Methyl 3-[(E,E)-3-phenyl­prop-2-enyl­idene]dithio­carbazate

Tarafder, M.T.H.; Khan, S.S.; Islam, M.A.A.A.A.; Lorenzi, L.; Zangrando, E.

doi:10.1107/S1600536810041115

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2851

https://doi.org/10.1107/S1600536810041115

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Methyl 3-[(E,E)-3-phenylprop-2-enylidene]dithiocarbazate

M. T. H. Tarafder,^a ^* Sultana Shakila Khan,^a M. A. A. A. A. Islam,^b Lea Lorenzi ^c and Ennio Zangrando ^c

^aDepartment of Chemistry, Rajshahi University, Rajshahi 6205, Bangladesh, ^bDepartment of Chemistry, Rajshahi University of Engineering & Technology, Rajshahi 6204, Bangladesh, and ^cDipartimento di Scienze Chimiche, Via Licio Giorgieri 1, 34127 Trieste, Italy
^*Correspondence e-mail: ttofazzal@yahoo.com

(Received 6 October 2010; accepted 13 October 2010; online 20 October 2010)

In the title compound, C₁₁H₁₂N₂S₂, the dithiocarbazate group adopts an EE configuration with respect to the C=C and C=N bonds of the propenylidene group. The atoms of the propenylidene and dithiocarbazate unit are essentially co-planar, with a maximum deviation of 0.058 (1) Å; the phenyl ring forms a dihedral angle of 18.3 (1)° with this fragment. In the crystal, molecules form inversion dimers via pairs of N—H⋯S hydrogen bonds involving the terminal S atom.

Related literature

For the synthesis and a related structure, see: Tarafder et al. (2008 ).

Experimental

Crystal data

C₁₁H₁₂N₂S₂
M_r = 236.35
Monoclinic, P 2₁ /c
a = 10.408 (2) Å
b = 5.4950 (9) Å
c = 20.988 (2) Å
β = 100.697 (10)°
V = 1179.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 293 K
0.40 × 0.15 × 0.12 mm

Data collection

Enraf–Nonius DIP1030 image-plate diffractometer
6316 measured reflections
2048 independent reflections
1569 reflections with I > 2.0σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.116
S = 1.04
2048 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.86	2.67	3.4086 (19)	145
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: XPRESS (MacScience, 2002 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810041115/pv2336sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041115/pv2336Isup2.hkl

checkCIF report

Comment top

The molecule of the title compound is shown in Fig. 1. The atoms of propenylidene and dithiocarbazate moiety lie essentially in the same plane, with a maximum deviation from the mean plane of 0.058 (1) Å exhibited by S2, while the phenyl ring forms a dihedral angle of 18.3 (1)° with the cited fragment. The crystal packing evidences molecules connected in pairs about inversion centers and connected by N1—H1···S1 hydrogen bonds involving the terminal sulfur atom (Table 1). The structural features of the title compound are smilar to those observed in a benzyl derivative (Tarafder et al., 2008)). The Schiff base is potentially bidentate and coordinates via the β-nitrogen and the thiolate anion generated during complexation.

Related literature top

For the synthesis and a related structure, see: Tarafder et al. (2008).

Experimental top

The S-methyldithiocarbazate (2.44 g, 0.2 mol), prepared as previously described (Tarafder et al., 2008), was dissolved in hot absolute ethanol (30–40 ml). To this solution an equimolar amount of cinnamaldehyde in hot absolute ethanol (20 ml) was added and the mixture was heated for 20 min and then cooled. The orange precipitate thus formed was separated and dried in vacuo over anhydrous CaCl₂. Orange needle shaped single crystals of the Schiff base were obtained after recrysallization from acetone over 15 days; M. p. 443 K (very sharp and abrupt).

Structure description top

For the synthesis and a related structure, see: Tarafder et al. (2008).

Computing details top

Data collection: XPRESS (MacScience, 2002); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); 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

Fig. 1. ORTEP drawing of the title molecule; thermal ellipsoids are drawn at the 40% probability level.

Methyl 3-[(E,E)-3-phenylprop-2-enylidene]dithiocarbazate top

Crystal data top

C₁₁H₁₂N₂S₂	F(000) = 496
M_r = 236.35	D_x = 1.331 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 275 reflections
a = 10.408 (2) Å	θ = 3.6–20.7°
b = 5.4950 (9) Å	µ = 0.42 mm⁻¹
c = 20.988 (2) Å	T = 293 K
β = 100.697 (10)°	Needle, orange
V = 1179.5 (3) Å³	0.40 × 0.15 × 0.12 mm
Z = 4

