Hydrothermal synthesis, structure and quantum chemistry of transition metal complex supported by metal-oxo cluster [{Ni(phen)2}2(x-Mo8O26)]

A nickel-1,10-phenanthroline complex supported on an octamolybdate, {Ni(phen)2}2(x- Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2· 6H2O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to monoclinic P21/n space group, a = 1.2952(2), b = 1.6659(10), c = 1.3956(12) nm, b =106.273(8)°, V = 2.8906(5) nm3, Z = 2. 5604 observable reflections (I ＞2s(I)) were used for structure resolution and refinements to converge to final R1 = 0.0414, wR2 = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as x-isomer). The feature of x-Mo8O26]4- is that it is composed of Mo6O6 ring and two MoO6 octahedra located at cap positions on opposite faces. The Mo6O6 ring contains two octahedral and four trigonal-bipyramidal MoVI atoms. Each x-Mo8O26]4- unit is bonded with two Ni(phen)2]2+ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo6O6 ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method.