Heteropolymolybdates of Phosphate, Phosphonate, and Phosphite Functionalized by Glycine

The novel, functionalized heteropolymolybdates [RPMo6O21(O2CCH2NH3)3]2- (R = OH, CH3, C2H5, H) have been
synthesized and characterized by IR, 31P NMR spectroscopy, and elemental analysis. Single-crystal X-ray
analysis was carried out on K2[HOPMo6O21(O2CCH2NH3)3]·8.5H2O, which crystallizes in the orthorhombic
system, space group Pnma, with a = 14.118(2) Å, b = 20.660(3) Å, c = 12.191(2) Å, and Z = 4; K2[H3CPMo6O21(O2CCH2NH3)3]·8.5H2O, which crystallizes in the orthorhombic system, space group Pnma, with a = 14.1643(6) Å,
b = 20.8658(8) Å, c = 12.2235(5) Å, and Z = 4; and K2[HPMo6O21(O2CCH2NH3)3]·8H2O, which crystallizes in the
orthorhombic system, space group Pnma, with a = 14.092(3) Å, b = 20.696(2) Å, c = 12.199(4) Å, and Z = 4.
We also report on the synthesis and characterization of the isostructural derivative K2[H5C2PMo6O21(O2CCH2NH3)3]. The four title polyanions consist of an RP (R = OH, CH3, C2H5, H) hetero group surrounded by a ring of
six MoO6 octahedra sharing edges and corners alternatingly. Three glycine molecules are each bound to two
edge-sharing Mo centers via their carboxylate functionality on the same side of the ring. The central phosphorus
atom is located slightly above the plane of the six molybdenums, and its terminal R group is on the same side of
the ring as the glycines. NMR studies show that the solid state structures of the title compounds are preserved in
solution.