Solid state coordination chemistry: Structural consequences of varying diphosphonate tether length and fluoride incorporation in the copper–bisterpy/oxomolybdenum/organodiphosphonate system (bisterpy = 2,2′:4′,4″:2″,2″′-quarterpyridyl-6′,6″-di-2

The hydrothermal reactions of Cu(C2H3O2)2·H2O, MoO3, 2,2′:4′,4″:2″,2′″-quarterpyridyl-6′,6″-di-2-pyridine (bisterpy), and organodiphosphonate ligands of varying carbon chain length in the presence of HF yield a series of novel organic–inorganic hybrid materials of the oxomolybdenum–organophosphonate family. All compounds of the study were characterized by elemental analysis, IR spectroscopy, TGA, magnetic susceptibility and single crystal X-ray diffraction. A common feature within the architectures of both the three-dimensional structure of [{Cu2(bisterpy)(H2O)}Mo5O15{O3P(CH2)4PO3}]·4.5H2O (1) and the one-dimensional structure of [{Cu2(bisterpy)(H2O)2}Mo5O15{O3P(CH2)5PO3}] (2) is the presence of {Mo5O15(O3PR)2}4− clusters as building blocks. In the one-dimensional [{Cu2(bisterpy)(H2O)2}Mo2F6O4{HO3P(CH2)4PO3H}] (6), {Cu2(bisterpy)}Mo2F4O4{HO3P(CH2)5PO3H}2]·2H2O (7·2H2O), [{Cu2(bisterpy)(H2O)2}Mo4F8O8{O3P(CH2)6PO3}]·H2O (8·H2O) and [{Cu2(bisterpy)(H2O)2}Mo4F8O8{O3P(CH2)9PO3}] (9), the two-dimensional [{Cu2(bisterpy)(OH)}Mo2F3O4{O3P(CH2)PO3}]·11H2O (3·11H2O) and [{Cu2(bisterpy)(H2O)2}Mo4F4O10{O3P(CH2)2PO3}] (4), and the three-dimensional [{Cu2(bisterpy)}Mo4F6O9{O3P(CH2)3PO3}] (5), the pentamolybdate core has not been formed due to the incorporation of fluoride ions; rather a variety of {MoxFyOz} units link the copper–bisterpy units. All structures contain the secondary metal–ligand {Cu2(bisterpy)(H2O)x} binuclear unit. The materials of this study demonstrate the wide structural variety available to this family of compounds by modifying both the carbon chain length of the organodiphosphonate ligand and by incorporation of fluoride within the structure.