Modified polyoxometalates: Hydrothermal syntheses and crystal structures of three novel reduced and capped Keggin derivatives decorated by transition metal complexes

Three novel polyoxometalate derivatives decorated by transition metal complexes have been hydrothermally synthesized. Compound 1 consists of [(PMo6Mo2V8O44)-Mo-VI-V-V-O-IV{CO (2,2'-bipy)(2)(H2O)}(4)](3+) polyoxocations and [(PMo4Mo4V8O44)-Mo-IV-V-V-O-IV{Co(2,2'-bipy)(2)(H2O)}(2)](3-) polyoxoanions, which are both built on mixed-metal tetracapped [PMo8V8O44] subunits covalently bonded to four or two {Co(2,2'-bpy)(2)(H2O)}(2+), clusters via terminal oxo groups of the capping V atoms. Compound 2 is built on [(PMo8V6O42)-V-VI-O-IV{Cu-I(phen)}(2)](5-) clusters constructed from mixed-metal bicapped [(PMo8V6O42)-V-VI-O-IV](7-) subunits covalently bonded to two {Cu(phen)}(+) fragments in the similar way to 1. The structure of 3 is composed of [(PMo9Mo3O40)-Mo-VI-O-V](6-) units capped by two divalent Ni atoms via four bridging oxo groups. The crystal data for these are the following: C120H126Co6Mo16N24O103P2V16 (1), triclinic P (1) over bar, a = 15.6727(2) Angstrom, b = 17.3155(3) Angstrom, c = 19.5445(2) Angstrom, alpha = 86.1520(1)degrees, beta = 81.2010(1)degrees, gamma = 63.5970(1)degrees, Z = 1; C120H85Cu6Mo8N20O44PV6 (2), triclinic P (1) over bar, a = 14.565(4) Angstrom, b = 15.899(3) Angstrom, c = 16.246(4) Angstrom, alpha = 116.289(2)degrees, beta = 103.084(2)degrees, gamma = 94.796(2)degrees, Z = 1; C60H40Mo12N10Ni3O40P (3), monoclinic P2(1)/c, a = 14.804(3) Angstrom, b = 22.137(4) Angstrom, c = 25.162(5) Angstrom, alpha = 90degrees, beta = 98.59(3)degrees, gamma = 90degrees, Z = 4.