ORGANOAMMONIUM DIPHOSPHOPENTAMOLYBDATES(VI) - INFLUENCE OF ORGANIC CATIONS AND ANION PROTONATION ON CRYSTAL PACKING AND GEOMETRICAL FEATURES OF POLYANION

Four organoammonium diphosphopentamolybdate(VI) with the formulae (C5H 7N2)(6)[P2Mo5O23]. 5H(2)O (1), (C2H10N2)(3)[P2Mo5O23]. 6H(2)O (2), Al( C4H15N3)(4)[HP2Mo5O23]Cl-2 . 10H(2)O (3) and (C4H12N)(4)[H2P2Mo5O23]. 5H(2)O (4) have been synthesized. The crystal structures have been det ermined by means of single crystal X-ray diffraction data. The geometr ical characteristics of the [HgP2Mo5O23]((6-n)-) heteropolyanions have been compared with those described in the literature for other salts. Several relationships between the protonated state and topological ch anges in the heteropolyanions have been found. The crystal structure i n compound 1 is stabilized by electrostatic forces, an extensive netwo rk of hydrogen contacts involving anions, cations and water molecules and pi-pi interactions among 4-aminopyridinium cations. The anions of compound 2 are arranged in layers perpendicular to the [<(1)over bar 1 0>] direction. The interactions between anions are established through hydrogen contacts which involve water molecules and ethylenediammoniu m cations. The monohydrogendiphosphopentamolybdate (VI) anions in the crystal structure of compound 3 are joined along the [010] direction b y means of strong O-H ... O interactions (d(O ... O)=2.529(10) Angstro m) which lead to a polymeric structure of [HP2Mo5O23](5-) polyanions. Likewise, a similar anion polymeric arrangement is found in compound 4 in which the diprotonated polyanions are held together by means of tw o strong hydrogen bonds (d(O ... O)=2.591(6) and 2.596(6) Angstrom).