Topology Analysis Reveals Supramolecular Organisation of 96 Large Complex Ions into one Geometrical Object

It is shown that the highly complex crystal structure of [Ag(4-(pyrrolidin-1-yl)pyridine)2]NO3·1/2H2O, 1, with 12 symmetry-independent Ag+ ions and 96 units of complex ions in a unit cell can be understood by the ubiquitous srs topology, reducing thousands of atom positions into a single geometrical object in one go

Optimized Synthesis of Tetrafluoroterephthalic Acid: A Versatile Linking Ligand for the Construction of New Coordination Polymers and Metal-Organic Frameworks

Pure 2,3,5,6-tetrafluoroterephthalic acid (H(2)tfBDC) is obtained in high yields (95%) by reacting 1,2,4,5-tetrafluorobenzene with a surplus (>2 equiv) of n-butyllithium in tetrahydrofuran (THF) and subsequent carbonation with CO2 without any extensive purification procedure. A single crystal X-ray structure analysis of H2tfBDC (1) confirms former data obtained for a deuterated sample (P (1) over bar, Z = 1). Recrystallization from water/acetone leads to single crystals of H(2)tfBDC center dot 2H(2)O (2, P2(1)/c, Z. 2), where an extensive hydrogen bonding network is found. By reacting H2tfBDC with an aqueous ammonia solution, single crystals of (NH4)(2)tfBDC (3, C2/m, Z. 2) are obtained. 3 is thermally stable up to 250 degrees C and shows an enhanced solubility in water compared to H(2)tfBDC. Monosubstituted 2,3,5,6-tetrafluorobenzoic acid (H(2)tfBC, 4) is obtained by reacting 1,2,4,5-tetrafluorobenzene with stoichiometric amounts (1 equiv) of n-butyllithium in THF. Its crystal structure (Fdd2, Z = 16) shows dimeric units as characteristic structural feature

Synthesis, X-ray, Hirshfeld, and AIM Studies on Zn(II) and Cd(II) Complexes with Pyridine Ligands

The synthesis and crystal structures of three heteroleptic complexes of Zn(II) and Cd(II) with pyridine ligands (ethyl nicotinate (EtNic), N,N-diethylnicotinamide (DiEtNA), and 2-amino-5-picoline (2Ampic) are presented. The complex [Zn(EtNic)2Cl2] (1) showed a distorted tetrahedral coordination geometry with two EtNic ligand units and two chloride ions as monodentate ligands. Complexes [Zn(DiEtNA)(H2O)4(SO4)]·H2O (2) and [Cd(OAc)2(2Ampic)2] (3) had hexa-coordinated Zn(II) and Cd(II) centers. In the former, the Zn(II) was coordinated with three different monodentate ligands, which were DiEtNA, H2O, and SO42−. In 3, the Cd(II) ion was coordinated with two bidentate acetate ions and two monodentate 2Ampic ligand units. The supramolecular structures of the three complexes were elucidated using Hirshfeld analysis. In 1, the most important interactions that governed the molecular packing were O···H (15.5–15.6%), Cl···H (13.6–13.8%), Cl···C (6.3%), and C···H (10.3–10.6%) contacts. For complexes 2 and 3, the H···H, O···H, and C···H contacts dominated. Their percentages were 50.2%, 41.2%, and 7.1%, respectively, for 2 and 57.1%, 19.6%, and 15.2%, respectively, for 3. Only in complex 3, weak π-π stacking interactions between the stacked pyridines were found. The Zn(II) natural charges were calculated using the DFT method to be 0.8775, 1.0559, and 1.2193 for complexes 1–3, respectively. A predominant closed-shell character for the Zn–Cl, Zn–N, Zn–O, Cd–O, and Cd–N bonds was also concluded from an atoms in molecules (AIM) study

New Triazoloquinoxaline Ligand and its Polymeric 1D Silver(I) complex Synthesis, Structure, and Antimicrobial activity

The organic ligand 4-Benzyl-1-(N,N-dimethylamino)-[1,2,4]triazolo[4,3a]quinoxaline 1 (L) and its polymeric silver(I) complex, [Ag2L(NO3)2]n (2), have been synthesized and characterized. The organic ligand 1 crystallizes in the triclinic space group P¯1. The unit cell contains two parallel-stacked molecules. The complex [Ag2L(NO3)2]n (2) crystallizes in the monoclinic space group P21/n. The structure contains two different silver(I) ions. Ag(2) is coordinated by three oxygens (involving two nitrate groups) and to a nitrogen of the triazole ring of 1. These ligands form a strongly distorted tetrahedral, nearly planar coordination sphere. Ag(1) has an approximately tetrahedral geometry. It is bonded to one oxygen of a nitrate anion and a nitrogen of two different L; this aspect giving rise to an infinite chain structure. A final bond to Ag(1) involves the carbon of a phenyl group. It is more weakly bonded to the phenyl carbons on either side of this, so that the Ag(1)-phenyl bonding has aspects of an Ag-allyl bond. Ag(1) and Ag(2) participate in bonding to a common nitrate anion and alternate, the two distinct modes of bridging between them lead to a zig-zag chain structure. In addition to spectroscopic studies, the biological activities of the ligand and of the complex were scanned over a wide range of Gram positive and Gram negative flesh- and bone-eating bacteria. The results are discussed in comparison with well-known antibiotics

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

Chemical delithiation and exfoliation of LixCoO2

AbstractProgressive chemical .delithiation of commercially available lithium cobalt oxide (LiCoO2) showed consecutive changes in the crystal properties. Rietveld refinement of high resolution X-ray and neutron diffraction revealed an increased lattice parameter c and a reduced lattice parameter a for chemically delithiated samples. Using electron microscopy we have also followed the changes in the texture of the samples towards what we have found is a critical layer stoichiometry of about LixCoO2 with x=1/3 that causes the grains to exfoliate. The pattern of etches by delithiation suggests that unrelieved strain fields may produce chemical activity