Benzyl (E)-3-(4-meth-oxy-benzyl-idene)dithio-carbazate.

Abstract

The title compound, C(16)H(16)N(2)OS(2), was obtained from a condensation reaction of benzyl dithio-carbazate and 4-meth-oxy-benzaldehyde. In the mol-ecule, the meth-oxy-phenyl ring and dithio-carbazate fragment are located on opposite sides of the C=N double bond, showing an E configuration. The dithio-carbazate 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 meth-oxy-phenyl and phenyl rings. Inter-molecular N-H⋯S hydrogen bonds and weak C-H⋯π inter-actions are observed in the crystal structure.

Full text

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Benzyl (E)-3-(4-methoxybenzylidene)-
dithiocarbazate
Zheng Fan,aYan-Lan Huang,bZhao Wang,bHan-Qi Guob
and Shang Shanb*
aCollege of Biological and Environmental Engineering, Zhejiang University of
Technology, People’s Republic of China, andbCollege 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
Key indicators: single-crystal X-ray study; T = 294 K; mean ?(C–C) = 0.007 A ˚;
R factor = 0.055; wR factor = 0.129; data-to-parameter ratio = 15.6.
The title compound, C16H16N2OS2, was obtained from a
condensation reaction of benzyl dithiocarbazate and 4-meth-
oxybenzaldehyde. 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 A˚); 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???? 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
Mr= 316.43
Monoclinic, P21=c
a = 10.267 (5) A˚
b = 5.150 (2) A˚
c = 31.686 (11) A˚
? = 97.141 (5)?
V = 1662.4 (12) A˚3
Z = 4
Mo K? radiation
? = 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)
Tmin= 0.84, Tmax= 0.92
6025 measured reflections
2982 independent reflections
1869 reflections with I > 2?(I)
Rint= 0.035
Refinement
R[F2> 2?(F2)] = 0.055
wR(F2) = 0.129
S = 1.04
2982 reflections
191 parameters
H-atom parameters constrained
??max= 0.32 e A˚?3
??min= ?0.28 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
Cg is the centroid of the C1–C6 benzene ring.
D—H???A
N2—H2???S1i
C16—H16C???Cgii
Symmetry codes: (i) ?x þ 1;?y þ 1;?z þ 1; (ii) x;y ? 1;z.
D—HH???AD???AD—H???A
0.86
0.96
2.59
2.83
3.397 (4)
3.671 (5)
158
147
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refine-
ment: 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 (Shel-
drick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia,
1997); software used to prepare material for publication: WinGX
(Farrugia, 1999).
The work was supported by the Natural Science Foundation
of Zhejiang Province, China (No. M203027).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: XU5352).
References
Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl.
Cryst. 26, 343–350.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Hu, W., Sun, N. & Yang, Z. (2001). Chem. J. Chin. Univ. 22, 2014–2017.
Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678–1680.
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas,
USA.
Shan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008a). Acta Cryst.
E64, o1014.
Shan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008b). Acta Cryst.
E64, o1024.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
organic compounds
Acta Cryst. (2011). E67, o3011doi:10.1107/S1600536811042140 Fan et al.
o3011
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials

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supplementary materials
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Acta Cryst. (2011). E67, o3011 [ doi:10.1107/S1600536811042140 ]
Benzyl (E)-3-(4-methoxybenzylidene)dithiocarbazate
Z. Fan, Y.-L. Huang, Z. Wang, H.-Q. Guo and S. Shan
Comment
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).
Experimental
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.
Refinement
H atoms were placed in calculated positions with C—H = 0.93–0.97 Å and N—H = 0.86 Å, and refined in riding mode with
Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C,N) for the others.
Figures
Fig. 1. The molecular structure of the title compound with 30% probability displacement (ar-
bitrary spheres for H atoms).
Benzyl (E)-3-(4-methoxybenzylidene)dithiocarbazate
Crystal data
C16H16N2OS2
F(000) = 664
Dx = 1.264 Mg m−3
Mr = 316.43

