Sac Anions Research Articles

Stabilizing Zinc Anodes by Regulating the Electrical Double Layer with Saccharin Anions

Zn anodes suffer from poor Coulombic efficiency (CE) and serious dendrite formation due to the unstable anode/electrolyte interface (AEI). The electrical double layer (EDL) structure formed before cycling is of great significance for building stable solid electrolyte interphase (SEI) on Zn surface but barely discussed in previous research about the stabilization of Zn anode. Herein, saccharin (Sac) is introduced as electrolyte additive for regulating the EDL structure on the AEI. It is found that Sac derived anions are preferentially adsorbed on the Zn metal surface instead of water dipole, creating a new H2 O-poor EDL structure. Moreover, the unique SEI is also detected on the Zn surface due to the decomposition of Sac anions. Both are proved to be capable of modulating Zn deposition behavior and preventing side reactions. Encouragingly, Zn|Zn symmetric cells using Sac additive deliver a high cumulative plated capacity of 2.75 Ah cm-2 and a high average CE of 99.6% under harsh test condition (10mA cm-2 , 10 mAh cm-2 ). The excellent stability is also achieved at a high rate of 40mA cm-2 . The effectiveness of this Sac additive is further demonstrated in the Zn-MnO2 full cells.

Crystalline palmatine saccharinate pharmaceutical salt without reducing solubility and improving its hygroscopic stability with regard to palmatine chloride

In order to improve the hygroscopic stability of palmatine chloride (PMTCl) without reducing its solubility, on the basis of summarizing tetrahydroberberine and sulfophenyl acids pharmaceutical cocrystals/salts, we speculated that sodium saccharinate (SACNa), an organic acid salt with the same sulfonyl group, may be cocrystallized with ionic PMT. Consequently, an unreported PMT-SAC (C21H22NO4·C7H4NO3S) pharmaceutical salt was synthesized. The maximum solubility of PMT-SAC in pure water is essentially the same as that of PMTCl. As the hygroscopic stability of PMT-SAC is significantly improved, it is speculated that in the PMT-SAC pharmaceutical salt, PMT cations and SAC anions mainly rely on hydrogen bonds to accumulate, due to the fact that the hydrogen bonds acting between the groups of PMT cations and SAC anions are nearly saturated, it is therefore difficult for PMT cations to combine with external water molecules. This implies that a single crystal of pharmaceutical salt with the desired physicochemical properties will conceivably be obtained for ionic active pharmaceutical ingredients through the introduction of organic acid salts, which are able to form hydrogen bonds. Further to this, it is of note that the antibacterial activities in vitro of a pharmaceutical salt of PMT-SAC is improved, when compared with the corresponding parent compound (PMTCl).

Bis(N,N′-bis(2-hydroxyethyl)ethylenediamine)nickel(II) saccharinate: synthesis, characterization and crystal structure

A new nickel(II) saccharinate (sac) complex containing <em>N</em>,<em>N</em>′-bis(2-hydroxyethyl)ethylenediamine (bishydeten), [Ni(bishydeten)<sub>2</sub>](sac)<sub>2</sub>, has been synthesized and characterized by elemental analysis, FTIR and single crystal X-ray diffraction. The title complex consists of a [Ni(bishydeten)<sub>2</sub>]<sup>2+</sup> cation and two sac anions. In the complex cation, the nickel(II) ion is coordinated by two neutral bishydeten ligands, leading to a distorted octahedral NiN<sub>4</sub>O<sub>2</sub> coordination, while both sac anions remain outside the coordination sphere. In the crystal, the complex cations and sac anions are connected by an extensive network of N–H∙∙∙N, N–H∙∙∙O, O–H∙∙∙O and C–H∙∙∙O hydrogen bonds into a three-dimensional supramolecular lattice.

