The title di-thio-carbazate ester (I), C18H18N2S2 [systematic name: (E)-4-methyl-benzyl 2-[(E)-3-phenyl-allyl-idene]hydrazinecarbodi-thio-ate, comprises an almost planar central CN2S2 residue [r.m.s. deviation = 0.0131 Å]. The methyl-ene(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 mol-ecule approximates mirror symmetry with the 4-tolyl group bis-ected 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 thio-amide synthons, {⋯HNCS}2, are formed via N-H⋯S(thione) hydrogen bonds. Connections between the dimers via C-H⋯π inter-actions lead to a three-dimensional architecture. A Hirshfeld surface analysis shows that (I) possesses an inter-action 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).
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 thiol-ate-S and imine-N atoms derived from two di-thio-carbazate anions. The resulting geometry is distorted square-planar. In the crystal, π(chelate ring)-π(fur-yl) [inter-centroid separation = 3.6950 (14) Å and angle of inclination = 5.33 (13)°] and phenyl-C-H⋯π(phen-yl) inter-actions sustain supra-molecular layers lying parallel to (02). The most prominent inter-actions between layers, as confirmed by an analysis of the calculated Hirshfeld surface, are phenyl-H⋯H(phen-yl) contacts. Indications for Cu⋯Cg(fur-yl) contacts (Cu⋯Cg = 3.74 Å) were also found. Inter-action energy calculations suggest the contacts between mol-ecules are largely dispersive in nature.
Adsorption efficiency of a duo-material blend featuring the fabrication of modified chitosan adsorbents (powder (C-emimAc), bead (CB-emimAc) and sponge (CS-emimAc)) for the removal of Cd(II) from aqueous solution was investigated. The chitosan@activated carbon (Ch/AC) blend was developed in a green ionic solvent, 1-ethyl-3-methyl imidazolium acetate (EmimAc) and its characteristics was examined using FTIR, SEM, EDX, BET and TGA. The possible mechanism of interaction between the composites and Cd(II) was also predicted using the density functional theory (DFT) analysis. The interactions of various blend forms (C-emimAc, CB-emimAc and CS-emimAc) with Cd(II) gave better adsorption at pH 6. The composites also present excellent chemical stability in both acidic and basic conditions. The monolayer adsorption capacities obtained (under the condition 20 mg/L [Cd], adsorbent dosage 5 mg, contact time 1 h) for the CB-emimAc (84.75 mg/g) > C-emimAc (72.99 mg/g) > CS-emimAc (55.25 mg/g), as this was supported by their order of increasing BET surface area (CB-emimAc (120.1 m2/g) > C-emimAc (67.4 m2/g) > CS-emimAc (35.3 m2/g)). The feasible adsorption interactions between Cd(II) and Ch/AC occurs through the O-H and N-H groups of the composites, as supported by DFT analysis in which an electrostatic interactions was predicted as the dominant force. The interaction energy (-1309.35 eV) calculated via DFT shows that the Ch/AC with amino (-NH) and hydroxyl (-OH) groups are more effective with four significant electrostatic interactions with the Cd(II) ion. The various form of Ch/AC composites developed in EmimAc possess good adsorption capacity and stability for the adsorption Cd(II).
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 di-anionic Schiff base ligand and two methyl-ene-C atoms of the n-butyl substituents. The resultant C2NOS donor set defines a geometry inter-mediate between trigonal-bipyramidal and square-pyramidal. In the crystal, amine-N-H⋯O(meth-oxy) hydrogen bonding is found in a helical, supra-molecular chain propagating along the b-axis direction. The chains are assembled into a layer parallel to (01) with methyl-ene-C-H⋯π(phen-yl) inter-actions prominent; layers stack without directional inter-actions between them. The analysis of the calculated Hirshfeld surface showed the presence of weak methyl-ene-C-H⋯π(phen-yl) inter-actions and short H⋯H 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.
Six new organotin(IV) compounds of Schiff bases derived from S-R-dithiocarbazate [R = benzyl (B), 2- or 4-methylbenzyl (2M and 4M, respectively)] condensed with 2-hydroxy-3-methoxybenzaldehyde (oVa) were synthesised and characterised by elemental analysis, various spectroscopic techniques including infrared, UV-vis, multinuclear (¹H, 13C, 119Sn) NMR and mass spectrometry, and single crystal X-ray diffraction. The organotin(IV) compounds were synthesised from the reaction of Ph₂SnCl₂ or Me₂SnCl₂ with the Schiff bases (S2MoVaH/S4MoVaH/SBoVaH) to form a total of six new organotin(IV) compounds that had a general formula of [R₂Sn(L)] (where L = Schiff base; R = Ph or Me). The molecular geometries of Me₂Sn(S2MoVa), Me₂Sn(S4MoVa) and Me₂Sn(SBoVa) were established by X-ray crystallography and verified using density functional theory calculations. Interestingly, each experimental structure contained two independent but chemically similar molecules in the crystallographic asymmetric unit. The coordination geometry for each molecule was defined by thiolate-sulphur, phenoxide-oxygen and imine-nitrogen atoms derived from a dinegative, tridentate dithiocarbazate ligand with the remaining positions occupied by the methyl-carbon atoms of the organo groups. In each case, the resulting five-coordinate C₂NOS geometry was almost exactly intermediate between ideal trigonal-bipyramidal and square-pyramidal geometries. The cytotoxic activities of the Schiff bases and organotin(IV) compounds were investigated against EJ-28 and RT-112 (bladder), HT29 (colon), U87 and SJ-G2 (glioblastoma), MCF-7 (breast) A2780 (ovarian), H460 (lung), A431 (skin), DU145 (prostate), BE2-C (neuroblastoma) and MIA (pancreatic) cancer cell lines and one normal breast cell line (MCF-10A). Diphenyltin(IV) compounds exhibited greater potency than either the Schiff bases or the respective dimethyltin(IV) compounds. Mechanistic studies on the action of these compounds against bladder cancer cells revealed that they induced the production of reactive oxygen species (ROS). The bladder cancer cells were apoptotic after 24 h post-treatment with the diphenyltin(IV) compounds. The interactions of the organotin(IV) compounds with calf thymus DNA (CT-DNA) were experimentally explored using UV-vis absorption spectroscopy. This study revealed that the organotin(IV) compounds have strong DNA binding affinity, verified via molecular docking simulations, which suggests that these organotin(IV) compounds interact with DNA via groove-binding interactions.