Benzyl N-[1-(thio­phen-2-yl)ethyl­idene)]hydrazinecarbodi­thioate

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.

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

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S1. Comment

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).

S2. Experimental

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%.

S3. Refinement

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

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

	Fig. 1. : Molecular structure of the title compound, with the 50% probability displacement ellipsoids. Intramolecular hydrogen bonds are shown as dashed lines.
	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

Crystal data

C14H14N2S3	Z = 2
Mr = 306.45	F(000) = 320
Triclinic, P1	Dx = 1.376 Mg m^−3
a = 7.8297 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8086 (16) Å	Cell parameters from 5262 reflections
c = 11.0310 (18) Å	θ = 2.1–27.5°
α = 65.369 (3)°	µ = 0.49 mm^−1
β = 75.843 (3)°	T = 293 K
γ = 77.150 (3)°	Block, yellow
V = 739.7 (2) Å^3	0.46 × 0.30 × 0.21 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3405 independent reflections
Radiation source: fine-focus sealed tube	3012 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 83.66 pixels mm^-1	θmax = 27.5°, θmin = 2.1°
ω scan	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→12
Tmin = 0.807, Tmax = 0.905	l = −14→14
9682 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.063P)^2 + 0.1918P] where P = (Fo^2 + 2Fc^2)/3
3405 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.37330 (5)	0.09814 (5)	0.34859 (4)	0.05016 (14)
S2	0.33305 (7)	0.43778 (5)	0.19451 (5)	0.06214 (16)
S3	0.74689 (7)	−0.23321 (6)	0.20144 (5)	0.06809 (17)
N1	0.52191 (19)	0.23551 (16)	0.10104 (15)	0.0526 (3)
H1A	0.5426	0.3081	0.0236	0.063*
N2	0.59887 (19)	0.08931 (16)	0.11927 (15)	0.0500 (3)
C1	−0.0544 (3)	0.3186 (3)	0.5255 (2)	0.0639 (5)
H1	0.0011	0.3451	0.5765	0.077*
C2	−0.2325 (3)	0.3694 (3)	0.5196 (2)	0.0801 (7)
H2	−0.2964	0.4288	0.5674	0.096*
C3	−0.3149 (3)	0.3332 (3)	0.4441 (3)	0.0772 (7)
H3	−0.4345	0.3687	0.4392	0.093*
C4	−0.2215 (3)	0.2446 (3)	0.3756 (3)	0.0749 (6)
H4	−0.2776	0.2197	0.3239	0.090*
C5	−0.0440 (3)	0.1916 (2)	0.3826 (2)	0.0604 (4)