Structural diversity of lanthanum saccharinates induced by 1,10-phenanthroline: A synthetic and X-ray crystallographic study

Four new lanthanum(III) complexes of formulae [La(sac)3(phen)2(H2O)2]·(phen)(H2O)2 (1), [La(sac)3(phen)2(H2O)2]·(phen) (2), [La(sac)2(phen)(H2O)4]·(sac) (3) and [La(sac)2(phen)2(H2O)3]·(sac)(phen)(H2O) (4) (phen=1,10 phenanthroline, sac=saccharinate) have been synthesised and characterised by single crystal X-ray diffraction, IR, elemental analysis and thermogravimetric analysis. The binding mode of the sac anion was manipulated through the use of phen as structure inducer. In all four complexes the La(III) ion is in a nine-coordinate environment. The structures of 1 and 2 are similar, comprising of three sac anions coordinating in a monodentate fashion through the carbonyl O-atom, two bidentate phen and two water molecules coordinating directly to the same La(III) ion; a third, uncoordinated phen moiety also forms part of the unit cell. In addition, 1 is characterized by the presence of two crystallization water molecules which are absent in 2. In compound 3 the coordination sphere of La(III) is completed by a bidentate chelating sac through the N- and carbonyl O-atoms, a monodentate sac, a bidentate phen and four water ligands; a third, uncoordinated sac is also present in the crystal lattice. Compound 4 contains two bidentate phen, three water ligands and two monodentate O(carbonyl) sac ligands. The presence of three sac anions coordinating to the same lanthanide ion as well as a bidentate N–Ln–O chelating sac, confirmed by single crystal X-ray crystallography, is unprecedented for rare-earth saccharinates.

Palladium(II) and Platinum(II) Saccharinate Complexes with 2‐Aminomethylpyridine and 2‐Aminoethylpyridine: Synthesis, Characterization, Crystal Structures, and Thermal Properties

Abstracttrans‐[Pd(ampy)2](sac)2 (1), trans‐[Pt(ampy)2](sac)2 (2), trans‐[Pd(aepy)2](sac)2·2H2O (3) and trans‐[Pt(aepy)2](sac)2·2H2O (4) (sac = saccharinate, ampy = 2‐aminomethylpyridine and aepy = 2‐aminoethylpyridine) have been synthesized and characterized by elemental analysis, FTIR, and X‐ray single crystal diffraction. In all cases, the palladium(II) and platinum(II) ions sit on the center of symmetry and are coordinated by the bidentate chelating ampy or aepy ligands, and the sac ions remain as a counterion. In complex 2, the cations and sac anions are connected by N–H···O hydrogen bonds as well as aromatic π–π stacking interactions into a two‐dimensional supramolecular network, whereas in 3 and 4, they are linked by N–H···O hydrogen bonds into chains, which are further assembled into a two‐dimensional array by OW–H···O hydrogen bonds. All complexes were investigated by IR spectroscopy and thermal analyses.

Copper(II)-saccharinato complexes with piperazine and N-(2-aminoethyl)piperazine ligands

Two copper(II) complexes of the saccharinate anion (sac) with piperazine (ppz) and N-(2-aminoethyl)piperazine (aeppz), namely [Cu(sac) 2(ppz)(H 2O)] n ( 1) and trans-[Cu(sac) 2(aeppz) 2] ( 2), have been synthesized and characterized by elemental analyses, UV–Vis, FT-IR, TGA/DTA, X-ray diffraction and magnetic measurements. The ppz ligands in 1 bridge the copper(II) centers through both nitrogen atoms to form a 1D helical chain structure and the distorted trigonal-bipyramidal coordination geometry at each copper center is completed by an aqua and a pair of N-bonded sac ligands. The helical chains are linked by Ow–H⋯O hydrogen bonds to build a 2-D network. In complex 2, copper(II) ions are octahedrally coordinated by two sac anions and two neutral aeppz ligands, displaying a distorted octahedral coordination. Sac is O-bonded via the carbonyl group, while ppzea acts as a N, N′-bidentate chelating ligand. The molecules are connected by N–H⋯N and N–H⋯O hydrogen bonds, forming a linear chain. In the thermal decomposition of both complexes, the removal of the aqua and ppz or aeppz ligand takes place endothermically in the first stages and the sac moiety undergoes highly exothermic decomposition at higher temperatures to give CuO.

