SYNTHESES AND CHEMICAL, SPECTROSCOPIC AND STRUCTURAL STUDY OF 4-AMINOPYRIDINIUM SALTS OF DITHIOOXALATE LIGAND COMPLEXES, [M(S2C2O2)2]2- (M = NI-II, PD-II OR PT-II)

被引:16
作者
ROMAN, P
BEITIA, JI
LUQUE, A
GUTIERREZZORRILLA, JM
机构
[1] Departamento de Química Inorgánica, Universidad del País Vasco, 48080 Bilbao
关键词
4-AMINOPYRIDINIUM; DITHIOOXALATE; NICKEL; PALLADIUM; PLATINUM;
D O I
10.1016/0025-5408(92)90063-6
中图分类号
T [工业技术];
学科分类号
08 ;
摘要
The synthesis conditions, the solid state characterization and the crystal structures of three 4-aminopyridinium salts of planar inorganic dithiooxalato anions, (C5H7N2)2[M(S2C2O2)2].2H2O where M = Ni(II), Pd(II) and Pt(II) (hereafter abbreviated as NIDT4AP, PDDT4AP, and PTDT4AP, respectively), are described. The compounds have been prepared by reaction of 4-aminopyridinium hydrochloride and the corresponding K2[M(S2C2O2)2] in aqueous solution, and then recrystallized in N,N-dimethylformamide. The compounds have been identified by using IR, thermoanalytical, and X-ray diffraction techniques. X-ray diffraction analyses of these compounds show that all of them are isostructural and crystallize in monoclinic system, space group C2/m, Z = 2. The crystal and molecular structure of compound PDDT4AP was determined: a = 10.462(1), b = 12,020(4), c = 9.207(1) angstrom, beta = 114.44(5)-degrees, V = 1054.1(6) angstrom 3, Z = 2, F(000) = 576, mu = 12.866 cm-1, M = 572.98, D(o) = 1.80(1), D(x) = 1.81 Mg.m-3, and lambda(MoK-alpha) = 0.71069 angstrom. Final refinement led to R = 0.025 and wR = 0.030 for 1542 observed reflections with I > 3-sigma(I). The unit cell is made up of bis(dithiooxalato)palladate(II) anions and 4-aminopyridinium cations forming layers, and the water molecules occupy the space among them. In the crystal structure there are some significant pi-pi interactions between the aromatic cations and also d(z)2-pi interactions between the metal ion of the complex anion and the planar cations. There is also an extensive hydrogen bond network. All these types of interactions ensure the lattice cohesiveness and give to the compound a tridimensional character.
引用
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页码:339 / 347
页数:9
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