2-[1-(1,3-Dioxo-1,3-di­hydro-2H-inden-2-yl­idene)eth­yl]hydrazinecarbo­thio­amide

Omar Ali, N.H.S.; Sheikh Abdul Hamid, M.H.; Mirza, A.H.; Usman, A.

doi:10.1107/S2414314619015013

organic compounds

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ISSN: 2414-3146

Volume 4| Part 11| November 2019| x191501

https://doi.org/10.1107/S2414314619015013

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2-[1-(1,3-Dioxo-1,3-dihydro-2H-inden-2-ylidene)ethyl]hydrazinecarbothioamide

Nur Halilatul Sadiqin Omar Ali,^a Malai Haniti Sheikh Abdul Hamid,^a ^* Aminul Huq Mirza ^a and Anwar Usman ^a

^aChemical Sciences, Faculty of Science, Universiti Brunei Darussalam, Jalan, Tungku Link BE1410, Negara, Brunei Darussalam
^*Correspondence e-mail: haniti.hamid@ubd.edu.bn

Edited by H. Ishida, Okayama University, Japan (Received 30 September 2019; accepted 6 November 2019; online 12 November 2019)

The title compound, C₁₂H₁₁N₃O₂S, was synthesized by a condensation reaction of 2-acetylindan-1,3-dione and thiosemicarbazide in ethanol in the presence of glacial acetic acid. The molecule adopts a thioketone form. The dihedral angle between the mean planes of 1H-inden-1,3(2H)-dione and hydrazinecarbothioamide units is 86.32 (7)°. Weak intramolecular N—H⋯O and C—H⋯O hydrogen bonds are observed. In the crystal, molecules are linked via pairs of weak intermolecular N—H⋯O hydrogen bonds, forming inversion dimers. The dimers are further linked into a three-dimensional network through N—H⋯S and N—H⋯O hydrogen bonds, and π–π interactions [centroid–centroid distances = 3.5619 (10)–3.9712 (9) Å].

Keywords: crystal structure; enamine; synthesis; hydrogen bonds.

CCDC references: 1857321; 1857321

Structure description

Derivatives obtained from the reaction of 2-acetylindan-1,3-dione and thiosemicarbazide are not widely known in the literature (Sawhney & Lemke, 1983 ; Kumar et al., 2014 ). It is predicted that the reaction with thiosemicarbazide at the acetyl group will produce a thiosemicarbazone as a Schiff base, but in this work, we report the formation of the title compound, an enamine of 2-acetylindan-1,3-dionethiosemicarbazone.

The title compound is completely in a thioketone form and weak intramolecular N—H⋯O and C—H⋯O hydrogen bonds (N3—HN4⋯O2 and C12—H12B⋯O1; Table 1) are observed (Fig. 1). The dihedral angle between the mean planes of the 1H-indene-1,3(2H)-dione and hydrazinecarbothioamide units is 86.32 (7)°. The length of the C1—S1 bond [1.705 (2) Å] is intermediate between a single bond C—S (1.82 Å) and a double bond C=S (1.67 Å) (Allen et al., 1987 ), which implies that it possesses partial double-bond character indicative of possible delocalization over atoms S1, C1 and N1. This notion is supported by the C1—N1 bond length [1.318 (2) Å], which is shorter than C1—N2 [1.340 (2) Å], again indicative of some double-bond character of C1—N1. A similar feature has been observed in a thiosemicarbazone (Jouad et al., 2001 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯O1	0.98	2.26	3.033 (3)	135
N2—HN3⋯S1ⁱ	0.84 (2)	2.47 (2)	3.2796 (16)	163 (2)
N1—HN1⋯S1ⁱⁱ	0.85 (3)	2.63 (3)	3.3764 (19)	147 (2)
N1—HN2⋯O1ⁱⁱⁱ	0.84 (3)	2.11 (3)	2.816 (2)	142 (2)
N3—HN4⋯O2	0.89 (3)	2.05 (3)	2.7592 (19)	135 (2)
N3—HN4⋯O2^iv	0.89 (3)	2.30 (2)	3.0107 (19)	137 (2)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) -x+1, -y+1, -z+1.