Crystal structure of Na 4Li 4(saccharinate) 8·14H 2O and its comparison with other alkali metal saccharinates

Na 4Li 4(sac) 8·14H 2O was prepared by co-crystallisation of equimolar amounts of LiCl and Na-saccharinate from water. The asymmetric unit contains 4 Na + ions, 4 Li + ions, 8 sac anions and 14 water molecules. The present structure bears some structural similarities to the already reported structure of the “dihydrate” Na 16(sac) 16·30H 2O, and to Li 6(sac) 6·11H 2O, and helps in understanding these structures better.

Cis-bis(Saccharinato)cobalt(II) and -zinc(II) complexes with 2-dimethylaminoethanol: syntheses, crystal structures, spectroscopic and thermal studies

2-Dimethylaminoethanol (dmea) reacted with tetraaqua-bis(saccharinato)cobalt(II) and -zinc(II) in n-butanol to yield the new complexes cis-[Co(sac)2(dmea)2] (1), and cis-[Zn(sac)2(dmea)2] (2) (sac = saccharinate). The complexes were characterized by elemental analyses, IR spectroscopy, DTA-TG and X-ray crystallography. Both complexes are isomorphous and crystallize in the monoclinic space group P21/c. The cobalt(II) and zinc(II) ions are coordinated by two neutral dmea ligands and two sac anions in a distorted octahedral environment. The dmea ligand acts as a bidentate N, O donor through the amine N and hydroxyl O atoms, while the sac ligand exhibits non-equivalent coordination, behaving as an ambidentate ligand; one coordinates to the metal via the carbonyl oxygen atom, while the other is N-bonded. The packing of the molecules in the crystals of both complexes is achieved by aromatic π(sac)–π(sac) stacking interactions, C–H · π interactions and weak intermolecular C–H · O hydrogen bonds involving the methyl groups of dmea and the sulfonyl oxygen atoms of the sac ligands. IR and UV spectra and thermal analysis are in agreement with the crystal structures.

Synthesis and Characterization of Cadmium and Mercury Saccharinate Complexes with 2-Dimethylaminoethanol: cis-[Cd(sac)2(dmea)2] and [Hg(sac)2(dmea)(H2O)

The new cadmium and mercury saccharinate (sac) complexes, cis-[Cd(sac)2(dmea)2] (1) and [Hg(sac)2(dmea)(H2O)] (2) (dmea = 2-dimethylaminoethanol), have been prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. In complex 1, the cadmium(II) ion is coordinated by two neutral dmea ligands and two sac anions in a distorted octahedral CdN3O3 coordination geometry. The dmea ligand acts as a bidentate N, O chelate, while the sac ligands behave as an ambidentate ligands. One of them coordinates to the cadmium(II) ion through the carbonyl oxygen atom, while the other is N-bonded. In complex 2, the mercury(II) ion is coordinated by an aqua ligand, a chelating dmea ligand and two N-bonded sac ligands, forming a distorted trigonal bipyramidal coordination HgN3O2. The molecules interact with each other through O-H···O hydrogen bonds and aromatic π(sac)···π(sac) stacking interactions, leading to a three-dimensional supramolecular network.

Trans-Bis(saccharinato)zinc and -cadmium Complexes with N-(2-Aminoethyl)piperazine: Synthesis, Crystal Structures and IR Spectra

The reactions of N-(2-aminoethyl)piperazine (aeppz) with tetraaqua-bis(saccharinato)zinc(II) and -cadmium(II) in ethanol solution yield the new complexes trans-[Zn(sac)2(aeppz)2] (1), and trans- [Cd(sac)2(aeppz)2] (2) (sac = saccharinate), respectively. The complexes were characterized by elemental analyses, IR spectroscopy and X-ray crystallography. Both complexes 1 and 2 are mononuclear of Ci symmetry. The zinc(II) and cadmium(II) ions are coordinated by two neutral aeppz ligands and two sac anions in an elongated distorted octahedral environment. The aeppz ligand acts as a bidentate N, N’ donor through the central heterocyclic N atom and the N atom of the aminoethyl group, while the sac ligand is O-coordinated via the carbonyl O atom. The packing of the molecules in the crystals in both complexes is consolidated by arene π −π stacking interactions between the sac rings and by intermolecular hydrogen bonds involving the amine groups of aeppz and the sulfonyl oxygen atoms of the sac ligands

