(Z)-Benzyl 2-(5-methyl-2-oxoindolin-3-yl­idene)hydrazinecarbodi­thio­ate

The crystal structure of a new di­thio­carbazate imine, obtained from the condensation reaction of S-benzyl­dithio­carbazate and 5-methyl­isatin, is described.

Abstract

The title compound, C₁₇H₁₅N₃OS₂ was obtained from the condensation reaction of S-benzyl­dithio­carbazate and 5-methyl­isatin. In the solid-state, the mol­ecule adopts a Z configuration with the 5-methyl­isatin and di­thio­carbazate groups located on the same side of the C=N bond, involving an intra­molecular N—H⋯O hydrogen bond.

Structure description

Di­thio­carbazate-based imines and some of their metal complexes possess diverse biological applications (e.g., Manan & Cordes, 2022 ▸). In addition, the applications of these compounds have evolved in research areas such as semiconductor devices (Irfan et al., 2020 ▸) and the photocatalytic production of hydrogen (Wise et al., 2015 ▸). In a contin­uation of our previous work on isatin-based imines derived from di­thio­carbazate compounds (Manan et al., 2011 ▸), the title compound was synthesized and its crystal structure is reported herein.

The title compound, C₁₇H₁₅N₃OS₂ crystallizes in the triclinic space group P with one mol­ecule in asymmetric unit. The structure is present as the thio­amide tautomer and in the Z isomeric form (Fig. 1 ▸) as a consequence of the formation of an intra­molecular N3—H3⋯O1 hydrogen bond (Table 1 ▸). The C10=S10 and C10—S11 lengths of 1.6544 (16) and 1.7449 (16) Å, respectively, are comparable to those reported for S-benzyl 3–2(bromo­benzyl­idene)di­thio­carbazate (Qiu & Luo, 2007 ▸), benzyl 3-(3,4,5-tri­meth­oxy­benzyl­idene)di­thio­carbazate (Islam et al., 2016 ▸) and benzyl 3-(10-oxo-9,10-di­hydro­phenanthren-9-yl­idene)di­thio­carbazate (Liu et al., 2009 ▸). The observed C—S bond lengths are both inter­mediate between reference values of 1.82 Å for a C—S single bond and 1.56 Å for a C=S double bond (Tarafder et al., 2002 ▸), indicative of conjugation effects through the π-system. As a result of the delocalization of electrons in the 5-methyl­isatin ring, the N2—N3 bond distance of 1.3509 (19) Å is slightly shorter than the corresponding bond in the unsubstituted precursor compound (Shanmuga Sundara Raj et al., 2000 ▸).

Figure 1.

The mol­ecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1	0.91 (2)	2.00 (2)	2.7539 (17)	139 (2)
N9—H9⋯O1i	0.94 (2)	1.91 (2)	2.8341 (18)	166 (2)

Symmetry code: (i) .

The central CN₂S₂ residue in the title compound is close to planar (r.m.s deviation = 0.052 Å) and forms dihedral angles of 9.34 (3) and 72.80 (5)° with the substituted benzyl and 5-methyl­isatin rings, respectively, indicating a highly twisted mol­ecule; the dihedral angle between the rings is 70.87 (5)°. The N2—N3—C10—S10 fragment adopts an anti conformation with a torsion angle of 174.23 (11)°, while the N2—N3—C10—S11 fragment is syn with a torsion angle of −6.67 (19)°. This conformation is similar to those of three closely related compounds benzyl 2-(5-chloro-2-oxo-1,2-di­hydro-3H-indol-3-yl­idene)hydrazinecarbodi­thio­ate, benzyl 2-(5-fluoro-2-oxo-1,2-di­hydro-3H-indol-3-yl­idene)hydrazine­carbodi­thio­ate and benzyl 2-(5-bromo-2-oxo-1,2-di­hydro-3H-indol-3-yl­idene)hydrazinecarbodi­thio­ate (Manan et al., 2011 ▸).