Data collection top

Enraf–Nonius DIP1030 image-plate diffractometer	1569 reflections with I > 2.0σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.037
Graphite monochromator	θ_max = 25.3°, θ_min = 3.1°
φ–scans with narrow frames	h = −12→12
6316 measured reflections	k = −6→6
2048 independent reflections	l = −25→25

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.116	w = 1/[σ²(F_o²) + (0.0721P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2048 reflections	Δρ_max = 0.14 e Å⁻³
138 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.023 (4)

Crystal data top

C₁₁H₁₂N₂S₂	V = 1179.5 (3) Å³
M_r = 236.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.408 (2) Å	µ = 0.42 mm⁻¹
b = 5.4950 (9) Å	T = 293 K
c = 20.988 (2) Å	0.40 × 0.15 × 0.12 mm
β = 100.697 (10)°

Data collection top

Enraf–Nonius DIP1030 image-plate diffractometer	1569 reflections with I > 2.0σ(I)
6316 measured reflections	R_int = 0.037
2048 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.04	Δρ_max = 0.14 e Å⁻³
2048 reflections	Δρ_min = −0.21 e Å⁻³
138 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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

	x	y	z	U_iso*/U_eq
S1	1.15322 (6)	0.68232 (10)	0.57196 (3)	0.0759 (2)
S2	1.08034 (6)	0.51686 (10)	0.69852 (3)	0.0734 (2)
N1	0.99960 (18)	0.3187 (3)	0.58644 (8)	0.0682 (5)
H1	0.9962	0.2915	0.5458	0.082*
N2	0.92717 (19)	0.1751 (3)	0.62061 (9)	0.0680 (5)
C1	1.1813 (3)	0.7789 (4)	0.72034 (11)	0.0791 (6)
H1A	1.2653	0.7525	0.7089	0.119*
H1B	1.1918	0.8059	0.7662	0.119*
H1C	1.1407	0.9187	0.6976	0.119*
C2	1.0751 (2)	0.4996 (3)	0.61523 (10)	0.0625 (5)
C3	0.8633 (2)	0.0018 (3)	0.58766 (11)	0.0656 (5)
H3	0.8723	−0.0225	0.5449	0.079*
C4	0.7788 (2)	−0.1538 (3)	0.61562 (10)	0.0670 (5)
H4	0.7718	−0.1294	0.6587	0.080*
C5	0.7095 (2)	−0.3328 (3)	0.58259 (10)	0.0653 (5)
H5	0.7240	−0.3613	0.5408	0.078*
C6	0.6139 (2)	−0.4880 (3)	0.60503 (10)	0.0634 (5)
C7	0.5705 (3)	−0.4487 (4)	0.66304 (12)	0.0750 (6)
H7	0.6053	−0.3208	0.6898	0.090*
C8	0.4770 (3)	−0.5962 (5)	0.68147 (14)	0.0898 (7)
H8	0.4487	−0.5659	0.7202	0.108*
C9	0.4250 (3)	−0.7874 (5)	0.64316 (17)	0.0963 (9)
H9	0.3623	−0.8870	0.6560	0.116*
C10	0.4657 (3)	−0.8309 (4)	0.58615 (16)	0.0944 (8)
H10	0.4305	−0.9603	0.5601	0.113*
C11	0.5596 (3)	−0.6831 (4)	0.56675 (13)	0.0799 (7)
H11	0.5866	−0.7146	0.5277	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0761 (5)	0.0872 (4)	0.0662 (4)	−0.0152 (3)	0.0178 (3)	0.0061 (2)
S2	0.0809 (5)	0.0799 (4)	0.0592 (4)	−0.0143 (3)	0.0122 (3)	0.0035 (2)
N1	0.0743 (13)	0.0726 (10)	0.0600 (10)	−0.0089 (9)	0.0181 (9)	−0.0002 (7)
N2	0.0681 (12)	0.0698 (10)	0.0670 (10)	−0.0066 (8)	0.0150 (9)	0.0030 (8)
C1	0.0811 (17)	0.0813 (13)	0.0730 (14)	−0.0110 (12)	0.0092 (12)	−0.0046 (10)
C2	0.0574 (13)	0.0664 (12)	0.0636 (12)	0.0012 (9)	0.0112 (9)	0.0024 (8)
C3	0.0686 (15)	0.0647 (12)	0.0631 (12)	0.0011 (10)	0.0111 (10)	0.0014 (8)
C4	0.0698 (15)	0.0673 (11)	0.0631 (12)	−0.0028 (10)	0.0104 (10)	0.0010 (9)
C5	0.0682 (14)	0.0658 (12)	0.0611 (11)	0.0013 (10)	0.0099 (10)	−0.0002 (8)
C6	0.0633 (14)	0.0560 (10)	0.0683 (13)	0.0023 (8)	0.0057 (10)	0.0036 (8)
C7	0.0799 (17)	0.0700 (12)	0.0756 (14)	−0.0059 (11)	0.0160 (12)	0.0006 (10)
C8	0.090 (2)	0.0870 (15)	0.0964 (18)	−0.0020 (14)	0.0276 (15)	0.0160 (13)
C9	0.0772 (18)	0.0813 (16)	0.129 (3)	−0.0085 (13)	0.0151 (17)	0.0274 (16)
C10	0.091 (2)	0.0722 (15)	0.114 (2)	−0.0154 (13)	0.0022 (17)	−0.0017 (13)
C11	0.0866 (18)	0.0680 (13)	0.0813 (15)	−0.0038 (12)	0.0061 (13)	−0.0054 (10)

