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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1014.
Published online 2008 May 7. doi:  10.1107/S1600536808012944
PMCID: PMC2961347

Benzyl 3-[(E)-benzyl­idene]dithio­carbazate

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-o1014-scheme1.jpg

Experimental

Crystal data

  • C15H14N2S2
  • M r = 286.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1014-efi1.jpg
  • a = 5.0053 (18) Å
  • b = 23.075 (8) Å
  • c = 12.646 (5) Å
  • β = 97.652 (12)°
  • V = 1447.6 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.35 mm−1
  • T = 295 (2) K
  • 0.30 × 0.28 × 0.22 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: none
  • 15395 measured reflections
  • 2653 independent reflections
  • 2115 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.087
  • S = 1.05
  • 2653 reflections
  • 172 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 [triangle]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SIR92 (Altomare et al., 1993 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808012944/xu2422sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012944/xu2422Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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

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)

Figures

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].

Crystal data

C15H14N2S2F000 = 600
Mr = 286.40Dx = 1.314 Mg m3
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 mm1
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

Rigaku R-AXIS RAPID diffractometer2653 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

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 Å3
172 parametersΔρmin = −0.18 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 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)

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)

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, °)

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, °)

D—H···AD—HH···AD···AD—H···A
N2—H2N···S1i0.862.563.396 (2)165

Symmetry codes: (i) −x, −y+1, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2422).

References

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