N,N-Dimethyl-2-[(1E)-({[(methyl­sulfan­yl)methane­thio­yl]amino}­imino)­meth­yl]aniline

Sohtun, W.P.; Kannan, A.; Dhandayutham, S.; Velusamy, M.

doi:10.1107/S2414314618004613

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 3| March 2018| x180461

https://doi.org/10.1107/S2414314618004613

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N,N-Dimethyl-2-[(1E)-({[(methylsulfanyl)methanethioyl]amino}imino)methyl]aniline

Winaki P. Sohtun,^a Arunachalam Kannan,^b Saravanan Dhandayutham ^b and Marappan Velusamy ^a ^*

^aDepartment of Chemistry, North Eastern Hill University, Shillong 793 022, Meghalaya, India, and ^bDepartment of Chemistry, National College, Tiruchirappalli 620 001, Tamilnadu, India
^*Correspondence e-mail: mvelusamy@gmail.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 16 March 2018; accepted 21 March 2018; online 27 March 2018)

In the title compound, C₁₁H₁₅N₃S₂, the dithiocarbazate moiety is rotated by 18.73 (8)° with respect to the benzene ring. The dithiocarbazate group adopts an E configuration with respect to the C=N bond of the benzylidene group. Furthermore, in the solid state the compound exists in the thione tautomeric form. In the crystal, molecules are linked by pairs of weak N—H⋯S hydrogen bonds, forming inversion dimers which are arranged in layers parallel to (010).

Keywords: Schiff base; dithiocarbazate; ligand; crystal structure.

CCDC reference: 1831308

Structure description

Dithiocarbazate derivatives remain of interest to researchers because of their extensive variations in structure and promising biological and catalytic activities (Low et al., 2014 ). Metal complexes of ligands derived from dithiocarbazic acids have created a significant interest in their coordination chemistry (Mahapatra et al., 2013 ). As a part of our ongoing research on such molecules, we report herein on the synthesis and crystal structure of the title compound.

The molecule is not completely planar (r.m.s. deviation for all non-H atoms 0.375 Å). The thione sulfur atom (S1) is positioned trans to the azomethine nitrogen (N1) atom, Fig. 1. The C=S and C—S bond lengths of 1.6606 (17) and 1.7462 (19) Å, respectively, are of the order of those in related dithiocarbazate based Schiff bases (Basha et al., 2012 ). The observed bond lengths are intermediate between C—S and C=S bonds, indicating conjugation effects along the =N—NH—C(=S)—SCH₃ chain.

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 40% probability level.

In the crystal, the molecules are linked by N—H⋯S hydrogen bonds (Table 1, Fig. 2), forming inversion dimers.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H9⋯S1ⁱ	0.86	2.62	3.4566 (16)	166
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Figure 2
Dimer formation through N—H⋯S interactions.

Synthesis and crystallization

The synthesis of the title compound is illustrated in Fig. 3. A solution of 2-dimethylamino benzaldehyde (0.298 g, 2 mmol) in methanol (10 ml) was added to a stirred solution of S-methyl dithiocarbazate (0.25 g, 2 mmol) in ethanol (15 ml). The mixture was stirred for 10 min then refluxed for 6 h. The reaction mixture was then cooled to room temperature and the yellow solid obtained was filtered off, washed with cold methanol and dried under vacuum over anhydrous CaCl₂. This solid was recrystallized from methanol, yielding needle-shaped crystals that were suitable for X-ray diffraction studies.

Figure 3
Synthesis of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₅N₃S₂
M_r	253.38
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	20.5182 (12), 7.6402 (6), 16.6523 (12)
β (°)	96.863 (6)
V (Å³)	2591.8 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.39
Crystal size (mm)	0.46 × 0.40 × 0.38

Data collection
Diffractometer	Agilent EOS, Gemini
Absorption correction	Multi-scan (SCALE3 ABSPACK; Agilent, 2015 )
T_min, T_max	0.513, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	4778, 2638, 2136
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.04
No. of reflections	2638
No. of parameters	148
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.24
Computer programs: CrysAlis PRO (Agilent, 2015), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC reference: 1831308

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004613/bt4068sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004613/bt4068Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618004613/bt4068Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2015); cell refinement: CrysAlis PRO (Agilent, 2015); data reduction: CrysAlis PRO (Agilent, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL (Sheldrick, 2015b).