In the crystal, the title compound forms inversion dimers joined by pairs of N9—H9⋯O1 hydrogen bonds (Fig. 2 ▸, Table 1 ▸) in the common (8) motif (Bernstein et al., 1995 ▸). The dimers then pack into sheets propagating in the (001) plane through carbonyl-to-π [O⋯centroid distance = 3.418 (2) Å] and C—H⋯π [H⋯centroid distance = 3.142 (1) Å, C⋯centroid distance = 3.846 (2) Å] inter­actions. Equivalent dimers are observed in the 5-bromo and 5-chloro compounds mentioned above, as well as in 2-(5-nitro-2-oxo-1,2-di­hydro-3H-indol-3-yl­idene)hydrazinecarbodi­thio­ate (Pereira et al., 2021 ▸) and the parent compound 2-(2-oxo-1,2-di­hydro-3H-indol-3-yl­idene)hydrazinecarbodi­thio­ate (Ali et al., 2011 ▸). The aceto­nitrile solvate of the parent compound (Ali et al., 2011 ▸) does not form dimers and instead forms discrete N—H⋯N hydrogen bonds to the solvate. Unlike the majority of related compounds, the 5-fluoro compound (Manan et al., 2011 ▸) does not form dimers and instead packs through strong imine to π inter­actions (centroid⋯centroid separation = 3.213 Å), with weaker N—H⋯S=C hydrogen bonds involving the amide site.

Figure 2.

View of a hydrogen-bonded dimer of the title compound showing both intra­molecular and inter­molecular N—H⋯O hydrogen bonds. The right-hand mol­ecule is generated by the symmetry operation 2 − x, −y, 1 − z.

Synthesis and crystallization

The di­thio­carbazate precursor, SBDTC was prepared by a literature method (Ali & Tarafder, 1977 ▸). The title compound was prepared by adding 5-methyl­isatin (1.61 g, 10.0 mmol, 1.0 eq) dissolved in hot ethanol (10 ml), to a solution of the precursor, SBDTC (1.98 g, 10.0 mmol, 1.0 e.q) in hot ethanol (35 ml). The mixture was heated (80°C) with continuous stirring for 15 min and later allowed to stand for about 20 min at room temperature until a precipitate was formed, which was then filtered and dried over silica gel, yielding orange crystals on recrystallization from ethanol solution (yield: 2.73 g, 80%). m.p. 216–217°C; ¹H (400 MHz, d ₆-DMSO) δ: (p.p.m): 2.26 (3H, s), 4.52 (2H, s), 6.82–7.45 (8H, m), 11.26 (1H, s), 13.94 (1H, s); GCMS: [M]⁺ at m/z 341.

Refinement

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

Table 2. Experimental details.

Crystal data
Chemical formula	C17H15N3OS2
M r	341.44
Crystal system, space group	Triclinic, P
Temperature (K)	173
a, b, c (Å)	6.5733 (2), 8.0601 (2), 15.8280 (4)
α, β, γ (°)	95.442 (2), 99.527 (2), 90.360 (2)
V (Å3)	823.09 (4)
Z	2
Radiation type	Cu Kα
μ (mm−1)	2.99
Crystal size (mm)	0.12 × 0.09 × 0.02
Data collection
Diffractometer	Rigaku XtaLAB P100K
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 ▸)
T min, T max	0.748, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14207, 2876, 2623
R int	0.034
(sin θ/λ)max (Å−1)	0.595
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.034, 0.097, 1.07
No. of reflections	2876
No. of parameters	217
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.38, −0.18

Computer programs: CrysAlis PRO (Rigaku OD, 2023 ▸), SHELXT2018/2 (Sheldrick, 2015a ▸), SHELXL2018/3 (Sheldrick, 2015b ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

Supplementary Material

CCDC reference: 2293455

Additional supporting information: crystallographic information; 3D view; checkCIF report

full crystallographic data

Crystal data

C17H15N3OS2	Z = 2
Mr = 341.44	F(000) = 356
Triclinic, P1	Dx = 1.378 Mg m−3
a = 6.5733 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.0601 (2) Å	Cell parameters from 8603 reflections
c = 15.8280 (4) Å	θ = 2.8–66.0°
α = 95.442 (2)°	µ = 2.99 mm−1
β = 99.527 (2)°	T = 173 K
γ = 90.360 (2)°	Plate, yellow
V = 823.09 (4) Å3	0.12 × 0.09 × 0.02 mm

Data collection

Rigaku XtaLAB P100K diffractometer	2876 independent reflections
Radiation source: Rotating Anode, Rigaku MM-007HF	2623 reflections with I > 2σ(I)
Rigaku Osmic Confocal Optical System monochromator	Rint = 0.034
Detector resolution: 5.8140 pixels mm-1	θmax = 66.5°, θmin = 2.8°
shutterless scans	h = −7→7
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −9→9
Tmin = 0.748, Tmax = 1.000	l = −18→18
14207 measured reflections

Refinement

Refinement on F2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0626P)2 + 0.1676P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2876 reflections	Δρmax = 0.38 e Å−3
217 parameters	Δρmin = −0.17 e Å−3
2 restraints

Special details

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.

