Synthesis, Crystal Structure, Antibacterial and In Vitro Anticancer Activity of Novel Macroacyclic Schiff Bases and Their Cu (II) Complexes Derived from S-Methyl and S-Benzyl Dithiocarbazate.

A series of novel macroacyclic Schiff base ligands and their Cu (II) complexes were synthesised via reacting dicarbonyls of varying chain lengths with S-methyl dithiocarbazate (SMDTC) and S-benzyl dithiocarbazate (SBDTC) followed by coordination with Cu (II) ions. X-ray crystal structures were obtained for compound 4, an SBDTC-diacetyl analogue, and Cu7, an SMDTC-hexanedione Cu (II) complex. Anticancer evaluation of the compounds showed that Cu1, an SMDTC-glyoxal complex, demonstrated the highest cytotoxic activity against MCF-7 and MDA-MB-231 breast cancer cells with IC50 values of 1.7 µM and 1.4 µM, respectively. There was no clear pattern observed between the effect of chain length and cytotoxic activity; however, SMDTC-derived analogues were more active than SBDTC-derived analogues against MDA-MB-231 cells. The antibacterial assay showed that K. rhizophila was the most susceptible bacteria to the compounds, followed by S. aureus. Compound 4 and the SMDTC-derived analogues 3, 5, Cu7 and Cu9 possessed the highest antibacterial activity. These active analogues were further assessed, whereby 3 possessed the highest antibacterial activity with an MIC of <24.4 µg/mL against K. rhizophila and S. aureus. Further antibacterial studies showed that at least compounds 4 and 5 were bactericidal. Thus, Cu1 and 3 were the most promising anticancer and antibacterial agents, respectively.

Adsorptive Removal of Naproxen from Water Using Polyhedral Oligomeric Silesquioxane (POSS) Covalent Organic Frameworks (COFs).

Covalent organic frameworks are porous crystalline compounds made up of organic material bonded together by strong reversible covalent bonds (these are novel types of materials which have the processability of extended or repeated structures with high performance, like those of thermosets and thermoplastics that produce high surface coverage). These have a long-term effect on an arrangement's geometry and permeability. These compounds are entirely made up of light elements like H, B, C, N, O and Si. Pharmaceuticals and personal care products (PPCPs) have emerged as a new threatened species. A hazardous substance known as an "emerging toxin," such as naproxen, is one that has been established or is generated in sufficient amounts in an environment, creating permanent damage to organisms. COF-S7, OAPS and 2-methylanthraquionone(2-MeAQ), and COF-S12, OAPS and terephthalaldehyde (TPA) were effectively synthesized by condensation (solvothermal) via a Schiff base reaction (R1R2C=NR'), with a molar ratio of 1:8 for OAPS to linker (L1 and L2), at a temperature of 125 °C and 100 °C for COF-S7 and COF-S12, respectively. The compounds obtained were assessed using several spectroscopy techniques, which revealed azomethine C=N bonds, aromatic carbon environments via solid 13C and 29Si NMR, the morphological structure and porosity, and the thermostability of these materials. The remedied effluent was investigated, and a substantial execution was noted in the removal ability of the naproxen over synthesized materials, such as 70% and 86% at a contact time of 210 min and 270 min, respectively, at a constant dose of 0.05 g and pH 7. The maximum adsorption abilities of the substances were found to be 35 mg/g and 42 mg/g. The pH result implies that there is stable exclusion with a rise in pH to 9. At pH 9, the drop significance was attained for COF-S7 with the exception of COF-S12, which was detected at pH 11, due to the negative Foster charge, consequent to the repulsion among the synthesized COFs and naproxen solution. From the isotherms acquired (Langmuir and Freundlich), the substances displayed a higher value (close to 1) of correlation coefficient (R2), which showed that the substances fit into the Freundlich isotherm (heterogenous process), and the value of heterogeneity process (n) achieved (less than 1) specifies that the adsorption is a chemical process. Analysis of the as-prepared composites revealed remarkable reusability in the elimination of naproxen by adsorption. Due to its convenience of synthesis, significant adsorption effectiveness, and remarkable reusability, the as-synthesized COFs are expected to be able to be used as potential adsorbents for eliminating AIDs from water.

Erratum: N'-[Bis(benzyl-sulfan-yl)methyl-idene]benzo-hydrazide. Corrigendum.

[This corrects the article DOI: 10.1107/S1600536812019472.].

Crystal structure of 4-methyl-benzyl N'-[(thio-phen-2-yl)methyl-idene]hydrazinecarbodi-thio-ate.

