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Acta Cryst. (2008). E64, o1014    [ doi:10.1107/S1600536808012944 ]

Benzyl 3-[(E)-benzylidene]dithiocarbazate

S. Shan, Y.-L. Tian, S.-H. Wang, W.-L. Wang and Y.-L. Xu

Abstract top

Crystals of the title compound, C15H14N2S2, were obtained from a condensation reaction of benzyl dithiocarbazate and benzaldehyde. The molecule assumes an E configuration about the N=C double bond. The phenyl ring of the thioester group is nearly perpendicular to the dithiocarbazate plane, with a dihedral angle of 84.60 (5)°. In the crystal structure, intermolecular N-H...S hydrogen bonding links adjacent molecules to form a centrosymmetric supramolecular dimer.

Comment top

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

The molecular structure of the title compound is shown in Fig. 1. The N1—C7 bond distance (Table 1) indicates a typical C═N double bond; around the C═N bond the molecule assumes an E-configuration, similar to that found in methyl (β-N-phenylmethylene)dithiocarbazate (Shan et al., 2006). The dithiocarbazate moiety is coplanar with the C1-phenyl ring, the dihedral angle of 0.99 (11)° agrees with 3.00 (6)° found in methyl β-N-nitrophenylmethylenedithiocarbazate (Shan et al., 2008). In the thioester group, the C10-phenyl ring is nearly perpendicular to the dithiocarbazate plane with a dihedral angle of 84.60 (5)°. The S2—C8—N2 bond angle of 113.71 (12)° is much smaller than the S1—C8—N2 bond angle of 121.27 (13)°, which agrees with those found in related structures (Shan et al., 2006; Zhang et al., 2005).

In the crystal structure, adjacent molecules are linked into a centro-symmetric supra-molecular dimer by intermolecular N—H···S hydrogen bonding (Fig. 1 and Table 2).

Related literature top

For general background, see: Okabe et al. (1993); Hu et al. (2001). For related structures, see: Shan et al. (2006); Zhang et al. (2005); Shan et al. (2008). For synthesis, see: Hu et al. (2001).

Experimental top

Benzyl dithiocarbazate was synthesized in the manner reported previously (Hu et al., 2001). Benzyl dithiocarbazate (1.98 g, 10 mmol) and benzaldehyde (1.06 g, 10 mmol) were dissolved in ethanol (40 ml) and the solution was refluxed for 12 h. Yellow crystalline product appeared after cooling to room temperature. They were separated and washed with cold water three times. Single crystals of the title compound were obtained by recrystallization from an ethanol solution.

Refinement top

H atoms were placed in calculated positions with C—H = 0.97 (methylene), 0.93 Å (aromatic) and N—H = 0.86 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C,N)

