Benzyl (E)-3-(4-meth­oxy­benzyl­idene)dithio­carbazate

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

doi:10.1107/S1600536811042140

organic compounds

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Volume 67| Part 11| November 2011| Page o3011

doi:10.1107/S1600536811042140

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Benzyl (E)-3-(4-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 12 October 2011; online 22 October 2011)

The title compound, C₁₆H₁₆N₂OS₂, was obtained from a condensation reaction of benzyl dithiocarbazate and 4-methoxybenzaldehyde. In the molecule, the methoxyphenyl ring and dithiocarbazate fragment are located on opposite sides of the C=N double bond, showing an E configuration. The dithiocarbazate fragment is approximately planar (r.m.s. deviation = 0.0052 Å); its mean plane is oriented at dihedral angles of 8.19 (15) and 85.70 (13)°, respectively, to the methoxyphenyl and phenyl rings. Intermolecular N—H⋯S hydrogen bonds and weak C—H⋯π interactions are observed in the crystal structure.

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

Experimental

Crystal data

C₁₆H₁₆N₂OS₂
M_r = 316.43
Monoclinic, P 2₁ /c
a = 10.267 (5) Å
b = 5.150 (2) Å
c = 31.686 (11) Å
β = 97.141 (5)°
V = 1662.4 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 294 K
0.32 × 0.25 × 0.23 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.84, T_max = 0.92
6025 measured reflections
2982 independent reflections
1869 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.129
S = 1.04
2982 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.86	2.59	3.397 (4)	158
C16—H16C⋯Cgⁱⁱ	0.96	2.83	3.671 (5)	147
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, 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/S1600536811042140/xu5352sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042140/xu5352Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811042140/xu5352Isup3.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 0.0052 Å]; the mean plane of dithiocarbazate is oriented with respect to the methoxylphenyl and phenyl rings at 8.19 (15) and 85.70 (13)°, similar to those found in related structures (Shan et al. 2008a,b). Intermolecular N—H···S hydrogen bonding and weak C—H···π interaction are observed in the crystal structure (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). 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 4-methoxybenzaldehyde (0.27 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-(4-methoxybenzylidene)dithiocarbazate top

