Two novel organic-inorganic hybrid compounds {[Cu(o-phen)(H₂O)]₃[Mo₅P₂O₂₃]}•4.5H₂O (1) and {[Cu(o-phen)(H₂O)]₂[Mo₅Se₂O₂₁]} (2) (o-phen＝1,10-phenanthroline) have been synthesized by the hydrothermal reaction and structurally characterized by IR spectra and single crystal X-ray diffraction analysis. Their crystal structure determination reveals that the adjacent [Mo₅P₂O₂₃]^6－ or [Mo₅Se₂O₂₁]^4－ anions for the two molecular structures are joined by two bridging [Cu(o-phen)(H₂O)] units, thus making up a one dimensional chain in a wind-mill and double-side bridging style, respectively. In the lattice of compound 1, the bimetallic chains are linked through several hydrogen bonds to form a layer-like packing structure. The matching relationship between heteropolyoxomolybdate anion and secondary metal-ligand subunit was also discussed.

Key words: organic-inorganic hybrid compound, heteropolyoxomolybdate, phosphorous, selenium, copper-phenanthroline subunit, hydrothermal synthesis, crystal structure, IR spectrum