Refinement. Carbon-bound H atoms were included in calculated positions (C—H distances are 0.98 Å for methyl H atoms, 0.99 Å for methylene H atoms 0.95 Å for phenyl H atoms) and refined as riding atoms with Uiso(H) = 1.2 Ueq(parent atom, methylene and phenyl H atoms) or Uiso(H) = 1.5 Ueq(parent atom, methyl H atoms). Nitrogen-bound hydrogen atoms were located from the difference Fourier map and refined isotropically subject to a distance restraint.

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

	x	y	z	Uiso*/Ueq
S11	0.21331 (6)	0.33788 (5)	0.21855 (2)	0.03493 (14)
S10	0.58661 (6)	0.23720 (6)	0.13457 (3)	0.04020 (15)
O1	0.86838 (18)	0.08666 (16)	0.40267 (8)	0.0398 (3)
N3	0.5546 (2)	0.22521 (17)	0.29604 (9)	0.0341 (3)
N2	0.4614 (2)	0.26067 (17)	0.36534 (9)	0.0326 (3)
N9	0.7901 (2)	0.11126 (18)	0.54096 (9)	0.0358 (3)
C12	0.1188 (3)	0.5709 (2)	0.10260 (10)	0.0337 (3)
C1	0.7576 (2)	0.1314 (2)	0.45642 (11)	0.0335 (3)
C2	0.5567 (2)	0.22039 (19)	0.43850 (10)	0.0325 (3)
C10	0.4621 (2)	0.26451 (19)	0.21733 (10)	0.0319 (3)
C8	0.6299 (2)	0.1807 (2)	0.58149 (11)	0.0340 (3)
C3	0.4846 (2)	0.24993 (19)	0.52025 (10)	0.0324 (3)
C5	0.2894 (3)	0.3413 (2)	0.63055 (11)	0.0378 (4)
C11	0.1296 (3)	0.3858 (2)	0.10785 (10)	0.0359 (4)
H11A	0.227507	0.338283	0.071281	0.043*
H11B	−0.007988	0.333708	0.085640	0.043*
C4	0.3146 (3)	0.3301 (2)	0.54485 (11)	0.0365 (4)
H4	0.216108	0.376892	0.503346	0.044*
C7	0.6075 (3)	0.1888 (2)	0.66702 (11)	0.0394 (4)
H7	0.705150	0.140761	0.708391	0.047*
C6	0.4357 (3)	0.2702 (2)	0.69000 (11)	0.0415 (4)
H6	0.417242	0.277589	0.748510	0.050*
C17	−0.0561 (3)	0.6540 (2)	0.11867 (12)	0.0452 (4)
H17	−0.169973	0.593731	0.131545	0.054*
C13	0.2833 (3)	0.6589 (3)	0.08239 (12)	0.0478 (5)
H13	0.403301	0.602050	0.070803	0.057*
C9	0.1083 (3)	0.4309 (3)	0.65976 (12)	0.0474 (4)
H9A	0.023698	0.475703	0.610469	0.071*
H9B	0.158867	0.522536	0.703588	0.071*
H9C	0.024801	0.352666	0.684170	0.071*
C16	−0.0654 (5)	0.8257 (3)	0.11601 (14)	0.0685 (7)
