Crystal structure of (E)-4-{1-[2-(car­bamo­thio­yl)hydrazin-1-yl­idene]ethyl}phenyl 4-methyl­benzoate

Karthik Ananth Mani; Vijayan Viswanathan; S Narasimhan; Devadasan Velmurugan

doi:10.1107/S2056989014026942

. 2015 Jan 1;71(Pt 1):o43–o44. doi: 10.1107/S2056989014026942

Crystal structure of (E)-4-{1-[2-(carbamothioyl)hydrazin-1-ylidene]ethyl}phenyl 4-methylbenzoate

Karthik Ananth Mani ^a, Vijayan Viswanathan ^b, S Narasimhan ^a, Devadasan Velmurugan ^b,^*

PMCID: PMC4331904 PMID: 25705498

Abstract

The asymmetric unit of the title compound, C₁₇H₁₇N₃O₂S, consists of two independent molecules, A and B, with different conformations: in molecule A, the dihedral angles between the central benzene ring and the pendant tolyl and carbamothioylhydrazono groups are 71.12 (9) and 5.95 (8)°, respectively. The corresponding angles in molecule B are 50.56 (12) and 26.43 (11)°, respectively. Both molecules feature an intramolecular N—H⋯N hydrogen bond, which closes an S(5) ring. In the crystal, molecules are linked by N—H⋯O, N—H⋯S and C—H⋯O hydrogen bonds, generating a three-dimensional network.

Keywords: crystal structure, thiosemicarbazones derivatives, biological activity, hydrogen bonding, ester

Related literature

For background to the biological activity of thiosemicarbazone derivatives, see: Reis et al. (2013 ▸); Fatondji et al. (2013 ▸); Sau et al. (2003 ▸); Seena et al. (2006 ▸). graphic file with name e-71-00o43-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₇N₃O₂S
M _r = 327.40
Triclinic,
a = 8.068 (5) Å
b = 14.037 (5) Å
c = 15.221 (5) Å
α = 99.801 (5)°
β = 96.040 (5)°
γ = 98.533 (5)°
V = 1664.7 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.960, T _max = 0.980
25169 measured reflections
6809 independent reflections
5402 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.118
S = 0.99
6809 reflections
424 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014026942/hb7334sup1.cif

e-71-00o43-sup1.cif^{(28.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014026942/hb7334Isup2.hkl

e-71-00o43-Isup2.hkl^{(333.2KB, hkl)}

Click here for additional data file.^{(6.2KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014026942/hb7334Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989014026942/hb7334fig1.tif

The molecular structure of the title compound, showing displacement ellipsoids drawn at 30% probability level.

Click here for additional data file.^{(1.3MB, tif)}

b . DOI: 10.1107/S2056989014026942/hb7334fig2.tif

The crystal packing of the title compound viewed down b axis. H-atoms not involved in H-bonds have been excluded for clarity.

CCDC reference: 1038319

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N3AH3A1N1A	0.86	2.28	2.634(3)	105
N3BH3B1N1B	0.86	2.25	2.600(3)	105
N2AH2AS1B ⁱ	0.85(2)	2.66(2)	3.432(3)	153.5(8)
N2BH2BS1A ⁱⁱ	0.86	2.67	3.513(3)	169
N3AH3A2S1B ⁱⁱⁱ	0.86	2.58	3.444(3)	178
N3BH3B1O1A ^iv	0.86	2.42	3.159(3)	145
N3BN3B2S1A ^v	0.86	2.78	3.456(3)	136
C6AH6AO1B ^vi	0.93	2.53	3.354(3)	148

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

Acknowledgments

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection. VV thanks the DBT, Government of India, for providing a fellowship.

supplementary crystallographic information

S1. Comment

Thiosemicarbazone and its derivatives are a class of O, N, S-tridentate donor ligands capable of stabilizing both higher and lower oxidation states of transition metal ions. The biological activities of these ligands are linked to their chelating ability with transition metal ions through phenol O, azomethine N and thiolate S atoms (Seena et al., 2006). Thiosemicarbazones are significant intermediates in drugs synthesis, formation of metal complexes and heterocycles such as thiadiazolines preparation (Sau et al., 2003). Thiosemicarbazones are reported as compounds which present significant antifungal activity. Their metal complexes also exhibit antifungal properties (Reis et al., 2013).

Thiosemicarbnazones are inhibitors of DNA replication and also of many proteases. This inhibitory activity defends the level of interest given to them in the fight against microbial and parasitic diseases. Thiosemicarbazones have many biological activities such as antiviral, antibacterial, antitumor, African trypanosome (Fatondji et al., 2013).

The title compound, C₁₇H₁₇O₂N₃S₁, crystallizes in triclinic P -1 space group. The asymmetric unit of title compound contains two molecules which are shown in Fig.1. The acetophenone thiosemicarbazone fragment in molecule A is almost planar with maximum deviation -0.087 Å and in molecule B maximun deviation is -0.592 Å. The methylbenzoate (C1/C2-C8/O1/O2) and acetophenone thiosemicarbazone (C9-C16/N1/N2/C17/N3/S1) make a dihedral angle of 71.12 (1) ° in molecule A and 50.60 (1) ° in molecule B. The thiosemicarbazone group adopts an extended conformation,which can be seen from the torsion angle value of S1/C17/N2/N1 = -177.4 ° in molecule A and 174.1 ° in molecule B. The methylbenzoate and acetophenone thiosemicarbozone lie in a plane which is evidenced by the torsion angle value of C5/C8/O2/C9 = 179.4 ° in molecule A and 174.8 ° in molecule B.

The crystal structure features both intramolecular & intermolecular interactions of type N—H···N, C—H···O, C—H···N, N—H···S and N—H···O (Table. 1 & Fig. 2). In the crystal packing N—H···S type of intermolecular interaction shows R₂2 (8) dimer formation.

S2. Experimental

A 250-ml two neck RB flask was taken and fitted with condenser and an addition funnel. 0.5mol of 4- hydroxy acetophenone was taken and 200ml of chloroform was added to it with stirring. The reaction mixture was cooled at 5-10°c. 0.5mol of para-tolouyl chloride was added drop wise to the reaction mixture. Stirring was continued for another 15mins and 0.5mol of potassium carbonate was slowly added. Reaction was continued for 2 hours and monitored using TLC. The reaction mass was transferred into 1l beakers and washed twice with water (2x250ml). The chloroform layer was separated and washed with 10% NaOH solution (2x250ml). The chloroform layer was separated and dried with anhydrous sodium sulphate. The chloroform layer was filtered and concentrated under reduced pressure using rotary vacuum, cooled and hexane was added to it. Solid was precipitated, filtered and the product was air dried. Thiosemicarbazide (0.1mole) dissolved in 20 ml of 1N hydrochloric acid was added slowly in constant stirring to 4-Methyl-benzoic acid 4-acetyl-phenyl ester (0.1mole) dissolved in 50 ml of ethanol. After addition of thiosemicarbazide, novel 4-(1-(2-carbamothioylhydrazono)ethyl) phenyl 4-methylbenzoate (in solid form) was formed within 4 mins. The precipitate was filtered and washed with water, followed by Hexane wash and the product was air dried. After purification the compound was recrystallised from CHCl₃ solution to yield colourless blocks.