Synthesis, characterisation and biological activities of Ru(III), Mo(V), Cd(II), Zn(II) and Cu(II) complexes containing a novel nitrogen-sulphur macrocyclic Schiff base derived from glyoxal

A novel nitrogen-sulphur macrocyclic Schiff base, 4,11,20,27-tetrathioxo-3,12,19,28-tetrathia-5,6,9,10,21,22,25,26-octaazatricyclo[28.2.2.214,17]hexatriaconta 1(33),6,8,14(36),15,17(35),22,24,30(34),31-decaene-2,13,18,29-tetraone (TGSB) derived from terephthaloyl-bis-dithiocarbazate (TDTC) and glyoxal (ethane-1,2-dione) is synthesised via condensation. Metal complexes are formed by reacting the Schiff base with various metal salts such as Ru(III), Mo(V), Cd(II), Zn(II) and Cu(II). The complexes are expected to have a general formula of M2L or M3L with a square planar or square pyramidal geometry. These compounds were characterised by various physico-chemical and spectroscopic techniques. From the data, it is concluded that the azomethine nitrogen atom and the thiolate sulphur atom from the ligand are bonded to the metal ion. In the IR spectra of the complexes, the presence of the C=N band in the region of 1600 cm-1 indicates the successful formation of the Schiff base. The structures of the Schiff base and metal complexes are confirmed via FT-IR, GC-MS and NMR spectroscopic analysis. The magnetic susceptibility measurements, electronic spectral data and molar conductivity analysis support the desired geometry of the complexes. The Schiff base and its metal complexes are evaluated for their biological activities against the invasive human bladder carcinoma cell line (EJ-28) and the minimum-invasive human bladder carcinoma cell line (RT-112). The RuTGSB and CdTGSB complexes showed selective activity against RT-112

Crystal structure of 1-{(Z)-[(2E)-3-(4-chlorophenyl)-1-phenylprop-2-en-1-ylidene]amino}-3-ethylthiourea

In the title thiosemicarbazone compound, C18H18ClN3S, the CN3S residue is almost planar (r.m.s. deviation = 0.0031 Å) and forms dihedral angles of 65.99 (7) and 34.60 (10)° with the phenyl and chlorobenzene rings, respectively; the dihedral angle between the aromatic rings is 85.13 (8)°. The conformation about the C=N bond is Z, and that about the C=C bonds is E. The imine N and ethyl N atoms are syn and are linked by an ethyl–imine N—H...N hydrogen bond. This H atom also forms an intermolecular hydrogen bond to the thione S atom, resulting in a supramolecular helical chain propagating along the b axis. The chains are consolidated into a three-dimensional architecture by phenyl-C—H...Cl contacts and weak π–π interactions between centrosymmetrically related chlorobenzene rings [inter-centroid distance = 3.9127 (15) Å]

Crystal structure of 2′-hydroxyaceto-phenone 4-methylthiosemicarbazide

Support for this project came from Universiti Putra Malaysia (UPM) under their Research University Grant Scheme (RUGS No. 9419400), Malaysian Fundamental Research Grant Scheme (FRGS No. 5524425) and the ScienceFund (Science Fund No. 5450726). We also thank Siti Khadijah Densabali for collecting the X-ray data. JJ wishes to acknowledge the Malaysian Government for sponsorship under the SGRA Scheme.Peer reviewedPublisher PD

{S-Benzyl 3-[(6-methyl­pyridin-2-yl)­methyl­idene]dithio­carbazato}nickel(II) monohydrate

The structure of the title compound, [Ni(C15H14N3S2)2]·H2O, has one mol­ecule in the asymmetric unit, along with a solvent water mol­ecule. The two different Schiff base moieties coordinate to the central NiII ion as tridentate N,N′,S-chelating ligands, creating a six-coordinate distorted octa­hedral environment [the smallest angle being 77.43 (7)° and the widest angle being 169.99 (7)°]. The mean planes of the two ligands are nearly orthogonal to each other with an angle of 89.53 (6)°. The packing of the complex is supported by O—H⋯N and O—H⋯S hydrogen bonding between the solvent water mol­ecule and the uncoordinated N and S atoms of neighbouring ligands

Bis{S-benzyl 3-[(phen­yl)(pyridin-2-yl)methyl­idene]dithio­carbazato}zinc acetonitrile monosolvate

In the title compound, [Zn(C20H16N3S2)2]·CH3CN, two different Schiff base moieties coordinate to the central ZnII ion as tridentate N,N′,S-chelating ligands, creating a distorted octa­hedral environment [the smallest angle being 73.24 (6)° and the widest angle being 155.73 (7)°], with the two S atoms in cis positions. The dihedral angle between the mean planes of the two coordinating ligands is 83.65 (5)°. The crystal packing is consolidated by weak C—H⋯N hydrogen-bonding inter­actions

Benzyl 3-(2-methyl­phen­yl)dithio­carbazate

In the title compound, C15H16N2S2, the central C2N2S2 unit is essentially planar (r.m.s. deviation = 0.047 Å) and forms dihedral angles of 68.26 (4) and 65.99 (4)° with the phenyl and benzene rings, respectively, indicating a twisted mol­ecule. Supra­molecular chains with a step topology and propagating along [100] feature in the crystal packing, mediated through N—H⋯S hydrogen bonds. The chains are consolidated into a three-dimensional architecture by C—H⋯π inter­actions

Bis(N′-{(E)-[(2E)-1,3-diphenylprop-2-en-1-ylidene]amino}-N-ethylcarbamimidothioato-κ2 N′,S)zinc(II): crystal structure and Hirshfeld surface analysis

The title ZnII complex, [Zn(C18H18N3S)2], (I), features two independent but chemically equivalent molecules in the asymmetric unit. In each, the thiosemicarbazonate monoanion coordinates the ZnII atom via the thiolate-S and imine-N atoms, with the resulting N2S2 donor set defining a distorted tetrahedral geometry. The five-membered ZnSCN2 chelate rings adopt distinct conformations in each independent molecule, i.e. one ring is almost planar while the other is twisted about the Zn—S bond. In the crystal, the two molecules comprising the asymmetric unit are linked by amine-N—H...N(imine) and amine-N—H...S(thiolate) hydrogen bonds via an eight-membered heterosynthon, {...HNCN...HNCS}. The dimeric aggregates are further consolidated by benzene-C—H...S(thiolate) interactions and are linked into a zigzag supramolecular chain along the c axis via amine-N—H...S(thiolate) hydrogen bonds. The chains are connected into a three-dimensional architecture via phenyl-C—H...π(phenyl) and π–π interactions, the latter occurring between chelate and phenyl rings [inter-centroid separation = 3.6873 (11) Å]. The analysis of the Hirshfeld surfaces calculated for (I) emphasizes the different interactions formed by the independent molecules in the crystal and the impact of the π–π interactions between chelate and phenyl rings

Benzyl 3-(2-methyl­phen­yl)dithio­carbazate

In the title compound, C15H16N2S2, the central C2N2S2 unit is essentially planar (r.m.s. deviation = 0.047 Å) and forms dihedral angles of 68.26 (4) and 65.99 (4)° with the phenyl and benzene rings, respectively, indicating a twisted mol­ecule. Supra­molecular chains with a step topology and propagating along [100] feature in the crystal packing, mediated through N—H⋯S hydrogen bonds. The chains are consolidated into a three-dimensional architecture by C—H⋯π inter­actions