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In the title compound, C14H14N2S3, the benzyl and 1-(thio­phen-2-yl)ethyl­idene­amine groups are cis and trans to the thiono S atom across the C—S and C—N bonds, respectively. The di­thio­carb­aza­te plane makes dihedral angles of 9.14 (6) and 85.40 (8)° with the thio­phene­methyl­ene­amine and benzyl fragments, respectively. In the crystal structure, the mol­ecules are linked by N—H...S hydrogen bonds between the amino group and the thiono S atoms and are arranged as dimers parallel to ab face.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007517/ww6069sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007517/ww6069Isup2.hkl
Contains datablock I

CCDC reference: 214605

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.039
  • wR factor = 0.113
  • Data-to-parameter ratio = 19.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

As in the majority of the dithiocarbazate derivatives such as S-benzyldithiocarbazate (Shanmuga Sundra Raj et al., 2000) and S-methyl beta-N-(methylacetyl)methylenedithiocarbazate (Tarafder et al., 2001), the title compound, (I) (Fig.1) maintains the preferred conformation, which is cis for the benzyl group across the C—S bond, and trans for the 1-thiophene-yl-ethylideneamine (S3/C9/C10/C11/C12/C13/C14/N2) group across the C—N bond, both relative to the terminal thiono S atom·The C9—N2, N2—N1, N1—C8, C8—S2, C8—S1 bond lengths of 1.276 (2), 1.3766 (17), 1.342 (2), 1.6503 (7) and 1.7525 (17) Å, respectively, are typical of Schiff base compounds of the dithiocarbazate system and are within normal ranges (Allen et al., 1987).

There are two intramolecular interactions C5—H5···S1 and C7—H7B···S2, forming the two pseudo-five-membered rings S1···H5—C5—C6—C7 and S2···H7B—C7—S1—C8, respectively. In the crystal structure, the molecules are packed as dimers, via weak N1—H1A···S2i interactions (symmetry code as in Table 2), and arranged parallel to c-face. (Fig.2).

Experimental top

S-benzyldithiocarbazate (1.98 g, 0.01 mol), prepared as previously described (Shanmuga Sundra Raj et al., 2000), was dissolved in absolute ethanol (35 ml). To this solution,was added a solution of 2-acetylthiophene (1.26 g, 0.01 mol) in absolute ethanol (20 ml). The mixture was heated and continuously stirred for 15 min and allowed to stand until bright yellow crystals formed. The crystals were filtered, washed with ethanol and dried in vacuo over P2O5. Suitable crytals for X-ray investigation were obtained by recrystallization from ethanol. Yield: 72.6%; m.p 131.0–132.0°.; CHN Found:C,54.55%; N, 9.38%; S,31.28%; Calc for C14H15N2S3: C, 54.97%; H, 4.60%; N, 9.14%; S,31.39%.

Refinement top

After checking their location in a difference Fourier map, all H-atoms were included in the refinement in geometrically determined positions, and allowed to ride on the parent C or N atoms, with C—H = 0.97 Å and N—H = 0.89 Å.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON ( Spek, 1990).