H16	−0.184886	0.883158	0.127739	0.082*
C14	0.2728 (5)	0.8293 (3)	0.07910 (14)	0.0690 (8)
H14	0.385349	0.889230	0.064934	0.083*
C15	0.1000 (6)	0.9125 (3)	0.09623 (15)	0.0803 (10)
H15	0.094106	1.029931	0.094482	0.096*
H3	0.680 (3)	0.177 (3)	0.3057 (14)	0.052 (6)*
H9	0.901 (3)	0.053 (3)	0.5684 (14)	0.057 (6)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S11	0.0346 (2)	0.0399 (2)	0.0312 (2)	0.01365 (17)	0.00499 (16)	0.00834 (16)
S10	0.0370 (2)	0.0487 (3)	0.0375 (2)	0.00624 (18)	0.01188 (17)	0.00715 (18)
O1	0.0344 (6)	0.0487 (7)	0.0373 (6)	0.0126 (5)	0.0052 (5)	0.0097 (5)
N3	0.0297 (7)	0.0389 (7)	0.0345 (7)	0.0087 (6)	0.0044 (6)	0.0085 (6)
N2	0.0320 (7)	0.0332 (7)	0.0325 (7)	0.0056 (5)	0.0030 (5)	0.0060 (5)
N9	0.0306 (7)	0.0424 (8)	0.0334 (7)	0.0086 (6)	0.0001 (5)	0.0081 (6)
C12	0.0413 (9)	0.0329 (8)	0.0249 (7)	0.0039 (7)	−0.0017 (6)	0.0050 (6)
C1	0.0294 (8)	0.0337 (8)	0.0365 (8)	0.0042 (6)	0.0015 (6)	0.0063 (6)
C2	0.0300 (8)	0.0310 (8)	0.0360 (8)	0.0046 (6)	0.0021 (6)	0.0067 (6)
C10	0.0320 (8)	0.0278 (7)	0.0353 (8)	0.0019 (6)	0.0031 (6)	0.0046 (6)
C8	0.0306 (8)	0.0349 (8)	0.0351 (8)	0.0018 (6)	0.0005 (6)	0.0054 (6)
C3	0.0313 (8)	0.0317 (8)	0.0332 (8)	0.0019 (6)	0.0010 (6)	0.0055 (6)
C5	0.0335 (8)	0.0406 (9)	0.0386 (9)	−0.0002 (7)	0.0056 (7)	0.0010 (7)
C11	0.0403 (9)	0.0351 (8)	0.0303 (8)	0.0067 (7)	−0.0016 (6)	0.0055 (6)
C4	0.0338 (8)	0.0364 (9)	0.0383 (9)	0.0051 (7)	0.0021 (7)	0.0054 (7)
C7	0.0355 (9)	0.0483 (10)	0.0332 (8)	0.0024 (7)	−0.0010 (7)	0.0089 (7)
C6	0.0396 (9)	0.0511 (10)	0.0333 (9)	−0.0013 (8)	0.0056 (7)	0.0019 (7)
C17	0.0529 (11)	0.0452 (10)	0.0376 (9)	0.0157 (8)	0.0049 (8)	0.0083 (7)
C13	0.0509 (10)	0.0534 (11)	0.0367 (9)	−0.0098 (9)	−0.0009 (8)	0.0076 (8)
C9	0.0419 (10)	0.0576 (11)	0.0428 (10)	0.0067 (8)	0.0102 (8)	−0.0013 (8)
C16	0.105 (2)	0.0485 (12)	0.0467 (12)	0.0390 (13)	−0.0009 (12)	0.0012 (9)
C14	0.104 (2)	0.0527 (13)	0.0441 (12)	−0.0332 (14)	−0.0100 (12)	0.0135 (10)
C15	0.155 (3)	0.0294 (10)	0.0451 (12)	−0.0012 (15)	−0.0179 (15)	0.0056 (9)

