Benzyl N′-(1-methyl-1H-indol-3-yl­methyl­idene)hydrazinecarbodithio­ate

Khaledi, H.; Mohd Ali, H.; Ng, S.W.

doi:10.1107/S1600536808039330

organic compounds

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Volume 64| Part 12| December 2008| Page o2482

doi:10.1107/S1600536808039330

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Benzyl N′-(1-methyl-1H-indol-3-ylmethylidene)hydrazinecarbodithioate

Hamid Khaledi,^a Hapipah Mohd Ali ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 22 November 2008; accepted 22 November 2008; online 29 November 2008)

The N′-(1-methyl-1H-indol-3-ylmethylidene)hydrazinecarbodithioate portion of the title molecule, C₁₈H₁₇N₃S₂, is nearly planar; this unit and the phenyl ring subtend an angle of 112.9 (2)° at the methylene C atom.

Related literature

For the structure of S-benzyl N-1-(1H-indol-3-ylmethylidenehydrazinecarbodithioate, see: Khaledi et al. (2008 ).

Experimental

Crystal data

C₁₈H₁₇N₃S₂
M_r = 339.47
Monoclinic, P 2₁
a = 10.6111 (4) Å
b = 6.1134 (2) Å
c = 13.4961 (4) Å
β = 111.934 (2)°
V = 812.12 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 (2) K
0.30 × 0.10 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.908, T_max = 0.993
5513 measured reflections
3277 independent reflections
2802 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.087
S = 1.03
3277 reflections
213 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), 1261 Friedel pairs
Flack parameter: 0.01 (8)

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039330/tk2334sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039330/tk2334Isup2.hkl

checkCIF report

Related literature top

For the structure of S-benzyl N-1-(1H-indol-3-ylmethylidenehydrazinecarbodithioate, see: Khaledi et al. (2008).

Experimental top

N-Methylindole-3-carbaldehyde (1.59 g, 10 mmol) and S-benzyl dithiocarbazate (1.98 g, 10 mmol) were heated in ethanol (60 ml) for 1 h. Several drops of acetic acid were added. The solution yielded a solid on cooling. This was recrystallized from DMSO.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₈H₁₇N₂S₃ at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Benzyl N'-(1-methyl-1H-indol-3-ylmethylidene)hydrazinecarbodithioate top

Crystal data top

C₁₈H₁₇N₃S₂	F(000) = 356
M_r = 339.47	D_x = 1.388 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1721 reflections
a = 10.6111 (4) Å	θ = 3.1–27.1°
b = 6.1134 (2) Å	µ = 0.33 mm⁻¹
c = 13.4961 (4) Å	T = 100 K
β = 111.934 (2)°	Plate, yellow
V = 812.12 (5) Å³	0.30 × 0.10 × 0.02 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	3277 independent reflections
Radiation source: fine-focus sealed tube	2802 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.908, T_max = 0.993	k = −6→7
5513 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: constr
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0366P)² + 0.212P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3277 reflections	Δρ_max = 0.28 e Å⁻³
213 parameters	Δρ_min = −0.28 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1261 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (8)

Crystal data top

C₁₈H₁₇N₃S₂	V = 812.12 (5) Å³
M_r = 339.47	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 10.6111 (4) Å	µ = 0.33 mm⁻¹
b = 6.1134 (2) Å	T = 100 K
c = 13.4961 (4) Å	0.30 × 0.10 × 0.02 mm
β = 111.934 (2)°