Figure 1
The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at 50% probability level. Intramolecular N—H⋯O and C—H⋯O hydrogen bonds are shown as dashed lines.

In the crystal, two molecules are bound by a pair of N—H⋯O hydrogen bonds (N3—HN4⋯O2^iv; Table 1), forming a centrosymmetric dimeric structure (Fig. 2). The dimers are further connected by two N—H⋯S hydrogen bonds and one N—H⋯O hydrogen bond (N2—HN3⋯S1ⁱ, N1—HN1⋯S1ⁱⁱ, and N1—HN2⋯O1ⁱⁱⁱ; Table 1). The crystal packing also features π–π stacking interactions. The centroid–centroid distances are 3.8487 (10), 3.6271 (11), 3.5619 (10), 3.8614 (11) and 3.9712 (9) Å, respectively, for Cg1⋯Cg1^v, Cg1⋯Cg2^vi, Cg1⋯Cg3^vi, Cg2⋯Cg3^v and Cg3⋯Cg3^v; Cg1, Cg2 and Cg3 are the centroids of the C3–C5/C10/C11 and C5–C10 rings, and the C3–C11 ring system, respectively [symmetry codes: (v) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, z; (vi) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, z].

Figure 2
The inversion dimer of the title compound formed by a pair of N—H⋯O hydrogen bonds (dashed lines).

Synthesis and crystallization

The title compound was prepared by heating a mixed solution of 2-acetylindan-1,3-dione (0.50 g, 2.66 mmol) in absolute ethanol (20 ml) and thiosemicarbazide (0.24 g, 2.66 mmol) in absolute ethanol (55 ml). Three drops of glacial acetic acid were then added and the mixture was refluxed for 30 min. A yellow microcrystalline powder was obtained and it was recrystallized from an acetonitrile/methanol mixture solvent. The pale-brown crystals obtained were filtered, washed with cold acetonitrile and dried in vacuo [yield: 0.57 g (82%), m.p. 486–487 K]. Single crystals of the title compound suitable for X-ray analysis were grown by slow evaporation at room temperature from an acetonitrile/methanol mixture solvent.

IR (ν, cm⁻¹): 3336–3112 (w, N—H), 2945 (w, Ar C—H), 1696 (m, C=O), 1654 (s, C=O), 1573 and 1502 (s, aromatic C=C), 858 (s, C=S). EI–MS calculated for C₁₂H₁₁N₃O₂S, M^+·: 261.30, found: 261. ¹H NMR (DMSO-d₆) δ (p.p.m.): 11.48 (br, 1H, –NH), 10.00 (s, 1H, –NH), 7.99 (br, 2H, –NH₂), 7.67–7.72 (m, 4H, Ar-H), 3.33 (s, 3H, –CH₃). ¹³C NMR (DMSO-d₆) δ (p.p.m.): 192.34, 189.44, 182.36, 139.65, 138.09, 133.61, 133.53, 121.20, 120.94, 12.59. Analysis calculated for C₁₂H₁₁N₃O₂S: C 55.16, H 4.24, N 16.08%. Found: C 55.12, H 3.96, N 15.42%.

Refinement

Crystal data, data collection and structure refinement details of the title compound are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₁N₃O₂S
M_r	261.30
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	99
a, b, c (Å)	15.0751 (6), 7.6891 (4), 20.7891 (9)
V (Å³)	2409.75 (19)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.27
Crystal size (mm)	0.76 × 0.25 × 0.25

Data collection
Diffractometer	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.824, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	18247, 3382, 2712
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.694

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.173, 1.07
No. of reflections	3382
No. of parameters	181
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.79, −1.00
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC references: 1857321; 1857321

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619015013/is5524sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619015013/is5524Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619015013/is5524Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