N,N-Dimethyl-2-[(1E)-({[(methylsulfanyl)methanethioyl]amino}imino)methyl]aniline top

Crystal data top

C₁₁H₁₅N₃S₂	F(000) = 1072
M_r = 253.38	D_x = 1.299 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.5182 (12) Å	Cell parameters from 2638 reflections
b = 7.6402 (6) Å	θ = 3.8–26.4°
c = 16.6523 (12) Å	µ = 0.39 mm⁻¹
β = 96.863 (6)°	T = 293 K
V = 2591.8 (3) Å³	Needle, yellow
Z = 8	0.46 × 0.40 × 0.38 mm

Data collection top

Agilent EOS, Gemini diffractometer	R_int = 0.016
profile data from θ/2θ scans	θ_max = 26.4°, θ_min = 3.8°
Absorption correction: multi-scan (SCALE3 ABSPACK; Agilent, 2015)	h = −25→24
T_min = 0.513, T_max = 0.747	k = −9→9
4778 measured reflections	l = −20→11
2638 independent reflections	4386 standard reflections every 10 reflections
2136 reflections with I > 2σ(I)	intensity decay: 5%

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0435P)² + 1.4528P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2638 reflections	Δρ_max = 0.25 e Å⁻³
148 parameters	Δρ_min = −0.24 e Å⁻³

Special details top

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

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

	x	y	z	U_iso*/U_eq
S2	0.41502 (2)	0.68062 (8)	0.46488 (3)	0.04706 (17)
S1	0.53348 (2)	0.74013 (8)	0.37613 (3)	0.05367 (18)
N3	0.22176 (7)	0.6136 (2)	0.10219 (9)	0.0389 (4)
N2	0.41551 (7)	0.6548 (2)	0.31042 (9)	0.0418 (4)
H9	0.4306	0.6560	0.2644	0.050*
N1	0.35047 (6)	0.6156 (2)	0.31475 (9)	0.0408 (4)
C6	0.24224 (8)	0.5859 (2)	0.24910 (10)	0.0332 (4)
C1	0.19790 (8)	0.5987 (2)	0.17786 (10)	0.0343 (4)
C7	0.31255 (8)	0.6169 (2)	0.24855 (11)	0.0367 (4)
H7	0.3294	0.6374	0.2000	0.044*
C8	0.45484 (8)	0.6910 (2)	0.37801 (11)	0.0367 (4)
C5	0.21800 (9)	0.5579 (3)	0.32248 (11)	0.0421 (4)
H6	0.2473	0.5421	0.3690	0.051*
C4	0.15177 (9)	0.5530 (3)	0.32794 (13)	0.0508 (5)
H5	0.1363	0.5341	0.3775	0.061*
C2	0.13109 (9)	0.5980 (3)	0.18530 (12)	0.0485 (5)
H3	0.1010	0.6125	0.1394	0.058*
C10	0.17401 (10)	0.6747 (3)	0.03593 (12)	0.0568 (6)
H16A	0.1403	0.5881	0.0244	0.085*
H16B	0.1956	0.6937	−0.0113	0.085*
H16C	0.1547	0.7823	0.0512	0.085*
C11	0.25651 (11)	0.4594 (3)	0.07815 (13)	0.0552 (5)
H15A	0.2866	0.4196	0.1230	0.083*
H15B	0.2803	0.4888	0.0338	0.083*
H15C	0.2255	0.3684	0.0619	0.083*
C9	0.47913 (10)	0.7383 (3)	0.54339 (12)	0.0541 (5)
H12A	0.5182	0.6740	0.5362	0.081*
H12B	0.4656	0.7103	0.5951	0.081*
H12C	0.4879	0.8615	0.5409	0.081*
C3	0.10867 (9)	0.5764 (3)	0.25900 (13)	0.0554 (6)
H4	0.0638	0.5776	0.2624	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.0306 (2)	0.0678 (4)	0.0429 (3)	−0.0013 (2)	0.00473 (19)	0.0017 (2)
S1	0.0264 (2)	0.0880 (4)	0.0456 (3)	−0.0157 (2)	0.0003 (2)	0.0005 (3)
N3	0.0346 (8)	0.0473 (9)	0.0336 (8)	−0.0023 (7)	−0.0012 (6)	0.0035 (7)
N2	0.0237 (7)	0.0627 (10)	0.0384 (8)	−0.0056 (7)	0.0010 (6)	0.0039 (8)
N1	0.0224 (7)	0.0569 (10)	0.0420 (8)	−0.0057 (7)	−0.0008 (6)	0.0041 (7)
C6	0.0259 (8)	0.0370 (9)	0.0357 (9)	−0.0046 (7)	0.0003 (7)	0.0011 (7)
C1	0.0289 (8)	0.0352 (9)	0.0376 (9)	−0.0047 (7)	−0.0006 (7)	0.0018 (8)
C7	0.0289 (8)	0.0438 (10)	0.0368 (9)	−0.0036 (8)	0.0019 (7)	0.0039 (8)
C8	0.0267 (8)	0.0428 (10)	0.0397 (9)	−0.0005 (7)	0.0002 (7)	0.0054 (8)
C5	0.0351 (9)	0.0540 (11)	0.0359 (10)	−0.0072 (8)	−0.0011 (7)	0.0005 (8)
C4	0.0403 (10)	0.0688 (14)	0.0452 (11)	−0.0109 (10)	0.0126 (8)	0.0006 (10)
C2	0.0277 (9)	0.0663 (13)	0.0491 (11)	−0.0051 (9)	−0.0051 (8)	0.0071 (10)
C10	0.0465 (11)	0.0782 (15)	0.0428 (11)	−0.0069 (11)	−0.0069 (9)	0.0143 (11)
C11	0.0596 (13)	0.0564 (13)	0.0513 (12)	0.0007 (11)	0.0132 (10)	−0.0033 (10)
C9	0.0476 (12)	0.0704 (14)	0.0424 (11)	0.0024 (10)	−0.0018 (9)	−0.0041 (10)
C3	0.0257 (9)	0.0790 (16)	0.0625 (13)	−0.0057 (10)	0.0089 (9)	0.0060 (12)

