Benzyl (E)-3-(2-bromo-5-meth­oxy­benzyl­idene)dithio­carbazate

Fan, Z.; Huang, Y.-L.; Wang, Z.; Guo, H.-Q.; Shan, S.

doi:10.1107/S1600536811042826

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3015

doi:10.1107/S1600536811042826

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Benzyl (E)-3-(2-bromo-5-methoxybenzylidene)dithiocarbazate

Zheng Fan,^a Yan-Lan Huang,^b Zhao Wang,^b Han-Qi Guo ^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 7 October 2011; accepted 15 October 2011; online 22 October 2011)

The title compound, C₁₆H₁₅BrN₂OS₂, was obtained from the condensation reaction of benzyl dithiocarbazate and 2-bromo-5-methoxylbenzaldehyde. In the molecule, the bromomethoxyphenyl ring and dithiocarbazate fragment are located on the opposite sides of the C=N double bond, showing the E conformation. The dithiocarbazate fragment is approximately planar (r.m.s deviation 0.0187 Å); its mean plane is oriented with respect to the bromomethoxyphenyl and phenyl rings at 7.60 (12) and 60.08 (9)°, respectively. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds occur. A short Br⋯Br contact of 3.5526 (12) Å is observed in the crystal structure.

Related literature

For the potential application 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 ). For the synthesis, see: Hu et al. (2001).

Experimental

Crystal data

C₁₆H₁₅BrN₂OS₂
M_r = 395.33
Triclinic, $[P \overline 1]$
a = 6.260 (3) Å
b = 11.889 (5) Å
c = 12.235 (5) Å
α = 111.931 (5)°
β = 91.725 (4)°
γ = 99.771 (4)°
V = 828.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 2.74 mm⁻¹
T = 294 K
0.32 × 0.28 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.56, T_max = 0.72
5637 measured reflections
2988 independent reflections
2379 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.069
S = 1.02
2988 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.86	2.56	3.402 (3)	167
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/S1600536811042826/xu5353sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042826/xu5353Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811042826/xu5353Isup3.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 methoxylphenyl ring and dithiocarbazate fragment are located on the opposite sides of the C═N double bond, showing the E-configuration. The dithiocarbazate fragment is approximately planar [r.m.s deviation 0.0187 Å]; the mean plane of dithiocarbazate is oriented with respect to the methoxylphenyl and phenyl rings at 7.60 (12) and 60.08 (9)°, similar to those found in related structures (Shan et al. 2008a, 2008b). Intermolecular N—H···S hydrogen bonding is observed in the crystal structure (Table 1). The short Br···Brⁱ contact of 3.5526 (12) Å is also present in the crystal structure [symmetry code: (i) 1-x,-y,-z].

Related literature top

For the potential application 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). For the synthesis, see: Hu et al. (2001).

Experimental top

Benzyl dithiocarbazate was synthesized as described previously (Hu et al., 2001). Benzyl dithiocarbazate (0.40 g, 2 mmol) and 2-bromo-5-methoxybenzaldehyde (0.43 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 30% probability displacement (arbitrary spheres for H atoms).

Benzyl (E)-3-(2-bromo-5-methoxybenzylidene)dithiocarbazate top

Crystal data top

C₁₆H₁₅BrN₂OS₂	Z = 2
M_r = 395.33	F(000) = 400
Triclinic, P1	D_x = 1.586 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.260 (3) Å	Cell parameters from 2988 reflections
b = 11.889 (5) Å	θ = 3.3–25.2°
c = 12.235 (5) Å	µ = 2.74 mm⁻¹
α = 111.931 (5)°	T = 294 K
β = 91.725 (4)°	Block, yellow
γ = 99.771 (4)°	0.32 × 0.28 × 0.19 mm
V = 828.1 (6) Å³

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2988 independent reflections
Radiation source: fine-focus sealed tube	2379 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.2°, θ_min = 3.3°
ω scans	h = −5→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→11
T_min = 0.56, T_max = 0.72	l = −14→14
5637 measured reflections

Refinement top

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0276P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2988 reflections	Δρ_max = 0.25 e Å⁻³
201 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0123 (11)