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 ellipsoids (arbitrary spheres for H atoms). Dashed lines indicate hydrogen bonding [symmetry code: (i) -x,1 - y,2 - z].
Benzyl 3-[(E)-benzylidene]dithiocarbazate top
Crystal data top
C15H14N2S2F000 = 600
Mr = 286.40Dx = 1.314 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6568 reflections
a = 5.0053 (18) Åθ = 1.9–25.0º
b = 23.075 (8) ŵ = 0.36 mm−1
c = 12.646 (5) ÅT = 295 (2) K
β = 97.652 (12)ºPrism, yellow
V = 1447.6 (9) Å30.30 × 0.28 × 0.22 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2653 independent reflections
Radiation source: fine-focus sealed tube2115 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
Detector resolution: 10.00 pixels mm-1θmax = 25.5º
T = 295(2) Kθmin = 1.8º
ω scansh = −5→6
Absorption correction: nonek = −27→27
15395 measured reflectionsl = −15→13
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.087  w = 1/[σ2(Fo2) + (0.0424P)2 + 0.226P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2653 reflectionsΔρmax = 0.15 e Å−3
172 parametersΔρmin = −0.18 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C15H14N2S2V = 1447.6 (9) Å3
Mr = 286.40Z = 4
Monoclinic, P21/nMo Kα
a = 5.0053 (18) ŵ = 0.36 mm−1
b = 23.075 (8) ÅT = 295 (2) K
c = 12.646 (5) Å0.30 × 0.28 × 0.22 mm
β = 97.652 (12)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2653 independent reflections
Absorption correction: none2115 reflections with I > 2σ(I)
15395 measured reflectionsRint = 0.034
Refinement top
R[F2 > 2σ(F2)] = 0.032172 parameters
wR(F2) = 0.087H-atom parameters constrained
S = 1.05Δρmax = 0.15 e Å−3
2653 reflectionsΔρmin = −0.18 e Å−3
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
S1−0.16273 (11)0.58470 (2)0.94815 (4)0.06114 (17)
S20.02011 (10)0.602875 (18)0.73176 (4)0.05159 (15)
N10.3232 (3)0.50304 (6)0.78197 (11)0.0493 (4)
N20.1740 (3)0.51871 (6)0.86146 (11)0.0516 (4)
H2N0.18290.49790.91830.062*
C10.6444 (3)0.43585 (7)0.72802 (14)0.0486 (4)
C20.6602 (4)0.46157 (8)0.62992 (16)0.0599 (5)
H20.56210.49510.61090.072*
C30.8199 (5)0.43796 (10)0.56054 (17)0.0721 (6)
H30.82850.45540.49480.087*
C40.9663 (4)0.38875 (10)0.5882 (2)0.0764 (6)
H41.07360.37280.54110.092*
C50.9551 (4)0.36326 (10)0.68450 (19)0.0766 (6)
H51.05550.33000.70290.092*
C60.7955 (4)0.38637 (8)0.75514 (17)0.0632 (5)
H60.78940.36870.82090.076*
C70.4749 (4)0.45888 (7)0.80289 (15)0.0529 (4)
H70.47690.44070.86870.064*
C80.0160 (3)0.56550 (7)0.85190 (13)0.0458 (4)
C9−0.2180 (4)0.66100 (7)0.74434 (14)0.0531 (4)
H9A−0.39890.64550.74190.064*
H9B−0.17160.68100.81170.064*
C10−0.2041 (4)0.70207 (7)0.65275 (14)0.0494 (4)
C11−0.3930 (4)0.69963 (9)0.56287 (17)0.0667 (5)
H11−0.53130.67250.55940.080*
C12−0.3804 (5)0.73660 (11)0.47831 (19)0.0829 (7)
H12−0.50850.73400.41810.099*
C13−0.1794 (5)0.77726 (10)0.4826 (2)0.0791 (7)
H13−0.17270.80280.42610.095*
C140.0112 (5)0.77991 (9)0.5708 (2)0.0763 (6)
H140.14980.80690.57380.092*
C15−0.0015 (4)0.74263 (8)0.65529 (17)0.0646 (5)
H150.12880.74490.71490.077*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0859 (4)0.0527 (3)0.0517 (3)0.0075 (2)0.0347 (3)0.0005 (2)
S20.0620 (3)0.0500 (3)0.0471 (3)0.00360 (19)0.0232 (2)0.00234 (19)