H5	0.0179	0.1298	0.3366	0.073*
C6	0.0426 (2)	0.22882 (18)	0.45635 (16)	0.0456 (3)
C7	0.2357 (2)	0.1733 (2)	0.46939 (18)	0.0515 (4)
H7A	0.2404	0.0954	0.5592	0.062*
H7B	0.2884	0.2568	0.4639	0.062*
C8	0.4141 (2)	0.26343 (18)	0.20559 (17)	0.0463 (3)
C9	0.6901 (2)	0.06283 (18)	0.01655 (16)	0.0452 (3)
C10	0.7763 (2)	−0.09249 (18)	0.04300 (17)	0.0462 (3)
C11	0.8851 (3)	−0.3636 (2)	0.1462 (3)	0.0714 (6)
H11	0.9105	−0.4647	0.2018	0.086*
C12	0.9533 (3)	−0.3057 (2)	0.0147 (3)	0.0746 (6)
H12	1.0318	−0.3614	−0.0315	0.089*
C13	0.8915 (3)	−0.1482 (2)	−0.0467 (2)	0.0663 (5)
H13	0.9255	−0.0896	−0.1377	0.080*
C14	0.7158 (3)	0.1744 (2)	−0.12607 (19)	0.0626 (5)
H14A	0.6138	0.2510	−0.1398	0.094*
H14B	0.7301	0.1235	−0.1865	0.094*
H14C	0.8200	0.2207	−0.1438	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0456 (2)	0.0432 (2)	0.0506 (2)	0.00041 (16)	−0.00379 (17)	−0.01294 (18)
S2	0.0642 (3)	0.0408 (2)	0.0663 (3)	0.00181 (19)	0.0027 (2)	−0.0180 (2)
S3	0.0679 (3)	0.0564 (3)	0.0575 (3)	0.0049 (2)	−0.0046 (2)	−0.0102 (2)
N1	0.0521 (8)	0.0410 (7)	0.0516 (8)	−0.0001 (6)	−0.0003 (6)	−0.0130 (6)
N2	0.0465 (7)	0.0415 (7)	0.0530 (8)	0.0013 (5)	−0.0044 (6)	−0.0153 (6)
C1	0.0622 (11)	0.0729 (12)	0.0568 (10)	0.0068 (9)	−0.0130 (8)	−0.0316 (10)
C2	0.0653 (13)	0.0865 (16)	0.0727 (14)	0.0164 (11)	−0.0029 (11)	−0.0335 (12)
C3	0.0423 (10)	0.0777 (15)	0.0865 (15)	−0.0018 (9)	−0.0057 (10)	−0.0132 (12)
C4	0.0572 (11)	0.0761 (14)	0.0959 (16)	−0.0150 (10)	−0.0259 (11)	−0.0272 (12)
C5	0.0513 (10)	0.0668 (11)	0.0711 (12)	−0.0070 (8)	−0.0124 (8)	−0.0336 (10)
C6	0.0421 (8)	0.0468 (8)	0.0411 (7)	−0.0057 (6)	−0.0039 (6)	−0.0122 (6)
C7	0.0449 (8)	0.0608 (10)	0.0476 (8)	−0.0024 (7)	−0.0093 (7)	−0.0213 (8)
C8	0.0385 (7)	0.0424 (8)	0.0521 (8)	−0.0008 (6)	−0.0076 (6)	−0.0149 (7)
C9	0.0438 (8)	0.0427 (8)	0.0474 (8)	−0.0047 (6)	−0.0083 (6)	−0.0159 (7)
C10	0.0482 (8)	0.0438 (8)	0.0462 (8)	−0.0038 (6)	−0.0104 (6)	−0.0169 (7)
C11	0.0738 (13)	0.0457 (10)	0.0855 (15)	0.0049 (9)	−0.0194 (11)	−0.0195 (10)
C12	0.0923 (16)	0.0533 (11)	0.0783 (14)	0.0095 (10)	−0.0132 (12)	−0.0358 (11)
C13	0.0893 (14)	0.0516 (10)	0.0559 (10)	0.0015 (9)	−0.0079 (10)	−0.0267 (9)
C14	0.0812 (13)	0.0478 (9)	0.0500 (10)	−0.0075 (9)	−0.0069 (9)	−0.0132 (8)

