organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678-1680.]); Hu et al. (2001[Hu, W., Sun, N. & Yang, Z. (2001). Chem. J. Chin. Univ. 22, 2014-2017.]). For related structures, see: Shan et al. (2008a[Shan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008a). Acta Cryst. E64, o1014.],b[Shan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008b). Acta Cryst. E64, o1024.]). For the synthesis, see: Hu et al. (2001[Hu, W., Sun, N. & Yang, Z. (2001). Chem. J. Chin. Univ. 22, 2014-2017.]).

[Scheme 1]

Experimental

Crystal data
  • C16H16N2OS2

  • Mr = 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.84, Tmax = 0.92

  • 6025 measured reflections

  • 2982 independent reflections

  • 1869 reflections with I > 2σ(I)

  • Rint = 0.035

Refinement
  • R[F2 > 2σ(F2)] = 0.055

  • wR(F2) = 0.129

  • S = 1.04

  • 2982 reflections

  • 191 parameters

  • H-atom parameters constrained

  • Δρmax = 0.32 e Å−3

  • Δρmin = −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 DA D—H⋯A
N2—H2⋯S1i 0.86 2.59 3.397 (4) 158
C16—H16CCgii 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[Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); program(s) used to solve structure: SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


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 CN 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.

Refinement top

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.