2-[1-(1,3-Dioxo-1,3-dihydro-2H-inden-2-ylidene)ethyl]hydrazinecarbothioamide top

Crystal data top

C₁₂H₁₁N₃O₂S	D_x = 1.440 Mg m⁻³
M_r = 261.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 6090 reflections
a = 15.0751 (6) Å	θ = 2.4–29.6°
b = 7.6891 (4) Å	µ = 0.27 mm⁻¹
c = 20.7891 (9) Å	T = 99 K
V = 2409.75 (19) Å³	Rod, brown
Z = 8	0.76 × 0.25 × 0.25 mm
F(000) = 1088

Data collection top

Bruker D8 Venture diffractometer	2712 reflections with I > 2σ(I)
profile data from θ/2θ scans	R_int = 0.073
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 29.6°, θ_min = 2.4°
T_min = 0.824, T_max = 0.937	h = −20→18
18247 measured reflections	k = −8→10
3382 independent reflections	l = −28→28

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.063	Hydrogen site location: mixed
wR(F²) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.117P)² + 0.3104P] where P = (F_o² + 2F_c²)/3
3382 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.79 e Å⁻³
0 restraints	Δρ_min = −1.00 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
S1	0.43388 (3)	0.69858 (6)	0.75750 (2)	0.01816 (17)
O1	0.86124 (9)	0.5148 (2)	0.58244 (8)	0.0294 (4)
O2	0.58261 (8)	0.40510 (17)	0.48472 (6)	0.0202 (3)
N1	0.50396 (12)	0.8510 (2)	0.65405 (8)	0.0213 (4)
HN1	0.4960 (17)	0.948 (4)	0.6726 (15)	0.043 (8)*
HN2	0.5428 (16)	0.853 (3)	0.6251 (14)	0.025 (6)*
N2	0.52093 (10)	0.5557 (2)	0.66273 (7)	0.0162 (3)
HN3	0.5202 (14)	0.465 (3)	0.6853 (13)	0.024 (6)*
N3	0.57075 (10)	0.5469 (2)	0.60634 (7)	0.0150 (3)
HN4	0.5434 (15)	0.516 (3)	0.5700 (14)	0.027 (6)*
C1	0.49117 (11)	0.7065 (2)	0.68685 (8)	0.0152 (4)
C2	0.66012 (11)	0.5365 (2)	0.60836 (8)	0.0141 (3)
C3	0.70518 (11)	0.4833 (2)	0.55397 (8)	0.0151 (3)
C4	0.80153 (11)	0.4714 (2)	0.54558 (10)	0.0191 (4)
C5	0.81627 (12)	0.3939 (2)	0.48089 (10)	0.0209 (4)
C6	0.89580 (14)	0.3553 (3)	0.45015 (12)	0.0308 (5)
H6	0.951321	0.377395	0.470159	0.037*
