Synthesis, characterization, and structural studies of two heteroleptic Mn(II) complexes with tridentate <i>N,N,N</i>-pincer type ligand

<p>Molecular and supramolecular structures of two new Mn(II) complexes with tridentate <i>N,N,N</i>-pincer type ligand (L) are presented. [MnL(H₂O)₂Cl]Cl (<b>1</b>) and [MnL(H₂O)₃](NO₃)₂·H₂O (<b>2</b>) have octahedral coordination environments with different degrees of distortion. The molecular packing of <b>1</b> and <b>2</b> is dominated by strong O–H⋯Cl and O–H⋯O H-bonds, respectively, as well as weak C–H⋯O interactions. The percentage of Cl⋯H and O⋯H contacts are 15.5 and 31.5% for <b>1</b> and <b>2</b>, respectively, using Hirshfeld analysis. Based on atoms in molecules theory, the Mn–N, Mn–O, and Mn–Cl bonds have the characteristics of closed shell interactions. Thermal decomposition of L and its Mn(II) complexes are also presented.</p

Supplementary Information from Unexpected formation of polymeric silver(I) complexes of azine-type ligand via self-assembly of Ag-salts with isatin oxamohydrazide

Isatin oxamohydrazide (<b>L</b>) reacted with the aqueous solution of silver nitrate at room temperature afforded the polymeric silver(I) nitrato complex, [Ag₂L′(NO₃)₂]<i>_n</i>, <b>(1)</b> of the azine ligand (<b>L′</b>). Similarly, the reaction of <b>L</b> with silver(I) perchlorate gave the [Ag₂L′₂(ClO₄)₂]<i>_n</i>, <b>(2)</b> coordination polymer. Careful inspection of the crystals from the nitrato complex preparation showed the presence of another crystalline product which is found to be [Ag(Isatin-3-hydrazone)NO₃], <b>(3)</b> suggesting that the reaction between silver(I) nitrate and <b>L</b> proceeds first by the hydrolysis of <b>L</b> to the isatin hydrazone which attacks another molecule of <b>L</b> to afford <b>L′</b>. Testing metal salts such as Ni²⁺, Co²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ did not undergo any reaction with <b>L</b> either under the same reaction conditions or with heating under reflux up to 24 h. Treatment of the warm alcoholic solution of <b>L</b> with few drops of 1 : 1 (<i>v</i>/<i>v</i>) hydrochloric acid gave the free ligand (<b>L′</b>) in good yield. The [Ag₂L′(NO₃)₂]<i>_n</i> complex forms a two-dimensional infinite coordination polymer, while the [Ag₂L′₂(ClO₄)₂]<i>_n</i> forms one-dimensional infinite chains with an alternating silver-azine backbone. Quantitative analysis of the intermolecular interactions in their crystals is made using Hirshfeld surface analysis. Density functional theory studies were performed to investigate the coordination bonding in the studied complexes

Supplementary Information from Unexpected formation of polymeric silver(I) complexes of azine-type ligand via self-assembly of Ag-salts with isatin oxamohydrazide

Isatin oxamohydrazide (<b>L</b>) reacted with the aqueous solution of silver nitrate at room temperature afforded the polymeric silver(I) nitrato complex, [Ag₂L′(NO₃)₂]<i>_n</i>, <b>(1)</b> of the azine ligand (<b>L′</b>). Similarly, the reaction of <b>L</b> with silver(I) perchlorate gave the [Ag₂L′₂(ClO₄)₂]<i>_n</i>, <b>(2)</b> coordination polymer. Careful inspection of the crystals from the nitrato complex preparation showed the presence of another crystalline product which is found to be [Ag(Isatin-3-hydrazone)NO₃], <b>(3)</b> suggesting that the reaction between silver(I) nitrate and <b>L</b> proceeds first by the hydrolysis of <b>L</b> to the isatin hydrazone which attacks another molecule of <b>L</b> to afford <b>L′</b>. Testing metal salts such as Ni²⁺, Co²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ did not undergo any reaction with <b>L</b> either under the same reaction conditions or with heating under reflux up to 24 h. Treatment of the warm alcoholic solution of <b>L</b> with few drops of 1 : 1 (<i>v</i>/<i>v</i>) hydrochloric acid gave the free ligand (<b>L′</b>) in good yield. The [Ag₂L′(NO₃)₂]<i>_n</i> complex forms a two-dimensional infinite coordination polymer, while the [Ag₂L′₂(ClO₄)₂]<i>_n</i> forms one-dimensional infinite chains with an alternating silver-azine backbone. Quantitative analysis of the intermolecular interactions in their crystals is made using Hirshfeld surface analysis. Density functional theory studies were performed to investigate the coordination bonding in the studied complexes

Supplementary Information from Unexpected formation of polymeric silver(I) complexes of azine-type ligand via self-assembly of Ag-salts with isatin oxamohydrazide