Geometric parameters (Å, º)

S11—C10	1.7449 (16)	C5—C6	1.396 (3)
S11—C11	1.8260 (16)	C5—C9	1.510 (3)
S10—C10	1.6544 (16)	C11—H11A	0.9900
O1—C1	1.239 (2)	C11—H11B	0.9900
N3—N2	1.3509 (19)	C4—H4	0.9500
N3—C10	1.360 (2)	C7—H7	0.9500
N3—H3	0.912 (16)	C7—C6	1.392 (3)
N2—C2	1.293 (2)	C6—H6	0.9500
N9—C1	1.345 (2)	C17—H17	0.9500
N9—C8	1.413 (2)	C17—C16	1.390 (3)
N9—H9	0.938 (16)	C13—H13	0.9500
C12—C11	1.503 (2)	C13—C14	1.381 (3)
C12—C17	1.381 (3)	C9—H9A	0.9800
C12—C13	1.387 (2)	C9—H9B	0.9800
C1—C2	1.505 (2)	C9—H9C	0.9800
C2—C3	1.449 (2)	C16—H16	0.9500
C8—C3	1.402 (2)	C16—C15	1.384 (4)
C8—C7	1.381 (2)	C14—H14	0.9500
C3—C4	1.387 (2)	C14—C15	1.375 (4)
C5—C4	1.388 (2)	C15—H15	0.9500
C10—S11—C11	103.16 (8)	C12—C11—H11B	109.4
N2—N3—C10	119.92 (14)	H11A—C11—H11B	108.0
N2—N3—H3	116.6 (14)	C3—C4—C5	119.52 (16)
C10—N3—H3	123.4 (14)	C3—C4—H4	120.2
C2—N2—N3	117.17 (14)	C5—C4—H4	120.2
C1—N9—C8	111.27 (14)	C8—C7—H7	121.4
C1—N9—H9	123.9 (15)	C8—C7—C6	117.16 (16)
C8—N9—H9	124.7 (15)	C6—C7—H7	121.4
C17—C12—C11	119.66 (16)	C5—C6—H6	118.7
C17—C12—C13	119.77 (17)	C7—C6—C5	122.66 (16)
C13—C12—C11	120.57 (16)	C7—C6—H6	118.7
O1—C1—N9	127.80 (15)	C12—C17—H17	120.0
O1—C1—C2	125.75 (15)	C12—C17—C16	120.0 (2)
N9—C1—C2	106.46 (14)	C16—C17—H17	120.0
N2—C2—C1	128.01 (15)	C12—C13—H13	120.0
N2—C2—C3	125.68 (15)	C14—C13—C12	120.0 (2)
C3—C2—C1	106.30 (13)	C14—C13—H13	120.0
S10—C10—S11	128.14 (10)	C5—C9—H9A	109.5
N3—C10—S11	112.22 (12)	C5—C9—H9B	109.5
N3—C10—S10	119.64 (13)	C5—C9—H9C	109.5
C3—C8—N9	109.25 (14)	H9A—C9—H9B	109.5
C7—C8—N9	129.31 (15)	H9A—C9—H9C	109.5
C7—C8—C3	121.43 (16)	H9B—C9—H9C	109.5
C8—C3—C2	106.70 (14)	C17—C16—H16	120.1
C4—C3—C2	133.05 (15)	C15—C16—C17	119.8 (2)
C4—C3—C8	120.24 (16)	C15—C16—H16	120.1
C4—C5—C6	118.99 (16)	C13—C14—H14	119.9
C4—C5—C9	120.83 (16)	C15—C14—C13	120.3 (2)
C6—C5—C9	120.18 (16)	C15—C14—H14	119.9
S11—C11—H11A	109.4	C16—C15—H15	119.9
S11—C11—H11B	109.4	C14—C15—C16	120.1 (2)
C12—C11—S11	111.12 (11)	C14—C15—H15	119.9
C12—C11—H11A	109.4
O1—C1—C2—N2	2.5 (3)	C8—N9—C1—O1	179.33 (16)
O1—C1—C2—C3	−178.95 (16)	C8—N9—C1—C2	−0.72 (18)
N3—N2—C2—C1	−2.7 (2)	C8—C3—C4—C5	0.0 (2)
N3—N2—C2—C3	178.99 (14)	C8—C7—C6—C5	0.2 (3)
N2—N3—C10—S11	−6.67 (19)	C3—C8—C7—C6	−0.7 (3)
N2—N3—C10—S10	174.23 (11)	C11—S11—C10—S10	−2.51 (13)
N2—C2—C3—C8	177.57 (15)	C11—S11—C10—N3	178.48 (11)
N2—C2—C3—C4	−3.7 (3)	C11—C12—C17—C16	178.43 (17)
N9—C1—C2—N2	−177.48 (15)	C11—C12—C13—C14	−178.98 (16)
N9—C1—C2—C3	1.09 (17)	C4—C5—C6—C7	0.4 (3)
N9—C8—C3—C2	0.65 (18)	C7—C8—C3—C2	179.54 (15)
N9—C8—C3—C4	−178.28 (14)	C7—C8—C3—C4	0.6 (2)
N9—C8—C7—C6	177.93 (16)	C6—C5—C4—C3	−0.5 (3)
C12—C17—C16—C15	0.8 (3)	C17—C12—C11—S11	−84.17 (17)
C12—C13—C14—C15	0.3 (3)	C17—C12—C13—C14	0.5 (3)
C1—N9—C8—C3	0.07 (19)	C17—C16—C15—C14	0.1 (3)
C1—N9—C8—C7	−178.72 (17)	C13—C12—C11—S11	95.35 (16)
C1—C2—C3—C8	−1.05 (17)	C13—C12—C17—C16	−1.1 (3)
C1—C2—C3—C4	177.68 (17)	C13—C14—C15—C16	−0.7 (3)
C2—C3—C4—C5	−178.56 (16)	C9—C5—C4—C3	178.71 (16)
C10—S11—C11—C12	−109.04 (13)	C9—C5—C6—C7	−178.83 (16)
C10—N3—N2—C2	179.99 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1	0.91 (2)	2.00 (2)	2.7539 (17)	139 (2)
N9—H9···O1i	0.94 (2)	1.91 (2)	2.8341 (18)	166 (2)

Symmetry code: (i) −x+2, −y, −z+1.

Funding Statement

Funding for this research was provided by: Universiti Teknologi MARA (grant No. 600–RMC/SRC/5/3(043/2020)).