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supplementary materials
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Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 10.267 (5) Å
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2982 reflections
θ = 3.4–25.2°
µ = 0.32 mm−1
T = 294 K
Block, colorless
b = 5.150 (2) Å
c = 31.686 (11) Å
β = 97.141 (5)°
V = 1662.4 (12) Å3
Z = 4
0.32 × 0.25 × 0.23 mm
Data collection
Rigaku R-AXIS RAPID IP
diffractometer
Radiation source: fine-focus sealed tube
graphite
Detector resolution: 10.0 pixels mm-1
ω scans
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
Tmin = 0.84, Tmax = 0.92
6025 measured reflections
2982 independent reflections
1869 reflections with I > 2σ(I)
Rint = 0.035
θmax = 25.2°, θmin = 3.5°
h = −12→10
k = −5→6
l = −31→37
Refinement
Refinement on F2
Primary atom site location: structure-invariant direct
methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring
sites
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.055
wR(F2) = 0.129
H-atom parameters constrained
S = 1.04
w = 1/[σ2(Fo2) + (0.0512P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.32 e Å−3
Δρmin = −0.28 e Å−3
2982 reflections
191 parameters
0 restraints
Special details
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 mat-
rix. 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, convention-
al 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.

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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
0.65124 (8)
0.57408 (9)
−0.0078 (2)
0.4039 (2)
0.4768 (2)
0.4665
0.2443 (3)
0.1678 (3)
0.1740
0.0825 (3)
0.0315
0.0734 (3)
0.1509 (3)
0.1456
0.2355 (3)
0.2871
0.3302 (3)
0.3314
0.5635 (3)
0.6968 (4)
0.7778
0.6662
0.7200 (5)
0.8198 (6)
0.8712
0.8464 (8)
0.9153
0.7687 (13)
0.7830
0.6712 (12)
0.6231
0.6444 (7)
0.5758
−0.0915 (4)
−0.1487
−0.1431
−0.0392
y
0.64526 (18)
0.40404 (17)
−0.7274 (5)
0.1129 (5)
0.2797 (5)
0.2815
−0.2240 (6)
−0.3916 (6)
−0.3887
−0.5632 (6)
−0.6738
−0.5699 (6)
−0.4053 (7)
−0.4105
−0.2346 (6)
−0.1255
−0.0417 (6)
−0.0376
0.4391 (6)
0.6468 (7)
0.6104
0.8177
0.6388 (8)
0.4920 (11)
0.3939
0.4854 (16)
0.3870
0.6270 (17)
0.6173
0.7826 (15)
0.8854
0.7838 (11)
0.8830
−0.8990 (7)
−0.7997
−0.9991
−1.0135
z
0.54959 (2)
0.63003 (2)
0.62062 (8)
0.57509 (7)
0.55381 (7)
0.5265
0.56941 (8)
0.54309 (9)
0.5141
0.55848 (10)
0.5400
0.60140 (10)
0.62824 (10)
0.6573
0.61278 (9)
0.6313
0.55184 (9)
0.5226
0.57512 (8)
0.64781 (9)
0.6361
0.6383
0.69529 (11)
0.71552 (14)
0.6993
0.7592 (2)
0.7727
0.7815 (2)
0.8110
0.7635 (2)
0.7801
0.71840 (14)
0.7049
0.59433 (13)
0.5741
0.6117
0.5795
Uiso*/Ueq
0.0628 (3)
0.0631 (3)
0.0810 (7)
0.0545 (7)
0.0552 (7)
0.066*
0.0491 (7)
0.0582 (9)
0.070*
0.0608 (8)
0.073*
0.0572 (8)
0.0663 (9)
0.080*
0.0596 (9)
0.072*
0.0553 (8)
0.066*
0.0498 (8)
0.0725 (10)
0.087*
0.087*
0.0815 (12)
0.1309 (19)
0.157*
0.189 (4)
0.226*
0.199 (5)
0.239*
0.212 (5)
0.255*
0.138 (2)
0.166*
0.0942 (13)
0.141*
0.141*
0.141*
S1
S2
O1
N1
N2
H2
C1
C2
H2A
C3
H3
C4
C5
H5
C6
H6
C7
H7
C8
C9
H9A
H9B
C10
C11
H11
C12
H12
C13
H13
C14
H14
C15
H15
C16
H16A
H16B
H16C
Atomic displacement parameters (Å2)
U11
0.0604 (6)
0.0699 (6)
0.0753 (19)
U22
0.0731 (6)
0.0685 (6)
0.0729 (16)
U33
0.0556 (5)
0.0511 (4)
0.0980 (16)
U12
−0.0213 (5)
−0.0216 (5)
−0.0258 (14)
U13
0.0101 (4)
0.0086 (4)
0.0229 (14)
U23
0.0138 (4)
0.0112 (4)
0.0156 (14)
S1
S2
O1