Synthesis, IR Spectra, Thermal Analysis and Crystal Structures of Bis(saccharinato)mercury(II) Complexes with 2–Aminomethylpyridine and 2–Aminoethylpyridine

AbstractTwo bis(saccharinato) (sac) complexes of mercury(II) with 2–aminomethylpyridine (ampy) and 2–aminoethylpyridine (aepy) were synthesized and characterized by means of elemental analysis, FT–IR spectroscopy and thermal analysis and single crystal X–ray diffraction. trans–[Hg(sac)2(ampy)2] (1) crystallizes in the monoclinic space group P21/c [a = 10.8274(4), b = 16.4903(6), c = 7.7889(3) Å; β = 99.500(1)°] and [Hg(sac)2(aepy)] (2) also crystallizes monoclinic in space group P21/n [a = 9.0423(4), b = 14.0594(6), c = 18.0146(8) Å; ß = 98.806(1)°]. Both 1 and 2 consist of neutral monomeric units. The mercury(II) ion in 1 lies on an inversion centre and exhibit distorted octahedral coordination by two sac anions and two ampy ligands, whereas the mercury(II) ion in 2 is tetrahedrally coordinated by an aepy and two sac ligands. The sac ligands in both complexes are N–coordinated, while the ampy and aepy ligands act as a bidentate ligand forming two symmetrically chelate rings around the mercury(II) ion.

Trans‐bis(saccharinato)cadmium(II) Complexes with 2‐Aminomethylpyridine and 2‐Aminoethylpyridine — Synthesis, Crystal Structures, Spectral and Thermal Characterization of trans‐[Cd(sac)2(ampy)2] and trans‐[Cd(sac)2(aepy)2

AbstractTwo trans‐bis(saccharinato) (sac) complexes of cadmium(II) with 2‐aminomethylpyridine (ampy) and 2‐aminoethylpyridine (aepy) were synthesized and characterized by means of elemental analysis, FT‐IR spectroscopy and thermal analysis. In addition, their solid‐state structures were determined by single crystal X‐ray diffraction studies. The [Cd(sac)2(ampy)2] (1) and [Cd(sac)2(aepy)] (2) complexes consist of neutral monomeric units and crystallize in the orthorhombic (Pbca) and monoclinic (P21/c) crystal systems, respectively. The cadmium(II) ions in 1 and 2 sit on inversion centres andexhibit distorted octahedral coordination by two sac anions and two aminopyridine ligands. The sac ligands in both complexes are N‐coordinated and located in trans positions, while the ampy and aepy ligands act as a bidentate ligand forming two symmetrically chelate rings around cadmium(II). IR spectra and thermal decompositions of the complexes are also discussed.

The First Calcium(II) Complex with the Saccharinate Ligand: Synthesis, Crystal Structure, Spectral and Thermal Characterization of Trans—diaquabis[(2—hydroxyethyl)pyridinium]bis(saccharinato)calcium(II) Disaccharinate, [Ca(sac)2(H2O)2(Hpyet)2](sac)2

AbstractA new calcium(II) complex of the saccharinate ligand (sac) with 2—hydroxyethylpyridinium (Hpyet) was synthesized and characterized by elemental analysis, FT—IR spectroscopy, thermal analysis and single crystal X—ray diffractometry. The [Ca(sac)2(H2O)2(Hpyet)2](sac)2 complex crystallizes in the triclinic space group (P1¯) with the cell dimensions a = 7.4360(7)Å, b = 12.5263(12)Å, c = 12.8329(13)Å, α = 82.534(8)°, β = 75.202(8)° and γ = 89.662(8)° (293 K). The title complex consists of a complex cation and two sac anions. In the complex cation, the calcium(II) ion is six—coordinate, bonding to two aqua ligands, two Hpyet ligands andtwo sac ligands located in the trans positions. Two of the sac ions are coordinated to the calcium(II) ion through the carbonyl O atom, while the other two remain outside the coordination sphere as the counter—ions. Thermal decomposition of the complex in air results in elimination of aqua, Hpyet, and sac ions, respectively.