Geometric parameters (Å, º)

S1—C8	1.7525 (17)	C4—H4	0.9300
S1—C7	1.8009 (18)	C5—C6	1.371 (2)
S2—C8	1.6503 (17)	C5—H5	0.9300
S3—C11	1.700 (2)	C6—C7	1.510 (2)
S3—C10	1.7165 (17)	C7—H7A	0.9700
N1—C8	1.342 (2)	C7—H7B	0.9700
N1—N2	1.3765 (19)	C9—C10	1.460 (2)
N1—H1A	0.8600	C9—C14	1.490 (2)
N2—C9	1.276 (2)	C10—C13	1.373 (3)
C1—C2	1.381 (3)	C11—C12	1.335 (3)
C1—C6	1.383 (2)	C11—H11	0.9300
C1—H1	0.9300	C12—C13	1.426 (3)
C2—C3	1.360 (4)	C12—H12	0.9300
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.362 (4)	C14—H14A	0.9600
C3—H3	0.9300	C14—H14B	0.9600
C4—C5	1.381 (3)	C14—H14C	0.9600
C8—S1—C7	101.92 (8)	C6—C7—H7B	107.9
C11—S3—C10	91.97 (10)	S1—C7—H7B	107.9
C8—N1—N2	119.20 (14)	H7A—C7—H7B	107.2
C8—N1—H1A	120.4	N1—C8—S2	121.51 (13)
N2—N1—H1A	120.4	N1—C8—S1	112.89 (12)
C9—N2—N1	118.42 (14)	S2—C8—S1	125.60 (10)
C2—C1—C6	120.8 (2)	N2—C9—C10	116.05 (15)
C2—C1—H1	119.6	N2—C9—C14	126.35 (16)
C6—C1—H1	119.6	C10—C9—C14	117.60 (15)
C3—C2—C1	120.3 (2)	C13—C10—C9	127.77 (16)
C3—C2—H2	119.9	C13—C10—S3	110.35 (13)
C1—C2—H2	119.9	C9—C10—S3	121.86 (13)
C2—C3—C4	119.66 (19)	C12—C11—S3	112.98 (16)
C2—C3—H3	120.2	C12—C11—H11	123.5
C4—C3—H3	120.2	S3—C11—H11	123.5
C3—C4—C5	120.4 (2)	C11—C12—C13	111.98 (19)
C3—C4—H4	119.8	C11—C12—H12	124.0
C5—C4—H4	119.8	C13—C12—H12	124.0
C6—C5—C4	120.95 (19)	C10—C13—C12	112.73 (19)
C6—C5—H5	119.5	C10—C13—H13	123.6
C4—C5—H5	119.5	C12—C13—H13	123.6
C5—C6—C1	117.95 (17)	C9—C14—H14A	109.5
C5—C6—C7	123.59 (16)	C9—C14—H14B	109.5
C1—C6—C7	118.44 (16)	H14A—C14—H14B	109.5
C6—C7—S1	117.69 (12)	C9—C14—H14C	109.5
C6—C7—H7A	107.9	H14A—C14—H14C	109.5
S1—C7—H7A	107.9	H14B—C14—H14C	109.5
C8—N1—N2—C9	174.78 (15)	C7—S1—C8—S2	−2.12 (14)
C6—C1—C2—C3	−0.8 (4)	N1—N2—C9—C10	176.87 (14)
C1—C2—C3—C4	0.9 (4)	N1—N2—C9—C14	−3.3 (3)
C2—C3—C4—C5	0.0 (4)	N2—C9—C10—C13	−174.75 (19)
C3—C4—C5—C6	−1.1 (4)	C14—C9—C10—C13	5.4 (3)
C4—C5—C6—C1	1.2 (3)	N2—C9—C10—S3	3.4 (2)
C4—C5—C6—C7	179.29 (19)	C14—C9—C10—S3	−176.48 (14)
C2—C1—C6—C5	−0.3 (3)	C11—S3—C10—C13	−0.64 (16)
C2—C1—C6—C7	−178.5 (2)	C11—S3—C10—C9	−179.06 (15)
C5—C6—C7—S1	17.1 (2)	C10—S3—C11—C12	0.6 (2)
C1—C6—C7—S1	−164.82 (15)	S3—C11—C12—C13	−0.4 (3)
C8—S1—C7—C6	77.65 (15)	C9—C10—C13—C12	178.83 (18)
N2—N1—C8—S2	174.13 (12)	S3—C10—C13—C12	0.5 (2)
N2—N1—C8—S1	−5.8 (2)	C11—C12—C13—C10	−0.1 (3)
C7—S1—C8—N1	177.78 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S2^i	0.86	2.81	3.6450 (17)	165
C5—H5···S1	0.93	2.76	3.164 (2)	107
C7—H7B···S2	0.97	2.73	3.114 (2)	104

Symmetry code: (i) −x+1, −y+1, −z.