Crystal data top

C₁₆H₁₆N₂OS₂	F(000) = 664
M_r = 316.43	D_x = 1.264 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2982 reflections
a = 10.267 (5) Å	θ = 3.4–25.2°
b = 5.150 (2) Å	µ = 0.32 mm⁻¹
c = 31.686 (11) Å	T = 294 K
β = 97.141 (5)°	Block, colorless
V = 1662.4 (12) Å³	0.32 × 0.25 × 0.23 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2982 independent reflections
Radiation source: fine-focus sealed tube	1869 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.2°, θ_min = 3.5°
ω scans	h = −12→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −5→6
T_min = 0.84, T_max = 0.92	l = −31→37
6025 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0512P)²] where P = (F_o² + 2F_c²)/3
2982 reflections	(Δ/σ)_max = 0.001
191 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₆H₁₆N₂OS₂	V = 1662.4 (12) Å³
M_r = 316.43	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.267 (5) Å	µ = 0.32 mm⁻¹
b = 5.150 (2) Å	T = 294 K
c = 31.686 (11) Å	0.32 × 0.25 × 0.23 mm
β = 97.141 (5)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2982 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1869 reflections with I > 2σ(I)
T_min = 0.84, T_max = 0.92	R_int = 0.035
6025 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.04	Δρ_max = 0.32 e Å⁻³
2982 reflections	Δρ_min = −0.28 e Å⁻³
191 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
S1	0.65124 (8)	0.64526 (18)	0.54959 (2)	0.0628 (3)
S2	0.57408 (9)	0.40404 (17)	0.63003 (2)	0.0631 (3)
O1	−0.0078 (2)	−0.7274 (5)	0.62062 (8)	0.0810 (7)
N1	0.4039 (2)	0.1129 (5)	0.57509 (7)	0.0545 (7)
N2	0.4768 (2)	0.2797 (5)	0.55381 (7)	0.0552 (7)
H2	0.4665	0.2815	0.5265	0.066*
C1	0.2443 (3)	−0.2240 (6)	0.56941 (8)	0.0491 (7)
C2	0.1678 (3)	−0.3916 (6)	0.54309 (9)	0.0582 (9)
H2A	0.1740	−0.3887	0.5141	0.070*
C3	0.0825 (3)	−0.5632 (6)	0.55848 (10)	0.0608 (8)
H3	0.0315	−0.6738	0.5400	0.073*
C4	0.0734 (3)	−0.5699 (6)	0.60140 (10)	0.0572 (8)
C5	0.1509 (3)	−0.4053 (7)	0.62824 (10)	0.0663 (9)
H5	0.1456	−0.4105	0.6573	0.080*
C6	0.2355 (3)	−0.2346 (6)	0.61278 (9)	0.0596 (9)
H6	0.2871	−0.1255	0.6313	0.072*
C7	0.3302 (3)	−0.0417 (6)	0.55184 (9)	0.0553 (8)
H7	0.3314	−0.0376	0.5226	0.066*
C8	0.5635 (3)	0.4391 (6)	0.57512 (8)	0.0498 (8)
C9	0.6968 (4)	0.6468 (7)	0.64781 (9)	0.0725 (10)
H9A	0.7778	0.6104	0.6361	0.087*
H9B	0.6662	0.8177	0.6383	0.087*
C10	0.7200 (5)	0.6388 (8)	0.69529 (11)	0.0815 (12)
C11	0.8198 (6)	0.4920 (11)	0.71552 (14)	0.1309 (19)
H11	0.8712	0.3939	0.6993	0.157*
C12	0.8464 (8)	0.4854 (16)	0.7592 (2)	0.189 (4)
H12	0.9153	0.3870	0.7727	0.226*
C13	0.7687 (13)	0.6270 (17)	0.7815 (2)	0.199 (5)
H13	0.7830	0.6173	0.8110	0.239*
C14	0.6712 (12)	0.7826 (15)	0.7635 (2)	0.212 (5)
H14	0.6231	0.8854	0.7801	0.255*
C15	0.6444 (7)	0.7838 (11)	0.71840 (14)	0.138 (2)
H15	0.5758	0.8830	0.7049	0.166*
C16	−0.0915 (4)	−0.8990 (7)	0.59433 (13)	0.0942 (13)
H16A	−0.1487	−0.7997	0.5741	0.141*
H16B	−0.1431	−0.9991	0.6117	0.141*
H16C	−0.0392	−1.0135	0.5795	0.141*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0604 (6)	0.0731 (6)	0.0556 (5)	−0.0213 (5)	0.0101 (4)	0.0138 (4)
S2	0.0699 (6)	0.0685 (6)	0.0511 (4)	−0.0216 (5)	0.0086 (4)	0.0112 (4)
O1	0.0753 (19)	0.0729 (16)	0.0980 (16)	−0.0258 (14)	0.0229 (14)	0.0156 (14)
N1	0.0472 (16)	0.0563 (16)	0.0604 (14)	−0.0115 (14)	0.0078 (12)	0.0121 (13)
N2	0.0510 (17)	0.0639 (17)	0.0514 (13)	−0.0149 (14)	0.0087 (12)	0.0088 (13)
C1	0.0451 (19)	0.0492 (18)	0.0530 (17)	−0.0071 (15)	0.0060 (14)	0.0066 (14)
C2	0.056 (2)	0.067 (2)	0.0508 (16)	−0.0112 (18)	0.0042 (14)	0.0004 (16)
C3	0.053 (2)	0.058 (2)	0.069 (2)	−0.0126 (17)	−0.0002 (15)	−0.0007 (17)
C4	0.050 (2)	0.0486 (19)	0.074 (2)	−0.0096 (16)	0.0093 (16)	0.0115 (17)
C5	0.074 (2)	0.073 (2)	0.0528 (17)	−0.016 (2)	0.0123 (16)	0.0100 (17)
C6	0.063 (2)	0.060 (2)	0.0542 (18)	−0.0183 (18)	0.0026 (15)	−0.0033 (16)
C7	0.0455 (19)	0.064 (2)	0.0565 (17)	−0.0062 (17)	0.0073 (14)	0.0112 (16)
C8	0.0430 (18)	0.0526 (19)	0.0544 (16)	−0.0034 (15)	0.0088 (14)	0.0089 (15)
C9	0.088 (3)	0.071 (2)	0.0579 (18)	−0.030 (2)	0.0062 (17)	0.0061 (17)
C10	0.120 (4)	0.066 (2)	0.057 (2)	−0.034 (2)	0.006 (2)	0.004 (2)
C11	0.157 (5)	0.132 (4)	0.094 (3)	−0.011 (4)	−0.023 (3)	0.025 (3)
C12	0.271 (10)	0.173 (7)	0.099 (4)	−0.046 (7)	−0.069 (5)	0.040 (5)
C13	0.408 (15)	0.124 (7)	0.064 (4)	−0.114 (8)	0.031 (6)	−0.006 (4)
C14	0.433 (16)	0.110 (6)	0.105 (5)	−0.051 (7)	0.080 (7)	−0.021 (4)
C15	0.228 (7)	0.119 (4)	0.073 (3)	−0.013 (4)	0.040 (4)	−0.005 (3)
C16	0.072 (3)	0.067 (3)	0.145 (3)	−0.028 (2)	0.019 (2)	0.016 (3)