In the title compound, C15H16N2S3 {systematic name: [({[(4-methyl-phen-yl)meth-yl]sulfan-yl}methane-thio-yl)amino][1-(thio-phen-2-yl)ethyl-idene]amine}, the central CN2S2 residue is almost planar (r.m.s. deviation = 0.0061 Å) and forms dihedral angles of 7.39 (10) and 64.91 (5)° with the thienyl and p-tolyl rings, respectively; the dihedral angle between these rings is 57.52 (6)°. The non-thione S atoms are syn, and with respect to the thione S atom, the benzyl group is anti. In the crystal, centrosymmetrically related mol-ecules self-associate via eight-membered {⋯HNCS}2 synthons. The dimeric aggregates stack along the a axis and are are consolidated into a three-dimensional architecture via methyl-C-H⋯π(benzene) and benzene-C-H⋯π(thien-yl) inter-actions.

Crystal structure of 2-((1E)-{2-[bis-(2-methyl-benzyl-sulfan-yl)methyl-idene]hydrazin-1-yl-idene}meth-yl)-6-meth-oxy-phenol.

In the title compound, C25H26N2O2S2, the central CN2S2 atoms are almost coplanar (r.m.s. deviation = 0.0058 Å). One phenyl ring clearly lies to one side of the central plane, while the other is oriented in the plane but splayed. Despite the different relative orientations, the phenyl rings form similar dihedral angles of 64.90 (3) and 70.06 (3)° with the central plane, and 63.28 (4)° with each other. The benzene ring is twisted with respect to the central plane, forming a dihedral angle of 13.17 (7)°. The S2C=N, N-N and N-N=C bond lengths of 1.2919 (19), 1.4037 (17) and 1.2892 (19) Å, respectively, suggest limited conjugation over these atoms; the configuration about the N-N=C bond is E. An intra-molecular O-H⋯N hydrogen bond is noted. In the crystal, phen-yl-meth-oxy C-H⋯O and phen-yl-phenyl C-H⋯π inter-actions lead to supra-molecular double chains parallel to the b axis. These are connected into a layer via meth-yl-phenyl C-H⋯π inter-actions, and layers stack along the a axis, being connected by weak π-π inter-actions between phenyl rings [inter-centroid distance = 3.9915 (9) Å] so that a three-dimensional architecture ensues.

Crystal structure of 3-methyl-pyridine-2-carbaldehyde 4-methyl-thio-semi-carba-zone monohydrate.

In the title hydrate, C9H12N4S·H2O (systematic name: 3-methyl-1-{(E)-[(3-methyl-pyridin-2-yl)methyl-idene]amino}-thio-urea monohydrate), a small twist is noted between the pyridine ring and the rest of the organic mol-ecule [dihedral angle = 6.96 (5)°]. The imine and pyridine N atoms are syn, and the amine H atoms are anti. The latter arrangement allows for the formation of an intra-molecular N-H⋯N(imine) hydrogen bond. Both the N-bonded H atoms form hydrogen bonds to symmetry-related water mol-ecules, and the latter forms O-H hydrogen bonds with the pyridine N and thione S atoms. These inter-actions lead to supra-molecular layers that stack along the a-axis direction with no specific inter-actions between them.

Crystal structure of 2-{[2-(3-phenyl-allyl-idene)hydrazin-1-yl]thio-carbonyl-sulfanylmeth-yl}pyridinium chloride.

In the title salt of an S-substituted di-thio-carbazate, C16H16N3S2 (+)·Cl(-), the dihedral angles between the almost planar (r.m.s deviation = 0.005 Å) central CN2S2 residue and the terminal pyridinium and phenyl rings are 80.09 (11) and 3.82 (11)°, respectively, indicating the cation has an L-shape; the amine H and thione S atoms are syn. The conformation about each of the imine [1.376 (3) Å] and ethene [1.333 (4) Å] bonds is E. The shortened C-C bond [1.444 (4) Å] linking the double bonds is consistent with conjugation in this part of the mol-ecule. In the crystal, supra-molecular layers with a jagged topology are formed by charged-assisted amine-H⋯Cl(-) and pyridinium-N(+)-H⋯Cl(-) hydrogen bonds. The layers stack along the a axis with no specific directional inter-actions between them.

2,2-Dibenzyl-hydrazin-1-ium chloride.

In the title salt, C14H17N2(+)·Cl(-), the central N atom is pyramidal (sum of bond angles = 330.9°) and there is a near orthogonal relationship between the benzene rings [dihedral angle = 89.95 (10)°]. The crystal packing features N-H⋯Cl hydrogen bonds, which lead to a supra-molecular undulating ribbon along the a axis comprising edge-shared eight-membered {⋯HNH⋯Cl}2 synthons. The chains are connected into layers in the ab plane by C-H⋯π inter-actions.