Isatin oxamohydrazide (<b>L</b>) reacted with the aqueous solution of silver nitrate at room temperature afforded the polymeric silver(I) nitrato complex, [Ag₂L′(NO₃)₂]<i>_n</i>, <b>(1)</b> of the azine ligand (<b>L′</b>). Similarly, the reaction of <b>L</b> with silver(I) perchlorate gave the [Ag₂L′₂(ClO₄)₂]<i>_n</i>, <b>(2)</b> coordination polymer. Careful inspection of the crystals from the nitrato complex preparation showed the presence of another crystalline product which is found to be [Ag(Isatin-3-hydrazone)NO₃], <b>(3)</b> suggesting that the reaction between silver(I) nitrate and <b>L</b> proceeds first by the hydrolysis of <b>L</b> to the isatin hydrazone which attacks another molecule of <b>L</b> to afford <b>L′</b>. Testing metal salts such as Ni²⁺, Co²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ did not undergo any reaction with <b>L</b> either under the same reaction conditions or with heating under reflux up to 24 h. Treatment of the warm alcoholic solution of <b>L</b> with few drops of 1 : 1 (<i>v</i>/<i>v</i>) hydrochloric acid gave the free ligand (<b>L′</b>) in good yield. The [Ag₂L′(NO₃)₂]<i>_n</i> complex forms a two-dimensional infinite coordination polymer, while the [Ag₂L′₂(ClO₄)₂]<i>_n</i> forms one-dimensional infinite chains with an alternating silver-azine backbone. Quantitative analysis of the intermolecular interactions in their crystals is made using Hirshfeld surface analysis. Density functional theory studies were performed to investigate the coordination bonding in the studied complexes

Supplementary Information from Unexpected formation of polymeric silver(I) complexes of azine-type ligand via self-assembly of Ag-salts with isatin oxamohydrazide

Isatin oxamohydrazide (<b>L</b>) reacted with the aqueous solution of silver nitrate at room temperature afforded the polymeric silver(I) nitrato complex, [Ag₂L′(NO₃)₂]<i>_n</i>, <b>(1)</b> of the azine ligand (<b>L′</b>). Similarly, the reaction of <b>L</b> with silver(I) perchlorate gave the [Ag₂L′₂(ClO₄)₂]<i>_n</i>, <b>(2)</b> coordination polymer. Careful inspection of the crystals from the nitrato complex preparation showed the presence of another crystalline product which is found to be [Ag(Isatin-3-hydrazone)NO₃], <b>(3)</b> suggesting that the reaction between silver(I) nitrate and <b>L</b> proceeds first by the hydrolysis of <b>L</b> to the isatin hydrazone which attacks another molecule of <b>L</b> to afford <b>L′</b>. Testing metal salts such as Ni²⁺, Co²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ did not undergo any reaction with <b>L</b> either under the same reaction conditions or with heating under reflux up to 24 h. Treatment of the warm alcoholic solution of <b>L</b> with few drops of 1 : 1 (<i>v</i>/<i>v</i>) hydrochloric acid gave the free ligand (<b>L′</b>) in good yield. The [Ag₂L′(NO₃)₂]<i>_n</i> complex forms a two-dimensional infinite coordination polymer, while the [Ag₂L′₂(ClO₄)₂]<i>_n</i> forms one-dimensional infinite chains with an alternating silver-azine backbone. Quantitative analysis of the intermolecular interactions in their crystals is made using Hirshfeld surface analysis. Density functional theory studies were performed to investigate the coordination bonding in the studied complexes

Synthesis, X-ray crystal structure and DFT studies of two octahedral cobalt(II) complexes with <i>N,N,N</i>-tridentate triazine-type ligand

<p>Two new Co(II) complexes, [CoL₂]X₂∙2H₂O, with <i>N,N,N</i>-tridentate triazine type ligand (<b>L</b>) and X = Cl⁻ (<b>1</b>) or NO₃⁻ (<b>2</b>) are synthesized and characterized using elemental analysis, FTIR spectra, and single-crystal X-ray diffraction. Complexes <b>1</b> and <b>2</b> are crystallized in the centrosymmetric space groups <i>P-1</i> and <i>C2/c</i>, respectively. The Co atoms are surrounded by two neutral tridentate ligands coordinated via nitrogen atoms, thus forming a distorted octahedral coordination sphere. Hirshfeld topology analyses of the molecular packing revealed that the polar Cl⋯H, O⋯H and N⋯H contacts are the most important intermolecular interactions while the nonpolar C⋯H and C⋯C (<i>π</i>–<i>π</i> stacking) contacts are weak and insignificant, respectively. DFT calculations indicated that the high-spin state is energetically more favored than the low-spin case. The Co(II) center transfers its spin density to the ligand donor atoms via the spin delocalization mechanism. Based on the atoms in molecules (AIM) results, all Co–N interactions have a predominant covalent character. The strength of the Co–N interactions decreases in the order Co–N_(hydrazone) > Co–N_(triazine) > Co–N_(amine). The metal anti-bonding natural orbitals involved in the Co–N interactions have high and s-orbital characters. Both complexes showed good thermal stability up to 276°C and 250°C for complexes <b>1</b> and <b>2</b>, respectively.</p

Synthesis, X-Ray Structure Analysis, Computational Investigations, and In Vitro Biological Evaluation of New Thiazole-Based Heterocycles as Possible Antimicrobial Agents

The thiazole ring is found in many pharmaceutical and natural products. In this article, the convenient synthesis of two new hybrid molecules carrying the thiazole nucleus linked to pyrazole or pyridine rings is described. The structure of the synthesized hybrids is confirmed by spectroscopic and X-ray analysis. Using Hirshfeld analysis, the molecular packing of thiazolyl-pyrazole hybrid 2 is controlled by many weak S…S, S…C, S…H, C…N, N…H, C…C, C…H and H…H non-covalent interactions. The percentage contributions of these contacts in the molecular packing are 1.6, 0.2, 22.1, 0.7, 7.9, 0.4, 27.5, and 39.6%, respectively. DFT calculations predicted the natural atomic charges, polarity, and frontier molecular orbitals and their derived reactivity parameters. </p