Oxomolybdenum(V) polyanion clusters. Hydrothermal syntheses and structures of (NH4)5Na4{Na[Mo6O12(OH)3(O3PC6H5)4)]2}·6H2O (C6H5CH2NMe3)4K4{K2[Mo6O12(OH)3(O3PC6H5)4]2}·10H2O and their relationship to the binuclear (Et4N)[Mo2O4Cl3(H2O)3]·5H2O

The hydrothermal syntheses of the binuclear Mo(V) species (Et4N)[Mo2O4Cl3(H2O)3]·0.5H2O (3·0.5H2O) and of the hexanuclear (NH4)5Na4{Na[Mo6O12(OH)3(O3PC6H5)4)]2}·6H2O (1·6H2O) and (C6H5CH2NMe3)4K4{K2[Mo6O12(OH)3(O3PC6H5)4]2}·10H2O (2·10H2O) are described. X-ray crystallography revealed that both 1·6H2O and 1·10H2O contain the cyclic Mo(V) anion [Mo6O12(OH)3(O3PC6H5)4]5− as the fundamental structural motif. This hexanuclear core may be considered as a trimer constructed from {Mo2O10} units consisting of edge-sharing octahedra with alternating short-long Mo(V)Mo(V) distances. The structure of 3·0.5H2O provides a structural prototype for this binuclear unit. Crystal data: 1·6H2O, C48H78N5O60Na5P8Mo12, monoclinic C2/c, a = 31.254(7), b = 30.441(6), c = 13.455(3) Å, β = 112.87(2)°, V = 11 795(2) Å3, Z = 4, Dcalc = 1.80 g cm−3, 2162 reflections, R = 0.069; 2·10H2O, C88H130N4O64P8K6Mo12, monoclinic P2/c, a = 19.203(4), b = 17.221(4), c = 20.949(5) Å, b = 98.91(3)°, V = 6844(1) Å3, Z = 2, Dcalc = 1.86 g cm−3, 4181 reflections, R = 0.065; 3·0.5H2O, C8H27NO7.5Cl3Mo2, monoclinic P21/n, a = 7.923(2), b = 12.255(3), c = 20.511(3) Å, β = 100.83(2)°, V = 1956.2(6) Å3, Z = 4, Dcalc = 1.89 g cm−3, 2161 reflections, R = 0.060.