ABSTRACT
The ferromagnetic couplings were observed in an unpublished crystal that consists of binuclear copper(II) complexes, namely, [Cu(2)(µ(1,3)-SCN)(2)(PhenOH)(OCH(3))(2)(HOCH(3))(2)] (PhenOH = 2-hydroxy-1,10-phenanthroline), and in the binuclear complex Cu(ii) ion assumes a distorted octahedral geometry and thiocyanate anion functions as a µ(1,3)-SCN(-) equatorial-axial (EA) bridging ligand. The analysis for the crystal structure indicates that there are three types of magnetic coupling pathways, in which two pathways involve π-π stacking between the adjacent complexes and the third one is the µ(1,3)-SCN(-) bridged pathway. The fitting for the data of the variable-temperature magnetic susceptibilities shows that there is a ferromagnetic coupling between adjacent Cu(II) ions with J = 50.02 cm(-1). Theoretical calculations reveal that the two types of π-π stacking resulted in ferromagnetic couplings with J = 4.16 cm(-1) and J = 2.75 cm(-1), respectively, and the bridged thiocyanate anions pathway led to a weaker ferromagnetic interaction with J = 0.88 cm(-1). The theoretical calculations also indicate that the ferromagnetic coupling sign from the two types of π-π stacking does not accord with McConnell I spin-polarization mechanism. The analysis for the Wiberg bond indexes that originate from the π-π stacking atoms indicates that the Wiberg bond indexes are relevant to the associated magnetic coupling magnitude and the Wiberg bond index is one of the key factors that dominates the associated magnetic coupling magnitude.
Subject(s)
Copper/chemistry , Organometallic Compounds/chemistry , Computer Simulation , Crystallography, X-Ray , Models, Molecular , Organometallic Compounds/chemical synthesisABSTRACT
In the title mononuclear complex, [Ni(C(3)H(2)O(4))(C(15)H(10)N(4))(H(2)O)]·3H(2)O, the metal center is coordinated in a distorted NiN(3)O(3) geometry. In the crystal structure, inter-molecular O-Hâ¯O hydrogen bonds link the components into a two-dimensional network. In addition, there are weak π-π stacking inter-actions between symmetry-related phenanthroline rings, with a centroid-centroid distance of 3.6253â (17)â Å.
ABSTRACT
In the title complex, [Ni(NCS)(2)(C(14)H(13)N(3))(2)]·2CH(3)OH, the Ni(II) atom lies on a crystallographic twofold rotation axis and is in a slightly distorted octa-hedral NiN(6) coordination environment. The crystal structure is stabilized by a combination of weak π-π stacking inter-actions between symmetry-related 1,10-phenanthroline ligands [centroi-centroid distance between benzene rings = 3.5936â (18)â Å] and weak O-Hâ¯S, C-Hâ¯O and C-Hâ¯S hydrogen bonds between methanol and complex mol-ecules.
ABSTRACT
In the title complex, [Zn(NCS)(2)(C(13)H(10)N(2)O)], the Zn(II) ion is in a distorted tetra-hdral ZnN(2)Cl(2) coordination environment. In the crystal structure, there is a weak π-π stacking inter-action between adjacent 1,10-phenanthroline rings, with a pyridine centroid-centroid distance of 3.6620â (15)â Å.
ABSTRACT
There are two molecules of the title complex, [ZnCl(2)(C(13)H(10)N(2)O)], in the asymmetric unit. Each Zn atom assumes a distorted tetra-hedral ZnN(2)Cl(2) coordination geometry. There are weak π-π stacking inter-actions between adjacent 1,10-phenanthroline rings [centroid-centroid distances = 3.6356â (18) and 3.6353â (18)â Å].
