organic compounds
2-[1-(1,3-Dioxo-1,3-dihydro-2H-inden-2-ylidene)ethyl]hydrazinecarbothioamide
aChemical Sciences, Faculty of Science, Universiti Brunei Darussalam, Jalan, Tungku Link BE1410, Negara, Brunei Darussalam
*Correspondence e-mail: haniti.hamid@ubd.edu.bn
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.
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).
In the crystal, two molecules are bound by a pair of N—H⋯O hydrogen bonds (N3—HN4⋯O2iv; 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⋯Cg1v, Cg1⋯Cg2vi, Cg1⋯Cg3vi, Cg2⋯Cg3v and Cg3⋯Cg3v; 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) − x, − + y, z; (vi) − x, + y, z].
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 .
details of the title compound are summarized in Table 2
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Structural data
https://doi.org/10.1107/S2414314619015013/is5524sup1.cif
contains datablock I. DOI: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
Data collection: APEX2 (Bruker, 2014); cell
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).C12H11N3O2S | Dx = 1.440 Mg m−3 |
Mr = 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 |
Bruker D8 Venture diffractometer | 2712 reflections with I > 2σ(I) |
profile data from θ/2θ scans | Rint = 0.073 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | θmax = 29.6°, θmin = 2.4° |
Tmin = 0.824, Tmax = 0.937 | h = −20→18 |
18247 measured reflections | k = −8→10 |
3382 independent reflections | l = −28→28 |
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(Fo2) + (0.117P)2 + 0.3104P] where P = (Fo2 + 2Fc2)/3 |
3382 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.79 e Å−3 |
0 restraints | Δρmin = −1.00 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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···O2iv | 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
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Jouad, E. M., Riou, A., Allain, M., Khan, M. A. & Bouet, G. M. (2001). Polyhedron, 20, 67–74. Web of Science CSD CrossRef CAS Google Scholar
Kumar, D., Singh, V. K., Khiwar, S. S. & Saxena, N. (2014). J. Drug Deliv. Ther. 4, 73–83. Google Scholar
Sawhney, K. N. & Lemke, T. L. (1983). J. Org. Chem. 48, 4326–4329. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
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