Figures top
[Figure 1] Fig. 1. : Molecular structure of the title compound, with the 50% probability displacement ellipsoids. Intramolecular hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. : Packing diagram of (I), viewed down the c axis. The dashed lines denote the N—H···S hydrogen bonds.
N-(1-thiophene-2-yl-ethylidene)-hydrazinecarbodithioic acid benzyl ester top
Crystal data top
C14H14N2S3Z = 2
Mr = 306.45F(000) = 320
Triclinic, P1Dx = 1.376 Mg m3
a = 7.8297 (13) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.8086 (16) ÅCell parameters from 5262 reflections
c = 11.0310 (18) Åθ = 2.1–27.5°
α = 65.369 (3)°µ = 0.49 mm1
β = 75.843 (3)°T = 293 K
γ = 77.150 (3)°Block, yellow
V = 739.7 (2) Å30.46 × 0.30 × 0.21 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3405 independent reflections
Radiation source: fine-focus sealed tube3012 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
Detector resolution: 83.66 pixels mm-1θmax = 27.5°, θmin = 2.1°
ω scanh = 1010
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1212
Tmin = 0.807, Tmax = 0.905l = 1414
9682 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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.063P)2 + 0.1918P]
where P = (Fo2 + 2Fc2)/3
3405 reflections(Δ/σ)max < 0.001
173 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C14H14N2S3γ = 77.150 (3)°
Mr = 306.45V = 739.7 (2) Å3
Triclinic, P1Z = 2
a = 7.8297 (13) ÅMo Kα radiation
b = 9.8086 (16) ŵ = 0.49 mm1
c = 11.0310 (18) ÅT = 293 K
α = 65.369 (3)°0.46 × 0.30 × 0.21 mm
β = 75.843 (3)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3405 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3012 reflections with I > 2σ(I)
Tmin = 0.807, Tmax = 0.905Rint = 0.016
9682 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.04Δρmax = 0.31 e Å3
3405 reflectionsΔρmin = 0.29 e Å3
173 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.37330 (5)0.09814 (5)0.34859 (4)0.05016 (14)
S20.33305 (7)0.43778 (5)0.19451 (5)0.06214 (16)
S30.74689 (7)0.23321 (6)0.20144 (5)0.06809 (17)
N10.52191 (19)0.23551 (16)0.10104 (15)0.0526 (3)
H1A0.54260.30810.02360.063*
N20.59887 (19)0.08931 (16)0.11927 (15)0.0500 (3)
C10.0544 (3)0.3186 (3)0.5255 (2)0.0639 (5)
H10.00110.34510.57650.077*
C20.2325 (3)0.3694 (3)0.5196 (2)0.0801 (7)
H20.29640.42880.56740.096*
C30.3149 (3)0.3332 (3)0.4441 (3)0.0772 (7)
H30.43450.36870.43920.093*
C40.2215 (3)0.2446 (3)0.3756 (3)0.0749 (6)
H40.27760.21970.32390.090*
C50.0440 (3)0.1916 (2)0.3826 (2)0.0604 (4)
H50.01790.12980.33660.073*
C60.0426 (2)0.22882 (18)0.45635 (16)0.0456 (3)
C70.2357 (2)0.1733 (2)0.46939 (18)0.0515 (4)
H7A0.24040.09540.55920.062*
H7B0.28840.25680.46390.062*
C80.4141 (2)0.26343 (18)0.20559 (17)0.0463 (3)
C90.6901 (2)0.06283 (18)0.01655 (16)0.0452 (3)
C100.7763 (2)0.09249 (18)0.04300 (17)0.0462 (3)
C110.8851 (3)0.3636 (2)0.1462 (3)0.0714 (6)
H110.91050.46470.20180.086*
C120.9533 (3)0.3057 (2)0.0147 (3)0.0746 (6)
H121.03180.36140.03150.089*
C130.8915 (3)0.1482 (2)0.0467 (2)0.0663 (5)
H130.92550.08960.13770.080*
C140.7158 (3)0.1744 (2)0.12607 (19)0.0626 (5)
H14A0.61380.25100.13980.094*
H14B0.73010.12350.18650.094*
H14C0.82000.22070.14380.094*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0456 (2)0.0432 (2)0.0506 (2)0.00041 (16)0.00379 (17)0.01294 (18)
S20.0642 (3)0.0408 (2)0.0663 (3)0.00181 (19)0.0027 (2)0.0180 (2)
S30.0679 (3)0.0564 (3)0.0575 (3)0.0049 (2)0.0046 (2)0.0102 (2)
N10.0521 (8)0.0410 (7)0.0516 (8)0.0001 (6)0.0003 (6)0.0130 (6)
N20.0465 (7)0.0415 (7)0.0530 (8)0.0013 (5)0.0044 (6)0.0153 (6)
C10.0622 (11)0.0729 (12)0.0568 (10)0.0068 (9)0.0130 (8)0.0316 (10)
C20.0653 (13)0.0865 (16)0.0727 (14)0.0164 (11)0.0029 (11)0.0335 (12)
C30.0423 (10)0.0777 (15)0.0865 (15)0.0018 (9)0.0057 (10)0.0132 (12)
C40.0572 (11)0.0761 (14)0.0959 (16)0.0150 (10)0.0259 (11)0.0272 (12)
C50.0513 (10)0.0668 (11)0.0711 (12)0.0070 (8)0.0124 (8)0.0336 (10)
C60.0421 (8)0.0468 (8)0.0411 (7)0.0057 (6)0.0039 (6)0.0122 (6)