Data collection top

Bruker SMART APEX diffractometer	3277 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2802 reflections with I > 2σ(I)
T_min = 0.908, T_max = 0.993	R_int = 0.027
5513 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.087	Δρ_max = 0.28 e Å⁻³
S = 1.03	Δρ_min = −0.28 e Å⁻³
3277 reflections	Absolute structure: Flack (1983), 1261 Friedel pairs
213 parameters	Absolute structure parameter: 0.01 (8)
2 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.33191 (7)	0.50000 (12)	0.67816 (5)	0.01960 (16)
S2	0.48123 (7)	0.86601 (13)	0.61270 (5)	0.02642 (18)
N1	0.2902 (2)	0.7662 (4)	1.16590 (16)	0.0202 (5)
N2	0.3791 (2)	0.7502 (4)	0.85695 (16)	0.0181 (5)
N3	0.4323 (2)	0.8477 (4)	0.78860 (16)	0.0183 (5)
H3	0.480 (3)	0.967 (3)	0.796 (2)	0.035 (9)*
C1	0.2337 (3)	0.5789 (5)	1.1079 (2)	0.0178 (6)
C2	0.1584 (3)	0.4147 (5)	1.1303 (2)	0.0215 (6)
H2	0.1422	0.4143	1.1950	0.026*
C3	0.1075 (3)	0.2515 (5)	1.0548 (2)	0.0236 (6)
H3A	0.0531	0.1389	1.0668	0.028*
C4	0.1347 (3)	0.2496 (5)	0.9610 (2)	0.0215 (6)
H4	0.0983	0.1354	0.9106	0.026*
C5	0.2133 (3)	0.4101 (4)	0.9399 (2)	0.0193 (6)
H5	0.2326	0.4051	0.8767	0.023*
C6	0.2637 (3)	0.5795 (4)	1.01374 (19)	0.0166 (6)
C7	0.2743 (3)	0.8324 (5)	1.2645 (2)	0.0261 (7)
H7A	0.3162	0.9761	1.2867	0.039*
H7B	0.3186	0.7249	1.3206	0.039*
H7C	0.1774	0.8405	1.2524	0.039*
C8	0.3524 (3)	0.8815 (5)	1.11224 (19)	0.0201 (6)
H8	0.3981	1.0166	1.1357	0.024*
C9	0.3409 (3)	0.7767 (4)	1.01840 (19)	0.0168 (6)
C10	0.3932 (2)	0.8586 (5)	0.94249 (18)	0.0166 (5)
H10	0.4392	0.9952	0.9551	0.020*
C11	0.4177 (3)	0.7519 (5)	0.6953 (2)	0.0197 (6)
C12	0.3161 (3)	0.4207 (5)	0.54473 (19)	0.0229 (6)
H12A	0.3840	0.5019	0.5251	0.028*
H12B	0.3366	0.2627	0.5445	0.028*
C13	0.1765 (3)	0.4642 (5)	0.46213 (19)	0.0192 (6)
C14	0.1145 (3)	0.6657 (5)	0.4536 (2)	0.0220 (6)
H14	0.1606	0.7800	0.5010	0.026*
C15	−0.0137 (3)	0.7043 (5)	0.3773 (2)	0.0258 (7)
H15	−0.0550	0.8438	0.3726	0.031*
C16	−0.0816 (3)	0.5379 (6)	0.3078 (2)	0.0295 (8)
H16	−0.1693	0.5638	0.2552	0.035*
C17	−0.0220 (3)	0.3353 (5)	0.3150 (2)	0.0280 (7)
H17	−0.0686	0.2212	0.2677	0.034*
C18	0.1073 (3)	0.2984 (5)	0.3919 (2)	0.0240 (7)
H18	0.1486	0.1589	0.3966	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0229 (3)	0.0209 (4)	0.0149 (3)	−0.0023 (3)	0.0070 (2)	0.0006 (3)
S2	0.0317 (4)	0.0286 (4)	0.0252 (3)	−0.0013 (4)	0.0179 (3)	0.0058 (3)
N1	0.0225 (12)	0.0243 (13)	0.0158 (10)	0.0007 (10)	0.0094 (9)	−0.0026 (9)
N2	0.0191 (11)	0.0187 (13)	0.0176 (10)	−0.0022 (10)	0.0082 (9)	0.0036 (9)
N3	0.0232 (12)	0.0166 (13)	0.0178 (10)	−0.0018 (10)	0.0109 (9)	0.0023 (10)
C1	0.0179 (14)	0.0190 (15)	0.0159 (12)	0.0050 (12)	0.0056 (11)	0.0017 (11)
C2	0.0210 (14)	0.0248 (17)	0.0208 (13)	0.0049 (12)	0.0103 (11)	0.0051 (11)
C3	0.0217 (14)	0.0195 (16)	0.0298 (14)	−0.0007 (13)	0.0097 (12)	0.0052 (12)
C4	0.0225 (14)	0.0195 (15)	0.0208 (13)	−0.0007 (12)	0.0062 (11)	−0.0012 (12)
C5	0.0192 (13)	0.0213 (16)	0.0178 (12)	0.0031 (12)	0.0072 (11)	0.0025 (11)
C6	0.0145 (13)	0.0187 (15)	0.0169 (12)	0.0041 (11)	0.0063 (10)	0.0031 (11)
C7	0.0369 (17)	0.0297 (18)	0.0160 (12)	0.0016 (14)	0.0148 (12)	−0.0056 (12)
C8	0.0173 (13)	0.0194 (15)	0.0216 (12)	0.0007 (13)	0.0049 (10)	−0.0003 (12)
C9	0.0156 (13)	0.0182 (15)	0.0157 (12)	0.0003 (11)	0.0048 (10)	0.0016 (11)
C10	0.0180 (13)	0.0136 (13)	0.0168 (11)	−0.0014 (12)	0.0049 (10)	−0.0002 (11)
C11	0.0176 (13)	0.0225 (16)	0.0185 (12)	0.0038 (12)	0.0061 (11)	0.0040 (11)
C12	0.0298 (15)	0.0225 (16)	0.0182 (12)	0.0035 (12)	0.0109 (12)	−0.0016 (11)
C13	0.0230 (13)	0.0242 (17)	0.0130 (11)	−0.0008 (12)	0.0099 (10)	0.0005 (11)
C14	0.0230 (15)	0.0266 (17)	0.0157 (12)	−0.0016 (12)	0.0064 (11)	−0.0021 (11)
C15	0.0281 (16)	0.0256 (17)	0.0254 (14)	0.0045 (13)	0.0122 (12)	0.0060 (13)
C16	0.0244 (15)	0.044 (2)	0.0176 (12)	−0.0029 (14)	0.0055 (11)	0.0064 (13)
C17	0.0353 (17)	0.0324 (19)	0.0169 (12)	−0.0157 (15)	0.0105 (12)	−0.0049 (13)
C18	0.0366 (17)	0.0196 (16)	0.0202 (13)	−0.0043 (13)	0.0159 (13)	−0.0011 (11)