Crystal data top

C₁₆H₁₅BrN₂OS₂	γ = 99.771 (4)°
M_r = 395.33	V = 828.1 (6) Å³
Triclinic, P1	Z = 2
a = 6.260 (3) Å	Mo Kα radiation
b = 11.889 (5) Å	µ = 2.74 mm⁻¹
c = 12.235 (5) Å	T = 294 K
α = 111.931 (5)°	0.32 × 0.28 × 0.19 mm
β = 91.725 (4)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2988 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2379 reflections with I > 2σ(I)
T_min = 0.56, T_max = 0.72	R_int = 0.028
5637 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.069	H-atom parameters constrained
S = 1.02	Δρ_max = 0.25 e Å⁻³
2988 reflections	Δρ_min = −0.30 e Å⁻³
201 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	0.33444 (5)	0.11365 (3)	0.04397 (2)	0.05700 (14)
S1	1.10460 (10)	0.70610 (6)	0.10224 (6)	0.0458 (2)
S2	0.72189 (10)	0.76733 (6)	0.24288 (6)	0.0423 (2)
N1	0.5742 (3)	0.51783 (19)	0.15272 (15)	0.0336 (5)
N2	0.7654 (3)	0.54749 (19)	0.10904 (16)	0.0356 (5)
H2	0.8197	0.4905	0.0580	0.043*
O1	−0.0891 (3)	0.51964 (18)	0.35686 (15)	0.0501 (5)
C1	0.1988 (4)	0.2431 (2)	0.13964 (19)	0.0366 (6)
C2	0.0116 (5)	0.2108 (3)	0.1861 (2)	0.0487 (8)
H2A	−0.0459	0.1278	0.1682	0.058*
C3	−0.0907 (4)	0.2999 (3)	0.2586 (2)	0.0465 (7)
H3	−0.2169	0.2778	0.2900	0.056*
C4	−0.0045 (4)	0.4226 (3)	0.2843 (2)	0.0370 (6)
C5	0.1811 (4)	0.4548 (2)	0.23569 (19)	0.0341 (6)
H5	0.2356	0.5378	0.2518	0.041*
C6	0.2875 (4)	0.3660 (2)	0.16346 (19)	0.0314 (6)
C7	0.4884 (4)	0.4042 (2)	0.11732 (19)	0.0356 (6)
H7	0.5525	0.3453	0.0623	0.043*
C8	0.8663 (4)	0.6654 (2)	0.14642 (18)	0.0319 (6)
C9	0.8899 (4)	0.9158 (2)	0.2670 (2)	0.0414 (7)
H9A	1.0306	0.9241	0.3078	0.050*
H9B	0.9132	0.9233	0.1918	0.050*
C10	0.7736 (4)	1.0146 (2)	0.3410 (2)	0.0380 (6)
C11	0.5706 (5)	1.0236 (3)	0.3006 (2)	0.0489 (8)
H11	0.5048	0.9677	0.2267	0.059*
C12	0.4647 (5)	1.1145 (3)	0.3690 (3)	0.0587 (8)
H12	0.3299	1.1210	0.3404	0.070*
C13	0.5599 (6)	1.1955 (3)	0.4797 (3)	0.0624 (9)
H13	0.4869	1.2552	0.5269	0.075*
C14	0.7606 (6)	1.1886 (3)	0.5205 (2)	0.0636 (9)
H14	0.8250	1.2441	0.5948	0.076*
C15	0.8682 (5)	1.0989 (3)	0.4509 (2)	0.0487 (7)
H15	1.0059	1.0953	0.4786	0.058*
C16	−0.2653 (5)	0.4938 (3)	0.4202 (2)	0.0604 (9)
H16A	−0.3916	0.4475	0.3655	0.091*
H16B	−0.2973	0.5700	0.4744	0.091*
H16C	−0.2260	0.4464	0.4636	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0715 (2)	0.03141 (19)	0.0601 (2)	0.01393 (14)	0.01395 (15)	0.00643 (14)
S1	0.0383 (4)	0.0355 (4)	0.0532 (4)	0.0005 (3)	0.0211 (3)	0.0069 (3)
S2	0.0413 (4)	0.0289 (4)	0.0511 (4)	0.0051 (3)	0.0214 (3)	0.0084 (3)
N1	0.0292 (10)	0.0319 (13)	0.0367 (10)	0.0026 (9)	0.0078 (9)	0.0109 (9)
N2	0.0333 (11)	0.0297 (13)	0.0390 (11)	0.0034 (9)	0.0146 (9)	0.0083 (9)
O1	0.0423 (11)	0.0511 (13)	0.0580 (11)	0.0155 (9)	0.0225 (9)	0.0181 (9)
C1	0.0422 (15)	0.0286 (15)	0.0355 (13)	0.0030 (12)	0.0031 (11)	0.0101 (11)
C2	0.0553 (17)	0.0332 (17)	0.0505 (15)	−0.0061 (14)	0.0095 (14)	0.0140 (13)
C3	0.0389 (15)	0.0474 (19)	0.0507 (15)	−0.0051 (13)	0.0116 (13)	0.0214 (14)
C4	0.0309 (13)	0.0432 (17)	0.0362 (13)	0.0080 (12)	0.0038 (11)	0.0142 (12)
C5	0.0311 (13)	0.0265 (14)	0.0412 (13)	0.0006 (11)	0.0028 (11)	0.0113 (11)
C6	0.0302 (13)	0.0300 (15)	0.0313 (11)	0.0030 (11)	0.0013 (10)	0.0102 (10)
C7	0.0378 (14)	0.0294 (15)	0.0347 (12)	0.0050 (11)	0.0092 (11)	0.0070 (11)
C8	0.0327 (13)	0.0329 (15)	0.0276 (11)	0.0047 (11)	0.0044 (10)	0.0096 (10)
C9	0.0414 (15)	0.0293 (15)	0.0476 (14)	0.0016 (12)	0.0134 (12)	0.0097 (12)
C10	0.0443 (15)	0.0262 (15)	0.0444 (14)	0.0047 (12)	0.0165 (12)	0.0146 (12)
C11	0.0441 (16)	0.0421 (18)	0.0547 (16)	0.0045 (13)	0.0117 (13)	0.0133 (13)
C12	0.0470 (17)	0.054 (2)	0.084 (2)	0.0160 (15)	0.0236 (17)	0.0319 (18)
C13	0.085 (2)	0.043 (2)	0.068 (2)	0.0282 (17)	0.0390 (19)	0.0228 (16)
C14	0.102 (3)	0.0402 (19)	0.0437 (16)	0.0218 (18)	0.0107 (17)	0.0072 (14)
C15	0.0603 (18)	0.0353 (17)	0.0466 (15)	0.0094 (14)	0.0060 (14)	0.0113 (13)
C16	0.0449 (16)	0.085 (3)	0.0553 (16)	0.0222 (16)	0.0221 (14)	0.0258 (16)