Geometric parameters (Å, º) top

S1—C2	1.664 (2)	C5—C6	1.454 (3)
S2—C2	1.741 (2)	C5—H5	0.9300
S2—C1	1.791 (2)	C6—C7	1.392 (3)
N1—C2	1.339 (3)	C6—C11	1.395 (3)
N1—N2	1.381 (2)	C7—C8	1.376 (3)
N1—H1	0.8600	C7—H7	0.9300
N2—C3	1.287 (3)	C8—C9	1.372 (4)
C1—H1A	0.9600	C8—H8	0.9300
C1—H1B	0.9600	C9—C10	1.363 (4)
C1—H1C	0.9600	C9—H9	0.9300
C3—C4	1.428 (3)	C10—C11	1.388 (4)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.335 (3)	C11—H11	0.9300
C4—H4	0.9300

C2—S2—C1	102.02 (11)	C4—C5—H5	116.6
C2—N1—N2	121.39 (18)	C6—C5—H5	116.6
C2—N1—H1	119.3	C7—C6—C11	117.4 (2)
N2—N1—H1	119.3	C7—C6—C5	123.05 (18)
C3—N2—N1	114.92 (18)	C11—C6—C5	119.5 (2)
S2—C1—H1A	109.5	C8—C7—C6	121.1 (2)
S2—C1—H1B	109.5	C8—C7—H7	119.5
H1A—C1—H1B	109.5	C6—C7—H7	119.5
S2—C1—H1C	109.5	C9—C8—C7	120.6 (3)
H1A—C1—H1C	109.5	C9—C8—H8	119.7
H1B—C1—H1C	109.5	C7—C8—H8	119.7
N1—C2—S1	120.44 (16)	C10—C9—C8	119.7 (3)
N1—C2—S2	113.58 (15)	C10—C9—H9	120.1
S1—C2—S2	125.98 (12)	C8—C9—H9	120.1
N2—C3—C4	121.2 (2)	C9—C10—C11	120.4 (2)
N2—C3—H3	119.4	C9—C10—H10	119.8
C4—C3—H3	119.4	C11—C10—H10	119.8
C5—C4—C3	122.8 (2)	C10—C11—C6	120.8 (3)
C5—C4—H4	118.6	C10—C11—H11	119.6
C3—C4—H4	118.6	C6—C11—H11	119.6
C4—C5—C6	126.9 (2)

C2—N1—N2—C3	−177.27 (18)	C4—C5—C6—C11	−173.6 (2)
N2—N1—C2—S1	−175.70 (15)	C11—C6—C7—C8	−0.5 (3)
N2—N1—C2—S2	4.4 (2)	C5—C6—C7—C8	178.1 (2)
C1—S2—C2—N1	−177.67 (16)	C6—C7—C8—C9	0.6 (4)
C1—S2—C2—S1	2.41 (18)	C7—C8—C9—C10	−0.4 (4)
N1—N2—C3—C4	−176.76 (18)	C8—C9—C10—C11	0.1 (4)
N2—C3—C4—C5	178.9 (2)	C9—C10—C11—C6	0.0 (4)
C3—C4—C5—C6	−174.93 (19)	C7—C6—C11—C10	0.2 (3)
C4—C5—C6—C7	7.9 (3)	C5—C6—C11—C10	−178.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.86	2.67	3.4086 (19)	145

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₂S₂
M_r	236.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.408 (2), 5.4950 (9), 20.988 (2)
β (°)	100.697 (10)
V (Å³)	1179.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.40 × 0.15 × 0.12

Data collection
Diffractometer	Enraf–Nonius DIP1030 image-plate diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2.0σ(I)] reflections	6316, 2048, 1569
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.116, 1.04
No. of reflections	2048
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.21

Computer programs: XPRESS (MacScience, 2002), DENZO (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.86	2.67	3.4086 (19)	145

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

MTHT, SSK and MAAAAI are grateful to the Department of Chemistry, Rajshahi University, for the provision of laboratory facilities. EZ thanks MIUR, Rome (PRIN No. 2007HMTJWP_002) for financial support.

References

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