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
[Figure 1] 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
C16H16N2OS2F(000) = 664
Mr = 316.43Dx = 1.264 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2982 reflections
a = 10.267 (5) Åθ = 3.4–25.2°
b = 5.150 (2) ŵ = 0.32 mm1
c = 31.686 (11) ÅT = 294 K
β = 97.141 (5)°Block, colorless
V = 1662.4 (12) Å30.32 × 0.25 × 0.23 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer
2982 independent reflections
Radiation source: fine-focus sealed tube1869 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
Detector resolution: 10.0 pixels mm-1θmax = 25.2°, θmin = 3.5°
ω scansh = 1210
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 56
Tmin = 0.84, Tmax = 0.92l = 3137
6025 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0512P)2]
where P = (Fo2 + 2Fc2)/3
2982 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C16H16N2OS2V = 1662.4 (12) Å3
Mr = 316.43Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.267 (5) ŵ = 0.32 mm1
b = 5.150 (2) ÅT = 294 K
c = 31.686 (11) Å0.32 × 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)
Tmin = 0.84, Tmax = 0.92Rint = 0.035
6025 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.129H-atom parameters constrained
S = 1.04Δρmax = 0.32 e Å3
2982 reflectionsΔρmin = 0.28 e Å3
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
xyzUiso*/Ueq
S10.65124 (8)0.64526 (18)0.54959 (2)0.0628 (3)
S20.57408 (9)0.40404 (17)0.63003 (2)0.0631 (3)
O10.0078 (2)0.7274 (5)0.62062 (8)0.0810 (7)
N10.4039 (2)0.1129 (5)0.57509 (7)0.0545 (7)
N20.4768 (2)0.2797 (5)0.55381 (7)0.0552 (7)
H20.46650.28150.52650.066*
C10.2443 (3)0.2240 (6)0.56941 (8)0.0491 (7)
C20.1678 (3)0.3916 (6)0.54309 (9)0.0582 (9)
H2A0.17400.38870.51410.070*
C30.0825 (3)0.5632 (6)0.55848 (10)0.0608 (8)
H30.03150.67380.54000.073*
C40.0734 (3)0.5699 (6)0.60140 (10)0.0572 (8)
C50.1509 (3)0.4053 (7)0.62824 (10)0.0663 (9)
H50.14560.41050.65730.080*
C60.2355 (3)0.2346 (6)0.61278 (9)0.0596 (9)
H60.28710.12550.63130.072*
C70.3302 (3)0.0417 (6)0.55184 (9)0.0553 (8)
H70.33140.03760.52260.066*
C80.5635 (3)0.4391 (6)0.57512 (8)0.0498 (8)
C90.6968 (4)0.6468 (7)0.64781 (9)0.0725 (10)
H9A0.77780.61040.63610.087*
H9B0.66620.81770.63830.087*
C100.7200 (5)0.6388 (8)0.69529 (11)0.0815 (12)
C110.8198 (6)0.4920 (11)0.71552 (14)0.1309 (19)
H110.87120.39390.69930.157*
C120.8464 (8)0.4854 (16)0.7592 (2)0.189 (4)
H120.91530.38700.77270.226*
C130.7687 (13)0.6270 (17)0.7815 (2)0.199 (5)
H130.78300.61730.81100.239*
C140.6712 (12)0.7826 (15)0.7635 (2)0.212 (5)
H140.62310.88540.78010.255*
C150.6444 (7)0.7838 (11)0.71840 (14)0.138 (2)
H150.57580.88300.70490.166*
C160.0915 (4)0.8990 (7)0.59433 (13)0.0942 (13)
H16A0.14870.79970.57410.141*
H16B0.14310.99910.61170.141*
H16C0.03921.01350.57950.141*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0604 (6)0.0731 (6)0.0556 (5)0.0213 (5)0.0101 (4)0.0138 (4)
S20.0699 (6)0.0685 (6)0.0511 (4)0.0216 (5)0.0086 (4)0.0112 (4)
O10.0753 (19)0.0729 (16)0.0980 (16)0.0258 (14)0.0229 (14)0.0156 (14)
N10.0472 (16)0.0563 (16)0.0604 (14)0.0115 (14)0.0078 (12)0.0121 (13)
N20.0510 (17)0.0639 (17)0.0514 (13)0.0149 (14)0.0087 (12)0.0088 (13)
C10.0451 (19)0.0492 (18)0.0530 (17)0.0071 (15)0.0060 (14)0.0066 (14)
C20.056 (2)0.067 (2)0.0508 (16)0.0112 (18)0.0042 (14)0.0004 (16)
C30.053 (2)0.058 (2)0.069 (2)0.0126 (17)0.0002 (15)0.0007 (17)
C40.050 (2)0.0486 (19)0.074 (2)0.0096 (16)0.0093 (16)0.0115 (17)
C50.074 (2)0.073 (2)0.0528 (17)0.016 (2)0.0123 (16)0.0100 (17)
C60.063 (2)0.060 (2)0.0542 (18)0.0183 (18)0.0026 (15)0.0033 (16)
C70.0455 (19)0.064 (2)0.0565 (17)0.0062 (17)0.0073 (14)0.0112 (16)