C70.0449 (8)0.0608 (10)0.0476 (8)0.0024 (7)0.0093 (7)0.0213 (8)
C80.0385 (7)0.0424 (8)0.0521 (8)0.0008 (6)0.0076 (6)0.0149 (7)
C90.0438 (8)0.0427 (8)0.0474 (8)0.0047 (6)0.0083 (6)0.0159 (7)
C100.0482 (8)0.0438 (8)0.0462 (8)0.0038 (6)0.0104 (6)0.0169 (7)
C110.0738 (13)0.0457 (10)0.0855 (15)0.0049 (9)0.0194 (11)0.0195 (10)
C120.0923 (16)0.0533 (11)0.0783 (14)0.0095 (10)0.0132 (12)0.0358 (11)
C130.0893 (14)0.0516 (10)0.0559 (10)0.0015 (9)0.0079 (10)0.0267 (9)
C140.0812 (13)0.0478 (9)0.0500 (10)0.0075 (9)0.0069 (9)0.0132 (8)
Geometric parameters (Å, º) top
S1—C81.7525 (17)C4—H40.9300
S1—C71.8009 (18)C5—C61.371 (2)
S2—C81.6503 (17)C5—H50.9300
S3—C111.700 (2)C6—C71.510 (2)
S3—C101.7165 (17)C7—H7A0.9700
N1—C81.342 (2)C7—H7B0.9700
N1—N21.3765 (19)C9—C101.460 (2)
N1—H1A0.8600C9—C141.490 (2)
N2—C91.276 (2)C10—C131.373 (3)
C1—C21.381 (3)C11—C121.335 (3)
C1—C61.383 (2)C11—H110.9300
C1—H10.9300C12—C131.426 (3)
C2—C31.360 (4)C12—H120.9300
C2—H20.9300C13—H130.9300
C3—C41.362 (4)C14—H14A0.9600
C3—H30.9300C14—H14B0.9600
C4—C51.381 (3)C14—H14C0.9600
C8—S1—C7101.92 (8)C6—C7—H7B107.9
C11—S3—C1091.97 (10)S1—C7—H7B107.9
C8—N1—N2119.20 (14)H7A—C7—H7B107.2
C8—N1—H1A120.4N1—C8—S2121.51 (13)
N2—N1—H1A120.4N1—C8—S1112.89 (12)
C9—N2—N1118.42 (14)S2—C8—S1125.60 (10)
C2—C1—C6120.8 (2)N2—C9—C10116.05 (15)
C2—C1—H1119.6N2—C9—C14126.35 (16)
C6—C1—H1119.6C10—C9—C14117.60 (15)
C3—C2—C1120.3 (2)C13—C10—C9127.77 (16)
C3—C2—H2119.9C13—C10—S3110.35 (13)
C1—C2—H2119.9C9—C10—S3121.86 (13)
C2—C3—C4119.66 (19)C12—C11—S3112.98 (16)
C2—C3—H3120.2C12—C11—H11123.5
C4—C3—H3120.2S3—C11—H11123.5
C3—C4—C5120.4 (2)C11—C12—C13111.98 (19)
C3—C4—H4119.8C11—C12—H12124.0
C5—C4—H4119.8C13—C12—H12124.0
C6—C5—C4120.95 (19)C10—C13—C12112.73 (19)
C6—C5—H5119.5C10—C13—H13123.6
C4—C5—H5119.5C12—C13—H13123.6
C5—C6—C1117.95 (17)C9—C14—H14A109.5
C5—C6—C7123.59 (16)C9—C14—H14B109.5
C1—C6—C7118.44 (16)H14A—C14—H14B109.5
C6—C7—S1117.69 (12)C9—C14—H14C109.5
C6—C7—H7A107.9H14A—C14—H14C109.5
S1—C7—H7A107.9H14B—C14—H14C109.5
C8—N1—N2—C9174.78 (15)C7—S1—C8—S22.12 (14)
C6—C1—C2—C30.8 (4)N1—N2—C9—C10176.87 (14)
C1—C2—C3—C40.9 (4)N1—N2—C9—C143.3 (3)
C2—C3—C4—C50.0 (4)N2—C9—C10—C13174.75 (19)
C3—C4—C5—C61.1 (4)C14—C9—C10—C135.4 (3)
C4—C5—C6—C11.2 (3)N2—C9—C10—S33.4 (2)
C4—C5—C6—C7179.29 (19)C14—C9—C10—S3176.48 (14)
C2—C1—C6—C50.3 (3)C11—S3—C10—C130.64 (16)
C2—C1—C6—C7178.5 (2)C11—S3—C10—C9179.06 (15)
C5—C6—C7—S117.1 (2)C10—S3—C11—C120.6 (2)
C1—C6—C7—S1164.82 (15)S3—C11—C12—C130.4 (3)
C8—S1—C7—C677.65 (15)C9—C10—C13—C12178.83 (18)
N2—N1—C8—S2174.13 (12)S3—C10—C13—C120.5 (2)
N2—N1—C8—S15.8 (2)C11—C12—C13—C100.1 (3)
C7—S1—C8—N1177.78 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···S2i0.862.813.6450 (17)165
C5—H5···S10.932.763.164 (2)107
C7—H7B···S20.972.733.114 (2)104
Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC14H14N2S3
Mr306.45
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.8297 (13), 9.8086 (16), 11.0310 (18)
α, β, γ (°)65.369 (3), 75.843 (3), 77.150 (3)
V3)739.7 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.46 × 0.30 × 0.21
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.807, 0.905
No. of measured, independent and
observed [I > 2σ(I)] reflections
9682, 3405, 3012
Rint0.016
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.113, 1.04
No. of reflections3405
No. of parameters173
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.29

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON ( Spek, 1990).

Selected geometric parameters (Å, º) top
S1—C81.7525 (17)N1—C81.342 (2)
S1—C71.8009 (18)N1—N21.3765 (19)
S2—C81.6503 (17)N2—C91.276 (2)
C8—S1—C7101.92 (8)N1—C8—S1112.89 (12)
C9—N2—N1118.42 (14)S2—C8—S1125.60 (10)
N1—C8—S2121.51 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···S2i0.862.813.6450 (17)165
C5—H5···S10.932.763.164 (2)107
C7—H7B···S20.972.733.114 (2)104
Symmetry code: (i) x+1, y+1, z.
 

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