Geometric parameters (Å, º) top

S1—C11	1.759 (3)	C7—H7A	0.9800
S1—C12	1.811 (3)	C7—H7B	0.9800
S2—C11	1.657 (3)	C7—H7C	0.9800
N1—C8	1.347 (3)	C8—C9	1.383 (4)
N1—C1	1.390 (4)	C8—H8	0.9500
N1—C7	1.460 (3)	C9—C10	1.426 (4)
N2—C10	1.290 (3)	C10—H10	0.9500
N2—N3	1.384 (3)	C12—C13	1.508 (4)
N3—C11	1.345 (3)	C12—H12A	0.9900
N3—H3	0.875 (10)	C12—H12B	0.9900
C1—C2	1.386 (4)	C13—C14	1.381 (4)
C1—C6	1.420 (4)	C13—C18	1.394 (4)
C2—C3	1.384 (4)	C14—C15	1.386 (4)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.400 (4)	C15—C16	1.389 (4)
C3—H3A	0.9500	C15—H15	0.9500
C4—C5	1.385 (4)	C16—C17	1.378 (5)
C4—H4	0.9500	C16—H16	0.9500
C5—C6	1.398 (4)	C17—C18	1.395 (4)
C5—H5	0.9500	C17—H17	0.9500
C6—C9	1.445 (4)	C18—H18	0.9500

