Zirconium Phosphates of Variable Dimension Templated by Ethylene Diamine: Crystal Structures of 1-D [enH₂][Zr(HPO₄)₃] and 2-D [enH₂]_0.5[Zr(PO₄)(HPO₄)]

Hydrothermal reaction of Zr(OPr)₄with H₃PO₄in the presence of ethylene diamine and HF yields three crystalline phases; the 1-D [enH₂][Zr(HPO₄)₃], 1, which can grow as needles over 1 mm in length, the 2-D [enH₂]_0.5[Zr(PO₄)(HPO₄)], 2, which is found as thin plates, and the previously reported fluorinated 3-D open-framework compound [enH₂]_0.5[Zr₂(PO₄) ₂(HPO₄)F]. H₂O, 3. The 1-D phase is the first of its type, with each Zr linked to neighboring metal atoms in the chain by three bridging phosphate groups via Zr-O-P-O-Zr linkages. Its crystals are monoclinic, space groupC2/c,a=8.996(3),b=15.373(5),c=9.582(4) Å,β=102.97(2)°,V=1287(1) ų. Compound 2 is orthorhombic, space groupPnnm,a=24.087(4),b=5.381(1),c=6.660(1) Å,V=863.0(4) ų. It is related to the 'double layer' sheet compoundγ-ZrP and its ion exchanged analogues.