratory and its crystal structure is presented here.

In the molecules, the benzene ring and dithiocarbazate fragment are located on the opposite sides of the C═N bond, showing the E-configuration. This agrees with those found in the structures reported previously (Shan et al., 2008a,b). The dithiocarbazate fragment is approximately planar, the r.m.s deviation being 0.0281 Å; its mean plane is oriented with respect to the benzene ring at 11.38 (15)°, similar to that found in a related structure (Shan et al. 2008c). In the crystal structure, intermolecular N—H···S hydrogen bonding links molecules to form the centro-symmetric dimers (Table 1).

Related literature top

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 top

Methyl dithiocarbazate was synthesized as described previously by Hu et al. (2001). Methyl dithiocarbazate (0.24 g, 2 mmol) and 2-bromo-4,5-dimethoxybenzaldehyde (0.49 g, 2 mmol) were dissolved in ethanol (20 ml), then acetic acid (0.2 ml) was added to the ethanol solution with stirring. The mixture solution was refluxed for 6 h. After cooling to room temperature, microcrystals appeared. The microcrystals were separated from the solution and washed with cold water three times. Recrystallization was performed twice with absolute methanol to obtain colourless single crystals of the title compound.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); 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).

Figures top

Fig. 1. The molecular structure of the title compound with 40% probability displacement (arbitrary spheres for H atoms).

Methyl (E)-3-(2-bromo-4,5-dimethoxybenzylidene)dithiocarbazate top

Crystal data top

C₁₁H₁₃BrN₂O₂S₂	Z = 2
M_r = 349.26	F(000) = 352
Triclinic, P1	D_x = 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

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2553 independent reflections
Radiation source: fine-focus sealed tube	2051 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.2°, θ_min = 2.8°
ω scans	h = −5→6
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→11
T_min = 0.73, T_max = 0.82	l = −14→14
5185 measured reflections

Refinement top

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(F_o²) + (0.037P)²] where P = (F_o² + 2F_c²)/3
2553 reflections	(Δ/σ)_max = 0.001
166 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₁H₁₃BrN₂O₂S₂	γ = 101.874 (4)°
M_r = 349.26	V = 710.4 (4) Å³
Triclinic, P1	Z = 2
a = 5.2460 (12) Å	Mo Kα radiation
b = 11.781 (5) Å	µ = 3.18 mm⁻¹
c = 12.400 (5) Å	T = 293 K
α = 102.347 (3)°	0.42 × 0.28 × 0.25 mm
β = 100.930 (4)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2553 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2051 reflections with I > 2σ(I)
T_min = 0.73, T_max = 0.82	R_int = 0.026
5185 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.02	Δρ_max = 0.32 e Å⁻³
2553 reflections	Δρ_min = −0.35 e Å⁻³
166 parameters

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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃BrN₂O₂S₂
M_r	349.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.2460 (12), 11.781 (5), 12.400 (5)
α, β, γ (°)	102.347 (3), 100.930 (4), 101.874 (4)
V (Å³)	710.4 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.18
Crystal size (mm)	0.42 × 0.28 × 0.25

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.73, 0.82
No. of measured, independent and observed [I > 2σ(I)] reflections	5185, 2553, 2051
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.079, 1.02
No. of reflections	2553
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.35

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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) −x+2, −y+1, −z.

Acknowledgements

The work was supported by the Natural Science Foundation of Zhejiang Province, China (No. M203027).

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