Seema Pratap

N-(naphthyl)-N′-(methoxy carbonyl)thiocarbamide and its Cu(I) complex: synthesis, spectroscopic, X-ray, DFT and in vitro cytotoxicity study

The structural characterization of two new compounds N-naphthyl-N′-methoxycarbonyl thiocarbamide (NMCT) (1) and its Cu(I) complex, bis(N-naphthyl-N′-methoxycarbonyl thiocarbamide) copper(I) chloride [(NMCT)2CuCl] (1a) have been done by spectroscopic techniques (FT-IR, 1H NMR, 13C NMR and electronic spectroscopy) and X-ray crystallography. To get a deeper insight of vibrational frequencies and electronic transitions, DFT and TD-DFT studies have also been performed. X-ray study revealed trigonal planar geometry around copper(I). The ligand coordinates through thione sulfur only. The cytotoxicity of 1 and 1a has been assayed in five human carcinoma cell lines, 2008, C13* (cervical carcinoma), A2780, A2780/CP and IGROV-1 (ovarian carcinoma). Both the compounds exhibited cytotoxicity. The inhibitory activity of copper complex was better than ligand against all the cell lines. Graphical Abstract

1-(Naphthalen-1-yl)-3-[(thio­phen-2-yl)carbon­yl]thio­urea

In the title compound, C16H12N2OS2, the dihedral angles between the mean planes of the central thiourea core and the thiophene ring and the naphthalene ring system are 1.8 (2) and 6.45 (18)°, respectively. The molecule adopts a trans–cis conformation with respect to the position of thiophenoyl and naphthyl groups relative to the S atom across the thiourea C—N bonds. Both the thiophene ring and the sulfanylidene S atom are disordered over two sets of sites with occupancies of 0.862 (3):0.138 (3) and 0.977 (3):0.023 (3), respectively. An intramolecular N—H⋯O hydrogen bond is observed. The crystal packing features two N—H⋯S hydrogen bonds.

Synthesis, molecular structure exploration and in vitro cytotoxicity screening of five novel N, N′- disubstituted thiocarbamide derivatives

GRAPHICAL ABSTRACT ABSTRACT The synthesis of five N,N″-substituted thiocarbamides, namely N-(naphthyl)-N″-(pentoxycarbonyl) thiocarbamide (H2L1), N-(2-Chloro-4-nitrophenyl)-N″-(pentoxycarbonyl) thiocarbamide(H2L2), N-(2-methoxy-4-nitrophenyl)-N″-(pentoxycarbonyl) thiocarbamide (H2L3), N-(3-nitrophenyl)-N″-(pentoxycarbonyl) thiocarbamide (H2L4) and N-(naphthyl)-N″-(2, 2, 2-trichloroethoxycarbonyl) thiocarbamide (H2L5) was performed by the reaction of pentoxycarbonyl chloroformate with naphthyl amine, 2-chloro-4-nitroaniline, 2-methoxy-4-nitroaniline, 3-nitroaniline, respectively, for the first four and by the reaction of 2, 2, 2-trichloroethoxycarbonyl chloroformate with naphthyl amine for the last compound. These compounds were fully characterized by using various spectroscopic (FT-IR, 1H and 13C NMR) and single crystal X-ray studies of H2L1 and H2L5. In the crystal structure of both the compounds the (C˭S) and (C˭O) groups are trans to each other across the C−N bond. The crystal packing of H2L1 shows that the molecules form centrosymmetric dimers connected by N2−H····S hydrogen bonds. In H2L5 an offset face-to-face π–π stacking is observed between two naphthalene rings of two molecules. In vitro cytotoxicity of synthesized compounds was evaluated using five human carcinoma cell lines 2008, C13* (cervical carcinoma), A2780, A2780/CP and IGROV-1 (ovarian carcinoma). The IC50 values of compounds H2L2 ─ H2L4 demonstrated them to be very promising anticancer agents.

N-(1,3-Thia-zol-2-yl)-N'-[(thio-phen-2-yl)carbon-yl]thio-urea hemihydrate.

The title compound, C9H7N3OS3·0.5H2O, crystallizes with two independent but similar molecules in the asymmetric unit, both of which are linked by a water molecule through O—H⋯N hydrogen bonds. In addition the water O atom is further linked by N—H⋯O hydrogen bonds to two additional main molecules, forming a tetrameric unit. These tetrameric units then form infinite ribbons parallel to the ac plane.The dihedral angle between the thiophenoyl and thiazolyl rings is 12.15 (10) and 21.69 (11)° in molecules A and B, respectively. The central thiourea core makes dihedral angles of 5.77 (11) and 8.61 (9)°, respectively, with the thiophenoyl and thiazolyl rings in molecule A and 8.41 (10) and 13.43 (12)° in molecule B. Each molecule adopts a trans–cis geometry with respect to the position of thiophenoyl and thiazole groups relative to the S atom across the thiourea C—N bonds. This geometry is stabilized by intramolecular N—H⋯O hydrogen bonds.

Methyl 2-(thio­phene-2-carboxamido)­benzoate

The title compound, C13H11NO3S, was synthesized from methyl anthranilate, triethylamine and 2-thiophenoyl chloride in benzene. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond. The dihedral angle between the rings is 2.74 (12)°. In the crystal, C—H⋯O interactions link neighbouring molecules into a three-dimensional network.

CCDC 870264: Experimental Crystal Structure Determination

Related Article: Durga P. Singh, Seema Pratap, Sushil K. Gupta, Ray J. Butcher|2013|J.Mol.Struct.|1048|500|doi:10.1016/j.molstruc.2013.05.059

1-(2-Furo­yl)-3-(2-meth­oxy-4-nitro­phen­yl)thio­urea

The asymmetric unit of the title compound, C13H11N3O5S, contains two independent molecules, which are linked by a pair of intermolecular N—H⋯S hydrogen bonds, forming an R 2 2(8) ring motif. The central thiourea core forms dihedral angles of 3.02 (12) and 14.00 (10)° with the essentially planar furoyl groups [maximum deviations = 0.030 (2) and 0.057 (2) Å] in the two molecules and dihedral angles of 2.43 (13) and 8.03 (12)° with the benzene rings. The dihedral angles between the furoyl and benzene rings in the two molecules are 3.97 (10) and 5.98 (9)°. The trans–cis geometry of the thiourea group is stabilized by three intramolecular N—H⋯O hydrogen bonds involving carbonyl and methoxy O atoms with the H atom of the cis-thioamide group and between furan O atom and the other thioamide H atom. There is also a weak intramolecular C—H⋯S interaction in each molecule.

3-[(Furan-2-yl)carbon­yl]-1-(pyrimi­din-2-yl)thio­urea

The title compound, C10H8N4O2S, was synthesized from furoyl isothiocynate and 2-aminopyrimidine in dry acetone. The two N—H groups are in an anti conformation with respect to each other and one N—H group is anti to the C=S group while the other is syn. The amide C=S and the C=O groups are syn to each other. The mean plane of the central thiourea fragment forms dihedral angles of 13.50 (14) and 5.03 (11)° with the furan and pyrimidine rings, respectively. The dihedral angle between the furan and pyrimidine rings is 18.43 (10)°. The molecular conformation is stabilized by an intramolecular N—H⋯N hydrogen bond generating an S(6) ring motif. In the crystal, molecules are linked by pairs of N—H⋯N and weak C—H⋯S hydrogen bonds to form inversion dimers.