2-[(1E)-({[(Benzylsulfanyl)methanethioyl]amino}- imino)methyl]-6-methoxyphenol: crystal structure and Hirshfeld surface analysis

The title di­thio­carbazate ester, C16H16N2O2S2, comprises two almost planar residues, i.e. the phenyl ring and the remaining 14 non-H atoms (r.m.s. deviation = 0.0410 Å). These are orientated perpendicularly, forming a dihedral angle of 82.72 (5)°. An intra­molecular hy­droxy-O—H⋯N(imine) hydrogen bond, leading to an S(6) loop, is noted. An analysis of the geometric parameters is consistent with the mol­ecule existing as the thione tautomer, and the conformation about the C=N bond is E. The thione S and imine H atoms lie to the same side of the mol­ecule, facilitating the formation of inter­molecular N—H⋯S hydrogen bonds leading to eight-membered {⋯HNCS}2 synthons in the crystal. These aggregates are connected by phenyl-C—H⋯O(hy­droxy) inter­actions into a supra­molecular layer in the bc plane; these stack with no directional inter­actions between them. An analysis of the Hirshfeld surface confirms the nature of the inter­molecular inter­actions

Crystal structure of 2-((1E)-{2-[bis(2-methylbenzylsulfanyl) methylidene]-hydrazin-1-ylidene}methyl)-6-methoxy-phenol

We thank the Department of Chemistry, Universiti Putra Malaysia for facilities. This research was funded by Universiti Putra Malaysia (UPM) and the Malaysian Government under the Geran UPM Scheme (RUGS No. IBT/2013/9419400), the Malaysian Fundamental Research Grant Scheme (FRGS No.01–02-13–1344FR) and the ScienceFund under the Ministry of Science, Technology and Innovation (MOSTI 06–01-04-SF1810). ENMY wishes to thank UPM for the award of a Graduate Research Fellowship.Peer reviewedPublisher PD

Bis{4-methylbenzyl 2-[4-(propan-2-yl)benzylidene]hydrazinecarbodithioato-κ2N2,S}nickel(II): crystal structure and Hirshfeld surface analysis

The complete molecule of the title hydrazine carbodithioate complex, [Ni(C19H21N2S2)2], is generated by the application of a centre of inversion. The NiII atom is N,S-chelated by two hydrazinecarbodithioate ligands, which provide a trans-N2S2 donor set that defines a distorted square-planar geometry. The conformation of the five-membered chelate ring is an envelope with the NiII atom being the flap atom. In the crystal, p-tolyl-C—H...π(benzene-iPr), iPr-C—H...π(p-tolyl) and π–π interactions [between p-tolyl rings with inter-centroid distance = 3.8051 (12) Å] help to consolidate the three-dimensional architecture. The analysis of the Hirshfeld surface confirms the importance of H-atom contacts in establishing the packing

A cinnamaldehyde Schiff base ofS-(4-methylbenzyl) dithiocarbazate: crystal structure, Hirshfeld surface analysis and computational study

The title dithiocarbazate ester (I), C18H18N2S2 [systematic name: (E)-4-methylbenzyl 2-[(E)-3-phenylallylidene]hydrazinecarbodithioate, comprises an almost planar central CN2S2 residue [r.m.s. deviation = 0.0131 Å]. The methylene(tolyl-4) group forms a dihedral angle of 72.25 (4)° with the best plane through the remaining non-hydrogen atoms [r.m.s. deviation = 0.0586 Å] so the molecule approximates mirror symmetry with the 4-tolyl group bisected by the plane. The configuration about both double bonds in the N—N=C—C=C chain is E; the chain has an all trans conformation. In the crystal, eight-membered centrosymmetric thioamide synthons, {...HNCS}2, are formed via N—H...S(thione) hydrogen bonds. Connections between the dimers via C—H...π interactions lead to a three-dimensional architecture. A Hirshfeld surface analysis shows that (I) possesses an interaction profile similar to that of a closely related analogue with an S-bound benzyl substituent, (II). Computational chemistry indicates the dimeric species of (II) connected via N—H...S hydrogen bonds is about 0.94 kcal mol−1 more stable than that in (I)

Synthesis, characterisation and structure determination of 3-[(1Z)-{2-[bis({[(2-methylphenyl)methyl]sulfanyl})methylidene]hydrazin-1-ylidene}methyl]benzene-1,2-diol

A light-yellow crystalline product (1), which was isolated after one week from the filtrate of the reaction between S-2-methylbenzyldithiocarbazate and 2,3-dihydroxybenzaldehyde, was characterised by single crystal X-ray diffraction, FTIR and NMR spectroscopic analyses. The experimental molecular structure of 1 has been established by X-ray crystallography and showed, to a first approximation, a planar C2N2S2 + dihydroxyphenyl region that has an almost orthogonal relationship to the rings of the pendant S-bound benzyl groups. This structure has been verified via density functional theory calculations using the B3LYP/6311G(d,p) level of theory. The molecular packing featured linear supramolecular chains along the b-axis sustained by tolyl-C–H…N(imine) and tolyl-C–H…π(tolyl) interactions; the importance of these contacts is indicated by a Hirshfeld surface analysis