An eight-coordinate strontium complex with two tetradentate triethanolamine ligands: synthesis, IR spectra, thermal analysis and crystal structure of bis(triethanolamine)strontium(II) saccharinate

Bis(triethanolamine)strontium(II) saccharinate, [Sr(tea) 2](sac) 2 was synthesized and characterized by IR spectroscopy, thermal analysis and X-ray diffraction techniques. The compound crystallizes in orthorhombic system and consists of two sac anions and a complex cation, in which each tea ligand behaves as a tetradentate ligand and their configuration results in an eight-coordinate strontium(II) complex with a bicapped trigonal prism geometry. The anions and cations are linked by the intermolecular hydrogen bonds between the hydroxyl hydrogens of the tea ligands and the amine N, and carbonyl O atoms of the neighbouring sac ions, forming one-dimensional chains running parallel to c. The adjacent chains are held together by van der Waals interactions, creating a three-dimensional network. The FTIR spectra and thermal decomposition of the complex were discussed.

Saccharin complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) with ethanolamine and diethanolamine: synthesis, spectroscopic and thermal characteristics. Crystal structures of [Zn(ea) 2(sac) 2] and [Cu 2(μ-dea) 2(sac) 2

New mixed ligand Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) complexes of saccharin (sac) with ethanolamine (ea) and diethanolamine (dea) were synthesized and characterized by elemental analyses, magnetic moments, UV–Vis and IR spectra. The Co(II)–ea, Co(II)–dea and Cu(II)–dea complexes are dimeric, while all the other complexes of ea and dea are mononuclear. The crystal structures of [Zn(ea) 2(sac) 2] and [Cu 2(μ-dea) 2(sac) 2] complexes were determined by single crystal X-ray diffraction. In the Zn(II) complex, the Zn(II) ion sits on a center of symmetry and is octahedrally coordinated by two bidentate ea (N, O) and two monodentate sac (N) ligands. The centrosymmetric binuclear Cu(II) complex contains two strongly distorted square-planarly coordinated Cu(II) ions bridged by two alkoxo groups of the deprotonated dea. The dea ligand also coordinates to the Cu(II) ions through its nitrogen, while the other ethanolic group does not involve in coordination. The saccharinate anion coordinates to the Cu(II) ion with its nitrogen. Thermal behavior of the complexes was studied using DTA and TG in nitrogen atmosphere. Endothermic degradation of the ea and dea ligands occurs in the first stages of decomposition and the sac anions decompose at higher temperatures to give corresponding metal oxides or metals.

Trans-Bis(ethanolamine-N,O)bis(saccharinato-N)copper(II).

In the title complex, [Cu(C(7)H(4)NO(3)S)(2)(C(2)H(7)NO)(2)], the Cu(II) centre lies on an inversion centre and exhibits octahedral coordination, with the two ethanolamine (Hea) and two saccharinate [sac; anionic 1,2-benzisothiazol-3(2H)-one 1,1-dioxide] ligands in a trans configuration. The bidentate Hea ligands bridge axial and equatorial positions and the sac anions occupy equatorial sites around the distorted octahedral copper(II) centre [Cu--O = 2.3263 (16), Cu--N(Hea) = 1.9923 (16) and Cu--N(sac) = 2.1776 (16) A].

Bis(triethanolamine-N,O,O′)nickel(II) bis(saccharinate)

The structure of the title compound, [Ni(C6H15NO3)2](C7H4NO3S)2, consists of a cationic [Ni(TEA)2]2+ and two anionic (SAC)− moieties (TEA is triethano­lamine and SAC is the saccharinate anion). Two TEA ligands coordinate to the NiII ion through four O atoms and two N atoms acting as tridentate ligands (N,O,O′) in a distorted octahedral environment, with the bond distances [d(Ni—O) = 2.078 (2) and 2.082 (2) Å, and d(Ni—N) = 2.108 (2) Å]. SAC anions participate in intermolecular hydrogen bonding with the hydroxyl H atoms of the TEA ligands to form a three-dimensional network.