N′-[Bis(methyl­sulfan­yl)methyl­idene]-2-meth­oxy­benzohydrazide

Nath, P.; Bharty, M.K.; Butcher, R.J.; Jasinski, J.P.

doi:10.1107/S2414314617004898

organic compounds

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ISSN: 2414-3146

Volume 2| Part 4| April 2017| x170489

https://doi.org/10.1107/S2414314617004898

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N′-[Bis(methylsulfanyl)methylidene]-2-methoxybenzohydrazide

Paras Nath,^a Manoj K. Bharty,^a ^* Ray J. Butcher ^b and Jerry P. Jasinski ^c

^aDepartment of Chemistry, Banaras Hindu University, Varanasi 221 005, India, ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and ^cDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH, 03435-2001, USA
^*Correspondence e-mail: manoj_vns2005@yahoo.co.in

Edited by K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 16 March 2017; accepted 29 March 2017; online 4 April 2017)

In the title compound, C₁₁H₁₄N₂O₂S₂, the diethyl dithioate groups are inclined slightly to the benzoyl ring, making a dihedral angle of 14.0 (3)°. A short intramolecular N—H⋯O contact generates an S(6) ring. In the crystal, C—H⋯O contacts generate a C(8) chain motif along [010].

Keywords: crystal structure; dithiocarbazate; hydrogen bonding; ester.

CCDC reference: 1540858

Structure description

Dithiocarbazates and their S-alkyl/aryl esters containing nitrogen–sulfur donor atoms have shown interesting biological properties (Bharti et al., 2000 ). Some dimethyl benzoylcarbonohydrazonodithioates exhibit activity against Mycobacterium tuberculosis (Gobis et al., 2011 ). The S-alkyl/aryl esters exhibit efficient capacity for coordination with metals to form complexes (Ali et al., 2008 ; Singh et al., 2010 , 2012 ). The S-alkyl/aryl esters derived from potassium salts of N-aroylhydrazinecarbodithioates have been found to be more stable towards cyclization compared to potassium N-aroylhydrazinecarbodithioates and form stable complexes with transition metal ions (Singh et al., 2009 ; Bharty et al., 2012 ).

In the title compound, the sum of the bond angles around C9 (360°) and the S1—C9—S2 bond angle of 117.39 (11)° clearly indicate sp² behavior similar to other reported bis-alkyl dithioesters (Nath et al., 2015 ; Gobis et al., 2011). The dihedral angle between the bis-methylsulfanylmethylidene group and the benzoyl ring is 14.0 (3)°. The C8—N1 and C9—N2 bond lengths [1.347 (2) and 1.285 (3) Å, respectively] are intermediate between typical C—N and C=N bond lengths, suggesting delocalization of the π electron density over the C8/N1/N2/C9 linkage (Jasinski et al., 2010 ). In addition, an intramolecular N—H⋯O hydrogen bond is observed (Fig. 1 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1	0.78 (3)	1.97 (3)	2.627 (2)	141 (2)
C10—H10A⋯O2ⁱ	0.98	2.37	3.326 (3)	166
C11—H11A⋯O2ⁱⁱ	0.98	2.61	3.341 (3)	131
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y, z.

Figure 1
The molecular structure of title compound, C₁₁H₁₄N₂O₂S₂ with displacement ellipsoids drawn at the 30% probability level.

The crystal packing features intermolecular C—H⋯O hydrogen bonds between H atoms of the bis-methylsulfanylmethylidene group and the O atom of the benzoyl group, forming zigzag chains along the b axis direction (Table 1, Fig. 2).

Figure 2
The packing of title compound, C₁₁H₁₄N₂O₂S₂ viewed along the a axis. Dashed lines indicate intramolecular N—H⋯O and intermolecular C—H⋯O hydrogen bonds.

