Crystal structure of (E)-2-[4-(4-hy­droxy­phen­yl)butan-2-yl­idene]hydrazine-1-carbo­thio­amide

Adriano Bof de Oliveira; Johannes Beck; Christian Landvogt; Bárbara Regina Santos Feitosa; Fillipe Vieira Rocha

doi:10.1107/S2056989014026401

. 2015 Jan 1;71(Pt 1):o33–o34. doi: 10.1107/S2056989014026401

Crystal structure of (E)-2-[4-(4-hydroxyphenyl)butan-2-ylidene]hydrazine-1-carbothioamide

Adriano Bof de Oliveira ^a,^*, Johannes Beck ^b, Christian Landvogt ^b, Bárbara Regina Santos Feitosa ^a, Fillipe Vieira Rocha ^c

PMCID: PMC4331873 PMID: 25705493

Abstract

The title compound, C₁₁H₁₅N₃OS, is a thiosemicarbazone derivative of the raspberry ketone rheosmin [systematic name: 4-(4-hydroxyphenyl)butane-2-one]. The molecule deviates from planarity, with the bridging C—C—C=N torsion angle equal to −101.3 (2)°. The maximum deviation from the mean plane of the non-H atoms of the thiosemicarbazone fragment [C=N—N—C(= S)—N] is 0.085 (5) Å for the Schiff base N atom, and the dihedral angle between this mean plane and the aromatic ring is 50.31 (8)°. In the crystal, molecules are linked by N—H⋯O, N—H⋯S and O—H⋯S hydrogen bonds, forming a three-dimensional structure, with the molecules stacked along [011].

Keywords: crystal structure, thiosemicarbazone, raspberry ketone, hydrogen bonding, three-dimensional

Related literature

For one of the first reports of thiosemicarbazone derivatives synthesis, see: Freund & Schander (1902 ▸). For a report concerning the synthesis of the raspberry ketone, see: Hoffmann & Degner (1981 ▸). For the biological properties of thiosemicarbazone compounds as well as for their importance in coordination chemistry, see: Lobana et al. (2009 ▸). graphic file with name e-71-00o33-scheme1.jpg

Experimental

Crystal data

C₁₁H₁₅N₃OS
M _r = 237.32
Monoclinic,
a = 13.5604 (7) Å
b = 9.7578 (6) Å
c = 9.3079 (4) Å
β = 95.194 (3)°
V = 1226.56 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.17 × 0.13 × 0.09 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▸) T _min = 0.929, T _max = 0.994
12737 measured reflections
2806 independent reflections
1587 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.116
S = 0.98
2806 reflections
205 parameters
All H-atom parameters refined
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▸); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▸); data reduction: DENZO (Otwinowski & Minor, 1997 ▸) and SCALEPACK; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: DIAMOND (Brandenburg, 2006 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸) and WinGX (Farrugia, 2012 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S2056989014026401/su5031sup1.cif

e-71-00o33-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014026401/su5031Isup2.hkl

e-71-00o33-Isup2.hkl^{(137.8KB, hkl)}

Click here for additional data file.^{(4.6KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014026401/su5031Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989014026401/su5031fig1.tif

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

Click here for additional data file.^{(1,003.3KB, tif)}

. DOI: 10.1107/S2056989014026401/su5031fig2.tif

A view of the intermolecular hydrogen bonding (dashed lines) in the crystal of the title compound (see Table 1 for details of the hydrogen bonding and the symmetry codes).

Click here for additional data file.^{(1.8MB, tif)}

c . DOI: 10.1107/S2056989014026401/su5031fig3.tif

Crystal packing of the title compound viewed along the c axis, with the molecules stacking along the [011] direction. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1036979

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1S1ⁱ	0.89(4)	2.32(4)	3.206(2)	175(3)
N3H10AO1ⁱⁱ	0.85(2)	2.22(2)	2.936(2)	143(2)
N3H10BS1ⁱⁱⁱ	0.91(3)	2.73(3)	3.585(2)	156.6(19)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

BRSF thanks the CNPq/UFS for the award of a PIBIC scholarship and FVR acknowledges FAPESP for a Post-Doctoral scholarship (Proc. No. 2013/20156–5).

supplementary crystallographic information

S1. Structural commentary

Our work is actually dedicated to the synthesis and structural determination of thiosemicarbazone derivatives of natural products. The thiosemicarbazone unit is well known for its biological properties as well as for its importance in coordination chemistry (Lobana et al., 2009). Herein, we contribute to the thiosemicarbazone chemistry by the synthesis and crystal structure of raspberry ketone thiosemicarbazone. The raspberry ketone is a natural product with great demand on the market and its synthesis has already been reported and optimized (Hoffmann & Degner, 1981).

In the title molecule, Fig. 1, the thiosemicarbazone unit is nearly planar showing a torsion angle for the N1—N2—C10—N3 entity of -3.1 (3)°. The maximum deviation from the mean plane of the non-H atoms of the C9/C10/N1/N2/N3/S1 fragment amounts to 0.085 (5)°. The angle between this mean plane and the aromatic ring is 50.31 (8)°. This strong tilting is possiblly due to free rotation around the sp³-hybridized C7 and C8 atoms (Fig. 1).

In the crystal, molecules are connected by N—H···O, N—H···S and O—H···S hydrogen bonds, with bridging sulfur atoms, into a three-dimensional H-bonded network (Figs. 2 and 3, and Table 1). The molecules are arranged along the [011] direction, but the hydrogen bonding interactions are present along all three directions (Fig. 3).

S2. Synthesis and crystallization

The synthesis of the title compound was adapted from a procedure reported previously (Freund & Schander, 1902). In a hydrochloric acid catalyzed reaction, a mixture of 4-(4-hydroxyphenyl)-2-butanone (raspberry ketone) (10 mmol) and thiosemicarbazide (10 mmol) in ethanol (80 mL) was refluxed for 5 h. After cooling and filtering, the title compound was obtained. Yellow crystals suitable for X-ray diffraction were obtained by slow evaporation of asolution in methanol.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All the hydrogen atoms were located in a difference Fourier map and freely refined.