(Pyridin-4-yl)methyl N'-(3-phenyl-allyl-idene)hydrazinecarbodithio-ate.

In the title compound, C(16)H(15)N(3)S(2), the central C(2)N(2)S(2) residue is planar (r.m.s. deviation = 0.045 Å) and the pyridyl and benzene rings are inclined and approximately coplanar to this plane, respectively [dihedral angles = 72.85 (9) and 10.73 (9)°], so that, overall, the mol-ecule adopts an L-shape. The conformation about each of the N=C [1.290 (3) Å] and C=C [1.340 (3) Å] bonds is E. Supra-molecular chains along [1-10] are stabilized by N-H⋯N(pyridine) hydrogen bonding and these are connected into a double layer that stacks along the c-axis direction by C-H⋯π(pyridine) inter-actions.

Bis{benzyl 2-[4-(4-meth-oxy-phen-yl)butan-2-yl-idene]hydrazinecarbodithio-ato-κ(2)N(2),S}nickel(II).

The complete mol-ecule of the title complex, [Ni(C(19)H(21)N(2)OS(2))(2)], is generated by the application of twofold symmetry. The Ni(II) atom is N,S-chelated by two hydrazinecarbodithio-ate ligands, which provide an N(2)S(2) donor set that defines a distorted square-planar geometry, the S atoms being approximately cis. The conformation of the chelate ring is an envelope with the Ni(II) atom being the flap atom. The dihedral angle between the least-squares planes through the chelate rings = 30.10 (6)°. Supra-molecular chains propagated by glide symmetry along the c axis and mediated by C-H⋯N contacts feature in the crystal packing.

N'-[Bis(benzyl-sulfan-yl)methyl-idene]benzohydrazide.

In the title hydrazonodithio-ate, C(21)H(19)N(3)OS(2), the amide group is twisted out of the plane through the S(2)C=N atoms: the C-N-N-C torsion angle is 139.71 (13)°. The pyridine ring forms dihedral angles of 52.96 (8) and 86.46 (8)° with the phenyl rings, and the latter are approximately orthogonal [dihedral angle = 76.42 (9)°]. Supra-molecular chains sustained by N-H⋯O hydrogen bonds and propagated by glide symmetry along the c axis are found in the crystal structure. The chains are consolidated into a three-dimensional architecture by C-H⋯O and C-H⋯N inter-actions.

1-Methyl-2-({[(2-methyl-phen-yl)meth-yl]disulfan-yl}meth-yl)benzene.

In the title disulfide, C(16)H(18)S(2), the mol-ecule is twisted about the central S-S bond [the C-S-S-C torsion angle = 93.24 (7)°] and the dihedral angle between the benzene rings is 72.84 (7)°, indicating an almost orthogonal relationship; the methyl groups are orientated to the same side of the mol-ecule. The crystal packing features C-H⋯.π inter-actions which consolidate a three-dimensional architecture.

Benzyl 3-(2-methyl-phen-yl)dithio-carbazate.

In the title compound, C(15)H(16)N(2)S(2), the central C(2)N(2)S(2) 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 mol-ecule. Supra-molecular 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 inter-actions.

1-{(E)-[4-(4-Meth-oxy-phen-yl)butan-2-yl-idene]amino}-3-methyl-thio-urea.

Two independent mol-ecules comprise the asymmetric unit of the title compound, C(13)H(19)N(3)OS, which differ in the conformations of the residues linking the thio-urea and the terminal benzene ring, as manifested in the C(m)-C(m)-C(a)-C(a) torsion angles [78.03 (16) and -93.64 (16)°, respectively; m = methyl-ene and a = aromatic]. The dihedral angles [84.40 (4) and 88.28 (5)°] formed between the thio-urea residue and the benzene ring indicate an almost orthogonal relationship. In each thio-urea residue, the N-H hydrogen atoms are anti, and the terminal N-H hydrogen atom forms an intra-molecular N-H⋯N hydrogen bond with the imine-N atom. In each case, the conformation about the imine C=N double bond [1.2812 (17) and 1.2801 (17) Å] is E. In the crystal, the mol-ecules are connected by N-H⋯S hydrogen bonds and these are connected into four mol-ecule aggregates via N-H⋯O hydrogen bonds, which are assembled into a two-dimensional array parallel to (011) via C-H⋯π and π-π inter-actions [ring centroid-centroid distance = 3.8344 (9) Å].