Synthesis and crystallization

The title compound was synthesized by the dropwise addition of methyl iodide (20.0 mmol, 1.30 ml) to a suspension of potassium (2-methoxybenzoyl)hydrazinecarbodithioate (10.0 mmol, 2.38 g) in ethanol (20 ml) and stirring the reaction mixture for a period of 3–4 h. The resulting solution was acidified with dilute CH₃COOH (20% v/v), which yielded a white precipitate. This was washed with water and dried in vacuo. Colorless crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution over a period of 7 d (Fig. 3). (Yield 65%; m.p. 400–402 K). Analysis calculated for C₁₁H₁₄N₂O₂S₂ (%): C, 48.87; H, 5.20; N, 10.36; S, 23.71. Found: C, 49.12; H, 5.35; N, 10.22; S, 23.44. IR (selected, KBr): 3261 [ν(N—H)], 1654 [ν(C=O)], 1078 [ν(N—N)], 756 [ν(C—S)] cm^{-1. 1}H NMR (DMSO-d₆); δ (p.p.m.) = 11.19 (s, 1H, NH), 7.96–7.01 (m, 4H, C₆H₄, phenyl), 3.96 (s, 3H, –OCH₃), 2.43 (s, 6H, –CH₃). ¹³C NMR (DMSO-d₆); δ (p.p.m.) = 165.3 (C9), 160.3 (C8), 157.6 (C1), 134.2 (C3), 131.8 (C5), 121.8 (C4), 121.0 (C6), 112.6 (C2), 56.8 (C7), 17.7–15.5 (C10, C11).

Figure 3
Reaction scheme showing the synthesis of the title compound, C₁₁H₁₄N₂O₂S₂.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₂S₂
M_r	270.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	7.7829 (3), 7.4284 (3), 21.9087 (7)
β (°)	94.399 (3)
V (Å³)	1262.91 (8)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	3.77
Crystal size (mm)	0.50 × 0.47 × 0.15

Data collection
Diffractometer	Agilent Xcalibur, Eos, Gemini
Absorption correction	Multi-scan (SCALE3 ABSPACK in CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.290, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4470, 2367, 2189
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.125, 1.08
No. of reflections	2367
No. of parameters	162
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.33
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1540858

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617004898/ff4015sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617004898/ff4015Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617004898/ff4015Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 20015b).

N'-[Bis(methylsulfanyl)methylidene]-2-methoxybenzohydrazide top

Crystal data top

C₁₁H₁₄N₂O₂S₂	F(000) = 568
M_r = 270.36	D_x = 1.422 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
a = 7.7829 (3) Å	Cell parameters from 2383 reflections
b = 7.4284 (3) Å	θ = 6.7–71.3°
c = 21.9087 (7) Å	µ = 3.77 mm⁻¹
β = 94.399 (3)°	T = 173 K
V = 1262.91 (8) Å³	Thick plate, colorless
Z = 4	0.50 × 0.47 × 0.15 mm

Data collection top

Agilent Xcalibur, Eos, Gemini diffractometer	2367 independent reflections
Radiation source: fine-focus sealed X-ray tube	2189 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm^-1	R_int = 0.039
ω scans	θ_max = 71.4°, θ_min = 4.1°
Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlisPro; Rigaku OD, 2015)	h = −9→7
T_min = 0.290, T_max = 1.000	k = −8→8
4470 measured reflections	l = −26→26

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.0789P)² + 0.3498P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.125	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.37 e Å⁻³
2367 reflections	Δρ_min = −0.33 e Å⁻³
162 parameters	Extinction correction: SHELXL2014/7 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0078 (13)