N10.0549 (9)0.0477 (8)0.0489 (8)−0.0014 (7)0.0201 (7)−0.0032 (6)
N20.0653 (9)0.0477 (8)0.0461 (8)0.0036 (7)0.0230 (7)0.0024 (6)
C10.0480 (10)0.0471 (9)0.0524 (11)−0.0032 (7)0.0134 (8)−0.0040 (8)
C20.0651 (12)0.0590 (10)0.0583 (12)0.0062 (9)0.0185 (10)0.0013 (9)
C30.0781 (15)0.0856 (15)0.0573 (13)0.0032 (12)0.0262 (11)−0.0024 (11)
C40.0655 (14)0.0940 (16)0.0730 (16)0.0107 (12)0.0213 (11)−0.0231 (13)
C50.0759 (15)0.0712 (13)0.0842 (17)0.0250 (11)0.0162 (12)−0.0062 (12)
C60.0666 (13)0.0602 (11)0.0645 (13)0.0083 (9)0.0144 (10)0.0046 (9)
C70.0610 (11)0.0505 (9)0.0502 (11)0.0008 (8)0.0179 (9)0.0027 (8)
C80.0546 (10)0.0411 (8)0.0442 (10)−0.0077 (7)0.0156 (8)−0.0042 (7)
C90.0545 (11)0.0533 (10)0.0550 (11)0.0019 (8)0.0197 (9)−0.0007 (8)
C100.0528 (10)0.0460 (9)0.0519 (11)0.0087 (8)0.0166 (8)−0.0021 (8)
C110.0584 (12)0.0711 (13)0.0704 (14)0.0066 (10)0.0081 (10)0.0072 (11)
C120.0804 (16)0.0956 (17)0.0710 (15)0.0220 (14)0.0040 (12)0.0202 (13)
C130.0980 (18)0.0725 (14)0.0732 (16)0.0309 (13)0.0347 (14)0.0260 (12)
C140.0918 (17)0.0560 (11)0.0876 (17)−0.0046 (11)0.0362 (14)0.0068 (11)
C150.0734 (13)0.0599 (11)0.0619 (13)−0.0063 (10)0.0146 (10)−0.0004 (9)
Geometric parameters (Å, °) top
S1—C81.6636 (17)C5—H50.9300
S2—C81.7495 (17)C6—H60.9300
S2—C91.8153 (18)C7—H70.9300
N1—C71.277 (2)C9—C101.505 (2)
N1—N21.3777 (19)C9—H9A0.9700
N2—C81.334 (2)C9—H9B0.9700
N2—H2N0.8600C10—C151.377 (3)
C1—C21.387 (3)C10—C111.379 (3)
C1—C61.387 (3)C11—C121.376 (3)
C1—C71.454 (2)C11—H110.9300
C2—C31.375 (3)C12—C131.371 (3)
C2—H20.9300C12—H120.9300
C3—C41.372 (3)C13—C141.370 (3)
C3—H30.9300C13—H130.9300
C4—C51.360 (3)C14—C151.380 (3)
C4—H40.9300C14—H140.9300
C5—C61.382 (3)C15—H150.9300
C8—S2—C9101.79 (8)N2—C8—S2113.71 (12)
C7—N1—N2115.03 (14)S1—C8—S2125.02 (10)
C8—N2—N1121.23 (14)C10—C9—S2107.43 (11)
C8—N2—H2N119.4C10—C9—H9A110.2
N1—N2—H2N119.4S2—C9—H9A110.2
C2—C1—C6118.64 (17)C10—C9—H9B110.2
C2—C1—C7122.28 (16)S2—C9—H9B110.2
C6—C1—C7119.08 (17)H9A—C9—H9B108.5
C3—C2—C1120.55 (19)C15—C10—C11117.96 (18)
C3—C2—H2119.7C15—C10—C9121.28 (17)
C1—C2—H2119.7C11—C10—C9120.75 (17)
C4—C3—C2120.1 (2)C12—C11—C10121.2 (2)
C4—C3—H3120.0C12—C11—H11119.4
C2—C3—H3120.0C10—C11—H11119.4
C5—C4—C3120.2 (2)C13—C12—C11120.2 (2)
C5—C4—H4119.9C13—C12—H12119.9
C3—C4—H4119.9C11—C12—H12119.9
C4—C5—C6120.5 (2)C14—C13—C12119.4 (2)
C4—C5—H5119.7C14—C13—H13120.3
C6—C5—H5119.7C12—C13—H13120.3
C5—C6—C1120.0 (2)C13—C14—C15120.3 (2)
C5—C6—H6120.0C13—C14—H14119.9
C1—C6—H6120.0C15—C14—H14119.9
N1—C7—C1122.63 (16)C10—C15—C14121.0 (2)
N1—C7—H7118.7C10—C15—H15119.5
C1—C7—H7118.7C14—C15—H15119.5
N2—C8—S1121.27 (13)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···S1i0.862.563.396 (2)165
Symmetry codes: (i) −x, −y+1, −z+2.
Table 1
Selected geometric parameters (Å) top
S1—C81.6636 (17)N1—C71.277 (2)
S2—C81.7495 (17)N1—N21.3777 (19)
S2—C91.8153 (18)N2—C81.334 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···S1i0.862.563.396 (2)165
Symmetry codes: (i) −x, −y+1, −z+2.
Acknowledgements top

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

references
References top

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