Counter Anion Effects on the Formation and Structural Transformations of Mo(vi)-Hydrazone Coordination Assemblies: Salts, Solvates, Co-Crystals, and Neutral Complexes

Crystals

Danijela Musija¹  Marina Cindrić²  Biserka Prugovečki²  Ivana Kekez²  Višnja Vrdoljak²  Mirna Mandarić²  Jelena Parlov Vuković³ 

[1] Department of Chemistry and Biochemistry, School of Medicine, University of Zagreb, Šalata 3, 10000 Zagreb, Croatia;Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia;Product Development Department, Refining & Marketing Business Division, INA-Industrija Nafte d.d., Lovinčićeva bb, 10002 Zagreb, Croatia;

关键词: molybdenum;    hydrazone;    solvates;    complex salts;    co-crystals;    coordination polymer;   

DOI  :  10.3390/cryst12040443

来源: DOAJ

【 摘 要 】

Complex salts [1H]X and [1H](XA)_0.5·2MeOH, and co-crystals [1H]X·0.5VA (X = chloride or bromide, XA = chloranilate or bromanilate, VA = o-vanillin azine), comprising [MoO₂(HL)(MeOH)]⁺ ([1H]⁺) cation (H₂L = 3-methoxysalicylaldehyde isonicotinoyl hydrazone), were prepared either by solution-based synthesis or by mechanochemical synthesis. Whereas [1H]X salts were extremely sensitive to humidity, their stability could be reinforced by the azine incorporation into the complex network. Solvent-mediated transformations of [1H]X led to methanol co-ligand replacement and afforded complexes [MoO₂(HL)X] (2Cl·MeOH, 2Cl, and 2Br·0.5MeCN). However, solvates [1H](XA)_0.5·2MeOH, under the same conditions, gave stable complexes [1H](XA)_0.5 in which methanol remained coordinated. The differences in the assembly’s behavior were attributed to the packing arrangements, the relative orientation of cations and anions, and interactions between them. Polymorph [MoO₂(L)(MeOH)] (1), not attainable by other routes, was the only product when compounds [MoO₂(HL)X] were treated with a weak base at low temperatures. Tetranuclear [MoO₂(L)]₄ and polynuclear [MoO₂(L)]_n (2) supramolecular isomers, concomitantly crystallized when the reaction was conducted solvothermally. All of the complexes were characterized using X-ray diffraction methods (SCXRD and PXRD), spectroscopic methods (ATR-IR and solution-state and solid-state MAS NMR), and elemental and thermal analyses. The cytotoxicity of the different types of compounds against THP-1 and HepG2 cells was also evaluated.

【 授权许可】

Unknown