A Nine‐Coordinated ZrIV Complex and a Self‐Assembling System Obtained from a Proton Transfer Compound Containing 2,6‐Pyridinedicarboxylate and 2,6‐Pyridinediammonium; Synthesis and X‐ray Crystal Structure

Starting with a zirconium salt and LH₂ , (pydaH₂)²⁺(pydc)^2?, (pyda=2, 6‐pyridinediamine; pydcH₂=2,6‐pyridinedicarboxylic acid), as a 1:1 proton transfer self‐associated compound, two different compounds were resulted. One of them is a new complex of Zr^IV with a flat pyridine containing ligand and structure of (pydaH)₂[Zr(pydc)₃] · 5H₂O (1) and the other, (pydaH)⁺(NO₃)^? (2) is an ion pair with no zirconium ion. The zirconium(IV) complex (1) is crystallized in triclinic system with space group and Z = 2, the crystallographic parameters are: a = 10.612(5) Å, b = 10.617(5) Å, c = 16.815(8) Å, α = 103.654(9)°, β = 95.821(9)°, γ = 98.891(9)° and R‐value for 16767 collected reflections is 0.0592. The ion pair (2) has crystals of monoclinic system with P2₁ space group and Z = 2. Its crystallographic parameters are: a = 3.6227(11) Å, b = 10.034(4) Å, c = 10.296(4) Å, β = 93.422(9)° and R‐value for 4031 collected reflections is 0.0521. The two compounds were characterized with elemental analysis, ESI/MS, NMR and IR spectroscopy.