Geometric parameters (Å, º) top

S1—C8	1.665 (3)	C6—H6	0.9300
S2—C8	1.739 (3)	C7—H7	0.9300
S2—C9	1.814 (3)	C9—C10	1.494 (4)
O1—C4	1.360 (4)	C9—H9A	0.9700
O1—C16	1.427 (4)	C9—H9B	0.9700
N1—C7	1.269 (4)	C10—C15	1.356 (6)
N1—N2	1.371 (3)	C10—C11	1.367 (6)
N2—C8	1.331 (3)	C11—C12	1.376 (7)
N2—H2	0.8600	C11—H11	0.9300
C1—C2	1.376 (4)	C12—C13	1.345 (11)
C1—C6	1.390 (4)	C12—H12	0.9300
C1—C7	1.446 (4)	C13—C14	1.352 (13)
C2—C3	1.376 (4)	C13—H13	0.9300
C2—H2A	0.9300	C14—C15	1.423 (8)
C3—C4	1.375 (4)	C14—H14	0.9300
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.381 (4)	C16—H16A	0.9600
C5—C6	1.368 (4)	C16—H16B	0.9600
C5—H5	0.9300	C16—H16C	0.9600

C8—S2—C9	101.16 (14)	C10—C9—S2	108.1 (2)
C4—O1—C16	117.8 (3)	C10—C9—H9A	110.1
C7—N1—N2	115.5 (2)	S2—C9—H9A	110.1
C8—N2—N1	120.6 (2)	C10—C9—H9B	110.1
C8—N2—H2	119.7	S2—C9—H9B	110.1
N1—N2—H2	119.7	H9A—C9—H9B	108.4
C2—C1—C6	118.2 (3)	C15—C10—C11	119.8 (4)
C2—C1—C7	120.2 (3)	C15—C10—C9	119.9 (4)
C6—C1—C7	121.6 (3)	C11—C10—C9	120.2 (4)
C3—C2—C1	121.9 (3)	C10—C11—C12	121.9 (6)
C3—C2—H2A	119.0	C10—C11—H11	119.1
C1—C2—H2A	119.0	C12—C11—H11	119.1
C4—C3—C2	119.4 (3)	C13—C12—C11	117.3 (8)
C4—C3—H3	120.3	C13—C12—H12	121.3
C2—C3—H3	120.3	C11—C12—H12	121.3
O1—C4—C3	125.3 (3)	C12—C13—C14	123.8 (7)
O1—C4—C5	115.4 (3)	C12—C13—H13	118.1
C3—C4—C5	119.2 (3)	C14—C13—H13	118.1
C6—C5—C4	121.1 (3)	C13—C14—C15	117.8 (8)
C6—C5—H5	119.4	C13—C14—H14	121.1
C4—C5—H5	119.4	C15—C14—H14	121.1
C5—C6—C1	120.1 (3)	C10—C15—C14	119.2 (7)
C5—C6—H6	119.9	C10—C15—H15	120.4
C1—C6—H6	119.9	C14—C15—H15	120.4
N1—C7—C1	122.2 (3)	O1—C16—H16A	109.5
N1—C7—H7	118.9	O1—C16—H16B	109.5
C1—C7—H7	118.9	H16A—C16—H16B	109.5
N2—C8—S1	121.0 (2)	O1—C16—H16C	109.5
N2—C8—S2	113.5 (2)	H16A—C16—H16C	109.5
S1—C8—S2	125.59 (18)	H16B—C16—H16C	109.5

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.86	2.59	3.397 (4)	158
C16—H16C···Cgⁱⁱ	0.96	2.83	3.671 (5)	147

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂OS₂
M_r	316.43
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	10.267 (5), 5.150 (2), 31.686 (11)
β (°)	97.141 (5)
V (Å³)	1662.4 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.32 × 0.25 × 0.23

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.84, 0.92
No. of measured, independent and observed [I > 2σ(I)] reflections	6025, 2982, 1869
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.129, 1.04
No. of reflections	2982
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.28

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

Cg is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.86	2.59	3.397 (4)	158
C16—H16C···Cgⁱⁱ	0.96	2.83	3.671 (5)	147

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z.

Acknowledgements

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

References

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doi:10.1107/S1600536811042140

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