C7	0.89078 (15)	0.2830 (3)	0.38902 (12)	0.0366 (6)
H7	0.944060	0.256797	0.366630	0.044*
C8	0.81003 (16)	0.2482 (3)	0.35982 (11)	0.0349 (5)
H8	0.809265	0.197883	0.318095	0.042*
C9	0.72982 (15)	0.2855 (3)	0.39040 (10)	0.0268 (5)
H9	0.674394	0.261752	0.370510	0.032*
C10	0.73498 (12)	0.3592 (2)	0.45145 (8)	0.0177 (4)
C11	0.66251 (11)	0.4159 (2)	0.49572 (8)	0.0149 (3)
C12	0.70463 (12)	0.5863 (3)	0.67010 (9)	0.0215 (4)
H12A	0.684628	0.702208	0.683240	0.026*
H12B	0.769069	0.587450	0.663875	0.026*
H12C	0.689323	0.501675	0.703566	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0289 (3)	0.0173 (3)	0.0083 (2)	−0.00088 (16)	0.00634 (15)	−0.00102 (15)
O1	0.0189 (7)	0.0388 (9)	0.0304 (9)	0.0005 (6)	−0.0073 (6)	0.0053 (6)
O2	0.0190 (6)	0.0289 (7)	0.0128 (6)	0.0048 (5)	−0.0024 (5)	−0.0033 (5)
N1	0.0347 (9)	0.0172 (8)	0.0120 (8)	0.0020 (7)	0.0095 (6)	0.0015 (6)
N2	0.0263 (8)	0.0151 (7)	0.0073 (7)	0.0003 (6)	0.0054 (6)	0.0000 (6)
N3	0.0190 (7)	0.0219 (8)	0.0042 (7)	0.0015 (5)	0.0020 (5)	−0.0013 (5)
C1	0.0193 (8)	0.0168 (8)	0.0094 (8)	−0.0013 (6)	−0.0018 (6)	−0.0021 (6)
C2	0.0188 (8)	0.0141 (8)	0.0095 (8)	−0.0012 (6)	−0.0021 (6)	0.0032 (6)
C3	0.0164 (8)	0.0179 (8)	0.0110 (8)	0.0020 (6)	−0.0013 (6)	0.0028 (6)
C4	0.0167 (8)	0.0207 (9)	0.0200 (9)	0.0026 (6)	0.0004 (6)	0.0086 (7)
C5	0.0232 (9)	0.0171 (9)	0.0223 (10)	0.0058 (7)	0.0088 (7)	0.0080 (7)
C6	0.0256 (10)	0.0230 (10)	0.0436 (13)	0.0052 (8)	0.0169 (9)	0.0101 (9)
C7	0.0424 (13)	0.0228 (11)	0.0444 (14)	0.0086 (9)	0.0313 (11)	0.0070 (9)
C8	0.0565 (14)	0.0243 (11)	0.0239 (11)	0.0098 (10)	0.0237 (10)	0.0024 (9)
C9	0.0420 (12)	0.0239 (10)	0.0146 (9)	0.0070 (8)	0.0083 (8)	0.0011 (7)
C10	0.0240 (9)	0.0173 (8)	0.0118 (8)	0.0053 (7)	0.0066 (6)	0.0043 (7)
C11	0.0200 (8)	0.0164 (8)	0.0082 (8)	0.0048 (6)	0.0020 (6)	0.0029 (6)
C12	0.0263 (9)	0.0268 (10)	0.0113 (8)	−0.0015 (7)	−0.0062 (7)	−0.0009 (7)