Geometric parameters (Å, º) top

Br—C1	1.902 (3)	C6—C7	1.465 (3)
S1—C8	1.658 (3)	C7—H7	0.9300
S2—C8	1.745 (2)	C9—C10	1.505 (4)
S2—C9	1.808 (3)	C9—H9A	0.9700
N1—C7	1.267 (3)	C9—H9B	0.9700
N1—N2	1.370 (3)	C10—C15	1.381 (3)
N2—C8	1.333 (3)	C10—C11	1.385 (4)
N2—H2	0.8600	C11—C12	1.382 (4)
O1—C4	1.368 (3)	C11—H11	0.9300
O1—C16	1.424 (3)	C12—C13	1.378 (4)
C1—C2	1.377 (4)	C12—H12	0.9300
C1—C6	1.387 (4)	C13—C14	1.365 (5)
C2—C3	1.372 (4)	C13—H13	0.9300
C2—H2A	0.9300	C14—C15	1.384 (4)
C3—C4	1.378 (4)	C14—H14	0.9300
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.382 (3)	C16—H16A	0.9600
C5—C6	1.385 (3)	C16—H16B	0.9600
C5—H5	0.9300	C16—H16C	0.9600

C8—S2—C9	101.87 (12)	C10—C9—S2	107.86 (17)
C7—N1—N2	116.98 (19)	C10—C9—H9A	110.1
C8—N2—N1	119.40 (18)	S2—C9—H9A	110.1
C8—N2—H2	120.3	C10—C9—H9B	110.1
N1—N2—H2	120.3	S2—C9—H9B	110.1
C4—O1—C16	118.1 (2)	H9A—C9—H9B	108.4
C2—C1—C6	121.2 (2)	C15—C10—C11	118.5 (2)
C2—C1—Br	117.7 (2)	C15—C10—C9	120.4 (2)
C6—C1—Br	121.16 (18)	C11—C10—C9	121.0 (2)
C3—C2—C1	120.6 (3)	C12—C11—C10	120.8 (3)
C3—C2—H2A	119.7	C12—C11—H11	119.6
C1—C2—H2A	119.7	C10—C11—H11	119.6
C2—C3—C4	119.3 (2)	C13—C12—C11	119.7 (3)
C2—C3—H3	120.3	C13—C12—H12	120.2
C4—C3—H3	120.3	C11—C12—H12	120.2
O1—C4—C3	124.7 (2)	C14—C13—C12	120.3 (3)
O1—C4—C5	115.2 (2)	C14—C13—H13	119.8
C3—C4—C5	120.0 (2)	C12—C13—H13	119.8
C4—C5—C6	121.3 (2)	C13—C14—C15	119.9 (3)
C4—C5—H5	119.3	C13—C14—H14	120.1
C6—C5—H5	119.3	C15—C14—H14	120.1
C5—C6—C1	117.6 (2)	C10—C15—C14	120.8 (3)
C5—C6—C7	119.6 (2)	C10—C15—H15	119.6
C1—C6—C7	122.8 (2)	C14—C15—H15	119.6
N1—C7—C6	119.7 (2)	O1—C16—H16A	109.5
N1—C7—H7	120.1	O1—C16—H16B	109.5
C6—C7—H7	120.1	H16A—C16—H16B	109.5
N2—C8—S1	121.55 (17)	O1—C16—H16C	109.5
N2—C8—S2	113.22 (17)	H16A—C16—H16C	109.5
S1—C8—S2	125.23 (15)	H16B—C16—H16C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.86	2.56	3.402 (3)	167

Symmetry code: (i) −x+2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅BrN₂OS₂
M_r	395.33
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	6.260 (3), 11.889 (5), 12.235 (5)
α, β, γ (°)	111.931 (5), 91.725 (4), 99.771 (4)
V (Å³)	828.1 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.74
Crystal size (mm)	0.32 × 0.28 × 0.19

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.56, 0.72
No. of measured, independent and observed [I > 2σ(I)] reflections	5637, 2988, 2379
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.069, 1.02
No. of reflections	2988
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.30

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—H2···S1ⁱ	0.86	2.56	3.402 (3)	167

Symmetry code: (i) −x+2, −y+1, −z.

Acknowledgements

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

References

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