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
S1	0.56603 (7)	0.46135 (8)	0.25046 (2)	0.0268 (2)
S2	0.78152 (6)	0.59368 (8)	0.36113 (2)	0.0251 (2)
O1	0.63724 (17)	0.6970 (2)	0.51244 (6)	0.0216 (3)
O2	0.17729 (18)	0.7559 (2)	0.40453 (6)	0.0264 (4)
N1	0.4544 (2)	0.6643 (2)	0.40715 (7)	0.0154 (4)
H1N	0.539 (3)	0.652 (3)	0.4280 (12)	0.023 (6)*
N2	0.4351 (2)	0.5994 (2)	0.34749 (7)	0.0176 (4)
C1	0.4993 (2)	0.7762 (3)	0.53693 (8)	0.0147 (4)
C2	0.5060 (3)	0.8398 (3)	0.59679 (8)	0.0223 (5)
H2A	0.6093	0.8281	0.6225	0.027*
C3	0.3628 (3)	0.9202 (3)	0.61912 (9)	0.0266 (5)
H3A	0.3692	0.9649	0.6599	0.032*
C4	0.2108 (3)	0.9360 (3)	0.58261 (10)	0.0250 (5)
H4A	0.1123	0.9903	0.5979	0.030*
C5	0.2049 (3)	0.8710 (3)	0.52332 (9)	0.0177 (4)
H5A	0.1000	0.8809	0.4983	0.021*
C6	0.3460 (2)	0.7921 (2)	0.49882 (8)	0.0127 (4)
C7	0.7980 (3)	0.6926 (3)	0.54850 (11)	0.0292 (5)
H7A	0.8859	0.6375	0.5247	0.044*
H7B	0.7856	0.6216	0.5856	0.044*
H7C	0.8329	0.8156	0.5599	0.044*
C8	0.3180 (2)	0.7356 (3)	0.43279 (8)	0.0139 (4)
C9	0.5758 (3)	0.5576 (3)	0.32388 (8)	0.0170 (4)
C10	0.3382 (3)	0.4499 (4)	0.23262 (11)	0.0396 (6)
H10A	0.3141	0.3849	0.1940	0.059*
H10B	0.2911	0.5721	0.2286	0.059*
H10C	0.2846	0.3865	0.2655	0.059*
C11	0.9276 (3)	0.4888 (3)	0.31271 (10)	0.0295 (5)
H11A	1.0464	0.5108	0.3291	0.044*
H11B	0.9104	0.5393	0.2714	0.044*
H11C	0.9057	0.3588	0.3111	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0328 (3)	0.0384 (4)	0.0097 (3)	−0.0020 (2)	0.0038 (2)	−0.01010 (19)
S2	0.0212 (3)	0.0391 (4)	0.0151 (3)	−0.0011 (2)	0.0019 (2)	−0.0105 (2)
O1	0.0139 (7)	0.0363 (8)	0.0139 (7)	0.0024 (6)	−0.0031 (5)	0.0007 (6)
O2	0.0198 (7)	0.0460 (10)	0.0123 (7)	0.0050 (7)	−0.0051 (5)	−0.0039 (6)
N1	0.0165 (8)	0.0251 (9)	0.0042 (7)	0.0005 (7)	−0.0025 (6)	−0.0027 (6)
N2	0.0224 (8)	0.0240 (9)	0.0061 (7)	−0.0018 (7)	−0.0007 (6)	−0.0024 (6)
C1	0.0175 (9)	0.0174 (9)	0.0093 (8)	−0.0038 (7)	0.0008 (7)	0.0041 (7)
C2	0.0279 (11)	0.0293 (11)	0.0087 (9)	−0.0072 (9)	−0.0056 (7)	0.0024 (8)
C3	0.0404 (13)	0.0306 (11)	0.0090 (9)	−0.0068 (9)	0.0024 (8)	−0.0052 (8)
C4	0.0316 (12)	0.0270 (11)	0.0174 (10)	0.0010 (9)	0.0096 (9)	−0.0043 (8)
C5	0.0191 (9)	0.0203 (9)	0.0138 (9)	−0.0011 (7)	0.0013 (7)	0.0004 (7)
C6	0.0177 (9)	0.0139 (8)	0.0064 (8)	−0.0024 (7)	0.0006 (6)	0.0030 (6)
C7	0.0166 (10)	0.0377 (13)	0.0317 (12)	−0.0021 (9)	−0.0093 (8)	0.0064 (10)
C8	0.0157 (9)	0.0190 (9)	0.0068 (8)	−0.0019 (7)	−0.0013 (6)	0.0027 (7)
C9	0.0234 (10)	0.0193 (9)	0.0084 (8)	−0.0014 (7)	0.0013 (7)	−0.0004 (7)
C10	0.0357 (14)	0.0588 (17)	0.0227 (11)	0.0033 (12)	−0.0086 (10)	−0.0190 (11)
C11	0.0262 (11)	0.0416 (13)	0.0210 (11)	0.0064 (10)	0.0047 (9)	−0.0059 (10)