Geometric parameters (Å, º) top

S1—C1	1.7050 (18)	C4—C5	1.488 (3)
O1—C4	1.228 (2)	C5—C6	1.391 (3)
O2—C11	1.229 (2)	C5—C10	1.395 (3)
N1—C1	1.318 (2)	C6—C7	1.389 (4)
N1—HN1	0.85 (3)	C6—H6	0.9500
N1—HN2	0.84 (3)	C7—C8	1.386 (4)
N2—C1	1.340 (2)	C7—H7	0.9500
N2—N3	1.394 (2)	C8—C9	1.396 (3)
N2—HN3	0.84 (2)	C8—H8	0.9500
N3—C2	1.350 (2)	C9—C10	1.392 (3)
N3—HN4	0.89 (3)	C9—H9	0.9500
C2—C3	1.381 (2)	C10—C11	1.493 (2)
C2—C12	1.498 (2)	C12—H12A	0.9800
C3—C11	1.466 (2)	C12—H12B	0.9800
C3—C4	1.466 (2)	C12—H12C	0.9800

C1—N1—HN1	119 (2)	C7—C6—C5	117.3 (2)
C1—N1—HN2	119.0 (17)	C7—C6—H6	121.3
HN1—N1—HN2	114 (2)	C5—C6—H6	121.3
C1—N2—N3	122.48 (15)	C8—C7—C6	121.71 (18)
C1—N2—HN3	120.3 (17)	C8—C7—H7	119.1
N3—N2—HN3	115.8 (16)	C6—C7—H7	119.1
C2—N3—N2	120.94 (15)	C7—C8—C9	121.4 (2)
C2—N3—HN4	118.1 (15)	C7—C8—H8	119.3
N2—N3—HN4	118.4 (15)	C9—C8—H8	119.3
N1—C1—N2	119.14 (16)	C10—C9—C8	116.8 (2)
N1—C1—S1	123.34 (14)	C10—C9—H9	121.6
N2—C1—S1	117.46 (13)	C8—C9—H9	121.6
N3—C2—C3	118.86 (15)	C9—C10—C5	121.78 (17)
N3—C2—C12	117.30 (15)	C9—C10—C11	129.77 (18)
C3—C2—C12	123.84 (16)	C5—C10—C11	108.44 (16)
C2—C3—C11	124.43 (15)	O2—C11—C3	127.43 (15)
C2—C3—C4	127.10 (16)	O2—C11—C10	125.64 (16)
C11—C3—C4	108.34 (15)	C3—C11—C10	106.93 (14)
O1—C4—C3	129.43 (19)	C2—C12—H12A	109.5
O1—C4—C5	124.29 (17)	C2—C12—H12B	109.5
C3—C4—C5	106.28 (16)	H12A—C12—H12B	109.5
C6—C5—C10	121.0 (2)	C2—C12—H12C	109.5
C6—C5—C4	129.0 (2)	H12A—C12—H12C	109.5
C10—C5—C4	109.99 (15)	H12B—C12—H12C	109.5

C1—N2—N3—C2	97.7 (2)	C4—C5—C6—C7	−179.82 (18)
N3—N2—C1—N1	4.8 (3)	C5—C6—C7—C8	−0.9 (3)
N3—N2—C1—S1	−178.07 (12)	C6—C7—C8—C9	0.5 (3)
N2—N3—C2—C3	163.37 (16)	C7—C8—C9—C10	0.0 (3)
N2—N3—C2—C12	−17.4 (2)	C8—C9—C10—C5	−0.2 (3)
N3—C2—C3—C11	−7.9 (3)	C8—C9—C10—C11	179.00 (18)
C12—C2—C3—C11	172.90 (16)	C6—C5—C10—C9	−0.2 (3)
N3—C2—C3—C4	176.93 (16)	C4—C5—C10—C9	−179.77 (17)
C12—C2—C3—C4	−2.3 (3)	C6—C5—C10—C11	−179.53 (16)
C2—C3—C4—O1	−4.8 (3)	C4—C5—C10—C11	0.9 (2)
C11—C3—C4—O1	179.40 (19)	C2—C3—C11—O2	4.2 (3)
C2—C3—C4—C5	175.41 (17)	C4—C3—C11—O2	−179.82 (17)
C11—C3—C4—C5	−0.42 (19)	C2—C3—C11—C10	−175.02 (16)
O1—C4—C5—C6	0.3 (3)	C4—C3—C11—C10	0.94 (19)
C3—C4—C5—C6	−179.83 (19)	C9—C10—C11—O2	0.3 (3)
O1—C4—C5—C10	179.86 (18)	C5—C10—C11—O2	179.61 (16)
C3—C4—C5—C10	−0.3 (2)	C9—C10—C11—C3	179.59 (18)
C10—C5—C6—C7	0.7 (3)	C5—C10—C11—C3	−1.14 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O1	0.98	2.26	3.033 (3)	135
N2—HN3···S1ⁱ	0.84 (2)	2.47 (2)	3.2796 (16)	163 (2)
N1—HN1···S1ⁱⁱ	0.85 (3)	2.63 (3)	3.3764 (19)	147 (2)
N1—HN2···O1ⁱⁱⁱ	0.84 (3)	2.11 (3)	2.816 (2)	142 (2)
N3—HN4···O2	0.89 (3)	2.05 (3)	2.7592 (19)	135 (2)
N3—HN4···O2^iv	0.89 (3)	2.30 (2)	3.0107 (19)	137 (2)

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+3/2, y+1/2, z; (iv) −x+1, −y+1, −z+1.

Acknowledgements

We are grateful to the Chemical Sciences, Faculty of Science, Universiti Brunei Darussalam for the necessary support in carrying out the research work. We also thank the National University of Singapore for running the spectroscopic, analytical data and the collection of the X-ray diffraction data.

References

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