Synthesis, characterisation and structure determination of 3-[(1Z)-{2- [bis({[(2-methylphenyl)methyl]sulfanyl})methylidene]hydrazin-1- ylidene}methyl]benzene-1,2-diol

A light-yellow crystalline product (1), which was isolated after one week from the filtrate of the reaction between S-2-methylbenzyldithiocarbazate and 2,3-dihydroxybenzaldehyde, was characterised by single crystal X-ray diffraction, FTIR and NMR spectroscopic analyses. The experimental molecular structure of 1 has been established by X-ray crystallography and showed, to a first approximation, a planar C2N2S2 + dihydroxyphenyl region that has an almost orthogonal relationship to the rings of the pendant S-bound benzyl groups. This structure has been verified via density functional theory calculations using the B3LYP/6311G(d,p) level of theory. The molecular packing featured linear supramolecular chains along the b-axis sustained by tolyl-CH…N(imine) and tolyl-CH … π(tolyl) interactions; the importance of these contacts is indicated by a Hirshfeld surface analysis

Di-n-butyl[N′-(3-methoxy-2-oxidobenzylidene)-N-phenylcarbamohydrazonothioato]tin(IV): crystal structure, Hirshfeld surface analysis and computational study

The title diorganotin Schiff base derivative, [Sn(C4H9)2(C15H13N3O2S)], features a penta-coordinated tin centre defined by the N,O,S-donor atoms of the dianionic Schiff base ligand and two methylene-C atoms of the n-butyl substituents. The resultant C2NOS donor set defines a geometry intermediate between trigonal–bipyramidal and square-pyramidal. In the crystal, amine-N—HO(methoxy) hydrogen bonding is found in a helical, supramolecular chain propagating along the b-axis direction. The chains are assembled into a layer parallel to (101) with methylene-C—H(phenyl) interactions prominent; layers stack without directional interactions between them. The analysis of the calculated Hirshfeld surface showed the presence of weak methylene-C—H(phenyl) interactions and short HH contacts in the inter-layer region. Consistent with the nature of the identified contacts, the stabilization of the crystal is dominated by the dispersion energy term

Bis[S-benzyl 3-(furan-2-ylmethylidene)dithiocarbazato-κ2 N 3,S]copper(II): crystal structure and Hirshfeld surface analysis

The title CuII complex, [Cu(C13H11N2OS2)2], features a trans-N2S2 donor set as a result of the CuII atom being located on a crystallographic centre of inversion and being coordinated by thiolate-S and imine-N atoms derived from two dithiocarbazate anions. The resulting geometry is distorted square-planar. In the crystal, π(chelate ring)–π(furyl) [inter-centroid separation = 3.6950 (14) A ˚ and angle of inclination = 5.33 (13)˚] and phenyl-C—H...π(phenyl) interactions sustain supramolecular layers lying parallel to (102). The most prominent interactions between layers, as confirmed by an analysis of the calculated Hirshfeld surface, are phenyl-H...H(phenyl) contacts. Indications for Cu...Cg(furyl) contacts (Cu...Cg = 3.74 A ˚ ) were also found. Interaction energy calculations suggest the contacts between molecules are largely dispersive in natur

Unusual saccharin-N,O (carbonyl) coordination in mixed-ligand copper(II) complexes: synthesis, X-ray crystallography and biological activity

Three tridentate Schiff bases containing N and S donor atoms were synthesized via the condensation reaction between S-2-methylbenzyldithiocarbazate with 2-acetyl-4-methylpyridine (S2APH); 4-methyl-3-thiosemicarbazide with 2-acetylpyridine (MT2APH) and 4-ethyl-3-thiosemicarbazide with 2-acetylpyridine (ET2APH). Three new, binuclear and mixed-ligand copper(II) complexes with the general formula, [Cu(sac)(L)]2 (sac = saccharinate anion; L = anion of the Schiff base) were then synthesized, and subsequently characterized by IR and UV/Vis spectroscopy as well as by molar conductivity and magnetic susceptibility measurements. The Schiff bases were also spectroscopically characterized using NMR and MS to further confirm their structures. The spectroscopic data indicated that the Schiff bases behaved as a tridentate NNS donor ligands coordinating via the pyridyl-nitrogen, azomethine-nitrogen and thiolate-sulphur atoms. Magnetic data indicated a square pyramidal environment for the complexes and the conductivity values showed that the complexes were essentially non-electrolytes in DMSO. The X-ray crystallographic analysis of one complex, [Cu(sac)(S2AP)]2 showed that the Cu(II) atom was coordinated to the thiolate-S, azomethine-N and pyridyl-N donors of the S2AP Schiff base and to the saccharinate-N from one anion, as well as to the carbonyl-O atom from a symmetry related saccharinate anion yielding a centrosymmetric binuclear complex with a penta-coordinate, square pyramidal geometry. All the copper(II) saccharinate complexes were found to display strong cytotoxic activity against the MCF-7 and MDA-MB-231 human breast cancer cell lines