Geometric parameters (Å, º) top

S1—C9	1.7564 (19)	C3—H3A	0.9500
S1—C10	1.788 (3)	C4—C5	1.383 (3)
S2—C9	1.761 (2)	C4—H4A	0.9500
S2—C11	1.792 (2)	C5—C6	1.389 (3)
O1—C1	1.369 (2)	C5—H5A	0.9500
O1—C7	1.428 (2)	C6—C8	1.506 (2)
O2—C8	1.225 (2)	C7—H7A	0.9800
N1—C8	1.347 (2)	C7—H7B	0.9800
N1—N2	1.391 (2)	C7—H7C	0.9800
N1—H1N	0.78 (3)	C10—H10A	0.9800
N2—C9	1.285 (3)	C10—H10B	0.9800
C1—C2	1.391 (3)	C10—H10C	0.9800
C1—C6	1.408 (2)	C11—H11A	0.9800
C2—C3	1.386 (3)	C11—H11B	0.9800
C2—H2A	0.9500	C11—H11C	0.9800
C3—C4	1.381 (3)

C9—S1—C10	101.07 (10)	O1—C7—H7A	109.5
C9—S2—C11	104.77 (10)	O1—C7—H7B	109.5
C1—O1—C7	118.23 (16)	H7A—C7—H7B	109.5
C8—N1—N2	119.76 (16)	O1—C7—H7C	109.5
C8—N1—H1N	117.2 (19)	H7A—C7—H7C	109.5
N2—N1—H1N	122.7 (19)	H7B—C7—H7C	109.5
C9—N2—N1	115.35 (16)	O2—C8—N1	122.69 (16)
O1—C1—C2	122.80 (17)	O2—C8—C6	120.62 (16)
O1—C1—C6	117.25 (16)	N1—C8—C6	116.69 (15)
C2—C1—C6	119.95 (18)	N2—C9—S1	119.27 (15)
C3—C2—C1	120.40 (18)	N2—C9—S2	123.33 (14)
C3—C2—H2A	119.8	S1—C9—S2	117.39 (11)
C1—C2—H2A	119.8	S1—C10—H10A	109.5
C4—C3—C2	120.53 (18)	S1—C10—H10B	109.5
C4—C3—H3A	119.7	H10A—C10—H10B	109.5
C2—C3—H3A	119.7	S1—C10—H10C	109.5
C3—C4—C5	118.7 (2)	H10A—C10—H10C	109.5
C3—C4—H4A	120.7	H10B—C10—H10C	109.5
C5—C4—H4A	120.7	S2—C11—H11A	109.5
C4—C5—C6	122.66 (19)	S2—C11—H11B	109.5
C4—C5—H5A	118.7	H11A—C11—H11B	109.5
C6—C5—H5A	118.7	S2—C11—H11C	109.5
C5—C6—C1	117.76 (16)	H11A—C11—H11C	109.5
C5—C6—C8	115.35 (16)	H11B—C11—H11C	109.5
C1—C6—C8	126.88 (16)

C8—N1—N2—C9	170.57 (17)	C2—C1—C6—C8	178.17 (18)
C7—O1—C1—C2	−5.0 (3)	N2—N1—C8—O2	−4.3 (3)
C7—O1—C1—C6	174.99 (17)	N2—N1—C8—C6	176.21 (15)
O1—C1—C2—C3	179.51 (18)	C5—C6—C8—O2	−1.7 (3)
C6—C1—C2—C3	−0.5 (3)	C1—C6—C8—O2	179.63 (19)
C1—C2—C3—C4	1.0 (3)	C5—C6—C8—N1	177.76 (17)
C2—C3—C4—C5	−0.4 (3)	C1—C6—C8—N1	−0.9 (3)
C3—C4—C5—C6	−0.6 (3)	N1—N2—C9—S1	176.15 (13)
C4—C5—C6—C1	1.0 (3)	N1—N2—C9—S2	−4.5 (3)
C4—C5—C6—C8	−177.78 (18)	C10—S1—C9—N2	−1.1 (2)
O1—C1—C6—C5	179.54 (16)	C10—S1—C9—S2	179.49 (14)
C2—C1—C6—C5	−0.5 (3)	C11—S2—C9—N2	173.48 (18)
O1—C1—C6—C8	−1.8 (3)	C11—S2—C9—S1	−7.15 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.78 (3)	1.97 (3)	2.627 (2)	141 (2)
C10—H10A···O2ⁱ	0.98	2.37	3.326 (3)	166
C11—H11A···O2ⁱⁱ	0.98	2.61	3.341 (3)	131

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1, y, z.

Acknowledgements

MKB is thankful to the Science and Engineering Research Board, New Delhi, India for the award of a Young Scientist Project (No. YSS/2015/001201). JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

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