C80.0430 (18)0.0526 (19)0.0544 (16)0.0034 (15)0.0088 (14)0.0089 (15)
C90.088 (3)0.071 (2)0.0579 (18)0.030 (2)0.0062 (17)0.0061 (17)
C100.120 (4)0.066 (2)0.057 (2)0.034 (2)0.006 (2)0.004 (2)
C110.157 (5)0.132 (4)0.094 (3)0.011 (4)0.023 (3)0.025 (3)
C120.271 (10)0.173 (7)0.099 (4)0.046 (7)0.069 (5)0.040 (5)
C130.408 (15)0.124 (7)0.064 (4)0.114 (8)0.031 (6)0.006 (4)
C140.433 (16)0.110 (6)0.105 (5)0.051 (7)0.080 (7)0.021 (4)
C150.228 (7)0.119 (4)0.073 (3)0.013 (4)0.040 (4)0.005 (3)
C160.072 (3)0.067 (3)0.145 (3)0.028 (2)0.019 (2)0.016 (3)
Geometric parameters (Å, º) top
S1—C81.665 (3)C6—H60.9300
S2—C81.739 (3)C7—H70.9300
S2—C91.814 (3)C9—C101.494 (4)
O1—C41.360 (4)C9—H9A0.9700
O1—C161.427 (4)C9—H9B0.9700
N1—C71.269 (4)C10—C151.356 (6)
N1—N21.371 (3)C10—C111.367 (6)
N2—C81.331 (3)C11—C121.376 (7)
N2—H20.8600C11—H110.9300
C1—C21.376 (4)C12—C131.345 (11)
C1—C61.390 (4)C12—H120.9300
C1—C71.446 (4)C13—C141.352 (13)
C2—C31.376 (4)C13—H130.9300
C2—H2A0.9300C14—C151.423 (8)
C3—C41.375 (4)C14—H140.9300
C3—H30.9300C15—H150.9300
C4—C51.381 (4)C16—H16A0.9600
C5—C61.368 (4)C16—H16B0.9600
C5—H50.9300C16—H16C0.9600
C8—S2—C9101.16 (14)C10—C9—S2108.1 (2)
C4—O1—C16117.8 (3)C10—C9—H9A110.1
C7—N1—N2115.5 (2)S2—C9—H9A110.1
C8—N2—N1120.6 (2)C10—C9—H9B110.1
C8—N2—H2119.7S2—C9—H9B110.1
N1—N2—H2119.7H9A—C9—H9B108.4
C2—C1—C6118.2 (3)C15—C10—C11119.8 (4)
C2—C1—C7120.2 (3)C15—C10—C9119.9 (4)
C6—C1—C7121.6 (3)C11—C10—C9120.2 (4)
C3—C2—C1121.9 (3)C10—C11—C12121.9 (6)
C3—C2—H2A119.0C10—C11—H11119.1
C1—C2—H2A119.0C12—C11—H11119.1
C4—C3—C2119.4 (3)C13—C12—C11117.3 (8)
C4—C3—H3120.3C13—C12—H12121.3
C2—C3—H3120.3C11—C12—H12121.3
O1—C4—C3125.3 (3)C12—C13—C14123.8 (7)
O1—C4—C5115.4 (3)C12—C13—H13118.1
C3—C4—C5119.2 (3)C14—C13—H13118.1
C6—C5—C4121.1 (3)C13—C14—C15117.8 (8)
C6—C5—H5119.4C13—C14—H14121.1
C4—C5—H5119.4C15—C14—H14121.1
C5—C6—C1120.1 (3)C10—C15—C14119.2 (7)
C5—C6—H6119.9C10—C15—H15120.4
C1—C6—H6119.9C14—C15—H15120.4
N1—C7—C1122.2 (3)O1—C16—H16A109.5
N1—C7—H7118.9O1—C16—H16B109.5
C1—C7—H7118.9H16A—C16—H16B109.5
N2—C8—S1121.0 (2)O1—C16—H16C109.5
N2—C8—S2113.5 (2)H16A—C16—H16C109.5
S1—C8—S2125.59 (18)H16B—C16—H16C109.5
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C1–C6 benzene ring.
D—H···AD—HH···AD···AD—H···A
N2—H2···S1i0.862.593.397 (4)158
C16—H16C···Cgii0.962.833.671 (5)147
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y1, z.

Experimental details

Crystal data
Chemical formulaC16H16N2OS2
Mr316.43
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)10.267 (5), 5.150 (2), 31.686 (11)
β (°) 97.141 (5)
V3)1662.4 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.32
Crystal size (mm)0.32 × 0.25 × 0.23
Data collection
DiffractometerRigaku R-AXIS RAPID IP
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.84, 0.92
No. of measured, independent and
observed [I > 2σ(I)] reflections
6025, 2982, 1869
Rint0.035
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.129, 1.04
No. of reflections2982
No. of parameters191
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2···S1i0.862.593.397 (4)158
C16—H16C···Cgii0.962.833.671 (5)147
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y1, z.
 

Acknowledgements

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

References

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First citationShan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008a). Acta Cryst. E64, o1014.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationShan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008b). Acta Cryst. E64, o1024.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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