Redetermination of the structure of 2-amino-8-thia-1,5-diazaspiro[4,5]dec-1-en-5-ium chloride monohydrate

The reaction of β-(thiomorpholin-1-yl)propioamidoxime with tosyl chloride in CHCl3 in the presence of DIPEA when heated at 343 K for 8 h afforded the title hydrated salt, C7H14N3S+·Cl−·H2O, in 84% yield. This course of the tosylation reaction differs from the result of tosylation obtained for this substrate at room temperature, when only 2-amino-8-thia-1,5-diazaspiro[4.5]dec-1-ene-5-ammonium tosylate was isolated in 56% yield. The structure of the reaction product was established by physicochemical methods, spectroscopy, and X-ray diffraction. The single-crystal data demonstrated that the previously reported crystal structure of this compound [Kayukova et al. (2021). Chem. J. Kaz, 74, 21–31] had been refined in a wrong space group. In the extended structure, the chloride anions, water molecules and amine groups of the cations form two-periodic hydrogen-bonded networks with the fes topology.

Zinc(II) and nickel(II) complexes of 3,5-dimethyl-1-(pyridin-2-yl)-1H-pyrazole: relationship between fluorescence and crystal packing

Two novel coordination complexes, namely, dichlorido[3,5-dimethyl-1-(pyridin-2-yl-κN)-1H-pyrazole-κN 2]zinc(II), [ZnCl2(C10H11N3)], 1, and aquachloridobis[3,5-dimethyl-1-(pyridin-2-yl-κN)-1H-pyrazole-κN 2]nickel(II) chloride monohydrate, [NiCl(C10H11N3)(H2O)]Cl·H2O, 2, have been synthesized. The crystal structure analyses revealed that complexes 1 and 2 are mononuclear and have ZnN2Cl2 distorted tetrahedral and NiN4OCl distorted octahedral structures, respectively. Complex 1 displays a dimer in the crystal structure, while complex 2 forms a chain along the [010] direction. The fluorescence properties of both complexes were also investigated. A search of the Cambridge Structural Database for other complexes of the ligand 3,5-dimethyl-1-(pyridin-2-yl)-1H-pyrazole (L) shows that there exist different coordination polyhedra with different arrangements as monomers, dimers and polycyclic structures. Here it has also been demonstrated that there is a relationship between the crystal packing and the fluorescence properties of ZnII and CdII complexes of L.

The crystal structure of 4-hydroxy-2,5-bis(1-methyl-1H-imidazol-3-ium-2-ylthio)-3,6-dioxocyclohexa-1,4-dienolate chloride monohydrate, C14H15N4O5S2Cl

C14H15N4O5S2Cl, orthorhombic, Pbca (no. 69), a = 16.1956(11) Å, b = 11.7856(8) Å, c = 18.7814(13) Å, V = 3584.9(4) Å3, Z = 8, Rgt(F) = 0.0459, wRref(F2) = 0.1218, T = 298(2) K.CCDC no.: 2034931

Manganese(II) complexes derived from acyclic ligands having flexible alcohol arms: structural chracterization and SOD and catalase mimetic studies

In this work, a series of seven MnII complexes of noncyclic flexible ligands derived from 2,6-diformylpyridine and ethanolamine or alkyl-substituted ethanolamines were prepared and characterized, six structurally by single-crystal X-ray diffraction studies. The complexes are dichlorido{2,2′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]diethanol}manganese(II), [MnCl2(C11H15N3O2)] or [MnCl2(L1)], (2), bis{μ-2,2′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]diethanol}bis[dithiocyanatomanganese(II)], [Mn2(NCS)4(C11H15N3O2)2] or [Mn2(NCS)4(L1)2], (3), chlorido{1,1′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-2-ol)}manganese(II) chloride monohydrate, [MnCl(C13H19N3O2)(H2O)]Cl·H2O or [MnCl(L2)(H2O)]Cl·H2O, (4), {1,1′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-2-ol)}dithiocyanatomanganese(II), [Mn(NCS)2(C13H19N3O2)] or [Mn(NCS)2(L2)], (5), aquadichlorido{2,2′-dimethyl-2,2′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-1-ol)}manganese(II) 0.3-hydrate, [MnCl2(C15H23N3O2)(H2O)]·0.3H2O or [MnCl2(L3)(H2O)]·0.3H2O, (6), (dimethylformamide){2,2′-dimethyl-2,2′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-1-ol)}dithiocyanatomanganese(II), [Mn(NCS)2(C15H23N3O2)(C3H7NO)] or [Mn(NCS)2(L3)(DMF)], (7), and (dimethylformamide){2,2′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(butan-1-ol)}dithiocyanatomanganese(II) dimethylformamide monosolvate, [Mn(NCS)2(C15H23N3O2)(C3H7NO)]·C3H7NO or [Mn(NCS)2(L4)(DMF)]·DMF, (8). The crystal structure of ligand L1 is also reported, but that of (5) is not. All four ligands (L1–L4) have five potential donor atoms in an N3O2 donor set, i.e. three N (pyridine/diimine donors) and two alcohol O atoms, to coordinate the MnII centre. The N3O2 donor set coordinates to the metal centre in a pentagonal planar arrangement; seven-coordinated MnII complexes were obtained via coordination of two auxiliary ligands (anions or water molecules) at the axial positions. However, in some cases, the alcohol O-atom donors remain uncoordinated, resulting in five- or six-coordinated MnII complexes. The structurally characterized complexes were tested for their catalytic scavenging of superoxide and peroxide. The results indicated that the complexes with coordinated exogenous water or chloride ligands showed higher SOD activity than those with exogenous thiocyanate ligands.