C11—S1—C12	102.48 (13)	C9—C8—H8	124.6
C8—N1—C1	108.8 (2)	C8—C9—C10	124.8 (3)
C8—N1—C7	126.3 (3)	C8—C9—C6	106.3 (2)
C1—N1—C7	124.7 (2)	C10—C9—C6	128.9 (2)
C10—N2—N3	115.8 (2)	N2—C10—C9	121.1 (3)
C11—N3—N2	120.3 (2)	N2—C10—H10	119.5
C11—N3—H3	109 (2)	C9—C10—H10	119.5
N2—N3—H3	131 (2)	N3—C11—S2	120.9 (2)
C2—C1—N1	129.5 (2)	N3—C11—S1	112.2 (2)
C2—C1—C6	122.6 (3)	S2—C11—S1	126.94 (17)
N1—C1—C6	108.0 (2)	C13—C12—S1	112.87 (19)
C3—C2—C1	117.4 (2)	C13—C12—H12A	109.0
C3—C2—H2	121.3	S1—C12—H12A	109.0
C1—C2—H2	121.3	C13—C12—H12B	109.0
C2—C3—C4	121.1 (3)	S1—C12—H12B	109.0
C2—C3—H3A	119.4	H12A—C12—H12B	107.8
C4—C3—H3A	119.4	C14—C13—C18	118.6 (2)
C5—C4—C3	121.6 (3)	C14—C13—C12	121.6 (2)
C5—C4—H4	119.2	C18—C13—C12	119.8 (3)
C3—C4—H4	119.2	C13—C14—C15	121.2 (3)
C4—C5—C6	118.6 (2)	C13—C14—H14	119.4
C4—C5—H5	120.7	C15—C14—H14	119.4
C6—C5—H5	120.7	C14—C15—C16	119.7 (3)
C5—C6—C1	118.8 (2)	C14—C15—H15	120.2
C5—C6—C9	135.2 (2)	C16—C15—H15	120.2
C1—C6—C9	106.0 (2)	C17—C16—C15	120.2 (3)
N1—C7—H7A	109.5	C17—C16—H16	119.9
N1—C7—H7B	109.5	C15—C16—H16	119.9
H7A—C7—H7B	109.5	C16—C17—C18	119.7 (3)
N1—C7—H7C	109.5	C16—C17—H17	120.2
H7A—C7—H7C	109.5	C18—C17—H17	120.2
H7B—C7—H7C	109.5	C13—C18—C17	120.7 (3)
N1—C8—C9	110.9 (3)	C13—C18—H18	119.7
N1—C8—H8	124.6	C17—C18—H18	119.7

C10—N2—N3—C11	−177.2 (2)	C1—C6—C9—C8	−0.2 (3)
C8—N1—C1—C2	−178.6 (3)	C5—C6—C9—C10	−1.0 (5)
C7—N1—C1—C2	−3.0 (4)	C1—C6—C9—C10	−178.3 (3)
C8—N1—C1—C6	0.3 (3)	N3—N2—C10—C9	179.1 (2)
C7—N1—C1—C6	175.9 (2)	C8—C9—C10—N2	179.5 (3)
N1—C1—C2—C3	176.3 (3)	C6—C9—C10—N2	−2.7 (4)
C6—C1—C2—C3	−2.4 (4)	N2—N3—C11—S2	−179.82 (19)
C1—C2—C3—C4	1.8 (4)	N2—N3—C11—S1	−1.8 (3)
C2—C3—C4—C5	0.0 (4)	C12—S1—C11—N3	175.97 (19)
C3—C4—C5—C6	−1.3 (4)	C12—S1—C11—S2	−6.1 (2)
C4—C5—C6—C1	0.8 (4)	C11—S1—C12—C13	−101.3 (2)
C4—C5—C6—C9	−176.2 (3)	S1—C12—C13—C14	50.8 (3)
C2—C1—C6—C5	1.1 (4)	S1—C12—C13—C18	−129.3 (2)
N1—C1—C6—C5	−177.9 (2)	C18—C13—C14—C15	0.0 (4)
C2—C1—C6—C9	178.9 (2)	C12—C13—C14—C15	179.9 (2)
N1—C1—C6—C9	−0.1 (3)	C13—C14—C15—C16	−0.1 (4)
C1—N1—C8—C9	−0.4 (3)	C14—C15—C16—C17	0.3 (4)
C7—N1—C8—C9	−175.9 (3)	C15—C16—C17—C18	−0.4 (4)
N1—C8—C9—C10	178.6 (2)	C14—C13—C18—C17	−0.2 (4)
N1—C8—C9—C6	0.4 (3)	C12—C13—C18—C17	180.0 (2)
C5—C6—C9—C8	177.1 (3)	C16—C17—C18—C13	0.4 (4)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₇N₃S₂
M_r	339.47
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	10.6111 (4), 6.1134 (2), 13.4961 (4)
β (°)	111.934 (2)
V (Å³)	812.12 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.30 × 0.10 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.908, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	5513, 3277, 2802
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.087, 1.03
No. of reflections	3277
No. of parameters	213
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.28
Absolute structure	Flack (1983), 1261 Friedel pairs
Absolute structure parameter	0.01 (8)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Acknowledgements

We thank the University of Malaya for funding this study (Science Fund Grants 12–02-03–2031 & 12–02-03–2051).

References

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