Geometric parameters (Å, º) top

S2—C8	1.7462 (19)	C5—H6	0.9300
S2—C9	1.795 (2)	C4—C3	1.375 (3)
S1—C8	1.6606 (17)	C4—H5	0.9300
N3—C1	1.410 (2)	C2—C3	1.371 (3)
N3—C11	1.458 (3)	C2—H3	0.9300
N3—C10	1.462 (2)	C10—H16A	0.9600
N2—C8	1.333 (2)	C10—H16B	0.9600
N2—N1	1.3781 (19)	C10—H16C	0.9600
N2—H9	0.8600	C11—H15A	0.9600
N1—C7	1.271 (2)	C11—H15B	0.9600
C6—C5	1.390 (2)	C11—H15C	0.9600
C6—C1	1.410 (2)	C9—H12A	0.9600
C6—C7	1.463 (2)	C9—H12B	0.9600
C1—C2	1.391 (2)	C9—H12C	0.9600
C7—H7	0.9300	C3—H4	0.9300
C5—C4	1.373 (2)

C8—S2—C9	102.56 (9)	C3—C4—H5	120.5
C1—N3—C11	114.42 (15)	C3—C2—C1	121.32 (17)
C1—N3—C10	115.30 (15)	C3—C2—H3	119.3
C11—N3—C10	110.87 (16)	C1—C2—H3	119.3
C8—N2—N1	119.56 (15)	N3—C10—H16A	109.5
C8—N2—H9	120.2	N3—C10—H16B	109.5
N1—N2—H9	120.2	H16A—C10—H16B	109.5
C7—N1—N2	116.69 (15)	N3—C10—H16C	109.5
C5—C6—C1	119.20 (15)	H16A—C10—H16C	109.5
C5—C6—C7	119.16 (15)	H16B—C10—H16C	109.5
C1—C6—C7	121.42 (15)	N3—C11—H15A	109.5
C2—C1—C6	117.94 (16)	N3—C11—H15B	109.5
C2—C1—N3	122.09 (15)	H15A—C11—H15B	109.5
C6—C1—N3	119.97 (15)	N3—C11—H15C	109.5
N1—C7—C6	119.68 (16)	H15A—C11—H15C	109.5
N1—C7—H7	120.2	H15B—C11—H15C	109.5
C6—C7—H7	120.2	S2—C9—H12A	109.5
N2—C8—S1	121.50 (14)	S2—C9—H12B	109.5
N2—C8—S2	113.21 (12)	H12A—C9—H12B	109.5
S1—C8—S2	125.29 (11)	S2—C9—H12C	109.5
C4—C5—C6	121.56 (17)	H12A—C9—H12C	109.5
C4—C5—H6	119.2	H12B—C9—H12C	109.5
C6—C5—H6	119.2	C2—C3—C4	120.80 (17)
C5—C4—C3	118.95 (18)	C2—C3—H4	119.6
C5—C4—H5	120.5	C4—C3—H4	119.6

C8—N2—N1—C7	166.28 (17)	N1—N2—C8—S1	−179.69 (13)
C5—C6—C1—C2	5.6 (3)	N1—N2—C8—S2	0.3 (2)
C7—C6—C1—C2	−168.92 (17)	C9—S2—C8—N2	−179.01 (15)
C5—C6—C1—N3	−175.15 (16)	C9—S2—C8—S1	1.01 (16)
C7—C6—C1—N3	10.3 (3)	C1—C6—C5—C4	−4.0 (3)
C11—N3—C1—C2	−114.6 (2)	C7—C6—C5—C4	170.62 (19)
C10—N3—C1—C2	15.7 (3)	C6—C5—C4—C3	0.0 (3)
C11—N3—C1—C6	66.2 (2)	C6—C1—C2—C3	−3.4 (3)
C10—N3—C1—C6	−163.50 (17)	N3—C1—C2—C3	177.38 (19)
N2—N1—C7—C6	−176.64 (15)	C1—C2—C3—C4	−0.6 (3)
C5—C6—C7—N1	0.9 (3)	C5—C4—C3—C2	2.4 (3)
C1—C6—C7—N1	175.40 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H9···S1ⁱ	0.86	2.62	3.4566 (16)	166

Symmetry code: (i) −x+1, y, −z+1/2.

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